WO2012141207A1 - リチウムイオン電池固体電解質材料用硫化リチウムの製造方法 - Google Patents
リチウムイオン電池固体電解質材料用硫化リチウムの製造方法 Download PDFInfo
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- WO2012141207A1 WO2012141207A1 PCT/JP2012/059889 JP2012059889W WO2012141207A1 WO 2012141207 A1 WO2012141207 A1 WO 2012141207A1 JP 2012059889 W JP2012059889 W JP 2012059889W WO 2012141207 A1 WO2012141207 A1 WO 2012141207A1
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- sulfide
- lithium sulfide
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- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/22—Alkali metal sulfides or polysulfides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/22—Alkali metal sulfides or polysulfides
- C01B17/24—Preparation by reduction
- C01B17/28—Preparation by reduction with reducing gases
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- 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
- C01P2006/80—Compositional purity
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
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- 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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- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention relates to a method for producing lithium sulfide (Li 2 S) that can be suitably used as a solid electrolyte of a lithium ion battery.
- Lithium-ion batteries are secondary batteries that have a structure in which lithium is melted as ions from the positive electrode during charging, moves to the negative electrode and is stored, and lithium ions return from the negative electrode to the positive electrode during discharge. It has been widely used as a power source for home appliances such as video cameras, portable electronic devices such as notebook computers and mobile phones, and power tools such as power tools. Then, it is applied also to the large sized battery mounted in an electric vehicle (EV) or a hybrid electric vehicle (HEV).
- EV electric vehicle
- HEV hybrid electric vehicle
- This type of lithium ion battery is composed of a positive electrode, a negative electrode, and an ion conductive layer sandwiched between the two electrodes.
- the ion conductive layer includes a separator made of a porous film such as polyethylene or polypropylene, and a nonaqueous electrolytic cell.
- the one filled with liquid is generally used.
- the electrolyte is an organic electrolyte that uses a flammable organic solvent as a solvent, improvements in structure and materials to prevent volatilization and leakage were necessary. It was also necessary to improve the structure and materials in order to prevent the occurrence of short circuits by installing safety devices that suppress the temperature rise.
- an all solid-state lithium battery obtained by solidifying a battery using a solid electrolyte using lithium sulfide (Li 2 S) as a raw material does not use a flammable organic solvent in the battery.
- the safety device can be simplified, and the manufacturing cost and productivity can be improved.
- Lithium sulfide (Li 2 S) suitable as a solid electrolyte material is not produced as a natural mineral product, so it must be synthesized.
- Conventional methods for producing this kind of lithium sulfide include, for example, 1) a method in which lithium sulfate is heated and reduced with an organic substance such as sucrose or starch in an inert gas atmosphere or in a vacuum, or 2) an inert gas atmosphere or in a vacuum. In this method, lithium sulfate is heated and reduced with carbon black or graphite powder, 3) a method of thermally decomposing lithium hydrogen sulfide ethanolate in a hydrogen stream, and 4) metallic lithium and hydrogen sulfide or sulfur vapor are subjected to normal pressure or pressure.
- a method of directly reacting by heating with is known.
- Patent Document 1 discloses a lithium sulfide production method in which lithium sulfide is synthesized by a reaction between lithium hydroxide and a gaseous sulfur source as a new method for synthesizing lithium sulfide.
- a method for producing lithium sulfide characterized in that the powder is 0.1 mm to 1.5 mm and the heating temperature during the reaction is 130 ° C. or higher and 445 ° C. or lower.
- Patent Document 2 discloses that hydrogen sulfide gas is blown into a slurry composed of lithium hydroxide and a hydrocarbon-based organic solvent to react lithium hydroxide and hydrogen sulfide, and water generated by the reaction is removed from the slurry.
- a method for producing lithium sulfide characterized in that after the reaction is continued and water in the system is substantially lost, blowing of hydrogen sulfide is stopped and inert gas is blown.
