Method and apparatus for treatment of a battery containing alkali metal

A safe and controllable method of treating a secondary battery having at least one component containing alkali metal, comprises the steps of opening the battery casing, and introducing a gas containing at least one of water vapor and alcohol vapor into a closed chamber containing the battery thereby to form alkali metal hydroxide. To control hydrogen concentration, the rate of introduction of water and/or alcohol vapor may be varied. Apparatus for carrying out this method is also described.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
This invention relates to a method of treating a secondary battery having 
at least one component containing alkali metal, e.g. lithium, and to 
apparatus for treatment of such a battery, in order to enable safe 
extraction and recovery of the alkali metal and optionally other 
components. In batteries, alkali metal may be present as the metal or in 
alloy form or as an intercalation compound, and the invention is 
applicable to all these forms. 
2. Description of the Prior Art 
A high energy density battery such as a lithium battery includes an active 
material of its negative electrode in the form of highly reactive alkali 
metal and an electrolytic solution containing LiPF.sub.6 or LiAsF.sub.6 
which are reactive with water to produce HF. The battery typically further 
includes a positive electrode containing metal components capable of being 
regenerated. However, there has been not described any method of 
industrially processing spent batteries such as lithium batteries or any 
apparatus for processing such batteries. 
The demand for high energy density batteries shows a yearly increase, and 
problems arise in terms of effective utilisation of chemical materials 
used in secondary batteries and of environmental pollution caused by 
batteries. For example, lithium and transition metal elements (Mn, Co) 
used in a lithium battery are valuable materials suitable to be 
regenerated. Moreover, a lithium secondary battery capable of being 
charged and discharged has been extensively used as a power supply for 
back-up of a computer or a power supply of small size domestic electric 
equipment, and is expected to be used for power storage or as a future 
power supply for an electric automobile. Accordingly, there must be 
developed a method of processing batteries and a method regenerating 
battery materials for suppressing environmental pollution due to chemical 
materials contained in the spent batteries and for effectively recovering 
such components used in batteries. 
European patent application 94105151.8 (now published as EP-A-618633) and 
pending U.S. patent application Ser. No. 08/220,220 describe a process of 
treating a lithium battery by contacting the lithium in the battery with a 
liquid alcohol, to form an insoluble reaction product, followed by supply 
of liquid water and alcohol to form LiOH. The solution of LiOH in water 
and alcohol can then be withdrawn from the battery. The present invention 
takes a different approach to the problem. 
SUMMARY OF THE INVENTION 
The object of the present invention is to provide a method of treating a 
battery containing an alkali metal component which is excellent in safety 
and efficiency, and enables recovery of chemical materials capable of 
being regenerated, and to provide an apparatus for processing a battery 
accordingly. 
The present inventors have analysed the problem of treating batteries 
containing alkali metal and reached the following conclusions. 
Since a high energy density battery using an alkali metal, such as a 
lithium battery, contains active materials, i.e. reactive alkali metal and 
electrolytic solution which is unstable in contact with water vapor, 
attention should be paid to controlling the atmospheric gas when 
destroying a battery vessel. For example, the negative electrode of a 
lithium battery utilises lithium metal, a lithium alloy, an intercalated 
lithium compound or a carbon compound electrochemically containing 
lithium, any of which reacts strongly with water to generate hydrogen gas. 
Moreover, a nonaqueous electrolytic solution containing a fluorine 
compound such as LiPF.sub.6 reacts with a water content in air, possibly 
to generate a harmful gas such as pentafluorophosphide or hydrogen 
fluoride. Accordingly, to destroy the vessel of a high energy density 
battery using an alkali metal and to expose battery components, the 
humidity of the external gas is desirably controlled. 
To inactivate a high energy density battery with safety, the following 
functions may be performed: the battery casing is opened in a dry 
atmosphere and then reactive battery components and electrolytic solution 
are decomposed in a controlled atmosphere based on an inert gas, nitrogen 
gas or air. Moreover, to suppress the abrupt decomposition of such active 
components of the battery and prevent explosion of an inflammable gas such 
as hydrogen, and to shorten the decomposition time as much as possible, it 
is desirable to use a method of controlling the decomposition rate. In the 
case where the concentration of valuable material contained in the waste 
liquid obtained after processing of the battery is low, there may be 
required an enriching process; accordingly, to improve the regenerating 
efficiency of valuable materials and to shorten the battery processing 
time, it is desirable to fractional-recover the battery processing liquids 
according to the contents of the valuable materials, that is to say to 
recover two or more separate liquids after contact with the battery 
components. 
According to the invention in one aspect, there is provided a method of 
treating a secondary battery comprising at least one component containing 
alkali metal, comprising the step of introducing a gas containing at least 
one of water vapor and alcohol vapor into a closed chamber containing at 
least this component, thereby to form alkali metal hydroxide or alkoxide. 
The chamber or the gas introduced may contain substantially no oxygen gas, 
but atmospheric air may be used as a carrier gas for the water vapor. 
The water content in the introduced gas is preferably in the range 0.5 to 3 
g per litre of gas. The gas temperature is preferably in the range 100 to 
150.degree. C. The alcohol content is preferably in the range 0.5 to 5 g 
per litre of gas. 
When processing a large amount of battery components, an abrupt evolution 
of hydrogen may occur if water is added to alkali metals contained in 
battery. A hydrogen explosion can take place if the hydrogen concentration 
is higher than 4% in air. However, the water decomposition method hardly 
controls the rate of hydrogen evolution, because water has an extremely 
high reactivity to alkali metals. On the other hand, addition of water 
vapor to battery components can solve this problem. Water vapor content in 
a gas is easily controlled, so that the evolution rate of hydrogen can be 
suppressed under the limit which makes hydrogen explosive. 
At the initial stage of the processing of alkali metals included in 
batteries, the water vapor content of the gas may be lower. The alkali 
metal is gradually decomposed into hydrogen and alkali hydroxide. As the 
decomposition rate decreases, the water vapor content is made higher to 
continue the decomposition reaction. After most of the active materials is 
decomposed, then liquid water may be added to complete the decomposition 
processing. 
