CN116315068A - Solid electrolyte, solid electrolyte composite electrode and preparation method thereof - Google Patents
Solid electrolyte, solid electrolyte composite electrode and preparation method thereof Download PDFInfo
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- CN116315068A CN116315068A CN202310208179.9A CN202310208179A CN116315068A CN 116315068 A CN116315068 A CN 116315068A CN 202310208179 A CN202310208179 A CN 202310208179A CN 116315068 A CN116315068 A CN 116315068A
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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 42
- 238000002360 preparation method Methods 0.000 title description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 50
- 239000011159 matrix material Substances 0.000 claims abstract description 49
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 14
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 14
- 229920006126 semicrystalline polymer Polymers 0.000 claims abstract description 11
- 239000010936 titanium Substances 0.000 claims description 61
- 239000002002 slurry Substances 0.000 claims description 35
- 238000001035 drying Methods 0.000 claims description 26
- 239000002135 nanosheet Substances 0.000 claims description 22
- 239000002033 PVDF binder Substances 0.000 claims description 19
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 19
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 15
- 239000003792 electrolyte Substances 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 14
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 239000011888 foil Substances 0.000 claims description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 11
- 239000007774 positive electrode material Substances 0.000 claims description 9
- 239000010416 ion conductor Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- RJEIKIOYHOOKDL-UHFFFAOYSA-N [Li].[La] Chemical compound [Li].[La] RJEIKIOYHOOKDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000011267 electrode slurry Substances 0.000 claims description 4
- -1 lithium aluminum lithium lanthanum zirconium oxide Chemical compound 0.000 claims description 4
- FVXHSJCDRRWIRE-UHFFFAOYSA-H P(=O)([O-])([O-])[O-].[Ge+2].[Al+3].[Li+].P(=O)([O-])([O-])[O-] Chemical compound P(=O)([O-])([O-])[O-].[Ge+2].[Al+3].[Li+].P(=O)([O-])([O-])[O-] FVXHSJCDRRWIRE-UHFFFAOYSA-H 0.000 claims description 2
- CVJYOKLQNGVTIS-UHFFFAOYSA-K aluminum;lithium;titanium(4+);phosphate Chemical compound [Li+].[Al+3].[Ti+4].[O-]P([O-])([O-])=O CVJYOKLQNGVTIS-UHFFFAOYSA-K 0.000 claims description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 claims description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 2
- 229910000659 lithium lanthanum titanates (LLT) Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims 1
- PSVBHJWAIYBPRO-UHFFFAOYSA-N lithium;niobium(5+);oxygen(2-) Chemical compound [Li+].[O-2].[O-2].[O-2].[Nb+5] PSVBHJWAIYBPRO-UHFFFAOYSA-N 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 27
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 27
- 230000005540 biological transmission Effects 0.000 abstract description 14
- 229910010413 TiO 2 Inorganic materials 0.000 abstract description 12
- 239000006185 dispersion Substances 0.000 abstract description 5
- 239000000945 filler Substances 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 2
- 238000007493 shaping process Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 29
- 239000000243 solution Substances 0.000 description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 14
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 10
- 239000013081 microcrystal Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 239000002064 nanoplatelet Substances 0.000 description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 8
- 230000002349 favourable effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000012546 transfer Methods 0.000 description 5
- 238000000498 ball milling Methods 0.000 description 4
- 238000010494 dissociation reaction Methods 0.000 description 4
- 230000005593 dissociations Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 239000005279 LLTO - Lithium Lanthanum Titanium Oxide Substances 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- UKGZHELIUYCPTO-UHFFFAOYSA-N dicesium;oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Cs+].[Cs+] UKGZHELIUYCPTO-UHFFFAOYSA-N 0.000 description 2
- 230000003203 everyday effect Effects 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910009178 Li1.3Al0.3Ti1.7(PO4)3 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- OCQSXFPWUMTHNA-UHFFFAOYSA-N [O-2].[Al+3].[Zr+4].[La+3].[Li+] Chemical compound [O-2].[Al+3].[Zr+4].[La+3].[Li+] OCQSXFPWUMTHNA-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000001913 cellulose Chemical class 0.000 description 1
- 229920002678 cellulose Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
- H01M10/056—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
-
- 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
- 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
-
- 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
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- 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)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Secondary Cells (AREA)
Abstract
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a solid electrolyte and a composite electrode. The solid electrolyte comprises the following components in percentage by mass: crystalline polymer matrix and/or semi-crystalline polymer matrix 59% -79% of crystalline polymer matrix and/or semi-crystalline polymer matrix, lithium salt 20% -40% and Ti 1‑δ O 2 4δ‑ (0<δ<1) 1% -9%. The invention introduces charged Ti into the solid electrolyte 1‑δ O 2 4δ‑ The material is mixed with general inert filler TiO 2 In comparison, because of its chargeability, its dispersion in the polymer is more uniform, facilitating the absence of the polymer matrixThe increase of the shaping area is beneficial to the transmission of lithium ions in the solid electrolyte, so that the assembled half cell has smaller internal resistance and higher charge-discharge capacity.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a solid electrolyte, a solid electrolyte composite electrode and a preparation method thereof.
