CN115395079A - Composite solid electrolyte membrane, preparation method thereof and lithium ion battery - Google Patents
Composite solid electrolyte membrane, preparation method thereof and lithium ion battery Download PDFInfo
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- CN115395079A CN115395079A CN202211029889.7A CN202211029889A CN115395079A CN 115395079 A CN115395079 A CN 115395079A CN 202211029889 A CN202211029889 A CN 202211029889A CN 115395079 A CN115395079 A CN 115395079A
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- borate
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 109
- 239000002131 composite material Substances 0.000 title claims abstract description 81
- 239000012528 membrane Substances 0.000 title claims abstract description 73
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 19
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910052796 boron Inorganic materials 0.000 claims abstract description 62
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 41
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 41
- 229920000642 polymer Polymers 0.000 claims abstract description 39
- 239000000654 additive Substances 0.000 claims abstract description 31
- 230000000996 additive effect Effects 0.000 claims abstract description 30
- 239000011256 inorganic filler Substances 0.000 claims abstract description 26
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 26
- 229910052744 lithium Inorganic materials 0.000 claims description 43
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 39
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000003792 electrolyte Substances 0.000 claims description 22
- 239000000945 filler Substances 0.000 claims description 20
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- 239000002203 sulfidic glass Substances 0.000 claims description 17
- -1 lithium tetrafluoroborate Chemical compound 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 14
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 10
- YZYKZHPNRDIPFA-UHFFFAOYSA-N tris(trimethylsilyl) borate Chemical group C[Si](C)(C)OB(O[Si](C)(C)C)O[Si](C)(C)C YZYKZHPNRDIPFA-UHFFFAOYSA-N 0.000 claims description 10
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 9
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 9
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 9
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical group [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 6
- 229910018130 Li 2 S-P 2 S 5 Inorganic materials 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 239000010416 ion conductor Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- UFBCAWKXDJDIOA-UHFFFAOYSA-N tris(triethylsilyl) borate Chemical compound CC[Si](CC)(CC)OB(O[Si](CC)(CC)CC)O[Si](CC)(CC)CC UFBCAWKXDJDIOA-UHFFFAOYSA-N 0.000 claims description 5
- WDACWRUFHSJMKX-UHFFFAOYSA-N OB1OOC2=NC=CC=C2OO1 Chemical compound OB1OOC2=NC=CC=C2OO1 WDACWRUFHSJMKX-UHFFFAOYSA-N 0.000 claims description 4
- UHUKRLXPOGPWJG-UHFFFAOYSA-N [Li+].[Li+].[Li+].[O-]B([O-])[O-].C1=CC=C2C=C(O)C(O)=CC2=C1.C1=CC=C2C=C(O)C(O)=CC2=C1 Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].C1=CC=C2C=C(O)C(O)=CC2=C1.C1=CC=C2C=C(O)C(O)=CC2=C1 UHUKRLXPOGPWJG-UHFFFAOYSA-N 0.000 claims description 4
- VKPWUPHIAVTZRB-UHFFFAOYSA-N trilithium;benzene-1,2-diol;borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].OC1=CC=CC=C1O.OC1=CC=CC=C1O VKPWUPHIAVTZRB-UHFFFAOYSA-N 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 229910005839 GeS 2 Inorganic materials 0.000 claims description 3
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 claims description 3
- 239000002228 NASICON Substances 0.000 claims description 3
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 229910001593 boehmite Inorganic materials 0.000 claims description 3
- 150000001642 boronic acid derivatives Chemical class 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- 229910052570 clay Inorganic materials 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- DTARXWGVBSGUFX-UHFFFAOYSA-N lithium;dihydrogen borate;2-hydroxybenzoic acid Chemical compound [Li+].OB(O)[O-].OC(=O)C1=CC=CC=C1O.OC(=O)C1=CC=CC=C1O DTARXWGVBSGUFX-UHFFFAOYSA-N 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 241000208152 Geranium Species 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000002227 LISICON Substances 0.000 claims 1
- PPTSBERGOGHCHC-UHFFFAOYSA-N boron lithium Chemical compound [Li].[B] PPTSBERGOGHCHC-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 18
- 238000011065 in-situ storage Methods 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 7
- 239000010405 anode material Substances 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 239000007787 solid Substances 0.000 abstract description 4
- 239000002001 electrolyte material Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 239000005518 polymer electrolyte Substances 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000007774 positive electrode material Substances 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 102220043159 rs587780996 Human genes 0.000 description 5
- SYRDSFGUUQPYOB-UHFFFAOYSA-N [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O SYRDSFGUUQPYOB-UHFFFAOYSA-N 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 101100537779 Homo sapiens TPM2 gene Proteins 0.000 description 2
- 229910021102 Li0.5La0.5TiO3 Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 102100036471 Tropomyosin beta chain Human genes 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910003480 inorganic solid Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- NHBALETWERXBJO-UHFFFAOYSA-N B([O-])([O-])[O-].B([O-])([O-])[O-].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+] Chemical compound B([O-])([O-])[O-].B([O-])([O-])[O-].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+] NHBALETWERXBJO-UHFFFAOYSA-N 0.000 description 1
- 229910009297 Li2S-P2S5 Inorganic materials 0.000 description 1
- 229910009228 Li2S—P2S5 Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000000462 isostatic pressing Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 1
- 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 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000012802 nanoclay Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000379 polypropylene carbonate Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Classifications
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- 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
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Conductive Materials (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a composite solid electrolyte membrane, a preparation method thereof and a lithium ion battery, and particularly relates to the technical field of electrolyte materials. The composite solid electrolyte membrane comprises the following components in percentage by mass: 20-80 wt% of polymer; 5-50 wt% of inorganic filler; 0.05wt% -2 wt% of boron-containing additive; 5-40 wt% of boron-containing lithium salt. The composite solid electrolyte membrane can carry out in-situ coating on the layered anode in the battery circulation process, thereby solving the problem of matching of the solid electrolyte membrane and the layered oxide anode material and improving the circulation performance of the solid battery based on the layered anode.
