WO2015001818A1 - 結晶性固体電解質及びその製造方法 - Google Patents
結晶性固体電解質及びその製造方法 Download PDFInfo
- Publication number
- WO2015001818A1 WO2015001818A1 PCT/JP2014/055136 JP2014055136W WO2015001818A1 WO 2015001818 A1 WO2015001818 A1 WO 2015001818A1 JP 2014055136 W JP2014055136 W JP 2014055136W WO 2015001818 A1 WO2015001818 A1 WO 2015001818A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- solid electrolyte
- crystalline solid
- mass
- content
- conductivity
- Prior art date
Links
Images
Classifications
-
- 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
-
- 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
- C01B17/20—Methods for preparing sulfides or polysulfides, in general
-
- 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
-
- 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
- H01M10/052—Li-accumulators
-
- 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
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
-
- 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
-
- 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
- H01M2300/008—Halides
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
-
- 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 crystalline solid electrolyte that can be suitably used as a solid electrolyte of a lithium secondary battery and a method for producing the same.
- the lithium secondary battery is a secondary battery having a structure in which lithium is melted as ions from the positive electrode during charging and transferred to the negative electrode and stored, and reversely, lithium ions are returned from the negative electrode to the positive electrode during discharging. Because of its long life, it is widely used as a power source for household appliances such as video cameras, portable electronic devices such as notebook computers and mobile phones, and power tools such as power tools. Recently, lithium secondary batteries have been applied to large batteries mounted on electric vehicles (EV), hybrid electric vehicles (HEV), and the like.
- EV electric vehicles
- HEV hybrid electric vehicles
- This type of lithium secondary 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 non-aqueous system.
- the one filled with the electrolytic solution 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 secondary battery obtained by solidifying the entire battery using a solid electrolyte does not use a flammable organic solvent, so that the safety device can be simplified and the manufacturing cost can be reduced. And excellent productivity. Furthermore, it has a feature that a high voltage can be achieved by stacking in series in the cell. In addition, since this type of solid electrolyte does not move except for Li ions, it is expected that the side reaction due to the movement of anions does not occur, leading to improvement in safety and durability.
- a sulfide-based solid electrolyte containing a crystal phase such as Li 7 PS 6 , Li 4 P 2 S 6 , Li 3 PS 4 is disclosed as a solid electrolyte exhibiting high lithium ion conductivity.
- a crystal phase such as Li 7 PS 6 , Li 4 P 2 S 6 , Li 3 PS 4 is disclosed as a solid electrolyte exhibiting high lithium ion conductivity.
- a crystalline solid electrolyte containing a crystal phase of Li 3 PS 4 is a material that is particularly attracting attention because it is chemically stable and has high electrical conductivity.
- a solid electrolyte with high crystallinity referred to as “crystalline solid electrolyte”.
- the solid electrolyte and a dispersion medium composed of an organic solvent are mixed and pulverized to form a slurry, and the obtained slurry is applied onto a substrate.
- a solid electrolyte layer forming coating film is formed and dried to form a solid electrolyte layer.
- the dispersion medium that can be used when preparing the slurry has been limited to nonpolar solvents such as toluene and heptane.
- Patent Document 3 discloses that as a solvent other than a nonpolar solvent, tertiary amine; ether; thiol; a functional group having 3 or more carbon atoms bonded to a carbon atom of an ester group and carbon bonded to an oxygen atom of the ester group.
- An ester having a functional group of 4 or more; and a dispersion medium composed of at least one ester having a benzene ring bonded to a carbon atom of the ester group is also used as a solvent for dispersing the sulfide solid electrolyte (dispersion medium). It can be used as.
- JP 2002-109955 A WO2011 / 118801 gazette JP 2012-212552 A
- a solvent that can be used as a dispersion medium when slurrying the sulfide solid electrolyte includes the solvent disclosed in Patent Document 3, It was limited to nonpolar or low polarity solvents such as toluene, heptane, triethylamine, tertiary amine, ether, and thiol. In addition, it has been found by the inventor's research that the sulfide-based solid electrolyte has high reactivity with a solvent, so that the conductivity decreases when dissolved in a solvent to form a paste.
- the present invention provides a dispersion medium for slurrying a polar solvent such as N-methyl-2-pyrrolidone (NMP), acetone, N, N-dimethylformamide (DMF), which is easy to use for slurrying. It is intended to provide a new crystalline solid electrolyte that can be used and that can suppress a decrease in conductivity when immersed in these solvents, and a method for producing the same.
- NMP N-methyl-2-pyrrolidone
- DMF N-dimethylformamide
- the present invention is a composition formula: Li x Si y P z S a Ha w (where, Ha is Br, Cl, .2.4 containing at least either one or two of the I and F ⁇ (x-y) /(Y+z) ⁇ 3.3), the S content is 55 to 73 mass%, the Si content is 2 to 11 mass%, and the Ha element content is 0.
- a crystalline solid electrolyte characterized by being 0.02% by mass or more is proposed.
- the crystalline solid electrolyte proposed by the present invention has high chemical stability, it can be slurried using a polar solvent such as NMP, acetone, or DMF. The rate can be kept high.
- FIG. 2 is an X-ray diffraction chart for the samples obtained in Examples 1 to 13 and Comparative Example 1.
- FIG. 1 is an X-ray diffraction chart for the samples obtained in Examples 1 to 13 and Comparative Example 1.
