CN113764723A - Polymer electrolyte, polymer electrolyte layer, and all-solid-state lithium ion battery - Google Patents
Polymer electrolyte, polymer electrolyte layer, and all-solid-state lithium ion battery Download PDFInfo
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- CN113764723A CN113764723A CN202111049494.9A CN202111049494A CN113764723A CN 113764723 A CN113764723 A CN 113764723A CN 202111049494 A CN202111049494 A CN 202111049494A CN 113764723 A CN113764723 A CN 113764723A
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- polymer electrolyte
- lithium
- formula
- electrolyte layer
- vacuum
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- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 127
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 35
- 239000000178 monomer Substances 0.000 claims abstract description 35
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 29
- 229920000642 polymer Polymers 0.000 claims abstract description 16
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 32
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 32
- 238000002360 preparation method Methods 0.000 claims description 31
- 238000001291 vacuum drying Methods 0.000 claims description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 27
- 239000001257 hydrogen Substances 0.000 claims description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 26
- 229910052760 oxygen Inorganic materials 0.000 claims description 26
- 239000001301 oxygen Substances 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 23
- 238000006116 polymerization reaction Methods 0.000 claims description 22
- 239000004014 plasticizer Substances 0.000 claims description 19
- 229910003002 lithium salt Inorganic materials 0.000 claims description 18
- 159000000002 lithium salts Chemical class 0.000 claims description 18
- -1 nitro, amino Chemical group 0.000 claims description 18
- 125000003342 alkenyl group Chemical group 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 229910052744 lithium Inorganic materials 0.000 claims description 13
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 239000012634 fragment Substances 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 125000004386 diacrylate group Chemical group 0.000 claims description 9
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 claims description 9
- 239000011888 foil Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims description 8
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 7
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 6
- 150000003949 imides Chemical class 0.000 claims description 6
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- 125000004076 pyridyl group Chemical group 0.000 claims description 6
- 125000000168 pyrrolyl group Chemical group 0.000 claims description 6
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 5
- 210000003097 mucus Anatomy 0.000 claims description 5
- 239000002985 plastic film Substances 0.000 claims description 5
- 229920006255 plastic film Polymers 0.000 claims description 5
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- MTPIZGPBYCHTGQ-UHFFFAOYSA-N 2-[2,2-bis(2-prop-2-enoyloxyethoxymethyl)butoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCC(CC)(COCCOC(=O)C=C)COCCOC(=O)C=C MTPIZGPBYCHTGQ-UHFFFAOYSA-N 0.000 claims description 3
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- 229910015013 LiAsF Inorganic materials 0.000 claims description 3
- 229910013075 LiBF Inorganic materials 0.000 claims description 3
- 229910013872 LiPF Inorganic materials 0.000 claims description 3
- 101150058243 Lipf gene Proteins 0.000 claims description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- SXWUDUINABFBMK-UHFFFAOYSA-L dilithium;fluoro-dioxido-oxo-$l^{5}-phosphane Chemical group [Li+].[Li+].[O-]P([O-])(F)=O SXWUDUINABFBMK-UHFFFAOYSA-L 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- AHKHZLVXUVZTGF-UHFFFAOYSA-M lithium dihydrogen phosphate oxalic acid Chemical compound P(=O)([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] AHKHZLVXUVZTGF-UHFFFAOYSA-M 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 3
- MRDKYAYDMCRFIT-UHFFFAOYSA-N oxalic acid;phosphoric acid Chemical compound OP(O)(O)=O.OC(=O)C(O)=O MRDKYAYDMCRFIT-UHFFFAOYSA-N 0.000 claims description 3
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 3
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims 1
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 28
- 239000003792 electrolyte Substances 0.000 description 23
- 239000000843 powder Substances 0.000 description 17
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 16
- 239000000463 material Substances 0.000 description 16
- 239000007787 solid Substances 0.000 description 15
- 239000004417 polycarbonate Substances 0.000 description 11
- 229920000515 polycarbonate Polymers 0.000 description 11
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- 150000002430 hydrocarbons Chemical group 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000002001 electrolyte material Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000005096 rolling process Methods 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000002178 crystalline material Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 239000004342 Benzoyl peroxide Substances 0.000 description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 238000004080 punching Methods 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000010280 constant potential charging Methods 0.000 description 2
- 238000010277 constant-current charging Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 229910001216 Li2S Inorganic materials 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- OPHUWKNKFYBPDR-UHFFFAOYSA-N copper lithium Chemical compound [Li].[Cu] OPHUWKNKFYBPDR-UHFFFAOYSA-N 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000005677 organic carbonates Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000005415 substituted alkoxy group Chemical group 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The application discloses a polymer electrolyte, a polymer electrolyte layer and an all-solid-state lithium ion battery. In the application, the polymer electrolyte is formed by polymerizing a monomer shown in a formula I, or the polymer electrolyte is formed by polymerizing a monomer shown in the formula I and a cross-linking agent and/or an oligomer rate-increasing additive. The polymer electrolyte provided by the invention adopts the structural monomer containing two sulfur-oxygen double bonds, and the formed polymer is more stable. The polymer electrolyte layer provided by the invention has good flexibility and good lithium ion conducting capacity. The polymer electrolyte layer provided by the invention is decomposed and reduced to Li with strong lithium ion conduction capability on the negative electrode side2And S, the conductivity of the lithium ions of the negative electrode is improved.
Description
Technical Field
The embodiment of the invention relates to the field of lithium ion batteries, in particular to a polymer electrolyte, a polymer electrolyte layer and an all-solid-state lithium ion battery.
Background
At present, organic carbonate electrolytes are generally adopted in commercial lithium ion batteries, but the electrolytes have the problems of easy leakage, easy combustion, easy explosion and the like, so that the safety requirements cannot be met. The all-solid-state polymer electrolyte battery has good safety performance, high energy density, wide working temperature range and long cycle life, and becomes a hotspot of research in the field of lithium ion batteries.
In the prior art, polyethylene oxide is adopted as a polymer matrix of the all-solid-state polymer electrolyte battery, but a polyethylene oxide-based system has high crystallinity and poor conductivity, and a polycarbonate compound contains a carbonate group with strong polarity inside the structure, so that the dielectric constant of an electrolyte layer is improved, and the conductivity is improved compared with that of the polyethylene oxide-based system. However, the inventors found that the polycarbonate system is incompatible with the sulfur-containing solid lithium ion battery, and the polycarbonate system has poor stability. Therefore, there is a need in the art to find a polymer electrolyte layer that is highly compatible with sulfur-containing solid state lithium ion batteries.
Disclosure of Invention
The invention aims to provide a polymer electrolyte and a polymer electrolyte layer which have good ionic conductivity, wide electrochemical window and good stability and are compatible with a sulfur-containing solid lithium ion battery.
Another object of the present invention is to provide an all solid-state lithium ion battery.
