CN117887109A - Crosslinked polymer, synthesis method of crosslinked polymer and solid polymer electrolyte - Google Patents
Crosslinked polymer, synthesis method of crosslinked polymer and solid polymer electrolyte Download PDFInfo
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- CN117887109A CN117887109A CN202211262050.8A CN202211262050A CN117887109A CN 117887109 A CN117887109 A CN 117887109A CN 202211262050 A CN202211262050 A CN 202211262050A CN 117887109 A CN117887109 A CN 117887109A
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- crosslinking
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- crosslinked
- polymer
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- 229920006037 cross link polymer Polymers 0.000 title claims abstract description 132
- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 79
- 239000007787 solid Substances 0.000 title claims abstract description 66
- 238000001308 synthesis method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 121
- 238000004132 cross linking Methods 0.000 claims abstract description 92
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 72
- 229920000642 polymer Polymers 0.000 claims abstract description 52
- -1 amino, hydroxy Chemical group 0.000 claims abstract description 27
- 125000003396 thiol group Chemical class [H]S* 0.000 claims abstract description 11
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 94
- 229920000570 polyether Polymers 0.000 claims description 76
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 71
- 229920001519 homopolymer Polymers 0.000 claims description 67
- 229910052744 lithium Inorganic materials 0.000 claims description 45
- 125000000217 alkyl group Chemical group 0.000 claims description 44
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 43
- 229910001416 lithium ion Inorganic materials 0.000 claims description 43
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 39
- 229910003002 lithium salt Inorganic materials 0.000 claims description 33
- 159000000002 lithium salts Chemical class 0.000 claims description 31
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 29
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 23
- 125000003118 aryl group Chemical group 0.000 claims description 21
- 230000015572 biosynthetic process Effects 0.000 claims description 21
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 20
- 125000005647 linker group Chemical group 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 20
- 150000002500 ions Chemical class 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 230000005012 migration Effects 0.000 claims description 15
- 238000013508 migration Methods 0.000 claims description 15
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- 125000001072 heteroaryl group Chemical group 0.000 claims description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 14
- 239000004593 Epoxy Substances 0.000 claims description 13
- 150000002431 hydrogen Chemical class 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 12
- 150000002367 halogens Chemical class 0.000 claims description 12
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 12
- 125000002947 alkylene group Chemical group 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 125000005529 alkyleneoxy group Chemical group 0.000 claims description 10
- 239000007810 chemical reaction solvent Substances 0.000 claims description 10
- 125000004474 heteroalkylene group Chemical group 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 239000004971 Cross linker Substances 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 8
- 125000004475 heteroaralkyl group Chemical group 0.000 claims description 8
- 230000002194 synthesizing effect Effects 0.000 claims description 8
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 7
- 125000003368 amide group Chemical group 0.000 claims description 7
- 125000005099 aryl alkyl carbonyl group Chemical group 0.000 claims description 7
- 230000001351 cycling effect Effects 0.000 claims description 7
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 229910001868 water Inorganic materials 0.000 claims description 7
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 229920000734 polysilsesquioxane polymer Polymers 0.000 claims description 6
- 125000006254 cycloalkyl carbonyl group Chemical group 0.000 claims description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- 125000003158 alcohol group Chemical group 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 4
- QBVXKDJEZKEASM-UHFFFAOYSA-M tetraoctylammonium bromide Chemical compound [Br-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC QBVXKDJEZKEASM-UHFFFAOYSA-M 0.000 claims description 4
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 claims description 4
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 4
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- OALSNYDESGVYDZ-UHFFFAOYSA-N tetraoctylazanium;azide Chemical compound [N-]=[N+]=[N-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC OALSNYDESGVYDZ-UHFFFAOYSA-N 0.000 claims description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 3
- MXSVLWZRHLXFKH-UHFFFAOYSA-N triphenylborane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 MXSVLWZRHLXFKH-UHFFFAOYSA-N 0.000 claims description 3
- NPNAXGKROXIVMJ-UHFFFAOYSA-N (2,3,4-trifluorophenyl)boron Chemical compound [B]C1=CC=C(F)C(F)=C1F NPNAXGKROXIVMJ-UHFFFAOYSA-N 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 230000037427 ion transport Effects 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 30
- 238000012360 testing method Methods 0.000 description 29
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 26
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 22
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 21
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 18
- 239000003792 electrolyte Substances 0.000 description 16
- 229910001220 stainless steel Inorganic materials 0.000 description 15
- 239000010935 stainless steel Substances 0.000 description 15
- 125000003277 amino group Chemical group 0.000 description 14
- 125000004432 carbon atom Chemical group C* 0.000 description 14
- 229920006254 polymer film Polymers 0.000 description 14
- 230000008901 benefit Effects 0.000 description 13
- 239000011259 mixed solution Substances 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- 239000007784 solid electrolyte Substances 0.000 description 12
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 11
- 125000005842 heteroatom Chemical group 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 125000004185 ester group Chemical group 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000004090 dissolution Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 8
- 238000007142 ring opening reaction Methods 0.000 description 8
- 125000001424 substituent group Chemical group 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 238000013461 design Methods 0.000 description 7
- 239000012528 membrane Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000011244 liquid electrolyte Substances 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 125000005587 carbonate group Chemical group 0.000 description 5
- 210000004027 cell Anatomy 0.000 description 5
- 210000001787 dendrite Anatomy 0.000 description 5
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 125000000623 heterocyclic group Chemical group 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 5
- 238000004736 wide-angle X-ray diffraction Methods 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 125000000962 organic group Chemical group 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- NCZYUKGXRHBAHE-UHFFFAOYSA-K [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] Chemical compound [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] NCZYUKGXRHBAHE-UHFFFAOYSA-K 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000001033 ether group Chemical group 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000002950 monocyclic group Chemical group 0.000 description 3
- 125000003367 polycyclic group Chemical group 0.000 description 3
- 239000003115 supporting electrolyte Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 101150104466 NOCT gene Proteins 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000004305 biphenyl Chemical group 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
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- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000000842 isoxazolyl group Chemical group 0.000 description 2
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 description 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
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- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
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- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- IUHFWCGCSVTMPG-UHFFFAOYSA-N [C].[C] Chemical group [C].[C] IUHFWCGCSVTMPG-UHFFFAOYSA-N 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical group [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
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- 239000004480 active ingredient Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 238000012653 anionic ring-opening polymerization Methods 0.000 description 1
- 150000001450 anions Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000012650 click reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
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- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
-
- 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
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/02—Polyalkylene oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
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- Materials Engineering (AREA)
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Abstract
The present invention provides a crosslinked polymer, a synthesis method, and a solid polymer electrolyte, wherein the crosslinked polymer contains a crosslinked structure formed by a reaction of a crosslinking agent and a polymer chain connected to the crosslinked structure, the polymer chain comprising a first structural unit and a second structural unit, wherein the polymer chain is connected to the crosslinked structure through the first structural unit. The crosslinking agent contains at least two crosslinking groups for crosslinking, so that each crosslinking structure is respectively connected with at least two first structural units, and the crosslinking groups are selected from one or more of the following: amino, hydroxy or mercapto. The crosslinked polymer has excellent mechanical property and ion conductivity, and has good application prospect in solid polymer electrolyte.
Description
Technical Field
The invention relates to the field of high polymers, in particular to a crosslinked polymer, a synthesis method of the crosslinked polymer and a solid polymer electrolyte.
Background
The electrochemical energy storage technology with high energy density and high safety performance has very wide application prospect in a large-scale energy storage system, and development of the efficient electrochemical energy storage technology has great social and economic benefits for improving the existing power generation system, guaranteeing the large-scale development of renewable energy sources and safe and economic operation of a power grid. Lithium batteries have attracted considerable attention from researchers because of their high energy density, light weight, high operating voltage, and lack of memory effects. The lithium metal negative electrode is the most promising negative electrode material of the high-energy lithium battery due to the high theoretical specific capacity, the lowest electrochemical potential and the low density. The electrolyte is one of important components of the battery, and the performance of the electrolyte directly influences the energy density, the cycle life, the safety performance and the like of the lithium battery. Although liquid electrolytes have been commercially used, liquid electrolytes have the disadvantage of being volatile, leak-prone and side-reactive with lithium metal anodes. Lithium metal batteries based on liquid electrolytes are easily pierced by lithium dendrites, causing internal micro-shorts, and severe cases can lead to thermal runaway, fires and even explosions.
The solid electrolyte is used for replacing the liquid electrolyte, so that the potential safety problem of the current battery is hopefully solved while the energy density of the battery is improved, and the requirements and the expectations of future large-scale energy storage technologies are met. All-solid electrolytes generally fall into two broad categories, solid inorganic electrolytes and solid polymer electrolytes. Among them, the solid inorganic electrolyte, although having advantages in terms of ion conductivity and lithium ion mobility, tends to have problems of poor interfacial compatibility and complicated preparation process, and has not been applied on a large scale so far. In contrast, the solid polymer electrolyte has the advantages of flexibility, processability, good interface adhesion and the like, and is expected to be applied to the fields of solid batteries, flexible electronics and the like. However, solid polymer electrolytes generally suffer from low ionic conductivity at room temperature, low lithium ion transfer number, and insufficient mechanical modulus, and are in need of solution.
Disclosure of Invention
The present invention is directed to a crosslinked polymer and a method for synthesizing the crosslinked polymer, which are used for solving the above problems.
The invention provides a crosslinked polymer, which comprises a crosslinked structure generated by a crosslinking agent and a polymer chain connected with the crosslinked structure, wherein the polymer chain comprises a first structural unit and a second structural unit, the first structural unit is a structure shown in a formula (1-1) and/or a formula (1-2), the second structural unit is a structure shown in a formula (2), the polymer chain is connected with the crosslinked structure through the first structural unit, and the connection point connected with the crosslinked structure is represented by the formula (1-1) and the formula (1-2);
Formula (1-1):formula (1-2):Formula (2):
The crosslinking agent contains at least two crosslinking groups for crosslinking, so that each crosslinking structure is respectively connected with at least two first structural units, and the crosslinking groups are selected from one or more of the following: amino, hydroxy or mercapto; wherein R1 is selected from substituted or unsubstituted alkylene, alkyleneoxy, or heteroalkylene; r2 is selected from hydrogen, halogen, or substituted or unsubstituted alkyl, heteroalkyl.
The crosslinked polymer provided by the invention can form a film, has good mechanical properties and structural advantages, and has a wide application prospect.
Alternatively, the crosslinked polymer is formed by crosslinking a polyether homopolymer having a cyclic carbonate on a side group with the crosslinking agent, the polyether homopolymer being represented by formula (3):
formula (3):
wherein n represents the polymerization degree and has a value of 5 to 10000; a part of cyclic carbonate side groups of the repeating units in the polyether homopolymer are crosslinked with the crosslinking agent to form the first structural unit, and the other part of repeating units are not crosslinked to form the second structural unit; r is R 1 Selected from substituted or unsubstituted alkylene, alkyleneoxy or heteroalkylene; r is R 2 Selected from hydrogen, halogen, or from substituted or unsubstituted alkyl, heteroalkyl.