Description
Technical Field
The invention relates to the technical field of electrolyte materials, in particular to a composite solid electrolyte membrane, a preparation method thereof and a lithium ion battery.
Background
Lithium ion batteries are an important component of current clean energy, have been widely applied to various 3C products and electric vehicles, and the continuous development of the lithium battery industry is an important way to achieve the goals of carbon peak reaching and carbon neutralization. With the increasing performance requirements of people on lithium ion batteries, the improvement of energy density and the solution of the safety problem of flammability and even explosion of the conventional liquid lithium ion batteries are urgent, and research on developing all-solid-state lithium ion batteries by using solid electrolytes instead of liquid electrolytes becomes a global hotspot.
The solid electrolyte membrane is a key component of the all-solid-state lithium ion battery, and has the functions of isolating the positive electrode and the negative electrode and providing a lithium ion transmission channel. Currently, solid electrolytes can be classified into three categories: polymer solid electrolytes, inorganic solid electrolytes, and organic-inorganic composite solid electrolytes. Among them, the organic-inorganic composite solid electrolyte polymer electrolyte combines the advantages of the inorganic solid electrolyte and the polymer solid electrolyte, and becomes the main research direction of the solid electrolyte.
At present, the existing composite solid electrolyte membrane is mostly formed by compounding a polymer, a lithium salt and an inorganic filler, and although the addition of the lithium salt and the inorganic filler can improve the ionic conductivity of the electrolyte, the electrochemical window and the ionic conductivity of the polymer electrolyte are also improved to a certain extent. For example, patent CN114512714A discloses a composite polymer electrolyte and a preparation method thereof, which is to mix a polymer matrix, lithium salt, nanoclay, polypropylene carbonate and an organic solvent, form a film, and dry to obtain a composite electrolyte film. The patent solves the problem of low room temperature ionic conductivity of polymer electrolyte, but does not solve the problem of matching with a layered cathode material. The capacity actually exerted by the layered positive electrode material is gradually increased along with the increase of the charge cut-off voltage, the circulation stability of the general polymer-based composite electrolyte and the high-voltage positive electrode is poor under the condition of the cut-off voltage higher than 4V, and particularly when the layered positive electrode material is in large-area contact with the positive electrode, the solid electrolyte can generate serious oxidative decomposition reaction under the catalytic action of transition metal ions or conductive carbon at about 4V, so that the large-scale application is difficult to realize. Therefore, it is highly desirable to develop a solid electrolyte membrane that can be matched with a layered structure cathode material.
Disclosure of Invention
In view of the above disadvantages of the prior art, the present invention provides a composite solid electrolyte membrane, a method for preparing the same, and a lithium ion battery, so as to improve the matching problem between the solid electrolyte membrane and the layered oxide cathode material and improve the cycle performance of the solid battery based on the layered cathode.
In order to achieve the above objects and other related objects, the present invention provides a composite electrolyte membrane comprising the following components in mass percent: 20wt% -80 wt% of polymer; 5-50 wt% of inorganic filler; 0.05wt% -2 wt% of boron-containing additive; 5 to 40 weight percent of boron-containing lithium salt.
In an example of the present invention, the polymer is at least one selected from the group consisting of polyethylene oxide, polyvinylidene fluoride-hexafluoropropylene, polymethyl methacrylate, and polyacrylonitrile.
In one example of the present invention, the boron-containing lithium salt is selected from at least two of lithium tetrafluoroborate, lithium bis (oxalato) borate, lithium difluoro (oxalato) borate, lithium bis (catechol) borate, lithium bis (2, 3-naphthalenediol) borate, lithium bis (2, 2-biphenyldioxy) borate, lithium bis (salicylic) borate, lithium bis (2, 3-pyridinedioxy) borate, lithium bis (oxalato) borate, and lithium bis (malonato) borate.
In an example of the present invention, the inorganic filler includes at least one of an oxide-based filler and a sulfide-based filler, the oxide-based filler being selected from one or a combination of more of a non-ionic conductor-based oxide, a garnet-type solid electrolyte, an NASICON-type solid electrolyte, and a perovskite-type solid electrolyte; the sulfide-based filler is selected from binary Li 2 S-P 2 S 5 One or more of system sulfide solid electrolyte, thio-LICION type sulfide solid electrolyte and Geranite type sulfide solid electrolyte.
In one example of the present invention, the non-ionic conductor is oxygenThe compound comprises one or more of boehmite, alumina, silica, magnesia, titania, clay and kaolin; the garnet-type solid electrolyte comprises Li 7-3x-y+ z A x La 3 Zr 2-y B y O 12+z/2 Or Li 7-3x-2k+z A x La 3 Zr 2-k C k O 12+z/2 Wherein A is Al and/or Ga, B is Ta and/or Nb, C is W and/or Te, x is more than or equal to 0 and less than or equal to 0.4, y is more than or equal to 0 and less than or equal to 1, k is more than or equal to 0 and less than or equal to 0.7, and z is more than or equal to 0 and less than or equal to 1.4; the NASICON type solid electrolyte comprises Li 1+ x Al x Ti 2-x (PO 4 ) 3 、Li 1+y Al y Ge 2-y (PO 4 ) 3 And Li 1+z Zr 2 P 3-z Si z O 12 Wherein x is more than or equal to 0 and less than or equal to 0.6, y is more than or equal to 0 and less than or equal to 0.6, and z is more than or equal to 0 and less than or equal to 3; the perovskite type solid electrolyte is Li 3x La 2/3-x TiO 3 Wherein x is more than 0.04 and less than 0.17.