In order to solve the above technical problems, a first aspect of the present invention provides a polymer electrolyte, wherein the polymer electrolyte is formed by polymerizing a monomer represented by formula I, or formed by polymerizing a monomer represented by formula I with a crosslinking agent and/or a plasticizer,
in the formula, R1And R2Are each independently selected from C1～20Alkyl radical, C1～20Alkoxy radical, C2～20Alkenyl, phenyl, pyridyl, pyrrolyl, at least one hydrogen by R1-1Substituted C1～20Alkyl, at least one hydrogen by R1-1Substituted C1～20Alkoxy, at least one hydrogen by R1-1Substituted C2～20Alkenyl, at least one hydrogen by R1-1Substituted phenyl, at least one hydrogen being replaced by R1-1Substituted pyridyl, at least one hydrogen being replaced by R1-1Substituted pyrrolyl and
wherein R is3Is C2～20An alkenyl group;
R1-1selected from halogen, nitro, amino, C1～6Alkyl radical, C3～6Cycloalkyl radical, C1～6An alkoxy group;
R1and R2At least one of which has a carbon-carbon unsaturated bond;
R1and R2At least part of a structural fragment of any one of the above may be bonded to at least part of a structural fragment of another to form a ring.
In some preferred embodiments, R1And R2Are each independently selected from C1～20Alkyl radical, C1～20Alkoxy radical, C2～20Alkenyl, at least one hydrogen by R1-1Substituted C1～20Alkyl, at least one hydrogen by R1-1Substituted C1～20Alkoxy or at least one hydrogen by R1-1Substituted C2～20An alkenyl group.
In some preferred embodiments, R1And R2Is not bonded to form a ring, and R1And R2All having carbon-carbon unsaturated bonds.
In some preferred embodiments, R1Partial structural fragment of (1) and R2And bonding to form a ring.
In some preferred embodiments, R1Partial structural fragment of (1) and R2Bonded to form a ring, and the ring has carbon-carbon unsaturated bonds.
In some preferred embodiments, R1And R2And bonding to form a ring.
In some preferred embodiments, R1And R2Bonded to form a ring, and the ring has carbon-carbon unsaturated bonds.
In some preferred embodiments, the monomer of formula I has the structure of formula I ' -1, I ' -2, or I ' -3:
in the formula, Y1And Y2Each independently selected from carbon or oxygen, R11And R12Are each independently selected from C1～6Alkyl radical, C1～6Alkoxy or C2～6An alkenyl group.
In some preferred embodiments, the monomer of formula I has any one of the following structures:
in some preferred embodiments, the crosslinking agent has at least two carbon-carbon double bonds.
In some preferred embodiments, the crosslinking agent is selected from any one of formula II, formula III or formula IV,
in the formula II, R4、R5、R6And R7Are each independently selected from C1～10Alkyl or
And R is4、R5、R6And R7At least two of which are
Wherein m is 0-20, X1、X2And X3Each independently selected from carbon or oxygen, and X1And X2Not being oxygen at the same time, X2And X3Not being oxygen at the same time, X1And X3Not being oxygen at the same time;
in the formula III, n is 0 to 20, X4、X5And X6Each independently selected from carbon or oxygen, and X4And X5Not being oxygen at the same time, X5And X6Not being oxygen at the same time, X6And X7Not being oxygen at the same time;
in the formula IV, R8And R9Is selected from C1～20An alkenyl group.
In some preferred embodiments, the cross-linking agent is selected from at least one of 1, 6-hexanediol diacrylate, triethylene glycol diacrylate, trimethylolpropane ethoxylate triacrylate, propoxylated trimethylolpropane triacrylate, pentaerythritol tetraacrylate, and vinyl sulfone, preferably vinyl sulfone.
In some preferred embodiments, the plasticizer is an oligomer plasticizer.
In some preferred embodiments, the plasticizer is selected from at least one of polyethylene glycol methacrylate, poly (ethylene glycol) diacrylate, methoxypolyethylene glycol acrylate, trimethylolpropane ethoxytriacrylate, propoxylated trimethylolpropane triacrylate, and 2, 3-epoxypropyl acrylate, preferably polyethylene glycol methacrylate.
In some preferred embodiments, the polymerization is carried out in the presence of an initiator.
In some preferred embodiments, the initiator is selected from at least one of Azobisisobutyronitrile (AIBN), Azobisisoheptonitrile (AIVN), dimethyl azobisisobutyrate, hydrogen peroxide, ammonium persulfate, potassium persulfate Benzoyl Peroxide (BPO), benzoyl t-butyl peroxide, or methyl ethyl ketone peroxide.
In some preferred embodiments, the preparation of the polymer electrolyte comprises the steps of:
the monomer shown in the formula I, a cross-linking agent, a plasticizer and an initiator are mixed and heated for polymerization, and the polymer is obtained.
In some preferred schemes, the molar ratio of the monomer shown in the formula I, the cross-linking agent, the plasticizer and the initiator is a: b: c: d, wherein a is 90-98, b is 1-5, c is 0.5-3 or d is 0.1-2. For example: a, b, c, d, 94:3:2.5: 0.5.
In some preferred embodiments, the temperature for the heating polymerization is 50 to 70 ℃, preferably 60 ℃.
In some preferred embodiments, the time for the heating polymerization is 20 to 40 hours, preferably 24 to 36 hours.
In some preferred embodiments, the heating polymerization further comprises purification, and the purification comprises vacuum drying and washing and drying.
In some preferred embodiments, the vacuum drying step is specifically: and (3) placing the polymerization product in a vacuum oven, and heating for 20-30 hours in vacuum at the temperature of 70-90 ℃.
In some preferred schemes, the step of washing and drying specifically comprises: and sequentially washing the vacuum-dried polymerization product by deionized water and dimethyl carbonate, and drying.
A second aspect of the present invention provides a polymer electrolyte layer comprising the polymer electrolyte and a lithium salt.
In some preferred embodiments, the preparation of the polymer electrolyte layer comprises the steps of:
(1) mixing the polymer electrolyte, succinonitrile and dimethyl sulfoxide to form a polymer electrolyte solution;
(2) dissolving a lithium salt in the polymer electrolyte solution to form a viscous liquid;
(3) and coating the mucus on a current collector, and drying in vacuum to form the polymer electrolyte layer.
In some preferred embodiments, in the polymer electrolyte solution, the mass ratio of the polymer electrolyte, the succinonitrile and the dimethyl sulfoxide is l: m: n, wherein l is 45 to 50, m is 1 to 5, n is 45 to 50, and l + m + n is 100. For example, l: m: n: 48:2: 50.
In some preferred embodiments, the solid content in the polymer electrolyte solution is 45% to 55%, for example 50%.
