WO2013099834A1 - Electrolyte solide de type sulfure - Google Patents

Electrolyte solide de type sulfure Download PDF

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Publication number
WO2013099834A1
WO2013099834A1 PCT/JP2012/083397 JP2012083397W WO2013099834A1 WO 2013099834 A1 WO2013099834 A1 WO 2013099834A1 JP 2012083397 W JP2012083397 W JP 2012083397W WO 2013099834 A1 WO2013099834 A1 WO 2013099834A1
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Prior art keywords
sulfide
solid electrolyte
lithium
powder
battery
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PCT/JP2012/083397
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English (en)
Japanese (ja)
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宮下　徳彦
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三井金属鉱業株式会社
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • 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
    • H01B1/10—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances 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
    • H01M10/056—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
    • 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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/002—Inorganic electrolyte
    • 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

Definitions

  • the present invention relates to a sulfide-based solid electrolyte 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), a hybrid electric vehicle (HEV), etc.
  • 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.
  • an organic electrolyte using a flammable organic solvent as a solvent is used as the electrolyte, it was necessary to improve the structure and materials to prevent volatilization and leakage. 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) or the like as a starting material does not use a flammable organic solvent.
  • Li 2 S lithium sulfide
  • this type of solid electrolyte does not move except for Li ions, it is expected that side reactions due to the movement of anions will not occur, leading to improvements in safety and durability.
  • Solid electrolytes used in such batteries are required to have as high conductivity as possible and to be electrochemically stable.
  • lithium halide, lithium nitride, lithium oxyacid salt, or derivatives thereof are used.
  • Patent Document 2 as a material which is crystalline and has a very high ionic conductivity of 6.49 ⁇ 10 ⁇ 5 Scm ⁇ 1 at room temperature, the general formula Li 2 S—GeS 2 is used.
  • a sulfide-based solid electrolyte characterized by containing a lithium ion conductive material as a composite compound represented by —X (where X represents at least one of Ga 2 S 3 and ZnS). ing.
  • the present invention is to provide a new sulfide-based solid electrolyte that can remarkably increase the electrical conductivity as compared with conventional sulfide-based solid electrolytes and can further improve battery characteristics in all-solid-state lithium batteries. It is.
  • the present invention has a composition formula having a structural skeleton of Li 7 PS 6 and substituting part of P with Si: Li 7 + x P 1-y Si y S 6 (where x is ⁇ 0.6 to 0 .6, y is proposed to be a sulfide-based solid electrolyte containing 0.1 to 0.6).
  • the sulfide-based solid electrolyte proposed by the present invention can significantly increase the electrical conductivity as compared to conventional sulfide-based solid electrolytes, and is an all solid produced using the sulfide-based solid electrolyte proposed by the present invention. Battery characteristics in the lithium battery can be further enhanced.
  • the sulfide-based solid electrolyte (referred to as “the present solid electrolyte”) according to the present embodiment has a Li 7 PS 6 structural skeleton, and a part of P is replaced by Si.
  • x is preferably ⁇ 0.6 to 0.6, and in particular, x is ⁇ 0.4 or more and 0.4 or less, and among these, x is It is particularly preferably 0.0 or more or 0.4 or less. Further, y is preferably 0.1 to 0.6, more preferably 0.2 or more and 0.5 or less, and particularly preferably 0.3 or more and 0.4 or less.
  • a sulfide-based solid electrolyte is excellent in ionic conductivity, can easily form an interface with an active material at room temperature, and can reduce interface resistance compared to an oxide.
  • this solid electrolyte is remarkably excellent in electrical conductivity at room temperature.
  • the solid electrolyte in the above composition formula: Li 7 + x P 1-y Si y S 6 , when x is ⁇ 0.6 to 0.6 and y is 0.1 to 0.6, the solid electrolyte The conductivity at room temperature is from the latter half of the 10 ⁇ 4 S / cm level to the 10 ⁇ 3 S / cm level, and an extremely high conductivity can be obtained.
  • the skeleton structure of Li 7 PS 6 has two crystal structures of an orthorhombic crystal and a high cubic crystal having low ion conductivity, a phase transition point around 170 ° C., and a crystal structure around room temperature. Is an orthorhombic crystal with low ion conductivity. Therefore, as shown in Patent Document 3, in order to obtain a cubic crystal having high ion conductivity, usually, a rapid cooling treatment is required after heating once to a phase transition point or higher.
