CN113764723B - 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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- CN113764723B CN113764723B CN202111049494.9A CN202111049494A CN113764723B CN 113764723 B CN113764723 B CN 113764723B CN 202111049494 A CN202111049494 A CN 202111049494A CN 113764723 B CN113764723 B CN 113764723B
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- polymer electrolyte
- lithium
- electrolyte layer
- vacuum
- formula
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- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 117
- 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 34
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 25
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-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
- 238000000034 method Methods 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- 239000004014 plasticizer Substances 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 18
- 229910003002 lithium salt Inorganic materials 0.000 claims description 18
- 159000000002 lithium salts Chemical class 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 15
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- 229910052744 lithium Inorganic materials 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 11
- 210000003097 mucus Anatomy 0.000 claims description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical group C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 claims description 9
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 150000003949 imides Chemical class 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 6
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 6
- 229910001486 lithium perchlorate Inorganic materials 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
- 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 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 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
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 3
- AUBNQVSSTJZVMY-UHFFFAOYSA-M P(=O)([O-])(O)O.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.[Li+] Chemical compound P(=O)([O-])(O)O.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.[Li+] AUBNQVSSTJZVMY-UHFFFAOYSA-M 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 125000004386 diacrylate group Chemical group 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
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- 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 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
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000005030 aluminium foil Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000012528 membrane Substances 0.000 claims 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- 239000000758 substrate Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 13
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 30
- 239000003792 electrolyte Substances 0.000 description 24
- 125000000217 alkyl group Chemical group 0.000 description 21
- 125000003342 alkenyl group Chemical group 0.000 description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 20
- 229910052760 oxygen Inorganic materials 0.000 description 20
- 239000001301 oxygen Substances 0.000 description 20
- 239000000843 powder Substances 0.000 description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 18
- 239000001257 hydrogen Substances 0.000 description 18
- 229910052739 hydrogen Inorganic materials 0.000 description 18
- 239000000463 material Substances 0.000 description 16
- 125000003545 alkoxy group Chemical group 0.000 description 14
- 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 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 12
- 239000004417 polycarbonate Substances 0.000 description 12
- 229920000515 polycarbonate Polymers 0.000 description 12
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 9
- 239000002001 electrolyte material Substances 0.000 description 9
- 239000012634 fragment Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011888 foil Substances 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 150000002430 hydrocarbons Chemical group 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 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 description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 6
- 125000000753 cycloalkyl group Chemical group 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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-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
- 239000004215 Carbon black (E152) Substances 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
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000002985 plastic film Substances 0.000 description 4
- 229920006255 plastic film Polymers 0.000 description 4
- 238000004080 punching Methods 0.000 description 4
- 125000004076 pyridyl group Chemical group 0.000 description 4
- 125000000168 pyrrolyl group Chemical group 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 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 description 2
- 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
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-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
- 238000010281 constant-current constant-voltage charging Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- SXWUDUINABFBMK-UHFFFAOYSA-L dilithium;fluoro-dioxido-oxo-$l^{5}-phosphane Chemical group [Li+].[Li+].[O-]P([O-])(F)=O SXWUDUINABFBMK-UHFFFAOYSA-L 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 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
- 150000005677 organic carbonates Chemical class 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
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 2
- 238000012719 thermal polymerization Methods 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- WVQUCYVTZWVNLV-UHFFFAOYSA-N boric acid;oxalic acid Chemical compound OB(O)O.OC(=O)C(O)=O WVQUCYVTZWVNLV-UHFFFAOYSA-N 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
- 150000001721 carbon Chemical group 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
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000013329 compounding Methods 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
- 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
- 125000004855 decalinyl group Chemical group C1(CCCC2CCCCC12)* 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
- 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
- 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 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
- 239000007784 solid electrolyte Substances 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
- 238000000967 suction filtration Methods 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
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The application discloses a polymer electrolyte, a polymer electrolyte layer and an all-solid-state lithium ion battery. In the present application, the polymer electrolyte is formed by polymerizing a monomer shown in formula I, or the polymer electrolyte is formed by polymerizing a monomer shown in formula I with a crosslinking agent and/or an oligomer accelerating additive. The polymer electrolyte provided by the invention adopts the structural monomer containing two sulfur-oxygen double bonds, so that the formed polymer is more stable. The polymer electrolyte layer provided by the invention has good flexibility and good lithium ion conducting capability. The polymer electrolyte layer provided by the invention is decomposed and reduced to Li with strong lithium ion conducting capability at the negative electrode side 2 S, the conductivity of the negative electrode lithium ions 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 commonly adopted in commercial lithium ion batteries, but the organic carbonate 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 the advantages of good safety performance, high energy density, wide working temperature range and long cycle life, and becomes a hot spot for research in the field of lithium ion batteries.
