CA2436600C - Synthesis of lithium transition metal sulphides - Google Patents

Synthesis of lithium transition metal sulphides Download PDF

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CA2436600C
CA2436600C CA2436600A CA2436600A CA2436600C CA 2436600 C CA2436600 C CA 2436600C CA 2436600 A CA2436600 A CA 2436600A CA 2436600 A CA2436600 A CA 2436600A CA 2436600 C CA2436600 C CA 2436600C
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lithium
sulphide
molten
mixture
transition metal
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CA2436600A1 (en
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Andrew Grahame Ritchie
Peter George Bowles
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Qinetiq Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/007—Titanium sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G33/00—Compounds of niobium
    • C01G33/006—Compounds containing niobium, with or without oxygen or hydrogen, and containing two or more other elements
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G39/00—Compounds of molybdenum
    • C01G39/006—Compounds containing molybdenum, with or without oxygen or hydrogen, and containing two or more other elements
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G39/00—Compounds of molybdenum
    • C01G39/06—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/009—Compounds containing iron, with or without oxygen or hydrogen, and containing two or more other elements
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/12—Sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

A process for the production of a lithium transition metal sulphide such as lithium iron sulphide, the process comprising reacting a transition metal sulphide with lithium sulphide in a solvent comprising a molten salt or a mixture of molten salts. Lithium transition metal sulphides obtained using this process are also claimed and are useful in the production of electrodes, in particular for rechargeable lithium batteries.

Description

SYNTHESIS OF LITHIUM TRANSITION METAL SULPHIDES

The present invention relates to processes for the production of sulphides, in particular lithium transition metal sulphides useful in the production of batteries.
In the 1980's, there was extensive research into lithium metal rechargeable batteries, particularly using sulphides, -but also selenides, as cathode materials. Many fithium metal / moiybdenum disulphide (Li/MOSZ) batteries were produced but these were withdrawn following an incident in which a fire was attributed to the malfunction of such a battery. Other sulphides, such as iron disulphide FeS2, titanium disulphide TiS2 and selenides, such as niobium triselenide NbSe3 have also been particularly investigated as alternative cathode materials.
Although the use of fithium metal rechargeable batteries is now limited for reasons of safety, they are still used in the laboratory testing of materials.
Lithium metal primary batteries using iron disulphide cathodes are manufactured.
Virtually all modern lithium rechargeable batteries are of the lithium - ion type, in which the negative electrode (anode) comprises- lithium absorbed into a carbon suppori. These use a lithium containing cathode materiai, which is usually lithium cobalt oxide LiCo02 although lithium nickel oxide LiNi02, lithium manganese oxide LiMn204 and mixed oxides are also known to have been used.
Due to their high cost, the use of lithium rechargeable batteries at present is mainly limited to premium applications, such as portable computers or telephones. To gain access to wider markets, for example in applications such as the powering of electric vehicles, the cost must be reduced. Hence there is a strong demand for the ;
high performance obtainable from lithium - ion batteries at much rnore economical prices.
On first inspection, the use of sulphides as=cathode materials is not as attractive as the use of oxides. This is because the voltage achievable from sulphides is generally only about half of that achievable using corresponding oxides.
However, the capacity of batteries incorporating suiphide based cathodes, measured in ampere hours per gram of material, is about 3 times greater than corresponding batteries incorporating oxide based cathodes. This leads to an overall advantage of about 1.5 times in terms of cathode energy density for batteries with sulphide based cathodes.
A further advantage is that iron sulphides, in particular ferrous sulphide (FeS) and iron disulphide (FeS2) are inexpensive materials which may be dug out of the ground 16-11-2002 GB010,~20~
as natural occurring minerals. By contrast, lithium cobalt oxide is an expensive material, due mainly to the high cost of cobalt metal.
Binary transition metal sulphides are however not suitable for direct use in iithium - ion cells as they do not contain lithium. Lithium transition metal ternary sulphides, such as lithium molybdenum sulphide, lithium titanium sulphide, lithium niobium sulphide and lithium iron sulphide have been suggested as electrode materials for batteries (see for example, Japanese Kokai No 10208782 and Solid State lonics 117 (1999) 273 - 276). The conventional synthesis of lithium iron sulphide is via a solid state reaction in which lithium sulphide, LiZS, and ferrous sulphide, FeS, are intimately mixed together and heated under an inert atmosphere at a temperature of ca. 800 C. The reaction is diffusion controlled and the kinetics are slow. Consequently, the reaction can take up to 1 month at temperature to reach completion. This is highly inconvenient and is costly in terms of energy input. The economics of this synthesis for battery production are clearly unfavourable.
On a laboratory scale, lithium iron sulphide can be made by an electrochemical synthesis route in which a lithium metal / iron disulphide cell is discharged, and the lithium metal is removed and replaced by a carbon anode. This process however, is not amenable to scaling up. A further laboratory synthesis of lithium iron sulphide is the solid state reaction of lithium nitride, Li3N, with iron disulphide, FeS2, but again, this method is unsuitable for large scale use because of the high cost and shock sensitivity of lithium nitride.
The applicants have developed an economicai synthesis which can be operated on a large scale to produce Li2FeS2, which has useful electrochemical properties.
The present invention provides a process for the synthesis of lithium iron sulphide LiZFeS2, in which reactants consisting of lithium sulphide Li'S and iron suiphide FeS react, under an inert atmosphere, in a solvent consisting essentially of a molten lithium halide salt, or a mixture of molten lithium halide salts, so as to produce Li2FeS2 as the dominant product phase, and recovering the product by dissolution of the molten salt or mixture of molten salts in at least one organic liquid.
Ferrous sulphide, FeS, is inexpensive and a readily available naturally occurring mineral.