  • the composition formula: Li 7 + x P 1-y Si y S 6 when x is ⁇ 0.6 to 0.6 and y is 0.1 to 0.6, the temperature is higher than room temperature. Therefore, the crystal structure can maintain a cubic system with high ion conductivity even at room temperature, so that high electrical conductivity can be secured without treatment such as rapid cooling. Particularly preferred in this respect.
  • the raw material composition was adjusted so that x was ⁇ 0.4 to 0.4 and y was 0.2 to 0.5.
  • the Li 7 PS 6 structure which is the skeleton of Li 7 + x P 1-y Si y S 6 , is likely to be generated, and the resulting product phase does not contain or contains unreacted lithium sulfide. Is also preferable because it is possible to secure higher conductivity.
  • the present solid electrolyte does not substantially contain a phase composed of lithium sulfide.
  • substantially free of a phase composed of lithium sulfide means that the peak intensity of lithium sulfide is less than 3% of the peak intensity of Li 7 + x P 1-y Si y S 6 in the XRD chart. That means.
  • this solid electrolyte is composed of a single phase of the composition formula: Li 7 + x P 1-y Si y S 6 (where x is ⁇ 0.0 to 0.4, y is 0.3 to 0.4). Particularly preferred are those which do not contain a phase comprising lithium sulfide.
  • the amount of S contained in the crystal structure is preferably 95 at% or more of the theoretical amount calculated from the stoichiometric composition, more preferably 97 at% or more, and more preferably 99 at% or more.
  • the amount of S contained in the crystal structure is preferably 95 at% or more of the theoretical amount calculated from the stoichiometric composition, as described later, lithium sulfide (Li 2 S) powder and phosphorus sulfide (P 2 S 5 It is preferable to mix the powder with silicon sulfide (SiS 2 ) powder and fire at 600 to 700 ° C. in an atmosphere containing hydrogen sulfide gas.
  • This solid electrolyte is obtained by weighing and mixing, for example, lithium sulfide (Li 2 S) powder, phosphorus sulfide (P 2 S 5 ) powder, and silicon sulfide (SiS 2 ) powder, and pulverizing them with a ball mill, bead mill, homogenizer, or the like. It can be obtained by drying as necessary, then calcining under the flow of hydrogen sulfide gas (H 2 S), crushing or pulverizing as necessary, and classifying as necessary. At this time, the raw material and the fired product are extremely unstable in the atmosphere, decompose by reacting with moisture, generate hydrogen sulfide gas, and oxidize. Therefore, through a glove box or the like replaced with an inert gas atmosphere It is preferable to perform a series of operations for setting the raw material in the furnace and taking out the fired product from the furnace.
  • Li 2 S lithium sulfide
  • P 2 S 5 phosphorus sulfide
  • SiS 2 silicon
  • the present solid electrolyte can be obtained without losing S in the sulfide.
  • H 2 S hydrogen sulfide gas
  • the temperature of the sulfide material rises S is easily lost and S deficiency is likely to occur, so that conventionally, the sulfide material was enclosed in a quartz sample or the like and fired.
  • by firing at 600 ° C. or higher under the flow of hydrogen sulfide gas (H 2 S) the S partial pressure in the firing atmosphere increases, so there is almost no S deficiency and the sulfide has almost stoichiometric composition.
  • This solid electrolyte can be produced.
  • the firing temperature is 600 ° C. or higher, and particularly preferably 650 ° C. or higher or 700 ° C. or lower.
  • H 2 S hydrogen sulfide gas
  • the amount of S contained in the crystal structure becomes 95 at% or more of the theoretical amount calculated from the stoichiometric composition, and S defects in the crystal structure can be reduced. And stable with time. Therefore, if an all-solid-state lithium ion battery is produced using the present solid electrolyte, cycle characteristics that are battery characteristics can be improved.
  • the exhaust gas is completely burned with a burner or the like, then neutralized with a sodium hydroxide solution and treated as sodium sulfide or the like.
  • the present solid electrolyte can be used as a solid electrolyte layer of an all-solid lithium secondary battery or an all-solid lithium primary battery, a solid electrolyte mixed in a positive electrode / negative electrode mixture, or the like.
  • an all-solid lithium secondary battery can be formed by forming a layer made of the above solid electrolyte between the positive electrode, the negative electrode, and the positive electrode and the negative electrode.
  • the layer made of the solid electrolyte is prepared by, for example, dropping a slurry made of the solid electrolyte, a binder and a solvent onto the substrate and scrubbing with a doctor blade, etc., cutting with an air knife after contacting the slurry, screen printing, etc. can do.
  • a powder compact of a solid electrolyte by pressing or the like and then process it appropriately.
  • the positive electrode material a positive electrode material used as a positive electrode active material of a lithium ion battery can be used as appropriate.