In some preferred embodiments, in the slime, the lithium salt is selected from lithium fluorophosphate (LiPF)6) Lithium tetrafluoroborate (LiBF)4) Lithium perchlorate (LiClO)4) Lithium hexafluoroarsenate (LiAsF)6) Lithium trifluoromethanesulfonate (LiCF)3SO3) Lithium tetrafluoro oxalate phosphate (litfo), lithium tris oxalate phosphate (LiTOP), lithium bis (trifluoromethylsulfonyl) imide (LiTFSI), lithium bis (perfluoroethylsulfonyl) imide (LiFSI), (trifluoromethylsulfonyl) (n-perfluorobutylsulfonyl) imide (LiFNTFSI), lithium (fluorosulfonyl) (n-perfluorobutylsulfonyl) imide (LiFNFSI), lithium bis (LiBOB) oxalate.
In some preferred embodiments, the concentration of the lithium salt in the mucus is 1 to 2mol/L, such as 1.5 mol/L.
In some preferred embodiments, in step (3), the current collector is an aluminum foil, an aluminum plastic film CPP, or a release paper.
In order to remove the dimethyl sulfoxide sufficiently, in some preferred schemes, in the step (3), the vacuum drying time is 18-30 hours, such as 24 hours; the temperature of vacuum drying is 80-100 ℃.
In order to prevent the side reaction of the electrolyte material during vacuum drying, in some preferable schemes, during vacuum drying, the vacuum degree is firstly adjusted to be less than or equal to 0.1Pa, then the temperature is raised for vacuum drying, and then the vacuum is opened after the temperature is reduced.
A third aspect of the invention provides an all-solid lithium ion battery including the polymer electrolyte layer.
Compared with the prior art, the invention has at least the following advantages:
(1) the polymer electrolyte provided by the invention adopts the structural monomer containing two sulfur-oxygen double bonds, and the formed polymer is more stable.
(2) The polymer electrolyte layer provided by the invention has good flexibility and good lithium ion conducting capacity.
(3) The polymer electrolyte layer provided by the invention is decomposed and reduced to Li2S with strong lithium ion conducting capacity on the negative electrode side, and the conductivity of negative electrode lithium ions is improved.
(4) The polymer electrolyte layer provided by the invention has good compatibility with a sulfur-containing all-solid-state lithium ion battery.
It is to be understood that within the scope of the present invention, the above-described features of the present invention and those specifically described below (e.g., in the examples) may be combined with each other to form new or preferred embodiments. Not to be reiterated herein, but to the extent of space.
Detailed Description
In the existing all-solid-state polymer electrolyte battery, the polymer electrolyte layer has poor conductivity and stability, and is not beneficial to use. As a result of extensive studies, the inventors have found that the use of the monomer of the present invention represented by the formula I (wherein R is1And R2The definition of the base is described in the summary of the invention) and the polymer electrolyte layer prepared by using the polymer electrolyte formed by polymerization as a raw material has better conductivity and higher stability.
Preferably, the monomer shown in formula I and the cross-linking agent are copolymerized, so that the flexibility of the polymer electrolyte layer can be increased, the movement of lithium ions is facilitated, and the formed polymer electrolyte is used as a raw material to prepare the polymer electrolyte layer with better conductivity.
Preferably, the monomer represented by formula I and the oligomer plasticizer are copolymerized, so that the crystallinity of the obtained polymer electrolyte layer can be reduced, the flexibility of the electrolyte layer can be increased, and the conductivity of the electrolyte layer can be improved.
Preferably, the monomer shown in formula i, the cross-linking agent and the oligomer plasticizer are mixed and copolymerized, and the obtained polymer electrolyte layer can combine the advantages of the cross-linking agent and the oligomer plasticizer, so that the obtained electrolyte layer has better flexibility and higher conductivity (as in example 1).
Preferably, as the monomer represented by formula i, when a plurality of oxygens (more than two oxygens) are contained in its molecular structure, lithium ion complexing sites increase, thereby increasing the conductivity of the resulting polymer electrolyte layer.
Preferably, as the monomer represented by formula i, when its molecular structure is cyclic, its structure is more easily complexed with lithium ions, thereby increasing the conductivity of the resulting polymer electrolyte layer.
Preferably, as the cross-linking agent, when the molecular structure of the cross-linking agent contains sulfur, the cross-linking agent has better affinity with the monomer shown in the formula I, and the compatibility of the obtained polymer electrolyte layer and the solid-state lithium ion battery is increased.
Preferably, as the crosslinking agent, when the double bonds are more contained, the crosslinking sites become more, the network structure is more easily formed, and the lithium ions are more densely distributed.
Preferably, as the crosslinking agent, the less the double bonds it contains, the more flexible the polymer electrolyte and the more conductive the electrical properties are.
Term(s) for
As used herein, the term "alkyl" refers to a linear or branched saturated monovalent hydrocarbon group, wherein the alkyl group may be optionally substituted with one or more substituents. In a particular embodiment, the alkyl group is a cyclic alkyl having 1 to 20 (C)1-20) 1 to 15 (C)1-15) 1 to 12 (C)1-12) 1 to 10 (C)1-10) Or 1 to 6 (C)1-6) Linear saturated monovalent hydrocarbon groups of carbon atoms, or having 3 to 20 (C)3-20) 3 to 15 (C)3-15) 3 to 12 (C)3-12) 3 to 10 (C)3-10) Or 3 to 6 (C)3-6) A branched saturated monovalent hydrocarbon group of carbon atoms. Linear C as used herein1-6And with a branched chain C3-6Alkyl groups are also referred to as "lower alkyl". Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl (including all isomeric forms), n-propyl, isopropyl, butyl (including all isomeric forms), n-butyl, isobutyl, tert-butyl, pentyl (including all isomeric forms), and hexyl (including all isomeric forms). E.g. C1-6The alkyl group means a linear saturated monovalent hydrocarbon group having 1 to 6 carbon atoms or a branched saturated monovalent hydrocarbon group having 3 to 6 carbon atoms.
As used herein, the term "alkenyl" refers to a linear or branched monovalent hydrocarbon group having one or more (in one embodiment, one to five) carbon-carbon double bonds. The alkenyl group may be optionally substituted with one or more substituents. It will be understood by those of ordinary skill in the art that the term "alkenyl" may also include groups having "cis" and "trans" configurations, or alternatively, "E" and "Z" configurations.
As used herein, the term "alkenyl" includes both linear and branched alkenyl groups. E.g. C2-20Alkyl refers to a linear unsaturated monovalent hydrocarbon group having 2 to 20 carbon atoms or a branched unsaturated monovalent hydrocarbon group having 3 to 20 carbon atoms. In particular embodiments, alkenyl is a linear monovalent hydrocarbon group having 2 to 20(C2-20), 2 to 15(C2-15), 2 to 12(C2-12), 2 to 10(C2-10), or 2 to 6(C1-6) carbon atoms, or a branched monovalent hydrocarbon group having 3 to 20(C3-20), 3 to 15(C3-15), 3 to 12(C3-12), 3 to 10(C3-10), or 3 to 6(C3-6) carbon atoms. Examples of alkenyl groups include, but are not limited to, vinyl, propen-1-yl, propen-2-yl, allyl, butenyl, and 4-methylbutenyl.