Background
With the development and progress of new energy technology, lithium batteries are currently the hottest new energy technology, and the safety requirements of people on lithium batteries are gradually improved, so that solid electrolyte batteries are considered by researchers to be favorable competitors of new-generation electrolytes. Currently, solid electrolytes can be largely divided into the following categories: polymer electrolytes, oxides and sulfides. Among them, polymer electrolytes have been receiving attention in the industry for their advantages of excellent mechanical properties and light weight. Currently, polymer solid electrolyte matrices mainly include polyethylene oxide (PEO), polyacrylonitrile (PAN), polyvinyl alcohol (PVA), polyvinylidene fluoride (PVDF), and the like.
At present, in the polymer solid electrolyte matrix, PVDF-HFP is a copolymer of crystalline polyvinylidene fluoride and amorphous hexafluoropropylene, on one hand, the polar group (-F) of the PVDF-HFP can be favorable for dissociation of lithium salt, on the other hand, the amorphous region chain segment of the PVDF-HFP can transmit lithium ions, and the PVDF-HFP has strong oxidation resistance and can resist higher voltage due to the existence of strong hydrogen bonds, so that the PVDF-HFP is strongly focused by researchers. However, the contact between the solid electrolyte and the electrode interface is poor, the wettability is poor, and the like, which results in high interface impedance, thereby affecting Li + The transmission between the solid electrolyte and the electrode further influences the charge-discharge capacity and other performances of the whole lithium battery. In order to solve the problem of poor contact between the solid electrolyte and the electrode, researchers have made continuous efforts over the years, such as preparing a solid composite electrolyte with the electrode as a support, wherein a portion of the electrolyte permeates into the interstices of the porous electrode due to the influence of gravity in the solid electrolyte slurry above the electrode sheet, and the preparation of the solid composite electrolyte improves the contact effect of the electrolyte with the electrode and reduces the interface impedance. Also for example, inorganic inert fillers TiO 2 Al and Al 2 O 3 And the like are introduced into the solid electrolyte of the organic polymer, which is favorable for breaking the crystal structure in the polymer, increasing the amorphous area of the solid electrolyte and being favorable for Li + Is transmitted by the base station. However, it has been found that the method for preparing a solid composite electrolyte using an electrode as a support is due to the crystallinity of the polymer matrix itselfThe chain segment movement is not strong, so that the transmission rate of lithium ions in the solid electrolyte is too low, the transmission of lithium ions transmitted by the electrode is limited, and the internal resistance is large, the first-ring efficiency is low and the charge-discharge capacity is not high enough after the battery is assembled; addition of an inorganic inert filler TiO to a polymer solid electrolyte 2 Al and Al 2 O 3 Etc. due to conventional TiO 2 The powder is easy to agglomerate in the polymer matrix, so that the powder is unevenly dispersed in the polymer matrix, and is unfavorable for the transmission of lithium ions in the solid electrolyte, so that the internal resistance is large, the first-ring efficiency is low and the discharge capacity is low after the battery is assembled.
Disclosure of Invention
To solve the drawbacks and disadvantages of the prior art, a primary object of the present invention is to provide a solid electrolyte.
Another object of the present invention is to provide a solid electrolyte composite electrode.
It is still another object of the present invention to provide a method for producing the above solid electrolyte composite electrode.
The invention aims at realizing the following technical scheme:
the solid electrolyte comprises the following components in percentage by mass:
59% -79% of crystalline polymer matrix and/or semi-crystalline polymer matrix
20 to 40 percent of lithium salt
Ti 1-δ O 2 4δ -(0<δ<1) 1％-9％。
Preferably, the solid electrolyte comprises the following components in percentage by mass:
59% -78% of crystalline polymer matrix and/or semi-crystalline polymer matrix
20 to 38 percent of lithium salt
Ti 1-δ O 2 4δ -(0<δ<1) 2％-6％。
More preferably, the solid electrolyte comprises the following components in percentage by mass:
60-70% of crystalline polymer matrix and/or semi-crystalline polymer matrix
27 to 38 percent of lithium salt
Ti 1-δ O 2 4δ -(0<δ<1) 2％-6％。
Preferably, the semi-crystalline polymer matrix comprises one or more of vinylidene fluoride-co-hexafluoropropylene (PVDF-HFP), polyacrylonitrile (PAN) and polyvinyl alcohol (PVA), and the crystalline polymer matrix comprises one or more of polyethylene oxide (PEO) and polyvinylidene fluoride (PVDF).
