Carbonaceous insertion compounds and use as anodes in rechargeable batteries

Abstract: Carbonaceous insertion compounds and methods for preparation are described wherein the compounds comprise a pre-graphitic carbonaceous host and atoms of an element capable of alloying with alkali metal atoms, the alloying atoms being incorporated predominantly as monodispersed atoms in the host. A carbonaceous insertion compound with large reversible capacity for lithium can be prepared if the alloying atoms incorporated are Si. Such insertion compounds can be prepared by simple pyrolysis of suitable polymers containing silicon and carbon at an appropriate temperature. These insertion compounds may be suitable for use as high capacity anodes in lithium ion batteries.

Description: FIELD OF THE INVENTION The invention pertains to the field of carbonaceous materials and, in particular, to pre-graphitic carbonaceous insertion materials. Additionally, the invention pertains to the field of rechargeable batteries and, in particular, to rechargeable batteries comprising carbonaceous anode materials. BACKGROUND OF THE INVENTION Within the enormous group consisting of carbonaceous compounds is a set of pre-graphitic compounds that are generally prepared at low temperatures (eg: less than about 2000°C) from various organic sources and that tend to graphitize when annealed at higher temperatures. There are however both hard and soft pre-graphitic carbon compounds, the former being difficult to graphitize substantially even at temperatures of order of 3000°C, and the latter, on the other hand, being virtually completely graphitized around 3000°C. The aforementioned set of compounds has been of great interest lately for use as anode materials in what is called lithium-ion or rocking chair type batteries. These batteries represent the state of the art in small rechargeable power sources for commercial electronics applications. Typically, these batteries have about twice the energy density (Wh/L) of conventional rechargeable systems (such as NiCd or lead acid batteries). Additionally, lithium ion batteries operate around 3½ volts which is often sufficiently high such that a single cell can suffice for many electronics applications. Lithium ion batteries use two different insertion compounds for the active cathode and anode materials. Insertion compounds are those that act as a host solid for the reversible insertion of guest atoms (in this case, lithium atoms). The structure of the insertion compound host is not significantly altered by the insertion. In a lithium ion battery, lithium is extracted from the anode material while lithium is concurrently inserted into the cathode on discharge of the battery. The reverse processes occur on recharge of the battery. Lithium atoms travel or "rock" from one electrode to the other as ions dissolved in a non-aqueous electrolyte with associated electrons travelling in the circuit external to the battery. The two electrode materials for lithium ion batteries are chosen such that the chemical potential of the inserted lithium within each material differs by about 3 to 4 electron volts thus leading to a 3 to 4 volt battery. It is also important to select insertion compounds that reversibly insert lithium over a wide stoichiometry range thus leading to a high capacity battery. A 3.6 V lithium ion battery based on a LiCoO 2 / pre-graphitic carbon electrochemistry is commercially available (produced by Sony Energy Tec.) wherein the carbonaceous anode can reversibly insert about 0.65 Li per six carbon atoms. (The pre-graphitic carbon employed is a disordered form of carbon which appears to be similar to coke.) However, the reversible capacity of lithium ion battery anodes can be increased by using a variety of alternatives mentioned in the literature. For example, the crystal structure of the carbonaceous material affects its ability to reversibly insert lithium (as described in J.R. Dahn et al., "Lithium Batteries, New Materials and New Perspectives", edited by G. Pistoia, Elsevier North-Holland, pl-47, (1993)). Graphite for instance can reversibly incorporate one lithium per six carbon atoms which corresponds electrochemically to 372 mAh/g. This electrochemical capacity per unit weight of material is denoted as the specific capacity for that material. Graphitized carbons and/or graphite itself can be employed under certain conditions (as for example in the presentation by Matsushita, 6th International Lithium Battery Conference, Muenster, Germany, May 13, 1992, or in U.S. Patent No. 5,130,211). Other alternatives for increasing the specific capacity of carbonaceous anode materials have included the addition of other elements to the carbonaceous compound. For example, European Patent Application No. EP486950 and Japanese Application Laid-Open No. 03-245458 mention the addition of small amounts of phosphorous and boron respectively to enhance the anode specific capacity. The mechanism behind this effect is unclear but it may be a result of modifications to the microstructure of the carbonaceous compound. Also, Canadian Application Serial No. 2,098,248 discloses a means for enhancing anode capacity by substituting electron acceptors (such as boron, aluminum, and the like) for carbon atoms in the structure of the carbonaceous compound. Most recently, two groups have prepared carbonaceous materials with very high reversible capacity by pyrolysis of suitable starting materials. K. Sato et al. in Science 264 , 556, (1994) disclosed a carbonaceous material prepared by heating polyparaphenylene at 700°C which has a reversible capacity of 680 mAh/g. At the Seventh International Meeting on Lithium Batteries, Extended Abstracts Page 212, Boston, Mass. (1994), A. Mabuchi et al. disclosed a low density (about 1.5 g/cc) carbonaceous material prepared by heating coal tar pitch at 700°C which has a reversible capacity of about 750 mAh/g. These values are much greater than that of pure graphite. However, both materials have a very large irreversible capacity as evidenced by first discharge capacities of over 1000 mAh/g for the former and about 1200 mAh/g for the latter. Both materials also are crystalline enough to exhibit x-ray patterns from which the parameters d 002 , L c , a, and L a can be determined. Neither material therefore incorporates additional elements (such as electron acceptors) and neither material is amorphous based on x-ray diffraction. It is unknown yet why these carbonaceous materials exhibit such high capacity. Historically, however, metallic lithium was preferred as an anode material during development of rechargeable lithium