As used herein, the term "alkoxy" refers to a stable straight or branched chain, or cyclic hydrocarbon group, or combinations thereof, consisting of the indicated number of carbon atoms and one or more (in one embodiment, one to three) O atoms. Examples of alkoxy groups include, but are not limited to-O-CH3、-O-CF3、-O-CH2-CH3、-O-CH2-CH2-CH3、-O-CH-(CH3)2and-O-CH2-CH2-O-CH3. In one embodiment, the alkoxy group is an optionally substituted alkoxy group described elsewhere herein.
As used herein, the term "cycloalkyl" refers to a cyclic fully or partially saturated bridged and/or unbridged hydrocarbyl group or ring system, which may be optionally substituted with one or more substituents. In a particular embodiment, the cycloalkyl group has 3 to 20 (C)3-20) 3 to 15 (C)3-15) 3 to 12 (C)3-12)、3 to 10 (C)3-10) Or 3 to 7 (C)3-7) Carbon atoms. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, decahydronaphthyl, and adamantyl.
As used herein, the term "R1Partial structural fragment of (1) and R2Bonded to form a ring "means that R1At least part of with R2And bonding to form a ring. For example, when R is1Is n-propyl group ((γ1)CH3-(β1)CH2-(α1)CH2-)，R2Is n-propyl group ((γ2)CH3-(β2)CH2-(α2)CH2-, R is1Carbon at position beta 1 of (1) and R2The carbon at the middle gamma-2 position is bonded to form a ring, R is considered to be1Is a partial structural segment in the n-propyl group-(β1)CH2-(α1)CH2- ", and R2((γ2)CH3-(β2)CH2-(α2)CH2-) bond formation
The term "R1And R2Bonded to form a ring "means that R1Integer with R2The whole is bonded into a ring structure. For example, when R is1Is n-propyl group ((γ1)CH3-(β1)CH2-(α1)CH2-)，R2Is n-propyl group ((γ2)CH3-(β2)CH2-(α2)CH2-1And R2Bonded to form a ring "means R1Carbon at position γ 1 of (1) and R2Formation of carbon bonding at the middle gamma 2 position
In a preferred embodiment of the present invention, the present invention provides a polymer electrolyte formed by polymerizing a monomer represented by formula I, or formed by polymerizing a monomer represented by formula I with a crosslinking agent and/or a plasticizer,
in the formula, R1And R2Are each independently selected from C1～20Alkyl radical, C1～20Alkoxy radical, C2～20Alkenyl, phenyl, pyridyl, pyrrolyl, at least one hydrogen by R1-1Substituted C1～20Alkyl, at least one hydrogen by R1-1Substituted C1～20Alkoxy, at least one hydrogen by R1-1Substituted C2～20Alkenyl, at least one hydrogen by R1-1Substituted phenyl, at least one hydrogen being replaced by R1-1Substituted pyridyl, at least one hydrogen being replaced by R1-1Substituted pyrrolyl and
wherein R is3Is C2～20An alkenyl group;
R1-1selected from halogen, nitro, amino, C1～6Alkyl radical, C3～6Cycloalkyl radical, C1～6An alkoxy group;
R1and R2At least one of which has a carbon-carbon unsaturated bond;
R1and R2At least part of a structural fragment of any one of the above may be bonded to at least part of a structural fragment of another to form a ring.
In some preferred embodiments, R1And R2Are each independently selected from C1～20Alkyl radical, C1～20Alkoxy radical, C2～20Alkenyl, at least one hydrogen by R1-1Substituted C1～20Alkyl, at least one hydrogen by R1-1Substituted C1～20Alkoxy or at least one hydrogen by R1-1Substituted C2～20An alkenyl group.
In some preferred embodiments, R1And R2Is not bonded to form a ring, and R1And R2All have carbon-carbon unsaturationAnd a key.
In some preferred embodiments, R1Partial structural fragment of (1) and R2And bonding to form a ring.
In some preferred embodiments, R1And R2And bonding to form a ring.
In some preferred embodiments, the monomer of formula I has any one of the following structures:
in some preferred embodiments, the crosslinking agent has at least two carbon-carbon double bonds.
In some preferred embodiments, the crosslinking agent is selected from any one of formula II, formula III or formula IV,
in the formula II, R4、R5、R6And R7Are each independently selected from C1～10Alkyl or
And R is4、R5、R6And R7At least two of which are
Wherein m is 0-20, X1、X2And X3Each independently selected from carbon or oxygen, and X1And X2Not being oxygen at the same time, X2And X3Not being oxygen at the same time, X1And X3Not being oxygen at the same time;
in the formula III, n is 0 to 20, X4、X5And X6Each independently selected from carbon or oxygen, and X4And X5Not being oxygen at the same time, X5And X6Not being oxygen at the same time, X6And X7Not being oxygen at the same time;
in the formula IV, R8And R9Is selected from C1～20An alkenyl group.
In some preferred embodiments, the cross-linking agent is selected from at least one of 1, 6-hexanediol diacrylate, triethylene glycol diacrylate, trimethylolpropane ethoxylate triacrylate, propoxylated trimethylolpropane triacrylate, pentaerythritol tetraacrylate, and vinyl sulfone, preferably vinyl sulfone.
In some preferred embodiments, the plasticizer is an oligomer plasticizer.
In some preferred embodiments, the plasticizer is selected from at least one of polyethylene glycol methacrylate, poly (ethylene glycol) diacrylate, methoxypolyethylene glycol acrylate, trimethylolpropane ethoxytriacrylate, propoxylated trimethylolpropane triacrylate, and 2, 3-epoxypropyl acrylate, preferably polyethylene glycol methacrylate.
In some preferred embodiments, the polymerization is carried out in the presence of an initiator.
In some preferred embodiments, the initiator is selected from at least one of Azobisisobutyronitrile (AIBN), Azobisisoheptonitrile (AIVN), dimethyl azobisisobutyrate, hydrogen peroxide, ammonium persulfate, potassium persulfate Benzoyl Peroxide (BPO), benzoyl t-butyl peroxide, or methyl ethyl ketone peroxide.
In some preferred embodiments, the preparation of the polymer electrolyte comprises the steps of:
the monomer shown in the formula I, a cross-linking agent, a plasticizer and an initiator are mixed and heated for polymerization, and the polymer is obtained.
In some preferred schemes, the molar ratio of the monomer shown in the formula I, the cross-linking agent, the plasticizer and the initiator is a: b: c: d, wherein a is 90-98, b is 1-5, c is 0.5-3 or d is 0.1-2. For example: a, b, c, d, 94:3:2.5: 0.5.
In some preferred embodiments, the temperature for the heating polymerization is 50 to 70 ℃, preferably 60 ℃.