AMENDED SHEET

16-11-2002 cA 02436600 2003-06-05 GB010520~
Preferably, the molten lithium halide salt or mixture of molten lithium halide salts comprises at least one of lithium fluoride, lithium chloride, lithium bromide or lithium iodide.
The reaction temperature should be sufficient to liquefy the molten salt or mixture of molten saits. This need not necessarily be the melting point of the molten lithium halide salt or mixture of molten salts as the addition of the reactants may depress the melting point. Typically, reaction temperatures of less than 1000 C and most often less than 700 C are suitabie, however dependent on the choice of solvent, reaction temperatures of less than 300 C may be used.
The reaction proceeds more rapidly than previously known processes. On a laboratory scale, the reaction can be completed in a few hours, with the actual reaction tirne dependent largeiy on the heating time of the furnace.
Although lithium sulphide may be bought commercially, for large scale production it is more economical to produce lithium sulphide via the reduction of lithium sulphate. One convenient method is to heat tithium sulphate above its melting point of 860 C in the presence of carbon. Other standard reduction methods may equally be used, as weil known in the art.
After the reaction is compiete and allowed to cool, the product must be recovered from the solvent. in the present process, the product is recovered by dissolution of the solvent in an organic liquid. The organic liquid chosen is dependent on the composition of the solvent used, however some examples include, pyridine, ether and acetonitrile which are suitabfe for the dissoVution of lithium chloride, lithium bromide and lithiurn iodide respectively. Numerous other suitable liquids will be known to those skilled in the art. When a mixed salt solvent is used it may be necessary to perform more than one dissolution process. For example, a reaction using a mixture of iithium chloride and lithium bromide as a solvent may require a first dissolution process using pyridine to remove the lithium chloride, followed by a second dissolution process using ether to remove the lithium bromide.

AMENDED SHEET

GBO i 05209 LizFeS2 obtained by the above described process is useful in the production of electrodes for use in batteries. In particular, they are useful in the production of electrodes for rechargeable batteries. These electrodes form the cathode, and suitable anodes are lithium ion anodes as are known in the art. Suitable electrolytes are also well known and include mixtures of inorganic carbonates, for example ethylene carbonate, propylene carbonate, diethyl or dimethyl carbonates, ethyl methyl carbonate together with a lithium salt, usually lithium hexafluorophosphate, LiPFB, or lithium trifluoromethane sulphonate (`trifiates'), LiCF3S03 or lithium tetrafluoroborate, LiBF4.
Molten salts and mixtures of molten salts are not conventional solvents and their use, acting like solvents in the production of sulphides, is an important part of the invention.
The invention will now be particularly described by way of example only with reference to the following drawings in which;
Figure 1 shows an x-ray diffraction trace for the product obtained using a frrst example of a process according to the present invention;
Figure 2 shows cycling curves for the product obtained using a first example of a process according to the present invention;
Figure 3 shows an x-ray diffraction trace for the product obtained using a second example of a process according to the present invention;
Figure 4 shows an x-ray diffraction trace for the product obtained using a third exampfe of a process according to the present invention;
Figure 5 shows cycling curves for the product obtained using a third example of a process according to the present invention; and, Figure 6 shows an x-ray diffraction trace for the product obtained using a fourth example of a process, which process falls outside the present invention.