Optionally, the crosslinker is composed of formula (4):
formula (4): a- (B) b
Wherein B is the crosslinking group optionally substituted on A, and has the structural formula of-NH 2 -OH or-SH, b representing the number of said crosslinking groups, and having a value of 2 or more; a is a linking group having two or more linking sites selected from the following substituted or unsubstituted groups: alkyl, heteroalkyl, alkylcarbonyl, heteroalkylcarbonyl, heterocycloalkyl, heterocycloalkylcarbonyl, alkylaliphatic, aryl, aralkyl, heteroaryl, heteroaralkyl, aralkylcarbonyl, heteroaralkylcarbonyl, cycloalkyl, cycloheteroalkyl, cycloalkylcarbonyl, cycloheteroalkylcarbonyl, cage polysilsesquioxane.
Alternatively, a is selected from the following groups: alkyl, aryl, aralkyl, alkoxy, heteroaralkyl, aralkylcarbonyl, amido, amidalkyl, amidalkoxy.
Alternatively, a is selected from the following structural formulae:
wherein represents the point of attachment to crosslinking group B; n is 2-10000; x is x 1 ,x 2 ,x 3 ,x 4 The range of the values of (2) is 1-1000 respectively.
Alternatively, R 1 Selected from the following structures:
wherein n ranges from 1 to 100; * Representing the connection point.
Alternatively, R 2 Selected from the following structures:
Wherein X is selected from halogen atoms; * Representing the connection point.
Optionally, the amount of the first structural unit relative to the sum of the first structural unit and the second structural unit in the crosslinked polymer is 10% to 80%.
The invention also provides a synthesis method of the crosslinked polymer, which is used for synthesizing the crosslinked polymer, and comprises the steps of carrying out crosslinking reaction on polyether homopolymer represented by a formula (3) and the crosslinking agent to obtain the crosslinked polymer;
formula (3):
wherein n represents the polymerization degree and has a value of 5-10000; a portion of the cyclic carbonate side groups of the repeating units in the polyether homopolymer are crosslinked with the crosslinking agent to form the first structural unit, and another portion of the repeating units are not crosslinked to form the second structural unit.
Optionally, the polyether homopolymer and the cross-linking agent are subjected to cross-linking reaction, wherein the reaction temperature of the cross-linking reaction is 25-180 ℃, the reaction time is 0.5-72 hours, and the reaction solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, dichloromethane, tetrahydrofuran, acetonitrile, dimethyl carbonate, diethyl carbonate, 1, 3-dioxane and acetone.
Optionally, the reaction temperature is 25-120 ℃, the reaction time is 1-48 hours, and the reaction solvent is one or more of N, N-dimethylformamide, tetrahydrofuran, acetonitrile, dimethyl carbonate and acetone.
Alternatively, the molar ratio of the crosslinking groups in the crosslinker to the cyclic carbonate groups on the pendant polyether homopolymer groups is selected to be in the range of 0.1 to 0.8.
Optionally, the synthesis of the polyether homopolymer is also included: ring-opening polymerization reaction is carried out by taking epoxy monomers as raw materials to form the polyether homopolymer, wherein the epoxy monomers consist of a formula (5):
formula (5):
wherein R is 1 Selected from substituted or unsubstituted alkylene, alkyleneoxy or heteroalkylene; r is R 2 Selected from hydrogen, halogen, or from substituted or unsubstituted alkyl, heteroalkyl.
Optionally, in the ring-opening polymerization reaction, the initiator is an onium salt, the catalyst is an aluminum complex and/or a boron complex, and the terminator is an alcohol containing active proton hydrogen, ammonia, water, an organic or inorganic acid.
Optionally, the initiator is one or more of tetraoctyl ammonium bromide, tetrabutyl ammonium chloride, tetrabutyl ammonium bromide, tetraoctyl ammonium azide and ditriphenyl phosphoranylic ammonium chloride; the catalyst is one or more of triethylboron, triisobutylaluminum, triethylaluminum, triphenylboron and trifluorophenyl boron; the terminator is one or more of water, methanol, ethanol, formic acid and acetic acid.
Optionally, in the ring-opening polymerization reaction, the reaction temperature is-30-60 ℃, and the reaction solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, dichloromethane, tetrahydrofuran, acetonitrile, toluene, benzene, cyclohexane and chlorobenzene.
The invention also provides a solid polymer electrolyte comprising the crosslinked polymer.
Optionally, the solid polymer electrolyte further comprises a lithium salt, wherein the mass fraction of the crosslinked polymer in the solid polymer electrolyte is 10% -95%, and the mass fraction of the lithium salt in the solid polymer electrolyte is 5% -90%.
Alternatively, the solid polymer electrolyte has a room temperature ionic conductivity of 10 -5 S/cm or more, and the migration number of lithium ions is 0.2 or more.
The invention also provides an electrochemical device comprising the solid polymer electrolyte.
The invention also provides the use of a solid polymer electrolyte as described above in an electrochemical device or a flexible device, in particular in a lithium ion or lithium metal battery, more in particular in improving the ion conductivity and/or the lithium ion transport number of a lithium ion battery solid electrolyte and/or the electrochemical stability window of a lithium ion battery and/or the rate capability and cycle performance of a lithium metal battery.
Drawings
FIG. 1 is a schematic diagram of a structural model of a polyether homopolymer containing cyclic carbonate side groups;
FIG. 2 is a schematic structural diagram showing an embodiment of a crosslinked polymer formed by crosslinking a polyether homopolymer containing cyclic carbonate side groups with an amino crosslinking agent;
FIG. 3 is a chart of infrared absorption spectra of a cross-linked polymer formed after a cross-linking reaction of a polyether homopolymer containing cyclic carbonate side groups at the position and an amino cross-linking agent;
FIG. 4 is a temperature swing ionic conductivity diagram of a solid polymer electrolyte prepared in accordance with an exemplary embodiment;
FIG. 5 is a graph of lithium ion mobility test for a solid polymer electrolyte;
FIG. 6 is a graph of cycling of a lithium-lithium symmetric battery at different current densities with an embodiment as a solid polymer electrolyte;
FIG. 7 is a graph of cycling a lithium-lithium symmetric battery using an embodiment as a solid polymer electrolyte;
FIG. 8 is a graph of cycling results for a lithium iron phosphate-lithium full cell with an example as a solid polymer electrolyte;
FIG. 9 is a wide angle X-ray diffraction pattern of PEOEC-1 with lithium salt LiTFSI in example 3;
fig. 10 is an ion conductivity chart obtained by testing the solid polymer electrolyte of comparative example 2.
Detailed Description
Further advantages and effects of the present invention will become apparent to those skilled in the art from the disclosure of the present specification, by describing the embodiments of the present invention with specific examples. While the description of the invention will be described in connection with the preferred embodiments, it is not intended to limit the inventive features to the implementation. Rather, the purpose of the invention described in connection with the embodiments is to cover other alternatives or modifications, which may be extended by the claims based on the invention. The following description contains many specific details for the purpose of providing a thorough understanding of the present invention. The invention may be practiced without these specific details. Furthermore, some specific details are omitted from the description in order to avoid obscuring the invention. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
It should be noted that in this specification, like reference numerals and letters denote like items in the following figures, and thus once an item is defined in one figure, no further definition or explanation thereof is necessary in the following figures.
Definition:
the prefix "alkylene" is added before a group indicates that the group is a divalent moiety, e.g., alkylene is a divalent moiety of alkyl, alkyleneoxy is a divalent moiety of alkoxy, and heteroalkylene is a divalent moiety of heteroalkyl.
The term "alkyl" refers to all possible variants for the various numbers of carbon atoms in the alkyl group, i.e., methyl, ethyl; for 3 carbon atoms: n-propyl and isopropyl; for 4 carbon atoms: n-butyl, isobutyl and tert-butyl; for 5 carbon atoms: n-pentyl, 1-dimethyl-propyl, 2-dimethylpropyl, 2-methyl-butyl, etc., for 8 carbon atoms: and so on. The hydrogen on the alkyl groups defined herein may each be substituted with one or more substituents (e.g., phenyl, halogen, etc.). The alkyl groups according to the invention may for example contain saturated straight-chain or branched hydrocarbon groups of 1 to 20 carbon atoms, preferably of 1 to 12 carbon atoms, in particular of 1 to 6 (for example 1, 2, 3 or 4) carbon atoms.
The term "heteroalkyl" refers to an alkyl group in which one or more (preferably 1, 2 or 3) carbon atoms have been replaced by an oxygen, nitrogen, phosphorus, boron, selenium, silicon or sulfur atom. I.e. containing both C chains and heteroatoms in the main chain. Ether linkages, hetero ether groups (ether groups containing heteroatoms such as N, S) and the like are all heteroalkyl groups.
The term "alkylcarbonyl" refers to a group in the backbone that contains both alkyl and carbonyl groups.
The term "heteroalkylcarbonyl" refers to a group containing both a heteroatom, an alkyl group, and a carbonyl group in the backbone.
The term "heterocycloalkyl" means a chain containing a heterocycle and an alkyl group in the main chain, the heterocycle and alkyl group being linked to form a chain.
The term "heterocycloalkylcarbonyl" is understood with reference to the above "heterocycloalkyl" and refers to a backbone containing heterocycles, alkyl groups and carbonyl groups in the backbone, with the heterocycles, alkyl groups and carbonyl groups being linked to form the backbone of the linking group.
The term "alkyl ester" is understood with reference to the above "alkylcarbonyl" and refers to a polymer containing both alkyl and ester groups in the backbone.
The term "aryl" refers to: organic groups derived from aromatics and including monocyclic and polycyclic groups, examples of aryl groups include phenyl, biphenyl, naphthyl, and the like. For example, the number of carbons in the aryl group may be 6 to 18. Including divalent aryl groups denote aromatic organic groups derived by removal of two hydrogens, and similarly trivalent and tetravalent aryl groups denote aromatic organic groups derived by removal of three hydrogens and four hydrogens, respectively.
The term "aralkyl" refers to an aryl-alkyl complex group, wherein alkyl and aryl are as defined above, and examples of aralkyl include benzyl, phenethyl, and the like.
The term "aromatic" refers to both aryl (e.g., benzene, naphthalene, biphenyl) and heteroaryl.
The term "heteroaryl" refers to a monocyclic or polycyclic aromatic ring containing carbon atoms in the ring structure and independently selected from one or more heteroatoms (e.g., nitrogen, oxygen, sulfur). Heteroaryl groups include, but are not limited to, pyridyl, pyrrolyl, pyridazinyl, furyl, pyrazinyl, pyrimidinyl, piperazinyl, triazinyl, pyrazolyl, imidazolyl, tetrazolyl, thienyl, isoxazolyl, thiazolyl, isoxazolyl, oxazolyl, and the like. Heteroaryl groups may be unsubstituted or substituted with one, two or more suitable substituents. Heteroaryl groups may be monocyclic, wherein the ring may contain 1-5 carbon atoms and 1-4 heteroatoms.
The term "heteroaralkyl" is understood with reference to the above "heterocycloalkyl" and refers to a backbone containing heteroaryl and alkyl groups in the backbone, with the heteroaryl and alkyl groups forming the backbone of the linking group.
The term "aralkylcarbonyl" is understood with reference to the above "heterocycloalkylcarbonyl" and refers to a backbone containing aryl, alkyl and carbonyl groups in the backbone, with the aryl, alkyl and carbonyl groups forming the backbone of the linking group.