In some preferred embodiments, the time for the heating polymerization is 20 to 40 hours, preferably 24 to 36 hours.
In some preferred embodiments, the heating polymerization further comprises purification, and the purification comprises vacuum drying and washing and drying.
In some preferred embodiments, the vacuum drying step is specifically: and (3) placing the polymerization product in a vacuum oven, and heating for 20-30 hours in vacuum at the temperature of 70-90 ℃.
In some preferred schemes, the step of washing and drying specifically comprises: and sequentially washing the vacuum-dried polymerization product by deionized water and dimethyl carbonate, and drying.
In another preferred embodiment of the present invention, the present invention provides a polymer electrolyte layer comprising the polymer electrolyte and a lithium salt.
In some preferred embodiments, the preparation of the polymer electrolyte layer comprises the steps of:
(1) mixing the polymer electrolyte, succinonitrile and dimethyl sulfoxide to form a polymer electrolyte solution;
(2) dissolving a lithium salt in the polymer electrolyte solution to form a viscous liquid;
(3) and coating the mucus on a current collector, and drying in vacuum to form the polymer electrolyte layer.
In some preferred embodiments, in the polymer electrolyte solution, the mass ratio of the polymer electrolyte, the succinonitrile and the dimethyl sulfoxide is l: m: n, wherein l is 45 to 50, m is 1 to 5, n is 45 to 50, and l + m + n is 100. For example, l: m: n: 48:2: 50.
In some preferred embodiments, the solid content in the polymer electrolyte solution is 45% to 55%, for example 50%.
In some preferred embodiments, in the slime, the lithium salt is selected from lithium fluorophosphate (LiPF)6) Lithium tetrafluoroborate (LiBF)4) Lithium perchlorate (LiClO)4) Lithium hexafluoroarsenate (LiAsF)6) Lithium trifluoromethanesulfonate (LiCF)3SO3) Lithium tetrafluoro oxalate phosphate (littop), lithium tris oxalate phosphate (LiTOP), bis (trifluoromethanesulfonic acid)Lithium imide (LiTFSI), lithium bis (perfluoroethylsulfonyl) imide (LiFSI), (lithium trifluoromethanesulfonyl) (n-perfluorobutylsulfonyl) imide (LiFNTFSI), and lithium fluorosulfonyl) (n-perfluorobutylsulfonyl) imide (LiFNFSI) lithium bis (LiBOB) oxalate.
In some preferred embodiments, the concentration of the lithium salt in the mucus is 1 to 2mol/L, such as 1.5 mol/L.
In some preferred embodiments, in step (3), the current collector is an aluminum foil, an aluminum plastic film CPP, or a release paper.
In order to remove the dimethyl sulfoxide sufficiently, in some preferred schemes, in the step (3), the vacuum drying time is 18-30 hours, such as 24 hours; the temperature of vacuum drying is 80-100 ℃.
In order to prevent the side reaction of the electrolyte material during vacuum drying, in some preferable schemes, during vacuum drying, the vacuum degree is firstly adjusted to be less than or equal to 0.1Pa, then the temperature is raised for vacuum drying, and then the vacuum is opened after the temperature is reduced.
In another preferred embodiment of the present invention, the present invention provides an all solid-state lithium ion battery including the polymer electrolyte layer.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the present invention is further described below with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers. Unless otherwise indicated, percentages and parts are percentages and parts by weight. The test materials and reagents used in the following examples are commercially available without specific reference.
Unless otherwise defined, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs, and it is to be noted that the terms used herein are merely for describing particular embodiments and are not intended to limit example embodiments of the present application.
In the following embodiments, the preparation processes of the polymer electrolyte, the polymer electrolyte layer and the all-solid-state lithium ion battery are completely performed in an argon environment glove box with water less than or equal to 0.1ppm, oxygen less than or equal to 0.1ppm and carbon dioxide less than or equal to 0.1ppm, before experimental operation, water removal work needs to be performed on materials such as propenyl-1, 3-sultone and vinyl sulfone, and a molecular sieve is used for removing water to ensure that the water content of the materials is less than or equal to 10 ppm. Defined below in terms of material mole fractions.
Example 1 preparation method of Polymer electrolyte Material (monomer is propenyl-1, 3-sultone)
Adding 94 mol percent of propenyl-1, 3-sultone, 3 mol percent of vinyl sulfone, 2.5 mol percent of PEGMEMA (polyethylene glycol monoethyl ether methacrylate) and 0.5 mol percent of azobisisobutyronitrile into a cyclohexane solvent for mixing to form a mixed solution with the solid content of about 20-50%. The resulting mixture was poured into a round bottom flask, a rotor was placed, and a reflux condenser tube was placed above the rotor. And (3) placing the round-bottom flask in an oil bath, heating the oil bath to 60 ℃, turning on a reflux condensing device and a magnetic stirring device, keeping heating and stirring for 24-36 hours, and stirring and heating to obtain a yellow or light yellow crystalline material. The material was removed from the round bottom flask and crushed to a powder to give a powdered polymer. The resulting powdered polymer was placed in a vacuum oven for vacuum drying to remove a portion of the unreacted propenyl-1, 3-sultone, vinylsulfone, PEGMEMA. The procedure for vacuum drying was as follows: vacuum heating at 80 deg.c for 24 hr to vacuum degree not higher than 0.1 Pa. Respectively washing the powdery polymer after vacuum drying in deionized water and dimethyl carbonate for multiple times, performing suction filtration and drying, and completely removing unreacted allyl-1, 3-sultone, vinyl sulfone and PEGMEMA; thus obtaining the purified polymer electrolyte material powder.
Example 2 preparation of Polymer electrolyte layer (monomer is propenyl-1, 3-sultone)
The preparation process is carried out under the dew point condition of less than or equal to-40 ℃.
The polymer electrolyte material powder prepared in example 1, succinonitrile and dimethyl sulfoxide were prepared into a solution with a solid content of 50% according to a mass ratio of 48:2: 50. LiTFSI was added to prepare a mixed solution having a lithium salt concentration of 1.5mol/L and a higher viscosity. And coating the prepared solution on the surface of the aluminum plastic film CPP, the aluminum foil or the release paper by using a scraper, wherein the distance between the scrapers is 50 mu m. Putting the coated solution into an oven for vacuum drying, and firstly adjusting the vacuum degree to be less than or equal to 0.1 Pa; then adjusting the temperature to 80-100 ℃, and vacuumizing for 24 hours to ensure that dimethyl sulfoxide is removed; the temperature reduction process is the same, the temperature is reduced to room temperature, and then the vacuum is opened, so that the side reaction of the electrolyte material at high temperature is prevented. And drying in vacuum to obtain the polymer electrolyte layer, wherein the thickness of the electrolyte layer is measured to be about 20-30 mu m.