In one example of the present invention, the binary Li 2 S-P 2 S 5 The chemical formula of the system sulfide solid electrolyte and the sulfide solid electrolyte of the Geranium sulfide is xLi 2 S·(100-x-z)A y S n zB, x is more than 0 and less than 100, y is 0, 1 or 2, n is 2y or 2y +1, z is more than or equal to 0 and less than 100-x, A is B 3+ 、P 3+ 、P 5+ 、Si 4+ Or Ge 4+ B is LiCl, liBr, liI, P 2 O 5 、GeS 2 、Li 3 PO 4 、Li 4 SiO 4 Or P 2 S 3 (ii) a The chemical formula of the thio-LICION type sulfide solid electrolyte is Li 4-x A 1-y B y S 4 Or Li 10+z K l+ z P 2-z S 12 A is selected from one of Si and Ge, B is selected from one of Al, P, zn and Ga, x is more than or equal to 0 and less than or equal to 2, y is more than or equal to 0 and less than or equal to 1, K is selected from one or more of third, fourth or fifth main group elements, and z is more than or equal to 0 and less than or equal to 1.
In one example of the invention, the boron-containing additive is selected from tris (trimethylsilyl) borate or tris (triethylsilyl) borate.
Another aspect of the present invention provides a method for preparing the composite solid electrolyte membrane, which at least includes the following steps:
fully mixing a polymer, a boron-containing lithium salt, a boron-containing additive, an inorganic filler and an organic solvent to obtain a mixed solution;
and pouring the electrolyte mixed solution into a mould, forming a film, drying and slicing to obtain the composite solid electrolyte film.
In one example of the present invention, the composite solid electrolyte membrane is prepared under an inert atmosphere.
In one example of the present invention, the preparation process of the preparation method is performed under an inert atmosphere.
In one example of the present invention, the drying temperature is 50 to 150 ℃, and the drying time is 0.2 to 24 hours.
The invention also provides a lithium ion battery, and the lithium ion battery comprises the composite solid electrolyte membrane or the composite solid electrolyte membrane prepared by the preparation method.
According to the composite solid electrolyte membrane, the inorganic filler, the boron-containing additive and the boron-containing lithium salt are added into the polymer, so that the composite solid electrolyte membrane has high room-temperature ionic conductivity; meanwhile, the boron-containing additive and the boron-containing lithium salt have a synergistic effect, so that the oxidation resistance of the electrolyte membrane is enhanced, and the composite solid electrolyte membrane has a higher electrochemical window. In addition, the high catalytic oxygen can lead the boron-containing additive to be decomposed earlier than the polymer electrolyte by oxidation in the battery cycle process to generate lithium borate Li 3 BO 3 (Li + +O 2- +TMSB→Li 3 BO 3 ) So that the reaction product can carry out in-situ coating on the layered oxide anode material, thereby preventing the catalytic oxidation caused by the direct contact of the layered oxide anode and the polymer electrolyte. The in-situ coating layer is Li with high ionic conductivity 3 BO 3 Is Li + The transmission of (2) provides a channel, which is beneficial to the normal exertion of capacity. Secondly, the composite solid electrolyte membrane of the present invention comprises at least two kinds of boron-containing lithiumThe salt can make up the disadvantage of a single lithium salt, and various boron-containing lithium salts have a synergistic effect and have a film-forming effect to a certain extent.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a flow chart of a method for producing a composite solid electrolyte membrane according to the present invention;
FIG. 2 is a flowchart of step S1 of FIG. 1;
FIG. 3 is a flow chart illustrating a method for manufacturing a composite solid electrolyte membrane according to an embodiment of the present invention;
FIG. 4 is an SEM image of a composite solid electrolyte membrane according to an embodiment of the invention;
fig. 5 is a TEM image of an in-situ coated layered cathode material formed during cycling of a lithium ion battery of the present invention.
Detailed Description
The following embodiments of the present invention are provided by specific examples, and other advantages and effects of the present invention will be readily apparent to those skilled in the art from the disclosure of the present invention. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It is to be noted that the features in the following embodiments and examples may be combined with each other without conflict. It is also to be understood that the terminology used in the examples herein is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention. Test methods in which specific conditions are not specified in the following examples are generally carried out under conventional conditions or under conditions recommended by the respective manufacturers.
In the present invention, the source of each component is not particularly limited, unless otherwise specified, and any commercially available product that is conventional to those skilled in the art may be used.
The invention provides a composite solid electrolyte membrane, a preparation method thereof and a lithium ion battery, wherein a layered anode can be coated in situ in the battery cycle process, so that the problem of matching of the solid electrolyte membrane and a layered oxide anode material is solved, and the cycle performance of the solid battery based on the layered anode is improved.
The invention provides a composite solid electrolyte membrane, which comprises the following components in percentage by mass: 20 to 80 weight percent of polymer, 5 to 50 weight percent of inorganic filler, 0.05 to 2 weight percent of boron-containing additive and 5 to 40 weight percent of boron-containing lithium salt.