Instead of water vapor, alcohol vapor such as methanol, ethanol, propanol, 
butanol and the like is the alternative which can be used in processing 
alkali metals included in batteries at the initial stage. The alcohol 
reacts with alkali metals yielding hydrogen and alkali metal alkoxides. As 
solubilities of the alkoxides in alcohols are low, they cover the surface 
of the active materials as the processing advances. Accordingly, water 
vapor or mixture of water vapor and alcohol vapor may be supplied instead 
of the alcohol vapor. Water in the gas can decompose the alkoxide into 
alkali hydroxides and alcohols, which are very soluble into water. After 
most of the active materials is decomposed, liquid water may be added to 
complete the decomposition processing. 
For safety reasons, it is preferred to control the hydrogen concentration. 
Preferably, the method includes controlling the hydrogen gas concentration 
in the chamber to below 4% by volume. The hydrogen concentration may be 
controlled by adjusting at least one of the rate of introduction of water 
or alcohol vapor into the chamber, the temperature in the chamber and the 
temperature of the introduced gas. Suitably, at least one of the water 
concentration in the gas and the temperature of the gas is increased 
during the treatment of the battery. 
The method may include the step of contacting components of the battery 
with an aprotic solvent to remove electrolyte therefrom, before contacting 
the component containing alkali metal with the introduced gas. 
The invention in its method aspect can also provide a method of treating a 
secondary battery comprising at least one component containing alkali 
metal, to extract alkali metal therefrom, comprising the steps of exposing 
the component containing alkali metal to a gas containing at least one of 
water vapor and alcohol vapor so as to form alkali metal hydroxide or 
alkoxide, and separating the alkali metal hydroxide or alkoxide from other 
constituents of the battery. 
The step of separating the alkali metal hydroxide may comprise adding water 
to form a solution thereof and separating the solution from remaining 
solid constituents. 
Yet further, the invention provides a method of converting an alkali metal 
in a secondary battery into alkali metal hydroxide or alkoxide by 
contacting the alkali metal with water, wherein the improvement comprises 
contacting the alkali metal with a gas containing at least one of water 
vapor and alcohol vapor, and controlling the hydrogen concentration by 
control of the supply rate of water vapor. 
The invention also provides a method of converting alkali metal present in 
a secondary battery to alkali metal hydroxide, comprising exposing the 
alkali metal to a gas containing at least one of water vapor and alcohol 
vapor in a closed chamber and extracting hydrogen gas evolved in said 
chamber by reaction of the vapor with the alkali metal, so as to maintain 
a concentration of hydrogen gas in said chamber below a predetermined safe 
concentration thereof. 
Apparatus according to the invention for treatment of a battery comprising 
a component containing an alkali metal, comprises means for opening an 
outer casing of the battery, a closable chamber to receive the battery, 
and means for introducing to said chamber a gas containing at least one of 
water vapor and alcohol vapor. Preferably there are means for separating 
alkali metal hydroxide formed by reaction with said alkali metal from 
solid components of the battery. 
This apparatus may have a hydrogen concentration sensor for sensing 
hydrogen concentration in the chamber and means for adjusting the rate of 
introduction of the water vapor or alcohol vapor in dependence on the 
sensed hydrogen concentration. Further, it may have a temperature sensor 
for sensing temperature in the chamber and means for adjusting the rate of 
introduction of the water vapor or alcohol vapor in dependence on the 
sensed temperature. 
In another aspect, the invention provides apparatus for treatment of a 
battery comprising a component containing an alkali metal, comprising 
means for opening an outer casing of the battery, a closable chamber to 
receive the battery, means for introducing to the chamber a gas containing 
at least one of water vapor and alcohol vapor, a sensor for monitoring the 
reaction with alkali metal in said chamber and means for controlling the 
introduction of said gas in dependence on an output of said sensor. The 
sensor is preferably selected from (a) a pressure sensor for sensing 
pressure in the chamber, (b) a temperature sensor for sensing temperature 
in the chamber and (c) a hydrogen concentration sensor for sensing 
hydrogen concentration in the chamber. 
In yet another aspect, the invention provides apparatus for treatment of a 
battery comprising a component containing an alkali metal, said apparatus 
comprising a closable chamber having a plurality of intercommunicating 
compartments comprising at least (a) a first compartment provided with 
means for opening an outer casing of said battery, and (b) a second 
compartment having means for introducing thereto a gas containing water 
vapor for reaction with said alkali metal. 
The apparatus may include means for agitating, e.g. vibrating, the battery 
components during the treatment or means for stirring the battery 
components. 
Further preferred and optional features of the invention and methods and 
apparatus of carrying it out will now be described generally. 
To efficiently and safely decompose and recover active materials such as a 
battery active material and electrolytic solution contained in a high 
energy density battery, the battery is processed while controlling the 
decomposition rate of the target materials. The method of processing a 
battery according to the present invention has an advantage in that the 
decomposition rate of an active material of the negative electrode can be 
controlled by use of a processing gas containing the vapor of a material 
reactive with the active material, and further by adjusting at least one 
of the supply rate, concentration and temperature of the processing gas. 
As for the electrolytic solution, it may be separately recovered using a 
suitable cleaning liquid. 
The battery processing apparatus of the present invention typically 
includes a processing chamber for processing an active material of a 
battery in a controlled atmosphere, which may be based on a dry inert gas, 
nitrogen gas or air. It is desirable to prevent the entrapment of an 
external water content in the processing chamber when a battery is moved 
between the processing chamber and the outside of the apparatus. For this 
purpose, there is proposed a method of using an inlet chamber (lock 
chamber) capable of replacing the gas atmosphere from the atmospheric air 
with the dry gas by means of a vacuum pump. In this method, a port of the 
preparing chamber is first opened to move the battery into the inlet 
chamber; the port is closed to allow evacuation of the atmospheric air in 
the preparing chamber; dry atmospheric gas is introduced into the inlet 
chamber; and a port separating the inlet chamber from the processing 
chamber is opened to allow the battery to move into the processing 
chamber. In this method, since the processing chamber is not opened to the 
atmospheric air, the dry state in the processing chamber is maintained. 
Moreover, to improve the operability of the battery processing apparatus, 
to reduce the operational cost, and to shorten the battery processing 
time, there may be provided an inlet chamber having an air curtain 
mechanism of a dry gas at the entry port of the processing chamber, 
thereby maintaining the dry state of the interior of the processing 
chamber in a more simple manner as compared with the above-described gas 
replacement system. 