batteries. Lithium metal has a specific capacity of 3.86 Ah/g, significantly greater than presently known alternatives. There are however numerous problems associated with the use of metallic lithium as an anode, most notably its poor safety record in larger battery sizes (of order of AA size or greater). The use of lithium metal anodes in rechargeable batteries has effectively been limited to very small consumer configurations (such as coin cells) or to military applications and the like. Anode materials other than pure lithium have also been proposed and include a class of lithium alloys such as those listed in the following Table 1. Mixed alloys have also been proposed as illustrated in Y. Toyoguchi et al., Progress in Batteries and Solar Cells, 6 , 58 (1987). As shown in Table 1, lithium alloys can comprise significant amounts of lithium that can be extracted and re-alloyed in principle. However, in practice, there are large volume charges associated with varying the stoichiometry of lithium in these alloys between the limits shown. These volume changes have several effects in a battery application. Firstly, the alloy anode tends to crack and fragment upon repeated alloying/extraction cycles which reduces the anode to "dust". This can result in integrity problems for the anode. Secondly, as a result of said fragmentation, the surface area of the anode increases. Since these materials are close to the chemical potential of lithium, the lithium within the alloy gets continually consumed via reaction with the battery electrolyte in the formation of passivating films on newly exposed anode surface. This reaction is undesirable since it consumes lithium irreversibly, thus resulting in overall capacity loss in a battery. Finally, an increase in surface area of a reactive anode can lead to increased sensitivity to thermal runaway, a major safety concern. LI-ALLOY ANODE MATERIALS FOR SECONDARY LI BATTERIES Material Range of x Specific Capacity mAh/g of alloying element Average Voltage versus Li (V) Reference Li x Sn 0.4-4.5 902 0.5 2 Li x Al 0.0-1.0 992 0.3 3 Li x Si 0.0-4.2 4017 0.2 4 Li x Cd 1.0-3.0 476 0.07 2 Li x Pb 1.0-4.4 440 0.2 4 Li x Bi 0.0-3.0 384 0.8 4 Li x Sb 0.0-3.0 658 0.95 4 Li x C 6 0.0-1.0 372 0.1 1 The use of carbonaceous insertion compounds as anodes has avoided the aforementioned problems with lithium alloy anodes. Since the volume changes associated with lithium insertion are small, little or no fragmentation of the carbonaceous compounds occurs. Thus, anode integrity can be maintained more easily and the anode surface area can be kept from increasing. No significant capacity loss due to further passivation film formation on fresh surfaces need occur and the thermal stability of the battery need not worsen with cycle number. Commercial batteries with carbonaceous insertion compound anodes have achieved over a thousand charge-discharge cycles without significant capacity loss and with an actual slight improvement in safety to abuse (as shown in K. Ozawa et al., The Tenth International Seminar On Primary And Secondary Battery Technology And Application, March 1-4, 1993, Deerfield Beach, Florida). Co-pending EP-A-0 685 896 discloses carbonaceous insertion compounds that comprise a pre-graphitic carbonaceous host, having both organized and disorganized structural regions, and atoms of an element capable of forming alloys with an alkali metal. The alloying atoms are incorporated into the carbonaceous host without substantially affecting the structure of the organized regions, as evidenced by x-ray diffraction measurements. The alloying atoms can be incorporated predominantly as monodispersed atoms in the disorganized regions of the host. (The term 'monodispersed' is intended to include single atoms and/or small clusters of the alloying element such that the resulting compound exhibits properties more characteristic of single atoms of the alloying element than that of a bulk compound of the alloying element.) Certain compounds of this invention are attractive for use as anode materials in lithium ion batteries. When the alloying atoms are silicon for example, the reversible capacity of the compounds of the invention can be increased over that of the carbonaceous host alone while still maintaining cycling performance similar to the carbonaceous host. Thus, it appears that the compounds of the invention can combine to some extent the attractive features of the capacity of the alloying element with the cycling stability of a carbonaceous compound. Example compounds in the aforementioned European patent application were prepared by chemical vapour deposition methods although it was expected that similar results could be obtained by pyrolysis of suitable polymer precursors. Other carbonaceous compounds with high specific capacity have been prepared by such pyrolysis techniques. For example, Sony Energy Tec (in European Patent Publication Number 357,001) has reported preparing a carbonaceous compound containing phosphorus with a specific capacity of about 450 mAh/g by pyrolyzing polyfurfuryl alcohol. The polyfurfuryl alcohol in turn had been prepared from the monomer polymerized in the presence of phosphoric acid. JP-A-6096759, which is considered to constitute the closest prior art, describes a battery using as an electrode active material, a thermally treated material of an organic Si compound having one or more coupling parts of Si having an organic group and O or a one having Li stored therein. An organosiloxane such as Si oil which is a polymer consisting of a main chain in which Si having an organic group and O are alternately bonded to each other is used. This compound is treated at 200-600 deg. C in the open atmosphere or at 300-1000 deg.C in vacuo or an inert atmosphere. The optimum temperature differs depending on starting materials. The thermally treated material or a mixing agent of the thermally treated material with a conductive agent and a binder is moulded to form one electrode, and a current is applied thereto with a Li-contained material as a counter electrode to store Li ions. As an electrolyte, a solution which LiClO 4 is dissolved in gamma-butyrolactone. This electrode can stably store and release Li ions within the range of 0-3V to the metal Li in nonaqueous electrolyte, and is used as the negative electrode and/or positive electrode of a secondary battery. The subject matter of the invention includes methods of preparing carbonaceous insertion compounds, compounds obtained by said methods, and the use of said compounds as electrode materials in electrochemical devices in general. The method of preparing the carbonaceous insertion