Carbon for a lithium secondary battery, lithium secondary battery, and manufacturing methods therefor

A superior lithium secondary battery having high total discharge capacity, high effective discharge capacity, high total discharge efficiency, and high effective discharge rate can be obtained by using, as a carbon electrode for a lithium secondary battery, a carbon for a lithium secondary battery obtained by successively conducting a halogenation treatment, a dehalogenation treatment, and a pore adjustment treatment on a dry-distilled charcoal, or by successively conducting a crushing treatment, a molding treatment, and a carbonization treatment on a dry-distilled charcoal.

TECHNICAL FIELD 
The present invention relates to a carbon for a lithium secondary batteries 
which is suitable as electrode material for rechargeable lithium secondary 
batteries; to a manufacturing method therefor, and to a lithium secondary 
battery. 
BACKGROUND ART 
As the starting material for a carbon for an electrode, carbonized plant 
and animal material such as lignite, brown coal, anthracite coal, coke, 
wood charcoal, coconut shell char; any kind of resin such as phenol resin, 
furan resin, vinylidene chloride copolymer, etc., which have been heated 
(dry-distilled) in an inert gas, and the like may be used. 
Because carbonaceous materials are chemically inactive, they are used in a 
wide range of applications such as adsorption agents, catalysts, electrode 
materials, structural materials for use in machines, etc.; however, these 
applications are closely related to the structure of the carbon. 
That carbon which is referred to as porous carbon has special effects due 
to the development of pores. For example, using the adsorption phenomena, 
there are mixture separation and refining actions. In addition, the carbon 
used in electrical double layer capacitors, the carbon used in lithium 
secondary batteries, and the like display electrochemical storage effects. 
The structure of the carbonaceous material can take various forms depending 
on the starting material and the manufacturing method. Char and activated 
carbon obtained by activating char comprise microcrystalline carbon 
(crystallite), and carbon which takes on a chain structure. When the 
carbonaceous material is a nongraphitizing carbon, the crystallites take 
on a structure which is layered in a disorderly manner, and a wide range 
of pores, from micropores to macropores, are formed in the gaps between 
these crystallites. 
The crystallites are layers of net planes of six membered carbon rings of 
several parallel layers, and graphite carbon which has a six membered 
carbon ring structure bonds using hybridized orbitals SP.sup.2. A net 
plane comprising six membered ring carbon is called a basal plane. 
A graphitizing carbon develops crystallites by means of heating at a high 
temperature, and finally becomes graphite. 
A nongraphitizing carbon and a graphitizing carbon which has not been 
completely graphitized usually contain unorganized carbon. Unorganized 
carbon refers to carbon other than graphite carbon which is chemically 
bonded to graphite carbon only; carbon which has a chain structure; carbon 
which is stuck around six membered ring carbon; carbon which is in the 
periphery (the prism plane) of six membered ring carbon; carbon which is 
held in cross-linked structures with other six membered carbon rings 
(crystallites), and the like. Unorganized carbon is bonded with oxygen 
atoms, hydrogen atoms, and the like in forms such as C--H, C--OH, C--OOH, 
and C.dbd.O; or is in the form of double bonded carbon (--C=C--). 
Lithium secondary batteries which use porous carbonaceous material in the 
negative electrode are charged by means of the uptake (doping) of lithium 
ions by the carbonaceous material of the negative electrode and are 
discharged by the release (un-doping) of lithium ions. In this lithium 
secondary battery, the charging capacity is determined by the amount of 
lithium ions with which the carbonaceous material is doped and the 
discharging capacity is determined by the un-doping amount. The efficiency 
of the electrical charging and discharging is defined as the ratio of the 
charging capacity to the discharging capacity. 
When using graphite as the above-mentioned carbonaceous material, the 
lithium ions are taken in between the layers of the net planes of the 
carbon. In this case, the opinion is that the theoretical maximum for the 
doping quantity is when there is one lithium ion for every six carbon 
atoms. However, there are reports that, when non-graphitizing carbonaceous 
material is used, charging capacities which exceed the above-mentioned 
theoretical maximum amount can be obtained. 
To the present, various proposals have been made for manufacturing methods 
for electrode carbon for lithium secondary batteries. For example, those 
recited in Japanese Patent Application, First Publication, No. Hei 
2-66856; Japanese Patent Application, First Publication, No. Hei 6-187972; 
Japanese Patent Application, First Publication, No. Sho 61-218060; 
Japanese Patent Application, First Publication, No. Hei 5-335017; Japanese 
Patent Application, First Publication, No. Hei 2-230660; Japanese Patent 
Application, First Publication, No. Hei 5-89879; Japanese Patent 
Application, First Publication, No. Hei 5-182668; Japanese Patent 
Application, First Publication, No. Hei 3-245473; and Japanese Patent 
Application, First Publication, No. Hei 5-144440. 
Japanese Patent Application, First Publication, No. Hei 2-66856 discloses 
that a carbon in which the distance d.sub.002 of the crystals is 3.80 
.ANG. and for which the density is 1.55 g/cm.sup.3 can be obtained by 
carbonizing furfuryl alcohol resin at 500.degree. C., and then 
heat-treating it at 1100.degree. C., and that it is possible to dope the 
spaces between the carbon net planes with a large amount of lithium ions. 
Japanese Patent Application, First Publication, No. Hei 6-187972 obtains a 
carbonaceous material by reacting a condensed polynuclear aromatic 
compound and a cross linking agent such as paraxyleneglycol, and baking 
the generated resin at a temperature of 1000.degree. C. or greater. The 
aromatic component forms a crystallized graphite structure and the 
cross-linking agent forms a non-crystallized domain, and this is suitable 
as a carbonaceous material for a lithium secondary battery. 
Japanese Patent Application, First Publication, No. Sho 61-218060 discloses 
that a substance obtained by heat-treating an aromatic condensed resin, 
such as polyacene, and which has a H/C atomic ratio of 0.5.about.0.05, a 
BET specific surface area of 600 m.sup.2 /g or greater, and communicating 
pores having an average pore size of 10 .mu.m is suitable. It discloses 
that it is possible to manufacture a carbon having the above-mentioned 
characteristics by means of adjusting an aqueous solution of an initial 
polymer and an inorganic salt such as zinc chloride, and then 
heat-treating this at a temperature of 350.about.800.degree. C. which 
causes a three dimensional network structure to develop. 
(Problem to be Solved By the Present Invention) 
Lithium secondary batteries are used as power sources for portable 
telephones, small size personal computers and the like, however, when used 
for these applications, the total discharge capacity, total discharge 
efficiency, effective discharge capacity, and effective discharge ratio 
(these are called discharging characteristics) are insufficient, and 
improvements in these are desired. 
Lithium secondary batteries, in general, have the problems of irreversible 
charging and discharging due to which the whole of the charging capacity 
cannot be discharged, and that the total discharge capacity and effective 
discharge capacity are low. 
In addition, in a secondary battery which is used at a certain fixed 
voltage, large effective discharge capacity which can maintain that 
voltage, and large effective discharge ratio are sought, and conventional 
lithium secondary batteries do not have satisfactory discharging 
characteristics. 
The present invention learning from the above circumstances, aims to 
provide a carbon for a lithium secondary battery which can be used in the 
manufacture of lithium secondary batteries which have excellent 
discharging characteristics by using this carbon in the electrode material 
of chargeable lithium secondary batteries, a manufacturing method 
therefor, and a lithium secondary battery. 
DISCLOSURE OF INVENTION 
A first aspect of the present invention is a manufacturing method for a 
carbon for a lithium secondary battery comprising a halogenation step in 
which a halogenated dry-distilled charcoal is obtained by bringing a gas 
which contains halogen into contact with dry-distilled charcoal; a 
dehalogenation step in which a dehalogenation treated carbon is obtained 
by eliminating a part or all of the halogen in the above-mentioned 
halogenated dry-distilled charcoal; and a pore adjustment step in which 
this dehalogenation treated carbon is brought into contact with thermally 
decomposable hydrocarbon. 
In this first aspect, the above-mentioned dry-distilled charcoal may be a 
dry-distilled phenol resin. 
The above-mentioned halogen may be one selected from the group consisting 
of chlorine, bromine, and a combination of chlorine and bromine. 
The above-mentioned halogenation step may be a heat treatment conducted at 
a temperature of 350.about.1000.degree. C. in a gas containing halogen 
diluted with an inert gas. 
The above-mentioned dehalogenation step may include at least one 
dehalogenation treatment selected from the group consisting of a) a 
dehalogenation treatment in which a halogenated dry-distilled charcoal is 
heated at a temperature of 700.about.1400.degree. C. in an inert gas or 
under vacuum evacuation; b) a dehalogenation treatment in which heating is 
conducted at a temperature of 600.about.850.degree. C. in lower 
hydrocarbon gas or in steam diluted with an inert gas; and c) a 
dehalogenation treatment in which heating is conducted at a temperature of 
600.about.1400.degree. C. in hydrogen gas diluted with an inert gas. 
This dehalogenation step may be any one step selected from the group 
consisting of: a step in which the above-mentioned treatment a) is 
conducted; a step in which the above-mentioned treatment b) or the 
above-mentioned treatment c) is conducted; a step in which the 
above-mentioned treatment a) is conducted, and, thereafter, either one of 
the above-mentioned treatment b) or the above-mentioned treatment c) is 
conducted; and a step in which either one of the above-mentioned treatment 
b) or the above-mentioned treatment c) is conducted, and, thereafter, the 
above-mentioned treatment a) is conducted. 
After the above-mentioned dehalogenation step, a crushing step in which the 
above-mentioned dehalogenation treated carbon is crushed may be included, 
and after the above-mentioned crushing step, the above-mentioned pore 
adjustment step may be conducted. 
The above-mentioned pore adjustment step may be a heat treatment conducted 
at a temperature of 600.about.1100.degree. C. in a thermally decomposable 
hydrocarbon diluted with an inert gas. 
The above-mentioned thermally decomposable hydrocarbon may generate carbon 
when thermally decomposed and may be at least one hydrocarbon selected 
from the group consisting of aromatic hydrocarbons, cyclic hydrocarbons, 
saturated chain hydrocarbons, and unsaturated chain hydrocarbons. 
From the completion of the above-mentioned dehalogenation step to the 
beginning of the above-mentioned pore adjustment step, it is preferable 
for the above-mentioned dehalogenation treated carbon to be handled in an 
inert gas. 
A molding step in which one of either of the above-mentioned dry-distilled 
charcoal or the above-mentioned halogenated dry-distilled charcoal and an 
organic binding agent added thereto are molded may be included. 
When the above-mentioned molding step is a step in which a molding 
treatment is conducted in which the above-mentioned dry-distilled charcoal 
and an organic binding agent added thereto are molded, a second 
dry-distillation step may be conducted in which this organic binding agent 
is carbonized by heating the dry-distilled charcoal in an inert gas after 
the molding step, and after this second dry-distillation step, the 
above-mentioned halogenation step may be conducted. 
When the above-mentioned molding step is a step in which a molding 
treatment is conducted in which the above-mentioned halogenated 
dry-distilled charcoal and an organic binding agent added thereto are 
molded, the above-mentioned dehalogenation step may be conducted after 
this molding step. In this case, the dehalogenation step may be a heat 
treatment in which the rate of temperature increase is 
20.about.500.degree. C./h. 
A carbonization step in which the above-mentioned organic binding agent in 
the halogenated dry-distilled charcoal after the above-mentioned molding 
step is carbonized can also be conducted. This carbonization step can be a 
heat treatment in which heating is conducted in an inert gas at a 
temperature of 450.about.1300.degree. C. with a rate of temperature 
increase of 20.about.500.degree. C./h. 
By means of the manufacturing method of the above-mentioned first aspect, a 
carbon for a lithium secondary battery can be obtained. 
This carbon for a lithium secondary battery can have a density of 
0.7.about.1.2 g/cm.sup.3. 
In a manufacturing method for a lithium secondary battery comprising a 
carbon electrode, a lithium electrode, and an electrolytic solution 
provided between these electrodes, a lithium secondary battery can be 
manufactured by means of conducting an assembly step in which a lithium 
secondary battery is assembled in a dried inert gas using a carbon for a 
lithium secondary battery obtained by means of the manufacturing method of 
the above-mentioned first aspect as the carbon electrode. 
In addition, in a lithium secondary battery comprising a carbon electrode, 
a lithium electrode, and an electrolytic solution provided between these 
electrodes, a carbon for a lithium secondary battery obtained by means of 
the manufacturing method of the above-mentioned first aspect may be used 
as the carbon electrode. 
A second aspect of the present invention is a manufacturing method for a 
carbon for a lithium secondary battery comprising a crushing step in which 
a dry-distilled charcoal is crushed; a molding step in which a molded 
article is obtained by conducting a molding treatment on this crushed 
dry-distilled charcoal and an organic binding agent added thereto; and a 
carbonization step in which the above-mentioned organic binding agent in 
the above-mentioned molded article is carbonized. 
The above-mentioned dry-distilled charcoal may be a phenol resin which has 
been dry-distilled. 
The above-mentioned carbonization step may be a heat treatment in an inert 
gas in which the temperature is raised at a rate of 20.about.500.degree. 
C./h, and heating is conducted at a temperature of 700.about.1400.degree. 
C. 
After the above-mentioned carbonization step, a pore adjustment step can be 
conducted in which the molded article is brought into contact with a 
thermally decomposable hydrocarbon. 
The above-mentioned pore adjustment step may be a heat treatment conducted 
at a temperature of 600.about.1100.degree. C. in a thermally decomposable 
hydrocarbon diluted with an inert gas. 
The above-mentioned thermally decomposable hydrocarbon may generate carbon 
when thermally decomposed and may be at least one hydrocarbon selected 
from the group consisting of aromatic hydrocarbons, cyclic hydrocarbons, 
saturated chain hydrocarbons, and unsaturated chain hydrocarbons. 
From the completion of the above-mentioned carbonization step to the 
beginning of the above-mentioned pore adjustment step, it is preferable 
for the above-mentioned carbonization treated molded article to be handled 
in an inert gas. 
By means of the manufacturing method of the above-mentioned second aspect, 
a carbon for a lithium secondary battery can be obtained. 
This carbon for a lithium secondary battery can have a density of 
0.7.about.1.2 g/cm.sup.3. 
In addition, this carbon for a lithium secondary battery can have a pore 
volume of 0.15.about.0.4 cm.sup.3 /g. 
In a manufacturing method for a lithium secondary battery comprising a 
carbon electrode, a lithium electrode, and an electrolytic solution 
provided between these electrodes, a lithium secondary battery can be 
manufactured by means of conducting an assembly step in which a lithium 
secondary battery is assembled in a dried inert gas using a carbon for a 
lithium secondary battery obtained by means of the manufacturing method of 
the above-mentioned second aspect as the carbon electrode. 
In addition, in a lithium secondary battery comprising a carbon electrode, 
a lithium electrode, and an electrolytic solution provided between these 
electrodes, a carbon for a lithium secondary battery obtained by means of 
the manufacturing method of the above-mentioned second aspect may be used 
as the carbon electrode.

BEST MODE FOR CARRYING OUT THE INVENTION 
Suitable modes of the invention are set out below. 
First Mode 
A process diagram for a manufacturing method for a carbon for a lithium 
secondary battery according to a first mode of the present invention is 
shown in FIG. 1. 
According to the manufacturing method for a carbon for a lithium secondary 
battery shown in FIG. 1A, carbon for a lithium secondary battery is 
manufactured by successively conducting a halogenation step in which a 
halogenation treatment is conducted to obtain a halogenated dry-distilled 
charcoal by bringing a dry-distilled charcoal into contact with a halogen 
gas; a dehalogenation step in which a dehalogenation treatment is 
conducted to obtain a dehalogenation treated carbon by eliminating a part 
or all of the halogen in the above-mentioned halogenated dry-distilled 
charcoal; and a pore adjustment step in which a pore adjustment treatment 
is conducted in which this halogenation treated carbon is brought into 
contact with a thermally decomposable hydrocarbon. 
In addition, according to the manufacturing method for a carbon for a 
lithium secondary battery shown in FIG. 1B, after the above-mentioned 
dehalogenation step in the manufacturing method shown in the 
above-mentioned FIG. 1A, a crushing step is conducted in which a crushing 
treatment for crushing the above-mentioned dehalogenation treated carbon 
is conducted, and by means of conducting the above-mentioned pore 
adjustment treatment on the dehalogenation treated carbon crushed in this 
way, a carbon for a secondary lithium battery is manufactured. 
In this first mode, it is preferable for the above-mentioned dehalogenation 
treatment to be a treatment of at least one of a high temperature 
dehalogenation treatment and a low temperature dehalogenation treatment. A 
treatment in which a halogenation treatment and a dehalogenation treatment 
are conducted is called a halogen treatment. 
As the dry-distilled charcoal used in the manufacturing method for a carbon 
for a lithium secondary battery of the present invention, a substance 
obtained by the dry-distillation of any kind of starting material such as 
carbonized plant and animal material such as lignite, brown coal, 
anthracite coal, coke, wood charcoal, coconut shell char; any kind of 
resin such as phenol resin, furan resin, vinylidene chloride copolymer, 
etc., can be used, and from among these, phenol resin is preferably used. 
