CN113285050A - Li-M-X-based solid lithium battery anode and preparation method thereof - Google Patents
Li-M-X-based solid lithium battery anode and preparation method thereof Download PDFInfo
- Publication number
- CN113285050A CN113285050A CN202110448703.0A CN202110448703A CN113285050A CN 113285050 A CN113285050 A CN 113285050A CN 202110448703 A CN202110448703 A CN 202110448703A CN 113285050 A CN113285050 A CN 113285050A
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- based solid
- lithium battery
- solid electrolyte
- carbon
- 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 54
- 239000007787 solid Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 35
- 239000007774 positive electrode material Substances 0.000 claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- 238000000576 coating method Methods 0.000 claims abstract description 17
- 239000011230 binding agent Substances 0.000 claims abstract description 15
- 239000006258 conductive agent Substances 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011888 foil Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000011267 electrode slurry Substances 0.000 claims abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000011889 copper foil Substances 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- 239000002002 slurry Substances 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 18
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 239000003273 ketjen black Substances 0.000 claims description 12
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 8
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 239000001856 Ethyl cellulose Substances 0.000 claims description 5
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 5
- 229920000459 Nitrile rubber Polymers 0.000 claims description 5
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 5
- 229920001249 ethyl cellulose Polymers 0.000 claims description 5
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 5
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 5
- 239000006230 acetylene black Substances 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 4
- 150000002602 lanthanoids Chemical class 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052706 scandium Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 229920000858 Cyclodextrin Polymers 0.000 claims description 2
- 239000001116 FEMA 4028 Substances 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims description 2
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 2
- 229960004853 betadex Drugs 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 claims description 2
- 229910052716 thallium Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000007772 electrode material Substances 0.000 abstract description 7
- 239000000843 powder Substances 0.000 abstract description 6
- 238000003825 pressing Methods 0.000 abstract description 5
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 2
- 239000010405 anode material Substances 0.000 abstract description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 2
- 238000005507 spraying Methods 0.000 abstract description 2
- 230000014759 maintenance of location Effects 0.000 description 8
- 238000005245 sintering Methods 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000006183 anode active material Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
Images
Classifications
-
- 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
- H01M4/0419—Methods of deposition of the material involving spraying
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/582—Halogenides
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
Abstract
The invention relates to the field of solid-state lithium batteries, in particular to a positive electrode of a Li-M-X-based solid-state lithium battery and a preparation method thereof. Adding a positive electrode material into a solvent to prepare positive electrode slurry, coating the positive electrode slurry (including common coating modes such as spraying) on a carbon-coated aluminum foil, an aluminum foil or a copper foil, and then carrying out drying processes such as natural airing or drying to obtain a positive electrode plate; the positive electrode material includes a positive electrode active material, a Li-M-X-based solid electrolyte, a conductive agent, and a binder. Compared with the anode of the Li-M-X-based solid lithium battery prepared by powder dry pressing, the anode of the Li-M-X-based solid lithium battery prepared by the coating method has the advantages that all components of the anode material are uniformly dispersed, the charge transfer resistance between the electrode material and the solid electrolyte can be effectively reduced, and the electrochemical performance of the battery is improved. The positive electrode of the Li-M-X-based solid lithium battery and the preparation method thereof provided by the invention are compatible with the existing coating process of the lithium ion battery, and can be suitable for commercial large-scale production.
Description
Technical Field
The invention relates to the field of solid-state lithium batteries, in particular to a positive electrode of a Li-M-X-based solid-state lithium battery and a preparation method thereof.
Background
Inorganic all-solid-state lithium batteries have the advantage of high energy density and are considered to be promising next-generation energy storage technologies. Wherein Li3MX6The system solid electrolyte has high ionic conductivity and good chemical and electrochemical stability, is an excellent solid electrolyte and can well meet the requirements of solid lithium batteries. The positive active material of the Li-M-X-based solid-state lithium battery can be lithium cobaltate, nickel cobalt manganese ternary material, lithium iron phosphate or some other positive material. However, the contact between the solid electrolyte and these positive electrode materials is solid-to-solid, unlike conventional liquid batteries. As a result, a large charge transfer resistance is generated between the electrode material and the solid electrolyte, thereby seriously affecting the performance of the battery. At present, the positive electrode of an inorganic all-solid-state lithium battery is generally a composite positive electrode, the composite positive electrode mainly comprises an electrode material and a solid electrolyte, and the electrode material and the solid electrolyte are uniformly mixed by using some methods, such as grinding, to prepare the composite positive electrode material, and then the composite positive electrode material is used for assembling the solid-state lithium battery. In addition, since some electrode materials are not very conductive, a conductive agent may be added to the composite positive electrode material.