- Solid electrolyte Crystalline solid electrolyte according to the present embodiment (referred to as “solid electrolyte”) the composition formula (1): in Li x Si y P z S a Ha w (wherein, Ha is Br, Cl, I and F Any one or two or more of them, represented by 2.4 ⁇ (xy) / (y + z) ⁇ 3.3), the S content is 55 to 73 mass%, and the Si content
- the crystalline solid electrolyte is characterized in that is 2 to 11% by mass and the content of the Ha element is 0.02% by mass or more.
- a solid electrolyte is a solid that passes ions such as Li + instead of electrons.
- this solid electrolyte has high chemical stability, it can be slurried using polar solvents, such as NMP, acetone, DMF, for example.
- the conductivity after being immersed in these solvents can be kept high.
- the conductivity (room temperature) after being immersed in N-methyl-2-pyrrolidone (NMP) can be set to 1 ⁇ 10 ⁇ 5 S ⁇ cm ⁇ 1 or more.
- mechanical milling treatment is not required, and it can be produced by mixing by means such as a normal ball mill, so that it is practical in terms of productivity and economy.
- the Li content (% by mass) is preferably 11.5 to 14.9% by mass, more preferably 11.5% by mass or more or 13.8% by mass or less, of which 11.5% by mass More preferably, it is 13.6% by mass or less.
- the P content (% by mass) is preferably 4.6 to 14.0% by mass, and more preferably 4.8% by mass or 13.7% by mass, of which 5.0% by mass. More preferably, it is 13.5% by mass or less.
- the Si content is preferably 2 to 11% by mass. Even when the Si content is less than 2% by mass or more than 11% by mass, the solid electrolyte has a crystal structure with low ionic conductivity, so that the initial conductivity is low. A tendency to decrease is observed. Even if it is stable with respect to a polar solvent, if the initial conductivity is low, it becomes a problem in use, which is not preferable. From this point of view, the Si content is preferably 2 to 11% by mass, more preferably 3% by mass or more and 9% by mass or less, and particularly preferably 4.5% by mass or more or 8.0% by mass or less. Further preferred.
- the content of the Ha element is preferably 0.02% by mass or more.
- the content of the Ha element is less than 0.02% by mass, the reactivity with the polar solvent becomes strong and the chemical stability becomes low, so that the conductivity after immersion in the solvent (for example, NMP) becomes small.
- the content of the Ha element is preferably 0.02% by mass or more, more preferably 10% by mass or less, and particularly preferably 3% by mass or less.
- the content of the S element is preferably 55 to 73% by mass.
- a content of S element of 55 to 73% by mass is preferable in that a crystal structure with high Li ion conductivity can be easily obtained and the conductivity can be increased.
- the content of S element is preferably 55 to 73% by mass, more preferably 57% by mass or more and 72% by mass or less, and particularly preferably 60% by mass or more or 71% by mass or less. .
- this solid electrolyte contains Li, Si, P, S, and Ha in the said range, it is also possible to contain another element.
- the electrical conductivity after being immersed in a solvent can be maintained further high.
- the conductivity (room temperature) after being immersed in N-methyl-2-pyrrolidone (NMP) can be set to 1 ⁇ 10 ⁇ 4 S ⁇ cm ⁇ 1 or more.
- the solid electrolyte is prepared by mixing raw materials containing lithium sulfide, phosphorus sulfide, silicon sulfide, and a halogen compound, pulverizing them at an appropriate strength, drying them as necessary, and heating them at 500 ° C. in a sulfide gas atmosphere. It can be produced by a production method including a step of baking in a temperature range of ⁇ 650 ° C., pulverizing or pulverizing as necessary, and classifying as necessary. However, it is not limited to this manufacturing method.
- the resulting solid electrolyte When pulverizing after mixing the raw materials, if the strength is pulverized like a vibration mill or mechanical milling, the resulting solid electrolyte will have a crystal structure (stable structure) with low ionic conductivity, resulting in a decrease in initial conductivity. Will end up. Therefore, it is preferable to grind with a ball mill, a bead mill, a homogenizer or the like so as to have a metastable structure. At this time, it is not necessary to reduce the crystallinity by at least grinding with a vibration mill or mechanical milling.
- Firing is preferably carried out under a flow of hydrogen sulfide gas (H 2 S) in a temperature range of 500 ° C. to 650 ° C., particularly 600 ° C. or less, and more preferably 575 ° C. or less.
- a solid electrolyte with high crystallinity can be obtained by firing at 500 ° C. or higher under the flow of hydrogen sulfide gas (H 2 S) as described above. Moreover, it can be set as a solid electrolyte with little electronic conduction by baking at 650 degrees C or less. Furthermore, firing at 575 ° or less has a peak derived from the Li—Si—PS type crystal structure (that is, metastable structure), which is particularly preferable.
- 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., a method of cutting with an air knife after contacting the slurry, a screen printing method, etc. can do.
- a green compact by pressing the solid electrolyte powder by pressing or the like and then processing it appropriately.
- the positive electrode material a positive electrode material used as a positive electrode active material of a lithium secondary battery can be used as appropriate.
- a positive electrode material used as a positive electrode active material of a lithium secondary battery can be used as appropriate.
- the negative electrode material a positive electrode material used as a positive electrode active material of a lithium secondary battery can be used as appropriate.