Starting materials such as phenol resin are made into dry-distilled 
charcoal by suitably heating (dry distillation) them at a temperature of 
550.about.1100.degree. C. in an inert gas such as nitrogen gas or argon. 
In this dry distillation, in order to manufacture uniform dry-distilled 
charcoal, it is preferable to make the starting material into granules or 
cylinders of several millimeters, and then dry-distill them in an inert 
gas. In addition, powdered starting material and an organic binder added 
thereto may be molded, and then dry-distilled. 
In the manufacturing method for carbon for a lithium secondary battery 
according to this first mode, firstly, a porous carbonaceous material is 
manufactured by conducting a halogenation treatment on a dry-distilled 
charcoal. In this halogenation treatment, it is possible to use any 
halogen, however, chlorine gas and bromine gas are preferably used. 
Using chlorinated dry-distilled charcoal as an example, the degree of 
chlorination of the halogenated dry-distilled charcoal is expressed by the 
atomic ratio of chlorine and carbon (Cl/C). This atomic ratio in the 
chlorination step is a molar ratio of the numbers of atoms which are 
obtained by the conversion from the weight of carbon and the weight of 
chlorine, in which the weight of the carbonized charcoal before the 
chlorination step is assumed to be the weight of carbon and the weight 
increase due to the chlorination step is assumed to be the weight of 
chlorine. In addition, in the dechlorination step, the degree of 
dechlorination is calculated from the value which is obtained by taking 
the weight decrease due to the dechlorination step to be the reduction in 
the quantity of chlorine, converting this into the number of atoms, and 
subtracting it from the number of chlorine atoms in the chlorinated 
carbon. 
In real halogen treatments, due to the destructive distillation action 
accompanying the progress of carbonization, the activated action by steam 
(the gasification of carbon) and the like, the ratio of the number of 
atoms according to the above definition can also be a negative value. 
The halogenation treatment is, when using chlorine gas for example, carried 
out by means of conducting a treatment in which dry-distilled charcoal is 
heated at a temperature of 350.about.1000.degree. C., preferably 
400.about.800.degree. C., and more preferably at 500.about.700.degree. C. 
in chlorine gas which has been diluted with an inert gas such as nitrogen. 
In addition, when using bromine in place of chlorine, a treatment is 
conducted in which dry-distilled charcoal is heated at a temperature of 
350.about.1000.degree. C., and preferably 400.about.800.degree. C. in 
bromine gas which has been diluted with an inert gas such as nitrogen. 
In the halogenation treatment, when the temperature of the heat treatment 
of the chlorination treatment (for example) exceeds 1000.degree. C., due 
to the reduction in the quantity of hydrogen atoms as the carbonization 
progresses, the degree of chlorination is reduced, and therefore this is 
not desirable. In addition, when the temperature of the heat treatment of 
the chlorination treatment is less than 350.degree. C., because the 
reaction rate of the unorganized carbon and the chlorine is too slow, a 
long period of time is required for the chlorination treatment, and 
therefore this is not desirable. This is the same for bromination 
treatments. 
With regard to the supply rate for the chlorine gas, when the concentration 
of the chlorine gas is 10% by volume, the superficial velocity in the 
column is of the level of 0.05.about.0.3 NL/(min.cm.sup.2)(NL expresses 
the volume of the gas under standard conditions; this is the same 
hereinafter). The time for the chlorination treatment is about 
30.about.120 minutes when in the high temperature region of the 
above-mentioned temperature range; however, about 120.about.240 minutes 
are required when in the low temperature range close to 400.degree. C. In 
addition, with regard to the supply rate for bromine gas, when the 
concentration of the bromine gas is 10% by volume, the superficial 
velocity in the column is of the level of 0.05.about.0.3 
NL/(min.cm.sup.2). The time for the bromination treatment is about 
30.about.120 minutes when in the high temperature region; however, about 
120.about.240 minutes are required when in the lower temperature region. 
In the halogenation treatment, in the main, since hydrogen atoms in the 
dry-distilled charcoal are replaced by halogen atoms, such as chlorine 
atoms, halogenated hydrogen, such as hydrogen chloride (HCl) and hydrogen 
bromide (HBr), is detected in the exhaust gas. 
Here, the inert gases are nitrogen, rare gases such as helium and argon, or 
mixes of these gases. 
By means of the above-mentioned halogenation treatment, halogenated 
dry-distilled charcoals such as a chlorinated dry-distilled charcoal 
having an atomic ratio of chlorine to carbon (Cl/C) of 0.03 or greater, 
and preferably of 0.07 or greater, and a brominated dry-distilled charcoal 
having an atomic ratio of bromine to carbon (Br/C) of 0.01 or greater, and 
preferably 0.03 or greater can be obtained. Moreover, it is not desirable 
for this atomic ratio to be less than the above-mentioned minimum values, 
since the formation of micropores is insufficient, and when the 
manufactured carbonaceous material is used in lithium secondary battery, 
good charging and discharging properties cannot be obtained. In addition, 
the upper limit of the above-mentioned atomic ratio is determined by the 
carbonization temperature and the quantity of hydrogen atoms in the 
halogenated dry-distilled charcoal, and is not particularly limited; 
however, it is understood that when the atomic ratio (Cl/C) is 0.315 or 
less, and when the carbonaceous material is used in a lithium secondary 
battery, improvements in the charging and discharging properties can be 
obtained. 
The low temperature dehalogenation treatment is a treatment in which the 
above-mentioned halogenated dry-distilled charcoal is heated in a lower 
hydrocarbon gas or in steam which has been diluted with an inert gas, and 
the halogen eliminated; and it is a treatment in which heating is 
conducted at a temperature of 600.about.850.degree. C., and preferably 
650.about.750.degree. C. In addition, the low temperature dehalogenation 
treatment is a treatment in which the halogen is eliminated by heating the 
halogenated dry-distilled charcoal in hydrogen gas diluted with an inert 
gas, and the heating is conducted at a temperature of 
600.about.1400.degree. C., and preferably at 650.about.1200.degree. C. 
When the temperature is less than 600.degree. C., the rate of the 
dehalogenation is slow, and therefore this is not desirable. When the 
above-mentioned hydrogen compound is steam, and when the heat treatment 
exceeds a temperature of 850.degree. C., since activation effects due to 
the steam progress too far, the formation of micropores is obstructed, the 
carbon yield is reduced, and the effects of the present invention are 
reduced. When the hydrogen compound is hydrogen, since there are no 
activation effects, the upper limit of the temperature for the heat 
treatment of the low temperature dehalogenation can be 1400.degree. C. 
When the upper temperature exceeds 1400.degree. C., the pore structure 
formation is obstructed and the effects of the present invention are 
reduced. 
The time for the heat treatment is approximately 20.about.60 minutes. 
With regard to the degree of dehalogenation, when the halogen is chlorine, 
the above-mentioned atomic ratio (Cl/C) is preferably 0.02 or less, and 
when the halogen is bromine, the above-mentioned atomic ratio (Br/C) is 
preferably 0.01 or less, however, this is not a limitation, and the 
effects of the present invention can be obtained if a part of the halogen 
remains. 
In the dehalogenation treatment, the halogen in the dry-distilled charcoal 
is mainly eliminated as halogenated hydrogen such as hydrogen chloride and 
hydrogen bromide, and as a result hydrogen chloride and hydrogen bromide 
can be detected in the exhaust gas. 
Here, the hydrogen compound gas is steam (H.sub.2 O); hydrogen; lower 
hydrocarbons, such as methane (CH.sub.4), ethane (C.sub.2 H.sub.6), 
ethylene (C.sub.2 H.sub.4), propane (C.sub.3 H.sub.8), propylene (C.sub.3 
H.sub.6), butane (C.sub.4 H.sub.10), and butylene (C.sub.4 H.sub.8); and 
mixtures of these gases. As a hydrogen compound gas in an inert gas, the 
exhaust gas of LPG (liquid petroleum gas) which has been incompletely 
burned is suitable for industrial use. The composition of the 
above-mentioned exhaust gas is, for example, steam: 13.about.17% by 
volume; carbon dioxide: 9.about.12% by volume; carbon monoxide: 
0.01.about.1% by volume; nitrogen: 68.about.74% by volume; and unburned 
lower hydrocarbons: 0.01.about.3% by volume. 
When the above-mentioned hydrogen compound is steam, the concentration of 
the steam is not particularly limited; however, when the superficial 
velocity in the column is from 0.05 to 0.15 NL/(min.cm.sup.2), 3% by 
volume is sufficient. 
When the above-mentioned hydrogen compound is a lower hydrocarbon such as 
methane, the concentration of the lower hydrocarbon is not particularly 
limited; however, when the superficial velocity in the column is from 0.05 
to 0.15 NL/(min.cm.sup.2), 40% by volume is sufficient. 
The high temperature dehalogenation treatment is a heat treatment conducted 
in an inert gas at a temperature of 700.about.1400.degree. C., and 
preferably 800.about.1300.degree. C. In addition, when the high 
temperature dehalogenation treatment is conducted under vacuum evacuation, 
the heat treatment is conducted at a temperature of 700.about.1400.degree. 
C., and preferably 800.about.1300.degree. C. The degree of vacuum 
evacuation is not particularly limited, however, 10 Torr is suitable. A 
time of approximately 30.about.120 minutes is necessary for the heat 
treatment. When the temperature of the high temperature dehalogenation is 
a temperature of less than 700.degree. C., a long period of time is 
necessary to eliminate the halogen, and therefore efficiency is poor, and 
when the temperature exceeds 1400.degree. C., the effects of heat 
shrinkage are too great and this is not desirable for pore structure 
formation. 
The high temperature dehalogenation treatment has the action of eliminating 
halogen as well as the action of reducing porosity by heat shrinking the 
entire porous carbonaceous material. 
In this first mode, the preferable dehalogenation step is any one of a step 
in which a low temperature dehalogenation treatment or a high temperature 
dehalogenation treatment is independently conducted; a step in which a low 
temperature dehalogenation treatment and then a high temperature 
dehalogenation treatment are conducted; and a step in which a high 
temperature dehalogenation treatment and then a low temperature 
dehalogenation treatment are conducted. The atomic ratio for the halogen 
which remains after this dehalogenation treatment with regard to the 
carbon is preferably, for a chlorine treatment, a Cl/C of 0.02 or less, 
and, for a bromination treatment, a Br/C of 0.01 or less, however, these 
are not limitations, and the effects of the present invention can be 
obtained even if some part of the halogen remains. 
The porous carbonaceous material obtained by means of the above-mentioned 
halogen treatment adsorbs oxygen and nitrogen in an amount of 
12.5.about.20 cc/g, and this is an increase in adsorption of 15.about.50% 
compared with that of convention carbonaceous material. 
A pore adjustment treatment in which a thermally decomposable hydrocarbon 
is brought into contact with dehalogenation treated carbonaceous material 
is conducted. The carbon before it is given the pore adjustment treatment 
is called electrode carbon precursor. 
In one embodiment of the pore adjustment in which contact is made with 
thermally decomposable carbon, a heat treatment may be conducted on a 
electrode carbon precursor at a temperature of 600.about.1100.degree. C., 
preferably 700.about.1050.degree. C., and more preferably 
800.about.1000.degree. C., in a thermally decomposable hydrocarbon diluted 
with an inert gas. The pore adjustment treatment is conducted in order to 
adjust the size of the pores so that the organic solvent in the 
electrolytic solution does not enter the pores, and pores of the desired 
size can be obtained by appropriately selecting the type of thermally 
decomposable hydrocarbon, the treatment temperature, and the treatment 
time. When the heating temperature exceeds 1100.degree. C., it becomes 
difficult to control the impregnation of the thermally decomposed carbon, 
and the formation of the desired pores in the carbon becomes difficult. 
When the temperature is less than 600.degree. C., the rate of thermal 
decomposition of the hydrocarbon becomes slow and a long period of time is 
necessary for the pore adjustment, and therefore this is undesirable. 
With regard to the above-mentioned thermally decomposable hydrocarbon, at 
least one hydrocarbon which generates carbon when decomposed, selected 
from the group consisting of aromatic hydrocarbons, cyclic hydrocarbons, 
saturated chain hydrocarbons, and unsaturated chain hydrocarbons can be 
used. As this thermally decomposable hydrocarbon, for example, benzene, 
toluene, xylene, ethylbenzene, naphthalene, methylnapthalene, biphenyl, 
cyclohexane, methylcyclohexane, 1,1-dimethylcyclohexane, 
1,3,5-trimethylcyclohexane, cycloheptane, methane, isobutane, hexane, 
heptane, isooctane, acetylene, ethylene, butadiene, ethanol, isopropanol, 
isobutylene, and the like can be used, and preferably benzene and toluene 
are used. 
Another embodiment of the pore adjustment treatment in which contact is 
made with a thermally decomposable hydrocarbon is conducted on a electrode 
carbon precursor by means of thermal decomposition of a liquid hydrocarbon 
compound with which the electrode carbon precursor is impregnated. One 
practical example is, for example, impregnating the above-mentioned 
precursor from 1 to 20% by volume with 2,4-xylenol, quinoline, or 
creosote; then, under a nitrogen gas current, these hydrocarbon compounds 
are decomposed by heating at a temperature at which these hydrocarbon 
compounds will decompose, for example 600.about.1200.degree. C.; the 
carbon is deposited, and the deposited carbon makes the pores of the 
precursor narrower. In addition, as the thermally decomposable 
hydrocarbon, pitch, resin, and the like can be used. 
The pore adjustments by contact with thermally decomposable hydrocarbon of 
both of the above-mentioned embodiments can also be used in the second and 
third modes. 
In this first mode, after conducting the pore adjustment, a crushing 
treatment is conducted, and from this crushed product, electrodes can be 
manufactured. However, when the average particle size of the particles 
after crushing is extremely small, the pore adjustment effects may be 
reduced, and, therefore, in another method of the first mode, after a 
dehalogenation treatment, a crushing treatment is conducted, and then the 
above-mentioned pore adjustment treatment can be conducted, and this is a 
more preferable method. 
In the above-mentioned crushing treatment, the precursor is crushed to an 
average particle size of several .mu.m to tens of .mu.m using normal 
methods such as a vibrating ball mill. 
After the above-mentioned dehalogenation treatment is completed or after 
the above-mentioned crushing treatment, and until the above-mentioned pore 
treatment begins, it is preferable for the carbon precursor to be 
preserved and treated in an inert gas. It is desirable for the step of 
manufacturing the carbon electrode from the pore-adjusted carbon, and the 
steps of assembling the evaluation cell and the battery to be conducted in 
a dried inert gas. By doing this, reactions and adsorption of oxygen and 
steam can be prevented, and the battery efficiency is improved. Carbon 
given a pore adjustment treatment, and carbon which has been molded into a 
fixed shape for the purpose of measuring its charging and discharging 
characteristics are called "battery carbon" or abbreviated to "carbon", 
and that which has been impregnated with electrolytic solution is called 
"carbon electrode" (this is the same hereinafter). 
The carbon for a lithium secondary battery obtained by means of the 
above-mentioned manufacturing method is superior in total discharge 
capacity, total discharge efficiency, effective discharge capacity, and 
effective discharge ratio. 
An evaluation cell for measuring charging and discharging capacity and 
efficiency is shown in FIG. 2. This cell comprises carbon electrode 1; 
lithium electrode 2 used as the opposite electrode; separator 3 provided 
between the carbon electrode 1 and the lithium electrode 2; electrolytic 
solution 4 which is in contact with these electrodes; and reference 
electrode 5 comprising lithium arranged in electrolytic solution. In 
addition, in the evaluation cell shown in FIG. 2, strictly speaking, 
carbon electrode 1 is the positive electrode and doping of lithium ions 
into carbon electrode 1 is discharging, however, from the point of view of 
convenience and in line with actual batteries, this process will be called 
charging, and in reverse, the process in which lithium ions are taken out 
of carbon electrode 1 is called discharging. 
The test method for evaluating the charging and discharging capacity and 
efficiency is explained in accordance with the graph of current-potential 
curve shown in FIG. 3. 
In the initial charging process, the initial electric potential of the 
carbon electrode of the negative electrode is approximately 1.5 V with 
respect to the lithium reference electrode 5, and the application of 
electric current is begun at a fixed electric current having a current 
density of 0.53 mA/cm.sup.2. The potential of the carbon electrode 1 is 
gradually reduced, and when it reaches 0 mV, a switch over from the fixed 
electric current to the fixed electric potential is made; when the current 
density is sufficiently reduced, the power source is cut off; recharging 
is completed when the potential recovers to 10 mV or less after a two hour 
pause. 
Next, after a 2 hour pause from the completion of the charging, the 
discharging process is conducted. Discharging is started at a fixed 
current of 0.53 mA/cm.sup.2, and at the point of time that the potential 
reaches 1.5 V, a switch over is made to a fixed electric potential, and 
discharging is complete when the current density is 0.05 mA/cm.sup.2 or 
less. 