In the prior art, the all-solid-state polymer electrolyte battery adopts polyethylene oxide as a polymer matrix, but the polyethylene oxide system has high crystallinity and poor conductivity, and the polycarbonate compound has a structure internally provided with a strong polar carbonate group, so that the dielectric constant of an electrolyte layer is improved, and compared with the polyethylene oxide system, the conductivity of the polycarbonate compound is improved. However, the inventor finds that the polycarbonate system is incompatible with the sulfur-containing solid-state lithium ion battery, and the stability of the polycarbonate system is poor. Accordingly, 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 are good in ionic conductivity, wide in electrochemical window and good in stability and are compatible with a sulfur-containing solid-state 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 formed by polymerizing a monomer represented by formula I or by polymerizing a monomer represented by formula I with a crosslinking agent and/or a plasticizer,
wherein R is 1 And R is 2 Are independently selected from C 1～20 Alkyl, C 1～20 Alkoxy, C 2～20 Alkenyl, phenyl, pyridinyl, pyrrolyl, at least one hydrogen being replaced by R 1-1 Substituted C 1～20 Alkyl, at least one hydrogen being replaced by R 1-1 Substituted C 1～20 Alkoxy, at least one hydrogen being replaced by R 1-1 Substituted C 2～20 Alkenyl, at least one hydrogen being replaced by R 1-1 Substituted phenyl, at least one hydrogen being replaced by R 1-1 Substituted pyridinyl, at least one hydrogen being replaced by R 1-1 Substituted pyrrolyl
Wherein R is 3 Is C 2～20 Alkenyl groups;
R 1-1 selected from halogen, nitro, amino, C 1～6 Alkyl, C 3～6 Cycloalkyl, C 1～6 An alkoxy group;
R 1 and R is 2 Having a carbon-carbon unsaturated bond;
R 1 and R is 2 At least a portion of the structural fragments of any one may be bonded to at least a portion of the structural fragments of the other to form a loop.
In some preferred embodiments, R 1 And R is 2 Are independently selected from C 1～20 Alkyl, C 1～20 Alkoxy, C 2～20 Alkenyl, at least one hydrogen being replaced by R 1-1 Substituted C 1～20 Alkyl, at least one hydrogen being replaced by R 1-1 Substituted C 1～20 Alkoxy or at least one hydrogen is replaced by R 1-1 Substituted C 2～20 Alkenyl groups.
In some preferred embodiments, R 1 And R is 2 Is not bonded to form a ring, and R 1 And R is 2 All have carbon-carbon unsaturated bonds.
In some preferred embodiments, R 1 Partial structural fragment of (2) and R 2 Bonded to form a ring.
In some preferred embodiments, R 1 Partial structural fragment of (2) and R 2 Bond to form a ring, and the ring has a carbon-carbon unsaturated bond.
In some preferred embodiments, R 1 And R is 2 Bonded to form a ring.
In some preferred embodiments, R 1 And R is 2 Bond to form a ring, and the ring has a carbon-carbon unsaturated bond.
In some preferred embodiments, the monomer of formula I has a structure as shown in formula I ' -1, I ' -2 or I ' -3:
wherein Y is 1 And Y 2 Each independently selected from carbon or oxygen, R 11 And R is 12 Are independently selected from C 1～6 Alkyl, C 1～6 Alkoxy or C 2～6 Alkenyl groups.
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 of formula II, formula III, or formula IV,
in the formula II, R 4 、R 5 、R 6 And R is 7 Are independently selected from C 1～10 Alkyl orAnd R is 4 、R 5 、R 6 And R is 7 At least two of which are->Wherein m is 0 to 20, X 1 、X 2 And X 3 Independently selected from carbon or oxygen, and X 1 And X 2 Not simultaneously being oxygen, X 2 And X 3 Not simultaneously being oxygen, X 1 And X 3 Not both oxygen;
in the formula III, n is 0 to 20, X 4 、X 5 And X 6 Independently selected from carbon or oxygen, and X 4 And X 5 Not simultaneously being oxygen, X 5 And X 6 Not simultaneously being oxygen, X 6 And X 7 Not both oxygen;
in the formula IV, R 8 And R is 9 Selected from C 1～20 Alkenyl groups.
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 oligomeric 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 ethoxyester triacrylate, 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 tert-butyl peroxide, or methyl ethyl ketone peroxide.
In some preferred embodiments, the preparation of the polymer electrolyte comprises the steps of:
blending the monomer shown in the formula I, a cross-linking agent, a plasticizer and an initiator, and heating and polymerizing to obtain the modified polyurethane.
In some preferred embodiments, the molar ratio of the monomer of formula I, the crosslinking agent, the plasticizer and the initiator is a:b:c:d, wherein a is from 90 to 98, b is from 1 to 5, c is from 0.5 to 3, or d is from 0.1 to 2. For example: a: b: c: d=94:3:2.5:0.5.
In some preferred embodiments, the temperature of the heated polymerization is 50 to 70 ℃, preferably 60 ℃.
In some preferred embodiments, the time of the thermal polymerization is 20 to 40 hours, preferably 24 to 36 hours.
In some preferred embodiments, the heated polymerization is followed by purification, which includes vacuum drying and washing and drying.
In some preferred embodiments, the step of vacuum drying specifically comprises: the polymerization product is placed in a vacuum oven and heated in vacuum for 20 to 30 hours at the temperature of between 70 and 90 ℃.
In some preferred embodiments, the washing and drying steps specifically include: and washing and vacuum-drying the polymerized product by deionized water and dimethyl carbonate in sequence, and drying.
The second aspect of the present invention provides a polymer electrolyte layer including the polymer electrolyte and a lithium salt.