compounds comprises taking (a) a pre-graphitic carbonaceous host C; (b) atoms of Li inserted into the host C, the amount of Li being in the range from greater than or equal to zero; and (c) atoms of Si incorporated into the host C, wherein the atoms of Si are incorporated as monodispersed atoms in the host C, said process comprising: pyrolysing a polymer selected from poly(silmethylenes); poly(siloxanesilphenylenes) polysilanes, poly(silphenylenes) and polyphenylsesquisiloxanes wherein the pyrolysis is performed at a temperature above the decomposition temperature of the polymer and below the minimum of the temperatures for forming a carbide or oxide of Si from the pyrolysed polymer, so that a carbonaceous insertion compound is obtained having a reversible specific capacity for Li greater than graphite. The monodispersed atoms of Si of the carbonaceous compounds obtainable by this method include single atoms or small clusters of Si such that the resulting compound exhibits properties that are more characteristic of single atoms of Si than that of a bulk compound of Si. The structure of the carbonaceous insertion compound can be predominantly disorganized resulting in an x-ray diffraction pattern of the compound that is very poorly developed or amorphous. Other elements can be present in silicon containing carbonaceous insertion compounds of the invention. Such compounds can be represented by the formula Li x Si y C 1-y O z H n wherein O is oxygen, H is hydrogen, and x,y,z,n are numbers; x being greater than or equal to zero; y being in the range from greater than zero to less than about 0.3; the ratio z/y being greater than or equal to zero and less than or equal to about 1.5; and n being less than about 0.3. The polymer containing silicon and carbon can be polyphenylsesquisiloxane and the pyrolysis temperature in this instance can be above about 500°C and in particular about 1000°C. Other polymers containing silicon and carbon used to prepare silicon containing carbonaceous insertion compounds of the invention are selected from the groups of poly(siloxane-silphenylenes), poly(silmethylenes), polysilanes, or poly(silphenylenes). The silicon containing product of the aforementioned processes may have no Li metal inserted as prepared and Li atoms can be inserted thereafter via chemical or electrochemical means. Electrochemical devices of the invention comprise an electrode wherein a portion of the electrode comprises a carbonaceous insertion compound of the invention. The device can be a battery and, in particular, can be a non-aqueous battery comprising: a cathode comprising a lithium insertion compound; a non-aqueous electrolyte comprising a lithium salt dissolved in a mixture of non-aqueous solvents; and an anode comprising the carbonaceous insertion compound of the invention. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows the chemical structures for potential precursors or groups of precursors for compounds of the invention. The groups R, R', R'', R''' denote alkyl, aryl, or general ligands. The specific ligands methyl and phenyl are denoted Me and Ph respectively where appropriate. Figure 2 shows a cross-sectional view of a conventional lithium ion spiral-wound type battery. Figure 3 depicts an exploded view of the laboratory coin cell battery used in the examples. Figure 4 shows the x-ray diffraction pattern for the material of Comparative Example 1. Peaks from the stainless steel holder are indicated with an H. Peaks from the carbon are indicated by their Miller indices. Figure 5 shows the x-ray diffraction pattern for the material of Comparative Example 2. Figures 6a, b, and c show the powder x-ray diffraction patterns of the samples III, IV, and V of Inventive Example 1 respectively. Figure 7 shows a comparison between the voltage versus capacity profiles for comparative sample I and reference sample III. Figures 8a, b, and c show the voltage versus capacity profiles for the batteries comprising reference samples III, IV, and V respectively. Figure 9 shows the voltage versus time plot of the battery comprising reference sample V over representative cycles 10-14. Figure 10 shows the capacity versus cycle number data for the battery comprising reference sample V. The open data points were measured at a current of 37.2 mA/g and the solid points were measured at a current of 74 mA/g. Figures 11a, b, and c show a comparison of the powder x-ray diffraction patterns of the samples V, Va, and Vb of Reference Example 1. Figures 12a, b, and c compare the voltage versus capacity profiles for the batteries comprising samples V, Va, and Vb respectively. Figure 13 shows the powder x-ray diffraction patterns of inventive sample VI and reference sample IV. Figure 14 shows the weight loss versus temperature curve for polyphenylsesquisiloxane as determined by TGA in Inventive Example 1. Figure 15 shows a comparison of the voltage versus capacity profiles for the batteries comprising comparative sample I and samples III and VI. DETAILED DESCRIPTION OF THE SPECIFIC EMBODIMENTS OF THE INVENTION The carbonaceous insertion compounds of the invention comprise a pre-graphitic carbonaceous host C, atoms of Li inserted into the host, and atoms of Si incorporated into the host, wherein Si is capable of forming alloys with Li. The atoms of Si are incorporated predominantly as monodispersed atoms in the host wherein the term monodispersed is intended to include single atoms and/or small clusters of the alloying element such that the resulting compound exhibits properties more characteristic of single atoms of Si than that of a bulk compound of Si. The amount of Si present must be greater than zero. The structure of the carbonaceous insertion compound can be predominantly disorganized resulting in an x-ray diffraction pattern of the compound that is very poorly developed or amorphous. This suggests that the compounds are not necessarily the same as those described in the aforementioned co-pending EP-A-0 685 896. Certain compounds of this invention are attractive for use as anode materials in lithium ion batteries. With the alloying atoms being silicon, the reversible capacity of the compound of the invention can be increased over that of the carbonaceous host alone while still maintaining cycling performance similar to the carbonaceous host. Thus, it appears that the compounds of the invention can combine to some extent the attractive features of the capacity of the alloying element with the cycling stability of a carbonaceous compound. While compounds of the invention may exhibit characteristics or properties that are similar to those of the carbonaceous