Total charge capacity A is represented by the area shown by the hatched 
portion A in FIG. 3. Total discharge capacity is represented by the area 
shown by the hatched portion (x+y+z) in FIG. 3. Charging capacity and 
discharging capacity are shown as capacity per 1 g of carbonaceous 
material. Total discharge efficiency K (B/A) is calculated from 
B.div.A.times.100 (%). 
In the discharging process, discharging is started at a fixed current of 
0.53 mA/cm.sup.2, and the effective discharge capacity C is the capacity 
of the discharge which occurs up to the point at which the electric 
potential reaches EV (in the present invention it is 0.3V). Effective 
discharge capacity C is represented by the area shown by the cross-hatched 
portion x in FIG. 3. 
In addition, the capacity of the discharge which occurs up to the point of 
at which the electric potential reaches 1.5V is fixed current discharge 
capacity D. Fixed current discharge capacity D is represented by the area 
shown by the hatched portion (x+y) of FIG. 3. Effective discharge ratio K 
(C/D) is calculated from C.fwdarw.D.times.100(%). 
For a lithium secondary battery, the larger the discharge capacity up to 
reaching electric potential E, the better. At this time the largest 
discharge capacity is the discharge capacity D which can be maintained at 
a fixed current of 0.53 mA/cm.sup.2. The extent to which the effective 
discharge ratio is high, the smaller the initial slope of the electric 
potential increase curve, and the slope at the time approaching the 
completion of discharge is steep. When the electric potential increase 
curve shows this type of condition, the discharge properties are said to 
be good. 
As the electrolytic solution, any electrolyte dissolved in an organic 
solvent can be used, however, as an example, as electrolytes: LiClO.sub.4, 
LiAsF.sub.6, LiPF.sub.6, LiBF.sub.4, and the like can be used; and, as 
organic solvents: propylene carbonate, ethylene carbonate, diethyl 
carbonate, dimethyl carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane, 
.gamma.-butyllactone, tetrahydrofuran, 2-methyltetrahydrofuran, diethyl 
ether, acetonitrile, and the like can be used. This is also the same in 
the second and third modes. 
The basis for manufacturing a carbon for a lithium secondary battery having 
superior discharging properties by means of the above-mentioned 
manufacturing method is explained below. 
In the halogenation treatment, the halogen, chlorine for example, which is 
brought into contact with the dry-distilled charcoal reacts with the 
unorganized carbon. In these reactions, there are addition reactions of 
chlorine to double bonded carbons, exchange reactions of chlorine atoms 
for hydrogen atoms which are bonded to the unorganized carbon (hydrogen 
chloride in a molar equivalent to chlorine is generated), dehydrogenation 
reactions (hydrogen chloride twice that of the chlorine is generated), and 
so on. 
In the dehalogenation treatment, the halogen, chlorine for example, which 
is bonded to the above-mentioned unorganized carbon is eliminated. It is 
believed that new bonds between carbons (hereinafter, called carbon bonds) 
are formed by occurrence of a reaction, shown in the following formula, 
which occurs in the halogenation (chlorine) treatment, the low temperature 
dehalogenation (chlorine) treatment and the high temperature 
dehalogenation (chlorine) treatment. In the following formula (i), the 
mark .vertline. located to the side of a C indicates that it is an 
unorganized carbon. 
EQU C.vertline.--Cl+C.vertline.--H.fwdarw.C--C+HCl (i) 
By means of the formation of these new carbon bonds, actions such as the 
action of repairing defects in the polyaromatic ring structure of the 
crystallites or the carbon net planes, the action of growth of the 
crystallites, and the action of changes in the aggregation condition of 
crystallites are believed to take place, but these details are unclear. 
However, by means of these actions, it is believed that a large number of 
micropores (0.8.about.2 nm) and/or sub-micropores (&lt;0.8 nm) are formed 
which are suitable for the adsorption of gases which have small molecular 
diameters such as oxygen and nitrogen. In addition, it is believed that 
these pores are effectively active in the uptake and discharge of lithium 
ions. 
Another action of the high temperature dehalogenation treatment is the 
action of reducing the porosity by shrinking the entire porous carbon 
obtained by means of the halogen treatment. In other words, an action of 
tightening the aggregation of crystals is carried out. As a result, the 
pore size is also reduced. 
A theory about the mechanism of pore adjustment has not been established 
but it is believed that the molecules of the solvent which have large 
molecular diameters cannot penetrate into the pores as a result of the 
narrowing of the openings of the micropores by thermally decomposed 
carbon. However, since the lithium ions which have small ionic diameters 
can pass, charging and discharging are possible. The penetration of the 
molecules of the solvent into the pores is believed to reduce the 
discharging capacity. 
Carbon which has been dehalogenation treated, and carbon which has 
developed new cleavage planes due to crushing bond easily with oxygen and 
adsorb water. When heat-treated in order to conduct a pore adjustment, 
carbon which has bonded with oxygen, and carbon which has adsorbed water 
undergo carbon activation (gasification) easily. For this reason, pores 
formed by means of the halogen treatment and which are suitable for the 
uptake and release of lithium ions become disturbed. Consequently, it is 
believed that problems such as these can be avoided by preservation after 
the dehalogenation treatment, preservation during the crushing, and until 
the pore adjustment carried out after the crushing, in an inert gas such 
as nitrogen, argon, or the like. 
It is believed that the carbon for a lithium secondary battery manufactured 
by means of the manufacturing method according to this first mode has 
improved discharging characteristics, such as total discharge capacity and 
total discharge efficiency, due to each of the above effects acting 
synergistically. 
A lithium battery can be made using the carbon for a lithium secondary 
battery manufactured by means of the manufacturing method of this first 
mode as the negative electrode and using lithium or a lithium compound as 
the positive electrode. A negative electrode comprising the carbon of the 
present invention is called a carbon electrode, and a positive electrode 
comprising lithium or a lithium compound is called a lithium electrode. 
The combination of the carbon electrode of the present invention, the 
components of the positive electrode, the shape, the composition 
concentration of the electrolytic solution, and the like are all suitably 
set in accordance with the use of the lithium secondary battery. 
Second Mode 
FIG. 4 is a process diagram showing a second mode of the manufacturing 
method for a lithium secondary battery according to the present invention. 
According to the manufacturing method for a carbon for a lithium secondary 
battery shown in FIG. 4A, carbon for a lithium secondary battery is 
manufactured by successively conducting a crushing step in which a 
dry-distilled charcoal is given a crushing treatment, a molding step in 
which a molded article is obtained by conducting a molding treatment on 
this crushed dry-distilled charcoal and a binding agent added thereto; and 
a carbonization step in which a carbonization treatment for carbonizing 
this organic binder in this molded article is conducted. 
In addition, according to the manufacturing method for a carbon for a 
lithium secondary battery shown in FIG. 4B, after the above-mentioned 
carbonization treatment step in the manufacturing method shown in the 
above-mentioned FIG. 4A, a carbon for a secondary lithium battery is 
manufactured by conducting a pore adjustment step in which a pore 
adjustment treatment is conducted by bringing the above-mentioned 
carbonization treated molded article into contact with a thermally 
decomposable hydrocarbon. 
The starting materials used by the manufacturing method according to this 
second mode are the same as the starting materials in the above-mentioned 
first mode, that is, various starting materials such as carbonized plant 
and animal material such as lignite, brown coal, anthracite coal, coke, 
wood charcoal, coconut shell char; any kind of resin such as phenol resin, 
furan resin, vinylidene chloride copolymer, etc. can be used, and from 
among these, phenol resin is preferably used. 
Starting materials such as phenol resin are made into dry-distilled 
charcoal by suitably heating (dry distillation) them at a temperature of 
550.about.1100.degree. C. in an inert gas such as nitrogen gas or argon. 
In this dry distillation, in order to manufacture uniform dry-distilled 
charcoal, it is preferable to make the starting material into granules or 
cylinders of several millimeters, and then dry-distill it in an inert gas. 
In addition, powdered starting material and an organic binding agent added 
thereto may also be molded, and then dry-distilled. 
When the manufactured dry-distilled charcoal is in a lumpy condition, the 
dry-distilled charcoal is crushed in order to obtain a suitable molded 
article. In this crushing treatment, the dry-distilled charcoal is crushed 
to an average particle size of several .mu.m to tens of .mu.m using normal 
crushing treatment methods such as a vibrating ball mill. 
Molding (molding treatment) conducted by adding organic binding agent to 
the crushed dry-distilled charcoal. 
This molding treatment is conducted by kneading crushed dry-distilled 
charcoal to which an organic binding agent has been added, inserting it 
into a metallic mold, and press molding it. The molding pressure is not 
particularly limited, and with a usual pressure of 500 kgf/cm.sup.2, a 
suitable molded article can be obtained. Moreover, the molding method is 
not limited to press molding methods, molding methods which are generally 
conducted such as extrusion molding methods can be applied. 
As the organic binding agent used in this molding treatment, those organic 
binding agents which are used in general molding treatments such as 
polyvinylidene fluoride, polyvinyl acetate, polyvinyl alcohol, polyvinyl 
pyrrolidone, acrylic resin, urea resin, melamine resin, phenol resin, 
epoxy resin, glycerin, dextrin, starch, syrup, pitch, coal tar, and the 
like may be used. 
In addition to this, in order to adjust fluidity, it is preferable to add a 
solvent such as ethanol, cyclohexane, acetone, benzene, toluene, etc., and 
in order to improve mold separation properties, it is preferable to add a 
mold separation agent such as liquid paraffin. 
When the amount of organic binding agent added to the dry-distilled 
charcoal is too great, efficiency as an electrode is reduced, and when it 
is too small, physical strength when made into a molded article is 
reduced, therefore, suitable combinations are added with consideration to 
efficiency as an electrode and to the physical strength of the molded 
body. When phenol resin is used as the organic binding agent, the total of 
the phenol resin, the solvent, and the liquid paraffin added is preferably 
30.about.60 parts by weight with regard to 100 parts by weight of 
dry-distilled charcoal. 
Next, the molded article obtained by the molding treatment is heated, and 
the organic binding agent within the molded article is carbonized 
(carbonization treatment). 
It is preferable for this carbonization treatment to be conducted on the 
molded article in an inert gas, such as nitrogen gas or argon gas, at 
700.about.1400.degree. C., and preferably at 800.about.1300.degree. C. 
When the temperature of this carbonization treatment is less than 
700.degree. C., the carbonization of the organic binding agent is 
insufficient, and when it exceeds 1400.degree. C., the effects from heat 
shrinkage are too great, and therefore these situations are not desirable. 
The time required for the carbonization treatment is approximately 
30.about.120 minutes. 
By means of this carbonization treatment, the organic binding agent within 
the molded article is carbonized by dry-distillation. The density of the 
carbonization treated molded article is 0.70.about.1.20 g/cm.sup.3, and 
the pore volume is 0.15.about.0.4 cm.sup.3 /g. 
In another method of the second mode, a pore adjustment is conducted on the 
carbonaceous material obtained by means of the carbonization treatment 
(pore adjustment treatment). This pore adjustment treatment is a treatment 
in which the carbonaceous material obtained by means of the carbonization 
treatment is heated in a thermally decomposable hydrocarbon diluted with 
an inert gas for 5.about.180 minutes at a temperature of 
600.about.1100.degree. C., preferably at 700.about.1050.degree. C., and 
more preferably at 800.about.1000.degree. C. When this heating temperature 
exceeds 1100.degree. C., it becomes difficult to control the amount of 
impregnation of the thermally decomposed carbon, and when it is less than 
600.degree. C., the rate of the thermal decomposition of the thermally 
decomposable hydrocarbon is slow, and a long period of time is necessary 
for the pore adjustment, therefore, these situations are undesirable. 
The thermally decomposable hydrocarbon used in this pore adjustment 
treatment can be the same as those used in the pore adjustment treatment 
of the above-mentioned first mode. 
When conducting this pore adjustment treatment, it is preferable to handle 
the carbonaceous material (electrode carbon precursor) which has been 
carbonization treated and on which the pore adjustment treatment is being 
conducted in an inert gas such as nitrogen gas, argon gas, or the like. By 
means of handling the electrode carbon precursor in an inert gas in this 
way, since it is possible to prevent the electrode carbon precursor from 
reactions and adsorption of oxygen and water, the effects of pore 
adjustment are sufficiently obtained. 
In addition, the manufacturing method for an lithium secondary battery is 
characterized by conducting the lithium secondary battery assembly process 
which uses the manufactured molded electrode carbon as negative electrode 
material in a dried inert gas. In other words, the processing of the 
carbonaceous material after the carbonization treatment, preservation 
after completion of the pore adjustment treatment, and assembly of the 
battery, such as during immersion in electrolytic solution, are preferably 
conducted in a dried inert gas. 
In this manufacturing method for a carbon for a lithium secondary battery 
according to this second mode, a carbon powder obtained by conducting a 
crushing treatment on a dry-distilled charcoal and an organic binding 
agent added thereto, and then the organic binding agent is carbonized by 
means of heating in an inert gas, and thereby an electrode carbon for 
which the entire electrode has a unitary structure comprising carbon is 
obtained. Consequently, by being carbonized by means of the carbonization 
treatment, the organic binding agent added during the molding treatment is 
changed to carbon which can take up lithium ions and contribute to 
discharging, and, therefore, the charging and discharging capacity per 
unit of weight and per unit of volume of the electrode is increased. In 
addition, since the carbonized organic binding agent has conductive 
properties, it does not become a cause for increased resistance. In 
another method of the second mode, after the carbonization treatment, a 
pore adjustment treatment is conducted by contact with a thermally 
decomposable hydrocarbon diluted with an inert gas, and as a result, the 
inlets of the pores of the electrode carbon become narrower, and pores are 
formed into which it is possible for lithium ions which have a small ionic 
diameter to pass, but into which solvent molecules which have a large 
molecular diameter cannot penetrate, thereby making it possible to prevent 
reductions in the discharging capacity produced by adsorption of solvent 
molecules in the pores, and making it possible to improve the discharging 
characteristics of the lithium secondary battery. 
When a carbon powder is given a pore adjustment and then molded into a 
sheet by the addition of a binding agent, there are occasions when some 
part of the carbon powders break; however, in the manufacturing method 
according to this example, since the pore adjustment is given to a molded 
carbon obtained by conducting a carbonization treatment on a molded 
article, the carbon electrode obtained by conducting a pore treatment on a 
molded article can be used in a lithium secondary battery as it is, and 
the best advantages of the above-mentioned pore adjustment can be 
obtained. 
In this pore adjustment treatment, when a carbon to which oxygen and water 
have been adsorbed is heated for the purpose of giving it a pore 
adjustment, activation (gasification) of the carbon can occur easily, and 
therefore, the narrowing of the inlets of the pores during the pore 
adjustment may be incomplete. However, in the manufacturing method for 
lithium secondary battery according to this example, the adjustment of the 
diameter of the inlets of the pores by means of the pore adjustment can 
occur with certainty due to the fact that the handling of the molded 
carbon after conducting the carbonization treatment and before conducting 
the pore adjusting treatment is conducted in an inert gas such as nitrogen 
gas or argon gas. 
In addition, when manufacturing a lithium secondary battery, it is possible 
to prevent the problem of reductions in the charging characteristics due 
to absorption of oxygen and water by the carbon for a battery and the 
electrolytic solution by means of conducting the assembly process for the 
lithium secondary battery which uses the carbon manufactured by means of 
the above-mentioned method in a dry inert gas. 
When the carbon for a lithium secondary battery obtained by the 
above-mentioned manufacturing process is used as a negative electrode for 
a lithium secondary battery, the total discharge capacity and the total 
discharge efficiency are increased, and superior discharging 
characteristics are obtained. 
Third Mode 
FIG. 5 is a process diagram showing a third mode of the manufacturing 
method for a lithium secondary battery according to the present invention. 
In this third mode, a molding step is conducted in which a molding 
treatment is given by the addition of an organic binding agent to the 
above-mentioned dry-distilled charcoal or the above-mentioned halogenated 
dry-distilled charcoal of the manufacturing method of the first mode which 
is shown in FIG. 1A. 
According to the manufacturing method for a carbon for a lithium secondary 
battery shown in FIG. 5A, after the above-mentioned halogenation treatment 
in the manufacturing method of the first mode shown in FIG. 1A, by means 
of conducting a molding step in which a molding treatment is given to the 
above-mentioned halogenation treated carbon by the addition of an organic 
binding agent, and by conducting the above-mentioned dehalogenation step 
after said molding treatment, a carbon for a lithium secondary battery is 
manufactured. 
According to the manufacturing method for a carbon for a lithium battery 
shown in FIG. 5B, after the above-mentioned molding step in the 
manufacturing method shown in FIG. 5A, by means of conducting a 
carbonization step by conducting a carbonization treatment in which the 
above-mentioned organic binding agent in the molding treated halogenated 
dry-distilled charcoal is carbonized, and by conducting the 
above-mentioned dehalogenation treatment after this carbonization step, a 
carbon for a lithium secondary battery is manufactured. 
