CN105470564A - Solid electrolyte membrane, preparation method of solid electrolyte membrane and lithium ion battery - Google Patents
Solid electrolyte membrane, preparation method of solid electrolyte membrane and lithium ion battery Download PDFInfo
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- CN105470564A CN105470564A CN201610061128.8A CN201610061128A CN105470564A CN 105470564 A CN105470564 A CN 105470564A CN 201610061128 A CN201610061128 A CN 201610061128A CN 105470564 A CN105470564 A CN 105470564A
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- ion battery
- lithium ion
- solid electrolyte
- glass ceramic
- electrolyte membrane
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 49
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 41
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000012528 membrane Substances 0.000 title claims abstract description 18
- 229910021525 ceramic electrolyte Inorganic materials 0.000 claims abstract description 22
- 239000002241 glass-ceramic Substances 0.000 claims abstract description 22
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 11
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 11
- 239000011247 coating layer Substances 0.000 claims abstract description 7
- 239000004745 nonwoven fabric Substances 0.000 claims description 23
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 10
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 8
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 229920006231 aramid fiber Polymers 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 229910010941 LiFSI Inorganic materials 0.000 claims description 5
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 5
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- 229910018130 Li 2 S-P 2 S 5 Inorganic materials 0.000 claims description 4
- 238000010041 electrostatic spinning Methods 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000011324 bead Substances 0.000 claims description 2
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 4
- 230000001351 cycling effect Effects 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 abstract 1
- 239000002861 polymer material Substances 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 1
- 230000007704 transition Effects 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
- 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
-
- 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
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a solid electrolyte membrane of a lithium ion battery, and relates to the field of lithium ion batteries. The solid electrolyte membrane is composed of a glass ceramic electrolyte and a coating layer with which the surface of the glass ceramic electrolyte is coated. The coating layer is prepared from lithium salt and a polymer material at the molar ratio of 1:5-1:10. The electrolyte membrane can reduce the interface impedance of the full-solid-state lithium ion battery to a great extent, so that the cycling stability of the full-solid-state lithium ion battery is improved, and the service life of the full-solid-state lithium ion battery is prolonged. The invention further discloses a preparation method of the solid electrolyte membrane and the full-solid-state lithium ion battery comprising the solid electrolyte membrane. The solid electrolyte membrane of the lithium ion battery is high in mechanical strength and excellent in electrochemical performance, and meanwhile the preparation technology is simple and convenient to popularize.
Description
Technical field:
The present invention is specifically related to a kind of solid electrolyte film and preparation method thereof and the solid Li-ion battery containing this dielectric film.
Background technology:
From the nineties in 20th century first piece of commercial applications lithium ion battery be born since, the advantages such as lithium ion battery is high with its energy density, power output large, memory-less effect, are used widely in fields such as PC, mobile electronic device, electric automobile, electric tool, energy storage devices.Along with the progress of technology, every chemical property such as energy density, the cycle performance etc. of lithium ion battery are also obtained for great lifting.But because current lithium ion battery still widely uses liquid state organic electrolyte, its safety high is not still solved at all.
Different from conventional lithium ion battery, solid lithium ion battery, due to not containing liquid organic solvent, fundamentally can stop the risk of cells burst blast.Thus, for the mankind provide one new type lithium ion battery safely and effectively.But, in miscellaneous solid electrolyte, inorganic sulfenyl glass ceramic electrolyte closest to practical level very easily reacts with the power and water pole active material of trace and decomposes, form higher Ion transfer impedance in the interface of solid electrolyte and electrode material, thus have a strong impact on every chemical property of solid Li-ion battery.
Summary of the invention:
In view of this, first aspect present invention provides a kind of solid electrolyte film that significantly can reduce above-mentioned interface impedance.By coated method, one coating layer is set on glass ceramic electrolyte surface, thus forms a transition zone at solid electrolyte and electrode material interface, reduce interface ion migration impedance.Second aspect present invention provides the preparation method of this solid electrolyte membrane.Third aspect present invention provides the solid Li-ion battery containing this solid electrolyte film.