- the present invention provides a process for preparing lithium sulfide (Li 2 S) in dry method, it is possible to produce lithium sulfide (Li 2 S) in a more easy and low cost. Moreover, as the solid electrolyte of a lithium ion battery The present invention proposes a new method for producing lithium sulfide (Li 2 S) capable of achieving fine powdering of lithium sulfide (Li 2 S) so that excellent performance can be exhibited.
- the present invention relates to a method for producing lithium sulfide (Li 2 S) for a lithium ion battery solid electrolyte material used as a solid electrolyte material for a lithium ion battery, wherein a lithium carbonate powder and a gas containing sulfur (S) are dry-processed. And a method for producing lithium sulfide (Li 2 S) for a solid electrolyte material of a lithium ion battery, wherein the lithium carbonate powder is obtained by heating the lithium carbonate.
- lithium sulfide (Li 2 S) can be manufactured in a dry state, it can be manufactured more easily and at low cost. Moreover, since lithium carbonate as a Li raw material is neither ignitable nor hygroscopic, it is easy to handle, and by atomizing lithium carbonate powder, the obtained lithium sulfide (Li 2 S) is atomized. Therefore, the reactivity as a solid electrolyte of a lithium ion battery can be further enhanced.
- the method for producing lithium sulfide (Li 2 S) according to the present embodiment is a lithium carbonate powder and a gas containing sulfur (S) (referred to as “S-containing gas”). In a dry manner, and the lithium carbonate powder is obtained by heating the lithium carbonate.
- Lithium carbonate powder does not have hygroscopic properties such as lithium hydroxide, and the particle size can be adjusted, and the particle size can be particularly reduced. Have.
- the particle size of the lithium carbonate in the powder form By adjusting the particle size of the lithium carbonate powder as a raw material, the particle size of the obtained lithium sulfide (Li 2 S) can be adjusted. That is, by atomizing the lithium carbonate powder, it is possible to atomize the obtained lithium sulfide (Li 2 S). For example, if the average particle size of the lithium carbonate powder (D 50) of about 1 [mu] m, an average particle size of the lithium sulfide obtained by (D 50) can be about 1.5 [mu] m ⁇ 3 [mu] m.
- lithium sulfide (Li 2 S) can be achieved in this way, the reactivity of the solid electrolyte can be increased.
- the reactivity of lithium sulfide (Li 2 S) can be enhanced by setting the average particle diameter (D 50 ) of lithium sulfide (Li 2 S) to 20 ⁇ m or less.
- the average particle diameter (D 50 ) of lithium sulfide (Li 2 S) In order to obtain fine lithium sulfide having an average particle diameter (D 50 ) of 20 ⁇ m or less, lithium carbonate having an average particle diameter of 1/3 to 2/3 of the average particle diameter (D 50 ) of the target fine lithium sulfide is used. Lithium carbonate having an average particle diameter (D 50 ) of 2/5 to 3/5 is more preferably used.
- the use of the average particle size (D 50) lithium carbonate powder of 8 [mu] m ⁇ 12 [mu] m it is possible to average particle diameter of the lithium sulfide (D 50) and 20 ⁇ m or less, an average of lithium carbonate powder If the particle diameter (D 50 ) is 4 ⁇ m to 6 ⁇ m, the average particle diameter (D 50 ) of lithium sulfide can be 10 ⁇ m or less, and the average particle diameter (D 50 ) of the lithium carbonate powder is 0.8 ⁇ m to 1 ⁇ m. When the thickness is set to 2 ⁇ m, the average particle diameter (D 50 ) of lithium sulfide can be set to 2 ⁇ m or less.
- the S-containing gas examples include hydrogen sulfide gas (H 2 S), carbon disulfide gas (CS 2 ), and sulfur gas obtained by evaporating solid sulfur (S) to a boiling point or higher. Since lithium carbonate decomposes into lithium oxide (Li 2 O), when reacting with the S-containing gas, it is mixed with a reducing gas such as hydrogen (H) or carbon (C) together with the S-containing gas, Since lithium oxide (Li 2 O) is reduced, high-purity lithium sulfide containing no oxygen can be obtained.