Example 3 preparation of all solid-state lithium ion Battery
The preparation process of the battery is that the battery is prepared under the condition that the dew point condition is less than or equal to minus 40 ℃, and before the battery is prepared, the anode material and the cathode material are dried;
(1) preparation of positive pole piece
Firstly, dissolving the polymer electrolyte material obtained in the example 1 in dimethyl sulfoxide, adjusting the solid content to be 25%, then adding LITFSI, and adjusting the concentration of lithium salt to be about 0.75mol/L to obtain a polymer electrolyte Binder mixture;
mixing single crystal NCM811, a conductive agent Super-P and the polymer electrolyte Binder mixture according to the mass ratio of an active substance, a polymer electrolyte Binder mixture (polymer electrolyte and lithium salt) to the conductive agent of 75:22:3, adding dimethyl sulfoxide to adjust the solid content to 75%, uniformly mixing, stirring for 10 minutes at 2000rmp by using a Thinky defoaming stirrer, and then defoaming and stirring for 5 minutes at 500 rmp; coating the aluminum foil with a scraper coater to a thickness of about 100 mu m, drying at 80 ℃ after coating, putting the prepared positive plate into a vacuum oven to dry under the condition that the surface has no organic solvent, drying at 120 ℃ for 24 hours, and obtaining the positive plate after drying;
rolling the dried positive pole piece, wherein the rolling gap is 50 microns, the rolling temperature is 60 ℃, the speed is 10mm/s, and the rolled pole piece is 50-60 microns to obtain a finished positive pole piece;
(2) preparation of the electrolyte layer
Preparing an electrolyte layer according to the method of the embodiment 2 and compounding the prepared electrolyte layer with a positive pole piece;
(3) preparation of the Battery
And (3) punching the compounded positive electrode and electrolyte layer, wherein the diameter of the punched sheet is 12mm, and assembling the punched sheet and the lithium metal negative electrode into a button cell after punching is finished to obtain the all-solid-state lithium ion battery.
Example 4 preparation of all solid-state lithium ion Battery
Adding 94.5% of ethylene carbonate, 3% of ethylene glycol (glycol) diacrylate, 2.5% of PEGMEMA and 0.5% of azobisisobutyronitrile into a cyclohexane solvent, and mixing to form a mixed solution, wherein the solid content of the mixed solution is about 20-50%. Pouring the obtained mixed solution into a round-bottom flask, putting a rotor, and placing a reflux condenser pipe above the rotor; the round bottom flask was placed in an oil bath, the temperature of the oil bath was heated to 60 ℃ and the reflux condenser and magnetic stirrer were turned on. Keeping heating and stirring for 24-36 hours. Stirring and heating to obtain a light yellow crystalline material; the pale yellow crystalline material was taken out of the round-bottom flask and crushed into powder to give a powdery polymer. The resulting powdered polymer was placed in a vacuum oven for vacuum drying to remove a portion of the unreacted ethylene carbonate, ethylene glycol (diol) diacrylate, PEGMEMA, the procedure for vacuum drying was as follows: vacuum heating at 80 deg.c for 24 hr to vacuum degree not higher than 0.1 Pa. Cleaning the powder polymer after vacuum drying in cyclohexane and dimethyl carbonate for many times, filtering, drying, and completely removing unreacted ethylene carbonate, ethylene glycol (glycol) diacrylate, and PEGMEMA; obtaining the purified polymer electrolyte material powder.
The preparation process of the battery is that the battery is prepared under the condition that the dew point condition is less than or equal to minus 40 ℃, and before the battery is prepared, the anode material and the cathode material are dried;
(1) preparation of positive pole piece
Firstly, dissolving the polymer electrolyte material in dimethyl sulfoxide, adjusting the solid content to be 25%, then adding LITFSI, and adjusting the concentration of lithium salt to be about 0.75mol/L to obtain a polymer electrolyte Binder mixture;
mixing single crystal NCM811, a conductive agent Super-P and the polymer electrolyte Binder mixture according to the mass ratio of an active substance, the polymer electrolyte Binder mixture (polymer electrolyte and lithium salt) to the conductive agent of 75:22:3, adding dimethyl sulfoxide to adjust the solid content to 75%, uniformly mixing, stirring for 10 minutes at 2000rmp by using a Thinky defoaming stirrer, and then defoaming and stirring for 5 minutes at 500 rmp; coating the aluminum foil with a scraper coater to a thickness of about 100 mu m, drying at 80 ℃ after coating, putting the prepared positive plate into a vacuum oven to dry under the condition that the surface has no organic solvent, drying at 120 ℃ for 24 hours, and obtaining the positive plate after drying;
rolling the dried positive pole piece, wherein the rolling gap is 50 microns, the rolling temperature is 60 ℃, the speed is 10mm/s, and the rolled pole piece is 50-60 microns to obtain a finished positive pole piece;
(2) preparation of the electrolyte layer
An electrolyte layer was prepared according to the method of example 2; after the preparation is finished, taking down the electrolyte layer, and compounding the electrolyte layer with the positive pole piece;
(3) preparation of the Battery
And (3) punching the compounded positive electrode and electrolyte layer, wherein the diameter of the punched sheet is 12mm, and assembling the punched sheet and the lithium metal negative electrode into a button cell after punching is finished to obtain the all-solid-state lithium ion battery.
Example 5 preparation of Polymer electrolyte layer
In this example, the method for producing a polymer electrolyte material powder was substantially the same as in example 1, and the method for producing a polymer electrolyte layer was substantially the same as in example 2, except that the following monomer was used:
monomer structure:
example 6 preparation of Polymer electrolyte layer
In this example, the method for producing a polymer electrolyte material powder was substantially the same as in example 1, and the method for producing a polymer electrolyte layer was substantially the same as in example 2, except that the following monomer was used:
monomer structure:
example 7 preparation of Polymer electrolyte layer
In this example, the method for producing a polymer electrolyte material powder was substantially the same as in example 1, and the method for producing a polymer electrolyte layer was substantially the same as in example 2, except that the following monomer was used:
monomer structure:
example 8 preparation of Polymer electrolyte layer
In this example, the method for producing the polymer electrolyte material powder was substantially the same as in example 1, and the method for producing the polymer electrolyte layer was substantially the same as in example 2, except that triethylene glycol diacrylate was used as the crosslinking agent.
Example 9 preparation of Polymer electrolyte layer
In this example, the method for producing a polymer electrolyte material powder was substantially the same as in example 1, and the method for producing a polymer electrolyte layer was substantially the same as in example 2, except that the crosslinking agent used was pentaerythritol tetraacrylate.