- solid electrolyte means all substances that can move ions such as Li + in the solid state.
- X to Y (X and Y are arbitrary numbers) is described, 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. Further, when “X or more” (X is an arbitrary number) or “Y or less” (Y is an arbitrary number), the intention of “preferably larger than X” or “preferably smaller than Y” Is included.
- Example 1 Lithium sulfide (Li 2 S), phosphorus sulfide (P 2 S 5 ), silicon sulfide (SiS 2 ), and lithium bromide (LiBr) as lithium halide so that the composition formula shown in Table 1 is obtained.
- 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. After raising the temperature, firing was performed at 550 ° C. for 4 hours, and the temperature was lowered. Thereafter, the sample was crushed in a mortar and sized with a sieve having an opening of 53 ⁇ m to obtain a powdery sample. At this time, all of the above weighing, mixing, setting in the electric furnace, taking out from the electric furnace, crushing and sizing are all performed in the glove box replaced with sufficiently dried Ar gas (dew point -60 ° C or less). It carried out in.
- H 2 S hydrogen sulfide gas
- Example 2-9 Samples were prepared and evaluated in the same manner as in Example 1 except that the composition of the raw materials was changed so as to be in Table 1.
- Example 10-13 In Example 3, samples were prepared and evaluated by changing the firing temperature to 575 ° C. (Example 10), 525 ° C. (Example 11), 650 ° C. (Example 12), and 600 ° C. (Example 13), respectively. .
- Example 1 (Comparative Example 1-3) In Example 1, a sample was prepared and evaluated in the same manner as in Example 1 except that the composition of the raw material was changed so as to be in Table 1.
- Example 4 (Comparative Example 4) In Example 3, Ar was flowed instead of H 2 S, and baking was performed at 650 ° C. to prepare and evaluate a sample.
- Example 5 (Comparative Example 5) In Example 3, the mixed powder was used as it was without firing and evaluated.
- Example 6 (Comparative Example 6) In Example 3, a sample was prepared and evaluated in the same manner as in Example 3 except that the firing temperature was changed to 700 ° C.
- FIG. 1 shows X-ray diffraction charts for the samples obtained in Examples 1 to 13 and Comparative Example 1. ICP analysis was performed on Li, Si, P, Ha, and S, and the value (xy) / (y + z) was shown after converting the analysis value (mass%) to the number of moles.
- pellets were produced by uniaxial pressure molding in a glove box, then CIP molding was performed at 200 MPa, and after applying a carbon paste as an electrode on both the upper and lower surfaces of the pellet, heat treatment was performed at 180 ° C. for 30 minutes, A sample for measuring ionic conductivity was prepared. The ion conductivity was measured by the AC impedance method at room temperature (25 ° C.).
- the AC impedance method is a method of measuring the resistance component, which is an impedance component, while changing the frequency of the AC voltage, and separates each resistance component according to the frequency dependency of each resistance component in the measurement sample, that is, the difference in relaxation time. be able to.
- Solid electrolytes exhibit electrical conductivity through lithium ion conduction, but the relaxation time is empirically known to be smaller in the order of bulk resistance ⁇ grain boundary resistance ⁇ electrode interface resistance.
- the impedance referred to as a Cole-Cole plot
- the magnitude of each resistance component can be obtained. Therefore, in this example, the sum of the bulk resistance component and the grain boundary resistance component was calculated as the ionic conductivity.
- the solid electrolyte is a solid that passes ions such as Li + instead of electrons. However, when the measurement sample has electronic conductivity, reading cannot be performed in this way.
- “Unreadable” in the table indicates the result that the measurement sample has electronic conductivity and cannot be read.
- “impossible to measure” in the table indicates that the measured signal is smaller than noise and does not give an accurate value, and is less than 1 ⁇ 10 ⁇ 6 S ⁇ cm ⁇ 1 as a specific number. It is.
- composition formula Li x Si y P z S a H a w (where Ha is any one of Br, Cl, I and F or In the crystalline solid electrolyte represented by 2.4 ⁇ (xy) / (y + z) ⁇ 3.3), the S content is 55 to 73% by mass, and the Si content When the amount is 2 to 11% by mass and the Ha element content is 0.02% by mass or more, for example, N-methyl-2-pyrrolidone (NMP), acetone, N, N-dimethylformamide (DMF) It has been found that a polar solvent such as can be used as a dispersion medium when slurried, and that the conductivity can be suppressed from being lowered when immersed in these solvents.