Preferably, the Ti is 1-δ O 2 4δ -wherein 0.09. Ltoreq.delta. Ltoreq.0.13;
further preferably, the Ti is 1-δ O 2 4δ -is Ti 0.87 O 2 0.52 -or Ti 0.91 O 2 0.36 -；
Preferably, ti 1-δ O 2 4δ -nano-platelets. Ti according to the invention 1-δ O 2 4δ -(0<δ<1) The titanium oxide nanoplatelets can be prepared, for example, when δ=0.13 or 0.09, by reference to methods conventional in the art, by the following steps:
TiO is mixed with 2 、K 2 CO 3 And Li (lithium) 2 CO 3 Mixed according to the molar ratio of 10.4:2.4:0.8 and reacted for 20 hours at 1173K to obtain titanic acid microcrystal (K) 0.8 [Ti 1.73 Li 0.27 ]O 4 ) The microcrystals are stirred in HCl solution for 2-3 days at room temperature, and the protonated product H is collected by filtration 1.07 Ti 1.73 O 4 Cleaning, air drying, and then adding H 1.07 Ti 1.73 O 4 Immersion (CH) 3 ) 4 In NOH solution, ti is obtained 0.87 O 2 0.52- A nanosheet;
TiO is mixed with 2 And Cs 2 CO 3 Mixing according to the mol ratio of 1:5.3, and reacting for 20 hours at 1073K to obtain layered cesium titanate microcrystal(Cs 0.7 Ti 1.825 O 4 ) The microcrystals are stirred in HCl solution for 2-3 days at room temperature, and the protonated product H is collected by filtration 0.7 Ti 1.825 O 4 And then H is taken up 0.7 Ti 1.825 O 4 Reacting in TBAOH (tetrabutylammonium hydroxide) solution at room temperature for 10-40 days to obtain Ti 0.91 O 2 0.36- A nano-sheet.
Preferably, the lithium salt comprises LiFSI (lithium bis-fluorosulfonyl imide), liTFSI (lithium bis-trifluoromethanesulfonyl imide), liPF 6 (lithium hexafluorophosphate), C 4 BLiO 8 (lithium Dioxalato borate), C 2 BF 2 LiO 4 (lithium difluorooxalato borate) or LiClO 4 (lithium perchlorate) one or more of the following.
Preferably, the solid electrolyte further comprises a dispersing agent, wherein the dispersing agent can be added to further improve the uniformity of the nano-sheets in the polymer matrix, the mass percentage of the nano-sheets in the solid electrolyte can be 0.2% -0.5%, and the dispersing agent can be one or more of polyacrylamide, fatty acid polyethylene glycol ester and cellulose derivatives.
A solid electrolyte composite electrode comprises an electrode and a solid electrolyte coated on the electrode.
The electrode comprises a positive electrode material, conductive carbon black and a binder, wherein the mass percentages of the components are as follows:
80 to 90 percent of positive electrode material
Conductive carbon black 5-10%
3% -10% of binder.
Further preferably, the electrode further comprises the following components in percentage by mass: 2% -8% of fast ion conductor.
The fast ion conductor adopts any one or more of Lithium Aluminum Titanium Phosphate (LATP), lithium Lanthanum Zirconate (LLZO), lithium Lanthanum Niobate (LLNO), lithium Neodymium Titanium Oxide (LNTO), lithium Aluminum Germanium Phosphate (LAGP), lithium aluminum lanthanum zirconium oxide (LLZAO) and Lithium Lanthanum Titanate (LLTO).
The positive electrode material can be lithium cobaltate (LiCoO) 2 ) Lithium manganate (LiMn) 2 O 4 ) Lithium iron phosphate (L)iFePO 4 ) And the like.
The binder may be polyvinylidene fluoride (PVDF).
The preparation of the solid electrolyte composite electrode comprises the following steps:
(1) Dissolving each component in the electrode in an organic solvent to obtain electrode slurry, coating the electrode slurry on an aluminum foil, and then drying in vacuum to obtain the electrode for later use;
(2) Crystalline polymer matrix and/or semi-crystalline polymer matrix, lithium salt and Ti 1-δ O 2 4δ -dissolving in an organic solvent to obtain a solid electrolyte slurry for use;
(3) And coating the solid electrolyte slurry on the electrode, and then drying in vacuum to obtain the solid electrolyte composite electrode.
Preferably, the organic solvent of step (1) and step (2) independently comprises at least one of N-methylpyrrolidone (NMP), acetonitrile, acetone or N, N-Dimethylformamide (DMF).
Preferably, the vacuum drying in the step (3) is performed at 50-60 ℃ for 20 hours.
Compared with the prior art, the invention has the following advantages:
(1) Charged Ti 1-δ O 2 4δ -with the general inert filler TiO 2 In comparison, due to its chargeability, its dispersion in the polymer is more uniform, facilitating the increase of the amorphous region of the polymer matrix and the transport of lithium ions in the solid electrolyte.