AMENDED SHEET

Lithium iron sulph+de, Li2FeS2 was synthesised according to the following equation:
Li2S + FeS --+ Li2FeS2 Stoichiometric amounts of lithium sulphide, Li2S, and iron sulphide, FeS, were intimately mixed with a roughly equ'tvalent weight of a salt or mixture of salts whicti constituted the solvent. The resulting mixture was placed into a nickel crucible and heated under an inert atmosphere to effect reaction. After the reaction was complete, the crucible and its contents were allowed to cool whilst still under an inert atmosphere, before being transferred to an inert atrnosphere glove box. The salt or mixture of salts was then removed from the desired product by refluxing the powdered contents of the crucible with an organic liquid. After filtering and drying, the resultant product was analysed by x-ray powder diffraction (XRD) using a Philips PW1830 Diffractometer and CuKa radiation.
Cell cycling tests were carried out on the product as follows. Cathode sheets were made by the doctor blade method. The product was mixed with graphite and a solution of ethylene propylene diene monomer (EPDM) in cyclohexane to form a slurry. This was then coated onto an aluminium backing sheet. Negative electrodes were made by a similar method except that the active material was carbon in the form of graphite with some carbon black added, the binder was polyvinylidene fluoride dissolved in N- methyl pyrrolidinone (NMP) and the metallic backing sheet was copper. The electrolyte was ethylene carbonate (EC) ! diethyl carbonate (DEC) molar lithium hexafluorophosphate (LiPF6). Cells were cycled at room temperature.
This celi cycling procedure is described in more detail by A. Gilmour, C. O.
Giwa, J.
C. Lee and A. G. Ritchie, in the Journal of Power Sources, volurne 65, pages 224.

Example 1.
Li2S and FeS were reacted together in a molten salt solvent of lithium chloride, LiCl, at 650 C for ca. 2 hours, under an argon atmosphere. After completion, the LiC1 was removed by refluxing in pyridine for 8 hours. Fig. 1 shows an XRD trace of the product obtained. The vertical lines 1 represent the standard trace for pure Li2FeSZ
taken from the JCPDS database. The main peaks are co-incident with and have similar relative intensities to these lines 1, indicating that the dominant product phase AMENDED SHEET

16-11-2002 . G6010520~

obtained was LiLFeSz. The remaining peaks correspond to sma11 amounts of unreacted starting materials.
The product obtained was used to manufacture a cathode as described above.
Fig. 2 illustrates three cycling curves which indicate that the cathode could be repeatedly charged and discharged. This demonstrates that the product was suitable for use as a cathode material for a lithium rechargeable battery.

Example 2.
Li2S and FeS were reacted together in a molten salt solvent of lithiurn bromide, LiBr, at 550 C for ca. 2 hours, under an argon atmosphere. After completion, the LiBr was removed by refluxing in diethyl ether for 8 hours. Fig. 3 shows an XRD
trace of the product obtained. The vertical lines 1 represent the standard trace for pure Li2FeSZ taken from the JCPDS database. The main peaks are co-incident with and have similar relative intensities to these lines 1, indicating that the dominant product phase obtained was Li2FeS2. The remaining peaks correspond to small amounts of unreacted starting materials.

Example 3.
LiZS and FeS were reacted together in a molten salt solvent of lithiurn iodide, Lil, at 450 C for ca. 2 hours, under an argon atmosphere. After completion, the Li( was removed by refluxing in acetonitrile for 8 hours. Fig. 4 shows an XRD
trace of the product obtained. The vertical lines 1 represent the standard trace for pure Li2FeS, taken from the JCPDS database. The main peaks are co-incident with and have similar relative intensities to these lines 1, indicating that the dorninant product phase obtained was Li2FeS2. The remaining peaks correspond to small arnounts of unreacted starting materiais.
The product obtained was used to manufacture a cathode as described above.
Fig. 5 illustrates three cycling curves which indicate that the cathode could be repeatedly charged and discharged. This demonstrates that the product was suitable for use as a cathode material for a lithium rechargeable battery.
Comparative Example 4.
By way of comparison, a further experiment was conducted in which Li2S and FeSZ were reacted together in a mo{ten salt solvent of lithium chloride, LiCI, at 700 C
for ca. 2 hours, under an argon atmosphere. After completion the lithium chloride was removed by refluxing in pyridine for 8 hours. Fig 6 shows an XRD trace of the product obtained. The main peaks are coincident with the lithium iron AMENDED SHEET