The term "arylheteroalkanoyl" refers to a backbone containing aryl, heteroalkyl, and carbonyl groups in the backbone, with the aryl, heteroalkyl, and carbonyl groups forming the linking group.
The term "heteroarylheteroalkyl" refers to a backbone containing heteroaryl, heteroalkyl, and carbonyl groups in the backbone, with the heteroaryl, heteroalkyl, and carbonyl groups forming the linking group.
The term "cycloalkyl" refers to a saturated cyclic group containing one or more rings (preferably 1 or 2) and containing a plurality of ring carbon atoms (e.g. 3-14), preferably 3-10 (especially 3, 4, 5, 6 or 7) ring carbon atoms. The hydrogen on cycloalkyl groups as defined herein may each be substituted with one or more substituents, such as methyl, fluoro, chloro, bromo or iodo atoms, and the like.
The term "cycloheteroalkyl" is a non-aromatic cyclic radical, meaning a cycloalkyl radical containing at least one heteroatom, e.g., having at least one heteroatom such as oxygen, sulfur, nitrogen, or phosphorus on the ring. For example:wherein represents the point of attachment to other groups.
The term "cycloalkylcarbonyl" refers to a ring formed by the attachment of an alkyl group and a carbonyl group.
The term "cycloheteroalkylcarbonyl" is understood with reference to the above-mentioned "cycloheteroalkyl" and refers to a group on the ring containing both a heteroatom, an alkyl group and a carbonyl group, the heteroatom, alkyl and carbonyl groups forming a ring.
The term "halogen" is for example fluorine, chlorine, bromine, iodine.
The cage polysilsesquioxane is POSS, and has a general formula (RSiO) 3/2 ) n Wherein R is a group to which eight top angle Si atoms are attached. The cage polysilsesquioxane is a group formed by replacing hydrogen on an R group in the cage polysilsesquioxane, wherein a plurality of substitution sites can be provided.
The term "amide group" refers to a group whose backbone is of an amide structure.
The term "alkoxy" refers to an alkyl group in which one or more (preferably 1, 2 or 3) carbon atoms have been replaced by oxygen atoms.
The term "aminoalkyl" refers to a backbone having both an amide group and an alkyl group in the backbone, with the amide group and the alkyl group forming the linking group.
The term "amidoalkoxy" refers to a backbone containing amide groups and alkoxy groups on the backbone, with the amide groups and alkoxy groups forming the linking group.
The above-mentioned alkyl group, cycloalkyl group, heteroalkyl group, alkylcarbonyl group, heteroalkylcarbonyl group, heterocycloalkyl group, heterocycloalkylcarbonyl group, alkylaliphatic group, aryl group, aralkyl group, heteroaryl group, heteroaralkyl group, aralkylcarbonyl group, heteroaralkylcarbonyl group, cycloalkyl group, cycloheteroalkyl group, cycloalkylcarbonyl group, cycloheteroalkylcarbonyl group and cage polysilsesquioxane group may be a linking group having a plurality of linking sites, the linking site of the above-mentioned chain group is on its main chain, the specific position on the main chain is arbitrary, and the linking site of the above-mentioned cyclic group is on the atom forming a ring. The attachment sites may be, for example, 2,3,4, 8, respectively, attached to the remainder of the molecule by 2,3,4 or 8 covalent bonds. For example, formula (4): a- (B) b Wherein B is optionally substitutedAnd a group on A, A is a linking group, B is connected with A, and B can take a value of 2 or more as a substituent. For example, when b is 2, the corresponding a is a linking group having two linking sites, when b is 3, the corresponding a is a linking group having 3 sites, and when b is 4, the corresponding a is a linking group having 4 linking sites. When b takes the value of n, the corresponding A has a linking group with n linking sites.
In the present invention, "substituted" in "substituted or unsubstituted" means that a hydrogen atom in a certain functional group is substituted with another atom or group (i.e., substituent). For example, a substituent may be substituted with one or more substituents selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, aryl, alicyclic, heterocyclic, heteroaryl, ester, ether, halogen, heteroatom, and the like. The present invention preferably uses as "substituted" groups inert groups which do not participate in the polymerization of the monomers and do not participate in the crosslinking reaction of the polymer with the crosslinking agent.
The meaning of active proton hydrogens is known in the art. For example, the hydrogens on the carboxyl, hydroxyl, amino, mercapto groups are all active proton hydrogens.
The inventor finds that oxygen atoms in the polyether polymer can be complexed with lithium ions, and the polyether polymer has higher dielectric constant, good lithium ion solubility and transmission capacity and has wide application prospect as an organic lithium ion conductor. However, polyether polymers have the problems of crystallization, low lithium ion migration number, poor room temperature ion conductivity, narrow electrochemical stability window and the like.
The inventors also contemplate that cyclic carbonate groups may also act as crosslinking points to undergo a crosslinking reaction to yield a crosslinked network polymer. The crosslinked polymer has good film forming property, and is expected to be applied to solid-state batteries as a self-supporting electrolyte film. However, polymer electrolytes containing cyclic carbonate groups often suffer from higher glass transition temperatures, poorer ion conductivity, and more brittle films due to rigid cyclic carbonate groups. The design synthesis and structural optimization of polymers containing cyclic carbonate groups are a major challenge to be addressed.
For this reason, the inventors have attempted to construct a polymer which can fully utilize the advantages of the above ether group and cyclic carbonate group while solving the above problems of the respective homopolymers. The inventor finds that through design synthesis of the epoxy monomer containing the cyclic carbonate group, polyether homopolymer with the cyclic carbonate side group can be obtained under proper initiation and catalysis conditions, and further through partial crosslinking of a proper crosslinking agent and the polymer cyclic carbonate side group, a crosslinked polymer is obtained, and the expected effect is achieved.
Specifically, the present invention provides a crosslinked polymer containing a crosslinked structure produced by a crosslinking agent and a polymer chain linked to the crosslinked structure. In the crosslinked polymer, two structural units are directly connected with a polyether main chain, wherein the first structural unit is a structure formed after a crosslinking reaction with a crosslinking agent, and the components containing hydroxyl and linear ester groups are structures shown in a formula (1-1) and/or a formula (1-2); the cyclic carbonate side group which does not undergo the crosslinking reaction in the polymer remains as the second structural unit, and has a structure represented by formula (2). The first structural units and the second structural units are randomly distributed on the main chain. Wherein the polymer chain is linked to the cross-linked structure via a first structural unit, and formulae (1-1) and (1-2) represent the point of attachment to the cross-linked structure:
formula (1-1):formula (1-2):Formula (2):
The crosslinking agent contains at least two crosslinking groups for crosslinking such that each of the crosslinking structures is linked to at least two first structural units, respectively. For the sake of a clearer description, the following description will be made as a specific example of a crosslinked polymer, taking a cross-linking agent having two crosslinking groups, taking the formula (1-1) as an example of a first structural unit, the first structural unit and a crosslinked structure provided by the cross-linking agent forming the following structure, denoted by the formula (6). The crosslinking agent has two crosslinking groups, and is schematically represented by the following formula (7) by taking the formula (1-2) as an example of the first structural unit, which forms the following structure with the crosslinking structure provided by the crosslinking agent. The crosslinking agent has two crosslinking groups, and the first structural units represented by the formulas (1-1) and (1-2) are exemplified, and the two first structural units are respectively connected with the crosslinking structure provided by the crosslinking agent, so that the following structure is formed, and is denoted by the formula (8).
The crosslinking group is selected from one or more of the following: amino, hydroxy or mercapto. Wherein R is 1 Selected from substituted or unsubstituted alkylene, alkyleneoxy or heteroalkylene; r is R 2 Selected from hydrogen, halogen, or from substituted or unsubstituted alkyl, heteroalkyl. When R is 2 When substituted, the alkyl group may be, for example, a haloalkyl group. R is R 3 For the crosslinked structure produced by the crosslinking agent, two first structural units are linked. R is R 3 The crosslinking group crosslinked with the first structural unit is an amino group, a hydroxyl group or a mercapto group. Two identical crosslinking groups, for example two amino groups, or two crosslinking groups, respectively, may be used as crosslinking points, for example groups which crosslink with two first building blocks are amino and hydroxyl groups, respectively, or hydroxyl and mercapto groups, respectively.
The first structural unit and the second structural unit form a crosslinked polymer as two structural units. The main chain of the crosslinked polymer is a polyether structure, and the side chain contains two different components, one of which is a component containing hydroxyl and linear ester groups, namely a first structural unit. The first structural unit is a structure formed by crosslinking with a crosslinking agent. The other is a component containing cyclic carbonate groups, i.e., a second structural unit. The first structural unit and the second structural unit are arranged in random order on the main chain. This random arrangement is in fact due to random cross-linking with the cross-linking agent. The cyclic carbonate on the polymer side group reacts with the crosslinking group on the crosslinking agent to form a first structural unit. The crosslinking group is amino, hydroxyl or mercapto. The cyclic carbonate reacts with the three crosslinking groups in a ring opening manner. One end of the ring opening part forms hydroxyl, and the other end is a linear ester group connected with a crosslinking group. The remainder of the polymer is not crosslinked and remains as the second structural unit. The ring-opening reaction of the amino group, the hydroxyl group or the mercapto group with the cyclic carbonate may form two structures, namely, the above-mentioned formula (1-1) or formula (1-2). These two structural formulae are generated only by the difference in ring opening positions, and specifically represent two ring opening positions of the cyclic carbonate side group as shown in the following reaction formulae (1) and (2), respectively. Although crosslinking can produce two different first structural units, they have no effect on the properties of the crosslinked polymer, i.e., the resulting crosslinked polymer behaves the same in terms of mechanical properties, electrochemical properties, etc., regardless of the ratio of formula (1-1) and formula (1-2) in the first structural units, respectively, in the crosslinked polymer. The present invention is not limited to the structural ratio of the formula (1-1) and the formula (1-2) in the first structural unit, and the crosslinked polymer formed may be all of the formula (1-1), all of the formula (1-2), or both the formula (1-1) and the formula (1-2), as long as the hydroxyl group and the linear ester group are formed by the ring-opening reaction of the cyclic carbonate.
The crosslinked polymers contemplated by the present invention possess two of the aforementioned structural units, namely a first structural unit and a second structural unit. The first structural unit generates a cross-linked network, so that the mechanical strength of the system is enhanced, the capability of inhibiting lithium dendrites is improved, and the polymer electrolyte can form a self-supporting electrolyte film; the second structural unit endows the polymer with high dielectric constant, can promote dissolution and dissociation of lithium salt, improve the ionic conductivity and lithium ion migration number of the system, and enhance the oxidation resistance of the polymer electrolyte. The two structural units complement each other and exert their advantages together.
The cross-linked polymer has various structures of hydroxyl, linear urethane, cyclic carbonate and ether oxygen groups, can form various hydrogen bonding actions, and the hydrogen bonding actions can further enhance the mechanical property of the cross-linked polymer, enhance the capability of inhibiting lithium dendrites and relieve the volume effect in the lithium ion deposition process.
The film formed by the crosslinked polymer has good mechanical properties, and the dynamic mechanical analysis test shows that the tensile strength of the crosslinked polymer film can reach more than 0.1MPa, and the elongation at break can be more than 10%.