Next, there will be described one preferred process of inactivating a high 
energy density battery containing an alkali metal. First, a battery is 
completely discharged outside the apparatus of the present invention. A 
suitable method of discharging the battery is by short-circuiting the 
terminals of the battery by way of a resistor or by dipping the battery in 
a solution containing sodium chloride or a dilute acid. In the latter 
method, the battery discharge is accompanied by corrosion of the battery 
casing so that a large number of small size batteries, of the AA size for 
example, may be treated together at one time. After being discharged in 
this way, the battery is carried into the processing chamber by way of the 
inlet chamber. A drive type transporting device such as a belt conveyor 
may be provided between the inlet chamber and the processing chamber for 
easy movement of the battery therebetween. The inlet chamber has a gas 
supply system and a gas exhaust system for communicating the dry 
atmospheric gas to the inlet chamber even when it uses either an air 
curtain system or gas replacement system. Moreover, to exhaust a 
combustible gas such as hydrogen gas generated in the inactivation of the 
battery or a harmful gas such as PF.sub.5 from the processing chamber, the 
processing chamber has a gas supply system and gas exhaust system. While 
the humidity in the processing chamber is controlled, the battery 
components are exposed using a battery crusher, such as a hammer crusher, 
having a function of crushing the battery together with the casing, or a 
battery disjointing device, such as a grinder or a diamond cutter, having 
a function of cutting the casing of the battery and taking out the battery 
components. The processing chamber is connected to a supply system and 
exhaust system of a processing gas and liquid. 
After the battery components are exposed inside or outside the battery 
casing, the electrolytic solution contained in the battery vessel, 
electrodes, separator and the like is removed using a cleaning liquid. As 
the cleaning liquid, there may be used an aprotic organic solvent such as 
propylene carbonate, 1,2-dimethoxyethane, diethoxyethane or the like. By 
distilling the waste cleaning liquid, the electrolyte can be recovered. 
Next, nitrogen gas, other inert gas (e.g. Ar or He) or air containing 
water or alcohol vapor in dilute form is introduced into the processing 
chamber, to gradually decompose the active material of the negative 
electrode. 
The water content in the introduced gas is preferably in the range 0.5-2 g 
per litre, and the preferred temperature of the gas is in the range 
100-150.degree. C. Relative humidity of the gas may be 80-100%. 
Alternatively, vapor of an alcohol such as methanol, ethanol, propanol and 
butanol is present in the gas. Preferable alcohol content in the 
processing gas is 0.5-5 g per litre. A mixture of water vapor and alcohol 
vapor (e.g. in the amounts given above), which is more reactive to alkali 
metal than the respective alcohol, is also useful in decomposition to 
alkali metals. The processing is performed by injecting the processing gas 
to the component. The processing gas may be introduced from the liquid 
supply system connected to the processing chamber. At the initial stage, 
the processing gas decomposes the negative electrode, and it may become 
less reactive to the electrode in the progress of the processing. In this 
case, liquid water or a liquid mixture of water and alcohol is sprayed or 
dropped onto the negative electrode. These liquids are introduced from the 
supply system of the processing gas, if the vapor generator is switched 
off. The spent processing gas is exhausted from the processing chamber by 
way of the liquid exhaust system. 
The concentration of hydrogen gas generated during the processing of the 
negative electrode desirably should for safety reasons be less than the 
explosion limit, preferably 4% or less. The hydrogen gas accumulating in 
the processing chamber is readily exhausted from the processing chamber 
together with the inert gas, nitrogen gas or air introduced into the 
processing chamber. A gas separator is mounted in the gas exhaust system 
for recovering hydrogen gas. 
For execution of the above described process, there may be used apparatus 
having a processing chamber and including: a processing gas supply system 
having storage vessels storing a plurality of processing materials, supply 
ports for processing gas, and a waste liquid exhaust system having exhaust 
ports for the spent processing liquids and waste liquid storage vessels. 
For processing the negative electrode using water vapor, a humidifying 
device having a function for controlling the water vapor concentration is 
mounted in the processing gas supply system. Gas flow rate control means 
are provided. A plurality of gas supply ports may be provided in the 
processing chamber; or supply ports for introducing different processing 
gases to a plurality of processing chambers may be provided in a plurality 
of the processing chambers, to process the batteries using processing 
gases which are different in reactivity in a stepwise manner from each 
other. The gas supply means may apply liquids, when the gas supply is 
stopped. 
The automation of the operation of the above-described battery processing 
apparatus is desirable to improve the efficiency and safety of the 
processing of the battery. To automate the apparatus, there are provided 
for example a flow rate controller for controlling the supply amount and 
exhaust amount of processing gas; a sensor for measuring the pressure, 
temperature and hydrogen concentration in the processing chamber; and an 
arithmetic and control unit for controlling the flow rate controller of 
the processing gas according to the state of the processing chamber 
monitored by the sensor. The flow rate controllers may be provided in the 
supply pipe and exhaust pipe connected to the inlet chamber and the 
processing chamber. The sensor is provided in the processing chamber, and 
may include a temperature sensor, infrared ray sensor or hydrogen sensor. 
The measured data such as the temperature and the hydrogen concentration 
in the processing chamber are transmitted from the sensor to the 
arithmetic control unit. The arithmetic and control unit operates the flow 
rate controllers and vapor generators according to the analyzed result of 
the measured data for adjusting the supply amount and exhaust amount of 
the processing gas or liquid, and the temperature of the gas and the vapor 
content, as desired. When an abnormal decomposition rate occurs midway in 
the processing of the battery, the introduction of the processing gas may 
instantly be stopped or a large amount of an inactive liquid may be added 
to the active material being decomposed, to suppress the decomposition. 
Moreover, it is possible to easily exhaust the combustible gas such as 
hydrogen which may be excessively generated, through the exhaust system. 
By incorporating such a controlling system in the apparatus, the operation 
of the battery processing apparatus can be automated, thus improving the 
efficiency and safety of the decomposition process of the battery. 