At present, most of solid lithium batteries based on Li-M-X system solid electrolytes adopt powder dry pressing to prepare anodes, namely, composite anode powder materials are directly dry pressed on the surfaces of the solid electrolytes to form anode sheets. The anode prepared by the powder dry pressing method has poor contact between an electrode material and a solid electrolyte, and can generate larger charge transfer resistance to influence the electrochemical performance of the battery. Also, it is highly likely that the various components in the composite positive electrode material are not uniformly dispersed with each other, resulting in poor ionic conductivity and electronic conductivity of the positive electrode portion of the battery. In addition, the method of dry pressing the powder to prepare the positive electrode of the lithium battery is not beneficial to the large-scale commercial production. Therefore, it is necessary to find a method for the commercial automatic mass production of the positive electrode of the lithium battery.
Disclosure of Invention
The invention aims to provide a positive electrode of a Li-M-X-based solid-state lithium battery and a preparation method thereof. The Li-M-X-based solid electrolyte has high ionic conductivity and good chemical and electrochemical stability, is an excellent solid electrolyte and can well meet the requirements of solid lithium batteries. The preparation of the positive electrode of the lithium battery provided by the invention needs to use an organic solvent compatible with the Li-M-X-based solid electrolyte and a suitable binder. The invention finds an organic solvent compatible with Li-M-X-based solid electrolyte and screens out a suitable binder. The components in the anode provided by the invention can be dispersed uniformly, and the solid electrolyte is tightly contacted with the anode active material, thereby being beneficial to improving the performance of the battery. Moreover, the positive electrode of the Li-M-X-based solid-state lithium battery and the preparation method thereof can be suitable for automatic large-scale production.
The technical scheme adopted by the invention for solving the technical problems is as follows:
one of the purposes of the invention is to provide a preparation method of a positive electrode of a Li-M-X-based solid-state lithium battery, which comprises the following steps: adding a positive electrode material into a solvent to prepare positive electrode slurry, coating the positive electrode slurry (including common coating methods such as spraying) on a carbon-coated aluminum foil, an aluminum foil or a copper foil, and then naturally airing or drying to obtain a positive electrode plate; the positive electrode material includes a positive electrode active material, a Li-M-X-based solid electrolyte, a conductive agent, and a binder.
Preferably, the positive active material is one of a nickel-cobalt-manganese ternary material, lithium iron phosphate and lithium cobaltate.
Preferably, the Li-M-X-based solid electrolyte isLi3MX6Wherein M is one or more of Sc, Y, Al, Ga, In, Tl or lanthanide, and X is one or more of F, Cl, Br or I.
Preferably, the conductive agent is one or more of activated carbon, conductive carbon black, acetylene black, ketjen black, graphene or carbon nanotubes.
Preferably, the binder is one or more of polymethyl methacrylate, ethyl cellulose, nitrile rubber, styrene butadiene rubber, polyethylene oxide or beta-cyclodextrin.
Preferably, the solvent is one or more of toluene, benzene, xylene, n-hexane or dibromomethane, or deionized water.
Preferably, the mass percentages of the positive active material, the Li-M-X-based solid electrolyte, the conductive agent and the binder in the positive material are (60-90): (1-30): 1-20).