In addition, the crosslinked polymer formed by the present invention is an amorphous polymer, which contributes to an improvement in ionic conductivity.
It has been found that the combination of polyether backbones with cyclic carbonate side groups can also increase the thermal decomposition temperature of the polymer and enhance the thermal stability of the polymer. The thermal decomposition temperatures of the polyether and the cyclic carbonate groups are respectively lower than 200 ℃, and the crosslinked polymer formed by combining the polyether and the cyclic carbonate groups can keep good thermal stability below 300 ℃. The higher thermal stability means that the crosslinked polymer can have higher safety when used as a solid electrolyte of a battery polymer.
It has also been found that the crosslinked polymers obtained by molecular design of the present invention are capable of exerting the respective advantages of polyether structures and cyclic carbonate structures, while solving the problems associated with the respective homopolymers. The polyether main chain in the crosslinked polymer can endow the polymer with flexibility, enhance the chain segment movement and improve the lithium ion conducting capacity. The cyclic carbonate functional groups are capable of dissolving a large amount of lithium salt, such as 80wt% lithium salt, which is also an important advantage of the crosslinked polymer as a solid polymer electrolyte. The high salt dissolution rate is advantageous for improving ion conductivity and lithium ion migration number, and forming a stable solid electrolyte interface film (SEI) film. The crosslinked polymer provided by the invention can form a film, has excellent mechanical properties and ion conductivity, and particularly can be used as a solid polymer electrolyte of an electrochemical device (such as a lithium battery and a sodium battery), and has good application prospects in the electrochemical field.
The component containing hydroxyl and linear ester groups essentially serves as a cross-linking point between the molecular chains of the cross-linked polymer, thereby enabling the different molecular chains to be linked together to form a cross-linked network. The crosslinked network makes the polymer electrolyte become a self-supporting electrolyte film through a chemical crosslinking mode, so that the mechanical strength of the polymer electrolyte is enhanced, and the capability of inhibiting lithium dendrites is improved. In addition, new hydroxyl groups and linear ester groups are formed after crosslinking, and the first structural unit described above is obtained. The hydroxyl groups and the linear ester groups in the first structural unit can be physically crosslinked through intermolecular hydrogen bonds, so that the mechanical properties of the electrolyte membrane are further enhanced.
Further, a crosslinked polymer is formed by crosslinking a polyether homopolymer having a cyclic carbonate on a side group with the crosslinking agent, the polyether homopolymer polymer being represented by formula (3):
formula (3):
wherein n represents the polymerization degree and has a value of 5-10000; a part of cyclic carbonate side groups of the repeating units in the polyether homopolymer are crosslinked with a crosslinking agent to form the first structural unit, and the other part of the repeating units are not crosslinked to form the second structural unit; r is R 1 Selected from substituted or unsubstituted alkylene, alkyleneoxy or heteroalkylene; r is R 2 Selected from hydrogen, halogen, or from substituted or unsubstituted alkyl, heteroalkyl. The crosslinked polymer of the present invention is formed by crosslinking the polyether homopolymer described above, and thus R in the polyether homopolymer 1 And R is 2 As in the crosslinked polymers.
In contrast to the design of the present invention, for polymers with cyclic carbonates in the backbone, e.g.The polymer has strong rigidity, insufficient molecular flexibility and high glass transition temperature, and has the defects of low ionic conductivity, brittle electrolyte membrane and brittleness when being used as solid polymer electrolyte.
In contrast to the design of the present invention, for polymers in which the cyclic carbonate is pendant but the backbone is C-C chain, e.g.The polyolefin carbon-carbon backbone imparts some flexibility to the polymer, but due to the direct attachment of the cyclic carbonate groups to the backbone and the air-blocking effect, the polymer has a higher glass transition temperature and a lower ionic conductivity when used as an electrolyte. Meanwhile, the polyolefin component which cannot conduct lithium ions can reduce the transmission of lithium ions in the electrolyte to a certain extent; in addition, the polymer can only be dissolved in DMF, DMAc, DMSO, NMP and other high-polarity high-boiling point solvents, and the high-boiling point solvents have the problems of difficult removal, serious side reactions with lithium metal and the like. The design of the invention can be dissolved in solvents such as THF, DOL and the like which have affinity with lithium metal and low boiling point and are easy to remove, and can be directly crosslinked on the surface of the lithium metal in situ to form a solid polymer electrolyte membrane. The chemical structure of a polyether homopolymer containing cyclic carbonate side groups and the chemical structure of a crosslinked polymer formed after the polyether homopolymer has been reacted with a crosslinking agent containing two amino groups is described below in a schematic fashion.
In the drawings, FIG. 1 is a schematic diagram of a structure of a polyether homopolymer containing cyclic carbonate side groups, and FIG. 2 is a schematic diagram of an embodiment of a crosslinked polymer formed by crosslinking a polyether homopolymer containing cyclic carbonate side groups with an amino crosslinking agent. The linear structure in FIG. 1 is a polyether backbone, and the circled structure at position C in the figure represents a pendant group containing a cyclic carbonate structure. FIG. 2 illustrates an example of a cross-linking agent having two amino groups that cross-link with a polyether homopolymer, where the amino groups at both ends of the cross-linking agent react with a pendant cyclic carbonate group, respectively, and the cyclic carbonate ring opens to link with the amino groups to form cross-linking sites. The position of the cross-linking agent connecting the side group is arbitrary, and the cross-linking agent can be used for connecting two side groups on the same chain or connecting side groups on different chains. The cross-linking agent and the polyether homopolymer containing the cyclic carbonate side group are subjected to cross-linking reaction to form the network-shaped cross-linked polymer. The structure circled at the D position in fig. 2 may be, for example, one of the above formulas (6) - (8).
Taking the example of having two crosslinking groups in the crosslinking agent, the following simplified structural formula is adopted, that is, formula (9) is only used to schematically represent the structural composition and the connection relationship of the formed crosslinked polymer, and not to completely show all the connection structures of the crosslinked polymer.
Formula (9):
the crosslinking agent is reacted with a polyether homopolymer containing cyclic carbonate side groups to form the connection schematic structure of the formula (9) as exemplified in the formula (1-1). The backbone of the first building block is linked to the backbone of the second building block to form a polymer chain in the crosslinked polymer, i.e., a linear structure represented by the E position in the crosslinked network structure in FIG. 2.
R in formula (9) 3 Is of a cross-linked structure, R 3 And the two ends of the polymer are cross-linking groups which are respectively connected with carbonyl groups on the lateral group.
R 3 Provided by a crosslinking agent, the crosslinking agent of the present invention is composed of the formula (4):
formula (4): a- (B) b
Wherein B is a crosslinking group optionally substituted on A, and has the structural formula of-NH 2 -OH or-SH, b represents the number of said crosslinking groups, and has a value of 2 or more, further may be 2 to 1000, and further may be, for example, 2 to 8.A is a linking group having a plurality of linking sites, the number of linking sites corresponding to the number of groups B. The linking group is selected from the following substituted or unsubstituted groups: alkyl, cycloalkyl, heteroalkyl, alkylcarbonyl, heteroalkylcarbonyl, heterocycloalkyl, heterocycloalkylcarbonyl, alkyl-aliphatic aryl, aralkyl, heteroaryl, heteroaralkyl, aralkylcarbonyl, heteroaralkyl Heteroalkylcarbonyl, cycloalkyl, cycloheteroalkyl, cycloalkylcarbonyl, and cycloheteroalkylcarbonyl.
When B is selected to be 2, the corresponding A is a linking group having two linking sites, with two substituents B being linked to A. Similarly, when b is selected to be 3, the corresponding a is a linking group having 3 sites. By analogy, the linking group is specifically an organic group. The connection to the polyether polymer when b is 4, i.e., when the crosslinking agent has four crosslinking groups, is exemplified below by the following reaction scheme (3). This reaction formula is only used to schematically represent the structural composition and the connection relationship of the formed crosslinked polymer, and not to fully reveal all the connection structures of the crosslinked polymer.
The cross-linking agent in the above reaction formula has four amino groups, which are respectively connected with four side groups in the polyether polymer containing the cyclic carbonate side groups. Specifically, a is selected from the following structural formulas:
wherein represents the point of attachment to crosslinking group B; n is 2-10000, and can be 2-5000; x is x 1 ,x 2 ,x 3 ,x 4 The range of the values of (2) is 1-1000 respectively.
Preferably, A is selected from the group consisting ofThe introduction of the alkyl chain structure is advantageous for increasing the mobility of the local segments in the crosslinked polymer.
Preferably, A is selected from the group consisting ofThe structure of the alkoxy chain can improve the activity of a local chain segment in the crosslinked polymer, and is beneficial to the dissolution and transmission of lithium ions.
Preferably, A is selected from the group consisting ofThe structure with the amide is beneficial to constructing multiple hydrogen bond structures in the crosslinked polymer, enhancing the mechanical strength and self-repairing capability of the system, improving the volume change adaptability of the system in the battery cycle process, and being beneficial to the inhibition of lithium dendrites.
Preferably, when A selects a structure containing one or more benzene rings, the introduction of the benzene ring structure is beneficial to enhancing the rigidity of the crosslinked polymer and improving the mechanical property of the crosslinked polymer.
Preferably, a is selected from nanoparticles such as POSS, the introduction of which can enhance the mechanical properties of the polymer while facilitating dissociation of the lithium salt and conduction of lithium ions.
Further, R in the crosslinked polymer 1 Selected from the following structures:
wherein n ranges from 1 to 100; * Representing the connection point. The above-mentioned connection points may be respectively connected to the main chain and the side groups.
Preferably, R 1 When selected from alkyl chain structures, the introduction of alkyl chains can enhance molecular flexibility, reduce the glass transition temperature of the polymer, simultaneously decouple the polyether backbone and the cyclic carbonate side groups, enhance the mobility of the cyclic carbonate side groups, and improve the solubility of the cyclic carbonate side groups in solvents and the ion conductivity of the cyclic carbonate side groups as solid electrolytes.
Preferably, R 1 When selected from alkoxy structures, in addition to having the advantages of similar alkyl chains as described above, lithium ion solvation sites can also be provided, facilitating lithium ion conduction.
Further, R in the crosslinked polymer 2 Selected from the following structures:
wherein X is selected from halogen atoms; * Representing the connection point. X is X 3 And X 2 Representing 3 or 2X atoms attached to C.
Preferably, R 2 When selected from hydrogen atoms, the steric hindrance of the cyclic carbonate group can be reduced, and the progress of the crosslinking reaction between the cyclic carbonate group and the crosslinking agent is facilitated.
Preferably, R 2 When the halogen atoms such as fluorine atoms are selected, the electrochemical stability window of the crosslinked polymer is favorably improved, the oxidation resistance of electrolyte is enhanced, can adapt to the positive electrode material with higher voltage and is also beneficial to generating a more stable SEI film.