- H 2 S hydrogen sulfide gas
- CS 2 carbon disulfide gas
- sulfur gas obtained by evaporating solid sulfur (S) to a boiling point or higher examples of the S-containing gas. Since lithium carbonate decomposes into lithium oxide (Li 2 O), when reacting with the S-containing gas, it is mixed with a reducing gas such as hydrogen (H) or carbon (C) together with the S-containing gas, Since lithium oxide (Li 2
- H 2 S hydrogen sulfide gas
- CS 2 carbon disulfide gas
- the reaction between the lithium carbonate and the S-containing gas is a dry reaction (solid-gas reaction). That is, it is a method in which solid lithium carbonate and gas are brought into contact with each other in a dry state without using a solvent such as water.
- the reaction formula is as follows when an H 2 S-containing gas is used as the S-containing gas. Li 2 CO 3 + H 2 S ⁇ Li 2 S + H 2 O ⁇ + CO 2 ⁇
- the reaction formula when CS 2 gas is used as the S-containing gas is as follows. Li 2 CO 3 + 1 / 2CS 2 ⁇ Li 2 S + 3 / 2CO 2 ⁇
- the lithium carbonate reacts with the S-containing gas while being decomposed.
- Lithium carbonate usually decomposes at 700 ° C. or higher, but S-containing gas, particularly CS 2 or H 2 S, contacts the lithium carbonate to promote the decomposition reaction and lower the decomposition temperature. It can be considered that decomposition occurs at 600 ° C. or higher.
- the melting point of lithium carbonate is 723 ° C. and dissolves at 800 ° C. or higher, the lithium carbonate powder is heated to a temperature range of 500 ° C. to 750 ° C., particularly 600 ° C. or higher, or 720 ° C. or lower. Is preferred.
- reaction products As an effective means for promoting the reaction, a method of increasing the surface area by reducing the particle size of lithium carbonate, or a method of sending out reaction products, that is, H 2 O and CO 2 out of the system in the above reaction formula Can be mentioned.
- the reaction apparatus may be a continuous type, a batch type or a fluid type.
- the concentration of the S-containing gas to be supplied is preferably 10 to 100 vol%.
- the concentration of the S-containing gas being 100 vol% means a gas composed only of the S-containing gas, that is, a pure gas. If it is less than 100 vol%, the S-containing gas and an inert gas such as Ar or nitrogen are used. This means a mixed gas with a reducing gas such as hydrogen.
- the concentration of the S-containing gas is 10 vol% or more, the contact reaction with lithium carbonate occurs sufficiently, lithium sulfide can be generated, and the remaining lithium carbonate can be prevented. Therefore, from this viewpoint, the S-containing gas concentration is more preferably 10 vol% to 100 vol%, and particularly preferably 50 vol% to 100 vol%.
- lithium sulfide (Li 2 S) can be produced by a dry method, and therefore can be produced more easily and at low cost.
- lithium carbonate as a Li raw material is neither ignitable nor hygroscopic, it is easy to handle, and by adjusting the particle size of the lithium carbonate powder, lithium sulfide (Li 2 S) particles obtained are obtained. The diameter can also be adjusted.
- lithium sulfide Li 2 S
- Li 2 S 5 lithium sulfide and diphosphorus pentasulfide
- Solid electrolytes such as Li 7 P 3 S 11 and Li 3 PS 4 can be produced.
- the time of the mechanical milling reaction can be shortened by using atomized lithium sulfide (Li 2 S) obtained by the present lithium sulfide production method.
- the target product phase can be produced at low temperature.
- Li 2 S lithium sulfide
- SiS 2 silicon sulfide
- GeS 2 germanium sulfide
- the “solid electrolyte” means any substance that can move ions such as Li + in the solid state.
- X to Y X and Y are arbitrary numbers
- it means “preferably greater than X” or “preferably greater than Y” with the meaning of “X to Y” unless otherwise specified.
- the meaning of “small” is also included.
- X or more” X is an arbitrary number
- Y or less Y is an arbitrary number
- S-containing gas H 2 S gas, concentration: 100 vol%
- S-containing gas H 2 S gas, concentration: 100 vol%
- Example 3 A sample (L 2 S) was obtained in the same manner as in Example 1 except that the heating and holding temperature in the electric furnace was 480 ° C. which was lower than the decomposition temperature of lithium carbonate.