Preferably, the mass ratio of the solvent to the positive electrode material is 10-50: 1.
preferably, the positive active material, the Li-M-Cl-based solid electrolyte, the conductive agent and the binder are added into toluene, and are stirred or ground in a mortar to prepare uniform slurry, and then the uniform slurry is sprayed or coated on the carbon-coated aluminum foil, and finally the positive plate is prepared by natural airing or drying. The positive active material is a nickel-cobalt-manganese ternary material, lithium iron phosphate or lithium cobaltate, and accounts for 60-80% of the positive material by mass. The Li-M-Cl-based solid electrolyte is Li3MX6Wherein M is one or the combination of Sc, Y, Ga, In or lanthanide, and the mass percentage of the solid electrolyte is 10-20%. The conductive agent is one or the combination of activated carbon, conductive carbon black, acetylene black, Ketjen black, graphene or carbon nano tube, and the mass percentage of the conductive agent is 1-10%. The binder is one or the combination of polymethyl methacrylate, ethyl cellulose, nitrile rubber or styrene butadiene rubber, and the mass percentage of the binder is 1-10%. Li-M-X based solid state prepared in the above process rangeThe positive electrode of the lithium battery has better performance.
The invention also aims to provide the Li-M-X-based solid-state lithium battery prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that: compared with the anode of the Li-M-X-based solid lithium battery prepared by powder dry pressing, the anode of the Li-M-X-based solid lithium battery prepared by the coating method has the advantages that all components of the anode material are uniformly dispersed, the charge transfer resistance between the electrode material and the solid electrolyte can be effectively reduced, and the electrochemical performance of the battery is improved. The positive electrode of the Li-M-X-based solid lithium battery and the preparation method thereof provided by the invention are compatible with the existing coating process of the lithium ion battery, and can be suitable for commercial large-scale production.
Drawings
Fig. 1 is an initial charge-discharge curve of a solid lithium battery in example 1;
fig. 2 is an initial charge-discharge curve of the solid lithium battery in example 2;
fig. 3 is an initial charge-discharge curve of the solid lithium battery in example 3;
fig. 4 is an initial charge-discharge curve of the solid lithium battery in example 4;
fig. 5 is an initial charge and discharge curve of the solid lithium battery in example 5.
Fig. 6 is an initial charge and discharge curve of the solid lithium battery in example 6.
Fig. 7 is an initial charge-discharge curve of the solid lithium battery in example 7.
Fig. 8 is a graph showing cycle characteristics of the solid lithium battery in example 1.
Fig. 9 shows cycle characteristics of the solid lithium battery of example 5.
Fig. 10 shows cycle characteristics of the solid lithium battery of example 6.
Fig. 11 shows cycle characteristics of the solid lithium battery in example 7.
Detailed Description
The technical solution of the present invention is further specifically described below by way of specific examples in conjunction with the accompanying drawings.
Example 1
(1) 2% of polymethyl methacrylate was dissolved in an appropriate amount of toluene solution.
(2) 75 percent of nickel-cobalt-manganese ternary material and 15 percent of Li3InCl6Adding the solid electrolyte and 8% Ketjen black into the solution obtained in the step (1) to prepare slurry.
(3) And (3) uniformly coating the slurry obtained in the step (2) on a carbon-coated aluminum foil, and then drying the carbon-coated aluminum foil at the temperature of 60 ℃ for 24 hours.
(4) And sintering the dried positive plate, and then compacting.
The battery formed by the anode of the Li3InCl 6-based solid-state lithium battery discharges between 2.5 and 4.2V, and the capacity of the first circle is 84mA h g-1The capacity retention rate after 100 cycles of charge and discharge was 75%.
Example 2
(1) 1% of polymethyl methacrylate was dissolved in an appropriate amount of toluene solution.
(2) 75 percent of nickel-cobalt-manganese ternary material and 15 percent of Li3InCl6Adding the solid electrolyte and 9% Ketjen black into the solution obtained in the step (1) to prepare slurry.
(3) And (3) uniformly coating the slurry obtained in the step (2) on a carbon-coated filter, and then naturally airing.
(4) And sintering the dried positive plate, and then compacting.
Obtained Li3InCl6Based on the anode of the solid-state lithium battery, the battery formed by the anode discharges between 2.5 and 4.2V, and the first-loop capacity is 62mA h g-1And the capacity retention rate is 57% after 100 cycles of charge and discharge.
Example 3
(1) 3% of polymethyl methacrylate was dissolved in an appropriate amount of toluene solution.
(2) 75 percent of nickel-cobalt-manganese ternary material and 15 percent of Li3InCl6Adding the solid electrolyte and 7% Ketjen black into the solution obtained in the step (1) to prepare slurry.
(3) And (3) uniformly coating the slurry obtained in the step (2) on a carbon-coated filter, and then drying the carbon-coated filter at the temperature of 60 ℃ for 24 hours.