Further, the amount of the first structural unit relative to the sum of the first structural unit and the second structural unit in the crosslinked polymer may be 5% to 99%, that is, the molar ratio may be 0.05 to 0.99. Taking the above formula (9) as an example, namely (n) 1 +n 3 )/(n 1 +n 2 +n 3 +n 4 )＝0.05～0.99。
Preferably, the first structural units in the crosslinked polymer have a number ratio of 10% to 80% relative to the sum of the first structural units and the second structural units, i.e., a molar ratio of 0.1 to 0.8, and the first structure has a ratio of 10% to 80% in the whole crosslinked polymer, which enables higher mechanical strength while maintaining higher ionic conductivity. Further, the number of the first structural units relative to the sum of the first structural units and the second structural units is 10% to 60%.
The tensile strength of the crosslinked polymer of each example is not less than 0.1MPa, and the elongation at break is not less than 10%. The tensile strength and elongation at break of the present invention were obtained by testing using a dynamic thermo-mechanical analysis (DMA) instrument in its tensile mode.
The invention also provides a synthesis method of the crosslinked polymer, which is used for synthesizing the crosslinked polymer, and comprises the steps of mixing polyether copolymer containing cyclic carbonate side groups and represented by a formula (3) with the crosslinking agent for crosslinking reaction to obtain the crosslinked polymer;
formula (3):
wherein n represents the polymerization degree and has a value of 5-10000; a portion of the cyclic carbonate side groups of the repeating units in the polyether homopolymer are crosslinked with the crosslinking agent to form the first structural unit, and another portion of the repeating units are not crosslinked to form the second structural unit.
Further, a cross-linking agent containing an amino group, a hydroxyl group or a mercapto group is subjected to a ring-opening reaction with a cyclic carbonate, thereby producing a cross-linked polymer. Compared with other crosslinking methods, the crosslinking synthesis method provided by the invention has the advantages that no chemical auxiliary agent is required to be added, the reaction system is clean, no impurity is generated, the reaction condition is mild, the reaction time is short, and the method has important significance for rapid forming of the polymer electrolyte membrane and improvement of the battery performance. For example, conventional crosslinked polymer electrolytes often require the addition of an equivalent amount of free radical initiator such as light, heat, etc., and small amounts of impurities generated after the reaction is completed may have an immeasurable impact on the final performance of the battery, which is detrimental to the improvement of the battery performance.
The invention provides a method for synthesizing a crosslinked polymer, which comprises the following steps: from the aspect of chemical reaction, the method can keep hundred percent of atom utilization rate, embody atom economy, accord with the concept of green chemistry, and realize the crosslinking reaction at room temperature, and has mild reaction conditions and short reaction time; from the perspective of electrolyte, the method avoids the influence which is difficult to predict and is caused by introducing impurities, optimizes the chemical environment of the electrolyte and is beneficial to the development of high-performance lithium batteries.
This type of reaction is explained below by way of an exemplary introduction of reaction formula (4) below.
Reaction formula (4):
in the formula, polyether homopolymer containing cyclic carbonate side groups and a butanediamine cross-linking agent are selected as raw materials for cross-linking reaction. By reaction of the reactive amino group with the cyclic carbonate group, part of the cyclic carbonate group is converted into another one of the number (n) 1 +n 3 ) And a component containing hydroxyl groups and linear ester groups, while the remaining amount in the crosslinked polymer is (n 2 +n 4 ) Unreacted cyclic carbonate moiety; it can be seen that one butanediamine molecule has two amino active groups and can react with two cyclic carbonate groups at the same time, so that a solid polymer film with a cross-linked structure can be formed. The first structural unit is not limited to the structure of the above-described reaction formula (4), and may include the structure of the present invention represented by the formula (1-2), and the reaction formula (4) is merely exemplified.
In the crosslinking reaction of the invention, the polyether homopolymer containing the carbonate side group and the crosslinking agent are dissolved in a solvent, and the reaction of the active amino group and the cyclic carbonate group can efficiently occur at room temperature. If the reaction temperature is increased to 50 degrees celsius, the reaction speed will be further increased. The reactive amino groups are capable of undergoing quantitative chemical reactions with the cyclic carbonate groups. Therefore, the proportion of the two components in the crosslinked polymer can be regulated and controlled by changing the molar ratio of the active amino group to the cyclic carbonate group, and the crosslinking density in the crosslinked polymer can be regulated and controlled. Generally, the higher the crosslink density, the greater the mechanical strength. The cyclic carbonate group not only can dissolve and dissociate lithium salt and conduct lithium ions, but also can be used as a crosslinking point to participate in crosslinking reaction, so that the polymer electrolyte can simultaneously consider ionic conductivity and mechanical property.
By using this type of reaction, it is possible to synthesize compounds having different (n 1 +n 3 ) And (n) 2 +n 4 ) The proportion of the crosslinked polymer, the composition of the crosslinked polymer is widely adjusted. For example, (n) 1 +n 3 ) The value range of (1) is 1-10000, (n) 2 +n 4 ) The value range of (2) is 1-10000. I.e. the first building block is in crossThe range of values in the linkage structure can be 1-10000, and the range of values of the second structural unit in the crosslinking structure can be 1-10000.
Such reactions can utilize different crosslinking agents to produce different inter-chain crosslinking structures. The reactive groups in the crosslinker may be amino, hydroxyl or mercapto groups. Further, in this reaction, a nucleophilic substitution reaction occurs in which a reactive nucleophilic group attacks the carbonyl group of a cyclic carbonate group, and the cyclic carbonate opens to produce a hydroxyl group and a linear ester group.
The method for synthesizing the crosslinked polymer provided by the invention benefits from quantitative reaction of the cyclic carbonate group and the active group amino, hydroxyl or mercapto. The cyclic carbonate and the active group of the cross-linking agent can react in equimolar ratio, so that the ring-opening reaction proportion of the cyclic carbonate group in the polyether homopolymer containing the cyclic carbonate side group can be accurately quantified by controlling the amount of the cross-linking agent added in the reaction, thereby accurately quantifying the composition of the first structural unit and the second structural unit in the cross-linked polymer. Meanwhile, the atomic utilization rate of the synthesis method of the crosslinked polymer can reach 100 percent. Compared with other types of crosslinking reactions, such as double bond polymerization crosslinking, sulfhydryl-double bond click reaction crosslinking or azido-alkynyl reaction crosslinking, the synthesis method of the crosslinked polymer provided by the invention has the characteristics of mild reaction conditions, high efficiency and clean system.
In the method for synthesizing the crosslinked polymer, polyether homopolymer and a crosslinking agent are dissolved in a reaction solvent to form a uniform solution for crosslinking reaction, the reaction temperature of the crosslinking reaction can be between 25 and 180 ℃, the reaction time is between 0.5 and 72 hours, and the reaction solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, dichloromethane, tetrahydrofuran, acetonitrile, dimethyl carbonate, diethyl carbonate, 1, 3-dioxane and acetone.
Further, the molar ratio of crosslinking groups in the selected crosslinking agent to cyclic carbonate groups on the pendant polyether homopolymer groups is from 0.1 to 0.8, i.e., the number of first structural units relative to the sum of the first structural units and the second structural units in the crosslinked polymer is from 10% to 80%.
The synthesis method further comprises the synthesis of polyether homopolymer containing cyclic carbonate side groups: the epoxy monomer is used as a raw material to carry out ring-opening polymerization reaction to form the polyether homopolymer, and the epoxy monomer is formed by a formula (5):
formula (5):
wherein R is 1 Selected from substituted or unsubstituted alkylene, alkyleneoxy or heteroalkylene; r is R 2 Selected from hydrogen, halogen, or from substituted or unsubstituted alkyl, heteroalkyl. Polyether homopolymer containing cyclic carbonate side group is synthesized by adopting the monomers, and then the crosslinking reaction is carried out.
In the ring-opening polymerization reaction, the initiator is onium salt, the catalyst is aluminum complex and/or boron complex, and the terminator is alcohol containing active proton hydrogen, ammonia, water, organic or inorganic acid. The invention adopts the polymerization reaction of epoxy monomer, belonging to anionic ring-opening polymerization. Further, under the action of an initiator and a catalyst, the epoxy monomer is activated, initiated and grown, and the reaction is terminated by a terminator. Wherein the initiator is tetraoctyl ammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetraoctyl ammonium azide and ditriphenyl phosphorane ammonium chloride; the catalyst is triethylboron, triisobutylaluminum, triethylaluminum, triphenylboron and tripentylphenylboron; the terminator is alcohol containing active proton hydrogen, ammonia, water, organic or inorganic acid.
Further, in the ring-opening polymerization reaction, preferably, the initiator is tetraoctylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide; the catalyst is triethylboron and triisobutylaluminum; the terminator is water, methanol, ethanol, formic acid or acetic acid.
Further, in the ring-opening polymerization reaction, the reaction solvent is N, N-dimethylformamide, N-dimethylacetamide, dichloromethane, tetrahydrofuran, acetonitrile, toluene, benzene, cyclohexane and chlorobenzene; the reaction temperature is-30-60 ℃. Preferably, the reaction solvent is dichloromethane, tetrahydrofuran, toluene; the reaction temperature is-10-25 ℃.
The polymerization method provided by the invention is monomer activated anion ring-opening polymerization. It is worth noting that the monomer has two active groups for ring opening polymerization of ternary epoxy ring and five-membered carbonate ring, and the invention provides a polymerization method for selectively opening ternary epoxy ring. The initiation-catalysis binary system can regulate the activities of monomers and end-group oxyanions in the polymerization process, and inhibit side reactions such as chain transfer and the like. Under the polymerization condition, the five-membered carbonate ring can be kept stable, and the obtained polymer has definite end group and narrow dispersity.
The present invention also proposes a solid polymer electrolyte comprising the crosslinked polymer of each of the above embodiments as an active ingredient in the solid polymer electrolyte. In addition, salts are included in the solid electrolyte. For lithium batteries, lithium salts may also be included in the solid state polymer electrolyte of the lithium battery. The lithium salt may be, for example, one or more of lithium trifluoromethane sulfonate, lithium bis (trifluoromethane sulfonyl) imide, lithium perchlorate, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium hexafluorosilicate, and lithium dioxalate borate; the mass fraction of the lithium salt in the solid polymer electrolyte is 5% -90%. The mass fraction of the crosslinked polymer in the solid polymer electrolyte is 10% -95%.
Preferably, the cross-linked polymer has a mass fraction in the solid polymer electrolyte of 20% to 75%; the lithium salt is lithium trifluoromethane sulfonate, lithium bis (trifluoromethane sulfonyl) imide or lithium dioxalate borate; preferably, the mass fraction of lithium salt in the solid polymer electrolyte is 25% -80%.
Compared with the traditional polyether solid electrolyte and the traditional poly cyclic carbonate solid electrolyte, the solid polymer electrolyte provided by the invention has the advantages that the ionic conductivity and the lithium ion migration number at room temperature are greatly improved. The solid polymer electrolyte is applied to a lithium metal battery, realizes the stable circulation of the all-solid lithium metal battery at room temperature, and shows excellent multiplying power performance, circulation performance and coulombic efficiency.
The solid polymer electrolyte obtained by the invention is at room temperatureThe conductivity of the lower ion can reach 10 -5 S/cm or more, and the migration number of lithium ions is 0.2 or more. Further, the ion conductivity was 1.0X10 -5 ～7.6×10 -5 S/cm, and the migration number of lithium ions is more than 0.5. Further, the lithium ion migration number is 0.7 or more.