(2) Inorganic filler Ti 1-δ O 2 4δ The introduction reduces the crystallinity of the polymer matrix and alters the local structure of the polymer chains, and according to the Lewis acid-base theory, the inorganic filler also favors the further dissociation of the Li salt, so that the half-cell assembled from it has a smaller internal resistance and a higher charge-discharge capacity.
(3) In a preferred embodiment, the nano-platelet-shaped Ti 1-δ O 2 4δ -in contrast to conventional spherical TiO 2 Is less prone to agglomeration and tends to be uniform in the polymer matrixThe regular arrangement of the polymer chain segments can be further changed by dispersing, and the crystallinity of the polymer matrix is reduced.
Drawings
FIG. 1 shows Ti as an embodiment of the invention 0.87 O 2 0.52- AFM image of nanoplatelets, which can be seen as two-dimensional platelet structure.
Fig. 2 is a graph showing the discharge capacity and coulombic efficiency of half cells assembled from the solid electrolyte composite electrodes provided in each example and comparative example at 0.1C for 40 cycles.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto. The raw materials related to the invention can be directly purchased from the market. For process parameters not specifically noted, reference may be made to conventional techniques.
LATP, ti used in examples and comparative examples 0.87 O 2 0.52- Nanoplatelets or Ti 0.91 O 2 0.36- Preparation of nanosheets:
(1) According to Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 Is measured by the stoichiometric ratio of Li 2 CO 3 2.91g (10 wt.% excess) of nano Al 2 O 3 0.84g、TiO 2 7.45g、H 6 NO 4 19.06g of P, ball milling for 6 hours, drying, and the ball milling speed is 300r/min; presintering for 3h at 800 ℃, ball milling for 6h, drying, and obtaining LATP powder at a ball milling speed of 300 r/min.
(2) TiO is mixed with 2 、K 2 CO 3 And Li (lithium) 2 CO 3 The mixture was charged into a Pt crucible at a molar ratio of 10.4:2.4:0.8, and reacted at 1173K for 20 hours to obtain a titanic acid microcrystal (K) 0.8 [Ti 1.73 Li 0.27 ]O 4 ) The microcrystals are placed at room temperature in a range of 0.5 to 3mol/dm 3 Stirring in HCl solution for 2 days, and changing acidic solution every day, collecting protonated product H by filtration 1.07 Ti 1.73 O 4 Washing with deionized water and absolute ethyl alcohol, and air-drying; immersing the protonized microcrystals in (CH) 3 ) 4 In NOH solution (molar ratio of concentration to exchangeable protons in proton microcrystals is 1:1, solid-to-liquid ratio is 4 g/L), ti is obtained 0.87 O 2 0.52- A nano-sheet.
(3) TiO is mixed with 2 And Cs 2 CO 3 Mixed and charged into a Pt crucible according to a molar ratio of 1:5.3, and reacted at 1073K for 20 hours to obtain layered cesium titanate microcrystals (Cs) 0.7 Ti 1.825 O 4 ) The microcrystals are stirred at room temperature in 1mol/L HCl solution for 3 days, and the acidic solution is replaced every day, and the protonated product H is collected by filtration 0.7 Ti 1.825 O 4 And then H is taken up 0.7 Ti 1.825 O 4 Reacting in 50-100mmol/L TBAOH solution at room temperature for 10-40 days to obtain Ti 0.91 O 2 0.36- Nanoplatelets (TBA in TBAOH) + And H is 0.7 Ti 1.825 O 4 H in (1) + The molar ratio is 1:4 to 4:1, TBA in TBAOH in this example + And H is 0.7 Ti 1.825 O 4 H in (1) + Molar ratio of 1:1
Example 1
(1) Weigh 2.4g LiFePO 4 0.3g of conductive carbon black, 0.3g PVDF,0.03g LiFSI (lithium difluorosulfonimide salt) and 0.03g of LATP were dissolved in 6mL of NMP, and the resulting uniform slurry was coated on an aluminum foil, followed by drying in a vacuum oven for 20 hours to obtain an LFP positive electrode sheet (electrode).
(2) 1.8g PVDF-HFP,0.2g PEO,0.8g LiFSI and 0.06g Ti were weighed out 0.87 O 2 0.52- The nanosheets were dissolved in 9ml of DMF solution at 60 ℃ to give a white solid electrolyte slurry.
(3) And uniformly coating the obtained white solid electrolyte slurry on an LFP positive plate, and then drying the LFP positive plate in a vacuum oven at 50 ℃ for 20 hours to obtain the solid electrolyte composite electrode.
Example 2
(1) Weigh 2.4g LiFePO 4 0.3g of conductive carbon black, 0.3g PVDF,0.03g LiFSI and 0.03g of LATP were dissolved in 6mL of NMP, the resulting homogeneous slurry was coated on aluminum foil, followed by drying in a vacuum oven for 20 hours,the LFP positive electrode sheet (electrode) was obtained.