The mass percentage of the polymer in the composite electrolyte membrane is 20wt% to 80wt%, and further 30wt% to 70wt%, for example, 30wt%, 50wt%, 60wt%, or 70wt%, and any value within the above range. The polymer used in the present invention is at least one selected from the group consisting of polyethylene oxide, polyvinylidene fluoride-hexafluoropropylene, polymethyl methacrylate, and polyacrylonitrile, that is, the polymer may be any one of the above-mentioned polymer species, or may be a combination of two or more of the above-mentioned polymer species. For example, the polymer is polyethylene oxide or polyvinylidene fluoride-hexafluoropropylene or polymethyl methacrylate or polyacrylonitrile; the polymer is a composition of polyethylene oxide and polyvinylidene fluoride or a composition of polyvinylidene fluoride and polyvinylidene fluoride-hexafluoropropylene or a composition of polyvinylidene fluoride-hexafluoropropylene, polymethyl methacrylate and polyacrylonitrile, the polymer is a composition of polyethylene oxide, polyvinylidene fluoride-hexafluoropropylene and polymethyl methacrylate, the polymer is a composition of polyethylene oxide, polyvinylidene fluoride-hexafluoropropylene, polymethyl methacrylate and polyacrylonitrile, and the like. The polymers can be combined in any two, three or four combinations, which are not listed here. The invention limits the types of the polymers to the range, and the obtained composite solid electrolyte has better conductivity. The polyvinylidene fluoride and the polyvinylidene fluoride-hexafluoropropylene contain fluorine atoms, so that the transportation of lithium ions is facilitated, and the performance of the lithium battery can be improved. When the polymer contains a combination of several of the above-mentioned species, the amount of each polymer is not particularly limited and may be mixed in any ratio.
The inorganic filler is present in the composite electrolyte membrane in an amount of 5wt% to 50wt%, further 10wt% to 40wt%, and may be present in any amount within the above range, for example, 10wt%, 20wt%, 30wt%, or 40wt%. The inorganic filler adopted by the invention for preparing the composite solid electrolyte membrane is a nano-scale inorganic filler and comprises at least one of an oxide filler and a sulfide filler, namely the inorganic filler can be a single oxide filler or a combination of a plurality of oxide fillers, can also be a single sulfide filler or a combination of a plurality of sulfide fillers, and can also be a combination of the oxide filler and the sulfide filler.
The oxide-based filler includes one or more of a non-ionic conductor-based oxide, a garnet-type solid electrolyte, a NASICON-type solid electrolyte, and a perovskite-type solid electrolyte. Wherein, the non-ionic conductor oxide is selected from one or more of boehmite, alumina, silica, magnesia, titania, clay, kaolin and the like; the garnet type solid electrolyte is cation-doped cubic phase Li 7 La 3 Zr 2 O 12 (LLZO) of the formula Li 7-3x-y+z A x La 3 Zr 2-y B y O 12+z/2 Or Li 7-3x-2k+z A x La 3 Zr 2-k C k O 12+z/2 Wherein A is a trivalent metal element, B is a pentavalent metal element, C is a hexavalent metal element, 0. Ltoreq. X.ltoreq.0.4, 0. Ltoreq. Y.ltoreq.1, 0. Ltoreq. K.ltoreq.0.7, 0. Ltoreq. Z.ltoreq.1.4, for example, A is Al and/or Ga, B is Ta and/or Nb, C is W and/or Te; NASICON type solid electrolyte is mainly Li 1+x Al x Ti 2-x (PO 4 ) 3 (LATP)、Li 1+y Al y Ge 2-y (PO 4 ) 3 (LAGP) and Li 1+z Zr 2 P 3-z Si z O 12 (LZSP) three types, x is more than or equal to 0 and less than or equal to 0.6, y is more than or equal to 0 and less than or equal to 0.6, and z is more than or equal to 0 and less than or equal to 3; the perovskite type solid electrolyte is Li 3x La 2/3-x TiO 3 (LLTO), 0.04 < x < 0.17. The oxide-based filler includes, but is not limited to, the above-listed substances, and other oxide solid electrolytes achieving the same effects may be used in the present invention.
The sulfide filler mainly refers to sulfide solid electrolyte and comprises binary Li 2 S-P 2 S 5 One or more of a system sulfide solid electrolyte, a thio-silicon sulfide solid electrolyte and a thiogenitic sulfide solid electrolyte. Wherein the chemical formulas of the binary Li2S-P2S5 system sulfide and the thiogermite type sulfide can be expressed as xLi 2 S(100-x-z)A y S n zB, x is more than 0 and less than 100, y is 0, 1 or 2, n is 2y or 2y +1, z is more than or equal to 0 and less than 100-x, A is B 3+ 、P 3+ 、P 5+ 、Si 4+ Or Ge 4+ B is LiCl, liBr, liI, P 2 O 5 、GeS 2 、Li 3 PO 4 、Li 4 SiO 4 Or P 2 S 3 . the chemical formula of the thio-LICION type sulfide solid electrolyte is Li 4-x A 1-y B y S 4 Or Li 10+z K l+z P 2-z S 12 A is selected from one of Si and Ge, B is selected from one of Al, P, zn and Ga, x is more than or equal to 0 and less than or equal to 2, y is more than or equal to 0 and less than or equal to 1, K is selected from one or more of third, fourth or fifth main group elements, and z is more than or equal to 0 and less than or equal to 1. The sulfide-based filler includes, but is not limited to, the above-listed substances, and other sulfide solid electrolytes that can achieve the same effects can be used in the present invention.
The amount of the boron-containing additive in the composite solid electrolyte is 0.05 to 2wt%, and further 0.1 to 1.5wt%, and may be any of the above-described ranges, for example, 0.1wt%, 0.5wt%, 1wt%, or 1.5 wt%. The boron-containing additive used for preparing the composite solid electrolyte membrane is selected from tri (trimethylsilyl) borate, tri (triethylsilyl) borate or other boron-containing additives with the same effect.