(4) And sintering the dried positive plate, and then compacting.
Obtained Li3InCl6Based on the anode of the solid-state lithium battery, the battery formed by the anode discharges between 2.5 and 4.2V, and the first-loop capacity is 57mA h g-1And the capacity retention rate after 100 cycles of charge and discharge is 89%.
Example 4
(1) 5% of polymethyl methacrylate was dissolved in an appropriate amount of toluene solution.
(2) 75 percent of nickel-cobalt-manganese ternary material and 15 percent of Li3InCl6Adding the solid electrolyte and 6% Ketjen black into the solution obtained in the step (1) to prepare slurry.
(3) And (3) uniformly coating the slurry obtained in the step (2) on a carbon-coated filter, and then naturally airing.
(4) And sintering the dried positive plate, and then compacting.
Obtained Li3InCl6Based on the anode of the solid lithium battery, the battery formed by the anode discharges between 2.5 and 4.2V, and the first-circle capacity is 41mA h g-1And the capacity retention rate is 46% after 100 circles of charge and discharge.
Example 5
(1) 2% ethyl cellulose was dissolved in an appropriate amount of toluene solution.
(2) 75 percent of nickel-cobalt-manganese ternary material and 15 percent of Li3InCl6Adding the solid electrolyte and 9% Ketjen black into the solution obtained in the step (1) to prepare slurry.
(3) And (3) uniformly coating the slurry obtained in the step (2) on a carbon-coated filter, and then drying the carbon-coated filter for 24 hours at the temperature of 60 ℃.
(4) And sintering the dried positive plate, and then compacting.
Obtained Li3InCl6Based on the anode of the solid-state lithium battery, the battery formed by the anode discharges between 2.5 and 4.2V, and the capacity of the first circle is 82mA h g-1And the capacity retention rate is 81% after 100 cycles of charge and discharge.
Example 6
(1) 2 percent of styrene butadiene rubber is dissolved in a proper amount of toluene solution.
(2) 75 percent of nickel-cobalt-manganese ternary material and 15 percent of Li3InCl6Solid state electricityAdding the electrolyte and 8% Ketjen black into the solution obtained in the step (1) to prepare slurry.
(3) And (3) uniformly coating the slurry obtained in the step (2) on a carbon-coated filter, and then naturally airing.
(4) And sintering the dried positive plate, and then compacting.
Obtained Li3InCl6The battery formed by the anode of the solid-state lithium battery discharges between 2.5 and 4.2V, and the first-circle capacity is 83mA h g-1The capacity retention rate after 100 cycles of charge and discharge was 79%.
Example 7
(1) 2 percent of nitrile rubber is dissolved in a proper amount of toluene solution.
(2) 75 percent of nickel-cobalt-manganese ternary material and 15 percent of Li3InCl6Adding the solid electrolyte and 8% Ketjen black into the solution obtained in the step (1) to prepare slurry.
(3) And (3) uniformly coating the slurry obtained in the step (2) on a carbon-coated filter, and then drying the carbon-coated filter at the temperature of 60 ℃ for 24 hours.
(4) And sintering the dried positive plate, and then compacting.
Obtained Li3InCl6Based on the anode of the solid-state lithium battery, the battery formed by the anode discharges between 2.5 and 4.2V, and the capacity of the first circle is 84mA h g-1And the capacity retention rate is 65% after 100 circles of charge and discharge.
Comparative example 1
(1) 75 percent of nickel-cobalt-manganese ternary material and 15 percent of Li3InCl6The solid electrolyte and 10% Ketjen black are added into a proper amount of toluene solution to prepare slurry.
(2) And (3) uniformly coating the slurry obtained in the step (1) on a carbon-coated filter, and then naturally drying.
(3) And sintering the dried positive plate, and then compacting.
Obtained Li3InCl6Based on the anode of the solid-state lithium battery, the battery formed by the anode discharges between 2.5 and 4.2V, and the first-circle capacity is 22mA h g-1And the capacity retention rate is 50% after 100 circles of charge and discharge.
The above-described embodiments are merely preferred embodiments of the present invention, which is not intended to be limiting in any way, and other variations and modifications are possible without departing from the scope of the invention as set forth in the appended claims.