(2) 1.8g PVDF-HFP,0.2g PEO,0.8g LiFSI and 0.15g Ti were weighed out 0.87 O 2 0.52- The nanosheets were dissolved in 9ml of DMF solution at 60 ℃ to give a white solid electrolyte slurry.
(3) And uniformly coating the obtained white solid electrolyte slurry on an LFP positive plate, and then drying the LFP positive plate in a vacuum oven at 50 ℃ for 20 hours to obtain the solid electrolyte composite electrode.
Example 3
(1) Weigh 2.4g LiFePO 4 0.3g of conductive carbon black, 0.3g PVDF,0.03g LiFSI and 0.03g of LATP were dissolved in 6mL of NMP, and the resulting uniform slurry was coated on aluminum foil, followed by drying in a vacuum oven for 20 hours to obtain an LFP positive electrode sheet (electrode).
(2) 1.8g PVDF-HFP,0.2g PEO,0.8g LiFSI and 0.06g Ti were weighed out 0.91 O 2 0.36- The nanosheets were dissolved in 9ml of DMF solution at 60 ℃ to give a white solid electrolyte slurry.
(3) And uniformly coating the obtained white solid electrolyte slurry on an LFP positive plate, and then drying the LFP positive plate in a vacuum oven at 50 ℃ for 20 hours to obtain the solid electrolyte composite electrode.
Example 4
(1) Weigh 2.4g LiFePO 4 0.3g of conductive carbon black, 0.3g PVDF,0.03g LiFSI and 0.03g of LLTO were dissolved in 6ml of lnmp, and the resulting uniform slurry was coated on an aluminum foil, followed by drying in a vacuum oven for 20 hours to obtain LFP positive electrode sheets (electrodes).
(2) 1.8g PVDF-HFP,0.2g PEO,0.8g LiFSI and 0.06g Ti were weighed out 0.91 O 2 0.36- The nanosheets were dissolved in 9ml of DMF solution at 60 ℃ to give a white solid electrolyte slurry.
(3) And uniformly coating the obtained white solid electrolyte slurry on an LFP positive plate, and then drying the LFP positive plate in a vacuum oven at 50 ℃ for 20 hours to obtain the solid electrolyte composite electrode.
Example 5
(1) Weigh 2.4g LiFePO 4 0.3g of conductive carbon black, 0.3g PVDF,0.03g LiFSI and 0.03g of LATP were dissolved in 6mL of NMP, and the resulting uniform slurry was coated on aluminum foil, followed by drying in a vacuum oven for 20 hours to obtain an LFP positive electrode sheet (electrode).
(2) 1.59g PVDF-HFP,0.18g PEO,1.2g LiFSI and 0.03g Ti were weighed out 0.87 O 2 0.52- The nanosheets were dissolved in 9ml of DMF solution at 60 ℃ to give a white solid electrolyte slurry.
(3) And uniformly coating the obtained white solid electrolyte slurry on an LFP positive plate, and then drying the LFP positive plate in a vacuum oven at 50 ℃ for 20 hours to obtain the solid electrolyte composite electrode.
Example 6
(1) Weigh 2.4g LiFePO 4 0.3g of conductive carbon black, 0.3g PVDF,0.03g LiFSI and 0.03g of LATP were dissolved in 6mL of NMP, and the resulting uniform slurry was coated on aluminum foil, followed by drying in a vacuum oven for 20 hours to obtain an LFP positive electrode sheet (electrode).
(2) 1.92g PVDF-HFP,0.21g PEO,0.6g LiFSI and 0.27g Ti were weighed out 0.87 O 2 0.52- The nanosheets were dissolved in 9ml of DMF solution at 60 ℃ to give a white solid electrolyte slurry.
(3) And uniformly coating the obtained white solid electrolyte slurry on an LFP positive plate, and then drying the LFP positive plate in a vacuum oven at 50 ℃ for 20 hours to obtain the solid electrolyte composite electrode.
Example 7
(1) Weigh 2.4g LiFePO 4 0.3g of conductive carbon black, 0.3g of PVDF and 0.03g of LiFSI were dissolved in 6mLNMP, and the obtained uniform slurry was coated on an aluminum foil, followed by drying in a vacuum oven for 20 hours, to obtain an LFP positive electrode sheet (electrode).
(2) 1.8g PVDF-HFP,0.2g PEO,0.8g LiFSI and 0.06g Ti were weighed out 0.91 O 2 0.36- The nanosheets were dissolved in 9ml of DMF solution at 60 ℃ to give a white solid electrolyte slurry.
(3) And uniformly coating the obtained white solid electrolyte slurry on an LFP positive plate, and then drying the LFP positive plate in a vacuum oven at 50 ℃ for 20 hours to obtain the solid electrolyte composite electrode.