Various materials can be recovered from the solutions produced by the 
methods of the invention. Alkali metal can be extracted from the hydroxide 
by distilling to obtain oxide, followed by electrolysis. Electrolyte may 
be recovered by vacuum distillation. Other metals such as Co, Ni, Fe and 
Al can be recovered from the battery components also, by processes such as 
incineration, reduction and electrolysis. 
The cost required to recover valuable materials from the waste liquid in 
processing of the battery is dependent on the concentration of the target 
material contained in the waste processing liquid exhausted from the 
battery processing apparatus. For recovering the target material from the 
waste liquid having a low concentration, a process of enriching the waste 
liquid by extraction or distillation is required, which increases the 
recovery cost. In the present invention, it becomes possible to 
fractional-recover the waste processing liquid exhausted from the battery 
processing chamber, to enrich only the processing liquid low in the 
concentration of the valuable material, and to recover the valuable 
material from all the waste processing liquid. Materials which may be 
recovered are alkali metals and transition metals such as Fe, Ni, Mn, Co. 
Alkali metal may be obtained by extraction and electrolysis, while 
transition metals may be obtained by various metallurgical processes such 
as incineration, reduction and electrolysis. The battery processing 
apparatus of the present invention makes it possible to fractional-recover 
the waste processing liquids of valuable materials having different 
concentrations, and to reduce the cost in regenerating the valuable 
materials. 
In the case of using water vapor as a reactive material for decomposing the 
negative electrode, a carrier gas such as an inert gas, nitrogen or air 
mixed with water vapor is contacted with the negative electrode, to 
decompose the active material of the negative electrode. When using water 
and alcohol vapors, the contents in the carrier gas may be controlled by 
varying the mixing ratio of alcohol and water. At the initial stage of 
decomposition, the concentration of water and/or alcohol vapor is kept low 
to reduce the reactivity of the processing, thus suppressing the abrupt 
decomposition of the active material of the negative electrode. As the 
decomposition proceeds, decomposition products such as alkoxides become 
deposited on the surface of the component. By increasing the water and/or 
alcohol vapor concentration as the decomposition rate of the negative 
electrode is lowered, the reactivity of the gas is increased and 
decomposition of the negative electrode is continued. Finally, liquid 
water may be directly contacted with the negative electrode, thus 
completing the decomposition and solution of the alkali metal as 
hydroxide. This method is effective to reduce the cost of the processing 
liquid and to reduce the environment load due to the waste processing 
liquid. 
The processing gas may initially contain an alcohol, or the alcohol may be 
included after an initial period when water vapor only is present in the 
processing gas. The water vapor reacts to generate alkali metal hydroxide. 
If a solution is produced in the chamber, it may be removed as it is, or 
water may be added, when the reactivity of the battery residue is much 
reduced, to form a solution to be withdrawn.

DESCRIPTION OF THE PREFERRED EMBODIMENTS 
In the several drawings, the same reference numerals identify the same or 
corresponding elements. 
FIG. 1 shows a battery processing apparatus of the present invention, which 
includes a processing chamber 1 and inlet and outlet chambers 2a and 2b 
respectively connected to opposite sides of the processing chamber 1. The 
processing chamber 1 and each of the chambers 2a and 2b have outer sizes 
of 1 m.times.1 m.times.2.5 m and 0.5 m.times.0.5 m.times.1 m, 
respectively. Ports 3a and 3b, each having an opening/closing plate, are 
respectively mounted at the outer side of the chambers 2a and 2b for 
maintaining the air-tightness of the chambers 2a and 2b. Ports 4a and 4b, 
each having an opening/closing plate, are provided between the chambers 2a 
and 2b and the processing chamber 1. A belt conveyor indicated at 5 is 
provided within this apparatus for transporting a battery, battery 
components and the like. Three sets of gas supply systems including a gas 
supply device 6 for drying and supplying an atmospheric gas, gas supply 
pipes 7a, 7b and 7c, and valves 8a, 8b and 8c are connected to the 
processing chamber 1 and the inlet and outlet chambers 2a and 2b. In this 
embodiment, as the atmospheric gas, nitrogen gas is used. 
To recover the hydrogen gas generated in the processing chamber 1 during 
the processing of a battery, the gas in the processing chamber 1 is 
transported to a gas separator 9 by way of a gas exhaust pipe 10 having a 
valve 8d. The hydrogen is separated from the gas at the gas separator 9, 
and is recovered in a gas storage vessel 14 connected to a transporting 
pipe 13 having a valve 8f. To store hydrogen gas, a hydrogen storage alloy 
such as LaNi.sub.5 is present in the gas storage vessel 14. The nitrogen 
gas remaining in the gas separator 9 is transported to the gas supply 
device 6 by way of a transporting pipe 11 having a gas transporting pump 
12 and a valve 8e. Upon decomposition of a negative electrode, nitrogen is 
circulated by opening the valves 8b, 8d and 8e and continuously driving 
the pump 12. 
The apparatus has means 21b for supplying humidified air via a flow rate 
control valve 22b, an optional liquid pump 23b through a pipe 25b and via 
a heater 29 to an injector 24b in the processing chamber. The water vapor 
content of the air can be adjusted. This arrangement is also capable of 
supplying liquid water. Alternatively, separate means for supplying 
humidified gas and liquid water respectively may be provided. 
EXAMPLE 1 
In this example, five 3 Wh lithium secondary batteries are processed, each 
of which includes a positive electrode made of LiCoO.sub.2, a negative 
electrode made of a lithium-lead alloy, and an electrolyte made of an 
organic electrolytic solution containing LiPF.sub.6. The battery has a 
cylindrical shape having a diameter of 18 mm .o slashed. and a length of 
65 mm. First, outside the battery processing apparatus shown in FIG. 1, 
each battery was short-circuited by way of a resistor of 10.OMEGA. to be 
perfectly discharged. The port 3a was opened, and each battery 15 was 
placed on the belt conveyor 5 in the inlet chamber 2a, after which the 
port 3a was closed. The valve 8a was then closed and a valve 17a mounted 
in a gas exhaust pipe 16a was opened. 