The invention also provides an electrochemical device comprising the solid polymer electrolyte. The electrochemical device may be, for example, a lithium metal battery, a sodium metal battery, or the like.
The invention also provides the use of the crosslinked polymer in electrochemical devices or flexible devices, in particular in solid polymer electrolytes for lithium-ion or lithium-metal batteries, more in particular in increasing the ion conductivity and/or the number of lithium-ion transitions of solid electrolytes for lithium batteries and/or the electrochemical stability window of lithium-ion batteries and/or the rate capability and cycle performance of lithium-metal batteries. The flexible device is for example a wearable electronic device, an electronic skin, a flexible sensor, etc.
The following describes the invention in terms of specific embodiments, which should not be construed as limiting the invention.
Example 1
1.0 g of epoxy monomer (5.75 mmol) was charged into a 25 ml high vacuum reactor, dried under vacuum at 50 ℃ for twelve hours, and 4 ml of dried dichloromethane solvent was transferred in vacuo to dissolve the monomer; under the protection of nitrogen atmosphere, 0.157 g NOct is added into the reactor in turn 4 Br (0.287 mmol) and 0.171 g Al (i-Bu) 3 (0.863 mmol); placing 25 ml of the reactor in an ice bath at 0 ℃ for reaction for 24 hours; finally, adding a trace of methanol into the reactor through a vacuum line to terminate the reaction. The reaction route is shown in the reaction formula (5).
Reaction formula (5):
the polymer nuclear magnetic hydrogen spectrum data obtained by polymerization based on the initiation system of example 1 are as follows: 1 H NMR(DMSO-d 6 )δ(ppm):4.92(s,1h) 4.52 (m, 1H), 4.26 (m, 1H), 3.76-3.42 (m, 7H). The number average molecular weight (M) n ): 3.5kg/mol, molecular weight dispersityT of the Polymer obtained by thermogravimetric analysis d,5％ (temperature corresponding to 5% thermal weight loss) was 298 ℃.
By adjusting the initiator NOct 4 Br and catalyst Al (i-Bu) 3 The ratio of the monomers to the cyclic carbonate group-containing homopolymer of different number average molecular weight (e.g., M n ＝7.8kg/mol,M n ＝12.2kg/mol,)
Example 2
1.0 g of epoxy monomer (5.75 mmol) was charged into a 25 ml high vacuum reactor, and vacuum heated at 50℃for twelve hours to remove trace moisture, and 4 ml of the calcium hydride-dried methylene chloride solvent was transferred through a vacuum line; under the protection of nitrogen flow, 0.0320 g NBu was added to the reactor via syringe 4 Cl (0.115 mmol) and 0.0686 g Al (i-Bu) 3 (0.345 mmol) the reactor was placed in a 0 degree celsius ice bath for 48 hours; finally, adding a little methanol by vacuum line distillation to terminate the polymerization reaction. The reaction scheme is shown in the following reaction formula (6).
Reaction formula (6):
the polymer nuclear magnetic hydrogen spectrum data obtained based on the reaction of the initiation system of example 2 are as follows: 1 H NMR(DMSO-d 6 ) Delta (ppm): 4.92 (s, 1H), 4.52 (m, 1H), 4.26 (m, 1H), 3.76-3.42 (m, 7H). The number average molecular weight obtained was characterized by gel permeation chromatography: 8.7kg/mol, molecular weight dispersity: 1.57.
example 3
20 mg of a polyether homopolymer having cyclic carbonate groups on its side groups, 66 mg of LiTFSI (EC/Li=1:2), and 3 mg of a diamine crosslinking agent represented by the formula (7) were weighed into a mixed system, and dissolved with 100. Mu.l of ultra-dry tetrahydrofuran, and shaken to thoroughly mix and dissolve the system in a uniform transparent state. The mixed solution is evenly spread on a lithium sheet or a stainless steel sheet. Standing at room temperature for two hours to obtain a polymer film with certain mechanical strength, which is named PEOEC-1. The cross-linked polymer obtained in this example has a ratio of 1:1 of the two components of the first structural unit and the second structural unit. In the infrared test, as shown in fig. 3, the characteristic peak of the stretching vibration of the raw material, which is attributed to the carbonyl group C=O of the cyclic carbonate, is located at 1789cm -1 . New appearance of product in infrared absorption spectrum is positioned at 1697cm -1 And 3350cm -1 The characteristic peaks of (2) are respectively attributed to the telescopic vibration of urethane groups and hydroxyl groups, which proves the formation of crosslinked products. The reaction scheme is shown in the following reaction formula (7).
Reaction formula (7):
by adjusting the contents of lithium salt LiTFSI and diamine cross-linking agent in the cross-linked polymer, the cross-linked polymer with different contents of lithium salt and different proportions of the first structural unit and the second structural unit is obtained, for example, in PEOEC-2, EC/Li=1:1, and the proportion of the first structural unit to the second structural unit is 1:1; EC/li=1:0.5 in PEOEC-3, the ratio of the two components of the first structural unit and the second structural unit is 1:2.
Example 4
20 mg of polyether homopolymer containing cyclic carbonate side groups, 16.5 mg of LiTFSI (EC/Li=1:0.5), and 2.2 mg of 1, 4-cyclohexanediamine crosslinker were weighed into a 2mL glass bottle, 100. Mu.L of tetrahydrofuran solvent was injected, and the mixture was slowly shaken until the lithium salt, polymer and crosslinker were completely dissolved, and the system was uniformly transparent. Homogenizing the mixed solution by a pipetteUniformly coating on the surface of a lithium sheet or a stainless steel sheet. Heating at 60 deg.c for six hr to obtain polymer film with certain mechanical strength. The cross-linked polymer obtained in this example had a ratio of 1:2 of the two components of the first structural unit and the second structural unit. The reaction scheme is shown in the following reaction formula (8). A position of 1697cm was observed in the IR spectrum, which was assigned to the linear urethane group and the hydroxyl group, respectively -1 And 3350cm -1 Demonstrating successful synthesis of the crosslinked polymer.
Reaction formula (8):
example 5
20 mg of a polyether homopolymer containing a cyclic carbonate group, 6.6 mg of LiTFSI (EC/Li=1:0.2), and 3.5 mg of a diamine crosslinking agent as in the reaction formula (9) were weighed into a glass bottle, and 100. Mu.l of an ultra-dry tetrahydrofuran solvent was injected by a pipette, and the system was thoroughly mixed and dissolved by shaking to be uniform and transparent. The mixed solution is evenly spread on a lithium sheet or a stainless steel sheet. Standing at 60 ℃ for two hours to obtain the polymer film with certain mechanical strength. A position of 1697cm was observed in the IR spectrum which was assigned to the linear urethane group and the hydroxyl group, respectively -1 And 3350cm -1 Demonstrating successful synthesis of the crosslinked polymer. The cross-linked polymer obtained in this example had a ratio of the first structural unit to the second structural unit of 1:3. The reaction scheme is shown in the following reaction formula (9).
Reaction formula (9):
example 6
A2 mL glass bottle was charged with weighed 20 mg of polyether homopolymer having cyclic carbonate groups on the pendant groups, 6.6 mg of lithium salt LiTFSI (EC/Li=1:0.2), 3.1 mg of glycol crosslinker as in equation (10), and dissolved with 100. Mu.l of ultra-dry tetrahydrofuran solvent, and the system was thoroughly mixed by shaking continuously, and the final system exhibited a homogeneous clear solution. The mixed solution was uniformly coated on a lithium sheet or a stainless steel sheet by a pipette. Heating at 80 deg.c for twelve hours to obtain polymer film with certain mechanical strength. The successful synthesis of the crosslinked polymer was demonstrated by observation of characteristic peaks of stretching vibrations in the infrared spectrum, which are assigned to the linear carbonate groups and hydroxyl groups, respectively. The cross-linked polymer obtained in this example had a ratio of the first structural unit to the second structural unit of 1:3. The reaction scheme is shown in the following reaction formula (10).
Equation (10):
example 7
20 mg of a polyether homopolymer containing cyclic carbonate groups, 16.5 mg of LiTFSI (EC/Li=1:0.5), and 7.6 mg of a polyether diol (M) as in the formula (11) were weighed out w =400) as a crosslinking agent for crosslinking reaction was added to the mixed system, 200 μl of tetrahydrofuran solvent was measured with a pipette, and the system was thoroughly mixed and dissolved by shaking continuously. The mixed solution was uniformly coated on a lithium sheet or a stainless steel sheet. Heating at 80 deg.c for twelve hours to obtain polymer film with certain mechanical strength. In infrared testing, the formation of linear carbonate groups and hydroxyl groups can be observed. The cross-linked polymer obtained in this example had a ratio of 1:2 of the two components of the first structural unit and the second structural unit. The reaction scheme is shown in the following reaction formula (11).
Reaction formula (11):
example 8
20 mg of polyether homopolymer containing cyclic carbonate groups on the side groups in the reaction formula (12), 26.6 mg of LiTFSI lithium salt (EC/Li=1:1) and 2.4 mg of glycol crosslinking agent in the reaction formula (12) are weighed into a reaction bottle, 100 microliters of ultra-dry tetrahydrofuran solvent is measured for dissolution, and shaking is carried out to enable the system to be fully mixed and dissolved, so that the system is uniform and transparent. The mixed solution is evenly spread on a lithium sheet or a stainless steel sheet. Heating at 60 deg.c for six hr to obtain polymer film with certain mechanical strength. In infrared testing, the formation of linear urethane and hydroxyl structures can be observed. The cross-linked polymer obtained in this example has a ratio of 1:1 of the two components of the first structural unit and the second structural unit. The reaction scheme is shown in the following reaction formula (12).
Equation (12):
example 9
20 mg of a polyether homopolymer having methyl-substituted cyclic carbonate groups in the side groups as in reaction formula (13), 30.5 mg of LiTFSI salt (EC/li=1:1), and 2.8 mg of a diamino crosslinking agent were weighed into a mixed system, 100 μl of an ultra-dry tetrahydrofuran solvent was measured for dissolution, and the system was thoroughly mixed by shaking continuously. The mixed solution was uniformly dropped on a lithium sheet or a stainless steel sheet by a pipette. Standing at 50 ℃ for two hours to obtain the polymer film with certain mechanical strength. In infrared testing, the formation of linear urethane groups and hydroxyl groups can be observed. The cross-linked polymer obtained in this example has a ratio of 1:1 of the two components of the first structural unit and the second structural unit. The reaction scheme is shown in the following reaction formula (13).
Reaction formula (13):
example 10
20 mg of polyether homopolymer with a side group containing fluorine atom substituted cyclic carbonate group in the reaction formula (14), 15.0 mg of LiTFSI (EC/Li=1:0.5) and 3.6 mg of dimercapto cross-linking agent are weighed into a mixed system, 100 microliters of ultra-dry tetrahydrofuran is measured for dissolution, and shaking are carried out to enable the system to be fully mixed and dissolved, so that the system is uniform and transparent. The mixed solution was uniformly dropped on a lithium sheet or a stainless steel sheet by a pipette. Standing at 60 ℃ for two hours to obtain the polymer film with certain mechanical strength. In infrared testing, the formation of thiocarbonate groups and hydroxyl groups can be observed. The cross-linked polymer obtained in this example has a ratio of 1:1 of the two components of the first structural unit and the second structural unit. The reaction scheme is shown in the following reaction formula (14).