- Example 4 A sample (L 2 S) was obtained in the same manner as in Example 1 except that the heating and holding temperature in the electric furnace was 800 ° C. which was higher than the melting point of lithium carbonate.
- Examples 5 to 7 A sample (L 2 S) was obtained in the same manner as in Example 1 except that the heating and holding temperature in the electric furnace was changed to the temperature shown in Table 1.
- Example 8 Except for changing the S-containing gas in the electric furnace to a mixed gas of S-containing gas (H 2 S gas) and inert gas (Ar gas) (H 2 S gas concentration 90 vol%, Ar gas concentration 10 vol%) In the same manner as in Example 2, a sample (L 2 S) was obtained.
- H 2 S gas S-containing gas
- Ar gas inert gas
- Example 9 The S-containing gas in the electric furnace was changed to a mixed gas of S-containing gas (H 2 S gas) and reducing gas (H 2 gas) (H 2 S gas concentration 90 vol%, H 2 gas concentration 10 vol%).
- a sample (L 2 S) was obtained in the same manner as in Example 2 except for the above.
- Example 1 In Examples 1, 2 and Examples 4 to 9, only the peak attributed to lithium sulfide (Li 2 S) was confirmed, and the resulting lithium sulfide powder was a single phase of lithium sulfide. I found out. On the other hand, in Example 3, an unreacted lithium carbonate peak was also confirmed in addition to the lithium sulfide peak. It was also found that the Li / S molar ratio of the obtained lithium sulfide was almost stoichiometric in Examples 1 and 2 and Examples 4 to 9. Moreover, regarding purity, it was confirmed that in Examples 1, 2, 4, 7, 8, and 9, it was 99% or more.
- the carbon concentration indicating the amount of unreacted lithium carbonate was less than 1,500 ppm, and it was confirmed that there was almost no remaining.
- Example 3 it became Li excess composition, and it was confirmed that reaction with hydrogen sulfide is still incomplete.
- the carbon concentration was as very high as 8,400 ppm, and it was confirmed that a large amount of unreacted lithium carbonate remained as shown in the X-ray diffraction measurement result.
- the average particle size (D50) of the lithium carbonate powder is set to 5 ⁇ m or less
- the average particle size (D 50 ) of lithium sulfide can be set to 10 ⁇ m or less.
- Example 4 if the heating is performed at a temperature equal to or higher than the temperature at which lithium carbonate melts as in Example 4, the resulting lithium sulfide particles become coarse, and the particle size cannot be adjusted. Therefore, it was found that it is preferable to heat to a temperature region where lithium carbonate does not melt.
- the lithium carbonate powder it is preferable to heat the lithium carbonate powder to a temperature range above the temperature at which lithium carbonate decomposes and at which lithium carbonate does not melt. Specifically, it has been found that heating is preferably performed in a temperature range of 500 ° C. to 750 ° C., particularly 600 ° C. or higher, or 720 ° C. or lower.
- Li 2 S lithium sulfide
- the reaction product was subjected to heat treatment at 300 ° C. for 1 hour in a glove box.
- the reaction product after the heat treatment is uniaxially pressed in a glove box at a pressure of 200 MPa to produce a pellet.
- a carbon paste as an electrode is applied to both the upper and lower surfaces of the pellet, and then 30 ° C. at 180 ° C.
- a fractional heat treatment was performed to prepare a sample for measuring ionic conductivity.
- the ionic conductivity was measured by the AC impedance method.
- the ionic conductivity of the produced reactant was 9.8 ⁇ 10 ⁇ 4 S / cm at room temperature.
- Example 2 The sample (Li 2 S) obtained in Example 2 was mechanically milled for 8 hours, 16 hours, or 24 hours in the same manner as described above to obtain a reaction product (white yellow powder).