After that, an exhaust pump 18a was operated, to evacuate air present in 
the inlet chamber 2a. After the inlet chamber 2a was evacuated, the valve 
17a was closed and the pump 18a was stopped. Next, dry nitrogen gas was 
supplied to the inlet chamber 2a by way of the gas supply pipe 7a. The 
port 4a was then opened, and the batteries 15 were moved to the processing 
chamber 1, after which the port 4a was closed. 
The casing of the batteries was crushed in the processing chamber 1 by 
means of a battery crusher 19 including a hammer crusher and a cutter 
mixer. The crushed pieces were stored in a polypropylene vessel 20 having 
its bottom surface provided with a polypropylene fibre mesh material as a 
filter. The time required for crushing was 20 min. 
In this example, 1,2-dimethoxyethane is used for cleaning the electrolytic 
solution adhering to the battery crushed pieces. A liquid storage vessel 
21a, in which 1,2-dimethoxyethane is stored, is connected to the 
processing chamber 1 by means of a pipe 25a including a valve 22a, a 
liquid transporting pump 23a and a sprayer 24a. 1,2-dimethoxyethane in an 
amount of 1 litre was sprayed onto the battery crushed pieces stored in 
the vessel 20 at a rate of 100 ml/min, to clean the electrolytic solution 
from the battery pieces. The bottom surface of the processing chamber 1 
was formed in a conical shape at two portions for collecting the cleaning 
liquid supplied from the sprayer 24a. The collected cleaning liquid was 
stored in a waste liquid storage vessel 28a by way of a processing liquid 
exhaust pipe 27a having a valve 26a. 
Next, the belt conveyor 5 was driven, and the vessel 20 was carried to a 
portion under the injector 24b. 
A telescopic joint capable of adjusting height was mounted on the liquid 
supply pipe 25b and the injector 24b was attached at the leading end 
thereof. The injector 24b was moved to be close to the vessel 20 
containing the crushed battery pieces, and it injected air at 100.degree. 
C. containing water vapor with a humidity of 90% to the crushed pieces at 
a rate of 1000 ml/min. Water bubbles were gradually generated from the 
crushed pieces, to thus decompose the active material of the negative 
electrode. 
After an elapse of 25 min, the heater 29 heated the humidified air to 
150.degree. C. The humidified air was then further injected onto the 
crushed pieces for 30 min at the same rate. Next, the supply of the 
humidified air from means 21b was stopped, and only water was supplied 
from the means 21b, so that water was added to the battery crushed pieces 
by the pump 23b at a rate of 100 ml/min. The waste water was stored in the 
waste liquid storage vessel 28b by way of the pipe 27b. After an elapse of 
about 15 min, the desired decomposition of the crushed pieces was 
completely finished, and the battery crushed pieces were then taken from 
the preparing chamber 2b as described below. 
The hydrogen gas generated during treatment of the batteries was exhausted 
to the gas separator 9 by way of the gas exhaust pipe 10 together with 
air. The hydrogen gas recovered by the gas separator 9 was stored in the 
storage vessel 14 including LaNi.sub.5 alloy by way of the pipe 13 having 
the valve 8f which was opened, and was stored in the storage vessel 14 
including LaNi.sub.5 alloy. The gas remaining in the gas separator 9 was 
returned to the gas supply device 6 by way of the pipe 11. 
To remove the residue of the batteries, the atmospheric air in the chamber 
2b was exhausted by a gas exhaust system including a valve 17b, a pump 18b 
and a gas exhaust pipe 16b. The valve 17b was then closed, after which the 
valve 8c was opened and dry nitrogen was introduced into the outlet 
chamber 2b by way of the gas supply pipe 7c. After the chamber 2b was 
filled with dry nitrogen, the plate of the port 4b was opened, and the 
vessel 20 was moved into the outlet chamber 2b. The plate of the port 4b 
was closed and the plate of the port 3b was then opened, and thus the 
vessel 20 containing the crushed pieces was taken from the chamber 2b. 
The waste water stored in the waste liquid storage vessel 28b was distilled 
and the lithium metal was recovered by electrolytic refining. Lithium was 
recovered from the crushed residue by extraction and electrolysis. The 
recovered ratio of lithium was 95% based on the total amount of lithium 
contained in five cylindrical lithium secondary batteries. 
From the 1,2-dimethoxyethane solution of LiPF.sub.6 stored in the waste 
liquid storage vessel 28a, LiPF.sub.6 was recovered by vacuum 
distillation. 
EXAMPLE 2 
50 cylindrical lithium secondary batteries each having the same 
specification as those processed in the Example 1, were previously 
discharged in a salt water containing sodium chloride or the like and 
processed in the battery processing apparatus shown in FIG. 1. First, each 
lithium battery was dipped for two days in a salt water containing sodium 
chloride in an amount of 50 g per 2 l of water. By this, part of the 
battery vessel was corroded. Each battery was carried into the processing 
chamber 1 by the same procedure as in Example 1, and was crushed using the 
battery crusher 19 having the hammer crusher and the cutter mixer. The 
crushed pieces were then stored in the polypropylene vessel 20 having the 
bottom surface provided with the mesh. The time required for crushing the 
batteries was 20-23 min. The batteries in the number being 10 times that 
of the batteries in the Example 1 were crushed for about the same time. As 
in this embodiment, by corroding the vessel of the batteries in a solution 
containing a salt such as sodium chloride or potassium chloride or a 
diluted hydrochloric acid, the time required for crushing of batteries 
could be shortened even when the number of the batteries was increased. 