Equation (14):
example 11
20 mg of a polyether homopolymer containing cyclic carbonate groups, 6.6 mg of LiTFSI (EC/Li=1:0.2), and 3.5 mg of a dimercapto crosslinking agent as in the reaction formula (15) were weighed into a 2mL glass reaction flask, dissolved in 200. Mu.L of an ultra-dry tetrahydrofuran solvent, and the system was thoroughly mixed and dissolved by shaking continuously. The mixed solution is uniformly coated on the surface of a lithium sheet or a stainless steel sheet by a pipette. Heating at 100 deg.c for six hr to obtain polymer film with certain mechanical strength. In infrared testing, the formation of linear thiocarbonates and hydroxyl groups can be observed. The cross-linked polymer obtained in this example had a ratio of the first structural unit to the second structural unit of 1:3. The reaction scheme is shown in the following reaction formula (15).
Reactive (15)
Example 12
20 mg of polyether homopolymer containing cyclic carbonate groups on the side groups, 6.6 mg of LiTFSI (EC/Li=1:0.2), and 4.7 mg of the tetrasulf cross-linking agent as in reaction formula (16) were weighed into a mixed system, 300. Mu.l of an ultra-dry tetrahydrofuran solvent was measured for dissolution, and the system was thoroughly mixed by shaking continuously. The mixed solution was uniformly dropped on a lithium sheet or a stainless steel sheet with a pipette. The mixture was allowed to stand at 80℃for six hours to obtain a polymer film having a certain mechanical strength. In infrared testing, the formation of linear thiocarbonate and hydroxyl structures can be observed. The cross-linked polymer obtained in this example had a ratio of 1:2 of the two components of the first structural unit and the second structural unit. The reaction scheme is shown in the following reaction formula (16).
Equation (16):
example 13
20 mg of a polyether homopolymer having cyclic carbonate groups on its side groups, 6.6 mg of LiTFSI (EC/Li=1:0.2), and 2.8 mg of a triamino crosslinking agent as in the reaction formula (17) were weighed into a reaction flask, dissolved in 100. Mu.l of an ultra-dry tetrahydrofuran solvent, and shaken to thoroughly mix and dissolve the system in a uniform transparent state. The mixed solution is evenly spread on a lithium sheet or a stainless steel sheet. Standing for six hours at room temperature to obtain the polymer film with certain mechanical strength. In infrared testing, the formation of linear urethane and hydroxyl structures can be observed. The cross-linked polymer obtained in this example has a ratio of 1:1 of the two components of the first structural unit and the second structural unit. The reaction scheme is shown in the following reaction formula (17).
Reaction type (17)
Example 14
20 mg of a polyether homopolymer having cyclic carbonate groups in the side groups, 6.6 mg of LiTFSI lithium salt (EC/Li=1:0.2), and 11.5 mg of a polyether triol crosslinking agent (Mw: 600) were weighed into a mixed system, 300. Mu.l of tetrahydrofuran was added for dissolution, and the system was thoroughly mixed and dissolved by shaking. The mixed solution is evenly dropped on the surface of a lithium sheet or a stainless steel sheet. Heating at 80 deg.c for twelve hr to obtain polymer film with certain mechanical strength. In infrared testing, the formation of linear carbonate groups and hydroxyl structures can be observed. The cross-linked polymer obtained in this example has a ratio of 1:1 of the two components of the first structural unit and the second structural unit. The reaction scheme is shown in the following reaction formula (18).
Equation (18):
example 15
20 mg of a polyether homopolymer containing cyclic carbonate groups, 6.6 mg of LiTFSI (EC/Li=1:0.2), and 5.5 mg of an octaamino POSS crosslinking agent were weighed into a mixed system, and dissolved with 100. Mu.l of ultra-dry tetrahydrofuran, and shaken to thoroughly mix and dissolve the system, and the system was uniform and transparent. The mixed solution is evenly spread on a lithium sheet or a stainless steel sheet. And standing at 60 ℃ for twelve hours to obtain the polymer film with certain mechanical strength. In infrared testing, the formation of linear urethane and hydroxyl structures can be observed. The cross-linked polymer obtained in this example has a ratio of 1:1 of the two components of the first structural unit and the second structural unit. The reaction scheme is shown in the following reaction formula (19).
Reaction formula (19):
example 16:
characterization of infrared absorption spectrum: IR spectrum characterization was performed on homopolymers and crosslinked polymers containing cyclic carbonate side groups at room temperature using a Fourier transform IR Spectrometer FT-IR Spectrometer. The spectrum ranges from 4000 cm to 650cm -1 . FIG. 3 shows PEOEC homopolymers containing cyclic carbonate side groups (homopolymers of example 1) and the homopolymers formed after reaction with 2,2' -diaminodiethyl ether crosslinker containing two amino groups Infrared absorption spectrum of crosslinked polymer. The infrared spectrum of the PEOEC homopolymer is located at 1789cm -1 The characteristic peak of (2) is attributed to the stretching vibration of carbonyl c=o in the cyclic carbonate side group; the infrared absorption spectrum of the crosslinked polymer exhibits a new characteristic peak, for example at 1697cm, compared to the homopolymer -1 Is characterized in that the peak of carbonyl stretching vibration of linear urethane structure formed after crosslinking is at 3350cm -1 The characteristic peak of stretching vibration of hydroxyl generated by the left and right broad peaks and the stretching vibration peak of NH in the urethane structure are positioned at 1534cm -1 And 1255cm -1 The characteristic peaks of (2) are respectively attributed to flexural vibration and telescopic vibration of the carbon nitrogen group in the linear urethane structure. The crosslinked polymer is located at 1050cm -1 The left and right characteristic peaks are attributed to the stretching vibration of the carbon oxygen group in the ether oxygen segment.
Example 17:
ion conductivity test: in an argon glove box (H) 2 O<0.01ppm,O 2 <0.01 ppm), the crosslinked polymer of example 3 above was assembled into a stainless steel-stainless steel button cell. The temperature-variable ionic conductivity was further tested on an AutoLab electrochemical platform and the PEOEC-1, PEOEC-2, and PEOEC-3 conductivity results are shown in FIG. 4. As shown in the figure, the room temperature conductivity of PEOEC-1 was highest, reaching 7.6X10, among the test samples -5 S/cm. The conductivities of PEOEC-2 and PEOEC-3 were 4.1X10, respectively -5 S/cm and 2.1X10 -5 S/cm. The room temperature conductivity of the solid polymer electrolyte prepared by the invention can be 2.1 multiplied by 10 -5 S/cm to 7.6X10 -5 S/cm.
Example 18:
ion migration number test: in an argon glove box (H 2 O<0.01ppm,O 2 <0.01 ppm), and the crosslinked polymer was assembled into a lithium-lithium coin cell. The lithium ion migration number was further tested on an autoLab electrochemical platform and the results of the lithium ion migration number measurement of the PEOEC-1 solid polymer electrolyte are shown in fig. 5. As shown in the figure, the lithium ion migration number of the prepared solid polymer electrolyte is 0.71, which is far higher than that of the conventional polyether electrolyte (0.1-0.2) and the small-molecule liquid electrolyte (0.3-0.4).
Example 19:
constant current cycle test of symmetrical battery: in an argon glove box (H) 2 O<0.01ppm,O 2 <0.01 ppm) a lithium-lithium symmetric battery was assembled using the PEOEC-1 solid polymer electrolyte of example 3, and a critical current density test was performed on the LAND-CT3002A test system. The test conditions were 30℃and one hour charge and one hour discharge, at different current densities (0.05-0.5 mA cm -2 ) The change in polarization voltage with cycle time was recorded. The experimental results are shown in FIG. 6, and found that PEOEC-1 assembled lithium-to-lithium battery was between 0.05 and 0.5mA cm -2 The system can stably circulate under the current density, and the polarization voltage almost linearly increases along with the increase of the current density, which shows that the concentration polarization is smaller and the deposition/stripping of lithium ion current is more uniform in the system.
Example 20:
constant current cycle test of symmetrical battery: in an argon glove box (H 2 O<0.01ppm,O 2 <0.01 ppm) lithium-lithium symmetric cells were assembled using a PEOEC-1 solid polymer electrolyte and a constant current cycling performance test was performed on a LAND-CT3002A test system. The test condition is 30 ℃, one hour of charging and one hour of discharging are carried out, and the current density is 0.2mA cm -2 The change in polarization voltage with cycle time was recorded. The experimental results are shown in FIG. 7, which shows that PEOEC-1 assembled lithium-to-lithium batteries can be stably cycled for more than 660 hours.
Example 21:
and (3) cycling test of the lithium iron phosphate-lithium metal battery: the lithium iron phosphate-lithium metal full cell was assembled in an argon glove box using the PEOEC-1 solid polymer electrolyte of example 3 and tested on a LAND-CT3002A test system. The test conditions were set as follows: the charge-discharge current is 0.5C, and the test temperature is 30 ℃. The charge and discharge test results of the all-solid-state battery are shown in fig. 8, the average coulombic efficiency is 99.96%, the capacity retention rate can reach more than 90% after the battery is stably cycled for 500 circles, and the performance of high capacity, high coulombic efficiency and long-term cycling stability is presented.
PEOEC-1 crosslinked Polymer described in example 3 as a solid Polymer electrolyteHas high room temperature ion conductivity (7.6X10) -5 S/cm) one to two orders of magnitude higher than common PEO-based electrolytes; meanwhile, the lithium ion migration number of the solid polymer electrolyte is as high as 0.71 and far higher than that of PEO polymer electrolyte (usually 0.1-0.2) and small-molecule liquid electrolyte (usually 0.3-0.4), so that the solid polymer electrolyte can simultaneously achieve high ion conductivity and high lithium ion migration number, has certain mechanical strength and can be used as a self-supporting polymer electrolyte membrane. In addition, the PEOEC-1 solid polymer electrolyte described in example 3 dissolves a large amount of lithium salt (23 wt% of the crosslinked polymer matrix and 77wt% of LiTFSI).
The sample of example 3 was characterized by wide angle X-ray diffraction and compared to pure lithium salt LiTFSI. FIG. 9 is a wide angle X-ray diffraction pattern of PEOEC-1 and pure lithium salt LiTFSI. The macro phase separation phenomenon of the polymer and the lithium salt is not found in the wide-angle X-ray diffraction experiment, and the polymer and the lithium salt are proved to have an all-amorphous structure. Thanks to its unique structural design of crosslinked polymer, the polymer electrolyte has a rather high dielectric constant, and is capable of dissolving a large amount of lithium salt without phase separation. Combining with excellent in-situ crosslinking means promotes the polymer electrolyte to be a solid polymer electrolyte with lithium ion conductivity and mechanical property.
The lithium salt itself is a crystalline structure that exhibits sharp peaks in wide-angle X-ray diffraction, while an amorphous structure exhibits inclusion peaks. The PEOEC-1 electrolyte in example 3 exhibited a wrap-around peak without sharp crystallization peaks of the lithium salt, demonstrating that the lithium salt was completely dissolved in the polymer matrix. Precipitation of lithium salts is detrimental to conduction of lithium ions in the polymer electrolyte, resulting in a decrease in ionic conductivity.