In some preferred embodiments, the preparation of the polymer electrolyte layer includes 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 mucus;
(3) The mucus is coated with a current collector and dried in vacuo 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, where l is 45 to 50, m is 1 to 5, n is 45 to 50, and l+m+n=100. For example, i: m: n=48:2:50.
In some preferred embodiments, the solids content of the polymer electrolyte solution is 45% to 55%, for example 50%.
In some preferred embodiments, in the mucus, the lithium salt is selected from lithium fluorophosphate (LiPF 6 ) Lithium tetrafluoroborate (LiBF) 4 ) Lithium perchlorate (LiClO) 4 ) Lithium hexafluoroarsenate (LiAsF) 6 ) Lithium triflate (LiCF) 3 SO 3 ) Lithium tetrafluorooxalate phosphate (LiTFOP), lithium trioxalate phosphate (LiTOP), bis (trifluoro)At least one of lithium methylsulfonyl) imide (LiTFSI), lithium bis (perfluoroethylsulfonyl) imide (LiLiFeI), lithium (trifluoromethylsulfonyl) (n-perfluorobutylsulfonyl) imide (LiFeNTFSI), lithium (fluorosulfonyl) (n-perfluorobutylsulfonyl) imide (LiFeFSI) and lithium bis (LiFeBI) oxalate borate.
In some preferred embodiments, the concentration of the lithium salt in the mucus is 1 to 2mol/L, for example 1.5mol/L.
In some preferred embodiments, in the step (3), the current collector is aluminum foil, aluminum plastic film CPP, or release paper.
In order to allow adequate removal of dimethyl sulfoxide, in some preferred embodiments, in step (3), the vacuum drying is carried out for a period of 18 to 30 hours, for example 24 hours; the temperature of the vacuum drying is 80-100 ℃.
In order to prevent side reactions of the electrolyte material during vacuum drying, in some preferred schemes, the vacuum degree is adjusted to be less than or equal to 0.1Pa during vacuum drying, then the temperature is increased for vacuum drying, and then the vacuum is opened after the temperature is reduced.
A third aspect of the present invention provides an all-solid lithium ion battery comprising 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, so that the formed polymer is more stable.
(2) The polymer electrolyte layer provided by the invention has good flexibility and good lithium ion conducting capability.
(3) The polymer electrolyte layer provided by the invention is decomposed and reduced to Li2S with strong lithium ion conducting capacity at the negative electrode side, so that 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 understood that within the scope of the present invention, the above-described technical features of the present invention and technical features specifically described below (e.g., in the examples) may be combined with each other to constitute new or preferred technical solutions. And are limited to a space, and are not described in detail herein.
Detailed Description
In the existing all-solid-state polymer electrolyte battery, the polymer electrolyte layer has poor conductivity and poor stability, and is not beneficial to use. The inventors have studied in detail and found that the use of the monomer of the formula I (R in the formula 1 And R is 2 Definition of the radicals is described in the summary of the invention), 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 the formula I and the cross-linking agent are used for copolymerization, so that the flexibility of the polymer electrolyte layer can be improved, the movement of lithium ions is facilitated, and the polymer electrolyte prepared by taking the formed polymer electrolyte as a raw material has better conductive performance.
Preferably, copolymerization of the monomer of formula I and the oligomer plasticizer of the present invention reduces the crystallinity of the resulting polymer electrolyte layer, increases the flexibility of the electrolyte layer, and increases the conductivity of the electrolyte layer.
Preferably, the monomer shown in the 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 the embodiment 1).
Preferably, as the monomer of formula I, when a plurality of oxygen (more than two oxygen) are contained in the molecular structure thereof, lithium ion complexing sites are increased, thereby increasing the conductivity of the resulting polymer electrolyte layer.
Preferably, as the monomer of 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 crosslinking agent, when sulfur is contained in the molecular structure thereof, the affinity with the monomer represented by formula I is better, and the resulting polymer electrolyte layer has increased compatibility with a solid-state lithium ion battery.
Preferably, as the crosslinking agent, as the number of double bonds contained therein increases, crosslinking sites become more numerous, a network structure is more easily formed, and lithium ions are more densely distributed.
Preferably, as the crosslinking agent, as the double bond it contains is less, the polymer electrolyte is improved in flexibility and enhanced in conductivity.
Terminology
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 compound 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 radicals 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 ) Branched saturated monovalent hydrocarbon groups of carbon atoms. Linear C as used herein 1-6 And branched C 3-6 Alkyl groups are also known 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). For example, C 1-6 Alkyl refers to 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 radical having one or more (in one embodiment, one to five) carbon-carbon double bonds. Alkenyl groups may be optionally substituted with one or more substituents. Those of ordinary skill in the art will appreciate that the term "alkenyl" may also include groups having "cis" and "trans" configurations, or alternatively, groups having "E" and "Z" configurations.
As used herein, the term "alkenyl" includes both linear and branched alkenyl groups. For example, C 2-20 Alkyl 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 radical 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 radical 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 a combination 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-CH 3 、-O-CF 3 、-O-CH 2 -CH 3 、-O-CH 2 -CH 2 -CH 3 、-O-CH-(CH 3 ) 2 and-O-CH 2 -CH 2 -O-CH 3 . In one embodiment, the alkoxy is an optionally substituted alkoxy as described elsewhere herein.