First aspect, the invention provides a kind of lithium ion battery solid electrolyte film, and comprise glass ceramic electrolyte and the coating layer being coated on its surface, described coating layer material comprises lithium salts and the polymeric material of mol ratio 1: 5 ~ 1: 10.Wherein, described glass ceramic electrolyte is Li
2s-P
2s
5with Li
10geP
2s
12in at least one; Described lithium salts be in LiTFSI and LiFSI at least; Described polymer is at least one in PEO, PAN, PMMA, PVDF.
Second aspect, the invention provides a kind of preparation method of lithium ion battery solid electrolyte film, it is characterized in that, comprise the following steps:
(1) getting appropriate glass ceramic electrolyte powder is dispersed in anhydrous toluene solution, is then uniformly coated on aramid fiber nonwoven fabrics with scraper, fully dry in inert environments.
(2) the dried nonwoven fabrics being coated with glass ceramic electrolyte is colded pressing, obtain glass ceramic electrolyte/nonwoven fabrics diaphragm.
(3) getting appropriate polymer beads is dissolved in anhydrous acetonitrile, then adds appropriate lithium salts, and ultrasonic process is dissolved completely to polymer and lithium salts, and the mol ratio of lithium salts and polymer controls between 1: 5 ~ 1: 10.
(4) step (3) gained solution is evenly arranged on step (2) gained glass ceramic electrolyte/nonwoven fabrics diaphragm by method of electrostatic spinning or liquid phase spraying process, in inert atmosphere, after drying, both obtained lithium ion battery solid electrolyte membrane.
Wherein, in described step (1), aramid fiber nonwoven fabrics material is PPTA, porosity ~ 70%, aperture ~ 30 μm.
The third aspect, the invention provides a kind of solid Li-ion battery, the solid electrolyte film comprising positive pole, negative pole and be placed between both positive and negative polarity.Preparation process is as follows: positive pole, solid electrolyte membrane, negative pole are obtained nude battery core by lamination process, battery core is encapsulated with aluminum plastic film, after changing into, obtain solid Li-ion battery.
Lithium ion battery solid electrolyte film mechanical strength of the present invention is high, electrochemical performance, and meanwhile, preparation technology is simple, is convenient to promote.
Embodiment:
For illustrating this aspect further, describe the preferred embodiments of the invention below in conjunction with specific embodiment, these describe just in order to further illustrate advantage of the present invention, instead of limiting to the claimed invention.
Embodiment 1
A preparation method for lithium ion battery solid electrolyte film, comprises the following steps:
(1) appropriate glass ceramic electrolyte powder Li is got
2s-P
2s
5be dispersed in anhydrous toluene solution, be then uniformly coated on aramid fiber nonwoven fabrics with scraper, fully dry in inert environments.
(2) the dried nonwoven fabrics being coated with glass ceramic electrolyte is colded pressing, obtain Li
2s-P
2s
5/ nonwoven fabrics diaphragm.
(3) getting appropriate PEO is dissolved in anhydrous acetonitrile, then adds appropriate LiTFSI, and ultrasonic process is dissolved completely to PEO and LiTFSI, and the mol ratio of PEO and LiTFSI is 1: 7.
(4) step (3) gained solution is evenly arranged on step (2) gained Li by method of electrostatic spinning
2s-P
2s
5on/nonwoven fabrics diaphragm, in inert atmosphere, after drying, both obtained lithium ion battery solid electrolyte membrane M1.
A preparation method for solid Li-ion battery, comprises the following steps:
(1) take LiCoO2 as positive electrode, add bonding agent Kynoar (PVDF), conductive agent conductive black is sized mixing in 1-methyl-9-pyrrolidinone solvent, gained slurry double-faced uniform is coated on aluminium foil, drying, roll extrusion, obtains anode pole piece after cutting.
