EP4356452A1 - Verfahren zur herstellung eines festelektrolyten - Google Patents
Verfahren zur herstellung eines festelektrolytenInfo
- Publication number
- EP4356452A1 EP4356452A1 EP22732269.0A EP22732269A EP4356452A1 EP 4356452 A1 EP4356452 A1 EP 4356452A1 EP 22732269 A EP22732269 A EP 22732269A EP 4356452 A1 EP4356452 A1 EP 4356452A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- solid electrolyte
- denotes
- chosen
- agent
- preparing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 150000003568 thioethers Chemical class 0.000 claims abstract description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 7
- 239000011593 sulfur Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 63
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 238000000576 coating method Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000005864 Sulphur Substances 0.000 claims description 5
- 230000001476 alcoholic effect Effects 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- 239000000976 ink Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000003849 aromatic solvent Substances 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- -1 poly(ethylene oxide) Polymers 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 230000032258 transport Effects 0.000 description 2
- 239000011149 active material Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/14—Sulfur, selenium, or tellurium compounds of phosphorus
-
- 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
- H01M10/056—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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
-
- 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
- H01M4/0402—Methods of deposition of the material
- H01M4/0407—Methods of deposition of the material by coating on an electrolyte layer
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
-
- 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
-
- 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
- TITLE Process for preparing a solid electrolyte
- the present invention relates to the field of all-solid batteries. More particularly, the present invention relates to a particular process for the preparation of a solid electrolyte.
- the present invention also relates to a method for preparing an all-solid-state battery cell.
- all-solid batteries comprise one or more positive electrodes, one or more negative electrodes, a solid electrolyte forming a separator, an anode current collector and a cathode current collector.
- the performance of a battery depends on the properties of ionic and electronic transport.
- ion transport at the electrode scale takes place through the network formed by the solid electrolyte.
- this network is percolated, forming ionic conduction paths through the entire volume of the electrode, to ensure the transport of ions to or from all the particles of active material. .
- All-solid batteries use different types of materials as solid electrolytes, for example polymers, such as poly(ethylene oxide) (PEO), ..., Oxides such as Garnets, perovskites, Nasicon, , .. or even sulphides (LGPS, LPS, LPSCL, etc.).
- polymers such as poly(ethylene oxide) (PEO), ..., Oxides such as Garnets, perovskites, Nasicon, , .. or even sulphides (LGPS, LPS, LPSCL, etc.).
- the synthesis of solid electrolyte materials from the oxide family is to be carried out at high temperature.
- the shaping of solid electrolytes of the family of oxides and sulphides is difficult.
- the ionic conductivities of solid electrolyte materials are also generally low.
- a subject of the invention is therefore a method for preparing a solid electrolyte comprising the following steps: a) mixing a solid electrolyte chosen from sulphides with an agent comprising at least sulphur; b) adding the mixture obtained at the end of step a) in an organic solvent; c) recovering the solid electrolyte obtained.
- Another object of the invention is a process for preparing a battery cell comprising the preparation of a solid electrolyte according to the process according to the invention.
- FIG. 1 represents diffractograms of argyrodite involving the implementation of a comparative process
- FIG 2 represents diffractograms of a solid electrolyte involving the implementation of a method according to the invention
- FIG 3 represents diffractograms of a solid electrolyte involving the implementation of a method according to the invention
- FIG 4 is a graph indicating the ionic conductivity of solid electrolytes obtained from various processes.
- a solid electrolyte chosen from sulphides is mixed with an agent comprising at least sulphur.
- the solid electrolyte chosen from sulphides is chosen from materials of formula:
- A denotes Cu, Ag or Li
- B denotes Ge, Si, Al or P
- Ch denotes O, S, Se or Te, preferably Ch denotes S
- X denotes Cl, Br or I;
- - n is equal to 3, 4 or 5;
- Liii-zM 2 -zPi +z Si2 in which M denotes Ge, Sn or Si and z varies from 0 to 1.75, preferably LF- t PS ô-t X, in which X denotes Cl, Br or I and t varies from 0 to 2, more preferentially LhPS X, in which X denotes Cl, Br or I, even more preferentially LhPS Cl.
- the agent comprising at least sulfur is chosen from P2S5, L14P2S6, Ss, L13PS4, L14P2S7 and their mixtures, preferably from P2S5, L14P2S7 and their mixture.
- the content of agent comprising at least sulfur ranges from 1 to 30% by weight, preferably from 5 to 15% by weight, more preferably from 8 to 12% by weight relative to the total weight of the mixture comprising the electrolyte solid chosen from sulphides and the agent comprising at least sulphur.
- step b) of the process according to the invention the mixture obtained at the end of step a) is added to an organic solvent.
- the organic solvent is chosen from alcoholic solvents, ethers such as tetrahydrofuran (THF), aromatic solvents such as toluene, and nitriles such as acetonitrile.
- the organic solvent is chosen from alcoholic solvents, more preferably ethanol.
- the method according to the invention may also comprise a step d) drying the solid electrolyte obtained at the end of step c) at a temperature ranging from 40 to 550° C., preferably from 40 to 150 °C.