According to the manufacturing method for a carbon for a lithium battery 
shown in the FIG. 5C, the molding step of the manufacturing method of the 
first mode shown in FIG. 1A is conducted by giving a molding treatment to 
the above-mentioned dry-distilled charcoal by the addition of an organic 
binding agent. Then after this molding treatment, a second carbonization 
step is conducted in which a second carbonization treatment is conducted 
in which this organic binding agent is carbonized by heating the 
dry-distilled charcoal which has been given the above-mentioned molding 
treatment in an inert gas. Then, after this second carbonization step, the 
above-mentioned halogenation treatment is conducted, and thereby, a carbon 
for a lithium secondary battery is manufactured. 
In this third mode, the dehalogenation step is preferably a step in which 
at least one of a high temperature dehalogenation treatment and a low 
temperature dehalogenation treatment is conducted. 
The starting materials used by the manufacturing method according to this 
second mode are the same as the starting materials in the above-mentioned 
first mode, that is, various starting materials such as carbonized plant 
and animal material such as lignite, brown coal, anthracite coal, coke, 
wood charcoal, coconut shell char; any kind of resin such as phenol resin, 
furan resin, vinylidene chloride copolymer, etc., and from among these, 
phenol resin is preferably used. 
These starting materials are made into dry-distilled charcoal by means of 
suitably heating at a temperature of 550.about.1100 in an inert gas such 
as nitrogen or argon. 
In this dry distillation, in order to manufacture uniform dry-distilled 
charcoal from the starting material carbon compound, it is preferable to 
make the starting material carbon compound into granules or cylinders of 
several millimeters, and then dry-distill it in an inert gas. In addition, 
powdered carbon material may also be molded by the addition of organic 
binder, and then dry-distilled. 
In the halogenation treatment of the manufacturing method of a carbon for a 
lithium secondary battery of this third mode, any halogen can be used, but 
chlorine gas and bromine gas are preferably used. 
By means of the above-mentioned halogenation treatment, halogenated 
dry-distilled charcoals such as a chlorinated dry-distilled charcoal 
having an atomic ratio of chlorine to carbon (Cl/C) of 0.03 or greater, 
and preferably of 0.07 or greater, and a brominated dry-distilled charcoal 
having an atomic ratio of bromine to carbon (Br/C) of 0.01 or greater, and 
preferably 0.03 or greater can be obtained. Moreover, it is not desirable 
for this atomic ratio to be less than the above-mentioned minimum values, 
since the formation of micropores is insufficient, and when the 
manufactured carbonaceous material is used in lithium secondary batteries, 
good charging and discharging properties cannot be obtained. In addition, 
the upper limit of the above-mentioned atomic ratio is determined by the 
carbonization temperature and the quantity of hydrogen atoms in the 
halogenated dry-distilled charcoal, and is not particularly limited; 
however, it is understood that when it is 0.315 or less, when the 
carbonaceous material is used in a lithium secondary battery, improvements 
in the charging and discharging properties can be obtained. 
When the dry-distilled charcoal or the halogenated dry-distilled charcoal 
are in a lumpy or pellet form, they can be crushed in order to make the 
molding treatment easier. In this crushing treatment, the dry-distilled 
charcoal or the halogenated dry-distilled charcoal is crushed to an 
average particle size of several .mu.m to tens of .mu.m using normal 
crushing treatment methods such as a vibrating ball mill. 
However, since it is possible to dry-distill starting material carbon 
compound in powdered form, and to conduct a halogenation treatment on 
dry-distilled charcoal in a powdered form, when dry-distilled charcoal in 
a powdered form or halogenated dry-distilled charcoal in a powdered form 
have been obtained, a crushing treatment is unnecessary. 
The molding treatment is conducted by kneading powdered dry-distilled 
charcoal or halogenated dry-distilled charcoal to which an organic binding 
agent has been added, inserting it into a metallic mold, and press 
molding. The molding pressure is not particularly limited, and with a 
usual pressure of 500 kgf/cm.sup.2, a suitable molded article can be 
obtained. Moreover, the molding method is not limited to press molding 
methods, molding methods which are generally conducted such as extrusion 
molding methods can be applied. 
As the organic binding agent used in this molding treatment, those organic 
binding agents which are used in general molding treatments such as 
polyvinylidene fluoride, polyvinyl acetate, polyvinyl alcohol, polyvinyl 
pyrrolidone, acrylic resin, urea resin, melamine resin, phenol resin, 
epoxy resin, glycerin, dextrin, starch, syrup, pitch, coal tar, and the 
like may be used. 
In addition to this, in order to adjust the fluidity, it is preferable to 
add a solvent such as ethanol, cyclohexane, acetone, benzene, toluene, 
etc., and in order to improve mold separation properties, it is preferable 
to add a mold separation agent such as liquid paraffin. 
When the amount of organic binding agent added is too great, efficiency as 
an electrode is reduced, and when it is too small, physical strength when 
made into a molded article is reduced, therefore, suitable combinations 
are added with consideration to efficiency as an electrode and to the 
physical strength of the molded body. When phenol resin is used as the 
organic binding agent, the total of the phenol resin, the solvent, and the 
liquid paraffin added is preferably 30.about.60 parts by weight with 
regard to 100 parts by weight of halogenated dry-distilled charcoal. 
The second carbonization treatment is a treatment conducted for the purpose 
of carbonizing the organic binding agent added in the molding treatment, 
and is a heat treatment in an inert gas such as nitrogen. The rate of 
temperature increase is 20.about.500.degree. C./h and preferably 
50.about.400.degree. C./h. When the temperature increase is less than 
20.degree. C./h, a long treatment time is necessary and efficiency is 
poor, and when 500.degree. C./h is exceeded, distortion and damage develop 
in the molded article, therefore, these conditions are not desirable. It 
is sufficient for the treatment temperature to be set at a temperature at 
which the organic binding agent is carbonized. 
In the carbonization treatment, the object is mainly the carbonization of 
the organic binding agent in the molded article by means of heating the 
above-mentioned molded article, however, it also has the effect of 
eliminating some of the halogen in the halogenated dry-distilled charcoal. 
In the carbonization treatment, the above-mentioned organic binder is 
carbonized by means of a treatment of heating the molded article to 
450.degree..about.1300.degree. C., and preferably to 550.about.900.degree. 
C. in an inert gas such as nitrogen or argon. When less than 450.degree. 
C. the carbonization is insufficient, and when 1300.degree. C. is exceeded 
pore structure formation is badly effected. 
In addition, the heating rate (rate of temperature increase) for the 
carbonization treatment is preferably 20.about.500.degree. C./h, and more 
preferably 50.about.400.degree. C./h. When the heating rate is less than 
20.degree. C./h, the treatment time is long and efficiency is poor, and 
when 500.degree. C. is exceeded, cracks and warping develop in the molded 
article, and a suitable shape can not be obtained. 
The low temperature dehalogenation treatment is a treatment in which a 
halogen is eliminated by putting the molded article in lower hydrocarbon 
gas or steam diluted with an inert gas such as nitrogen gas or argon, and 
heating it, and is conducted at 600.about.850.degree. C., and preferably 
at 650.about.750.degree. C. When the temperature of this dehalogenation 
treatment is less than 600.degree. C., a long period of time is required 
for completion of dehalogenation, therefore, this is not preferable. In 
addition, the low temperature dehalogenation treatment is a treatment in 
which the halogen is eliminated by heating the molded article in hydrogen 
gas diluted with an inert gas, and is conducted at a temperature of 
600.about.1400.degree. C., and preferably at 650.about.1200.degree. C. 
When this dehalogenation temperature is less than 600.degree. C., a long 
period of time is required for completion of the dehalogenation, 
therefore, this is not preferable. 
In addition, when the temperature exceeds 850.degree. C., and the 
above-mentioned hydrogen compound is steam, the activation effects due to 
the steam are large; and when the above-mentioned hydrogen compound is a 
hydrocarbon, impregnation due to thermal decomposition occurs, and in both 
situations, the formation of pore structure is badly effected, carbon 
yield is reduced, and the improved effects in the charging and discharging 
characteristics when the carbonaceous material is used in lithium 
secondary battery are not sufficiently obtained, therefore, these 
situations are not desirable. However, when the hydrogen compound is 
hydrogen, since there are no carbon impregnation effects due to activation 
effects or thermal decomposition, the upper limit for the above-mentioned 
dehalogenation temperature can be 1400.degree. C. At high temperatures 
exceeding 1400.degree. C., there are negative effects on the pore 
structure formation in the carbon. 
In addition, the heating rate of the dehalogenation treatment is preferably 
20.about.500.degree. C./h, and more preferably 50.about.400.degree. C./h. 
When the heating rate is less than 20.degree. C./h, the treatment time is 
long and efficiency is poor, and when 500.degree. C./h is exceeded, cracks 
and warping develop in the molded article, and a suitable shape cannot be 
obtained. 
The time for this dehalogenation treatment is preferably about 20.about.60 
minutes. 
In the dehalogenation treatment, the halogen in the dry-distilled charcoal 
is mainly eliminated as halogenated hydrogen such as hydrogen chloride and 
hydrogen bromide, and as a result hydrogen chloride and hydrogen bromide 
can be detected in the exhaust gas. 
Here, as the hydrogen compound gas, for example, steam (H.sub.2 O); 
hydrogen; lower hydrocarbons, such as methane (CH.sub.4), ethane (C.sub.2 
H.sub.6), ethylene (C.sub.2 H.sub.4), propane (C.sub.3 H.sub.8), propylene 
(C.sub.3 H.sub.6), butane (C.sub.4 H.sub.10), and butylene (C.sub.4 
H.sub.8); and mixtures of these gases can be used. As a hydrogen compound 
gas in an inert gas, the exhaust gas of LPG (liquid petroleum gas) which 
has been incompletely burned is suitable for industrial use. The 
composition of the above-mentioned exhaust gas is, for example, steam: 
13.about.17% by volume; carbon dioxide: 9.about.12% by volume; carbon 
monoxide: 0.01.about.1% by volume; nitrogen: 68.about.74% by volume; and 
unburned lower hydrocarbons: 0.01.about.3% by volume. 
When the above-mentioned hydrogen compound is steam, the concentration of 
the steam is not particularly limited; however, when the superficial 
velocity in the column is from 0.05 to 0.15 NL/(min.cm.sup.2), 3% by 
volume is sufficient. 
When the above-mentioned hydrogen compound is a lower hydrocarbon such as 
methane, the concentration of the lower hydrocarbon is not particularly 
limited; however, when the superficial velocity in the column is from 0.05 
to 0.15 NL/(min.cm.sup.2), 40% by volume is sufficient. 
The high temperature dehalogenation treatment is a treatment in which the 
halogen is eliminated by putting the molded article in an atmosphere of 
inert gas such as nitrogen gas or argon gas, or under vacuum evacuation, 
and then heating, and is preferably conducted at a temperature of 
700.about.1400.degree. C., and preferably 800.about.1300.degree. C. In the 
high temperature dehalogenation treatment, along with the action of 
eliminating halogen, there is also the action of reducing porosity by heat 
shrinking the entire porous carbon. When the temperature of this treatment 
is less than 700.degree. C., the effects of dehalogenation become 
difficult to obtain., and when 1400.degree. C. is exceeded, the heat 
shrinkage effects are too great, and therefore these situations are not 
desirable. When the above-mentioned carbonization treatment is conducted, 
the high temperature dehalogenation treatment can be omitted. 
A time of 30.about.120 minutes are necessary for this high temperature 
dehalogenation treatment. The degree of evacuation for the vacuum 
evacuation is not particularly limited, however, approximately 10 Torr is 
suitable. 
The density of the molded article which has been given the high temperature 
dehalogenation treatment is 0.70.about.1.20 g/cm.sup.3, and the pore 
volume is 0.15.about.0.4 cm.sup.3 /g. 
In this third mode, the preferable dehalogenation step is any one of a step 
in which a high temperature dehalogenation treatment or a low temperature 
dehalogenation treatment is independently conducted; a step in which a 
high temperature dehalogenation treatment and then a low temperature 
dehalogenation treatment are conducted; and a step in which a low 
temperature dehalogenation treatment and then a high temperature 
dehalogenation treatment are conducted. The atomic ratio for the halogen 
which remains after the dehalogenation treatment with regard to the carbon 
is preferably a 0.02 or less for a chlorination treatment (Cl/C), and 0.01 
or less for a bromination treatment (Br/C), however, these are not 
limitations and the effects of the present invention can be obtained even 
if some part of the halogen remains. 
The pore adjustment treatment is a treatment in which the carbonaceous 
material (electrode carbon precursor) obtained by means of the 
dehalogenation treatment is heated in a thermally decomposable hydrocarbon 
diluted with an inert gas at a temperature of 600.about.1100.degree. C., 
preferably at 700.about.1050.degree. C., and more preferably at 
800.about.1000.degree. C. When this heating temperature exceeds 
1100.degree. C., it is difficult to control the amount of impregnation of 
the thermally decomposed carbon, and when it is less than 600.degree. C., 
the rate of thermal decomposition of the thermally decomposable 
hydrocarbon is slow, and a long period of time is necessary for the pore 
adjustment, and this situation is not desirable. 
The time for the pore adjustment treatment is preferably 5.about.180 
minutes. 
From after the above-mentioned dehalogenation treatment until the start of 
the above-mentioned pore adjustment treatment, it is preferable for the 
electrode carbon precursor to be handled in an inert gas such as nitrogen 
or argon. By means of handling the electrode carbon precursor in an inert 
gas in this way, since it is possible to prevent the electrode carbon 
precursor from reactions and adsorption of oxygen and water, the effects 
of pore adjustment are sufficiently obtained. 
The assembly step for a lithium secondary battery which uses the carbon for 
electrode obtained by means of the above-mentioned manufacturing method is 
preferably handled in a dried inert gas. In more detail, when oxygen and 
water are absorbed or become adsorbed to the carbon for electrode or 
electrolytic solution, battery efficiency is reduced, therefore it is 
preferable that preservation of the carbon for electrode after the 
completion of the pore adjustment treatment, electrolytic solution 
immersion, and battery assembly be conducted in a dry inert gas. 
The carbon for a lithium secondary battery obtained by means of the 
above-mentioned manufacturing method has a density of 0.70.about.1.20 
g/cm.sup.3, and when used as a negative electrode for a lithium secondary 
battery, high total discharge capacity, high total discharge efficiency, 
and superior discharging characteristics are obtained. 
EXAMPLES 
In the following, examples according to the present invention are 
described, however, the following description are only illustrations of 
the present invention, and the present invention is not limited to these 
following examples. 
EXAMPLES ACCORDING TO THE FIRST MODE 
As Examples of the first mode, the carbonaceous materials of Examples 
1.about.9 were manufactured according to the present invention, and their 
charging and discharging characteristics are compared with the 
carbonaceous materials of Comparative Examples 1.about.3. 
Dry Distilled Charcoal 
The dry-distilled charcoal starting material was obtained by adding phenol 
resin (PGA-4560, product name: Resitop, manufactured by Gun-ei Chemical 
Industry (Ltd)) as a binder to phenol resin (R800, product name: BELL 
PEARL, manufactured by Kanebo Co., Ltd., molding it into a cylindrical 
shape of approximately 2 mm.times.5.about.6 mm, and then dry-distilling it 
at 700.degree. C. under a nitrogen gas current. 
Halogen Treatment 
A porous carbonaceous material was made by conducting the following halogen 
treatment on the dry-distilled charcoal starting material. 
Dry distilled charcoal starting material (approximately 15 g) was 
chlorinated by a heat treatment for 2 hours at 600.degree. C. under a 
current of nitrogen gas (2.7 NL/min) containing chlorine at 5% by volume. 
Next, it was dechlorinated by a heat treatment for 30 minutes at a 
temperature of 700.degree. C. under a current of nitrogen gas (3 NL/min) 
containing methane at 40% by volume, or which had been saturated with 
steam at 25.degree. C. 
In the bromine treatment, bromination was conducted by a heat treatment for 
2 hours at a temperature of 600.degree. C. under a current of nitrogen gas 
(3 NL/min) containing bromine gas at 5% by volume. Next, debromination was 
conducted by heating for 30 minutes at a temperature of 700.degree. C. 
under a current of nitrogen gas (3 NL/min) which had been saturated with 
steam at 25.degree. C. 
The high temperature dehalogenation treatment was conducted by a heat 
treatment for 60 minutes at a temperature of 800.degree. C., 1000.degree. 
C., or 1300.degree. C., under a nitrogen gas current (3 NL/min). 
Pore Adjustment Treatment 
The pore adjustment treatment was conducted by crushing the carbon which 
had been given the dehalogenation treatment (the average particle size was 
several to several tens of .mu.m), and then giving it a heat treatment for 
10 minutes at a temperature of 900.degree. C. under a current of nitrogen 
gas (3 NL/min) which had been saturated with benzene at 25.degree. C. In 
addition, Examples in which the crushing was conducted after the pore 
adjustment was given were also conducted. 
In addition, each of the above-mentioned treatments was conducted at 
approximately atmospheric pressure. After the dehalogenation treatment, 
preservation was in dry nitrogen gas. 