Comparative example 1 preparation of polycarbonate electrolyte layer
The preparation process is substantially the same as the preparation method of the polymer electrolyte in the embodiment 2, and the difference is that the used electrolyte material powder is polycarbonate electrolyte material powder. The specific method comprises the following steps:
the preparation method of the polycarbonate electrolyte material powder comprises the following steps: adding 94.5% of ethylene carbonate, 3% of ethylene glycol (glycol) diacrylate, 2.5% of PEGMEMA and 0.5% of azobisisobutyronitrile into a cyclohexane solvent, and mixing to form a mixed solution with the solid content of about 20-50%. Pouring the obtained mixed solution into a round-bottom flask, putting a rotor, and placing a reflux condenser pipe above the rotor; placing the round-bottom flask in an oil bath, heating the oil bath to 60 ℃, and turning on a reflux condensing device; the magnetic stirring device was turned on. Keeping heating and stirring for 24-36 hours. Stirring and heating to obtain a light yellow crystalline material; the pale yellow crystalline material was taken out of the round-bottom flask and crushed into powder to give a powdery polymer. The resulting powdered polymer was placed in a vacuum oven for vacuum drying to remove a portion of the unreacted ethylene carbonate, ethylene glycol (diol) diacrylate, PEGMEMA, the procedure for vacuum drying was as follows: and (2) heating the mixture in vacuum at the temperature of 80 ℃ for 24 hours with the vacuum degree of less than or equal to 0.1Pa, respectively washing the powdery polymer after vacuum drying in cyclohexane and dimethyl carbonate for multiple times, performing suction filtration and drying, and completely removing ethylene carbonate, ethylene glycol (glycol) diacrylate and PEGMEMA which are not completely reacted to obtain purified polycarbonate electrolyte material powder.
The preparation method of the polycarbonate electrolyte layer comprises the following steps: preparing polycarbonate electrolyte material powder, succinonitrile and dimethyl sulfoxide into a solution according to the mass ratio of 48:2:50, wherein the solid content is 50%. LiTFSI was added to prepare a mixed solution having a lithium salt concentration of 1.5mol/L and a higher viscosity. And coating the prepared solution on the surface of the aluminum plastic film CPP or the aluminum foil by using a scraper, wherein the distance between the scrapers is 50 mu m. Putting the coated solution into an oven for vacuum drying, and firstly adjusting the vacuum degree to be less than or equal to 0.1 Pa; then adjusting the temperature to 80-100 ℃, and vacuumizing for 24 hours to ensure that dimethyl sulfoxide is removed; the temperature reduction process is the same, the temperature is reduced to room temperature, and then the vacuum is opened, so that the side reaction of the electrolyte material at high temperature is prevented. And drying in vacuum to obtain the polycarbonate electrolyte layer.
Comparative example 2 preparation of all solid-state lithium ion Battery
The method of manufacturing the all solid-state lithium ion battery in comparative example 2 was substantially the same as in example 3, except that the polymer electrolyte layer used was the polycarbonate electrolyte layer prepared in comparative example 1.
Test example 1 conductivity test
The polymer electrolyte layers prepared in example 2 and comparative example 1 were punched in a glove box to assemble a structure of an aluminum foil | electrolyte layer | aluminum foil, and a conductivity test was performed using a die battery. The specific test conditions were: diameter 10mm, measured using a Bio-logic MTZ-35 impedance analyzer, frequency 35MHz-0.1 Hz. The test results are shown in Table 1.
Test example 2 tensile Strength test
The polymer electrolyte layers prepared in example 2 and comparative example 1 were subjected to a tensile strength test using a separator test tensile strength tester. The specific test conditions were: the all-solid electrolyte or solid electrolyte provided above was tested using a cell separator tensile strength tester (Labthink blue model XLW tensile tester). The test results are shown in Table 1.
Test example 3 direct current polarized electron conductivity test
The polymer electrolyte layers prepared in example 2 and comparative example 1 were subjected to a dc polarized electron conductivity test. The specific test conditions were: in a glove box, under the condition of 25 ℃, a die battery is used, blocking electrodes (electron conduction and ion blocking) are used at two ends, a corresponding polymer electrolyte layer is clamped in the middle, a constant voltage of 0.5V is applied for 3000s of direct current polarization, the current after the direct current 3000s is recorded, the electronic resistance is equal to the constant voltage/the direct current, and then the electronic conductivity is calculated through a conductivity test formula. The test results are shown in Table 1.
Test example 4 electrolyte layer electrochemical Window test
The polymer electrolyte layers prepared in example 2 and comparative example 1 were subjected to electrolyte layer electrochemical window test. The specific test conditions were: assembling a Li polymer electrolyte layer SUS button cell with a lithium ion blocking electrode stainless steel sheet on one side in a glove box at 25 ℃; one side is a lithium-copper composite belt of the lithium ion reversible electrode; in the middle is a corresponding polymer solid electrolyte layer. The sweep voltage of cyclic voltammetry was first swept from the open circuit voltage to-0.5V and then from-0.5V to 10V, and the sweep rate was cycled to 0.5mV/s, confirming the initial oxidation current position of the cell. The test results are shown in Table 1.
TABLE 1
Test example 5, Battery Performance test
Button cells were prepared as described in example 4 and tested for cell performance as follows.
(1) Initial coulombic efficiency based normal temperature capacity test
The first coulombic efficiency and the room temperature capacity were measured at 25 ℃ in the steps shown in table 2 below. Wherein the first coulombic efficiency is 0.1C discharge capacity/0.1C charge capacity 100%; the capacity at room temperature was 1/3C discharge capacity. The test results are shown in Table 5.
TABLE 2
(2) High temperature capacity test the high temperature capacity was tested at 45 ℃ in the steps shown in table 3 below.
TABLE 3
| Number of steps | Working steps | Mode of operation | Ambient temperature | Interval of sampling point |
| 1 | Standing still | Rest 30min； | 25℃ | 30s |
| 2 | Constant current and constant voltage charging | 0.1C CC to 4.2V，CV to 0.05C； | 25℃ | 5s |
| 3 | Standing still | Rest 5min； | 25℃ | 30s |
| 4 | Constant current discharge | 0.1C DC to 2.5V； | 25℃ | 5s |
| 5 | Standing still | Rest 5min； | 25℃ | 30s |
| 6 | Constant current and constant voltage charging | 1/3C CC to 4.2V，CV to 0.05C； | 25℃ | 5s |
| 7 | Standing still | Rest 60min； | 45℃ | 30s |
| 8 | Constant current discharge | 1/3C DC to 2.5V； | 45℃ | 5s |
| 9 | Standing still | Rest 5min； | 45℃ | 30s |
(3) Low temperature capacity test
The low temperature capacity was tested at-20 ℃ in the steps shown in Table 4 below.
TABLE 4
The results of the above battery performance tests are shown in table 5.
TABLE 5
It will be understood by those of ordinary skill in the art that the foregoing embodiments are specific examples for carrying out the invention, and that various changes in form and details may be made therein without departing from the spirit and scope of the invention in practice.