host and/or the alloying element, the compound is not however simply a mixture of a carbonaceous host and a bulk compound of the alloying element. The presence of a bulk compound of the alloying element is not indicated in x-ray diffraction measurements. Also, other characteristics expected of a bulk compound of the alloying element (such as rapid loss with cycle number of all the capacity attributed to the alloying element) are not evident in electrochemical cycling trials. Without wishing to be bound by theory, adversely or otherwise, it is expected that, in order to incorporate the Si as monodispersed atoms, it is necessary to maintain a sufficiently high carbon to alloying element atomic ratio in order to dilute the atoms of Si sufficiently. Also, in preparation processes that involve heating, formation of a carbide compound could be expected instead if said ratio is too low. It can additionally be advantageous to maintain a high carbon content for purposes of imparting reasonable electrical conductivity to the product compound. In a like manner, it is expected that a sufficiently high carbon to oxygen atomic ratio must be maintained to inhibit formation of oxides. Thus, a limit is required both to the amount of oxygen present in a precursor material and to the amount of oxygen gas present during any heating of the precursor or compound of the invention itself. (It may be of advantage however to allow for some slight oxidation of the product compound.) It may be possible to incorporate significant amounts of Si in the carbonaceous insertion compound. Additionally, other elements might also be present while still enabling use of the compound as an electrode material. For example, such possibilities include silicon containing compounds having the formula Li x Si y C 1-y O z H n wherein O (oxygen) and H (hydrogen) are additionally present. Based on values achieved in the following examples, it is expected that the ranges for y, z, and n in silicon containing compounds of the invention may be such that y is greater than zero and less than about 0.3, the ratio z/y is greater than or equal to zero and less than or equal to about 1.5, and n is greater than or equal to zero and less than about 0.3. For purposes of further illustration, the following discussion is provided for the specific example wherein there is little hydrogen and oxygen present (ie. z and n approximately zero). From the Silicon-Carbon phase information provided in R.W. Olesinski and G.J. Abbaschian, Bull. Alloy Phase Diagrams 5 , 486 (1984), the only equilibrium phases which form when mixtures of the atoms are cooled from high temperatures are carbon, silicon, and silicon carbide. The compounds of the invention are predominantly carbon, with some dispersed Si atoms within, and not simply a mixture of bulk Si and C nor a mixture of large grains of SiC and C as predicted at equilibrium. With regards to the structure as determined by x-ray diffraction methods, it is important to realize that silicon has 14 electrons per atom and carbon has only 6 electrons per atom. Since the scattered x-ray intensity from an atom is roughly proportional to the square of the number of electrons it has, the x-ray pattern should be very sensitive to the silicon. Silicon-carbon-oxygen compounds of the invention have been prepared containing substantial amounts of Si yet with no evidence of crystalline Si nor SiC nor SiO 2 in the x-ray patterns. (Amorphous silicon would have been expected to crystallize at the temperatures used in the preparation.) Thus, as in the aforementioned co-pending EP-A-0 685 896, the silicon atoms most likely are monodispersed along with oxygen within the host carbon. The method for making compounds of the invention is to pyrolyze a suitable precursor or mixture of precursors. The pyrolysis should be performed under a controlled atmosphere to prevent the formation of oxides of carbon and/or the alloying element. A suitable reaction system could consist of a reaction tube (quartz for example) installed in a conventional tube furnace wherein the tube has sealed inlet and outlet connections for purposes of controlling the atmosphere therein. The precursor/s could thus be pyrolyzed in the reaction tube under an inert gas flow or even under reduced pressure. Additionally, controlled partial reduction or oxidation can be achieved by admitting controlled amounts of an appropriate gas. To ensure good product yields, the precursor/s should substantially pyrolyze rather than simply evaporate. Thus, polymer precursors seem preferred. Such pyrolysis is performed at a temperature above the decomposition temperature of the polymer and below the minimum of the temperatures for forming a carbide or oxide of the alloying element B. (Depending on the precursors employed, oxygen may be present in the polymer itself and thus may react with B to form an oxide even in the absence of oxygen gas.) The temperature for forming said carbide or oxide will be dependent on the polymer used and thus varies accordingly. It may be advantageous to incorporate soaking periods at several temperatures as part of the heat treatment. For example, a low temperature soak below about 500°C could be used to gel a polymer (if it were a liquid initially) prior to a final heating to the pyrolysis temperature. The heating profile can be adjusted to maximize product yield and to control the product stoichiometry. As mentioned previously, a suitable silicon containing polymer is obviously used in the pyrolysis. A successful preparation involved use of polyphenylsesquisiloxane wherein the pyrolysis temperature in this instance was about 1000°C. Based on the preceding, other suitable silicon containing precursors are members of the groups of poly(siloxane-silphenylenes), poly(silmethylenes), polysilanes, or poly(silphenylenes). Members in each group are commercially available but the products of pyrolysis may not have been considered to be insertion compounds previously. Figure 1 shows the chemical structures for each of these precursors along with that of the aforementioned polyphenylsesquisiloxane. The groups R, R', R'', R''' in this figure denote alkyl, aryl, or general ligands in the usual notation of organic chemistry. The specific ligands methyl and phenyl are denoted Me and Ph respectively where appropriate. (A suitable reference in this regard is J.E. Mark, H.A. Allcock, and R. West, Inorganic Polymers, published by Prentice-Hall, Englewood Cliffs, New Jersey (1992) pp141-237.) The silicon containing product of the aforementioned process has no alkali metal inserted as prepared. Alkali metal atoms, in particular Li, can