Equipment for the Halogen Treatment and the Pore Adjustment Treatment 
An outline of the equipment for conducting the halogen treatment and the 
pore adjustment treatment is shown in FIG. 6. In the Figure, 11 is a pipe 
shaped electric kiln which is equipped with a temperature control device 
(the pipe shaped kiln is manufactured by Yoshida Seisakusho, the 
temperature control device is a thermocouple, JIS R, Model SU manufactured 
by Chino); 12 is a quartz pipe; 13 is a gas permeable container for 
carbonaceous material; 14 is a carbonaceous material; 15 is a nitrogen gas 
supply pipe; 16 is a supply pipe for halogen gas, steam, methane, 
thermally decomposable hydrocarbon, and the like; 17 is an exhaust gas 
output pipe; and 18 is a rubber stopper. In the halogenation treatment, 
nitrogen flows at a predetermined rate from pipe 15, and chlorine gas or 
bromine gas flows at a predetermined rate from pipe 16. In the low 
temperature dehalogenation treatment, a gas containing methane or steam 
flows from pipe 16 at a predetermined rate. In the high temperature 
dehalogenation treatment, nitrogen gas flows from pipe 15 at a 
predetermined rate. In the pore adjustment treatment, gas containing 
thermally decomposable hydrocarbon flows from pipe 16 at a predetermined 
rate. The flow rates of the gas were measured by a float-type area 
flowmeter (chlorine gas: PGF-N model manufactured by Ryutai Kogyo (Ltd); 
other gases: ST-4 model manufactured by Nippon Flowcell Co.). The 
flowmeter used for the chlorine gas was corrected and used for the bromine 
gas. 
Crushing 
Crushing was conducted for 30 minutes using small size vibrating ball mill, 
NB-0, manufactured by Nitto Kagaku (Ltd)). The container of the vibrating 
ball mill was filled with dry nitrogen gas. For the period after crushing 
and until the pore adjustment, preservation was also in dry nitrogen gas. 
Carbon For Battery 
The carbon obtained by the halogen treatment (chlorination treatment or 
bromination treatment), crushing treatment, or pore adjustment treatment 
was made into carbon for a battery (in a coin shape of 10 mm in diameter 
and 0.5 mm in thickness) by being made into a paste by the addition of 
polyvinyl fluoride equivalent to 9% by volume of carbon, and 
N-methyl-2-pyrrolidone, and then made into a sheet on a stainless steel 
plate for collecting electrode use. 
Evaluation Test for Charging and Discharging Capacity 
The electrolytic solution (1.0 mol/L) used was a solution of a one to one 
mixture of polycarbonate and dimethoxyethane to which lithium perchlorate 
(LiClO.sub.4) was added as a supporting electrolyte. A carbon electrode 
was formed by impregnating the above-mentioned carbon for a battery with 
the electrolytic solution. 
With regard to charging and discharging, the above-mentioned total charging 
capacity (A), total discharge capacity (B), effective discharge capacity 
(C), and fixed current discharging capacity (D) were measured using a 
charging and discharging testing device (model HJ-201B) manufactured by 
Hokuto Denko (Ltd). 
COMATIVE EXAMPLE 1 
No Halogen Treatment, 800.degree. C. Heat Treatment 
Dry distilled charcoal was given a heat treatment at a temperature of 
800.degree. C. under a current of nitrogen gas, and this was then crushed. 
Next, a pore adjustment treatment was conducted, binder added, carbon for 
a battery made, and the charging and discharging characteristics were 
measured using an evaluation cell. The results were A=775 mAh/g, B=570 
mAh/g, C=256 mAh/g, and D=511 mAh/g. The total discharge efficiency K(B/A) 
equals 73.5%, and the effective discharge ratio K(C/D) equals 50.1%. 
COMATIVE EXAMPLE 2 
No Halogen Treatment, 1000.degree. C. Heat Treatment 
With the exception that the heat treatment temperature was 1000.degree. C., 
the treatment was conducted under the same conditions as in Comparative 
Example 1. The charging and discharging characteristics were measured. The 
results were A=721 mAh/g, B=567 mAh/g, C=330 mAh/g, and D=541 mAh/g. The 
total discharge efficiency K(B/A) equals 78.6%, and the effective 
discharge ratio K(C/D) equals 61.0%. 
COMATIVE EXAMPLE 3 
No Halogen Treatment, 1300.degree. C. Heat Treatment 
With the exception that the heat treatment temperature was 1300.degree. C., 
the treatment was conducted under the same conditions as in Comparative 
Example 1. The charging and discharging characteristics were measured. The 
results were A=396 mAh/g, B=320 mAh/g, C=164 mAh/g, and D=301 mAh/g. The 
total discharge efficiency K(B/A) equals 80.8%, and the effective 
discharge ratio K(C/D) equals 54.5%. 
EXAMPLE 1 
Chlorine Treatment, 1000.degree. C. High Temperature Dechlorination, Steam 
Dechlorination, Crushing Conducted After Pore Adjustment 
Dry distilled carbon was given a chlorination treatment, next it was heated 
(high temperature dechlorination) to a temperature of 1000.degree. C. 
under a nitrogen gas current, and, additionally, a dechlorination 
treatment (low temperature dechlorination treatment) was conducted by 
heating under a current of nitrogen gas which contained steam. After 
giving this a pore adjustment treatment, it was crushed to an average 
particle size of approximately 13 .mu.m, then carbon for a battery was 
made by the above-mentioned method, and the charging and discharging 
characteristics were measured using an evaluation cell. The results were 
A=750 mAh/g, B=627 mAh/g, C=390 mAh/g, and D=604 mAh/g. The total 
discharge efficiency K(B/A) equals 83.6%, and the effective discharge 
ratio K(C/D) equals 64.6%. 
EXAMPLE 2 
Chlorine Treatment, Steam Dechlorination, 800.degree. C. High Temperature 
Dechlorination, Crushing Conducted After Pore Adjustment 
Dry distilled carbon was given a chlorination treatment, then a 
dechlorination treatment (low temperature dechlorination treatment) was 
conducted by heating under a current of nitrogen gas which contained 
steam, and, next, a heating treatment (high temperature dechlorination) to 
a temperature of 800.degree. C. under a nitrogen gas current was 
conducted. After giving this a pore adjustment treatment, it was crushed 
to an average particle size of approximately 13 .mu.m, then carbon for a 
battery was made by the above-mentioned method, and the charging and 
discharging characteristics were measured using an evaluation cell. The 
results were A=777 mAh/g, B=606 mAh/g, C=312 mAh/g, and D=553 mAh/g. The 
total discharge efficiency K(B/A) equals 78.0%, and the effective 
discharge ratio K(C/D) equals 56.4%. 
EXAMPLE 3 
Chlorine Treatment, Steam Dechlorination, 1000.degree. C. High Temperature 
Dechlorination, Crushing Conducted After Pore Adjustment 
Carbon for a battery was made under the same conditions as for Example 2 
with the exception that the temperature of the heating (high temperature 
dechlorination treatment) in nitrogen gas was 1000.degree. C. The results 
of the measurement of the charging and discharging characteristics were 
A=754 mAh/g, B=642 mAh/g, C=413 mAh/g, and D=618 mAh/g. The total 
discharge efficiency K(B/A) equals 85.1%, and the effective discharge 
ratio K(C/D) equals 66.8%. 
EXAMPLE 4 
Chlorine Treatment, Steam Dechlorination, 1000.degree. C. High Temperature 
Dechlorination, Crushing Conducted After Pore Adjustment 
Carbon for a battery was made under the same conditions as for Example 3 
with the exception that the average particle size of the crushed carbon 
was approximately 9 .mu.m. The results of the measurement of the charging 
and discharging characteristics were A=738 mAh/g, B=603 mAh/g, C=372 
mAh/g, and D=582 mAh/g. The total discharge efficiency K(B/A) equals 
81.7%, and the effective discharge ratio K(C/D) equals 63.9%. 
EXAMPLE 5 
Chlorine Treatment, Steam Dechlorination, 800.degree. C. High Temperature 
Dechlorination 
Dry distilled carbon was given a chlorination treatment, and then a 
dechlorination treatment (low temperature dechlorination treatment) by 
heating under a current of nitrogen gas which contained steam. Next, it 
was heated (high temperature dechlorination) at a temperature of 
800.degree. C. under a nitrogen gas current, crushed, and additionally 
given a pore adjustment treatment. The charging and discharging 
characteristics of this carbon were measured using an evaluation cell. The 
results were A=778 mAh/g, B=622 mAh/g, C=342 mAh/g, and D=574 mAh/g. The 
total discharge efficiency K(B/A) equals 79.9%, and the effective 
discharge ratio K(C/D) equals 59.6%. 
EXAMPLE 6 
Chlorine Treatment, Methane Dechlorination, 1000.degree. C. High 
Temperature Dechlorination 
The treatment was conducted under the same conditions as in Example 5 with 
the exceptions that the dechlorination (low temperature dechlorination 
treatment) was conducted by a heat treatment under a nitrogen gas current 
which contained methane, and that the temperature of the heating (high 
temperature dechlorination) under a nitrogen gas current was 1000.degree. 
C. The charging and discharging characteristics were measured. The results 
were A=771 mAh/g, B=679 mAh/g, C=453 mAh/g, and D=658 mAh/g. The total 
discharge efficiency K(B/A) equals 88.1%, and the effective discharge 
ratio K(C/D) equals 68.8%. 
EXAMPLE 7 
Chlorine Treatment, Methane Dechlorination, 1300.degree. C. High 
Temperature Dechlorination 
The treatment was conducted under the same conditions as in Example 5 with 
the exceptions that the dechlorination (low temperature dechlorination 
treatment) was conducted by a heating treatment under a nitrogen gas 
current which contained methane, and that the temperature of the heating 
(high temperature dechlorination) under a nitrogen gas current was 
1300.degree. C. The charging and discharging characteristics were 
measured. The results were A=471 mAh/g, B=404 mAh/g, C=237 mAh/g, and 
D=387 mAh/g. The total discharge efficiency K(B/A) equals 85.8%, and the 
effective discharge ratio K(C/D) equals 61.2%. 
EXAMPLE 8 
Bromine Treatment, Steam Debromination, 800.degree. C. High Temperature 
Dechlorination 
Dry distilled carbon was brominated under a current of nitrogen gas which 
contained bromine gas at 5% by volume. Next, it was debrominated (low 
temperature debromination treatment) by heating under a current of 
nitrogen gas which contained steam. Then, it was heated (high temperature 
debromination) at a 800.degree. C. under a nitrogen gas current, crushed, 
and additionally given a pore adjustment treatment. The charging and 
discharging characteristics of this carbon were measured. The results were 
A=780 mAh/g, B=624 mAh/g, C=355 mAh/g, and D=576 mAh/g. The total 
discharge efficiency K(B/A) equals 80.0%, and the effective discharge 
ratio K(C/D) equals 61.6%. Desirable charging and discharging performances 
were obtained for bromination treatments as well. 
EXAMPLE 9 
Bromine Treatment, Steam Debromination, 1000.degree. C. High Temperature 
Debromination 
Carbon was made under the same conditions as in Example 8 with the 
exception that the temperature of the heating (high temperature 
debromination treatment) in nitrogen gas was 1000.degree. C. The results 
of the measurement of the charging and discharging characteristics of this 
carbonaceous material were A=774 mAh/g, B=683 mAh/g, C=467 mAh/g, and 
D=660 mAh/g. The total discharge efficiency K(B/A) equals 88.2%, and the 
effective discharge ratio K(C/D) equals 70.8%. Desirable charging and 
discharging performances were obtained for bromination treatments as well. 
The treatment conditions, and the charging and discharging characteristics 
for the Examples and the Comparative Examples are shown in Table 1. 
TABLE 1 
__________________________________________________________________________ 
A B C D K (B/A) 
K (C/D) 
[1] [2] 
[3] mAh/g 
mAh/g 
mAh/g 
mAh/g 
% % 
__________________________________________________________________________ 
Comparative 
none 
800 
powder 
775 570 256 511 73.5 
50.1 
Example 1 
Comparative 
none 
1000 
powder 
721 567 330 541 78.6 
61.0 
Example 2 
Comparative 
none 
1300 
powder 
396 320 164 301 80.8 
54.5 
Example 3 
Example 1 
chlorine 
1000 
powder 
750 627 390 604 83.6 
64.6 
Example 2 
chlorine 
800 
powder 
777 606 312 553 78.0 
56.4 
Example 3 
chlorine 
1000 
powder 
754 642 413 618 85.1 
66.8 
Example 4 
chlorine 
1000 
powder 
738 603 372 582 81.7 
63.9 
Example 5 
chlorine 
800 
powder 
778 622 342 574 79.9 
59.6 
Example 6 
chlorine 
1000 
powder 
771 679 453 658 88.1 
68.8 
Example 7 
chlorine 
1300 
powder 
471 404 237 387 85.8 
61.2 
Example 8 
bromine 
800 
powder 
780 624 355 576 80.0 
61.6 
Example 9 
bromine 
1000 
powder 
774 683 467 660 88.2 
70.8 
__________________________________________________________________________ 
Numbers in the Table 
[1] Halogen Treatment 
[2] Temperature of the Heating Conducted in a Nitrogen Gas Current 
.degree. C. 
[3] Condition of the Carbon 
Electrodes made by giving a dry-distilled charcoal a chlorine treatment, 
conducting a pore adjustment on it, then crushing it, and adding a binding 
agent (Examples 1.about.4) were superior in total discharge capacity, 
effective discharge capacity, total discharge efficiency, and effective 
discharge ratio when compared with Comparative Examples which were not 
given a chlorine treatment. In this case, better performance was obtained 
for a larger particle size for the crushing conducted after the pore 
adjustment than for a smaller one. Examples 5.about.7 in which the pore 
adjustment was conducted after conducting the chlorination treatment and 
the crushing treatment had better performance when compared with methods 
in which the crushing was conducted after the pore adjustment. In 
addition, better performance was obtained for bromination treatments when 
compared with the Comparative Examples. 
The factor of the improvement in performance for each of Examples 5.about.7 
(in which a chlorination treatment was given) are shown in Table 2 using 
the Comparative Examples (in which a chlorination treatment was not given) 
as a standard, for situations in which the temperature of the heating in 
the nitrogen gas current was the same. Each of the total discharge 
capacity, the effective discharge capacity, the total discharge 
efficiency, and the effective discharge ratio improved. Total discharge 
capacity was greatest at a factor of 1.26 (a 26% increase), the effective 
discharge capacity was greatest at a factor of 1.45 (a 45% increase), the 
total discharge efficiency was greatest at a factor of 1.12 (a 12% 
increase), and the effective discharge ratio was greatest at a factor of 
1.19 (a 19% increase). 
TABLE 2 
__________________________________________________________________________ 
Temperature Total 
Effective 
Total 
Effective 
of heating in Discharge 
Discharge 
Discharge 
Discharge 
nitrogen current Capacity 
Capacity 
Efficiency 
Ratio 
__________________________________________________________________________ 
800.degree. C. 
Example 5/Comparative Example 1 
1.09 1.34 1.09 1.19 
1000.degree. C. 
Example 6/Comparative Example 2 
1.20 1.37 1.12 1.13 
1300.degree. C. 
Example 7/Comparative Example 3 
1.26 1.45 1.06 1.12 
__________________________________________________________________________ 
Data for the Examples according to the first mode and for the Comparative 
Examples are shown in FIG. 7 (total discharge capacity), FIG. 8 (effective 
discharge capacity), FIG. 9 (total discharge efficiency), and FIG. 10 
(effective discharge rate). 
In every case, the Examples show greater values than the Comparative 
Examples in which the temperature for the heating in the nitrogen gas 
current was the same. 
Coin shaped lithium secondary batteries like the one shown in FIG. 11 were 
manufactured using carbon manufactured according to the above-mentioned 
Examples 1 through 9. These lithium secondary batteries are made into a 
structure in which a positive electrode 22 (the main component of which is 
LiCoO.sub.2) and a negative electrode 23 (comprising the carbon electrode 
manufactured in the Examples) are positioned on opposite sides of 
separator 21 which has been impregnated with organic solvent containing 
lithium ions as an electrolyte; the periphery of these is covered by 
metallic casing 24 and cap 25; and the boundary between casing 24 and cap 
25 is fixed in an insulated condition by means of packing 26. 
The results from examination of the charging and discharging 
characteristics of these lithium secondary batteries by means of the 
above-mentioned battery charging and discharging tests confirmed 
performance improvements the same as those obtained for the 
above-mentioned evaluation cell. 
EXAMPLES ACCORDING TO THE SECOND MODE 
For Comparative Example 4, carbon for a battery was manufactured by a 
process of dry distillation.fwdarw.heat-treatment.fwdarw.crushing 
treatment. For Comparative Examples 5.about.7, carbon for a battery was 
manufactured by a process of dry distillation.fwdarw.heat 
treatment.fwdarw.crushing treatment.fwdarw.pore adjustment treatment. 
For Example 10, carbon for a battery was manufactured by a process of dry 
distillation.fwdarw.crushing treatment.fwdarw.molding 
treatment.fwdarw.carbonization treatment. For Examples 11.about.13, carbon 
for a battery was manufactured by a process of dry 
distillation.fwdarw.crushing treatment.fwdarw.molding 
treatment.fwdarw.carbonization treatment.fwdarw.pore adjustment treatment. 
For the dry-distilled charcoal starting material, the dry-distilled 
charcoal of the Examples of the above-mentioned first mode was used. 