- a peak of lithium sulfide (Li 2 S) as a raw material was slightly observed in a sample subjected to mechanical milling for 8 hours, but the sample treated for 16 and 24 hours. Then, lithium sulfide (Li 2 S) and other peaks were not confirmed, and it was confirmed that the obtained sample was in an amorphous state.
- lithium sulfide (Li 2 S) can be produced more easily and at low cost, and excellent performance as a solid electrolyte of a lithium ion battery can be obtained. It was found that the particle size of lithium sulfide (Li 2 S) as a raw material can be adjusted so that it can be exhibited.
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Abstract
Description
ところが、このように電解質として、可燃性の有機溶剤を溶媒とする有機電解液が使用されているため、揮発や漏出を防ぐための構造・材料面での改善が必要であったほか、短絡時の温度上昇を抑える安全装置の取り付けや短絡防止のための構造・材料面での改善も必要であった。
これに対し、硫化リチウム(Li2S)などを原料として用いた固体電解質を用いて、電池を全固体化してなる全固体型リチウム電池は、電池内に可燃性の有機溶媒を用いないので、安全装置の簡素化を図ることができ、製造コストや生産性に優れたものとすることができる。
この種の硫化リチウムの製造方法としては、従来、例えば1)不活性ガス雰囲気あるいは真空下で、硫酸リチウムを庶糖、澱粉などの有機物で加熱還元する方法や、2)不活性ガス雰囲気あるいは真空下で、硫酸リチウムをカーボンブラックや黒鉛粉末で加熱還元する方法、3)硫化水素リチウムエタノール化物を水素気流中で加熱分解する方法、4)金属リチウムと硫化水素や硫黄蒸気とを常圧や加圧下で加熱し直接反応させる方法などが知られている。
しかし、乾式法においては、従来提案されていたようにLi原料として水酸化リチウムを用いた場合、水酸化リチウムは吸湿性が高いため、凝集し易くて取り扱いが難しいばかりか、得られる硫化リチウム(Li2S)の微粉化を図ることが難しいという課題を抱えていた。
本実施形態に係る硫化リチウム(Li2S)の製造方法(以下「本硫化リチウム製法」と称する)は、炭酸リチウム粉末と、硫黄(S)を含有するガス(「S含有ガス」と称する)とを乾式にて接触させると共に、前記炭酸リチウムを加熱することにより、硫化リチウム粉末を得ることを特徴とする方法である。
炭酸リチウム粉末は、水酸化リチウムなどのような吸湿性がなく、粒径を調整することができ、特に粒径を小さくすることができるなど、他のリチウム塩の粉末に比べて有利な特徴を有している。
このように硫化リチウム(Li2S)の微粒化を図ることができれば、固体電解質の反応性を高めることができる。特に硫化リチウム(Li2S)の平均粒径(D50)を20μm以下とすることにより、硫化リチウム(Li2S)の反応性を高めることができる。
平均粒径(D50)が20μm以下の微粒硫化リチウムを得るためには、目的とする微粒硫化リチウムの平均粒径(D50)の1/3~2/3の平均粒径の炭酸リチウムを用いればよく、より好ましくは2/5~3/5の平均粒径(D50)の炭酸リチウムを用いるのがよい。より具体的には、例えば平均粒径(D50)が8μm~12μmの炭酸リチウム粉末を用いれば、硫化リチウムの平均粒径(D50)を20μm以下とすることができ、炭酸リチウム粉末の平均粒径(D50)を4μm~6μmとすれば、硫化リチウムの平均粒径(D50)を10μm以下とすることができ、炭酸リチウム粉末の平均粒径(D50)を0.8μm~1.2μmとすれば、硫化リチウムの平均粒径(D50)を2μm以下とすることができる。