- the invention also relates to a process for preparing a battery cell comprising a negative electrode, a positive electrode and a separator comprising the following steps:
- the coatings are dried at a temperature ranging from 40 to
- a diffractogram of the material in the initial state is produced, as shown in Figure 1 (material la).
- the characteristic peaks of argyrodite can be identified on this diffractogram.
- the argyrodite is added in ethanol, then dried at 40°C, to obtain the material lb.
- a diffractogram of material lb is then produced, as shown in Figure 1.
- the argyrodite is added in ethanol, then dried at 100°C, to obtain the material le.
- a diffractogram of the material is then produced, as shown in Figure 1. It clearly appears again that the structure of argyrodite was destroyed after dissolution in ethanol.
- Example 1 shows that such a material is not stable in an organic solvent. It cannot therefore be used in electrode coating processes when preparing a battery cell, in particular an all-solid-state battery cell. Indeed, a process for coating an electrode necessarily involves a step of dissolving it in an organic solvent.
- a diffractogram of the mixture of materials is produced, as shown in Figure 2 (material 2a).
- the mixture is added in ethanol, then dried at 40°C, to obtain material 2b.
- a diffractogram of material 2b is then produced, as shown in Figure 2.
- the mixture is added in ethanol, then dried at 100°C, to obtain material 2c.
- a diffractogram of material 2c is then produced, as shown in Figure 2.
- Example 2 clearly shows a beneficial effect of the presence of the material of formula P2S5 on the chemical stability of argyrodite.
- Argyrodite thanks to the presence of the material of formula P2S5, is chemically stable in an organic solvent. It can therefore be used in processes for coating electrodes during the preparation of a battery cell, in particular an all-solid battery cell.
- the mixture is added in ethanol, then dried at 40°C, to obtain material 3b.
- a diffractogram of material 3b is then produced, as shown in Figure 3.
- the mixture is added in ethanol, then dried at 100°C, to obtain material 3c.
- a diffratogram of material 3c is then produced, as shown in Figure 3.
- Example 3 clearly shows a beneficial effect of the presence of the material of formula L1 4 P 2 S 7 on the chemical stability of argyrodite.
- Argyrodite thanks to the presence of the material of formula L1 4 P 2 S 7, is chemically stable in an organic solvent. It can therefore be used in processes for coating electrodes during the preparation of a battery cell, in particular an all-solid battery cell. Ionic conductivity
- the ionic conductivity at 25°C was measured for each of the materials 1a to 3c.
- the set of measurements of the ionic conductivities can be found in figure 4.
- the ionic conductivity of material 3b is much higher than that of material 1b.
- the ionic conductivity of material 3c is much higher than that of material 1e.
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Secondary Cells (AREA)
- Conductive Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Primary Cells (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR2106345A FR3124027B1 (fr) | 2021-06-15 | 2021-06-15 | Procédé de préparation d’un électrolyte solide |
PCT/EP2022/065955 WO2022263344A1 (fr) | 2021-06-15 | 2022-06-13 | Procédé de préparation d'un électrolyte solide |
Publications (1)
Publication Number | Publication Date |
---|---|
EP4356452A1 true EP4356452A1 (de) | 2024-04-24 |
Family
ID=77021538
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP22732269.0A Pending EP4356452A1 (de) | 2021-06-15 | 2022-06-13 | Verfahren zur herstellung eines festelektrolyten |
Country Status (7)
Country | Link |
---|---|
US (1) | US20240234943A1 (de) |
EP (1) | EP4356452A1 (de) |
JP (1) | JP2024523365A (de) |
KR (1) | KR20240024184A (de) |
CN (1) | CN118077065A (de) |
FR (1) | FR3124027B1 (de) |
WO (1) | WO2022263344A1 (de) |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11699809B2 (en) * | 2016-07-01 | 2023-07-11 | Mitsui Mining & Smelting Co., Ltd. | Sulfide-based solid electrolyte for lithium secondary battery |
CN110400967A (zh) * | 2019-07-17 | 2019-11-01 | 浙江锋锂新能源科技有限公司 | 一种三层核壳结构硫化物固体电解质及其制备方法和全固态电池 |
-
2021
- 2021-06-15 FR FR2106345A patent/FR3124027B1/fr active Active
-
2022
- 2022-06-13 KR KR1020247001599A patent/KR20240024184A/ko unknown
- 2022-06-13 US US18/570,396 patent/US20240234943A1/en active Pending
- 2022-06-13 JP JP2023577666A patent/JP2024523365A/ja active Pending
- 2022-06-13 EP EP22732269.0A patent/EP4356452A1/de active Pending
- 2022-06-13 WO PCT/EP2022/065955 patent/WO2022263344A1/fr active Application Filing
- 2022-06-13 CN CN202280042553.6A patent/CN118077065A/zh active Pending
Also Published As
Publication number | Publication date |
---|---|
JP2024523365A (ja) | 2024-06-28 |
CN118077065A (zh) | 2024-05-24 |
FR3124027B1 (fr) | 2023-12-01 |
WO2022263344A1 (fr) | 2022-12-22 |
FR3124027A1 (fr) | 2022-12-16 |
US20240234943A1 (en) | 2024-07-11 |
KR20240024184A (ko) | 2024-02-23 |
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Legal Events
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Effective date: 20231207 |
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