1,2-dimethoxyethane stored in the liquid storage vessel 21a was added to 
the battery crushed pieces for 20 min at a rate of 100 ml/min, to clean 
the electrolytic solution stuck on the crushed pieces. The waste cleaning 
liquid was stored in the waste liquid storage vessel 28a. Subsequently, 
water stored in the liquid storage vessel 21b was heated at the heater 29 
to produce an air-water vapor mixture gas containing 0.5 g water per 1 l 
at 100.degree. C. The gas was injected onto the crushed pieces of the 
batteries at a rate of 1 l/min for 40 min. During decomposition of 
lithium-lead alloy particules in the crushed materials, the hydrogen 
concentration in the processing chamber was kept below 0.5% or less. No 
evolution of hydrogen from the crushed pieces was observed after supplying 
the gas for an elapse of 60 min. Finally 1 l of liquid was added to the 
crushed pieces to terminate decomposition of the lithium alloy. In this 
example, the total time required for processing fifty 3 Wh lithium 
secondary batteries 15 was about 1.8-2.0 hr. The volume of aqueous liquid 
containing lithium ions recovered in the waste liquid storage vessel 28b 
was 0.8-0.9 l. By electrolytic refining, 20% of lithium metal contained in 
the original lithium batteries was recovered. From the residue obtained 
from the vessel 20, lithium cobalt, iron, and aluminium was re-generated 
by incineration and reduction or electrolysis. Nearly 85% of the total 
amount of lithium metal in the lithium batteries was recovered. The 
regenerated amounts of cobalt, iron and aluminium were 75.about.80% of the 
amounts initially contained in the batteries. From the 1,2-dimethoxyethane 
solution of LiPF.sub.6 remaining in the waste liquid storage vessel 28a, 
93% of LiPF.sub.6 was recovered by vacuum distillation. 
EXAMPLE 3 
Using five pieces of the lithium batteries having the same specification as 
those in the Example 1, an experiment was made to shorten the time 
required for processing the batteries. 1,2-dimethoxyethane was used as a 
cleaning liquid for recovering an electrolytic solution of the batteries. 
Each battery was crushed using the battery crusher 19 having the hammer 
crusher and the cutter mixer in the same procedure as in the Example 1. 
The crushed pieces were stored in the polypropylene vessel 20 with a 
polypropylene filter. 1,2-dimethoxyethane in an amount of 1 l was added to 
the crushed battery components at a rate 100 ml/min from the sprayer 24a. 
The waste cleaning liquid was stored in the waste liquid storage vessel 
28a. The vessel 20 containing the battery crushed pieces was placed 
directly under the injector 24b. First, in such a state that the heater 29 
was operated, gas at 150.degree. C. was injected onto the battery crushed 
pieces at a rate of 1 l/min from the injector 24b using nitrogen gas 
carrier. Water content was 1 g per litre. The time required for supplying 
the processing gas was 30-35 min. The hydrogen concentration in the 
processing chamber 1 during the processing of the negative electrode was 
1% or less, and accordingly the negative electrode could be safely 
decomposed without the fear of explosion of hydrogen. Water in liquid form 
was added to complete the decomposition. The waste liquid stored in the 
waste liquid storage vessel 28a was distilled in vacuum, and thereby 95% 
of the total LiPF.sub.6 contained in the batteries was recovered. The 
waste liquid stored in the waste liquid storage vessel 28b was subjected 
to electrolytic refining, to recover 25% of the total lithium metal 
contained in the batteries. From the residue obtained from the vessel 20, 
lithium, cobalt, iron, and aluminium was regenerated by incineration and 
reduction or electrolysis. Nearly 83% of the total amount of lithium metal 
in the lithium batteries was recovered. The regenerated amounts of cobalt, 
iron and aluminium were 75.about.80% of the amounts initially contained in 
the batteries. 
EXAMPLE 4 
The battery processing time may be shortened by agitating crushed battery 
components during supply of the gas. Five pieces of the lithium secondary 
batteries having the same specification as those in Example 1 were 
processed. Each lithium battery was discharged through a resistor of 10 
.OMEGA. and was crushed using the battery crusher 19 having the hammer 
crusher and the cutter mixer in the processing chamber 1. The crushed 
pieces were put in the polypropylene (PP) vessel 20 with the PP filter. 
They were cleaned with 1,2-dimethoxyethane supplied from the liquid 
storage vessel 21a. The processing gas contains water vapor at 0.5 g/l at 
100.degree. C. It was supplied from the nozzle 24b to the crushed pieces 
of batteries in the PP vessel 20. The flow rate of processing gas was 1 
l/min. Next, a rotary mixer was inserted in the vessel 20 containing the 
battery crushed pieces, and the pieces were agitated. After the generation 
of hydrogen was no longer observed from the crushed pieces, the liquid 
product was discharged from the vessel 20 to the waste liquid storage 
vessel 28b by way of the liquid exhaust pipe 27b. Finally, 1 l of water at 
25.degree. C. was added to the crushed pieces from the nozzle 24b, after 
the steam generator 29 was switched off. The decomposition time by the gas 
was 18-20 min, and the total battery processing time was 1.3-1.4 hr. The 
battery processing time was shortened compared with Example 1 by the 
agitation of the crushed component. The waste liquid stored in the waste 
storage vessel 28a was distilled in vacuum, so that 95% of the total 
LiPF.sub.6 contained in the batteries was recovered. The waste processing 
liquid stored in the waste liquid storage vessel 28b and the residue of 
the crushed battery pieces was subjected to electrolytic refining, to 
recover 80% of the total lithium metal contained in the batteries. 
In FIG. 1 a hydrogen sensor 30 having a function of detecting the hydrogen 
concentration in the processing chamber 1 is provided in the processing 
chamber 1. The hydrogen sensor 30 was connected to an arithmetic and 
control unit 32 though a signal input cable 31. The arithmetic and control 
unit 32 is connected to the flow rate adjuster 22b and the liquid supply 
pump 23b by means of signal input cables 33a and 33b, respectively. The 
hydrogen sensor 30 measures the hydrogen concentration in the processing 
chamber 1, and transmits an electric signal proportional to the measured 
value to the arithmetic and control unit 32. The arithmetic and control 
unit 32 calculates the electric signal supplied from the hydrogen sensor 
30, and transmits the electric signal corresponding to the processing 
result to the flow rate adjuster 22b or the liquid supply pump 23b for 
controlling their operation. In this embodiment, the allowable value of 
hydrogen concentration and the total supply amount of the processing gas 
are previously stored in a memory unit of the arithmetic and control unit 
32, and the calculating condition of the arithmetic and control unit 32 
may for example be in accordance with the following items (1) to (5) 
singly or in combination. 
(1) When the hydrogen concentration in the processing chamber 1 is smaller 
than the allowable value, the arithmetic and control unit 32 controls the 
flow rate adjuster 22b for increasing the supply rate of the processing 
gas. In this embodiment, the permitted hydrogen concentration in dry gas 
is within the range from 0 to 4%. 