As used herein, the term "cycloalkyl" refers to a bridged and/or unbridged hydrocarbon group or ring system that is cyclic, fully or partially saturated, which may be optionally substituted with one or more substituents. In a particular embodiment, the cycloalkyl 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 ) A carbon atom. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, decalinyl, and adamantyl.
The term "R", as used herein 1 Partial structural fragment of (2) and R 2 Bonded to a ring "means R 1 At least part of (C) and R 2 Bonded to form a ring. For example, when R 1 Is n-propyl% (γ1) CH 3 - (β1) CH 2 - (α1) CH 2 -)，R 2 Is n-propyl% (γ2) CH 3 - (β2) CH 2 - (α2) CH 2 (-) at the same time, R 1 Carbon at position beta 1 and R in 2 The carbon at the gamma 2 position is bonded to form a ring, R is considered to be 1 Is a partial structural fragment in n-propyl group (β1) CH 2 - (α1) CH 2 - ", with R 2 ( (γ2) CH 3 - (β2) CH 2 - (α2) CH 2 Formation of (-) bond
The term "R 1 And R is 2 Bonded to a ring "means R 1 Integral with R 2 The whole bond is a ring structure. For example, when R 1 Is n-propyl% (γ1) CH 3 - (β1) CH 2 - (α1) CH 2 -)，R 2 Is n-propyl% (γ2) CH 3 - (β2) CH 2 - (α2) CH 2 In (-), "R 1 And R is 2 Bonded to a ring "represents R 1 Carbon at gamma 1 position and R 2 Carbon bonding formation at the gamma 2 position in the middle
In a preferred embodiment of the present invention, there is provided a polymer electrolyte formed by polymerizing a monomer represented by formula I or by polymerizing a monomer represented by formula I with a crosslinking agent and/or a plasticizer,
wherein R is 1 And R is 2 Are independently selected from C 1～20 Alkyl, C 1～20 Alkoxy, C 2～20 Alkenyl, phenyl, pyridyl, pyrrolyl,At least one hydrogen is represented by R 1-1 Substituted C 1～20 Alkyl, at least one hydrogen being replaced by R 1-1 Substituted C 1～20 Alkoxy, at least one hydrogen being replaced by R 1-1 Substituted C 2～20 Alkenyl, at least one hydrogen being replaced by R 1-1 Substituted phenyl, at least one hydrogen being replaced by R 1-1 Substituted pyridinyl, at least one hydrogen being replaced by R 1-1 Substituted pyrrolyl
Wherein R is 3 Is C 2～20 Alkenyl groups;
R 1-1 selected from halogen, nitro, amino, C 1～6 Alkyl, C 3～6 Cycloalkyl, C 1～6 An alkoxy group;
R 1 and R is 2 Having a carbon-carbon unsaturated bond;
R 1 and R is 2 At least a portion of the structural fragments of any one may be bonded to at least a portion of the structural fragments of the other to form a loop.
In some preferred embodiments, R 1 And R is 2 Are independently selected from C 1～20 Alkyl, C 1～20 Alkoxy, C 2～20 Alkenyl, at least one hydrogen being replaced by R 1-1 Substituted C 1～20 Alkyl, at least one hydrogen being replaced by R 1-1 Substituted C 1～20 Alkoxy or at least one hydrogen is replaced by R 1-1 Substituted C 2～20 Alkenyl groups.
In some preferred embodiments, R 1 And R is 2 Is not bonded to form a ring, and R 1 And R is 2 All have carbon-carbon unsaturated bonds.
In some preferred embodiments, R 1 Partial structural fragment of (2) and R 2 Bonded to form a ring.
In some preferred embodiments, R 1 And R is 2 Bonded 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 of formula II, formula III, or formula IV,
in the formula II, R 4 、R 5 、R 6 And R is 7 Are independently selected from C 1～10 Alkyl orAnd R is 4 、R 5 、R 6 And R is 7 At least two of which are->Wherein m is 0 to 20, X 1 、X 2 And X 3 Independently selected from carbon or oxygen, and X 1 And X 2 Not simultaneously being oxygen, X 2 And X 3 Not simultaneously being oxygen, X 1 And X 3 Not both oxygen;
in the formula III, n is 0 to 20, X 4 、X 5 And X 6 Independently selected from carbon or oxygen, and X 4 And X 5 Not simultaneously being oxygen, X 5 And X 6 Not simultaneously being oxygen, X 6 And X 7 Not both oxygen;
in the formula IV, R 8 And R is 9 Selected from C 1～20 Alkenyl groups.
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 oligomeric 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 ethoxyester triacrylate, 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 tert-butyl peroxide, or methyl ethyl ketone peroxide.
In some preferred embodiments, the preparation of the polymer electrolyte comprises the steps of:
blending the monomer shown in the formula I, a cross-linking agent, a plasticizer and an initiator, and heating and polymerizing to obtain the modified polyurethane.
In some preferred embodiments, the molar ratio of the monomer of formula I, the crosslinking agent, the plasticizer and the initiator is a:b:c:d, wherein a is from 90 to 98, b is from 1 to 5, c is from 0.5 to 3, or d is from 0.1 to 2. For example: a: b: c: d=94:3:2.5:0.5.
In some preferred embodiments, the temperature of the heated polymerization is 50 to 70 ℃, preferably 60 ℃.