The conditions for the dry distilled carbon as well as for the crushing 
treatment and the pore adjusting treatment were the same as the condition 
recited in the Examples of the first mode. The molding treatment, the 
carbonization treatment, and the manufacture of the carbon for a battery 
were conducted under the following conditions. 
Molding Treatment 
15 parts by weight of phenol resin and 8 parts by weight of ethanol were 
added to 100 parts by weight of powdered dry-distilled charcoal and 
kneaded, in addition, this was impregnated with 20 parts of liquid 
paraffin and kneaded, and then press molded at a pressure of 500 
kgf/cm.sup.2. This was hardened by drying for 1 hour at 160.degree. C. The 
press molding equipment used was a RIKEN POWER D3.5-300 model manufactured 
by Riken Seiki (Ltd). The size of the molded article was 
30.times.30.times.1 mm. The weight was approximately 1.2 g. 
Carbonization Treatment 
The carbonization treatment for Examples 10.about.13 was conducted by 
giving the molded article a heat treatment for 60 minutes at a temperature 
of 800.degree. C..about.1200.degree. C. under a nitrogen gas current (3 
NL/min) of approximately atmospheric pressure. 
Heat Treatment 
The heat treatment for Comparative Examples 4.about.7 was conducted by 
heat-treating a dry-distilled charcoal for 60 minutes at a temperature of 
800.degree. C..about.1200.degree. C. under a nitrogen gas current (3 
NL/min) of approximately atmospheric pressure. 
Pore Adjustment (Examples 11.about.13, Comparative Examples 5.about.7) 
In the pore adjustment for the Examples, carbon (molded article) which had 
been given a carbonization treatment was made into a disk of predetermined 
size, and then heat-treated for 10 minutes at a temperature of 900.degree. 
C. under a current (3 NL/min) of nitrogen which had been saturated with 
benzene at 25.degree. C. 
In the pore adjustment for the Comparative Examples, dry-distilled charcoal 
was crushed to an average particle size of several .mu.m to several tens 
of .mu.m, and then heat-treated for 10 minutes at a temperature of 
900.degree. C. under a current (3 NL/min) of nitrogen which had been 
saturated with benzene at 25.degree. C. 
The pore adjustment was also conducted under conditions of approximately 
atmospheric pressure. After the pore adjustment treatment, the carbon for 
a battery was preserved in dry argon gas. 
Carbon for Battery (Examples 10.about.13, molded article) 
Carbon for a battery was made by cutting carbonization treated carbon into 
disks of 10 mm in diameter, and grinding them to a thickness of 0.2 mm. 
This operation was conducted in dry argon gas, and the carbon for a 
battery was preserved in dry argon gas. In addition, in dry nitrogen gas, 
carbonization treated carbon was made into carbon for a battery by cutting 
it into disks of 10 mm in diameter, grinding it to a thickness of 0.2 mm, 
and then giving it a pore adjustment. After that, the carbon for a battery 
was preserved in argon gas. 
Carbon for Battery (Comparative Examples 4.about.7, Powdered Product) 
Carbon which had been crushing treated or carbon which had been obtained by 
a pore adjustment conducted after a crushing treatment were made into a 
paste by the addition of polyvinyl fluoride equivalent to 9% by weight of 
carbon, and N-methyl-2-pyrrolidone, this was made into a sheet on a 
stainless steel plate for collecting electrode use, and thereby carbon for 
a battery (in a disk shape of 10 mm in diameter and 0.2 mm in thickness) 
was obtained. These operations were conducted in dry argon gas. 
The evaluation tests for charging and discharging capacity were the same as 
the those for the Examples of the above-mentioned first mode. 
The above-mentioned carbonization treatment, heat treatment, and pore 
adjustment treatment used the same equipment as that used in the Examples 
of the above-mentioned first mode. When conducting the carbonization 
treatment and the heating treatment using this equipment, nitrogen gas is 
run from pipe 15 at a predetermined rate. In the pore adjustment 
treatment, gas containing thermally decomposable hydrocarbon is run from 
pipe 16 at a predetermined rate. 
Pore Volume and Density of the Molded Article 
The density is calculated for the measurement of the volume and the weight. 
Pore volume is calculated by measuring the amount of benzene adsorbed at 
saturation at 25.degree. C., and dividing by the density of liquid benzene 
(0.879 g/cm.sup.3). 
COMATIVE EXAMPLE 4 
No Pore Adjustment, Powdered Product 
Dry distilled charcoal was heat-treated at a temperature of 1100.degree. C. 
in a current of nitrogen gas, and then crushed. A binding agent was added 
to this carbon, carbon for a battery was made, and the charging and 
discharging properties were measured using an evaluation cell. The results 
were A=669 mAh/g, B=437 mAh/g, C=212 mAh/g, and D=399 mAh/g. The total 
discharge efficiency K(B/A) equals 65.3%, and the effective discharge 
ratio K(C/D) equals 53.1%. 
EXAMPLE 10 
No Pore Adjustment, Molded Article 
Dry distilled charcoal was crushed, molded and carbonization-treated by 
heating at a temperature of 1100.degree. C. in a current of nitrogen gas. 
Disked shaped carbon was made from this carbon, and the charging and 
discharging characteristics were measured using an evaluation cell. The 
results were A=731 mAh/g, B=485 mAh/g, C=249 mAh/g, and D=447 mAh/g. The 
total discharge efficiency K(B/A) equals 66.3%, and the effective 
discharge ratio K(C/D) equals 55.7%. 
COMATIVE EXAMPLE 5 
800.degree. C. Heat Treatment, Powdered Product 
Dry distilled charcoal was given a heat-treated at a temperature of 
800.degree. C. in a current of nitrogen gas, crushed, and then a pore 
adjustment treatment was conducted. Binding agent was added to this 
powdered carbonaceous material, carbon for a battery was made, and the 
charging and discharging characteristics were measured using an evaluation 
cell. The results were A=775 mAh/g, B=570 mAh/g, C=256 mAh/g, and D=511 
mAh/g. The total discharge efficiency K(B/A) equals 73.5%, and the 
effective discharge ratio K(C/D) equals 50.1%. 
COMATIVE EXAMPLE 6 
1000.degree. C. Heat Treatment, Powdered Product 
This was conducted under the same conditions as for Comparative Example 5 
with the exception that the temperature of the heat treatment was 
1000.degree. C. The charging and discharging characteristics were 
measured. The results were A=721 mAh/g, B=567 mAh/g, C=330 mAh/g, and 
D=541 mAh/g. The total discharge efficiency K(B/A) equals 78.6%, and the 
effective discharge ratio K(C/D) equals 61.0%. 
COMATIVE EXAMPLE 7 
1200.degree. C. Heat Treatment, Powdered Product 
This was conducted under the same conditions as for Comparative Example 5 
with the exception that the temperature of the heat treatment was 
1200.degree. C. The charging and discharging characteristics were 
measured. The results were A=505 mAh/g, B=408 mAh/g, C=223 mAh/g, and 
D=390 mAh/g. The total discharge efficiency K(B/A) equals 80.8%, and the 
effective discharge ratio K(C/D) equals 57.2%. 
EXAMPLE 11 
800.degree. C. Carbonization Treatment, Molded Article 
Dry distilled charcoal was crushed, molded, carbonization-treated by 
heating at a temperature of 800.degree. C. in a current of nitrogen gas, 
then ground, and thereby, a disk shaped carbonaceous material was 
manufactured. In addition, carbon for a battery was then made by 
conducting a pore adjustment treatment, and then the charging and 
discharging characteristics were measured. The results were A=860 mAh/g, 
B=671 mAh/g, C=307 mAh/g, and D=592 mAh/g. The total discharge efficiency 
K(B/A) equals 78.0%, and the effective discharge ratio K(C/D) equals 
51.9%. The density of the carbonization treated molded article was 0.80 
g/cm.sup.3, and the pore volume was 0.23 cm.sup.3 /g. The density of the 
molded article of the carbon for a battery which was given a pore 
adjustment treatment was 0.81 g/cm.sup.3. 
EXAMPLE 12 
1000.degree. C. Carbonization Treatment, Molded Article 
This was treated under the same conditions as Example 11 with the exception 
that the temperature of the carbonization treatment was 1000.degree. C. 
The charging and discharging characteristics were measured. The results 
were A=782 mAh/g, B=651 mAh/g, C=397 mAh/g, and D=606 mAh/g. The total 
discharge efficiency K(B/A) equals 83.2%, and the effective discharge 
ratio K(C/D) equals 65.5%. The density of the carbonization treated molded 
article was 0.83 g/cm.sup.3, and the pore volume was 0.26 cm.sup.3 /g. The 
density of the molded article of the carbon for a battery which was given 
a pore adjustment treatment was 0.84 g/cm.sup.3. 
EXAMPLE 13 
1200.degree. C. Carbonization Treatment, Molded Article 
This was treated under the same conditions as Example 11 with the exception 
that the temperature of the carbonization treatment was 1200.degree. C. 
The charging and discharging characteristics were measured. The results 
were A=553 mAh/g, B=476 mAh/g, C=270 mAh/g, and D=460 mAh/g. The total 
discharge efficiency K(B/A) equals 86.1%, and the effective discharge 
ratio K(C/D) equals 58.7%. The density of the carbonization treated molded 
article was 0.86 g/cm.sup.3, and the pore volume was 0.25 cm.sup.3 /g. The 
density of the molded article of the carbon for a battery which was given 
a pore adjustment treatment was 0.87 g/cm.sup.3. 
The treatment conditions and the charging and discharging properties for 
Comparative Examples 4.about.7 and Examples 10.about.13 are shown in Table 
3. 
TABLE 3 
__________________________________________________________________________ 
A B C D K (B/A) 
K (C/D) 
[1] [2] 
[3] 
mAh/g 
mAh/g 
mAh/g 
mAh/g 
% % 
__________________________________________________________________________ 
Comparative 
powder 
1100 
no 
669 437 212 399 65.3 
53.1 
Example 4 
Example 10 
sheet 
1100 
no 
731 485 249 447 66.3 
55.7 
Comparative 
powder 
800 
yes 
775 570 256 511 73.5 
50.1 
Example 5 
Comparative 
powder 
1000 
yes 
721 567 330 541 78.6 
61.0 
Example 6 
Comparative 
powder 
1200 
yes 
505 408 223 390 80.8 
57.2 
Example 7 
Example 11 
sheet 
800 
yes 
860 671 307 592 78.0 
51.9 
Example 12 
sheet 
1000 
yes 
782 651 397 606 83.2 
65.5 
Example 13 
sheet 
1200 
yes 
553 476 270 460 86.1 
58.7 
__________________________________________________________________________ 
Numbers in the Table 
[1] Condition of the Carbon 
[2] Temperature of the Heating in the Nitrogen Gas Current .degree. C. 
[3] Pore Adjustment Treatment (Yes/No) 
Table 4 shows the factor by which the performance improved for the Examples 
which were treated at carbonization temperature the same as the 
temperature of the heat treatment of the Comparative Examples. 
For situations in which a pore adjustment was not conducted, compared with 
the powder product of Comparative Example 4, the disk shaped molded carbon 
article of Example 10 had a total discharge capacity of 1.11 times (an 11% 
increase) that of the powder product of Comparative Example 4, an 
effective discharge capacity of 1.17 times (a 17% increase) that of the 
powder product of Comparative Example 4, a total discharge efficiency of 
1.02 times (a 2% increase) that of the powder product of Comparative 
Example 4, and an effective discharge ratio of 1.05 times (a 5% increase) 
that of the powder product of Comparative Example 4. 
When a pore adjustment treatment was conducted, and when comparing 
situations in which the heating treatment or carbonization treatment 
temperature were the same, each of the total discharge capacity, the 
effective discharge capacity, the total discharge efficiency and the 
effective discharge ratio were better for the Examples 11.about.13, in 
which the carbon electrode was made into a disk shaped molded article, 
than for the Comparative Examples, which were in a powdered condition. 
Total discharge capacity was greatest at a factor of 1.18 (a 18% 
increase), the effective discharge capacity was greatest at a factor of 
1.21 (a 21% increase), the total discharge efficiency was greatest at a 
factor of 1.07 (a 7% increase), and the effective discharge ratio was 
greatest at a factor of 1.07 (a 7% increase). 
TABLE 4 
__________________________________________________________________________ 
Temperature Total 
Effective 
Total 
Effective 
of heating in Discharge 
Discharge 
Discharge 
Discharge 
nitrogen current Capacity 
Capacity 
Efficiency 
Ratio 
__________________________________________________________________________ 
1100.degree. C. 
Example 10/Comparative Example 4 
1.11 1.17 1.02 1.05 
800.degree. C. 
Example 11/Comparative Example 5 
1.18 1.20 1.06 1.04 
1000.degree. C. 
Example 12/Comparative Example 6 
1.15 1.20 1.06 1.07 
1200.degree. C. 
Example 13/Comparative Example 7 
1.17 1.21 1.07 1.03 
__________________________________________________________________________ 
Data for the Examples according to the second mode and for the Comparative 
Examples are shown in FIG. 12 (total discharge capacity), FIG. 13 
(effective discharge capacity), FIG. 14 (total discharge efficiency), and 
FIG. 15 (effective discharge rate). As shown in these figures, when 
comparing Examples and Comparative Examples which have the same treatment 
temperatures, the Examples show greater values than those of the 
Comparative Examples. 
Coin shaped lithium secondary batteries like the one shown in FIG. 11 were 
manufactured using carbon manufactured according to Examples 10.about.13. 
The results from examination of the charging and discharging 
characteristics of these lithium secondary batteries by means of the 
above-mentioned battery charging and discharging tests confirmed 
performance improvements the same as those obtained for the 
above-mentioned evaluation cell. 
EXAMPLES ACCORDING TO THE THIRD MODE 
In Examples 14.about.16, carbon for a battery was manufactured by a process 
of chlorination.fwdarw.crushing.fwdarw.molding.fwdarw.(no 
carbonization).fwdarw.low temperature dechlorination.fwdarw.high 
temperature dechlorination.fwdarw.pore adjustment. In Examples 17 and 18, 
carbon for a battery was manufactured by a process of 
chlorination.fwdarw.crushing.fwdarw.molding.fwdarw.carbonization.fwdarw.hi 
gh temperature dechlorination.fwdarw.low temperature 
dechlorination.fwdarw.pore adjustment. In Examples 19.about.21, carbon for 
a battery was manufactured by a process of 
chlorination.fwdarw.crushing.fwdarw.molding.fwdarw.carbonization.fwdarw.lo 
w temperature dechlorination.fwdarw.high temperature 
dechlorination.fwdarw.pore adjustment. In Example 22, carbon for a battery 
was manufactured by a process of 
bromination.fwdarw.crushing.fwdarw.molding.fwdarw.(no 
carbonization).fwdarw.low temperature debromination.fwdarw.high 
temperature debromination.fwdarw.pore adjustment. In Examples 23 and 24, 
carbon for a battery was manufactured by a process of 
bromination.fwdarw.crushing.fwdarw.molding.fwdarw.carbonization.fwdarw.low 
temperature debromination.fwdarw.high temperature 
debromination.fwdarw.pore adjustment. In Examples 25.about.27, carbon for 
a battery was manufactured by a process of 
crushing.fwdarw.molding.fwdarw.chlorination.fwdarw.high temperature 
dechlorination.fwdarw.low temperature dechlorination.fwdarw.pore 
adjustment. In Example 28, carbon for a battery was manufactured by a 
process of crushing.fwdarw.molding.fwdarw.bromination.fwdarw.high 
temperature debromination.fwdarw.low temperature debromination.fwdarw.pore 
adjustment. 
On the other hand, in Comparative Examples 8.about.10, carbon for a battery 
was manufactured by a process of (no 
chlorination).fwdarw.crushing.fwdarw.molding.fwdarw.carbonization.fwdarw.h 
eat treatment.fwdarw.pore adjustment. In Comparative Examples 11.about.13, 
carbon for a battery was manufactured by a process of 
chlorination.fwdarw.low temperature dechlorination.fwdarw.high temperature 
dechlorination.fwdarw.crushing.fwdarw.pore adjustment. 
As the starting material dry-distilled charcoal, the dry-distilled charcoal 
of the Examples of the above-mentioned first mode was used. 
Halogen Treatment 
In the halogen treatment, dry-distilled charcoal starting material 
(approximately 15 g) or a molded article which had been carbonized again 
after the molding treatment was heat-treated for 2 hours at 600.degree. C. 
under a current of nitrogen gas (2.7 NL/min) containing chlorine at 5% by 
volume or bromine at 5% by volume. 
The low temperature dehalogenation was conducted by means of a heat 
treatment for 30 minutes at a temperature of 700.degree. C. under a 
current of nitrogen gas (3 NL/min) which had been saturated with steam at 
25.degree. C., or which contained methane at 40% by volume. In addition, 
in one Example, it was conducted by a heat treatment for 30 minutes at a 
temperature of 1000.degree. C. in a current of nitrogen gas (3 NL/min) 
which contained hydrogen at 50% by volume. 
The high temperature dehalogenation was conducted by means of a heat 
treatment for 60 minutes at a temperature of 800.degree. C., 1000.degree. 