なお、炭酸リチウムは分解すると酸化リチウム(Li2O)となるため、S含有ガスと反応させる場合、S含有ガスとともに水素(H)や炭素(C)などの還元性ガスと混合させることで、酸化リチウム(Li2O)が還元するため、酸素を含まない高純度な硫化リチウムを得ることができる。他方、S含有ガスとして硫化水素ガス(H2S)や二硫化炭素ガス(CS2)を用いる場合は、ガス成分として水素(H)や炭素(C)を含むため、酸素を含まない高純度な硫化リチウムを製造するにはより一層好ましい。
炭酸リチウムとS含有ガスとの反応は乾式反応(固気反応)である。つまり、水等の溶媒を用いることなく、固体の炭酸リチウムとガスとを乾式状態で接触させて反応させる方法である。
Li2CO3+H2S →Li2S+H2O↑+CO2↑
また、S含有ガスとしてCS2ガスを用いた場合の反応式は、次のようになる。
Li2CO3+1/2CS2 →Li2S+3/2CO2↑
炭酸リチウムは通常700℃以上で分解するが、S含有ガス、特にCS2やH2Sが炭酸リチウムと接触することで分解反応を促進して分解温度を低下させるため、500℃以上、好ましくは600℃以上であれば分解すると考えることができる。
他方、炭酸リチウムの融点は723℃であり、800℃以上では溶解してしまうため、炭酸リチウム粉末の加熱は、500℃~750℃、特に600℃以上、或いは720℃以下の温度領域に加熱するのが好ましい。
本硫化リチウム製法によれば、乾式方法で硫化リチウム(Li2S)を製造することができるため、より容易かつ低コストで製造することができる。しかも、Li原料としての炭酸リチウムは、発火性も吸湿性もないため、取り扱いが容易であるばかりか、炭酸リチウム粉末の粒径を調整することによって、得られる硫化リチウム(Li2S)の粒径を調整することもできる。特に、炭酸リチウム粉末の粒径を微粒化することで硫化リチウム(Li2S)を微粒化することができ、微粒化した反応性が高い微粒硫化リチウム(Li2S)を製造することができ、このような微粒硫化リチウム(Li2S)を用いることにより、リチウムイオン電池の硫化物系固体電解質の作製をより一層容易とすることができる。
本発明において「固体電解質」とは、固体状態のままイオン、例えばLi+が移動し得る物質全般を意味する。
本発明において「X~Y」(X、Yは任意の数字)と記載した場合、特にことわらない限り「X以上Y以下」の意と共に、「好ましくはXより大きい」或いは「好ましくはYより小さい」の意も包含する。
また、「X以上」(Xは任意の数字)或いは「Y以下」(Yは任意の数字)と記載した場合、「Xより大きいことが好ましい」或いは「Yより小さいことが好ましい」旨の意図を包含する。
炭酸リチウム及び硫化リチウムの粒度分布は、500~5,000倍のFE-SEM画像を用い、画像解析式粒度分布測定ソフトウェア(マウンテック社、Mac-View、Ver.4)を用いた。粒度分布を測定するために用いた粒子数は約1,000個程度であり、ソフトウェアの解析処理により得られたHeywood径(投影面積円相当径)を採用し、この解析結果より体積基準による平均粒径(D50)及びD90を求めた。
アルミナボート内に炭酸リチウム粉末(D50=4.1μm、D90=8.4μm)2gを充填し、ガス置換が可能な管状炉内に前記アルミナボートを装填した。そして、電気炉内を、S含有ガス(H2Sガス、濃度100vol%)で完全に置換させた後、電気炉の温度を加熱して700℃、4時間を保持し、その後、自然冷却して電気炉内から試料(L2S)を取り出した。
実施例1で用いた炭酸リチウム粉末を、ビーズミルで粉砕処理を行なって微粒化した炭酸リチウム粉末(D50=0.9μm、D90=2.2μm)2gを、アルミナボート内に充填し、ガス置換が可能な管状炉内に前記アルミナボートを装填した。そして、電気炉内を、S含有ガス(H2Sガス、濃度100vol%)で完全に置換させた後、電気炉の温度を加熱して700℃、4時間を保持し、その後、自然冷却して電気炉内から試料(L2S)を取り出した。
電気炉内加熱保持温度を、炭酸リチウムの分解温度よりも低い480℃とした以外は、実施例1と同様に行って試料(L2S)を得た。