The reduction of the lithium salt content in the solid polymer electrolyte (38 wt% polymer and 62wt% LiTFSI) in PEOEC-2 compared to PEOEC-1 also enables to obtain a better ionic conductivity (4.1X10 -5 S/cm) and a higher lithium ion transfer number (0.48), the electrochemical performance is also superior to that of the conventional PEO-based polymer electrolyte and the polymer electrolyte with cyclic carbonate groups in the main chain. In addition, compared with PEOEC-1, PEOEC-2 although the electrochemical properties are somewhat inferior, the mechanical properties are somewhat stronger because of the relatively low lithium salt content.
Comparative example 1
1.0g of ethylene carbonate monomer (VEC) was weighed into a vacuum flask, 0.1wt% AIBN initiator was added under nitrogen atmosphere, heated to 70℃in an inert atmosphere, and reacted for 48 hours. The polymer was obtained and named PVEC. The PVEC polymer obtained in this comparative example contains 40mol% of VEC monomers and low molecular weight oligomers. The crude product was purified by dissolution-precipitation to give pure PVEC polymer. The synthesis process is shown in the reaction formula (20).
Equation (20):
the nuclear magnetic hydrogen spectrum data of the PVEC polymer obtained by comparative example 1 are as follows: 1 H NMR(DMSO-d 6 ) Delta (ppm) 5.04-4.01 (m, 3H), 2.31-1.04 (m, 3H). The number average molecular weight obtained was characterized by gel permeation chromatography: 10.2kg/mol, molecular weight dispersity: 2.14. t of the Polymer obtained by thermogravimetric analysis d,5％ Is 195 ℃.
Comparative example 2
10 mg of the polymer PVEC of comparative example 1, 25.2 mg of LiTFSI (VEC/Li=1:1) was weighed into 100. Mu.l of ultra-dry N, N-dimethylformamide solution (DMF), and the system was thoroughly mixed into a uniform transparent state by shaking, and the mixed solvent was uniformly dropped onto a stainless steel sheet. The solvent was removed by vacuum drying at 80 degrees celsius for 12 hours to obtain a PVEC-based polymer electrolyte, designated PVEC-1.
FIG. 10 is an ion conductivity diagram of PVEC-1 in comparative example 2. Comparative example PVEC-1 solid Polymer electrolyte, which has a higher glass transition temperature due to its higher rigidity, has a lower ion conductivity at room temperature of 8.1X10 - 7 S/cm, which has poor performance as a solid polymer electrolyte. Meanwhile, because the solvent is poor in solubility, the solvent can only be dissolved in a solvent with high polarity and high boiling point, and the solvent is difficult to remove and is easy to remain in electricityIn the electrolyte. In addition, the solid electrolyte membrane formed based on PVEC is fragile and easy to break, and seriously affects the application of the solid electrolyte membrane in polymer electrolyte.
Comparative example 3
20 mg of polyether homopolymer containing cyclic carbonate groups and 66 mg of LiTFSI (EC/Li=1:2) are weighed, 100 microliters of ultra-dry tetrahydrofuran is used for dissolution, shaking is carried out to enable the system to be fully mixed and dissolved, the system is uniform and transparent, and the solvent in the system is removed by vacuum drying, so that the polymer electrolyte of the homopolymer which is not crosslinked and based on PEOEC is obtained. However, the polymer electrolyte which is not crosslinked is an electrolyte similar to gel and lacks mechanical strength, and exhibits a certain fluidity, which is disadvantageous for application to electrochemical devices such as solid-state batteries.
While the invention has been shown and described with reference to certain preferred embodiments thereof, it will be understood by those skilled in the art that the foregoing is a further detailed description of the invention with reference to specific embodiments, and it is not intended to limit the practice of the invention to those descriptions. Various changes in form and detail may be made therein by those skilled in the art, including a few simple inferences or alternatives, without departing from the spirit and scope of the present invention.
Claims (21)
1. A crosslinked polymer comprising a crosslinked structure formed by a crosslinking agent and a polymer chain linked to the crosslinked structure, the polymer chain comprising a first structural unit and a second structural unit, the first structural unit being of formula (1-1) and/or formula (1-2), the second structural unit being of formula (2), wherein the polymer chain is linked to the crosslinked structure by the first structural unit, and wherein formula (1-1) and formula (1-2) represent a point of attachment to the crosslinked structure;
Formula (1-1):formula (1-2):Formula (2):
The crosslinking agent contains at least two crosslinking groups for crosslinking, so that each crosslinking structure is respectively connected with at least two first structural units, and the crosslinking groups are selected from one or more of the following: amino, hydroxy or mercapto;
wherein R is 1 Selected from substituted or unsubstituted alkylene, alkyleneoxy or heteroalkylene; r is R 2 Selected from hydrogen, halogen, or from substituted or unsubstituted alkyl, heteroalkyl.
2. The crosslinked polymer of claim 1, wherein the crosslinked polymer is formed by crosslinking a polyether homopolymer having cyclic carbonates on side groups with the crosslinking agent, the polyether homopolymer being represented by formula (3):
formula (3):
wherein n represents the polymerization degree and has a value of 5-10000; a part of cyclic carbonate side groups of the repeating units in the polyether homopolymer are crosslinked with the crosslinking agent to form the first structural unit, and the other part of repeating units are not crosslinked to form the second structural unit; r is R 1 Selected from substituted or unsubstituted alkylene, alkyleneoxy or heteroalkylene; r is R 2 Selected from hydrogen, halogen, or from substituted or unsubstituted alkyl, heteroalkyl.
3. The crosslinked polymer of claim 1 wherein the crosslinking agent consists of formula (4):
formula (4): a- (B) b
Wherein B is the crosslinking group optionally substituted on A, and has the structural formula of-NH 2 (OH) or (SH)B represents the number of the crosslinking groups, and the value is 2 or more; a is a linking group having two or more linking sites selected from the following substituted or unsubstituted groups: alkyl, heteroalkyl, alkylcarbonyl, heteroalkylcarbonyl, heterocycloalkyl, heterocycloalkylcarbonyl, alkylaliphatic, aryl, aralkyl, heteroaryl, heteroaralkyl, aralkylcarbonyl, heteroaralkylcarbonyl, cycloalkyl, cycloheteroalkyl, cycloalkylcarbonyl, cycloheteroalkylcarbonyl, cage polysilsesquioxane.
4. A crosslinked polymer according to claim 3 wherein a is selected from the group consisting of: alkyl, aryl, aralkyl, alkoxy, heteroaralkyl, aralkylcarbonyl, amido, amidalkyl, amidalkoxy.
5. A crosslinked polymer according to claim 3 wherein a is selected from the following structural formulas:
wherein represents the point of attachment to crosslinking group B; n is 2-10000; x is x 1 ,x 2 ,x 3 ,x 4 The range of the values of (2) is 1-1000 respectively.
6. The crosslinked polymer of claim 1 wherein R 1 Selected from the following structures:
wherein n ranges from 1 to 100; * Representing the connection point.
7. The crosslinked polymer of claim 1 wherein R 2 Selected from the following structures:
wherein X is selected from halogen atoms; * Representing the connection point.
8. The crosslinked polymer of claim 1, wherein the amount of the first structural unit relative to the sum of the first structural unit and the second structural unit in the crosslinked polymer is from 10% to 80%.
9. A method for synthesizing a crosslinked polymer, characterized by being used for synthesizing the crosslinked polymer according to any one of claims 1 to 8, the method comprising crosslinking a polyether homopolymer represented by formula (3) with the crosslinking agent to obtain the crosslinked polymer;
formula (3):
wherein n represents the polymerization degree and has a value of 5-10000; a portion of the cyclic carbonate side groups of the repeating units in the polyether homopolymer are crosslinked with the crosslinking agent to form the first structural unit, and another portion of the repeating units are not crosslinked to form the second structural unit.
10. The synthesis method according to claim 9, wherein the polyether homopolymer and the crosslinking agent are subjected to a crosslinking reaction, the reaction temperature of the crosslinking reaction is 25-180 ℃, the reaction time is 0.5-72 hours, and the reaction solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, dichloromethane, tetrahydrofuran, acetonitrile, dimethyl carbonate, diethyl carbonate, 1, 3-dioxane and acetone.
11. The synthesis method according to claim 9, wherein the reaction temperature is 25-120 ℃, the reaction time is 1-48 hours, and the reaction solvent is one or more of N, N-dimethylformamide, tetrahydrofuran, acetonitrile, dimethyl carbonate and acetone.
12. The method of synthesis according to claim 9, wherein the molar ratio of the crosslinking groups in the crosslinker to cyclic carbonate groups on the pendant polyether homopolymer groups is selected to be from 0.1 to 0.8.
13. The synthetic method according to any one of claims 9 to 12, further comprising the synthesis of the polyether homopolymer: ring-opening polymerization reaction is carried out by taking epoxy monomers as raw materials to form the polyether homopolymer, wherein the epoxy monomers consist of a formula (5):
Formula (5):
wherein R is 1 Selected from substituted or unsubstituted alkylene, alkyleneoxy or heteroalkylene; r is R 2 Selected from hydrogen, halogen, or from substituted or unsubstituted alkyl, heteroalkyl.
14. The method according to claim 13, wherein in the ring-opening polymerization reaction, the initiator is an onium salt, the catalyst is an aluminum complex and/or a boron complex, and the terminator is an alcohol containing active proton hydrogen, ammonia, water, an organic or inorganic acid.
15. The method of synthesis according to claim 14, wherein the initiator is one or more of tetraoctylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetraoctylammonium azide, and ditriphenylphosphinyl ammonium chloride; the catalyst is one or more of triethylboron, triisobutylaluminum, triethylaluminum, triphenylboron and trifluorophenyl boron; the terminator is one or more of water, methanol, ethanol, formic acid and acetic acid.
16. The method according to claim 13, wherein in the ring-opening polymerization, the reaction temperature is-30 to 60 ℃, and the reaction solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, dichloromethane, tetrahydrofuran, acetonitrile, toluene, benzene, cyclohexane, and chlorobenzene.
17. A solid polymer electrolyte comprising the crosslinked polymer of any one of claims 1-8.
18. The solid polymer electrolyte of claim 17 wherein said solid polymer electrolyte further comprises a lithium salt, said crosslinked polymer being present in said solid polymer electrolyte in an amount of 10% to 95% by mass and said lithium salt being present in said solid polymer electrolyte in an amount of 5% to 90% by mass.
19. The solid polymer electrolyte of claim 17 or 18 wherein said solid polymer electrolyte has a room temperature ionic conductivity of 10 -5 S/cm or more, and the migration number of lithium ions is 0.2 or more.
20. An electrochemical device comprising the solid polymer electrolyte of any one of claims 17-19.
21. Use of a solid polymer electrolyte according to any of claims 17-19 in an electrochemical device or a flexible device, in particular in a solid polymer electrolyte for a lithium ion or lithium metal battery, more in particular in improving the ion conductivity and/or the lithium ion transport number and/or the electrochemical stability window of a lithium ion battery and/or the rate capability and cycling capability of a lithium metal battery.
Priority Applications (1)
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