- NMP N-methyl-2-pyrrolidone
- DMF N-dimethylformamide
- crystal structures of the samples obtained in Examples 1 to 13 and Comparative Examples 1 to 6 were analyzed based on the XRD patterns of the samples obtained in each Example and Comparative Example.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Conductive Materials (AREA)
- Primary Cells (AREA)
Abstract
Description
しかし、硫黄を含有する硫化物固体電解質は反応性が極めて高いため、スラリーを調製する際に使用可能な分散媒が、トルエン、ヘプタン等の非極性溶媒に限られていた。
また、硫化物系固体電解質は、溶媒との反応性が高いために、溶媒に溶かしてペーストとした際に導電率が低下してしまうことが、本発明者の研究により分かってきた。
本実施形態に係る結晶性固体電解質(「本固体電解質」と称する)は、組成式(1):LixSiyPzSaHaw(式中、HaはBr、Cl、I及びFのいずれか一種又は二種以上を含む。2.4<(x-y)/(y+z)<3.3)で示され、Sの含有量が55~73質量%であって、Siの含有量が2~11質量%であって、且つ、Ha元素の含有量が0.02質量%以上であることを特徴とする結晶性固体電解質である。
さらに言えば、後述するように、メカニカルミリング処理を必要とせず、例えば通常のボールミルなどの手段で混合することにより製造できるから、生産性及び経済性においても実用的である。
かかる観点から、「(x-y)/(y+z)」は、2.5~3.2であるのが好ましく、その中でも2.4~3.1であるのがさらに好ましい。
また、Pの含有量(質量%)としては、4.6~14.0質量%であるのが好ましく、中でも4.8質量%以上或いは13.7質量%以下、その中でも5.0質量%以上或いは13.5質量%以下であるのがさらに好ましい。
かかる観点から、Siの含有量は2~11質量%であるのが好ましく、中でも3質量%以上或いは9質量%以下、その中でも4.5質量%以上或いは8.0質量%以下であるのがさらに好ましい。
かかる観点から、Ha元素の含有量は0.02質量%以上であるのが好ましく、中でも10質量%以下、その中でも3質量%以下であるのがさらに好ましい。
かかる観点から、S元素の含有量は55~73質量%であるのが好ましく、中でも57質量%以上或いは72質量%以下、その中でも60質量%以上或いは71質量%以下であるのがより一層好ましい。
本固体電解質がこのようなXRDパターンを有する場合には、溶媒に浸漬した後の導電率をさらに高く維持することができる。具体的には、N-メチル-2-ピロリドン(NMP)に浸漬した後の導電率(室温)を1×10-4S・cm-1以上とすることができる。
例えばHa元素としてI(ヨウ素)を含む場合には、2θ=24.8°±0.5°の位置にピークが出現する。
また、Ha元素としてBr(臭素)を含む場合には、2θ=25.2°±0.5°の位置にピークが出現する。
また、Ha元素としてCl(塩素)を含む場合には、2θ=25.6°±0.5°の位置にピークが出現する。
そして、Ha元素としてF(フッ素)を含む場合には、2θ=26.1°±0.5°の位置にピークが出現する。
次に、本固体電解質の製造方法の一例について説明する。但し、ここで説明する製造方法はあくまでも一例である。
上記の如く硫化水素ガス(H2S)流通下、500℃以上で焼成することにより、結晶性の高い固体電解質を得ることができる。また、650℃以下で焼成することにより、電子伝導の少ない固体電解質とすることができる。さらに575°以下で焼成することにより、上記Li-Si-P-S型結晶構造(すなわち準安定構造)に由来するピークを有するものとなり、特に好ましい。
また、未反応のH2Sガスは、有毒ガスであるため、排気ガスをバーナーなどで完全燃焼させた後、水酸化ナトリウム溶液で中和させて亜硫酸ナトリウムなどとして処理するのが好ましい。
本固体電解質は、全固体リチウム二次電池又は全固体リチウム一次電池の固体電解質層や、正極・負極合材に混合する固体電解質等として使用できる。
例えば正極と、負極と、正極及び負極の間に上記の固体電解質からなる層を形成することで、全固体リチウム二次電池を構成することができる。
正極材としては、リチウム二次電池の正極活物質として使用されている正極材を適宜使用可能である。
負極材についても、リチウム二次電池の正極活物質として使用されている正極材を適宜使用可能である。
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。
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。
表1に示した組成式となるように、硫化リチウム(Li2S)と、硫化リン(P2S5)と、硫化ケイ素(SiS2)と、ハロゲン化リチウムとして臭化リチウム(LiBr)とをそれぞれ秤量して混合し、容量100mLのアルミナ容器に原料の合計質量の20倍質量のジルコニウムボールと原料とを入れ、入江商会社製卓上型ボールミル「V-1M」で12時間粉砕して混合粉末を調製した。この混合粉末をカーボン製の容器に充填し、これを管状電気炉にて硫化水素ガス(H2S、純度100%)を1.0L/min流通させながら、昇降温速度300℃/hにて昇温した後、550℃で4時間焼成し、降温した。その後、試料を乳鉢で解砕し、目開き53μmの篩いで整粒して粉末状の試料を得た。
この際、上記秤量、混合、電気炉へのセット、電気炉からの取り出し、解砕及び整粒作業は全て、十分に乾燥されたArガス(露点-60℃以下)で置換されたグローブボックス内で実施した。
また、得られた試料を下記のようにX線回折測定したところ、2θ=20.2°、24.0°、25.2°、27.0°、29.1°、29.7°の位置にピークを確認した。これらのうち、20.2°±0.5°、24.0°±0.5°、29.7°±0.5°及び24.8°±0.5°~26.1°±0.5°の各範囲のピーク値のみを表3に示した(下記実施例も同様)。
表1となるように原料の組成を変更した以外は、実施例1と同様にして試料を作製し、評価した。
実施例3において、焼成温度を575℃(実施例10)、525℃(実施例11)、650℃(実施例12)、600℃(実施例13)にそれぞれ変えて試料を作成し、評価した。
実施例1において、表1となるように原料の組成を変更した以外は、実施例1と同様にして試料を作製し、評価した。
実施例3において、H2Sの代わりにArをフローさせて650℃にて焼成を行って試料を作製し、評価した。
実施例3において、混合粉末を焼成しないでそのまま試料とし、評価した。
実施例3において、焼成温度を700℃に変更した以外は、実施例3と同様にして試料を作製し、評価した。