The mass percentage of the boron-containing lithium salt in the composite solid electrolyte is 5wt% to 40wt%, and further 10wt% to 35wt%, and may be any value within the above range, for example, 10wt%, 20wt%, 28wt%, or 35 wt%. Preferably, the composite solid electrolyte membrane of the present invention includes at least two different lithium salts containing boron. The boron-containing lithium salt is selected from at least two of lithium tetrafluoroborate, lithium bis (oxalato) borate, lithium difluoro (oxalato) borate, lithium bis (catechol) borate, lithium bis (2, 3-naphthalenediol) borate, lithium bis (2, 2-biphenyldioxy) borate, lithium bis (salicylate) borate, lithium bis (2, 3-pyridinedioxy) borate, lithium bis (borates), lithium bis (malonato) borate. That is, the boron-containing lithium salt may be any two combinations, three combinations or more combinations of the above-listed lithium salts, for example, the boron-containing lithium salt is a combination of lithium tetrafluoroborate and lithium bis (oxalato) borate, or a combination of lithium difluorooxalato borate, lithium bis (catechol) borate and lithium bis (2, 3-naphthalenediol) borate, or a combination of lithium bis (2, 2-biphenyldioxy) borate, lithium bis (salicylate) borate, lithium bis (2, 3-pyridinedioxy) borate, lithium bis (borates) and lithium bis (malonato) borate, etc., and so forth, and is not further listed herein. The amount of each lithium salt in the boron-containing lithium salt composition of the present invention is not particularly limited, and may be mixed in any ratio. The common use of multiple boron-containing lithium salts can make up for the disadvantages of a single lithium salt.
The composite solid electrolyte membrane of the invention introduces inorganic filler, boron-containing additive and a plurality of boron-containing lithium salts into the polymer matrix, so that the composite solid electrolyte membrane has higher room-temperature ionic conductivity; moreover, the boron-containing additive and the boron-containing lithium salt have synergistic effect, so that the oxidation resistance of the electrolyte membrane can be enhanced, and the composite solid electrolyte membrane has a higher electrochemical window; the high catalytic oxidation can lead the boron-containing additive to be preferentially oxidized and decomposed in preference to the polymer in the battery cycle process to generate the lithium borate Li 3 BO 3 (Li + +O 2- +TMSB→Li 3 BO 3 ) Reaction product Li 3 BO 3 The positive electrode can be coated in situ, so as to prevent the layered oxide positive electrode from being positioned in the polymer electrolyteThe catalytic oxidation occurs by direct contact.
Referring to fig. 1, the present invention provides a method for preparing the composite solid electrolyte membrane, including the following steps:
s1, fully and uniformly mixing a polymer, a boron-containing lithium salt, a boron-containing additive, an inorganic filler and an organic solvent to obtain a mixed solution;
and S2, pouring the mixed solution into a mold, forming a film, drying and slicing to obtain the composite solid electrolyte film.
Wherein the organic solvent in step S1 is at least one selected from the group consisting of N, N-dimethylformamide, N-methylpyrrolidone, acetonitrile, acetone, and tetrahydrofuran. That is, the organic solvent may be any one of the above-listed kinds, or may be a combination of any two or more kinds, and the proportions of the components in the organic solvent to be combined are not limited, and may be mixed in any proportions. The organic solvent is mainly used for dispersing the polymer, the lithium salt containing boron, the additive containing boron and the inorganic filler, the dosage of the organic solvent is not limited, as long as the polymer, the lithium salt containing boron, the additive containing boron and the inorganic filler can be fully dissolved, and the organic solvent can be completely volatilized in the subsequent treatment process. The polymer, the boron-containing lithium salt, the boron-containing additive and the inorganic filler are weighed according to the above-mentioned proportion, which is not described herein again.
Referring to fig. 1 and fig. 2, in an embodiment, the step S1 specifically includes:
s11, dispersing the polymer into an organic solvent, and fully mixing to completely dissolve the polymer;
s12, adding the boron-containing lithium salt and the boron-containing additive into the mixed solution obtained in the step S11, and fully mixing to uniformly disperse the boron-containing lithium salt and the boron-containing additive;
and S13, adding an inorganic filler into the mixed liquid obtained in the step S12, and fully mixing to uniformly disperse the inorganic filler.
The mixing method of the present invention is not particularly limited, and the polymer, the boron-containing lithium salt, the boron-containing additive and the inorganic filler may be dissolved in an organic solvent by a mixing method known to those skilled in the art. Preferably, the mixing can be carried out by a combination of ultrasound and stirring, wherein the ultrasound helps the raw materials to be dispersed in the organic solvent in a molecular form, and the stirring can realize the sufficient mixing of the raw materials. Preferably, the stirring is carried out at room temperature, so that the material is prevented from being unevenly dispersed due to volatilization of the organic solvent before film formation.
Referring to fig. 1, in step S2, the mixed solution prepared in step S1 is poured into a mold, and a composite solid electrolyte membrane is obtained by film formation, drying and slicing. The mold can be a mold for preparing an electrolyte film, which is well known to those skilled in the art, and the mixed solution film forming mode can be a conventional film forming mode such as pouring, casting and the like.
The drying temperature in step S2 is 50 to 150 ℃, preferably 60 to 120 ℃, for example, 60 ℃, 80 ℃, 100 ℃ or 120 ℃ or any value in the above range; the drying time is 0.2 to 24 hours, preferably 5 to 20 hours, for example, the drying time is any value within the above range such as 5 hours, 8 hours, 12 hours, 15 hours or 20 hours. The present invention limits the drying temperature and time within the above ranges, and can sufficiently remove the organic solvent in the mixed solution without affecting the performance of the composite solid electrolyte membrane.
Preferably, the preparation process of the composite solid electrolyte membrane of the present invention is performed in an inert atmosphere, such as a nitrogen atmosphere, so that the lithium salt can be prevented from absorbing water, and the influence of oxygen in the air on the performance of the composite solid electrolyte membrane can be avoided.