In some preferred embodiments, the time of the thermal polymerization is 20 to 40 hours, preferably 24 to 36 hours.
In some preferred embodiments, the heated polymerization is followed by purification, which includes vacuum drying and washing and drying.
In some preferred embodiments, the step of vacuum drying specifically comprises: the polymerization product is placed in a vacuum oven and heated in vacuum for 20 to 30 hours at the temperature of between 70 and 90 ℃.
In some preferred embodiments, the washing and drying steps specifically include: and washing and vacuum-drying the polymerized product by deionized water and dimethyl carbonate in sequence, and drying.
In another preferred embodiment of the present invention, the present invention provides a polymer electrolyte layer including the polymer electrolyte and a lithium salt.
In some preferred embodiments, the preparation of the polymer electrolyte layer includes 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 mucus;
(3) The mucus is coated on a current collector and dried 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, where l is 45 to 50, m is 1 to 5, n is 45 to 50, and l+m+n=100. For example, i: m: n=48:2:50.
In some preferred embodiments, the solids content of the polymer electrolyte solution is 45% to 55%, for example 50%.
In some preferred embodiments, in the mucus, the lithium salt is selected from lithium fluorophosphate (LiPF 6 ) Lithium tetrafluoroborate (LiBF) 4 ) Lithium perchlorate (LiClO) 4 ) Lithium hexafluoroarsenate (LiAsF) 6 ) Lithium triflate (LiCF) 3 SO 3 ) At least one of lithium tetrafluorooxalate phosphate (LiTFOP), lithium trioxalate phosphate (LiTOP), lithium bis (trifluoromethylsulfonyl) imide (LiTFSI), lithium bis (perfluoroethylsulfonyl) imide (LiLiLiFSI), lithium (trifluoromethylsulfonyl) (n-perfluorobutylsulfonyl) imide (LiNTFSI), and lithium (fluorosulfonyl) (n-perfluorobutylsulfonyl) imide (LiNFSI) lithium bisoxalato borate (LiBOB).
In some preferred embodiments, the concentration of the lithium salt in the mucus is 1 to 2mol/L, for example 1.5mol/L.
In some preferred embodiments, in the step (3), the current collector is aluminum foil, aluminum plastic film CPP, or release paper.
In order to allow adequate removal of dimethyl sulfoxide, in some preferred embodiments, in step (3), the vacuum drying is carried out for a period of 18 to 30 hours, for example 24 hours; the temperature of the vacuum drying is 80-100 ℃.
In order to prevent side reactions of the electrolyte material during vacuum drying, in some preferred schemes, the vacuum degree is adjusted to be less than or equal to 0.1Pa during vacuum drying, then the temperature is increased 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 lithium ion battery comprising the polymer electrolyte layer.
The present invention will be further described with reference to specific embodiments in order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. The experimental methods, in which specific conditions are not noted in the following examples, are generally conducted under conventional conditions or under conditions recommended by the manufacturer. Percentages and parts are weight percentages and parts unless otherwise indicated. The experimental materials and reagents used in the following examples were obtained from commercial sources unless otherwise specified.
Unless defined otherwise, 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, it is to be noted that the terms used herein are used merely to describe specific embodiments and are not intended to limit the exemplary embodiments of this application.
In the following examples, the preparation processes of the polymer electrolyte, the polymer electrolyte layer and the all-solid-state lithium ion battery are completely carried out 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, and the materials such as propenyl-1, 3-sultone, vinyl sulfone and the like are required to be dehydrated before experimental operation, and molecular sieve is used for removing water, so that the water content of the materials is less than or equal to 10ppm. The following is defined in terms of mole fraction of material.
Example 1 preparation of Polymer electrolyte Material (propylene-1, 3-sultone as monomer)
Adding 94% of propenyl-1, 3-sultone, 3% of vinyl sulfone, 2.5% of PEGMEMA (polyethylene glycol monoethyl ether methacrylate) and 0.5% of azodiisobutyronitrile into a cyclohexane solvent for mixing to form a mixed solution, wherein the solid content is about 20-50%. The resulting mixture was poured into a round bottom flask, placed in a rotor, and a reflux condenser was placed above. And placing the round bottom flask in an oil bath, heating the temperature of the oil bath to 60 ℃, opening a reflux condensing device and a magnetic stirring device, keeping heating and stirring for 24-36 hours, and obtaining the yellow or pale yellow crystalline material after stirring and heating. The material was removed from the round bottom flask and rolled to powder to give a polymer in powder form. The resulting powdered polymer was placed in a vacuum oven for vacuum drying to remove a portion of unreacted propenyl-1, 3-sultone, vinyl sulfone, PEGMEMA. The procedure for vacuum drying was as follows: vacuum heating at 80 deg.c for 24 hr to vacuum degree less than or equal to 0.1Pa. Washing the vacuum dried powdery polymer in deionized water and dimethyl carbonate for multiple times, and performing suction filtration and drying to completely remove unreacted complete propenyl-1, 3-sultone, vinyl sulfone and PEGMEMA; thus obtaining purified polymer electrolyte material powder.
Example 2 preparation of Polymer electrolyte layer (propylene-1, 3-sultone monomer)
The preparation process is carried out under the condition that the dew point is less than or equal to-40 ℃.