C. or 1200.degree. C. under a current of nitrogen gas (3 NL/min). 
These treatments were all conducted under conditions of approximately 
atmospheric pressure. After the dehalogenation treatment, the carbon for a 
battery was preserved in dry argon gas. 
Molding Treatment (Examples 14.about.28 and Comparative Examples 
8.about.10) 
The molding treatment was conducted in the following way. 100 parts by 
weight of powdered dry-distilled charcoal or powdered halogenated 
dry-distilled charcoal, and 15 parts by weight of phenol resin and 8 parts 
by weight of ethanol added thereto were kneaded, in addition, this was 
impregnated with 20 parts of liquid paraffin and kneaded, and then press 
molded at a pressure of 500 kgf/cm.sup.2. This was hardened by drying for 
1 hour at 160.degree. C. The press molding equipment used was a RIKEN 
POWER D3.5-300 model manufactured by Riken Seiki (Ltd). The shape of the 
molded article was 30.times.30.times.1 mm. The weight of the molded 
product was approximately 1.2 g. 
Carbonization Treatment (Examples 17.about.21, 23.about.24, and Comparative 
Examples 8.about.10) 
Under a nitrogen gas current (3 NL/min) of approximately atmospheric 
pressure, the molded article was raised to a temperature of 700.degree. C. 
at a heating rate of 200.degree. C./h, and then maintained at that 
temperature for 20 minutes. 
Processing of the Molded Article (Example 14.about.28 and Comparative 
Examples 8.about.10) 
In dry argon gas, dehalogenation treated carbon was cut into a disk of 10 
mm in diameter, and ground to a thickness of 0.2 mm. After that, and until 
the pore adjustment treatment, the carbon was preserved in dry argon gas. 
Pore Adjustment Treatment 
In the pore adjustment of Examples 14.about.28 and Comparative Examples 
8.about.10, the carbon (molded carbon article) which had been given a 
dehalogenation treatment was made into a disk of a predetermined size, and 
given a heat treatment for 10 minutes at a temperature of 900.degree. C. 
in a current of nitrogen gas (3 NL/min) which had been saturated with 
benzene at 25.degree. C. 
In the pore adjustment of Examples 11.about.13, powder of an average 
particle size of several .mu.m to several 10 s of .mu.m was made by a 
crushing treatment, and then treated under the same conditions as 
mentioned above. 
The pore adjustment was also conducted under conditions of approximately 
atmospheric pressure. After the pore adjustment the carbon was preserved 
in dry argon gas. 
Manufacture of Carbon for Battery (Comparative Examples 11.about.13, 
Powdered Product) 
Carbon for a battery (in a disk shape of 10 mm in diameter and 0.2 mm in 
thickness) was made by making powdered carbon which had been given a pore 
adjustment into a paste by the addition of polyvinyl fluoride equivalent 
to 9% by weight of carbon as a binding agent, and, additionally, by the 
addition of N-methyl-2-pyrrolidone, and making this into a sheet on a 
stainless steel plate for collecting electrode use. These operations were 
conducted in dry argon gas. 
The evaluation tests for charging and discharging capacity were the same as 
the those for the Examples of the first mode. 
The above-mentioned chlorine (and bromine) treatment, carbonization, and 
pore adjustment treatment used the same equipment as that used in the 
Examples of the above-mentioned first mode. 
When conducting the chlorination (or bromination) treatment using this 
equipment, nitrogen gas is run from pipe 15 at a predetermined rate and 
chlorine (or bromine) gas is run from pipe 16 at a predetermined rate. In 
the low temperature dechlorination (debromination) treatment, gas 
containing steam, methane or hydrogen is run from pipe 16 at a 
predetermined rate. In the high temperature dechlorination (debromination) 
treatment, nitrogen gas is run from pipe 15 at a predetermined rate. In 
the pore adjustment treatment, gas containing thermally decomposable 
hydrocarbon is run from pipe 16 at a predetermined rate. 
The density and the pore volume of the molded article were measured by 
means of the same method as that of the Examples of the second mode. 
COMATIVE EXAMPLE 8 
No Chlorine Treatment, 800.degree. C. Heat Treatment, Molded Article 
Dry distilled charcoal was crushed, organic binding agent added thereto, 
and then molded, next, the organic binding agent was carbonized by heating 
under a current of nitrogen gas. Next, it was given a heat treatment at a 
temperature of 800.degree. C. under a current of nitrogen gas, and then 
ground to make a disk shaped carbonaceous material. In addition, a pore 
adjustment treatment was conducted, carbon for a battery was made, and the 
charging and discharging characteristic measured. The results were A=860 
mAh/g, B=671 mAh/g, C=307 mAh/g, and D=592 mAh/g. The total discharge 
efficiency K(B/A) equals 78.0%, and the effective discharge ratio K(C/D) 
equals 51.9%. The density of the heat-treated molded article was 0.80 
g/cm.sup.3, and the pore volume was 0.18 cm.sup.3 /g. The density of the 
molded article of the carbon for a battery which was given a pore 
adjustment treatment was 0.81 g/cm.sup.3. 
COMATIVE EXAMPLE 9 
No Chlorine Treatment, 1000.degree. C. Heat Treatment, Molded Article 
This was conducted under the same conditions as Comparative Example 8 with 
the exception that the temperature of the heat treatment in nitrogen gas 
was 1000.degree. C. The charging and discharging characteristics were 
measured. The results were A=782 mAh/g, B=651 mAh/g, C=397 mAh/g, and 
D=606 mAh/g. The total discharge efficiency K(B/A) equals 83.2%, and the 
effective discharge ratio K(C/D) equals 65.5%. The density of the 
heat-treated molded article was 0.83 g/cm.sup.3, and the pore volume was 
0.19 cm.sup.3 /g. The density of the molded article of the carbon for a 
battery which was given a pore adjustment treatment was 0.84 g/cm.sup.3. 
COMATIVE EXAMPLE 10 
No Chlorine Treatment, 1200.degree. C. Heat Treatment, Molded Article 
This was conducted under the same conditions as Comparative Example 8 with 
the exception that the temperature of the heat treatment under a nitrogen 
gas current was 1200.degree. C. The charging and discharging 
characteristics were measured. The results were A=553 mAh/g, B=476 mAh/g, 
C=270 mAh/g, and D=460 mAh/g. The total discharge efficiency K(B/A) equals 
86.1%, and the effective discharge ratio K(C/D) equals 58.7%. The density 
of the heat-treated molded article was 0.86 g/cm.sup.3, and the pore 
volume was 0.19 cm.sup.3 /g. The density of the molded article of the 
carbon for a battery which was given a pore adjustment treatment was 0.87 
g/cm.sup.3. 
COMATIVE EXAMPLE 11 
Chlorine Treatment, Steam Dechlorination, 800.degree. C. High Temperature 
Dechlorination Treatment, Powdered Product 
Dry distilled charcoal was chlorinated and then dechlorinated (low 
temperature dechlorination treatment) by heating under a current of 
nitrogen gas which contained steam, next it was given a heat treatment 
(high temperature dechlorination treatment) at a temperature of 
800.degree. C. under a current of nitrogen gas. This was crushed, and a 
pore adjustment treatment conducted on the powdered carbon. A binding 
agent was added to this carbon to make carbon for a battery, and the 
charging and discharging characteristics were measured using an evaluation 
cell. The results were A=778 mAh/g, B=622 mAh/g, C=316 mAh/g, and D=567 
mAh/g. The total discharge efficiency K(B/A) equals 79.9%, and the 
effective discharge ratio K(C/D) equals 55.7%. 
COMATIVE EXAMPLE 12 
Chlorine Treatment, methane Dechlorination, 1000.degree. C. High 
Temperature Dechlorination, Powdered Product 
This was conducted under the same conditions as in Comparative Example 11 
with the exceptions that the dechlorination (low temperature 
dechlorination treatment) was a heat treatment in a nitrogen current which 
contained methane, and that the temperature of the heating (high 
temperature dechlorination treatment) in a nitrogen gas current was 
1000.degree. C. The charging and discharging characteristics were 
measured. The results were A=771 mAh/g, B=679 mAh/g, C=440 mAh/g, and 
D=658 mAh/g. The total discharge efficiency K(B/A) equals 88.1%, and the 
effective discharge ratio K(C/D) equals 66.9%. 
COMATIVE EXAMPLE 13 
Chlorine Treatment, Steam Dechlorination, 1200.degree. C. High Temperature 
Dechlorination, Powdered Product 
This was conducted under the same conditions as in Comparative Example 11 
with the exception that the temperature of the heat treatment (high 
temperature dechlorination treatment) in a current of nitrogen gas was 
1200.degree. C. The charging and discharging characteristics were 
measured. The results were A=554 mAh/g, B=471 mAh/g, C=284 mAh/g, and 
D=445 mAh/g. The total discharge efficiency K(B/A) equals 85.0%, and the 
effective discharge ratio K(C/D) equals 63.8%. 
EXAMPLE 14 
Chlorine Treatment, Steam Dechlorination, 800.degree. C. High Temperature 
Dechlorination, Molded Article 
Chlorination treated dry-distilled charcoal was crushed, a binding agent 
added thereto, and then molded, next, it was dechlorinated (low 
temperature dechlorination treatment) by heating under a current of 
nitrogen gas which contained steam. Next, it was heated (high temperature 
dechlorination treatment) at a temperature of 800.degree. C. under a 
current of nitrogen gas, and then ground to make a disk shaped 
carbonaceous material. Carbon for a battery was made by additionally 
conducting a pore adjustment treatment. The charging and discharging 
characteristics of this carbon for a electrode were measured using a 
evaluation cell. The results were A=867 mAh/g, B=682 mAh/g, C=341 mAh/g, 
and D=609 mAh/g. The total discharge efficiency K(B/A) equals 78.7%, and 
the effective discharge ratio K(C/D) equals 56.0%. 
EXAMPLE 15 
Chlorine Treatment, Steam Dechlorination, 1000.degree. C. High Temperature 
Dechlorination, Molded Article 
This was conducted under the same conditions as Example 14 with the 
exception that the temperature of the heating (high temperature 
dechlorination treatment) in the nitrogen gas current was 1000.degree. C. 
The charging and discharging characteristics were measured. The results 
were A=858 mAh/g, B=760 mAh/g, C=501 mAh/g, and D=719 mAh/g. The total 
discharge efficiency K(B/A) equals 88.6%, and the effective discharge 
ratio K(C/D) equals 69.7%. 
EXAMPLE 16 
Chlorine Treatment, Steam Dechlorination, 1200.degree. C. High Temperature 
Dechlorination, Molded Article 
This was conducted under the same conditions as Example 14 with the 
exception that the temperature of the heating (high temperature 
dechlorination treatment) in the nitrogen gas current was 1200.degree. C. 
The charging and discharging characteristics were measured. The results 
were A=635 mAh/g, B=559 mAh/g, C=375 mAh/g, and D=532 mAh/g. The total 
discharge efficiency K(B/A) equals 88.0%, and the effective discharge 
ratio K(C/D) equals 70.5%. 
EXAMPLE 17 
Chlorine Treatment, 1000.degree. C. High Temperature Dechlorination, Steam 
Dechlorination, Molded Article 
Chlorination treated dry-distilled charcoal was crushed, a binding agent 
added thereto, and molded, then it was carbonized by heating under a 
current of nitrogen gas. The carbonized molded article was heated (high 
temperature dechlorination treatment) at a temperature of 1000.degree. C. 
under a current of nitrogen gas, next, it was dechlorinated (low 
temperature dechlorination treatment) by heating under a current of 
nitrogen gas which contained steam, and then ground to make a disk shaped 
carbonaceous material. Carbon for a battery was made by additionally 
conducting a pore adjustment treatment. The charging and discharging 
characteristics of this carbon for a battery were measured using an 
evaluation cell. The results were A=862 mAh/g, B=782 mAh/g, C=528 mAh/g, 
and D=741 mAh/g. The total discharge efficiency K(B/A) equals 90.7%, and 
the effective discharge ratio K(C/D) equals 71.3%. The density of the 
dechlorination treated molded article was 0.86 g/cm.sup.3, and the pore 
volume was 0.26 cm.sup.3 /g. The density of the molded article of the 
carbon for a battery which was given the pore adjustment treatment was 
0.88 g/cm.sup.3. 
EXAMPLE 18 
Chlorine Treatment, 1000.degree. C. High Temperature Dechlorination, 
Hydrogen Gas Dechlorination, Molded Article 
Chlorination treated dry-distilled charcoal was crushed, a binding agent 
added thereto, and molded, then it was carbonized by heating under a 
current of nitrogen gas. The carbonized molded article was heat-treated 
(high temperature dechlorination treatment) at a temperature of 
1000.degree. C. under a current of nitrogen gas, next, it was heated (low 
temperature dechlorination treatment) for 30 minutes at a temperature of 
1000.degree. C. in a gas mixture of hydrogen gas at 50% by volume and 
nitrogen gas at 50% by volume, and then ground to make a disk shaped 
carbonaceous material. Carbon for a battery was made by additionally 
conducting a pore adjustment treatment. The charging and discharging 
characteristics of this carbon for a battery were measured using an 
evaluation cell. The results were A=862 mAh/g, B=781 mAh/g, C=530 mAh/g, 
and D=740 mAh/g. The total discharge efficiency K(B/A) equals 90.6%, and 
the effective discharge ratio K(C/D) equals 71.6%. The density of the 
dechlorination treated molded article was 0.86 g/cm.sup.3, and the pore 
volume was 0.26 cm.sup.3 /g. The density of the molded article of the 
carbon for a battery which was given the pore adjustment treatment was 
0.88 g/cm.sup.3. 
EXAMPLE 19 
Chlorine Treatment, Steam Dechlorination, 800.degree. C. High Temperature 
Dechlorination, Molded Article 
Chlorination treated dry-distilled charcoal was crushed, a binding agent 
added thereto, and molded, then, it was carbonized by heating under a 
current of nitrogen gas. The carbonized molded article was dechlorinated 
(low temperature dechlorination treatment) by heating under a current of 
nitrogen gas which contained steam, next, it was heat-treated (high 
temperature dechlorination treatment) at a temperature of 800.degree. C. 
under a current of nitrogen gas, and then ground to make a disk shaped 
carbonaceous material. Carbon for a battery was made by additionally 
conducting a pore adjustment treatment. The charging and discharging 
characteristics of this carbon for a battery were measured using an 
evaluation cell. The results were A=872 mAh/g, B=698 mAh/g, C=373 mAh/g, 
and D=625 mAh/g. The total discharge efficiency K(B/A) equals 80.0%, and 
the effective discharge ratio K(C/D) equals 59.7%. The density of the 
dechlorination treated molded article was 0.85 g/cm.sup.3, and the pore 
volume was 0.28 cm.sup.3 /g. The density of the molded article of the 
carbon for a battery which was given the pore adjustment treatment was 
0.86 g/cm.sup.3. 
EXAMPLE 20 
Chlorine Treatment, Methane Dechlorination, 1000.degree. C. High 
Temperature Dechlorination, Molded Article 
This was conducted under the same conditions as Example 19 with the 
exceptions that the dechlorination (low temperature dechlorination 
treatment) was conducted by heating under a current of nitrogen gas which 
contained methane, and that the temperature of the heating (high 
temperature dechlorination treatment) in a nitrogen gas current was 
1000.degree. C. The charging and discharging characteristics were 
measured. The results were A=863 mAh/g, B=784 mAh/g, C=531 mAh/g, and 
D=744 mAh/g. The total discharge efficiency K(B/A) equals 90.8%, and the 
effective discharge ratio K(C/D) equals 71.4%. The density of the 
dechlorination treated molded article was 0.86 g/cm.sup.3, and the pore 
volume was 0.28 cm.sup.3 /g. The density of the molded article of the 
carbon for a battery which was given the pore adjustment treatment was 
0.88 g/cm.sup.3. 
EXAMPLE 21 
Chlorine Treatment, Steam Dechlorination, 1200.degree. C. High Temperature 
Dechlorination, Molded Article 
This was conducted under the same conditions as Example 19 with the 
exception that the temperature of the heating (high temperature 
dechlorination treatment) in a nitrogen gas current was 1200.degree. C. 
The charging and discharging characteristics were measured. The results 
were A=640 mAh/g, B=580 mAh/g, C=393 mAh/g, and D=553 mAh/g. The total 
discharge efficiency K(B/A) equals 90.6%, and the effective discharge 
ratio K(C/D) equals 71.1%. The density of the dechlorination treated 
molded article was 0.87 g/cm.sup.3, and the pore volume was 0.27 cm.sup.3 
/g. The density of the molded article of the carbon for a battery which 
was given the pore adjustment treatment was 0.88 g/cm.sup.3. 