The preparation method of the composite solid electrolyte membrane is simple, and the prepared composite solid electrolyte membrane has a high electrochemical window and high ionic conductivity. In the battery cycle process, the boron-containing additive in the composite solid electrolyte can be preferentially oxidized and decomposed to generate lithium borate so as to carry out in-situ coating on the positive electrode, prevent the direct contact between the polymer electrolyte and the positive electrode and catalytic oxidation, and improve the cycle stability of the battery. In addition, the in-situ coating layer can reach the nanometer level and can be Li + The transmission of (2) provides a channel, which is beneficial to the normal exertion of capacity.
The invention also provides a lithium ion battery which comprises a positive electrode material, a negative electrode material and a solid electrolyte arranged between the positive electrode material and the negative electrode material, wherein the solid electrolyte adopts the composite solid electrolyte membrane or the composite solid electrolyte membrane prepared by the preparation method.
The preparation process of the lithium ion battery is not specially specified, and the composite solid electrolyte membrane provided by the invention can be used as an electrolyte material by adopting a lithium battery preparation method well known by the technical personnel in the field.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. The described embodiments are only some embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The preparation of the following examples is illustrated in FIG. 3.
Example 1
The raw materials comprise: 60wt% of polyethylene oxide, 5wt% of sulfide electrolyte Li 5.4 PS 4.4 Cl 1.6 (particle diameter D50=1 μm), 0.5wt% of tris (trimethylsilyl) borate and 34.5wt% of a combination of lithium difluorooxalato borate and lithium bis (oxalato) borate (mass ratio 1.
Referring to fig. 3, the preparation process of this embodiment is as follows:
according to the proportion, firstly, dissolving polyethylene oxide in anhydrous acetonitrile, and then adding tris (trimethylsilyl) borate, lithium difluoro (oxalato) borate and lithium bis (oxalato) borate to fully disperse the materials; addition of sulfide electrolyte Li 5.4 PS 4.4 Cl 1.6 (particle diameter D50=1 μm), sufficiently dispersed; and pouring the mixed solution into a polytetrafluoroethylene mold to form a film, drying at 60 ℃ for 12h, and then slicing to obtain the composite solid electrolyte film.
Example 2
The raw materials comprise: 80wt% of polyvinylidene fluoride and 5wt% of oxide electrolyte Li 0.5 La 0.5 TiO 3 (particle diameter D50=150 nm), 2wt% of tris (triethylsilyl) borate, 13wt% of lithium difluorooxalate borate and lithium bis-oxalate borate (mass ratio 1.
Referring to fig. 3, the preparation process of this embodiment is as follows: dissolving polyvinylidene fluoride in N-methyl pyrrolidone according to the proportion, and then adding tri (triethylsilyl) borate, lithium difluoro-oxalate borate and lithium bis-oxalate borate until the materials are completely dispersed; adding oxide electrolyte Li 0.5 La 0.5 TiO 3 Fully dispersing; pouring the mixed solution into a casting machine for casting to form a film, drying at 120 ℃ for 0.5h, and then slicing to obtain the composite solid electrolyte film.
Example 3
The raw materials comprise: 40wt% of polyacrylonitrile, 50wt% of oxide electrolyte Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12 (particle diameter D50=300 nm), 0.05wt% of tris (trimethylsilyl) borate, 9.95wt% of lithium tetrafluoroborate, lithium difluorooxalate borate and lithium bis-oxalate borate (mass ratio 1.
Referring to fig. 3, the preparation process of this embodiment: according to the proportion, firstly, dissolving polyacrylonitrile in N, N-dimethylformamide, and then adding tri (trimethylsilyl) borate, lithium tetrafluoroborate, lithium difluoro-oxalato-borate and lithium bis-oxalato-borate until the materials are completely dispersed; adding oxide electrolyte Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12 And after full dispersion, pouring the mixed solution into a polytetrafluoroethylene mold to form a film, drying at 120 ℃ for 8 hours, and slicing to obtain the composite solid electrolyte film.
Example 4
The raw materials comprise: a composition of 80wt% of polymethyl methacrylate, 13.5wt% of alumina (particle diameter D50=80 nm), 1.5wt% of tris (trimethylsilyl) borate, 5wt% of lithium bis-borate, lithium difluoro-oxalato-borate and lithium bis-oxalato-borate (mass ratio 1.
Referring to fig. 3, the preparation process of this embodiment: according to the mixture ratio, firstly dissolving polymethyl methacrylate in a mixed solvent (mass ratio is 1; and adding alumina, fully dispersing, pouring the mixed solution into a polytetrafluoroethylene mold to form a film, drying at 100 ℃ for 6 hours, and slicing to obtain the composite solid electrolyte film.
Comparative example 1
Comparative example 1 differs from example 1 in that: the boron-containing additive is not added, and the raw materials are as follows: 60% by weight of polyethylene oxide, 5% by weight of sulfide electrolyte Li 5.4 PS 4.4 Cl 1.6 35wt% lithium difluorooxalato borate and lithium bis-oxalato borate (mass ratio 1).
Comparative example 2
Comparative example 2 differs from example 1 in that: the inorganic filler is not added, and the raw material ratio is as follows: the same procedure as in example 1 was repeated except for using a composition of 65wt% of polyethylene oxide, 0.5wt% of tris (trimethylsilyl) borate, 34.5wt% of lithium difluorooxalate borate and lithium bis (oxalato) borate (mass ratio 1.