Comparative example 1
(1) Weigh 2.4g LiFePO 4 0.3g of conductive carbon black, 0.3g PVDF,0.03g LiFSI and 0.03g of LATP were dissolved in 6mLNMP, and the resulting uniform slurry was coated on aluminum foil, followed by drying in a vacuum oven for 20 hours to obtain an LFP positive electrode sheet (electrode).
(2) 1.8g PVDF-HFP,0.2g PEO and 0.8g LiFSI were weighed out and dissolved in 9ml DMF solution at 60℃to give a white solid electrolyte slurry.
(3) And uniformly coating the obtained white solid electrolyte slurry on an LFP positive plate, and then drying the LFP positive plate in a vacuum oven at 50 ℃ for 20 hours to obtain the solid electrolyte composite electrode.
Comparative example 2
(1) Weigh 2.4g LiFePO 4 0.3g of conductive carbon black, 0.3g PVDF,0.03g LiFSI and 0.03g of LATP were dissolved in 6mLNMP, and the resulting uniform slurry was coated on aluminum foil, followed by drying in a vacuum oven for 20 hours to obtain an LFP positive electrode sheet (electrode).
(2) 1.8g PVDF-HFP,0.2g PEO,0.8g LiFSI and 0.06g TiO were weighed 2 Powder, these materials were dissolved in 9ml of DMF solution at 60 ℃ to obtain white solid electrolyte slurry.
(3) And uniformly coating the obtained white solid electrolyte slurry on an LFP positive plate, and then drying the LFP positive plate in a vacuum oven at 50 ℃ for 20 hours to obtain the solid electrolyte composite electrode.
Comparative example 3
(1) Weigh 2.4g LiFePO 4 0.3g of conductive carbon black, 0.3g of PVDF and 0.03g of LiFSI were dissolved in 6mL of NMP, and the resulting uniform slurry was coated on an aluminum foil, followed by drying in a vacuum oven for 20 hours, to obtain an LFP positive electrode sheet (electrode).
(2) 1.8g PVDF-HFP,0.2g PEO and 0.8g LiFSI were weighed out and dissolved in 9ml DMF solution at 60℃to give a white solid electrolyte slurry.
(3) And uniformly coating the obtained white solid electrolyte slurry on an LFP positive plate, and then drying the LFP positive plate in a vacuum oven at 50 ℃ for 20 hours to obtain the solid electrolyte composite electrode.
Effects of action
The solid electrolyte layer thickness in the positive electrode sheets prepared in the above examples and comparative examples was about 80 to 90 μm.
Table 1 shows the internal resistances and the first-cycle efficiencies at 0.1C of the solid electrolyte composite electrodes of examples 1 to 7 and comparative examples 1 to 3. The battery model used for measuring the internal resistance is a solid electrolyte composite electrode/Li simulation battery, the measuring method adopts EIS, the impedance scanning range is 0.1Hz-100KHz, and the amplitude is 0.5mV.
The solid electrolyte composite electrodes provided in comparative examples 1 and 3 were supported with an electrode on which a solid electrolyte was coated; although under the action of gravity, part of electrolyte permeates into the gaps of the porous electrode, so that the contact effect between the electrolyte and the electrode is improved, the improvement is limited, the internal resistance is larger, the internal resistance is respectively 32.3 omega and 32.5 omega, the first cycle circulation efficiency is respectively 86.3 percent and 84.7 percent, and the reasons are mainly that the crystallinity of the polymer matrix is low, the chain segment movement is not strong, and the transmission rate of lithium ions in the solid electrolyte is too low. Comparative example 1 compared with comparative example 3, since the fast ion conductor was added to the electrode of comparative example 1, the lithium ions were relatively easily extracted and inserted from the positive electrode, so that the first cycle efficiency was slightly higher than that of comparative example 3.
Comparative example 2A conventional TiO was added to a solid electrolyte based on comparative example 1 2 The powder has internal resistance of 29.7Ω, the introduction of inorganic filler changes part of the structure of the polymer chain segment, reduces the crystallinity of the polymer matrix to a certain extent, and the chain segment movement is aggravated to be beneficial to the transfer of lithium ions in the solid electrolyte, so the first-turn efficiency of comparative example 2 is higher than that of comparative example 1. But due to conventional TiO 2 The powder is easy to agglomerate in the polymer matrix, so that the powder is unevenly dispersed in the polymer matrix, and the modification effect is not ideal.