(2) When the average hydrogen concentration in the processing chamber 1 is 
less than 0.01% for a selected period, e.g. in the range 1 to 5 minutes, 
the supply of processing gas or liquid is stopped. 
(3) When an electric signal transmitted from the hydrogen sensor 30 to the 
arithmetic and control unit 32 is abruptly increased to more than a 
hydrogen concentration allowable value, the flow rate adjuster 22b and 
pump 23b are closed by way of the signal input cables 33a and 33b, to stop 
the processing supply. The hydrogen concentration allowable value in this 
case may be set at 10%. 
(4) The arithmetic and control unit 32 accumulates the supply amount of the 
water and the accumulated value is stored in the memory unit of the 
arithmetic and control unit 32. 
(5) When the accumulated value in (4) reaches the upper limit of the total 
supply amount of the processing water stored in the memory unit of the 
arithmetic and control unit 32, the flow rate adjuster 22b and pump 23b 
are closed. 
EXAMPLE 5 
The apparatus shown in FIG. 1 was operated under the control conditions 
described above. Five lithium batteries 15 of the same specification as 
those in Example 1 were crushed in the battery crusher 19 and the 
electrolyte was cleaned off as in Example 1. Then the active materials of 
the negative electrodes were decomposed with the water vapor containing 
gas. The gas contained water of 0.5 g/l at 100.degree. C., and the carrier 
gas was nitrogen. It was supplied from the nozzle 24b to the crushed 
pieces of the batteries. The processing time was 25 min. After this 
treatment, water (1 l) was added to the pieces from nozzle 24b. The water 
amount supplied from the liquid storage vessel 21b was 41. The total time 
required for putting the batteries in the processing apparatus and taking 
the battery crushed pieces from the processing apparatus was 1.4-1.5 hr. 
The waste cleaning liquid stored in the waste liquid storage vessel 28a 
was distilled in vacuum, so that 95% of the total LiPF.sub.6 of the 
batteries was recovered. The water processing liquid stored in the waste 
liquid storage vessel 28b was subjected to electrolytic refining, and 23% 
of the total lithium metal of the batteries could be recovered. 
Metallurgical methods such as extraction and reduction recovered 60% 
lithium from the crushed pieces. In this embodiment, as compared with 
Example 1, it becomes possible to shorten the battery processing time, and 
to automate the battery processing allowing unmanned operation. 
In a variation of the embodiment of FIG. 1, to shorten the battery 
processing time, the preparing chambers 2a and 2b each have an air curtain 
mechanism. The ports 3a, 3b, 4a and 4b include sliding type 
opening/closing plates. In this apparatus, the gas storage vessel 6 was 
replaced by a supply device 6 for usually supplying dry air to the 
processing chamber 1 and the preparing chambers 2a and 2b. Moreover, the 
gas exhaust pumps 18a and 18b were not required. When the port 3a was 
opened, dry air was supplied from the dry air supply device 6 to the 
preparing chamber 2a. The dry air was discharged to the exterior of the 
apparatus through the gas exhaust pipe 16a by opening of the valve 17a. 
With this air curtain mechanism, humidified air outside the apparatus was 
not permitted to enter the processing chamber 1. Even when the processed 
battery components were taken from the preparing chamber 2b, dry air was 
supplied from the dry air supply device 6 to the preparing chamber 2b, and 
was communicated to the gas exhaust pipe 16b by opening of the valve 17b. 
EXAMPLE 6 
Five lithium batteries of the same specification as in Example 1 were 
processed in the modified apparatus just described, by the procedure of 
Example 3. The time required for the processing of the negative electrode 
by gas containing water vapor was 25-30 min as in Example 3, and the time 
required for crushing of the batteries was the same as in the Example 3. 
The hydrogen concentration in the processing chamber 1 during reaction 
between ethanol and the battery crushed pieces was maintained at 1% or 
less. In this embodiment, the gas replacement in the inlet and outlet 
chambers 2a and 2b was eliminated, thus shortening the total processing 
time to be 1 hr. 
FIG. 2 is a battery processing apparatus in which two sets of processing 
fluid supply systems and liquid exhaust systems are independently 
provided. A partitioning plate 34 is provided in the upper portion of the 
processing chamber 1 to provide two working areas and sprayers 24a and 24b 
are provided in the upper portion of the processing chamber 1. 
Diethoxyethane for cleaning electrolytic solution is stored in a liquid 
storage vessel 21a, and is introduced from the sprayer 24a to the first 
compartment of the processing chamber 1 by way of a liquid transporting 
pipe 25a having a valve 22a and a pump 23a. Ethanol and water are stored 
in vessels 21b and 21c and are supplied with a carrier gas (dry air) for 
decomposing a negative electrode from the injector 24b to the second 
compartment of the processing chamber 1 by way of pipe system 25b having 
valves 22b and 22c and pump 23b and 23c. The supply means 21b can also 
supply water vapor only in air, if required. For example a mixture of 50% 
ethanol and 50% water by weight is supplied. The liquid supply means 21b 
and 21c have the capability of generating vapors of the liquids by 
heating. 
To individually recover the cleaning liquids or processing liquids used in 
the partitioned areas, two portions of the bottom surface of the 
processing chamber 1 were formed in a conical shape, and two waste liquid 
exhaust pipes 27a and 27b are connected to the two portions. As another 
method of recovering waste liquids, a partitioning plate is arranged on 
the bottom surface of the processing chamber 1 under the belt conveyor 5, 
so that the waste liquids can be fractional-recovered without any mixing 
of the waste liquids. Valves 26a and 26b control the waste liquid exhaust 
pipes 27a and 27b, respectively. Dry air to be supplied to the processing 
chamber 1 and the inlet/outlet chambers 2a and 2c was introduced to the 
apparatus from a gas supply device 6 having a function of drying air. The 
dry air was continuously supplied from the gas supply device 6 to the 
chambers 2a and 2b of the battery processing apparatus by way of a pipe 
7a, and was exhausted from a gas exhaust pipe 16a by opening of the valve 
17a. 