Comparative example 3
Comparative example 3 differs from example 1 in that: the lithium salt containing boron is not used, and other lithium salts are used for replacing the lithium salt, and the mixture ratio of the raw materials is as follows: 60% by weight of polyethylene oxide, 5% by weight of sulfide electrolyte Li 5.4 PS 4.4 Cl 1.6 0.5wt% tris (trimethylsilyl) borate, 34.5wt% lithium bis (trifluoromethylsulfonyl) imide, and the other operations were the same as in example 1.
Comparative example 4
Comparative example 4 differs from example 1 in that: no inorganic filler and boron-containing additive are added, and the raw materials are as follows: 60wt% of polyethylene oxide, 40wt% of lithium difluorooxalato borate and lithium bis-oxalato borate (mass ratio 1.
The solid electrolyte membranes prepared in examples 1 to 4 and comparative examples 1 to 4 were applied to lithium ion batteries according to the following procedure:
the method comprises the following steps: preparing a positive electrode layer, weighing and adding a ternary positive electrode material (NCM 622), conductive carbon black (SP) as a conductive agent and polytetrafluoroethylene into N-methylpyrrolidone in a mass ratio of 96; uniformly coating the slurry on an aluminum foil (the thickness of the aluminum foil is 16 mu m), drying at 120 ℃, and tabletting by a roller press to obtain a positive electrode layer;
preparing a negative electrode film, wherein metal lithium is used as a negative electrode;
and step three, assembling the solid-state battery, namely cutting the positive electrode layer prepared in the step one, placing the cut positive electrode layer into a mold, sequentially overlapping the composite solid electrolyte membrane and the negative electrode membrane in the step two, and carrying out isostatic pressing at 60 ℃ and 20MPa to obtain the solid-state battery. Among them, the solid-state batteries corresponding to the composite solid electrolyte membranes of examples 1 to 4 were SSB-01, SSB-02, SSB-03, and SSB-04 in this order, and the solid-state batteries corresponding to the composite solid electrolyte membranes prepared in comparative examples 1 to 4 were SSB-05, SSB-06, SSB-07, and SSB-08 in this order.
Respectively carrying out performance detection on the solid-state batteries SSB-01-SSB-08, including cycle performance and an electrochemical window, wherein the specific test method comprises the following steps:
the electrochemical window was tested as follows: testing by adopting a principle battery mould, sequentially adding a lithium sheet, a composite solid electrolyte membrane and a stainless steel sheet, and carrying out cyclic voltammetry testing under the following test conditions: OCV → 0V → 5V → OCV, sweep rate is 0.5mV/s, turn 3; the test conditions are adjusted according to the electrochemical properties of the composite electrolyte itself.
The test method of the cycle performance is as follows: the method comprises the steps of testing by adopting a principle battery mould, wherein the testing temperature is 60 ℃, constant-current charging is carried out to 4.3V at a current of 0.1C, then constant-voltage charging is carried out to a current of 0.05C, the current is cut off, then standing is carried out for 20min, discharging is carried out to 2.7V at a current of 0.2C, standing is carried out for 20min, a cycle is completed, and the charge-discharge cycle test is carried out in a reciprocating mode.
The cycle performance and the electrochemical performance of the solid-state batteries SSB-01 to SSB-08 are respectively tested by adopting the method, and the test results are shown in Table 1.
Table 1: cycle performance and electrochemical performance detection results of solid-state batteries SSB-01-SSB-08
As can be seen from the performance test results of each solid-state battery in table 1, when no boron-containing additive is added or a boron-containing lithium salt is replaced with another lithium salt, the cycle performance of the battery is significantly reduced, and the composite solid electrolyte membrane provided by the present invention has a wider electrochemical window and more excellent cycle performance when applied to an all-solid-state battery.
Referring to fig. 4 and 5, the shapes of the composite solid electrolyte membrane of the present invention and the anode material after the solid-state battery using the composite solid electrolyte membrane of the present invention is cycled are respectively tested by a scanning electron microscope and a transmission electron microscope. It can be seen from fig. 4 that the composite solid electrolyte membrane has a relatively uniform structure, and the inorganic filler, the boron-containing additive, and the lithium salt containing boron are uniformly dispersed in the polymer. It is apparent from the transmission electron microscope image in fig. 5 that there is a coating layer on the outer side of the positive electrode material, which can prevent the direct contact between the polymer electrolyte and the positive electrode oxide layer, and avoid the catalytic oxidation reaction of the layered oxide positive electrode to the polymer-based electrolyte film.
According to the composite solid electrolyte membrane, the inorganic filler, the boron-containing additive and the boron-containing lithium salt are added into the polymer, so that the composite solid electrolyte membrane has high room-temperature ionic conductivity; meanwhile, the boron-containing additive and the boron-containing lithium salt have synergistic effect, so that the oxidation resistance of the electrolyte membrane is enhanced, and the composite solid electrolyte membrane has a higher electrochemical window. The composite solid electrolyte is applied to a solid battery, and the high catalytic oxygen can lead the boron-containing additive to be decomposed earlier than the polymer electrolyte in the battery circulation process to generate lithium borate Li 3 BO 3 The layered oxide anode material is coated in situ, so that catalytic oxidation caused by direct contact of the layered oxide anode and a polymer electrolyte is prevented, and the cycle stability of the solid-state battery is improved. Therefore, the invention effectively overcomes some practical problems in the prior art, thereby having high utilization value and use significance.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. A composite solid electrolyte membrane, characterized by comprising, in mass percent of the composite solid electrolyte membrane:
2. the composite solid electrolyte membrane according to claim 1, wherein the polymer is at least one selected from the group consisting of polyethylene oxide, polyvinylidene fluoride-hexafluoropropylene, polymethyl methacrylate, and polyacrylonitrile.