be inserted thereafter via chemical or electrochemical means (such as in a lithium or lithium ion battery). A variety of battery embodiments are possible using anode material prepared by the method of the invention. Miniature laboratory batteries employing a lithium metal anode are described in the examples to follow. However, a preferred construction for a lithium ion type product is that depicted for a conventional spiral-wound type battery in the cross-sectional view of Figure 2. A jelly roll 4 is created by spirally winding a cathode foil (not shown), an anode foil (not shown), and two microporous polyolefin sheets (not shown) that act as separators. Cathode foils are prepared by applying a mixture of a suitable cathode material, such as a lithiated transition metal oxide, possibly other powdered cathode material if desired, a binder, and a conductive dilutant onto a thin aluminum foil. Typically, the application method first involves dissolving the binder in a suitable liquid carrier. Then, a slurry is prepared using this solution plus the other powdered solid components. The slurry is then coated uniformly onto the substrate foil. Afterwards, the carrier solvent is evaporated away. Often, both sides of the aluminum foil substrate are coated in this manner and subsequently the cathode foil is calendered. Anode foils are prepared in a like manner except that a powdered carbonaceous compound of the invention is used instead of the cathode material and thin copper foil is usually used instead of aluminum. Anode foils are typically slightly wider than the cathode foils in order to ensure that anode foil is always opposite cathode foil. This feature is illustrated with the cathode upper edge 13, cathode lower edge 14, anode upper edge 12, and anode lower edge 15 depicted in Figure 2. The jelly roll 4 is inserted into a conventional battery can 3. A header 1 and gasket 10 are used to seal the battery 16. The header may include safety devices if desired. A combination safety vent and pressure operated disconnect device may be employed. Figure 2 shows one such combination that is described in detail in Canadian Patent Application No. 2,099,657. Additionally, a positive thermal coefficient device (PTC) may be incorporated into the header to limit the short circuit current capability of the battery. The external surface of the header 1 is used as the positive terminal, while the external surface of the can 3 serves as the negative terminal. Appropriate cathode tab 5 and anode tab 6 connections are made to connect the internal electrodes to the external terminals. Appropriate insulating pieces 2 and 7 may be inserted to prevent the possibility of internal shorting. Prior to crimping the header 1 to the can 3 in order to seal the battery, electrolyte 8 is added to fill the porous spaces in the jelly roll 4. Those skilled in the art will understand that the types of and amounts of the component materials must be chosen based on component material properties and the desired performance and safety requirements. The compounds prepared in the examples to follow have significantly increased irreversible capacity for lithium along with an increased reversible capacity over that of many typical commercial carbonaceous anode materials. This must be taken into account in the battery design. Alternately, compounds with reduced irreversible capacity must be employed. Generally an electrical conditioning step, involving at least the first recharge of the battery, is part of the assembly process. Again, the determination of an appropriate conditioning step along with the setting of the battery operating parameters (eg. voltage, current, and temperature limits) would be required of someone familiar with the field. Other configurations or components are possible for the batteries of the invention. For example, a prismatic format is considered highly desirable and possible. A miniature embodiment, eg. coin cell, is also possible and the general construction of such cells is described in the laboratory coin cell examples to follow. The following examples are provided to illustrate certain aspects of the invention but should not be construed as limiting in any way. Where indicated, powder x-ray diffraction was used to characterize samples. A Seimens D5000 diffractometer equipped with a copper target x-ray tube and a diffracted beam monochromator was used for these experiments. The samples were made by filling a 2mm deep well in a stainless steel block with powder and levelling the surface. The samples were sometimes loosely packed, and diffraction peaks from the stainless steel holder could occasionally be observed. Chemical analyses were performed on the samples as indicated using a variety of methods. Carbon, hydrogen, and nitrogen content was determined using a standard CHN analysis (gas chromatographic analysis after combustion of the samples in air) . However, as expected from the absence of nitrogen in the starting materials, only trace amounts of nitrogen were present. The results for carbon content were not considered to be strictly accurate because silicon tends to bind substantial amounts of carbon in the combustion and thus prevents it from reaching the gas phase. Nonetheless, the data was in rough agreement with values obtained by other methods. Laser-ablation inductively coupled mass spectroscopy (LA) was also employed to analyze some of the samples and estimate their carbon/silicon atomic ratio. In this method, a small quantity of sample is vaporized under a high powered laser beam. The vaporized fragments are carried in an inert gas stream to a plasma torch where they are atomized, ionized, and then injected into a mass spectrometer. A silicon carbide reference was used as a standard for calibration purposes. This method is believed to be quite accurate and agrees well with values inferred from CHN analyses coupled with the assumption that no Si is lost in the pyrolysis. An attempt was made to directly analyze for oxygen content using a technique that involves placing the sample on a nickel coated carbon substrate heated to 1100°C and hoping that the catalytic action of the nickel converts all the oxygen in the sample to CO, which is then detected by a gas chromatograph. However, only small amounts of oxygen were detected using this method. Consequently, this method is believed to be unreliable since it certainly gave results inconsistent with results inferred from other analyses performed herein. As explained in the following examples, both thermal gravimetric analysis (TGA) and residual gas analysis (RGA) techniques were also used to estimate the stoichiometry of the samples. Laboratory coin cell batteries were used to determine electrochemical characteristics. These were assembled using conventional 2325 hardware and with assembly taking place in an argon filled glove box as described in J.R. Dahn et al, Electrochimica Acta, 38, 1179 (1993). Figure 3 shows an exploded view of the coin cell type battery. For purposes of analysis, the samples were used as cathodes in these batteries opposite a lithium metal anode. A stainless steel cap 21 and special oxidation resistant case 30 comprise the container and also serve as negative and positive terminals respectively. A gasket 22 is used as a seal and also serves to separate the two terminals. Mechanical pressure is applied to the stack comprising lithium anode 25, separator 26, and sample cathode 27 by means of mild steel disc spring 23 and stainless disc 24. The disc spring was selected such that a pressure of about 15 bar was applied following closure of the battery. 