実施例・比較例で得られた試料について、生成相をX線回折法で測定した。また、各組成比をICP発光分析法で測定した。
図1には、実施例1~13及び比較例1で得られた試料についてのX線回折チャートを示した。
実施例Li、Si、P、Ha、SにつきICP分析を行い、それらの分析値(質量%)をモル数に換算したうえで(x-y)/(y+z)の値を示した。
実施例・比較例で得た試料について、先ず下記要領で導電率(初期)を測定した。
次に、サンプルに対して10倍量(質量)のN-メチル-2-ピロリドン(NMP)溶媒(温度25℃)又はその他の溶媒に浸漬し、300℃のホットプレートでNMP又はその他の溶媒を乾燥させた後、次のようにしてイオン導電率(単位S・cm-1)を測定した。
固体電解質は、リチウムイオン伝導により電気伝導性を発現するが、緩和時間については、経験的にバルク抵抗<粒界抵抗<電極界面抵抗の順で小さいことが知られているため、周波数に対してインピーダンスをプロット(コールコールプロットと称する)することで、各抵抗成分の大きさを求めることができる。そこで、本実施例では、バルク抵抗成分と粒界抵抗成分を合わせたものをイオン導電率として算出した。
この際、コールコールプロットにおいて、はっきりと横軸(位相差=0°)近傍にプロットが近づく点が現れない場合には、読み取りができないことになる。固体電解質は、電子ではなく、Li+などのイオンを通じる固体であるが、測定サンプルが電子伝導性を有する場合には、このように読み取りができなくなる。表中の「読取不能」とは、このように測定サンプルが電子伝導性を有しており、読み取りができなかった結果を示すものである。他方、表中の「測定不能」とは、測定される信号がノイズよりも小さいため正確な値をさせないことを示すものであり、具体的な数字として1×10-6S・cm-1未満である。
そして、このような新規Li-Si-P-S結晶構造を有すれば、溶媒に浸漬した後の導電率をさらに高く維持することができることが分かった。具体的には、N-メチル-2-ピロリドン(NMP)に浸漬した後の導電率(室温)を1×10-4S・cm-1以上とすることができることが分かった。
Claims (6)
- 組成式:LixSiyPzSaHaw(式中、HaはBr、Cl、I及びFのいずれか一種又は二種以上を含む。2.4<(x-y)/(y+z)<3.3)で示され、Sの含有量が55~73質量%であって、Siの含有量が2~11質量%であって、且つ、Ha元素の含有量が0.02質量%以上であることを特徴とする結晶性固体電解質。
- CuKα線を用いたX線回折測定で得られるXRDパターンにおいて、2θ=20.2°±0.5°、24.0°±0.5°及び29.7°±0.5°の位置に現れるピークと、2θ=24.8°±0.5°~26.1°±0.5°の位置にピークと、を有することを特徴とする請求項1に記載の結晶性固体電解質。
- 請求項2における、2θ=20.2°±0.5°、24.0°±0.5°及び29.7°±0.5°の位置に現れるピークは、Li-Si-P-S型結晶構造に由来するピークであり、当該Li-Si-P-S型結晶構造は、結晶格子中の位置座標においてa=bの正方晶であり、PS4またはSiS4四面体の中心がa=0、b=0、c=0.5の位置と、a=0、b=0.5、c=0.69の位置と、以下の対称性を満たす位置とに存在しており、その対称性はa=0、b=0.5を通るc軸がc=0.5ずつ並進する4回らせん対称を持っており、004面が110方向の映進面となり、220面が001方向の映進面となり、200面が鏡映面となっている結晶構造であることを特徴とする請求項2に記載の結晶性固体電解質。
- 請求項1~3の何れかに記載の結晶性固体電解質を用いてなる構成を備えたリチウム二次電池。
- 硫化リチウムと、硫化リンと、硫化ケイ素と、ハロゲン化合物とを含む原料を混合し、硫化ガス雰囲気下において、500~650℃で焼成する工程を備えた結晶性固体電解質の製造方法。
- ハロゲンが、Br、Cl、I及びFのいずれか一種又は二種以上であることを特徴とする請求項5に記載の結晶性固体電解質の製造方法。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP14820104.9A EP3018660B1 (en) | 2013-07-04 | 2014-02-28 | Crystalline solid electrolyte and production method therefor |
CN201480026450.6A CN105210154B (zh) | 2013-07-04 | 2014-02-28 | 结晶性固体电解质及其制造方法 |
JP2015525065A JP6025981B2 (ja) | 2013-07-04 | 2014-02-28 | 結晶性固体電解質及びその製造方法 |
US14/902,021 US10644348B2 (en) | 2013-07-04 | 2014-02-28 | Crystalline solid electrolyte and production method therefor |
KR1020157028151A KR101729091B1 (ko) | 2013-07-04 | 2014-02-28 | 결정성 고체 전해질 및 그 제조 방법 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013-140678 | 2013-07-04 | ||
JP2013140678 | 2013-07-04 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2015001818A1 true WO2015001818A1 (ja) | 2015-01-08 |
Family
ID=52143415
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2014/055136 WO2015001818A1 (ja) | 2013-07-04 | 2014-02-28 | 結晶性固体電解質及びその製造方法 |
Country Status (7)
Country | Link |
---|---|
US (1) | US10644348B2 (ja) |
EP (1) | EP3018660B1 (ja) |
JP (1) | JP6025981B2 (ja) |
KR (1) | KR101729091B1 (ja) |
CN (1) | CN105210154B (ja) |
TW (1) | TWI610485B (ja) |
WO (1) | WO2015001818A1 (ja) |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105914395A (zh) * | 2015-02-25 | 2016-08-31 | 丰田自动车株式会社 | 硫化物固体电解质材料、电池和硫化物固体电解质材料的制造方法 |