The polymer electrolyte material powder prepared in the example 1, succinonitrile and dimethyl sulfoxide are prepared into a solution according to a mass ratio of 48:2:50, and the solid content is 50%. LiTFSI is added to prepare a mixed solution with high viscosity and lithium salt concentration of 1.5mol/L. The prepared solution is coated on the surface of an aluminum plastic film CPP, an aluminum foil or release paper by a scraper, and the distance between the scrapers is 50 mu m. Placing the coated solution into a baking oven for vacuum drying, and firstly adjusting the vacuum degree to be less than or equal to 0.1Pa; then adjusting the temperature to 80-100 ℃ and the vacuum time to 24 hours to ensure that dimethyl sulfoxide is removed; the cooling process is the same, the temperature is firstly reduced to the room temperature, and then the vacuum is opened, so that the electrolyte material is prevented from side reaction at high temperature. And vacuum drying to obtain the polymer electrolyte layer, and measuring the thickness of the electrolyte layer 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 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 electrode plate
Firstly, dissolving the polymer electrolyte material obtained in the example 1 in dimethyl sulfoxide, adjusting the solid content to 25%, then adding LITFSI, and adjusting the lithium salt concentration to about 0.75mol/L to obtain a polymer electrolyte Binder mixture;
mixing single crystal NCM811, conductive agent Super-P and the polymer electrolyte Binder mixture according to the mass ratio of the active substances polymer electrolyte Binder mixture (polymer electrolyte+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; then coating the positive plate on an aluminum foil by using a knife coater, wherein the coating thickness is about 100 mu m, drying at 80 ℃ after coating is finished, and drying the prepared positive plate in a vacuum oven at 120 ℃ for 24 hours under the condition that the surface is free of organic solvent, thereby obtaining the positive plate after drying is finished;
rolling the dried positive pole piece, wherein the rolling gap is 50 mu m, the rolling temperature is 60 ℃, the speed is 10mm/s, and the rolled pole piece is 50-60 mu m, so that the finished positive pole piece is obtained;
(2) Preparation of electrolyte layer
Preparing an electrolyte layer according to the method of example 2 and compounding the prepared electrolyte layer with a positive electrode sheet;
(3) Preparation of a Battery
And (3) punching the composite positive electrode and the electrolyte layer, wherein the diameter of the punched sheet is 12mm, and assembling the punched sheet and a lithium metal negative electrode into a button cell after finishing punching, so as to obtain the all-solid-state lithium ion battery.
Example 4 preparation of all solid State lithium ion Battery
Adding 94.5% ethylene carbonate, 3% ethylene glycol diacrylate, 2.5% PEGMEMA and 0.5% azodiisobutyronitrile into cyclohexane solvent to mix, so as 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 into a rotor, and placing a reflux condenser above the rotor; the round bottom flask was placed in an oil bath, the oil bath temperature was heated to 60 ℃, and the reflux condensing unit and magnetic stirring unit were turned on. Heating and stirring are kept for 24-36 hours. After stirring and heating are completed, a pale yellow crystalline material is obtained; the pale yellow crystalline material was removed from the round bottom flask and rolled to powder to give a polymer as a powder. The resulting powdered polymer was placed in a vacuum oven and vacuum dried to remove a portion of unreacted ethylene carbonate, ethylene glycol diacrylate, PEGMEMA, the procedure for vacuum drying was as follows: vacuum heating at 80 deg.c for 24 hr to vacuum degree less than or equal to 0.1Pa. Washing the vacuum dried powdery polymer in cyclohexane and dimethyl carbonate for multiple times, filtering and drying, and completely removing unreacted ethylene carbonate, ethylene glycol diacrylate and PEGMEMA; and obtaining purified polymer electrolyte material powder.
The preparation process of the battery is that the battery is prepared under the condition that the dew point 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 electrode plate
Firstly, dissolving the polymer electrolyte material in dimethyl sulfoxide, adjusting the solid content to 25%, then adding LITFSI, and adjusting the lithium salt concentration to about 0.75mol/L to obtain a polymer electrolyte Binder mixture;
mixing single crystal NCM811, conductive agent Super-P and the polymer electrolyte Binder mixture according to the mass ratio of active substances polymer electrolyte Binder mixture (polymer electrolyte+lithium salt) to conductive agent of 75:22:3, adding dimethyl sulfoxide to adjust the solid content to 75%, stirring for 10 minutes at 2000rmp by using a Thinky defoaming stirrer after uniformly mixing, and then defoaming and stirring for 5 minutes at 500 rmp; then coating the positive plate on an aluminum foil by using a knife coater, wherein the coating thickness is about 100 mu m, drying at 80 ℃ after coating is finished, and drying the prepared positive plate in a vacuum oven at 120 ℃ for 24 hours under the condition that the surface is free of organic solvent, thereby obtaining the positive plate after drying is finished;
rolling the dried positive pole piece, wherein the rolling gap is 50 mu m, the rolling temperature is 60 ℃, the speed is 10mm/s, and the rolled pole piece is 50-60 mu m, so that the finished positive pole piece is obtained;
(2) Preparation of electrolyte layer
An electrolyte layer was prepared as in example 2; after the preparation is finished, the electrolyte layer is taken down and is compounded with the positive pole piece;
(3) Preparation of a Battery
And (3) punching the composite positive electrode and the electrolyte layer, wherein the diameter of the punched sheet is 12mm, and assembling the punched sheet and a lithium metal negative electrode into a button cell after finishing punching, so as to obtain the all-solid-state lithium ion battery.