3. The composite solid electrolyte membrane according to claim 1, wherein the lithium boron-containing salt is selected from at least two of lithium tetrafluoroborate, lithium bis (oxalato) borate, lithium difluoro (oxalato) borate, lithium bis (catechol) borate, lithium bis (2, 3-naphthalenediol) borate, lithium bis (2, 2-biphenyldioxy) borate, lithium bis (salicylate) borate, lithium bis (2, 3-pyridinedioxy) borate, lithium bis (borates), lithium bis (malonato) borate.
4. The composite solid electrolyte membrane according to claim 1, wherein the inorganic filler includes at least one of an oxide-based filler and a sulfide-based filler, the oxide-based filler being selected from one or a combination of more of a non-ionic conductor-based oxide, a garnet-type solid electrolyte, a NASICON-type solid electrolyte, and a perovskite-type solid electrolyte; the sulfide-based filler is selected from binary Li 2 S-P 2 S 5 System sulfide solid electrolyte, thio-LISICON type sulfide solid electrolyte and thiogenitic sulfurOne or more of a combination of solid electrolytes.
5. The composite solid electrolyte membrane according to claim 4, wherein the non-ionic conductor-type oxide comprises one or more combinations of boehmite, alumina, silica, magnesia, titania, clay, kaolin; the garnet-type solid electrolyte comprises Li 7-3x-y+z A x La 3 Zr 2-y B y O 12+z/2 Or Li 7-3x-2k+z A x La 3 Zr 2-k C k O 12+z/2 Wherein A is Al and/or Ga, B is Ta and/or Nb, C is W and/or Te, x is more than or equal to 0 and less than or equal to 0.4, y is more than or equal to 0 and less than or equal to 1, k is more than or equal to 0 and less than or equal to 0.7, and z is more than or equal to 0 and less than or equal to 1.4; the NASICON type solid electrolyte comprises Li 1+x Al x Ti 2-x (PO 4 ) 3 、Li 1+y Al y Ge 2-y (PO 4 ) 3 And Li 1+z Zr 2 P 3-z Si z O 12 Wherein x is more than or equal to 0 and less than or equal to 0.6, y is more than or equal to 0 and less than or equal to 0.6, and z is more than or equal to 0 and less than or equal to 3; the perovskite type solid electrolyte is Li 3x La 2/3-x TiO 3 Wherein x is more than 0.04 and less than 0.17.
6. The composite solid electrolyte membrane according to claim 4, characterized in that the binary Li 2 S-P 2 S 5 The chemical formula of the system sulfide solid electrolyte and the sulfide solid electrolyte of the Geranium sulfide is xLi 2 S·(100-x-z)A y S n zB,0 < x < 100, wherein y is 0, 1 or 2, n is 2y or 2y +1,0 < z < 100-x, A is B 3+ 、P 3+ 、P 5+ 、Si 4+ Or Ge 4+ B is LiCl, liBr, liI, P 2 O 5 、GeS 2 、Li 3 PO 4 、Li 4 SiO 4 Or P 2 S 3 (ii) a The chemical formula of the thio-LICION type sulfide solid electrolyte is Li 4-x A 1-y B y S 4 Or Li 10+z K l+z P 2-z S 12 And A is selectedB is selected from one of Al, P, zn and Ga, x is more than or equal to 0 and less than or equal to 2, y is more than or equal to 0 and less than or equal to 1, K is selected from one or more of third, fourth or fifth main group elements, and z is more than or equal to 0 and less than or equal to 1.
7. The composite solid electrolyte membrane according to claim 1, wherein the boron-containing additive is selected from tris (trimethylsilyl) borate or tris (triethylsilyl) borate.
8. A method for producing the composite solid electrolyte membrane according to claim 1, comprising the steps of:
fully and uniformly mixing a polymer, a boron-containing lithium salt, a boron-containing additive, an inorganic filler and an organic solvent to obtain a mixed solution;
and pouring the mixed solution into a mold, forming a film, drying and slicing to obtain the composite solid electrolyte film.
9. The method for producing a composite solid electrolyte membrane according to claim 8, wherein the drying temperature is 50 to 150 ℃, and the drying time is 0.2 to 24 hours.
10. A lithium ion battery comprising the composite electrolyte membrane according to any one of claims 1 to 7 or the composite solid electrolyte membrane produced by the production method according to any one of claims 9 to 10.
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| CN202211029889.7A CN115395079A (en) | 2022-08-25 | 2022-08-25 | Composite solid electrolyte membrane, preparation method thereof and lithium ion battery |
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| CN109994773A (en) * | 2018-01-03 | 2019-07-09 | 郑州宇通客车股份有限公司 | A kind of lithium ion battery solid union dielectric film and preparation method thereof, solid lithium ion battery |
| CN110380121A (en) * | 2019-07-26 | 2019-10-25 | 谢中淮 | A kind of electrolyte composition and its battery |
| CN113745653A (en) * | 2021-08-31 | 2021-12-03 | 西安交通大学 | In-situ solid battery preparation method based on PVDF-HFP polymer solid electrolyte |
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| CN109994773A (en) * | 2018-01-03 | 2019-07-09 | 郑州宇通客车股份有限公司 | A kind of lithium ion battery solid union dielectric film and preparation method thereof, solid lithium ion battery |
| CN110380121A (en) * | 2019-07-26 | 2019-10-25 | 谢中淮 | A kind of electrolyte composition and its battery |
| CN113745653A (en) * | 2021-08-31 | 2021-12-03 | 西安交通大学 | In-situ solid battery preparation method based on PVDF-HFP polymer solid electrolyte |
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| 闫春生等: "锂离子电池电解质锂盐的发展历程和新型锂盐的研究进展", 河南化工, vol. 33, no. 4, 15 April 2016 (2016-04-15), pages 14 - 17 * |
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