125 µ m thick metal foil was used as the lithium anode 25. Celgard® 2502 microporous polypropylene film was used as the separator 26. The electrolyte 28 was a solution of 1M LiN (CF 3 SO 2 ) 2 salt dissolved in a solvent mixture of ethylene carbonate and diethyl carbonate in a volume ratio of 50/50. Sample cathodes 27 were made using a mixture of powdered sample compound plus Super S (trademark of Ensagri) carbon black conductive dilutant and polyvinylidene fluoride (PVDF) binder (in amounts of about 5% and 10% by weight respectively to that of the sample) uniformly coated on thin copper foil. The powdered sample and the carbon black were initially added to a solution of 20% PVDF in N-methylpyrollidinone (NMP) to form a slurry such that 10% of the final electrode mass would be PVDF. Excess NMP was then added until the slurry reached a smooth syrupy viscosity. The slurry was then spread on small preweighed pieces of Cu foil (about 1.5 cm 2 in area) using a spreader, and the NMP was evaporated off at about 90°C in air. Once the sample cathode stock was dried, it was compressed between flat plates at about 25 bar pressure. These electrodes were then weighed and the weight of the foil, the PVDF, and the carbon black were subtracted to obtain the active electrode mass. After construction, the coin cell batteries were removed from the glove box, thermostatted at 30 ± 1°C, and then charged and discharged using constant current cyclers with ± 1% current stability. Data was logged whenever the cell voltage changed by more than 0.005 V. Currents were adjusted according to the amount of active material, depending on the desired test. For purposes of comparison, examples originally presented in the aforementioned co-pending EP-A-0 685 896 are given in the following two Comparative Examples. Comparative Example 1. Benzene was pyrolyzed in a CVD reactor under argon flow at 950°C. The fine powder product, denoted sample I, was recovered and analyzed by x-ray diffraction. Figure 4 shows the x-ray diffraction pattern for this material, which is typical of a soft carbon prepared at this temperature (see H. Shi et al., Journal of Applied Crystallography, 26 , 827, (1993)). Well developed Bragg Peaks are clearly observed. The chemical composition was estimated using CHN analysis results and the assumption that no oxygen nor silicon was present in the sample (since neither element should be present in the benzene precursor). The results of the chemical analysis and estimated stoichiometry are shown in the following Table 2. Additionally, a laboratory coin cell battery was prepared using this sample as described previously. The battery was then discharged, charged, and discharged again at currents corresponding to 3.7 mA/g of sample. Comparative Example 2 Benzene and dimethyldichlorosilane were co-pyrolyzed in a CVD reactor under argon flow at 950°C. The product, denoted sample II, was analyzed as in the preceding Example. Figure 5 shows the x-ray diffraction pattern for sample II and is similar to that of Figure 4. Silicon is incorporated within sample II (about 6 atomic percent silicon as shown later) yet it does not affect the diffraction pattern, strongly implying that the silicon is located within the disorganized regions of the host in this case. The chemical composition of this sample was estimated using a TGA method and results of the CHN analysis. The TGA method consists of heating a sample in air to 1100°C on the balance pan of a TGA instrument and measuring the weight loss. The sample consists mainly of carbon and silicon. Thus, if weight losses due to the presence of the small amount of hydrogen and/or oxygen is ignored, and if it is additionally assumed that the carbon is completely removed as CO 2 or CO and that the silicon is completely oxidized to SiO 2 , then the silicon and carbon content can be determined from the final to initial mass ratio. (The silicon content y in Si y C 1-y is given by y= 12 (m f /m i )/[60.1-16.1(m f /m i )] where m f and m i are the final and initial TGA masses respectively. X-ray diffraction results obtained on this and other Si containing samples tested in this way did indeed indicate the presence of SiO 2 only.) The results of the chemical analysis and estimated stoichiometry are shown in the following Table 2. Reference Example 1. Polymethylphenylsiloxane polymer precursor (Dow 710 fluid product of Dow) was pyrolyzed under flowing argon in a tube furnace apparatus as mentioned in the Description. Three samples, denoted III, IV, and V, were prepared by heating to 900°C, 1000°C, and 1100°C respectively. In each case, the sample temperature was ramped to the soaking temperature at a rate of about 20°C/min. Thereafter, the soaking temperature was maintained for 1 hour, followed by a cool down to room temperature. The argon flow was maintained until the sample temperature fell below 100°C. Alumina boats were used to contain the samples in a quartz reactor tube. The initial sample fluid mass was near 12 grams, while about 4 grams of solid black reaction product was obtained in each case after pyrolysis. About 30% of the liquid sample is estimated to have simply evaporated before actual pyrolysis occurred. Figures 6a, b, and c show the powder x-ray diffraction patterns of these samples III, IV, and V respectively. CHN and LA analyses were performed on these samples as described previously. Additionally, the stoichiometry was estimated for each sample using the results of these analyses and the assumption that neither silicon nor oxygen was lost during pyrolysis of the polymer precursor. Thus, the silicon:oxygen ratio in the samples will be the same as that of the