電気炉内加熱保持温度を、炭酸リチウムの融点よりも高い800℃とした以外は、実施例1と同様に行って試料(L2S)を得た。
電気炉内加熱保持温度を、表1に示した温度とした以外は、実施例1と同様に行って試料(L2S)を得た。
電気炉内のS含有ガスを、S含有ガス(H2Sガス)と不活性ガス(Arガス)との混合ガス(H2Sガス濃度90vol%、Arガス濃度10vol%)に変更した以外は、実施例2と同様に行って試料(L2S)を得た。
電気炉内のS含有ガスを、S含有ガス(H2Sガス)と還元性ガス(H2ガス)との混合ガス(H2Sガス濃度90vol%、H2ガス濃度10vol%)に変更した以外は、実施例2と同様に行って試料(L2S)を得た。
また、得られた硫化リチウムのLi/Sモル比は、実施例1、2及び実施例4~9では、ほぼ化学量論組成となっていることが分かった。また、純度に関しても、実施例1、2、4、7、8及び9では99%以上であることが確認された。更にこれらの実施例では、未反応の炭酸リチウム量を示す炭素濃度は1,500ppm未満となっており、ほとんど残存していないことが確認された。
その一方、実施例3では、Li過剰組成となっており、硫化水素との反応がまだ不完全であることが確認された。また炭素濃度も8,400ppmと非常に高く、X線回折測定結果でも示したように未反応の炭酸リチウムが多く残存していることが確認された。
実施例1で得た試料(Li2S)1.63gと、P2S5(アルドリッチ社製)3.37gとを、φ5mmのジルコニアボール90gとともに、約80mlのジルコニア製容器に入れ、上蓋と容器との間に真空グリースを塗布した後、密閉した。この際、上記計量、密閉作業は全て、十分に乾燥されたArガス(露点-60℃以上)で置換されたグローブボックス内で実施した。
またさらに、上記加熱処理後の反応物をグローブボックス内で200MPaの圧力にて一軸加圧成形してペレットを作製し、更にペレット上下両面に電極としてのカーボンペーストを塗布した後、180℃で30分熱処理を行い、イオン導電率測定用サンプルを作製した。イオン導電率測定は交流インピーダンス法にて行った。その結果、作製した反応物のイオン導電率は室温で、9.8×10-4S/cmであった。
この反応生成物のX線回折測定を行なった結果、メカニカルミリング処理8時間の試料では、原料である硫化リチウム(Li2S)のピークが僅かに観測されたが、16及び24時間処理した試料では、硫化リチウム(Li2S)やその他のピークは確認されず、得られた試料はアモルファス状態になっていることが確認された。
Claims (6)
- リチウムイオン電池の固体電解質材料として用いるリチウムイオン電池固体電解質材料用硫化リチウム(Li2S)の製造方法であって、炭酸リチウム粉末と、硫黄(S)を含有するガスとを乾式にて接触させると共に、前記炭酸リチウムを加熱することにより、硫化リチウム粉末を得ることを特徴とするリチウムイオン電池固体電解質材料用硫化リチウム(Li2S)の製造方法。
- 炭酸リチウム粉末の加熱は、炭酸リチウムが分解する温度以上で、かつ、炭酸リチウムが溶融しない温度領域に加熱することを特徴とする請求項1記載の硫化リチウム(Li2S)の製造方法。
- 請求項1又は2に記載の硫化リチウム(Li2S)の製造方法において、炭酸リチウム粉末の粒径を小さくすることにより、得られる硫化リチウム粉末の粒径を小さくすることを特徴とする微粒硫化リチウム(Li2S)の製造方法。
- 請求項1~3の何れかに記載された硫化リチウム(Li2S)の製造方法によって製造されたリチウムイオン電池固体電解質材料用硫化リチウム。
- 請求項4に記載された硫化リチウムを用いてなるリチウムイオン電池用固体電解質。
- 請求項5に記載された固体電解質を備えたリチウムイオン電池。
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US14/110,800 US20140037535A1 (en) | 2011-04-12 | 2012-04-11 | Method for Producing Lithium Sulfide for Lithium Ion Cell Solid Electrolyte Material |
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