(2) take graphite as negative material, add butadiene-styrene rubber (SBR), sodium carboxymethylcellulose (CMC), graphite sizes mixing in deionized water, gained slurry double-faced uniform is coated on Copper Foil, drying, roll extrusion, obtains cathode pole piece after cutting.
(3) anode pole piece, solid electrolyte film M1, cathode pole piece are done battery core by lamination process is obtained, be placed in baking oven with aluminum plastic film encapsulation and toast.Through shaping, change into after experimental solids lithium ion battery.
Embodiment 2
A preparation method for lithium ion battery solid electrolyte film, comprises the following steps:
(1) appropriate glass ceramic electrolyte powder Li is got
2s-P
2s
5be dispersed in anhydrous toluene solution, be then uniformly coated on aramid fiber nonwoven fabrics with scraper, fully dry in inert environments.
(2) the dried nonwoven fabrics being coated with glass ceramic electrolyte is colded pressing, obtain Li
2s-P
2s
5/ nonwoven fabrics diaphragm.
(3) getting appropriate PMMA is dissolved in anhydrous acetonitrile, then adds appropriate LiFSI, and ultrasonic process is dissolved completely to PMMA and LiFSI, and the mol ratio of PMMA and LiFSI is 1: 8.
(4) step (3) gained solution is evenly arranged on step (2) gained Li by method of electrostatic spinning
2s-P
2s
5on/nonwoven fabrics diaphragm, in inert atmosphere, after drying, both obtained lithium ion battery solid electrolyte membrane M2.
As described in Example 1, difference is only the lithium ion battery solid electrolyte membrane M2 using the present embodiment obtained to a kind of preparation method of solid Li-ion battery.
Embodiment 3
A preparation method for lithium ion battery solid electrolyte film, comprises the following steps:
(1) appropriate glass ceramic electrolyte powder Li is got
10geP
2s
12be dispersed in anhydrous toluene solution, be then uniformly coated on aramid fiber nonwoven fabrics with scraper, fully dry in inert environments.
(2) the dried nonwoven fabrics being coated with glass ceramic electrolyte is colded pressing, obtain Li
10geP
2s
12/ nonwoven fabrics diaphragm.
(3) getting appropriate PEO is dissolved in anhydrous acetonitrile, then adds appropriate LiTFSI, and ultrasonic process is dissolved completely to PEO and LiTFSI, and the mol ratio of PEO and LiTFSI is 1: 7.
(4) step (3) gained solution is evenly arranged on step (2) gained Li by liquid phase spraying process
10geP
2s
12on/nonwoven fabrics diaphragm, in inert atmosphere, after drying, both obtained lithium ion battery solid electrolyte membrane M3.
As described in Example 1, difference is only the lithium ion battery solid electrolyte membrane M3 using the present embodiment obtained to a kind of preparation method of solid Li-ion battery.
Comparative example 1
As described in Example 1, difference is only the Li obtained by preparation method's step 2 using a kind of lithium ion battery solid electrolyte film in embodiment 1 to a kind of preparation method of solid Li-ion battery
2s-P
2s
5/ nonwoven fabrics diaphragm is solid electrolyte membrane.
Effect detects:
By the experimental cell in comparative example 1 and embodiment 1 in the voltage range of 3.0 ~ 4.35V, carry out 0.5C discharge and recharge 600 weeks loop tests.In test result display embodiment 1, after experimental cell circulation, capability retention is 89%, and the capability retention of comparative example 1 experimental cell is 81%.As can be seen here, lithium ion battery solid electrolyte provided by the invention obviously can improve the performance of solid Li-ion battery.
Claims (7)
1. a lithium ion battery solid electrolyte film, is characterized in that, comprise glass ceramic electrolyte and the coating layer being coated on its surface, described coating layer material comprises lithium salts and the polymeric material of mol ratio 1: 5 ~ 1: 10.
2. a kind of lithium ion battery solid electrolyte film according to claim 1, is characterized in that, described glass ceramic electrolyte is Li
2s-P
2s
5with Li
10geP
2s
12in at least one.