JP2017117639A (ja) * | 2015-12-24 | 2017-06-29 | 出光興産株式会社 | 硫化物固体電解質、硫化物ガラス、電極合材及びリチウムイオン電池 |
JP2019501105A (ja) * | 2015-12-22 | 2019-01-17 | トヨタ・モーター・ヨーロッパToyota Motor Europe | 固体電解質用材料 |
WO2019131725A1 (ja) | 2017-12-28 | 2019-07-04 | 三井金属鉱業株式会社 | 固体電解質 |
JPWO2018110647A1 (ja) * | 2016-12-14 | 2019-10-24 | 出光興産株式会社 | 硫化物固体電解質の製造方法 |
WO2020095936A1 (ja) | 2018-11-08 | 2020-05-14 | 三井金属鉱業株式会社 | 硫化物固体電解質及び電池 |
WO2020095937A1 (ja) | 2018-11-08 | 2020-05-14 | 三井金属鉱業株式会社 | 硫黄含有化合物、固体電解質及び電池 |
WO2021049665A1 (ja) | 2019-09-13 | 2021-03-18 | 三井金属鉱業株式会社 | 電極合材並びにそれを用いた電極層及び固体電池 |
WO2021049414A1 (ja) * | 2019-09-11 | 2021-03-18 | 三井金属鉱業株式会社 | 硫化物固体電解質 |
WO2021192966A1 (ja) | 2020-03-24 | 2021-09-30 | 三井金属鉱業株式会社 | 活物質、該活物質を含む電極合剤及び電池 |
WO2022045302A1 (ja) | 2020-08-28 | 2022-03-03 | 三井金属鉱業株式会社 | 活物質及びその製造方法、電極合剤並びに電池 |
WO2022054705A1 (ja) | 2020-09-11 | 2022-03-17 | 三井金属鉱業株式会社 | 活物質及びその製造方法、電極合剤、並びに電池 |
WO2022210471A1 (ja) * | 2021-03-31 | 2022-10-06 | 三井金属鉱業株式会社 | 固体電解質 |
WO2022259755A1 (ja) | 2021-06-10 | 2022-12-15 | 三井金属鉱業株式会社 | 活物質及びその製造方法 |
WO2023090289A1 (ja) * | 2021-11-16 | 2023-05-25 | 三井金属鉱業株式会社 | 固体電解質及びその製造方法 |
WO2023090269A1 (ja) | 2021-11-17 | 2023-05-25 | 三井金属鉱業株式会社 | 電池 |
WO2023163071A1 (ja) | 2022-02-26 | 2023-08-31 | 三井金属鉱業株式会社 | 複合材料及びその製造方法 |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102443148B1 (ko) | 2013-05-15 | 2022-09-13 | 퀀텀스케이프 배터리, 인코포레이티드 | 배터리용 고상 캐소라이트 또는 전해질 |
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 |
KR20230164760A (ko) | 2014-06-04 | 2023-12-04 | 퀀텀스케이프 배터리, 인코포레이티드 | 혼합 입자 크기를 가진 전극 물질 |
WO2016210371A1 (en) | 2015-06-24 | 2016-12-29 | Quantumscape Corporation | Composite electrolytes |
CN108604705B (zh) | 2015-12-04 | 2022-03-01 | 昆腾斯科普电池公司 | 含锂、磷、硫、碘的电解质和阴极电解液组成,用于电化学装置的电解质膜,及制备这些电解质和阴极电解液的退火方法 |
KR101846695B1 (ko) * | 2016-08-18 | 2018-04-06 | 현대자동차주식회사 | 전고체 전지용 양극 슬러리 조성물 및 이를 포함하는 전고체 전지용 양극 |
US11342630B2 (en) | 2016-08-29 | 2022-05-24 | Quantumscape Battery, Inc. | Catholytes for solid state rechargeable batteries, battery architectures suitable for use with these catholytes, and methods of making and using the same |
EP3511948B1 (en) | 2016-09-12 | 2021-05-12 | Idemitsu Kosan Co.,Ltd. | Sulfide solid electrolyte |
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 |
JP6928122B2 (ja) | 2018-02-05 | 2021-09-01 | 富士フイルム株式会社 | 固体電解質組成物及びその製造方法、固体電解質含有シート、並びに、全固体二次電池用電極シート及び全固体二次電池の製造方法 |
JP7077766B2 (ja) * | 2018-05-18 | 2022-05-31 | トヨタ自動車株式会社 | 硫化物系固体電解質、当該硫化物系固体電解質の製造方法、及び、全固体電池の製造方法 |
EP3809425B1 (en) * | 2018-06-13 | 2022-08-17 | Mitsubishi Gas Chemical Company, Inc. | Lgps-based solid electrolyte and production method |
WO2019241642A1 (en) * | 2018-06-15 | 2019-12-19 | Georgia Tech Research Corporation | Solid electrolyte materials and methods of making the same |
WO2020213340A1 (ja) | 2019-04-19 | 2020-10-22 | 三井金属鉱業株式会社 | 硫化物固体電解質の製造方法 |
CN111977681B (zh) * | 2020-08-08 | 2023-10-10 | 天目湖先进储能技术研究院有限公司 | 硫化物固态电解质材料及其原料的气相合成方法及应用 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002109955A (ja) | 2000-10-02 | 2002-04-12 | Osaka Prefecture | 硫化物系結晶化ガラス、固体型電解質及び全固体二次電池 |