polymer precursor, or 1:1. (This assumption seems reasonable based on an analysis of the gaseous decomposition products during the pyrolysis. A small sample of polymethylphenylsiloxane was pyrolyzed in a TGA apparatus coupled to an RGA instrument. The gaseous decomposition products were analyzed as generated up to a temperature of about 700°C. It was found that benzene was the predominant species evolved. Only a very small amount of oxygen containing species was observed.) Results of these analyses and the estimated stoichiometry are shown in the following Table 2. Laboratory coin cell batteries were prepared as described previously and were then discharged, charged, and discharged again at currents corresponding to 14.8 mA/g. Figure 7 shows a comparison between the voltage versus capacity profiles for comparative sample I and reference sample III. The former attains a reversible capacity of about 300 mAh/g, while the latter attains a greater reversible capacity of about 550 mAh/g. (Herein, the average capacity of the first charge and the second discharge of the battery is taken to be the reversible capacity.) However, the irreversible capacity of sample III is much greater than that of sample I. This can be reduced somewhat by further heating however as is shown in Figure 8. Figures 8a, b, and c show the voltage versus capacity profiles for the batteries comprising reference samples III, IV, and V respectively. The reversible capacity is approximately maintained at higher pyrolysis temperatures while the irreversible capacity is somewhat reduced. The battery comprising sample V was further cycled at currents corresponding to 74 mA/g. Figure 9 shows the voltage versus time plot of this battery over representative cycles 10-14. The cycling behaviour is very reproducible. Figure 10 shows the capacity versus cycle number data for this battery. For illustrative purposes, some of sample V was used for pyrolysis experiments at higher temperatures. 1 gram amounts were heated under flowing argon for one hour at 1300°C and at 1500°C. These samples are denoted Va and Vb respectively. Figures 11a, b, and c compare the x-ray diffraction patterns for samples V, Va, and Vb respectively. Silicon carbide formation is clearly detected in samples Va and Vb. (It is suspected that the gaseous decomposition products at these temperatures are CO and H 2 . Using the estimated stoichiometry in Table 2, the removal of all the hydrogen and oxygen present in 1 gram of sample V would result in 0.64 grams of product. The recovered weight of sample Vb was 0.63 grams.) Laboratory coin cell batteries were also prepared using the latter two samples. Figures 12a, b, and c compare the voltage versus capacity profiles for samples V, Va, and Vb respectively. The reversible capacity of the latter two samples is greatly reduced compared to that of samples II, IV, or V. Thus, it appears that the pyrolysis temperature must be limited appropriately to maximize reversible capacity and to prevent formation of silicon carbide. Inventive Example 1. Polyphenylsesquisiloxane solid was obtained from United Chemical Technologies Inc. 3.66 grams of this solid was pyrolyzed under argon at 1000°C in the tube furnace apparatus used for Reference Example 1. 2.86 grams of shiny grey-black material was recovered and there was no evidence of evaporation of polymer from the boat. This sample is denoted sample VI. Figure 13 shows the powder x-ray diffraction patterns of sample VI and that of sample IV of Reference Example 1. The patterns of these materials are very similar. In a manner similar to Comparative Example 2, the stoichiometry of the sample was estimated using the weight loss observed as a result of pyrolysis and the assumption that said loss was entirely due to the evolution of benzene as the decomposition product. (Unlike Reference Example 1, significant evaporation of the precursor polymer was not observed and the TGA/RGA results mentioned in the following indicate that benzene only was the significant decomposition product.) The amount of hydrogen present was unknown in this case, so a guess of n=1 was used for the estimated stoichiometry shown in Table 2. A fresh sample of polyphenylsesquisiloxane was heated in the aforementioned TGA/RGA apparatus under argon where the temperature was ramped at 20°C per minute. The weight loss versus temperature curve for this sample is shown in Figure 14. Weight loss can be seen to occur at temperatures as low as 500°C. By 700°C, only about 80% of the sample remains. The RGA indicated that benzene was generated predominantly up to about 700°C. Some smaller amount of hydrogen was also generated. This suggests that samples similar to sample VI might be prepared at temperatures as low as 500°C. A laboratory coin cell battery was prepared as described previously and was then discharged, charged, and discharged again at currents corresponding to 14.8 mA/g. Figure 15 shows a comparison between the voltage versus capacity profiles for the batteries made with comparative sample I, reference sample III, and inventive sample VI. The reference and inventive samples are very similar electrochemically. Summary of Chemical Analysis Results and Estimated stoichiometry of the samples Sample H content by CHN (weight %) C content by CHN (weight %) C/Si by LA (atomic ratio) Estimated Stoichiometry I 0.41 98.9 Not available C 1 H 0.03 II 0.2 86.5 Not available Si 0.06 C 0.94 H 0.02 III 1.0 39 2.3 Si 0.26 C 0.74 O 0.26 H 0.26 IV 0.6 40 2.6 Si 0.26 C 0.74 O 0.26 H 0.15 V 0.5 Not available 2.7 Si 0.26 C 0.74 O 0.26 H 0.13 VI Not available Not available Not available Si 0.21 C 0.79 O 0.32 H 0.21 Compounds of the invention can be denoted by the formula Li x Si y C 1-y O z H n . Therefore, according to the preceding table, the maximum value for y in the examples appears to be less than or equal to approximately 0.26, or about 0.3. The ratio z/y is less than or equal to about 1.5 and the maximum value n is 0.26, or about 0.3. These examples illustrate that enhanced reversible capacity can be obtained (greater than that of pure graphite) and maintained without significant capacity loss upon cycling using compounds of the invention. The compounds appear predominantly amorphous with distinctively different x-ray diffraction patterns from those of the Comparative Examples. As will be apparent to those skilled in the art in the light of the foregoing disclosure, many alterations and modifications are possible in the practice of this invention without departing from the scope thereof as defined in the claims. For example, mixtures of more than one precursor may be used to prepare compounds.