3. a kind of lithium ion battery solid electrolyte film according to claim 1, is characterized in that, described lithium salts is at least one in LiTFSI and LiFSI.
4. a kind of lithium ion battery solid electrolyte film according to claim 1, is characterized in that, described polymer is at least one in PEO, PAN, PMMA, PVDF.
5. a preparation method for lithium ion battery solid electrolyte film, is characterized in that, comprises the following steps:
(1) getting appropriate glass ceramic electrolyte powder is dispersed in anhydrous toluene solution, is then uniformly coated on aramid fiber nonwoven fabrics with scraper, fully dry in inert environments;
(2) the dried nonwoven fabrics being coated with glass ceramic electrolyte is colded pressing, obtain glass ceramic electrolyte/nonwoven fabrics diaphragm;
(3) getting appropriate polymer beads is dissolved in anhydrous acetonitrile, then adds appropriate lithium salts, and ultrasonic process is dissolved completely to polymer and lithium salts, and the mol ratio of lithium salts and polymer controls between 1: 5 ~ 1: 10;
(4) step (3) gained solution is evenly arranged on step (2) gained glass ceramic electrolyte/nonwoven fabrics diaphragm by method of electrostatic spinning or liquid phase spraying process, in inert atmosphere, after drying, both obtained lithium ion battery solid electrolyte membrane.
6. the preparation method of a kind of lithium ion battery solid electrolyte film according to claim 5, is characterized in that, in described step (1), aramid fiber nonwoven fabrics material is PPTA, porosity ~ 70%, aperture ~ 30 μm.
7. a solid Li-ion battery, is characterized in that, comprises positive pole, negative pole and is placed on the solid electrolyte film as claimed in claim 1 between both positive and negative polarity.
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Family
ID=55608046
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Cited By (17)
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---|---|---|---|---|
CN106654362A (en) * | 2016-12-07 | 2017-05-10 | 珠海光宇电池有限公司 | Composite solid electrolyte membrane, preparation method and lithium-ion battery |
CN107195962A (en) * | 2017-06-19 | 2017-09-22 | 宁波力赛康新材料科技有限公司 | A kind of composite solid electrolyte and preparation method thereof |
CN107452983A (en) * | 2016-05-31 | 2017-12-08 | 比亚迪股份有限公司 | A kind of lithium ion battery composite electrolyte and preparation method thereof and lithium ion battery |
CN107978789A (en) * | 2017-11-26 | 2018-05-01 | 中国科学院青岛生物能源与过程研究所 | A kind of sulfide composite electrolyte of polymer conductive fibre toughness reinforcing |
CN108206300A (en) * | 2016-12-16 | 2018-06-26 | 现代自动车株式会社 | Low porosity solid electrolyte membrane and manufacturing method thereof |
CN108539261A (en) * | 2018-04-12 | 2018-09-14 | 上海空间电源研究所 | A kind of high stable solid electrolyte preparation method of surface deposition inorganic salts |
CN109167090A (en) * | 2018-08-28 | 2019-01-08 | 长沙矿冶研究院有限责任公司 | A kind of film build method of polymer-based solid state electrolyte |
CN109786817A (en) * | 2019-01-23 | 2019-05-21 | 蜂巢能源科技有限公司 | Solid-state lithium battery and its application and method for preparing non-woven reinforced solid-state electrolyte membrane |
CN110034330A (en) * | 2019-04-10 | 2019-07-19 | 华北电力大学 | A kind of preparation method of lithium/sode cell composite solid electrolyte |
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Cited By (30)
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CN107452983B (en) * | 2016-05-31 | 2020-05-22 | 比亚迪股份有限公司 | Lithium ion battery composite electrolyte, preparation method thereof and lithium ion battery |
CN107452983A (en) * | 2016-05-31 | 2017-12-08 | 比亚迪股份有限公司 | A kind of lithium ion battery composite electrolyte and preparation method thereof and lithium ion battery |
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