Claims (10)
1. A preparation method of a positive electrode of a Li-M-X-based solid-state lithium battery is characterized by comprising the following steps: adding the positive electrode material into a solvent to prepare positive electrode slurry, coating the positive electrode slurry on a carbon-coated aluminum foil, an aluminum foil or a copper foil, and then drying to obtain a positive electrode plate; the positive electrode material includes a positive electrode active material, a Li-M-X-based solid electrolyte, a conductive agent, and a binder.
2. The method of claim 1, wherein the positive active material is one of a nickel-cobalt-manganese ternary material, lithium iron phosphate, and lithium cobaltate.
3. The method of claim 1, wherein the Li-M-X-based solid-state electrolyte is Li3MX6Wherein M is one or more of Sc, Y, Al, Ga, In, Tl or lanthanide, and X is one or more of F, Cl, Br or I.
4. The method of claim 1, wherein the conductive agent is one or more selected from activated carbon, conductive carbon black, acetylene black, ketjen black, graphene, and carbon nanotubes.
5. The method of claim 1, wherein the binder is one or more of polymethyl methacrylate, ethyl cellulose, nitrile rubber, styrene butadiene rubber, polyethylene oxide, and beta-cyclodextrin.
6. The method of claim 1, wherein the solvent is one or more selected from toluene, benzene, xylene, n-hexane, and dibromomethane, or deionized water.
7. The method for preparing the positive electrode of the Li-M-X-based solid lithium battery as claimed in claim 1, wherein the mass percentages of the positive electrode active material, the Li-M-X-based solid electrolyte, the conductive agent and the binder in the positive electrode material are (60-90): (1-30): 1-20).
8. The method for preparing the positive electrode of the Li-M-X-based solid-state lithium battery as claimed in claim 1, wherein the mass ratio of the solvent to the positive electrode material is 10 to 50: 1.
9. the method of claim 1, wherein the positive electrode active material, the Li-M-Cl-based solid electrolyte, the conductive agent, and the binder are added to toluene to prepare a uniform slurry, and then the uniform slurry is coated on the carbon-coated aluminum foil, and finally the positive electrode sheet is prepared through a drying process.
10. The method of claim 9, wherein the positive active material is a nickel-cobalt-manganese ternary material, lithium iron phosphate, or lithium cobaltate, and the positive active material accounts for 60-80% of the positive material by mass; the Li-M-Cl-based solid electrolyte is Li3MX6Wherein M is one or a combination of more of Sc, Y, Ga, In or lanthanide, and the mass percentage of the solid electrolyte is 10-20%; the conductive agent is one or a combination of more of activated carbon, conductive carbon black, acetylene black, Ketjen black, graphene or carbon nano tubes, and the mass percentage of the conductive agent is 1-10%; the binder is one or a combination of a plurality of polymethyl methacrylate, ethyl cellulose, nitrile rubber or styrene butadiene rubber, and the mass percentage of the binder is 1-10%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110448703.0A CN113285050A (en) | 2021-04-25 | 2021-04-25 | Li-M-X-based solid lithium battery anode and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110448703.0A CN113285050A (en) | 2021-04-25 | 2021-04-25 | Li-M-X-based solid lithium battery anode and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113285050A true CN113285050A (en) | 2021-08-20 |
Family
ID=77277312
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110448703.0A Pending CN113285050A (en) | 2021-04-25 | 2021-04-25 | Li-M-X-based solid lithium battery anode and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113285050A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113707880A (en) * | 2021-08-23 | 2021-11-26 | 湖州南木纳米科技有限公司 | Positive pole piece containing solid electrolyte and preparation method and application thereof |
| CN115000503A (en) * | 2022-08-01 | 2022-09-02 | 江苏蓝固新能源科技有限公司 | Mixed conductive slurry and method for improving stability thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1246965A (en) * | 1996-10-11 | 2000-03-08 | 马萨诸塞州技术研究院 | Polymer electrolyte, intercalation compounds and electrodes for batteries |
| CN108232318A (en) * | 2018-01-30 | 2018-06-29 | 陕西煤业化工技术研究院有限责任公司 | A kind of production method of all solid state power lithium-ion battery |