EXAMPLE 22 
Bromination Treatment, 1000.degree. C. High Temperature Debromination, 
Molded Article 
Dry distilled charcoal was bromination treated by heating for 2 hours at a 
temperature of 600.degree. C. under a current of nitrogen gas which 
contained bromine at 5% by volume. The brominated dry-distilled charcoal 
was crushed, a binding agent added, and molded. Next, it was heated (low 
temperature debromination treatment) at a temperature of 700.degree. C. 
under a current of nitrogen gas which contained steam, and additionally 
heated (high temperature debromination treatment) at a temperature of 
1000.degree. C. under a current of nitrogen gas. Next, from this, a disk 
shaped carbonaceous material was manufactured, and carbon for a battery 
was made by conducting a pore adjustment treatment. The charging and 
discharging characteristics were measured. The results were A=865 mAh/g, 
B=766 mAh/g, C=509 mAh/g, and D=725 mAh/g. The total discharge efficiency 
K(B/A) equals 88.6%, and the effective discharge ratio K(C/D) equals 
70.2%. Good charging and discharging characteristics were also obtained by 
conducting a bromination treatment. The density of the molded article of 
the carbon for a battery which was given the pore adjustment treatment was 
0.89 g/cm.sup.3. 
EXAMPLE 23 
Bromination Treatment, 800.degree. C. High Temperature Debromination, 
Molded Article 
Dry distilled charcoal was bromination treated by heating for 2 hours at a 
temperature of 600.degree. C. under a current of nitrogen gas which 
contained bromine at 5% by volume. The brominated dry-distilled charcoal 
was crushed, a binding agent added, and molded; then it was carbonized 
under a current of nitrogen gas. The carbonized molded article was 
debrominated (low temperature debromination treatment) by heating for 30 
minutes at a temperature of 700.degree. C. under a current of nitrogen gas 
which had been saturated with steam at 25.degree. C. Next, it was heated 
(high temperature debromination treatment) at a temperature of 800.degree. 
C. under a current of nitrogen gas. From this, a disk shaped carbonaceous 
material was manufactured, and carbon for a battery was made by conducting 
a pore adjustment treatment. The charging and discharging characteristics 
of this carbon were measured. The results were A=869 mAh/g, B=695 mAh/g, 
C=371 mAh/g, and D=622 mAh/g. The total discharge efficiency K(B/A) equals 
80.0%, and the effective discharge ratio K(C/D) equals 59.6%. Good 
charging and discharging characteristics were also obtained by conducting 
a bromination treatment. The density of the molded article of the carbon 
for a battery which was given the pore adjustment treatment was 0.87 
g/cm.sup.3. 
EXAMPLE 24 
Bromination Treatment, 1000.degree. C. High Temperature Debromination, 
Molded Article 
Carbon for a battery was manufactured under the same conditions as Example 
23 with the exception that the temperature of the heating (high 
temperature debromination treatment) under a current of nitrogen gas was 
1000.degree. C. The results of the measurement of the charging and 
discharging characteristics were A=869 mAh/g, B=790 mAh/g, C=539 mAh/g, 
and D=751 mAh/g. The total discharge efficiency K(B/A) equals 90.9%, and 
the effective discharge ratio K(C/D) equals 71.8%. Good charging and 
discharging efficiencies were also obtained by conducting a bromination 
treatment. The density of the molded article of the carbon for a battery 
which was given the pore adjustment treatment was 0.89 g/cm.sup.3. 
EXAMPLE 25 
Molded Article, Chlorination Treatment, 800.degree. C. High Temperature 
Dechlorination 
Dry distilled charcoal was crushed, an organic binding agent added thereto, 
and molded; next a second dry distillation was conducted in which the 
organic binding agent was carbonized under a current of nitrogen gas by 
raising the temperature to 600.degree. C. at a rate of 100.degree. C./h. 
Next, it was chlorinated by a heat treatment for 2 hours at a temperature 
of 600.degree. C. under a current of nitrogen gas which contained chlorine 
at 5% by volume. Next it was heated (high temperature dechlorination 
treatment) at a temperature of 800.degree. C. under a current of nitrogen 
gas, and then dechlorinated (low temperature dechlorination treatment) by 
heating at 700.degree. C. under a current of nitrogen gas which contained 
steam. This was ground to make a disk shaped carbonaceous material, and 
then given a pore adjustment treatment. The results of the measurement of 
the charging and discharging characteristics were A=854 mAh/g, B=679 
mAh/g, C=360 mAh/g, and D=628 mAh/g. The total discharge efficiency K(B/A) 
equals 79.5%, and the effective discharge ratio K(C/D) equals 57.3%. 
Good efficiency was also obtained by conducting a chlorination treatment a 
molded article. 
EXAMPLE 26 
Molded Article, Chlorination Treatment, 1000.degree. C. High Temperature 
Dechlorination 
Dry distilled charcoal was crushed, an organic binding agent added thereto, 
and molded; next a second dry distillation was conducted in which the 
organic binding agent was carbonized under a current of nitrogen gas by 
raising the temperature to 600.degree. C. at a rate of 100.degree. C./h. 
Next, it was chlorinated by a heat treatment for 2 hours at a temperature 
of 600.degree. C. under a current of nitrogen gas which contained chlorine 
at 5% by volume. Next it was heated (high temperature dechlorination 
treatment) at 1000.degree. C. under a current of nitrogen gas, and then 
dechlorinated (low temperature dechlorination treatment) by heating at 
700.degree. C. under a current of nitrogen gas which contained steam. This 
was ground to make a disk shaped carbonaceous material, and then given a 
pore adjustment treatment. The results of the measurement of the charging 
and discharging characteristics were A=841 mAh/g, B=751 mAh/g, C=501 
mAh/g, and D=715 mAh/g. The total discharge efficiency K(B/A) equals 
89.3%, and the effective discharge ratio K(C/D) equals 70.1%. 
Good performance was also obtained by conducting a chlorination treatment a 
molded article. 
EXAMPLE 27 
Molded Article, Chlorination Treatment, 1200.degree. C. High Temperature 
Dechlorination 
Dry distilled charcoal was crushed, an organic binding agent added thereto, 
and molded; next, a second dry distillation was conducted in which the 
organic binding agent was carbonized under a current of nitrogen gas by 
raising the temperature to 600.degree. C. at a rate of 100.degree. C./h. 
Next, it was chlorinated by a heat treatment for 2 hours at a temperature 
of 600.degree. C. under a current of nitrogen gas which contained chlorine 
at 5% by volume. Next it was heated (high temperature dechlorination 
treatment) at 1200.degree. C. under a current of nitrogen gas, and then 
dechlorinated (low temperature dechlorination treatment) by heating at 
700.degree. C. under a current of nitrogen gas which contained steam. This 
was ground to make a disk shaped carbonaceous material, and then given a 
pore adjustment treatment. The results of the measurement of the charging 
and discharging characteristics were A=631 mAh/g, B=564 mAh/g, C=374 
mAh/g, and D=534 mAh/g. The total discharge efficiency K(B/A) equals 
89.4%, and the effective discharge ratio K(C/D) equals 70.0%. 
Good performance was also obtained by conducting a chlorination treatment a 
molded article. 
EXAMPLE 28 
Molded Article, Bromination Treatment, 1000.degree. C. High Temperature 
Debromination 
Dry distilled charcoal was crushed, an organic binding agent added thereto, 
and molded; next, a second dry distillation was conducted in which the 
organic binding agent was carbonized under a current of nitrogen gas by 
raising the temperature to 600.degree. C. at a rate of 100.degree. C./h. 
Next, it was brominated by a heat treatment for 2 hours at a temperature 
of 600.degree. C. under a current of nitrogen gas which contained bromine 
at 5% by volume. Next it was heated (high temperature debromination 
treatment) at 1000.degree. C. under a current of nitrogen gas, and then 
debrominated (low temperature debromination treatment) by heating at 
700.degree. C. under a current of nitrogen gas which contained steam. This 
was ground to make a disk shaped carbonaceous material, and then given a 
pore adjustment treatment. The results of the measurement of the charging 
and discharging characteristics were A=845 mAh/g, B=756 mAh/g, C=508 
mAh/g, and D=720 mAh/g. The total discharge efficiency K(B/A) equals 
89.5%, and the effective discharge ratio K(C/D) equals 70.6%. 
Good performance was also obtained by conducting a bromination treatment on 
a molded article. 
The treatment conditions and the charging and discharging characteristics 
of Comparative Examples 8.about.13 and Examples 14.about.28 are shown in 
Table 5. In Table 5, A represents total charging capacity, B represents 
total discharge capacity, C represents effective discharge capacity, D 
represents fixed current discharging capacity, K(B/A) represents total 
discharge efficiency, and K(C/D) represents effective discharge ratio. 
TABLE 5 
__________________________________________________________________________ 
[6] 
A B C D K (B/A) 
K (C/D) 
[1] [2] [3] [4] [5] 
.degree. C. 
mAh/g 
mAh/g 
mAh/g 
mAh/g 
% % 
__________________________________________________________________________ 
Comparative 
sheet 
none 
-- yes 
800 
860 671 307 592 78.0 
51.9 
Example 8 
Comparative 
sheet 
none 
-- yes 
1000 
782 651 397 606 83.2 
65.5 
Example 9 
Comparative 
sheet 
none 
-- yes 
1200 
553 476 270 460 86.1 
58.7 
Example 10 
Comparative 
powder 
chlorine 
steam 
-- 
800 
778 622 316 567 79.9 
55.7 
Example 11 
Comparative 
powder 
chlorine 
methane 
-- 
1000 
771 679 440 658 88.1 
66.9 
Example 12 
Comparative 
powder 
chlorine 
steam 
-- 
1200 
554 471 284 445 85.0 
63.8 
Example 13 
Example 14 
sheet 
chlorine 
steam 
no 
800 
867 682 341 609 78.7 
56.0 
Example 15 
sheet 
chlorine 
steam 
no 
1000 
858 760 501 719 88.6 
69.7 
Example 16 
sheet 
chlorine 
steam 
no 
1200 
635 559 375 532 88.0 
70.5 
Example 17 
sheet 
chlorine 
steam 
yes 
1000 
862 782 528 741 90.7 
71.3 
Example 18 
sheet 
chlorine 
hydrogen 
yes 
1000 
862 781 530 740 90.6 
71.6 
Example 19 
sheet 
chlorine 
steam 
yes 
800 
872 698 373 625 80.0 
59.7 
Example 20 
sheet 
chlorine 
methane 
yes 
1000 
863 784 531 744 90.8 
71.4 
Example 21 
sheet 
chlorine 
steam 
yes 
1200 
640 580 393 553 90.6 
71.1 
Example 22 
sheet 
bromine 
steam 
no 
1000 
865 766 509 725 88.6 
70.2 
Example 23 
sheet 
bromine 
steam 
yes 
800 
869 695 371 622 80.0 
59.6 
Example 24 
sheet 
bromine 
steam 
yes 
1000 
869 790 539 751 90.9 
71.8 
Example 25 
sheet 
chlorine 
steam 
no 
800 
854 679 360 628 79.5 
57.3 
Example 26 
sheet 
chlorine 
steam 
no 
1000 
841 751 501 715 89.3 
70.1 
Example 27 
sheet 
chlorine 
steam 
no 
1200 
631 564 374 534 89.4 
70.0 
Example 28 
sheet 
bromine 
steam 
no 
1000 
845 756 508 720 89.5 
70.6 
__________________________________________________________________________ 
Numbers in the Table 
[1] The Number of the Comparative Example or Example 
[2] Condition of the Carbonaceous Material 
[3] Type of Halogenation Treatment 
[4] Atmosphere of the Low Temperature Dehalogenation 
[5] Carbonization Treatment (Yes/No) 
[6] Temperature of the Heating in Nitrogen Gas Current .degree. C. 
Table 6 shows the factor by which the performance improved for the Examples 
(molded articles) with regard to the Comparative Examples (molded 
articles) which were not chlorination treated. 
When comparing situations having the same heat treatment temperature, each 
of the total discharge-capacity, the effective discharge capacity, the 
total discharge efficiency and the effective discharge ratio were better 
for Examples 19.about.21, in which dry-distilled charcoal was made into 
molded articles after the chlorination treatment, than for the Comparative 
Examples 8.about.10, in which dry-distilled charcoal was made into molded 
articles without conducting a chlorination treatment. Total discharge 
capacity was greatest at a factor of 1.22 (a 22% increase), the effective 
discharge capacity was greatest at a factor of 1.46 (a 46% increase), the 
total discharge efficiency was greatest at a factor of 1.09 (a 9% 
increase), and the effective discharge ratio was greatest at a factor of 
1.21 (a 21% increase). 
TABLE 6 
__________________________________________________________________________ 
Temperature of Total 
Effective 
Total 
Effective 
heating in nitrogen Discharge 
Discharge 
Discharge 
Discharge 
gas current Capacity 
Capacity 
Efficiency 
Ratio 
__________________________________________________________________________ 
800.degree. C. 
Example 19/Comparative Example 8 
1.04 1.21 1.03 1.15 
1000.degree. C. 
Example 20/Comparative Example 9 
1.20 1.34 1.09 1.09 
1200.degree. C. 
Example 21/Comparative Example 10 
1.22 1.46 1.05 1.21 
__________________________________________________________________________ 
Table 7 shows the factor by which efficiency improved for the Examples 
(molded articles) with regard to the Comparative Examples (powdered 
product). 
When comparing situations having the same temperature for the heat 
treatment, each of the total discharge capacity, the effective discharge 
capacity, the total discharge efficiency and the effective discharge ratio 
were better for Examples 19.about.21, in which carbon for a battery was 
made into disk shaped molded articles, than for the Comparative Examples 
in which the powder was used as it was. Total discharge capacity was 
greatest at a factor of 1.23 (a 23% increase), the effective discharge 
capacity was greatest at a factor of 1.38 (a 38% increase), the total 
discharge efficiency was greatest at a factor of 1.07 (a 7% increase), and 
the effective discharge ratio was greatest at a factor of 1.11 (a 11% 
increase). 
TABLE 7 
__________________________________________________________________________ 
Temperature of Total 
Effective 
Total 
Effective 
heating in nitrogen Discharge 
Discharge 
Discharge 
Discharge 
gas current Capacity 
Capacity 
Efficiency 
Ratio 
__________________________________________________________________________ 
800.degree. C. 
Example 19/Comparative Example 11 
1.12 1.18 1.00 1.07 
1000.degree. C. 
Example 20/Comparative Example 12 
1.15 1.21 1.03 1.07 
1200.degree. C. 
Example 21/Comparative Example 13 
1.23 1.38 1.07 1.11 
__________________________________________________________________________ 
Table 8 shows the changes in performance when comparing the molded articles 
which were not given a carbonization treatment (Examples 14.about.16) and 
the molded articles which were given a carbonization treatment (Examples 
19.about.21) for situations which had the same heating temperature under a 
nitrogen gas current. 
When the carbonization treatment is omitted, there is some reduction in 
performance for each of the total discharge capacity, the effective 
discharge capacity, the total discharge efficiency, and the effective 
discharge ratio when compared with situations in which a carbonization 
treatment was conducted. However, when compared with the powder product or 
with the molded article which was not given the chlorine treatment, the 
efficiencies improved. 
TABLE 8 
__________________________________________________________________________ 
Temperature of Total 
Effective 
Total 
Effective 
heating in nitrogen Discharge 
Discharge 
Discharge 
Discharge 
gas current Capacity 
Capacity 
Efficiency 
Ratio 
__________________________________________________________________________ 
800.degree. C. 
Example 19/Comparative Example 14 
1.02 1.09 1.02 1.07 
1000.degree. C. 
Example 20/Comparative Example 15 
1.03 1.06 1.02 1.02 
1200.degree. C. 
Example 21/Comparative Example 16 
1.04 1.05 1.03 1.01 
__________________________________________________________________________ 
Data for the Examples according to the third mode and for the Comparative 
Examples are shown in FIG. 16 (total discharge capacity), FIG. 17 
(effective discharge capacity), FIG. 18 (total discharge efficiency), and 
FIG. 19 (effective discharge rate). In addition, since the data of 
Examples 17 and 18 are approximately the same as the data of Example 20, 
the data of Examples 25.about.27 are approximately the same as the data of 
Examples 14 to 16 respectively, and the data of Example 28 is 
approximately the same as the data of Example 22, they have been omitted 
from FIGS. 16.about.19 for the purpose of simplifying the graphs. 
As shown in these figures, when comparing Examples and Comparative Examples 
which have the same temperature for the heat treatment under a nitrogen 
gas current, the Examples show greater values for all of the total 
discharge capacity (B), effective discharge capacity (C), total discharge 
efficiency (K(B/A)), and effective discharge rate (K(C/D)) than those of 
the Comparative Examples. 
Coin shaped lithium secondary batteries like the one shown in FIG. 11 were 
manufactured using carbon manufactured according to Examples 14 to 28. 
The results from examination of the charging and discharging 
characteristics of these lithium secondary batteries by means of the 
above-mentioned charging and discharging tests for batteries confirmed 
performance improvements the same as those obtained for the 
above-mentioned evaluation cell. 
INDUSTRIAL APPLICABILITY 
As explained above, by means of the present invention, it is possible to 
provide a superior carbon for a lithium secondary battery which has high 
total discharge capacity, high effective discharge capacity, high total 
discharge efficiency, and high effective discharge rate when used in a 
carbon electrode of a lithium secondary battery. In addition, by means of 
the present invention, it is possible to provide a superior lithium 
secondary battery which has high total discharge capacity, high effective 
discharge capacity, high total discharge efficiency, and high effective 
discharge rate.