Example 5 preparation of Polymer electrolyte layer
In this example, the method of preparing the polymer electrolyte material powder was substantially the same as in example 1, and the method of preparing the polymer electrolyte layer was substantially the same as in example 2, except that the following structure was used as the monomer:
monomer structure:
example 6 preparation of Polymer electrolyte layer
In this example, the method of preparing the polymer electrolyte material powder was substantially the same as in example 1, and the method of preparing the polymer electrolyte layer was substantially the same as in example 2, except that the following structure was used as the monomer:
monomer structure:
EXAMPLE 7 preparation of Polymer electrolyte layer
In this example, the method of preparing the polymer electrolyte material powder was substantially the same as in example 1, and the method of preparing the polymer electrolyte layer was substantially the same as in example 2, except that the following structure was used as the monomer:
monomer structure:
example 8 preparation of Polymer electrolyte layer
In this example, the method of preparing the polymer electrolyte material powder was substantially the same as in example 1, and the method of preparing the polymer electrolyte layer was substantially the same as in example 2, except that the crosslinking agent used was triethylene glycol diacrylate.
Example 9 preparation of Polymer electrolyte layer
In this example, the method for preparing the polymer electrolyte material powder was substantially the same as in example 1, and the method for preparing the polymer electrolyte layer was substantially the same as in example 2, except that pentaerythritol tetraacrylate was used as the crosslinking agent.
Comparative example 1 preparation of polycarbonate electrolyte layer
The preparation process was substantially the same as the polymer electrolyte preparation method in example 2 of the present application, except that the electrolyte material powder used was 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% ethylene carbonate, 3% ethylene glycol diacrylate, 2.5% PEGMEMA and 0.5% azodiisobutyronitrile into cyclohexane solvent, mixing to form a mixed solution, wherein the solid content is about 20-50%. Pouring the obtained mixed solution into a round-bottom flask, putting into a rotor, and placing a reflux condenser above the rotor; placing the round bottom flask in an oil bath, heating the temperature of the oil bath to 60 ℃, and opening a reflux condensing device; the magnetic stirring device is turned on. Heating and stirring are kept for 24-36 hours. After stirring and heating are completed, a pale yellow crystalline material is obtained; the pale yellow crystalline material was removed from the round bottom flask and rolled to powder to give a polymer as a powder. The resulting powdered polymer was placed in a vacuum oven and vacuum dried to remove a portion of unreacted ethylene carbonate, ethylene glycol diacrylate, PEGMEMA, the procedure for vacuum drying was as follows: vacuum heating at 80 deg.c for 24 hr with vacuum degree less than or equal to 0.1Pa, washing the vacuum dried polymer powder in cyclohexane and dimethyl carbonate for several times, suction filtering and drying to eliminate unreacted ethylene carbonate, glycol diacrylate and PEGMEMA completely 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 a mass ratio of 48:2:50, wherein the solid content is 50%. LiTFSI is added to prepare a mixed solution with high viscosity and lithium salt concentration of 1.5mol/L. The prepared solution is coated on the surface of an aluminum plastic film CPP or an aluminum foil by a scraper, and the distance between the scrapers is 50 mu m. Placing the coated solution into a baking oven for vacuum drying, and firstly adjusting the vacuum degree to be less than or equal to 0.1Pa; then adjusting the temperature to 80-100 ℃ and the vacuum time to 24 hours to ensure that dimethyl sulfoxide is removed; the cooling process is the same, the temperature is firstly reduced to the room temperature, and then the vacuum is opened, so that the electrolyte material is prevented from side reaction at high temperature. And (5) drying in vacuum to obtain the polycarbonate electrolyte layer.
Comparative example 2 preparation of all solid-state lithium ion Battery
The method of preparing an 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, assembled into a structure of aluminum foil |electrolyte layer|aluminum foil, and conductivity test was performed using a mold battery. The specific test conditions are as follows: diameter 10mm, testing was performed using a Bio-logic MTZ-35 impedance analyzer, frequency 35MHz-0.1Hz. The test results are shown in Table 1.
Test example 2, tensile Strength test
Tensile strength testing the polymer electrolyte layers prepared in example 2 and comparative example 1 were subjected to tensile strength testing using a separator test tensile strength tester. The specific test conditions are as follows: the above-provided all solid state electrolyte or solid state electrolyte was tested using a battery separator tensile strength tester (Labthink blue light, model XLW tensile tester). The test results are shown in Table 1.
Test example 3, DC polarized electron conductivity test
The polymer electrolyte layers prepared in example 2 and comparative example 1 were subjected to direct-current polarized electron conductivity test. The specific test conditions are as follows: in a glove box, using a die battery at 25 ℃, using blocking electrodes (electron conduction and ion blocking) at two ends, clamping a corresponding polymer electrolyte layer in the middle, starting to apply constant voltage of 0.5V DC polarization for 3000s, recording current after 3000s, and calculating electron conductivity through a conductivity test formula after electron resistance = constant voltage/current after DC. The test results are shown in Table 1.