16-11-2002 , CA 02436600 2003-06-05 GB010520~

sulphides, Li3Fe2S4i Li-,FeS2 and LiZ.33Fe0.67S2. Unlike the other examples, a single pure product was not obtained. This example falls outside the present invention, although the products are known to be suitable as battery cathode materials (A. G.
Ritchie and P. G. Bowles, Process for Producing a Lithium Transition Metal Sulphide, 3 A1, 28th December 2000).
The Examples 1-3 described above demonstrate that the process of the present invention is suitable for use in the production of Li2FeS2 and that the product so obtained can be used as a cathode material in the manufacture of lithium rechargeable batteries. The process is signifcantly quicker and requires considerably less energy input than the conventional solid state synthesis of lithium iron sulphide.
This {eads to significant reductions in the cost of the material.

AMENDED SHEET

Claims (3)

CLAIMS:
1. A process for the synthesis of lithium iron sulphide, Li2FeS2, in which reactants consisting of lithium sulphide, Li2S, and iron sulphide, FeS, react, under an inert atmosphere, in a solvent consisting essentially of a molten lithium halide salt, or a mixture of molten lithium halide salts, so as to produce Li2FeS2 as the dominant product phase, and recovering the dominant product phase by dissolution of the molten lithium halide salt or mixture of molten lithium halide salts in at least one organic liquid.
2. The process according to claim 1, wherein the molten lithium halide salt or mixture of molten lithium halide salts comprises at least one of lithium fluoride, lithium chloride, lithium bromide or lithium iodide.
3. A process for manufacturing a cathode involving producing lithium iron sulphide, Li2FeS2, by the process according to claim 1 or 2, and subsequently using the lithium iron sulphide so produced to manufacture the cathode.
CA2436600A 2000-12-08 2001-11-27 Synthesis of lithium transition metal sulphides Expired - Fee Related CA2436600C (en)

Applications Claiming Priority (3)

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GB0029958.6 2000-12-08
GBGB0029958.6A GB0029958D0 (en) 2000-12-08 2000-12-08 Synthesis of lithium transition metal sulphides
PCT/GB2001/005209 WO2002046102A1 (en) 2000-12-08 2001-11-27 Synthesis of lithium transition metal sulphides

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CA2436600C true CA2436600C (en) 2010-03-23

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EP (1) EP1341724B1 (en)
JP (1) JP4188685B2 (en)
KR (1) KR100755191B1 (en)
CN (1) CN1210826C (en)
AT (1) ATE272026T1 (en)
AU (1) AU2002223897A1 (en)
CA (1) CA2436600C (en)
DE (1) DE60104561T2 (en)
ES (1) ES2225655T3 (en)
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WO (1) WO2002046102A1 (en)

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JP6011989B2 (en) * 2013-03-18 2016-10-25 国立研究開発法人産業技術総合研究所 Lithium titanium sulfide, lithium niobium sulfide and lithium titanium niobium sulfide
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US10033040B2 (en) 2013-07-08 2018-07-24 The Board Of Trustees Of The Leland Standford Junior University Stable cycling of lithium sulfide cathodes through strong affinity with multifunctional binders
US10269465B2 (en) 2013-10-04 2019-04-23 National Institute Of Advanced Industrial Science And Technology Amorphous (lithium) niobium sulfide or (lithium) titanium niobium sulfide
JP6577222B2 (en) * 2015-04-17 2019-09-18 トヨタ自動車株式会社 Method for producing sulfide solid electrolyte and sulfur-based material
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CN108767234B (en) * 2018-06-05 2021-06-08 天津巴莫科技有限责任公司 A lithium-rich solid solution sulfur oxide cathode material and preparation method thereof
CN109052488B (en) * 2018-09-05 2020-12-29 中国工程物理研究院电子工程研究所 A kind of cobalt disulfide material with high storage stability and preparation method and application thereof
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US20040018141A1 (en) 2004-01-29
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GB0029958D0 (en) 2001-01-24
KR20040014436A (en) 2004-02-14
CN1489553A (en) 2004-04-14
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AU2002223897A1 (en) 2002-06-18
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