  • the negative electrode material a positive electrode material used as a positive electrode active material of a lithium ion battery can be used as appropriate.
  • 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,” with the meaning of “X to Y” unless otherwise specified.
  • the meaning of “smaller than Y” is also included.
  • X or more X is an arbitrary number
  • Y or less Y is an arbitrary number
  • Example 1 Lithium sulfide (Li 2 S) powder (3.03 g), phosphorus sulfide (P 2 S 5 ) powder (1.63 g), and silicon sulfide (SiS 2 ) powder (0.34 g) are mixed so that the composition formula shown in Table 1 is obtained. Each was weighed and mixed, and pulverized with a ball mill for 12 hours to prepare a mixed powder. The mixed powder is filled in a carbon container, and this is heated at a temperature rising / lowering rate of 300 ° C./h while flowing 1.0 L / min of hydrogen sulfide gas (H 2 S, purity 100%) in a tubular electric furnace. Baked at 600 ° C. for 4 hours.
  • H 2 S hydrogen sulfide gas
  • the sample was crushed in a mortar and sized with a sieve having an opening of 53 ⁇ m to obtain a powdery sample.
  • the above weighing, mixing, setting in the electric furnace, taking out from the electric furnace, crushing and sizing operations are all carried out in the glove box replaced with sufficiently dried Ar gas (dew point -60 ° C or higher). It carried out in.
  • Example 2-16 A sample was prepared in the same manner as in Example 1 except that the blending amount of each raw material was changed so that the composition formula shown in Table 1 was obtained, and the firing temperature was changed to the temperature shown in Table 1.
  • Example 1-14 A sample was prepared in the same manner as in Example 1 except that the blending amount of each raw material was changed so that the composition formula shown in Table 1 was obtained, and the firing temperature was changed to the temperature shown in Table 1.
  • Li 2 S trace amount
  • Li 2 S trace amount
  • the peak intensity of Li 2 S is c-Li 7 PS 6 peak. This is the case when the strength is less than 3%.
  • the amount of S was calculated only when the peak of lithium sulfide was not detected and only the peak of Li 7 + x P 1-y Si y S 6 was detected in the XRD measurement.
  • C-Li 7 PS 6 has a cubic crystal structure
  • o-Li 7 PS 6 has an orthorhombic crystal structure.
  • the samples of Examples 1 to 16 are Li 7 PS 6 having a cubic crystal structure as a main product phase, and no unreacted Li 2 S remains, or It was found that only a few remained. Further, the amount of S contained in Li 7 PS 6 was also 96 at% or more. Even when Li 2 S remains slightly, the amount of S contained in Li 7 PS 6 is considered to be 95 at% or more. The conductivity was 10 -4 S / cm or more for all samples, which was a very high value.
  • As the positive electrode 3.5 g of LiNi 1/3 Co 1/3 Mn 1/3 O 2 which is a ternary layered compound as an active material, samples obtained in Examples and Comparative Examples shown in Table 2 (“Example Sample”) ) was weighed and mixed, and pulverized with a ball mill for 12 hours to prepare a positive electrode mixed powder.
  • Example Sample 3.5 g of artificial graphite and 1.5 g of the example sample were weighed and mixed, and pulverized with a ball mill for 12 hours to prepare a negative electrode mixed powder.
  • the pellet type all solid state battery element having a diameter of 14 mm and a thickness of about 1 mm was obtained by uniaxial pressure molding at a pressure of 200 MPa. Connect lead wires to the upper surfaces of the positive and negative electrode layers of the all-solid-state battery element produced above, cover the lead wires that are not in contact with the positive and negative electrode layers with an insulating tape, and then insert the lead wires into an aluminum laminate bag. An all-solid battery was produced by sealing the top of the aluminum laminate bag so that it protrudes from the aluminum laminate bag.
  • the all solid state battery thus obtained is placed in an environmental test machine maintained at 25 ° C., the lead wire is connected to a charge / discharge measuring device, and the upper limit voltage is 4.3 V with a constant current of 0.1 mA.
  • a charge / discharge cycle for discharging to 2.0 V was performed 50 times.
  • the discharge capacity obtained in the first cycle was calculated as the initial discharge capacity, and the ratio of the discharge capacity after 50 cycles to the initial discharge capacity was evaluated as the cycle characteristics.
  • the sulfide-based solid electrolyte by firing in a hydrogen sulfide atmosphere, the amount of S contained in the crystal structure becomes 95 at% or more of the theoretical amount calculated from the stoichiometric composition, Since there are few S defects, it becomes chemically stable and changes with time are small. Therefore, in the all-solid-state lithium ion battery produced using this solid electrolyte, it is thought that the first time discharge capacity and cycling characteristics which are battery characteristics become favorable.