Examples 1 to 7 in comparison with comparative examples 1 to 3, a suitable amount of Ti was added to the solid electrolyte 1-δ O 2 4δ -(0<δ<1) The cycle first ring efficiency is higher than that of comparative examples 1-3 and the internal resistance is lower than that of comparative examples 1-3, the reason is mainly that the belt is addedElectric Ti 1-δ O 2 4δ Nanoplatelets. Charged Ti 1-δ O 2 4δ -with the general inert filler TiO 2 Compared with the prior art, the polymer matrix has more uniform dispersion in the polymer matrix due to the chargeability and the lamellar structure, and more ideal effect on reducing the crystallinity of the polymer matrix.
From examples 1 and 2, it is apparent that Ti 1-δ O 2 4δ -(0<δ<1) Assembled half-cell, as Ti 1-δ O 2 4δ -(0<δ<1) When the addition amount of (2) to (6%), the catalyst has more excellent first-cycle circulation efficiency performance.
Example 1 charged Ti was added at a mass fraction of 2.1% 0.87 O 2 0.52- Solid electrolyte composite electrode of nanosheets, example 2 was charged Ti added with mass fraction 5.1% 0.87 O 2 0.52- A solid electrolyte composite electrode of a nano-sheet. Example 2 compared to example 1, due to the charged Ti 0.87 O 2 0.52- The addition amount of the nano-sheets is increased to a certain extent, the crystallinity of the polymer matrix is reduced, the chain segment movement is aggravated, the transmission of lithium ions in the polymer matrix mainly depends on the molecular chain segment movement, when the crystallinity is reduced, the molecular chain segment movement aggravated is beneficial to the transmission of lithium ions in the solid electrolyte, the internal resistance of the solid electrolyte is reduced, and meanwhile, the first cycle circulation efficiency of the half battery assembled by the polymer matrix is improved.
Example 1 charged Ti was added at a mass fraction of 2.1% 0.87 O 2 0.52- Solid electrolyte composite electrode of nanoplatelets, example 3 was charged Ti added with mass fraction of 2.1% 0.91 O 2 0.36- A solid electrolyte composite electrode of a nano-sheet. From examples 1 and 3, various charged Ti species are known 1-δ O 2 4δ The internal resistance of the solid-state electrolyte can be reduced, while the first cycle efficiency of the half-cell assembled therefrom is improved.
As can be seen from examples 5, 6 and 1, the mass fraction of the polymer matrix in the solid electrolyte part is reduced, the mass fraction of the lithium salt is increased, and the reduction of the internal resistance indicates that the transmission of lithium ions in the solid electrolyte with high lithium salt content is more favorable, and the capacity of the positive electrode active material is also favorable.
As is apparent from comparative examples 1, 3, 4 and 7, the addition of the fast ion conductor improves the transmission capacity of lithium ions in the electrode during the preparation of the positive electrode sheet, improves the first cycle efficiency, and facilitates the deintercalation and intercalation of lithium ions in the electrode portion during the cycle, thus better representing the capacity of the positive electrode active material.
Example 1 compared with comparative example 2, due to the charged Ti 1-δ O 2 4δ -(0<δ<1) The nano-sheet is compared with the conventional TiO 2 The polymer matrix tends to be more uniformly dispersed, the crystallinity is reduced, the molecular chain segment movement is enhanced, the transmission of lithium ions in the solid electrolyte is facilitated, the internal resistance of the solid electrolyte is reduced, and meanwhile, the first cycle efficiency of the half battery assembled by the polymer matrix is improved.
Example 4 As compared with comparative example 3, since the electrode portion incorporates fast ionic conductors (LATP and LLTO), li is favored + Transmission in an electrode, and addition of charged Ti to a solid electrolyte 1-δ O 2 4δ -(0<δ<1) The nano-sheets are matched with higher lithium ion transmission rate, so that the capacity of the positive electrode active material is better reflected.
TABLE 1 internal resistance and first cycle efficiency at 0.1C for solid electrolyte composite electrodes of examples 1-7 and comparative examples 1-3
Fig. 2 is a graph showing the discharge capacity and coulombic efficiency of half cells assembled from the solid electrolyte composite electrodes of examples 1 to 7 and comparative examples 1 to 3 at 0.1C for 40 cycles. The battery model used for the measurement of charge-discharge cycle is a solid electrolyte composite LFP positive electrode/Li simulation battery, and the voltage range is 2.8-4.0V.
As can be seen from fig. 2, the discharge capacity of example 2 is higher than that of example 1. The reason is that the charged Ti in example 2 0.87 O 2 0.52- The addition amount of the nano-sheets is increased, the chain segment structure of the polymer is influenced to a greater extent, the chain segment movement of the polymer is aggravated by the reduction of the proportion of the crystallization area, and meanwhile, the dissociation capability of lithium salt is also enhanced, so that the transfer of lithium ions entering the solid electrolyte from the electrode is more favorable, and the capacity of the electrode active material is better.