| CN111146425A (en) * | 2019-12-30 | 2020-05-12 | 国联汽车动力电池研究院有限责任公司 | Method for coating solid electrolyte with electrode material, coating material and electrode prepared by using coating method |
| CN111224064A (en) * | 2020-01-15 | 2020-06-02 | 中山大学 | Solid-state lithium ion battery applying composite anode and assembling method and application thereof |
-
2021
- 2021-04-25 CN CN202110448703.0A patent/CN113285050A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1246965A (en) * | 1996-10-11 | 2000-03-08 | 马萨诸塞州技术研究院 | Polymer electrolyte, intercalation compounds and electrodes for batteries |
| CN108232318A (en) * | 2018-01-30 | 2018-06-29 | 陕西煤业化工技术研究院有限责任公司 | A kind of production method of all solid state power lithium-ion battery |
| CN111146425A (en) * | 2019-12-30 | 2020-05-12 | 国联汽车动力电池研究院有限责任公司 | Method for coating solid electrolyte with electrode material, coating material and electrode prepared by using coating method |
| CN111224064A (en) * | 2020-01-15 | 2020-06-02 | 中山大学 | Solid-state lithium ion battery applying composite anode and assembling method and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113707880A (en) * | 2021-08-23 | 2021-11-26 | 湖州南木纳米科技有限公司 | Positive pole piece containing solid electrolyte and preparation method and application thereof |
| CN115000503A (en) * | 2022-08-01 | 2022-09-02 | 江苏蓝固新能源科技有限公司 | Mixed conductive slurry and method for improving stability thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109103399B (en) | Functional diaphragm for lithium-sulfur battery, preparation method of functional diaphragm and application of functional diaphragm in lithium-sulfur battery | |
| CN109004220B (en) | Boric acid compound modified lithium ion battery silicon cathode and preparation method thereof | |
| CN203746972U (en) | Positive electrode plate | |
| CN109698354B (en) | Binder, negative electrode slurry using binder, and preparation method and application of negative electrode slurry | |
| CN107256969B (en) | Preparation method of negative electrode slurry of sodium-ion battery | |
| CN105470460A (en) | Negative electrode piece of lithium ion battery and fabrication method of negative electrode piece | |
| Cheng et al. | Oxidized multiwall carbon nanotube modified separator for high performance lithium–sulfur batteries with high sulfur loading | |
| CN109950546B (en) | Copper foil manufacturing process and negative current collector | |
| CN112687865A (en) | Lithium ion battery cathode slurry, preparation method and application thereof | |
| KR101503807B1 (en) | A manufacture method of lithium ion capacitor using lithium metal powder | |
| CN111106352A (en) | Cross-linking type water-based binder for lithium ion battery and electrode prepared from cross-linking type water-based binder | |
| CN113594415A (en) | Sandwich independent positive electrode for inhibiting shuttle effect of lithium-sulfur battery and preparation method thereof | |
| CN108172744B (en) | Sb for lithium-sulfur battery diaphragm2Se3Method for preparing composite material | |
| CN114665065A (en) | Positive pole piece and preparation method and application thereof | |
| CN113285050A (en) | Li-M-X-based solid lithium battery anode and preparation method thereof | |
| CN111697217A (en) | Preparation method of silicon/graphite composite cathode of lithium ion battery | |
| CN115411228A (en) | Lithium iron manganese phosphate positive plate and preparation method thereof | |
| CN108666533B (en) | Preparation method and application of sulfur electrode of lithium-sulfur battery | |
| CN105870401A (en) | Application method of graphene as conductive agent to negative electrode slurry of lithium ion battery | |
| CN109449492A (en) | A kind of ceramic base all-solid-state battery and preparation method thereof | |
| CN111370783B (en) | High-performance water-based chloride ion battery and preparation method thereof | |
| CN110838577A (en) | Sulfur-based positive electrode active material for solid-state battery and preparation method and application thereof | |
| CN110085800B (en) | Structure and preparation method of high-utilization-rate manganese oxide electrode of neutral zinc-manganese battery | |
| CN109802100A (en) | A kind of benzenetricarboxylic acid manganese water system Zinc ion battery anode and preparation method thereof | |
| CN109659475A (en) | A kind of preparation method of high-performance high-voltage lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210820 |
|
| RJ01 | Rejection of invention patent application after publication |