Test example 4 electrochemical window test of electrolyte layer
Electrolyte layer electrochemical window tests were performed on the polymer electrolyte layers prepared in example 2 and comparative example 1. The specific test conditions are as follows: assembling a Li|polymer electrolyte layer|SUS button cell in a glove box at 25 ℃, wherein one side of the button cell is a lithium ion blocking electrode stainless steel sheet; one side is a lithium ion reversible electrode lithium copper composite band; the middle is a corresponding polymer solid electrolyte layer. The cyclic voltammetry scanning voltage is firstly scanned from the open circuit voltage to-0.5V, then is scanned from-0.5V to 10V, and the cyclic voltammetry scanning voltage is circularly scanned at the speed of 0.5mV/s, so that the initial oxidation current position of the battery is confirmed. The test results are shown in Table 1.
TABLE 1
Test example 5, battery Performance test
A button cell was prepared in the manner described in example 4 and the following test cell performance was performed.
(1) First coulombic efficiency base room temperature capacity test
The first coulombic efficiency and the room temperature capacity were measured at 25℃in steps as shown in Table 2 below. Wherein, first coulombic efficiency = 0.1C discharge capacity/0.1C charge capacity 100%; normal temperature capacity=1/3C discharge capacity. The test results are shown in Table 5.
TABLE 2
(2) The high temperature capacity was measured at 45℃by the test of high Wen Rongliang in steps shown in Table 3 below.
TABLE 3 Table 3
| Step number | Step of working | Mode of operation | Ambient temperature | Sampling point interval |
| 1 | Standing still | Rest 30min； | 25℃ | 30s |
| 2 | Constant current 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 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 measured at-20℃in steps shown in Table 4 below.
TABLE 4 Table 4
The results of the above battery performance test 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 of 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.
Claims (12)
1. A polymer electrolyte is characterized in that the polymer electrolyte is formed by polymerizing a monomer shown in a formula I, a cross-linking agent and a plasticizer,
the monomer shown in the formula I has any one of the following structures:
the cross-linking agent is vinyl sulfone; the plasticizer is at least one selected from polyethylene glycol methacrylate, poly (ethylene glycol) diacrylate, methoxy polyethylene glycol acrylate, trimethylolpropane ethoxyester triacrylate, propoxylated trimethylolpropane triacrylate and 2, 3-epoxypropyl acrylate.
2. The polymer electrolyte of claim 1 wherein the polymerization is performed in the presence of an initiator.
3. A method of producing the polymer electrolyte according to any one of claims 1 to 2, characterized by comprising:
blending the monomer shown in the formula I, a cross-linking agent, a plasticizer and an initiator, and heating and polymerizing to obtain the modified polyurethane.
4. A method of making according to claim 3 wherein said blending comprises: blending the monomer shown in the formula I, the cross-linking agent, the plasticizer and the initiator in 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 also provided with
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.
5. The method of claim 4, wherein the vacuum drying comprises: the polymerization product is placed in a vacuum oven and heated in vacuum for 20 to 30 hours at the temperature of between 70 and 90 ℃.
6. The method according to claim 4, wherein the washing and drying comprises: washing and drying the polymerization product after vacuum drying by using deionized water and dimethyl carbonate in sequence.
7. A polymer electrolyte layer, characterized in that the polymer electrolyte layer comprises the polymer electrolyte according to any one of claims 1 to 3 and a lithium salt.
8. The polymer electrolyte layer of claim 7 wherein the lithium salt is selected from the group consisting of lithium hexafluorophosphate (LiPF 6 ) Lithium tetrafluoroborate (LiBF) 4 ) Lithium perchlorate (LiClO) 4 ) Lithium hexafluoroarsenate (LiAsF) 6 ) Lithium triflate (LiCF) 3 SO 3 ) At least one of lithium tetrafluorooxalate phosphate (LiTFOP), lithium trioxalate phosphate (LiTOP), lithium bis (trifluoromethylsulfonyl) imide (LiTFSI), lithium bis (perfluoroethylsulfonyl) imide (LiLiLiFSI), lithium (trifluoromethylsulfonyl) (n-perfluorobutylsulfonyl) imide (LiNTFSI), and lithium (fluorosulfonyl) (n-perfluorobutylsulfonyl) imide (LiNFSI) lithium bisoxalato borate (LiBOB).
9. A method of producing the polymer electrolyte layer according to claim 7, characterized by 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 mucus; and
coating the mucus on a substrate, and vacuum drying to form the polymer electrolyte layer;
wherein, the basement is aluminium foil, plastic-aluminum membrane CPP or from type paper.
10. The method of preparing according to claim 9, wherein the mixing comprises: mixing the polymer electrolyte, the succinonitrile and the dimethyl sulfoxide in a mass ratio of l to m to n, wherein l is 45 to 50, m is 1 to 5, n is 45 to 50, and l+m+n=100.
11. The method according to claim 9, wherein the concentration of the lithium salt in the mucus is 1 to 2mol/L; and/or the time of vacuum drying is 18-30 hours;
and/or, the vacuum drying comprises: firstly, regulating the vacuum degree to be less than or equal to 0.1Pa, heating up for vacuum drying, cooling and then opening vacuum.
12. An all-solid lithium ion battery, characterized in that it comprises the polymer electrolyte layer according to any one of claims 7 to 8.
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