EXAMPLE 7 
The lithium battery used in this example is a square lithium secondary 
battery including a positive electrode made of LiCoO.sub.2, a negative 
electrode made of carbon electrochemically absorbing and releasing lithium 
ions, and an electrolyte made of organic electrolytic solution in which 
LiPF.sub.6 is dissolved in a mixture of 50 vol % of ethylene carbonate and 
50% vol of 1,2-dimethoxyethane. The battery has a size of 50 mm.times.80 
mm.times.40 mm, and a rating capacity of 30 Wh. In this embodiment, five 
of these batteries were processed. First, each battery 15 was discharged 
using a resistor of 10 .OMEGA. outside the battery processing apparatus 
shown in FIG. 2. The sliding plate 3a of the inlet chamber 2a was opened, 
and each battery 15 was placed in the chamber 2a. The plate 3a was closed 
and the plate 4a was opened, and the batteries 15 was carried into the 
processing chamber 1. A battery disjointing machine 19 having a diamond 
cutter and a cutter mixer was provided in the processing chamber 1. The 
upper portion of each battery vessel was cut using the diamond cutter of 
the battery disjointing machine 19. The upper portion of each battery 15 
was removed, and battery components were taken out from the battery 
vessel. 
The electrolytic solution on a separator, the battery vessel and electrodes 
was cleaned by 1,2-dimethoxyethane supplied from the sprayer 24a. The 
waste cleaning liquid was stored in a waste liquid storage vessel 28a by 
way of a liquid exhaust pipe 27a. The cleaned negative electrode was 
finely cut using the cutter mixer of the battery disjointing machine 19, 
and was stored in the PP vessel 20 having the bottom surface provided with 
a PP filter. The other battery members were placed on a belt conveyor 5 as 
they were. The belt conveyor 5 was driven, and the vessel 20 was moved 
directly under the nozzle 24b. The nozzle 24b provided the air containing 
ethanol and water vapor at 50/50% weight ratio (total 0.5-3.0 g/l) at 3 
l/min to the negative electrode in the vessel 20. The processing time was 
50 min. 
The hydrogen concentration in the processing chamber 1 was 3% or less. 
After an elapse of about 40 min from the start of the processing, hydrogen 
was difficult to be generated as lithium alcoholate (alkoxide) with white 
color was precipitated, and the hydrogen concentration in the processing 
chamber 1 was 0.1% or less. After the supply of the ethanol+water vapor 
was stopped, the flow rate controller 22c was stopped, and only the air 
containing water vapor at 0.5 g/l was added to the negative electrodes 
from the nozzle 24b. The flow rate of air was 3 l/min. This processing 
time was 30 min. Finally, the air flow was switched off, and water (5 l) 
was supplied to the crushed pieces of the batteries. 
The plate 4b was opened, and the vessel 20 and the electrode members were 
carried into the outlet chamber 2b. The plate 4b was closed and the plate 
3b was opened, for removal of all of the processed battery components. The 
total time required for processing of the five batteries was 2.2-2.3 hr. 
The total volumes of the ethanol and water used in the processing of the 
negative electrodes were about 0.5 l and 6 l, respectively. In all of the 
processes of this embodiment, the hydrogen concentration in the processing 
chamber 1 was suppressed to be 3% or less. The waste liquid in the waste 
liquid storage vessel 28a was distilled in vacuum, so that 95% of the 
total LiPF.sub.6 contained in the five batteries could be recovered. The 
waste liquid obtained in the waste liquid storage vessels 28b was 
distilled, so that 30% of the total lithium contained in the batteries was 
recovered by electrolytic refining. From the crushed pieces obtained after 
the deactivation of negative electrodes, lithium was reproduced by 
extraction and reduction. The lithium amount was 55% of the total amount 
of lithium included in the batteries. 
A battery having energy capacity being 10 times that of the lithium 
secondary battery processed in FIG. 1 can be continuously processed using 
the battery processing apparatus shown in FIG. 2. The processing time for 
each battery can be short, and the hydrogen generated upon processing was 
recovered in a produced gas storage vessel 14 containing LaNi.sub.5 alloy, 
thereby ensuring the safety of the process. The waste processing liquids 
from respective processing chambers can be stored in separate tanks. This 
makes it possible to regenerate the electrolyte and lithium by 
fractional-recovering them, to simplify the distillation of the waste 
liquid stored in the waste liquid storage vessel 28b containing lithium 
ions of a high concentration, and to reduce the cost required in the 
process of enriching the waste liquid by the fractional-recovery. 
EXAMPLE 8 
A cylindrical 3 Wh lithium secondary battery including a positive electrode 
made of V.sub.6 O.sub.13, a negative electrode made of Li metal, and a 
solid high molecular electrolyte made of a mixture of polyethylene oxide 
and LiCF.sub.3 SO.sub.3 was processed using the battery processing 
apparatus shown in FIG. 2. In the same procedure as in the Example 6, five 
of the lithium secondary batteries were carried into the processing 
chamber 1, and were crushed using the battery crusher 19 having the hammer 
crusher and cutter mixer. The crushed pieces were put in the PP vessel 20 
having the bottom surface provided with the PP filter. 1,2-dimethoxyethane 
stored in the liquid storage vessel 21a was sprayed from the sprayer 24a 
onto the crushed pieces. The waste cleaning liquid was stored in the waste 
liquid storage vessel 28a by way of the liquid exhaust pipe 27a. The 
vessel 20 was then moved directly under the nozzle 24b by the belt 
conveyor 5, and the nozzle 24b injected the ethanol and water vapor as 
used in Example 6 onto the crushed pieces in the vessel 20. The processing 
time was 20 min. After 15 min the hydrogen generating rate was decreased. 
Then air containing 0.5 g water in 1 l was supplied from the nozzle 24b. 
The unreacted alloy contained in the negative electrode was started to be 
decomposed, and hydrogen was generated. The processing time was 20 min. 
The waste liquid in the waste liquid storage vessel 28a was distilled in 
vacuum, so that 90% of the total LiPF.sub.6 contained in the five 
batteries was recovered. The waste liquid obtained in the waste liquid 
storage vessel 28b was distilled, and 25% of the total lithium contained 
in the batteries was recovered by electrolytic refining. The recovered 
lithium from the crushed battery pieces was 57-60% of the total amount. 
While the invention has been illustrated by several embodiments, it is not 
limited to them, and many variations, modifications and improvements are 
possible, within the scope of the inventive concept.