CN109119687A - electrolyte and electrochemical energy storage device - Google Patents
electrolyte and electrochemical energy storage device Download PDFInfo
- Publication number
- CN109119687A CN109119687A CN201710481671.8A CN201710481671A CN109119687A CN 109119687 A CN109119687 A CN 109119687A CN 201710481671 A CN201710481671 A CN 201710481671A CN 109119687 A CN109119687 A CN 109119687A
- Authority
- CN
- China
- Prior art keywords
- electrolyte
- lithium
- sodium
- phosphoric acid
- acid ester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 59
- 238000012983 electrochemical energy storage Methods 0.000 title claims abstract description 24
- -1 phosphate ester quaternary ammonium salt Chemical class 0.000 claims abstract description 22
- 239000000654 additive Substances 0.000 claims abstract description 17
- 230000000996 additive effect Effects 0.000 claims abstract description 17
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 11
- 239000010452 phosphate Substances 0.000 claims abstract description 11
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical compound CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 claims description 44
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 38
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- 229910052744 lithium Inorganic materials 0.000 claims description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 16
- 239000011244 liquid electrolyte Substances 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000005518 polymer electrolyte Substances 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 150000001768 cations Chemical group 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 9
- 229910003002 lithium salt Inorganic materials 0.000 claims description 8
- 159000000002 lithium salts Chemical group 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 6
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 claims description 6
- 230000005611 electricity Effects 0.000 claims description 6
- 150000002466 imines Chemical class 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 claims description 5
- 125000001118 alkylidene group Chemical group 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 159000000000 sodium salts Chemical class 0.000 claims description 5
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical group CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 229910017048 AsF6 Inorganic materials 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- 229910001914 chlorine tetroxide Inorganic materials 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 3
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- IYDWBHJEYMDOBU-UHFFFAOYSA-N [Li+].[Li+].[Li+].[O-]B([O-])[O-].OC(=O)C(O)=O.OC(=O)C(O)=O Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].OC(=O)C(O)=O.OC(=O)C(O)=O IYDWBHJEYMDOBU-UHFFFAOYSA-N 0.000 claims description 2
- DGTVXEHQMSJRPE-UHFFFAOYSA-M difluorophosphinate Chemical compound [O-]P(F)(F)=O DGTVXEHQMSJRPE-UHFFFAOYSA-M 0.000 claims description 2
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 claims description 2
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 2
- HGJLYMGBCAKBLK-UHFFFAOYSA-N sodium;trifluoromethanesulfonic acid Chemical compound [Na].OS(=O)(=O)C(F)(F)F HGJLYMGBCAKBLK-UHFFFAOYSA-N 0.000 claims description 2
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims description 2
- LKSCJMIATJONBS-UHFFFAOYSA-K trilithium oxalic acid phosphate Chemical compound P(=O)([O-])([O-])[O-].[Li+].C(C(=O)O)(=O)O.[Li+].[Li+] LKSCJMIATJONBS-UHFFFAOYSA-K 0.000 claims description 2
- NDZWKTKXYOWZML-UHFFFAOYSA-N trilithium;difluoro oxalate;borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FOC(=O)C(=O)OF NDZWKTKXYOWZML-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 6
- 235000021317 phosphate Nutrition 0.000 claims 2
- PQVULHMTIQLUSL-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].[Li+].C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+].[Li+] Chemical class P(=O)([O-])([O-])[O-].[Li+].C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+].[Li+] PQVULHMTIQLUSL-UHFFFAOYSA-K 0.000 claims 1
- ZHQQEZVQYFNEAN-UHFFFAOYSA-N acetylene;sulfuric acid Chemical group C#C.OS(O)(=O)=O ZHQQEZVQYFNEAN-UHFFFAOYSA-N 0.000 claims 1
- 125000002947 alkylene group Chemical group 0.000 claims 1
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical compound OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 claims 1
- 150000003949 imides Chemical class 0.000 claims 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims 1
- 125000002270 phosphoric acid ester group Chemical group 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 11
- 150000002500 ions Chemical class 0.000 abstract description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 55
- 229910001416 lithium ion Inorganic materials 0.000 description 55
- 239000000126 substance Substances 0.000 description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 150000001721 carbon Chemical group 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 125000004122 cyclic group Chemical group 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229940125904 compound 1 Drugs 0.000 description 6