JP2010212058A (ja) * | 2009-03-10 | 2010-09-24 | Toyota Motor Corp | 固体電解質層の製造方法 |
WO2011118801A1 (ja) | 2010-03-26 | 2011-09-29 | 国立大学法人東京工業大学 | 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 |
JP2012212652A (ja) | 2011-03-18 | 2012-11-01 | Toyota Motor Corp | スラリー、固体電解質層の製造方法、電極活物質層の製造方法、および全固体電池の製造方法 |
JP2013016423A (ja) * | 2011-07-06 | 2013-01-24 | Toyota Motor Corp | 硫化物固体電解質材料、リチウム固体電池、および、硫化物固体電解質材料の製造方法 |
WO2013069243A1 (ja) * | 2011-11-07 | 2013-05-16 | 出光興産株式会社 | 固体電解質 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3284215B2 (ja) | 1992-09-29 | 2002-05-20 | 松下電器産業株式会社 | 硫化物系リチウムイオン導電性固体電解質の製造法 |
US20100047691A1 (en) * | 2006-10-25 | 2010-02-25 | Sumitomo Chemical Company, Limited | Lithium secondary battery |
JP5594253B2 (ja) * | 2011-08-08 | 2014-09-24 | トヨタ自動車株式会社 | 硫化物固体電解質材料、リチウム固体電池、および、硫化物固体電解質材料の製造方法 |
JP5888610B2 (ja) * | 2011-12-22 | 2016-03-22 | 国立大学法人東京工業大学 | 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 |
-
2014
- 2014-02-28 CN CN201480026450.6A patent/CN105210154B/zh active Active
- 2014-02-28 EP EP14820104.9A patent/EP3018660B1/en active Active
- 2014-02-28 JP JP2015525065A patent/JP6025981B2/ja active Active
- 2014-02-28 WO PCT/JP2014/055136 patent/WO2015001818A1/ja active Application Filing
- 2014-02-28 US US14/902,021 patent/US10644348B2/en active Active
- 2014-02-28 KR KR1020157028151A patent/KR101729091B1/ko active IP Right Grant
- 2014-03-12 TW TW103108609A patent/TWI610485B/zh active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002109955A (ja) | 2000-10-02 | 2002-04-12 | Osaka Prefecture | 硫化物系結晶化ガラス、固体型電解質及び全固体二次電池 |
JP2010212058A (ja) * | 2009-03-10 | 2010-09-24 | Toyota Motor Corp | 固体電解質層の製造方法 |
WO2011118801A1 (ja) | 2010-03-26 | 2011-09-29 | 国立大学法人東京工業大学 | 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 |
JP2012212652A (ja) | 2011-03-18 | 2012-11-01 | Toyota Motor Corp | スラリー、固体電解質層の製造方法、電極活物質層の製造方法、および全固体電池の製造方法 |
JP2013016423A (ja) * | 2011-07-06 | 2013-01-24 | Toyota Motor Corp | 硫化物固体電解質材料、リチウム固体電池、および、硫化物固体電解質材料の製造方法 |
WO2013069243A1 (ja) * | 2011-11-07 | 2013-05-16 | 出光興産株式会社 | 固体電解質 |
Cited By (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2016157630A (ja) * | 2015-02-25 | 2016-09-01 | 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 |
KR101826407B1 (ko) * | 2015-02-25 | 2018-02-06 | 도요타 지도샤(주) | 황화물 고체 전해질 재료, 전지 및 황화물 고체 전해질 재료의 제조 방법 |
US10333170B2 (en) | 2015-02-25 | 2019-06-25 | Toyota Jidosha Kabushiki Kaisha | Sulfide solid electrolyte material, battery, and method for producing sulfide solid electrolyte material |
CN105914395A (zh) * | 2015-02-25 | 2016-08-31 | 丰田自动车株式会社 | 硫化物固体电解质材料、电池和硫化物固体电解质材料的制造方法 |
US10879558B2 (en) | 2015-12-22 | 2020-12-29 | Toyota Motor Europe | Materials for solid electrolyte |
JP2019501105A (ja) * | 2015-12-22 | 2019-01-17 | トヨタ・モーター・ヨーロッパToyota Motor Europe | 固体電解質用材料 |
JP2017117639A (ja) * | 2015-12-24 | 2017-06-29 | 出光興産株式会社 | 硫化物固体電解質、硫化物ガラス、電極合材及びリチウムイオン電池 |
JPWO2018110647A1 (ja) * | 2016-12-14 | 2019-10-24 | 出光興産株式会社 | 硫化物固体電解質の製造方法 |
KR20200087207A (ko) | 2017-12-28 | 2020-07-20 | 미쓰이금속광업주식회사 | 고체 전해질 |