Claims: A method of preparing a carbonaceous insertion compound comprising: (a) a pre-graphitic carbonaceous host C; (b) atoms of Li inserted into the host C, the amount of Li being in the range from greater than or equal to zero; and (c) atoms of Si incorporated into the host C, wherein the atoms of Si are incorporated as monodispersed atoms in the host C, said process comprising: pyrolysing a polymer selected from poly(silmethylenes), poly(siloxanesilphenylenes), polysilanes, polyphenylsesquisiloxanes and poly(silphenylenes); wherein the pyrolysis is performed at a temperature above the decomposition temperature of the polymer and below the minimum of the temperatures for forming a carbide or oxide of Si from the pyrolysed polymer, so that a carbonaceous insertion compound is obtained having a reversible specific capacity for Li greater than graphite. A method of preparing a carbonaceous insertion compound as claimed in claim 1, wherein the polymer is pyrolysed at a temperature above the decomposition temperature of the polymer and below the minimum of the temperatures for forming SiC or SiO 2 from the pyrolysed polymer, so that a silicon-containing carbonaceous insertion compound is obtained having a reversible specific capacity for Li greater than graphite. A method as claimed in claim 2, wherein the carbonaceous insertion compound has the formula Li x Si y C 1-y O z H n wherein O is oxygen, H is hydrogen and x, y, z, n are numbers; x being greater than zero; y being in the range from greater than zero to less than about 0.3; the ratio z/y being greater than or equal to zero and less than or equal to about 1.5; and n being less than about 0.3. A method as claimed in claim 2, wherein the polymer is a poly(silmethylene), a polysilane or a poly(silphenylene). A method as claimed in claim 2, wherein the polymer is polyphenylsesquisiloxane. A method as claimed in any one of claims 1 to 5, wherein the pyrolysis is performed under an inert atmosphere. A method as claimed in claim any one of claims 1 to 6, wherein the pyrolysis is performed at a temperature above about 500°C. A method as claimed in any one of claims to 1 to 6, wherein the pyrolysis is performed at a temperature above or equal to about 900°C, and below or equal to about 1100°C. A method as claimed in any one of claims 1 to 6, wherein the pyrolysis is performed at a temperature about 1000°C. A carbonaceous insertion compound obtainable by a method as claimed in any one of claims 1 to 9 wherein said monodispersed atoms of Si includes single atoms or small clusters of Si such that the resulting compound exhibits properties that are more characteristic of single atoms of Si than that of a bulk compound of Si. A carbonaceous insertion compound as claimed in claim 10, wherein the structure of the compound is predominantly disorganized resulting in an X-ray diffraction pattern of the compound that is poorly developed or amorphous. An electrochemical device comprising an electrode wherein a portion of the electrode comprises a carbonaceous insertion compound as claimed in claim 10. An electrochemical device comprising an electrode wherein a portion of the electrode comprises a silicon-containing carbonaceous insertion compound as claimed in claim 10 when dependent upon claim 2 or claim 4. A battery comprising an electrode wherein a portion of the electrode comprises a carbonaceous insertion compound as claimed in claim 10. A battery comprising an electrode wherein a portion of the electrode comprises a silicon-containing carbonaceous insertion compound as claimed in claim 10 when dependent upon claim 2. A non-aqueous battery comprising: (a) a cathode comprising a lithium insertion compound; (b) a non-aqueous electrolyte comprising a lithium salt dissolved in a mixture of non-aqueous solvents; and (c) an anode comprising a carbonaceous insertion compound as claimed in claim 10. A non-aqueous battery comprising: (a) a cathode comprising a lithium insertion compound; (b) a non-aqueous electrolyte comprising a lithium salt dissolved in a mixture of non-aqueous solvent; and (c) an anode comprising a silicon-containing carbonaceous insertion compound as claimed in claim 10 when dependent upon claim 2 or claim 4. A method of operating an electrochemical device comprising an electrode, wherein a portion of the electrode comprises a carbonaceous insertion compound as claimed in claim 10 wherein said method includes the step of: repeatedly electrochemically reversibly inserting Li atoms into said carbonaceous insertion compound in an amount effective to provide a reversible specific capacity for said electrochemical device greater than 372 mAh per gram of said carbonaceous insertion compound. A method as claimed in claim 18, wherein the structure of said carbonaceous insertion compound is predominantly disorganised. A method as claimed in claim 18, wherein said carbonaceous insertion compound has the formula Li x Si y C 1-y O z H n , wherein O is oxygen, H is hydrogen and x,y, z, n are numbers; y being in the range from greater than zero to less than about 0.3; the ratio z/y being greater than or equal to zero and less than or equal to about 1.5; n being less than about 0.3, and x and z are greater than zero. A method as claimed in claim 18, wherein the electrochemical device is a battery. A method as claimed in claim 21, wherein the battery is non-aqueous and comprises: a cathode comprising a lithium insertion compound; a non-aqueous electrolyte comprising a lithium salt dissolved in a mixture of nonaqueous solvents; and an anode comprising the carbonaceous insertion compound.

Inventors: DAHN JEFFERY RAYMOND, WILSON ALDRED MACDONALD, DAHN, JEFFERY RAYMOND, WILSON, ALDRED MACDONALD
Applicants: MOLI ENERGY 1990 LTD, MOLI ENERGY (1990) LIMITED
Application year: 1995
Main classification: H01M4
IPC codes: H01M4, C01B33, H01M6, H01M2, C01B31