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Abstract

La présente invention concerne un nouvel électrolyte solide de type sulfure dont la conductivité électrique peut être significativement améliorée par rapport à celles des électrolytes solides classiques. L'invention décrit un électrolyte solide de type sulfure ayant comme formule compositionnelle : Li7+xP1-ySiyS6 (où x vaut de -0,6 à 0,6 et y vaut de 0,1 à 0,6) qui a comme squelette développé Li7PS6 et dans lequel certains des P sont remplacés par Si.
PCT/JP2012/083397 2011-12-28 2012-12-25 Electrolyte solide de type sulfure WO2013099834A1 (fr)

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JP2011-287353 2011-12-28
JP2011287353A JP5701741B2 (ja) 2011-12-28 2011-12-28 硫化物系固体電解質

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WO2016009768A1 (fr) * 2014-07-16 2016-01-21 三井金属鉱業株式会社 Électrolyte solide à base de sulfure pour batteries au lithium-ion
JP2019220487A (ja) * 2019-09-25 2019-12-26 古河機械金属株式会社 固体電解質材料、リチウムイオン電池および固体電解質材料の製造方法
US10879558B2 (en) 2015-12-22 2020-12-29 Toyota Motor Europe Materials for solid electrolyte
WO2021049665A1 (fr) 2019-09-13 2021-03-18 三井金属鉱業株式会社 Mélange d'électrode, et couche d'électrode et batterie à semi-conducteurs comprenant ledit mélange
US11114691B2 (en) * 2018-08-10 2021-09-07 Samsung Electronics Co., Ltd. Sulfide-based solid electrolyte for lithium battery, method of preparing the same, and lithium battery including the sulfide-based solid electrolyte
WO2021192966A1 (fr) 2020-03-24 2021-09-30 三井金属鉱業株式会社 Matériau actif, mélange d'électrode contenant ledit matériau actif, et batterie
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WO2022045302A1 (fr) 2020-08-28 2022-03-03 三井金属鉱業株式会社 Matériau actif, sa méthode de production, mélange d'électrode et batterie
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CN114551992A (zh) * 2022-03-17 2022-05-27 蜂巢能源科技(无锡)有限公司 一种硫化物固态电解质及其制备方法和应用
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JP6044588B2 (ja) 2014-05-15 2016-12-14 トヨタ自動車株式会社 硫化物固体電解質材料、電池および硫化物固体電解質材料の製造方法
EP3240089B1 (fr) 2014-12-26 2019-04-24 Mitsui Mining and Smelting Co., Ltd. Electrolyte solide a base de sulfure pour pile au lithium-ion, et compose electrolytique solide
JP6222134B2 (ja) 2015-02-25 2017-11-01 トヨタ自動車株式会社 硫化物固体電解質材料、電池および硫化物固体電解質材料の製造方法
WO2017091341A1 (fr) * 2015-11-24 2017-06-01 Sion Power Corporation Composés à conduction ionique et utilisations associées
KR20190040195A (ko) * 2016-08-23 2019-04-17 고쿠리츠다이가쿠호진 토쿄고교 다이가꾸 황화물 고체전해질
JP6686860B2 (ja) 2016-12-09 2020-04-22 トヨタ自動車株式会社 硫化物固体電解質の製造方法
CN108238616A (zh) * 2016-12-23 2018-07-03 华中科技大学 一种立方相硫化物及其制备方法
EP3407412B1 (fr) * 2017-05-24 2021-04-14 Basf Se Composés ioniquement conducteur et utilisations associées
CN110785885B (zh) 2017-05-24 2023-10-24 锡安能量公司 离子传导化合物和相关用途
JP6595152B2 (ja) 2017-07-07 2019-10-23 三井金属鉱業株式会社 リチウム二次電池の固体電解質及び当該固体電解質用硫化物系化合物
JP6961794B2 (ja) * 2017-08-04 2021-11-05 トヨタ・モーター・ヨーロッパToyota Motor Europe 全固体電池用の電極の製造方法
JP6738983B1 (ja) 2018-11-08 2020-08-12 三井金属鉱業株式会社 硫化物固体電解質及び電池
WO2020095937A1 (fr) 2018-11-08 2020-05-14 三井金属鉱業株式会社 Composé contenant du soufre, électrolyte solide, et batterie
TWI829873B (zh) * 2020-02-24 2024-01-21 日商三井金屬鑛業股份有限公司 硫化物固體電解質及電池

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EP3957600A4 (fr) * 2019-04-19 2022-06-15 Mitsui Mining & Smelting Co., Ltd. Procédé de fabrication d'électrolyte solide au sulfure
CN113631507A (zh) * 2019-04-19 2021-11-09 三井金属矿业株式会社 硫化物固体电解质的制造方法
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WO2021192966A1 (fr) 2020-03-24 2021-09-30 三井金属鉱業株式会社 Matériau actif, mélange d'électrode contenant ledit matériau actif, et batterie
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