- 239000006258 conductive agent Substances 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 238000002955 isolation Methods 0.000 description 6
- 239000007773 negative electrode material Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000002041 carbon nanotube Substances 0.000 description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 239000011356 non-aqueous organic solvent Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 238000004293 19F NMR spectroscopy Methods 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 3
- 229910001290 LiPF6 Inorganic materials 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011267 electrode slurry Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 3
- 230000005311 nuclear magnetism Effects 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 150000003462 sulfoxides Chemical class 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ZEEBGORNQSEQBE-UHFFFAOYSA-N [2-(3-phenylphenoxy)-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound C1(=CC(=CC=C1)OC1=NC(=CC(=C1)CN)C(F)(F)F)C1=CC=CC=C1 ZEEBGORNQSEQBE-UHFFFAOYSA-N 0.000 description 2
- ABRVLXLNVJHDRQ-UHFFFAOYSA-N [2-pyridin-3-yl-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound FC(C1=CC(=CC(=N1)C=1C=NC=CC=1)CN)(F)F ABRVLXLNVJHDRQ-UHFFFAOYSA-N 0.000 description 2
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000007767 bonding agent Substances 0.000 description 2
- NMJJFJNHVMGPGM-UHFFFAOYSA-N butyl formate Chemical compound CCCCOC=O NMJJFJNHVMGPGM-UHFFFAOYSA-N 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000005685 electric field effect Effects 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000003818 flash chromatography Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000037427 ion transport Effects 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- XQHAGELNRSUUGU-UHFFFAOYSA-M lithium chlorate Chemical compound [Li+].[O-]Cl(=O)=O XQHAGELNRSUUGU-UHFFFAOYSA-M 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 238000009966 trimming Methods 0.000 description 2
- YPGMOWHXEQDBBV-IMJSIDKUSA-N (4R,5R)-1,2-dithiane-4,5-diol Chemical compound O[C@H]1CSSC[C@@H]1O YPGMOWHXEQDBBV-IMJSIDKUSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 description 1
- 125000006091 1,3-dioxolane group Chemical class 0.000 description 1
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 1
- MBDUIEKYVPVZJH-UHFFFAOYSA-N 1-ethylsulfonylethane Chemical compound CCS(=O)(=O)CC MBDUIEKYVPVZJH-UHFFFAOYSA-N 0.000 description 1
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 description 1
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- 229910012265 LiPO2F2 Inorganic materials 0.000 description 1
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- 101150058243 Lipf gene Proteins 0.000 description 1
- LFZAGIJXANFPFN-UHFFFAOYSA-N N-[3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-thiophen-2-ylpropyl]acetamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CCC(C=1SC=CC=1)NC(C)=O)C LFZAGIJXANFPFN-UHFFFAOYSA-N 0.000 description 1
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- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 1
- CVNMBKFJYRAHPO-UHFFFAOYSA-N [chloro(methyl)phosphoryl]methane Chemical compound CP(C)(Cl)=O CVNMBKFJYRAHPO-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000011883 electrode binding agent Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- KLKFAASOGCDTDT-UHFFFAOYSA-N ethoxymethoxyethane Chemical compound CCOCOCC KLKFAASOGCDTDT-UHFFFAOYSA-N 0.000 description 1
- JKLNYGDWYRKFKR-UHFFFAOYSA-N ethyl methyl sulfate Chemical compound CCOS(=O)(=O)OC JKLNYGDWYRKFKR-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- 229910001547 lithium hexafluoroantimonate(V) Inorganic materials 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- HNBDRPTVWVGKBR-UHFFFAOYSA-N n-pentanoic acid methyl ester Natural products CCCCC(=O)OC HNBDRPTVWVGKBR-UHFFFAOYSA-N 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910001542 sodium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- YLKTWKVVQDCJFL-UHFFFAOYSA-N sodium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Na+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YLKTWKVVQDCJFL-UHFFFAOYSA-N 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/64—Liquid electrolytes characterised by additives
-
- 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
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The application relates to an electrolyte and an electrochemical energy storage device. The electrolyte comprises an additive which is phosphate ester quaternary ammonium salt. The phosphate quaternary ammonium salt can ensure that a compact and uniform SEI film with high ion conductivity can be formed on the surface of a negative electrode when the electrochemical energy storage device is formed, so that the first charge-discharge efficiency, the high-temperature cycle performance, the high-temperature storage performance and the rate capability of the electrochemical energy storage device can be obviously improved.
Description
Technical field
This application involves energy storage device field more particularly to a kind of electrolyte and electrochemical energy storage device.