WO2019131725A1 (ja) | 2017-12-28 | 2019-07-04 | 三井金属鉱業株式会社 | 固体電解質 |
US11631887B2 (en) | 2017-12-28 | 2023-04-18 | Mitsui Mining & Smelting Co., Ltd. | Solid electrolyte |
WO2020095937A1 (ja) | 2018-11-08 | 2020-05-14 | 三井金属鉱業株式会社 | 硫黄含有化合物、固体電解質及び電池 |
US11387487B2 (en) | 2018-11-08 | 2022-07-12 | Mitsui Mining & Smelting Co., Ltd. | Sulfur-containing compound, solid electrolyte, and battery |
KR20200108487A (ko) | 2018-11-08 | 2020-09-18 | 미쓰이금속광업주식회사 | 황화물 고체 전해질 및 전지 |
KR20200110810A (ko) | 2018-11-08 | 2020-09-25 | 미쓰이금속광업주식회사 | 황 함유 화합물, 고체 전해질 및 전지 |
WO2020095936A1 (ja) | 2018-11-08 | 2020-05-14 | 三井金属鉱業株式会社 | 硫化物固体電解質及び電池 |
US11108084B2 (en) | 2018-11-08 | 2021-08-31 | Mitsui Mining & Smelting Co., Ltd. | Sulfide solid electrolyte and battery |
WO2021049414A1 (ja) * | 2019-09-11 | 2021-03-18 | 三井金属鉱業株式会社 | 硫化物固体電解質 |
JPWO2021049414A1 (ja) * | 2019-09-11 | 2021-03-18 | ||
JP7002697B2 (ja) | 2019-09-11 | 2022-01-20 | 三井金属鉱業株式会社 | 硫化物固体電解質 |
WO2021049665A1 (ja) | 2019-09-13 | 2021-03-18 | 三井金属鉱業株式会社 | 電極合材並びにそれを用いた電極層及び固体電池 |
WO2021192966A1 (ja) | 2020-03-24 | 2021-09-30 | 三井金属鉱業株式会社 | 活物質、該活物質を含む電極合剤及び電池 |
WO2022045302A1 (ja) | 2020-08-28 | 2022-03-03 | 三井金属鉱業株式会社 | 活物質及びその製造方法、電極合剤並びに電池 |
WO2022054705A1 (ja) | 2020-09-11 | 2022-03-17 | 三井金属鉱業株式会社 | 活物質及びその製造方法、電極合剤、並びに電池 |
WO2022210471A1 (ja) * | 2021-03-31 | 2022-10-06 | 三井金属鉱業株式会社 | 固体電解質 |
WO2022259755A1 (ja) | 2021-06-10 | 2022-12-15 | 三井金属鉱業株式会社 | 活物質及びその製造方法 |
WO2023090289A1 (ja) * | 2021-11-16 | 2023-05-25 | 三井金属鉱業株式会社 | 固体電解質及びその製造方法 |
WO2023090269A1 (ja) | 2021-11-17 | 2023-05-25 | 三井金属鉱業株式会社 | 電池 |
WO2023163071A1 (ja) | 2022-02-26 | 2023-08-31 | 三井金属鉱業株式会社 | 複合材料及びその製造方法 |
Also Published As
Publication number | Publication date |
---|---|
CN105210154A (zh) | 2015-12-30 |
EP3018660A4 (en) | 2016-11-30 |
EP3018660A1 (en) | 2016-05-11 |
KR20150131127A (ko) | 2015-11-24 |
KR101729091B1 (ko) | 2017-04-21 |
TW201503454A (zh) | 2015-01-16 |
EP3018660B1 (en) | 2018-12-19 |
CN105210154B (zh) | 2017-07-14 |
TWI610485B (zh) | 2018-01-01 |
US10644348B2 (en) | 2020-05-05 |
JPWO2015001818A1 (ja) | 2017-02-23 |
US20160164136A1 (en) | 2016-06-09 |
JP6025981B2 (ja) | 2016-11-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6025981B2 (ja) | 結晶性固体電解質及びその製造方法 | |
CN111512397B (zh) | 固体电解质 | |
KR102162070B1 (ko) | 리튬 이차전지용 황화물계 고체 전해질 | |
CN110800149B (zh) | 锂二次电池的固体电解质及该固体电解质用硫化物系化合物 | |
JP5701741B2 (ja) | 硫化物系固体電解質 | |
JP5701808B2 (ja) | 硫化物系固体電解質の製造方法 | |
JP6595153B1 (ja) | 硫化物系固体電解質粒子 | |
WO2015011937A1 (ja) | リチウムイオン電池用硫化物系固体電解質 | |
WO2021049414A1 (ja) | 硫化物固体電解質 | |
CN112106230A (zh) | 固体电解质、电极合剂、固体电解质层及全固体电池 | |
JP7301005B2 (ja) | 硫化物系固体電解質及び全固体リチウムイオン電池 | |
TW202138293A (zh) | 固體電解質 | |
CN114600293A (zh) | 固体电解质和使用其的电极合剂、固体电解质层、固态电池 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 14820104 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2015525065 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20157028151 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14902021 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2014820104 Country of ref document: EP |