Claims (20)
1. A polymer electrolyte is characterized in that the polymer electrolyte is formed by polymerizing a monomer shown in a formula I, or the polymer electrolyte is formed by polymerizing a monomer shown in the formula I with a cross-linking agent and/or a plasticizer,
wherein R is1And R2Are each independently selected from C1～20Alkyl radical, C1～20Alkoxy radical, C2～20Alkenyl, phenyl, pyridyl, pyrrolyl, at least one hydrogen by R1-1Substituted C1～20Alkyl, at least one hydrogen by R1-1Substituted C1～20Alkoxy, at least one hydrogen by R1-1Substituted C2～20Alkenyl, at least one hydrogen by R1-1Substituted phenyl, at least one hydrogen being replaced by R1-1Substituted pyridyl, at least one hydrogen being replaced by R1-1Substituted pyrrolyl and
wherein R is3Is C2～20An alkenyl group;
R1-1selected from halogen, nitro, amino, C1～6Alkyl radical, C3～6Cycloalkyl radical, C1～6An alkoxy group;
R1and R2At least one of which has a carbon-carbon unsaturated bond;
R1and R2At least part of a structural fragment of any one of the above may be bonded to at least part of a structural fragment of another to form a ring.
2. According to claimThe polymer electrolyte as described in 1, wherein R is1And R2Are each independently selected from C1～20Alkyl radical, C1～20Alkoxy radical, C2～20Alkenyl, at least one hydrogen by R1-1Substituted C1～20Alkyl, at least one hydrogen by R1-1Substituted C1～20Alkoxy or at least one hydrogen by R1-1Substituted C2～20An alkenyl group.
3. The polymer electrolyte of claim 2, wherein R is1And R2Is not bonded to form a ring, and R1And R2All having carbon-carbon unsaturated bonds.
4. The polymer electrolyte of claim 2, wherein R is1Partial structural fragment of (1) and R2And bonding to form a ring.
5. The polymer electrolyte of claim 2, wherein R is1And R2And bonding to form a ring.
6. The polymer electrolyte of claim 2, wherein the monomer of formula i has any one of the following structures:
7. the polymer electrolyte of claim 2, wherein the cross-linking agent has at least two carbon-carbon double bonds.
8. The polymer electrolyte of claim 2, wherein the cross-linking agent is selected from any one of formula II, formula III, or formula IV,
in the formula II, R4、R5、R6And R7Are each independently selected from C1～10Alkyl or
And R is4、R5、R6And R7At least two of which are
Wherein m is 0-20, X1、X2And X3Each independently selected from carbon or oxygen, and X1And X2Not being oxygen at the same time, X2And X3Not being oxygen at the same time, X1And X3Not being oxygen at the same time;
in the formula III, n is 0 to 20, X4、X5And X6Each independently selected from carbon or oxygen, and X4And X5Not being oxygen at the same time, X5And X6Not being oxygen at the same time, X6And X7Not being oxygen at the same time;
in the formula IV, R8And R9Is selected from C1～20An alkenyl group.
9. The polymer electrolyte of claim 2, wherein the cross-linking agent is selected from at least one of 1, 6-hexanediol diacrylate, triethylene glycol diacrylate, trimethylolpropane ethoxylate triacrylate, propoxylated trimethylolpropane triacrylate, pentaerythritol tetraacrylate, and vinyl sulfone.
10. The polymer electrolyte of claim 2, wherein the plasticizer is selected from at least one of polyethylene glycol methacrylate, poly (ethylene glycol) diacrylate, methoxypolyethylene glycol acrylate, trimethylolpropane ethoxytriacrylate, propoxylated trimethylolpropane triacrylate, and 2, 3-epoxypropyl acrylate.
11. The polymer electrolyte of claim 2, wherein the polymerization is carried out in the presence of an initiator.
12. A method for preparing a polymer electrolyte according to any one of claims 1 to 11, wherein the method comprises:
the monomer shown in the formula I, a cross-linking agent, a plasticizer and an initiator are mixed and heated for polymerization, and the polymer is obtained.
13. The method of manufacturing according to claim 12, wherein the blending comprises: blending the monomer shown in the formula I, the cross-linking agent, the plasticizer and the initiator according to a molar ratio of a to b to c to d, wherein a is 90-98, b is 1-5, c is 0.5-3 or d is 0.1-2; and is
The temperature of the heating polymerization is 50-70 ℃;
and/or the heating polymerization time is 20-40 hours;
and/or after the heating polymerization, the preparation method further comprises purification, wherein the purification comprises vacuum drying and washing and drying.
14. The method of manufacturing according to claim 13, wherein the vacuum drying includes: putting the polymerization product into a vacuum oven, and heating for 20-30 hours at 70-90 ℃ in vacuum;
and/or, the washing and drying comprises the following steps: and washing and drying the vacuum-dried polymerization product by using deionized water and dimethyl carbonate in sequence.
15. A polymer electrolyte layer comprising the polymer electrolyte according to any one of claims 1 to 11 and a lithium salt.
16. The polymer electrolyte layer of claim 15 wherein the lithium salt is selected from lithium fluorophosphate (LiPF)6) Lithium tetrafluoroborate (LiBF)4) Lithium perchlorate (LiClO)4) Lithium hexafluoroarsenate (LiAsF)6) Lithium trifluoromethanesulfonate (LiCF)3SO3) Lithium tetrafluoro oxalate phosphate (litfo), lithium tris oxalate phosphate (LiTOP), lithium bis (trifluoromethylsulfonyl) imide (LiTFSI), lithium bis (perfluoroethylsulfonyl) imide (LiFSI), (trifluoromethylsulfonyl) (n-perfluorobutylsulfonyl) imide (LiFNTFSI), lithium (fluorosulfonyl) (n-perfluorobutylsulfonyl) imide (LiFNFSI), lithium bis (LiBOB) oxalate.
17. A method for producing a polymer electrolyte layer according to claim 15, comprising:
mixing the polymer electrolyte, succinonitrile and dimethyl sulfoxide to form a polymer electrolyte solution;
dissolving a lithium salt in the polymer electrolyte solution to form a viscous liquid; and
and coating the mucus on a current collector, and drying in vacuum to form the polymer electrolyte layer.
18. The method of manufacturing of claim 17, wherein the mixing comprises: mixing the polymer electrolyte, the succinonitrile and the dimethyl sulfoxide according to the mass ratio of l to m to n, wherein l is 45-50, m is 1-5, n is 45-50, and l + m + n is 100.
19. The method according to claim 17, wherein the concentration of the lithium salt in the viscous liquid is 1 to 2 mol/L;
and/or the current collector is an aluminum foil, an aluminum plastic film (CPP) or release paper;
and/or the vacuum drying time is 18-30 hours;
and/or, the vacuum drying comprises: firstly adjusting the vacuum degree to be less than or equal to 0.1Pa, then heating up and vacuum drying, then cooling down and opening the vacuum.
20. An all solid-state lithium ion battery comprising the polymer electrolyte layer according to any one of claims 15 to 16.
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