As can be seen from fig. 2, the discharge capacities of comparative examples 1 to 3 were lower than those of examples 1 to 7. The reason is that:
comparative examples 1 and 3 are solid electrolyte composite electrodes to which no inorganic filler is added, and since the crystallinity of the polymer matrix itself is not strong, the segment movement is not strong, resulting in an excessively low rate of lithium ion transfer in the solid electrolyte, the transfer of lithium ions transferred from the electrode is limited, the capacity of the electrode active material cannot be sufficiently exhibited, and thus the discharge capacity of the electrode active material is low.
Comparative example 2 is the addition of conventional TiO 2 Solid electrolyte composite electrode of powder, compared to charged Ti added in examples 1-7 1-δ O 2 4δ -(0<δ<1) Nanoplatelets, conventional TiO 2 The powder also reduces the crystallinity of the polymer matrix, but due to conventional TiO 2 The powder tends to agglomerate in the polymer matrix, resulting in uneven dispersion in the polymer matrix, which may lead to undesirable effects in reducing the crystallinity of the polymer matrix, resulting in a low rate of lithium ion transport in the solid electrolyte and uneven lithium ion flow.
While in examples 1 to 7 Ti 1-δ O 2 4δ -(0<δ<1) The charged characteristics and the lamellar structure of the alloy lead to more uniform dispersion in the polymer matrix, reduced proportion of crystalline regions and charged Ti 1-δ O 2 4δ -(0<δ<1) The nano-sheet is beneficial to dissociation of lithium salt in the electrolyte, transfer of lithium ions in the solid electrolyte and reduction of loss of lithium ions in the transmission process.
In addition, in comparative example 3, since the electrode part does not contain a fast ion conductor, the ability of lithium ions to be extracted and inserted in the electrode part is weak, and the ability of lithium ions to be transferred from the electrode to the electrolyte is weak, the discharge capacity thereof is lower than that of comparative example 1.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. The solid electrolyte is characterized by comprising the following components in percentage by mass:
59% -79% of crystalline polymer matrix and/or semi-crystalline polymer matrix
20 to 40 percent of lithium salt
Ti 1-δ O 2 4δ- 1％-9％
Where 0< delta <1.
2. The solid electrolyte of claim 1, wherein the solid electrolyte comprises the following components in percentage by mass:
59% -78% of crystalline polymer matrix and/or semi-crystalline polymer matrix
20 to 38 percent of lithium salt
Ti 1-δ O 2 4δ- 2％-6％
Where 0< delta <1.
3. A solid state electrolyte according to claim 1 or 2, wherein the semi-crystalline polymer matrix comprises one or more of vinylidene fluoride-co-hexafluoropropylene, polyacrylonitrile and polyvinyl alcohol, and the crystalline polymer matrix comprises one or more of polyethylene oxide and polyvinylidene fluoride.
4. A solid electrolyte according to claim 1 or 2, wherein,
the Ti is 1-δ O 2 4δ- Wherein delta is more than or equal to 0.09 and less than or equal to 0.13;
further preferably, the Ti is 1-δ O 2 4δ- Is Ti 0.87 O 2 0.52- Or Ti (Ti) 0.91 O 2 0.36- ；
Preferably, ti 1-δ O 2 4δ- Is nano-sheet.
5. A solid electrolyte composite electrode comprising an electrode and the solid electrolyte of any one of claims 1-4 coated on the electrode.
6. The solid electrolyte composite electrode according to claim 5, wherein the electrode comprises a positive electrode material, conductive carbon black and a binder, and the mass percentages of the components are as follows:
80 to 90 percent of positive electrode material
Conductive carbon black 5-10%
3% -10% of binder;
further preferably, the electrode further comprises the following components in percentage by mass:
2% -8% of fast ion conductor.
7. The solid state electrolyte composite electrode of claim 6 wherein the fast ionic conductor is at least one of lithium aluminum titanium phosphate, lithium lanthanum zirconate, lithium lanthanum niobate, lithium neodymium titanyl, lithium aluminum germanium phosphate, lithium aluminum lithium lanthanum zirconium oxide, and lithium lanthanum titanate.
8. The solid state electrolyte composite electrode of claim 6, wherein the positive electrode material is any one of lithium cobaltate, lithium manganate and lithium iron phosphate.
9. The solid state electrolyte composite electrode of claim 6 wherein the binder is polyvinylidene fluoride.
10. A method for producing a solid electrolyte composite electrode according to any one of claims 5 to 9, characterized by comprising the steps of:
(1) Dissolving each component in the electrode in an organic solvent to obtain electrode slurry, coating the electrode slurry on an aluminum foil, and then drying in vacuum to obtain the electrode for later use;
(2) Crystalline polymer matrix and/or semi-crystalline polymer matrix, lithium salt and Ti 1-δ O 2 4δ- Dissolving in an organic solvent to obtain solid electrolyte slurry for standby;
(3) And coating the solid electrolyte slurry on the electrode, and then drying in vacuum to obtain the solid electrolyte composite electrode.
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