Background technique
In recent years, being on the rise with the problems such as global environment deteriorates and energy shortage, relative to traditional ni-mh, nickel
Cadmium and lead-acid battery, using the lithium ion battery of liquid electrolyte due to higher specific energy density, better cyclicity
Energy, broader operating temperature and more friendly environment compatibility, thus its demand has obtained the growth of explosion type, especially right
It is even more to occupy dominating for application in the exigent high-end consumer electronic devices field of energy density and electric transporting vehicle field
Status.
In order to meet people to energy density increasingly higher demands, at high-pressure solid and the positive and negative plate of thick coating
Science and engineering skill has become industry for promoting the general policies of lithium ion battery energy density.But, the problem of bringing therewith be,
Liquid electrolyte is difficult the gap between complete wetting high-pressure solid and each active material particle of positive and negative electrode on piece of thick coating, from
And lithium ion battery is caused to will appear very big ohmic polarization (especially in low temperature environment) in charge and discharge, finally make lithium
The properties of ion battery sharply deteriorate.
It is well known that when lithium ion battery chemical conversion, certain chemical analysis in liquid electrolyte can preferentially by cathode also
Original is decomposed, to form one layer only to lithium ion conduction without the so-called solid electrolyte interface that conducts to electronics in negative terminal surface
Film (abbreviation SEI film).SEI film is the transmission channel inside lithium ion disengaging negative electrode active material particle, thus is control cathode
One key factor of kinetics.If the SEI film formed in lithium ion battery chemical conversion is too thick, lithium on the one hand will lead to
Limited activity lithium resource is excessively consumed in ion battery, on the other hand will lead to lithium ion disengaging negative electrode active material particle
Larger resistance is encountered when internal.In addition, if the SEI film formed in lithium ion battery chemical conversion is not form compact and stable enough, then group
It will gradually be dissolved by liquid electrolyte at certain metastable state substances of SEI film, so as to cause the negative electrode active material of fresh exposure
Material particle surface will continue to react constantly to repair SEI film with liquid electrolyte, will finally cause limited in lithium ion battery
Active lithium resource constantly consumed and capacity of lithium ion battery sharply declined.In consideration of it, special propose the application.
Summary of the invention
In view of the problems in the background art, the application is designed to provide a kind of electrolyte and electrochemical energy storage dress
It sets, additive phosphoric acid ester quat is contained in the electrolyte, the phosphoric acid ester quat can guarantee electrochemical energy storage device
One layer of dense uniform is capable of forming in negative terminal surface when chemical conversion and there is the SEI film compared with high ion-conductivity, so as to significantly change
First charge-discharge efficiency, high temperature cyclic performance, high-temperature storage performance and the high rate performance of kind electrochemical energy storage device.
In order to achieve the above object, in the one side of the application, this application provides a kind of electrolyte comprising addition
Agent, the additive are phosphoric acid ester quat.The phosphoric acid ester quat is selected from one of 1 compound represented of formula or several
Kind；Wherein, the phosphoric acid ester quat includes that anionic group (corresponds to) and cation group (removingExcept
Part).
In formula 1, R1、R2Be each independently selected from substituted or unsubstituted carbon atom number be 1~6 alkyl, replace or not
One of the monocyclic aryl that substituted carbon atom number is 6~16；R3It is 1~12 selected from substituted or unsubstituted carbon atom number
One of alkylidene；R4One of the alkyl for being 1~6 selected from substituted or unsubstituted carbon atom number；R5Selected from substitution or not
One of the alkylidene that substituted carbon atom number is 1~3；Alkyl that substituent group is 1~3 selected from carbon atom number, in halogen
It is one or more of；Selected from F-、[PF6]-、[AsF6]-、[BF4]-、[NO3]-、[ClO4]-、 One of.
In the another aspect of the application, this application provides a kind of electrochemical energy storage devices comprising the application is on the one hand
The electrolyte.
Compared with the existing technology, the application has the beneficial effect that
Contain additive phosphoric acid ester quat in the electrolyte of the application, phosphoric acid ester quat can guarantee electrochemical energy storage
One layer of dense uniform is capable of forming in negative terminal surface when device is melted into and there is the SEI film compared with high ion-conductivity, so as to aobvious
Write first charge-discharge efficiency, high temperature cyclic performance, high-temperature storage performance and the high rate performance for improving electrochemical energy storage device.
Detailed description of the invention
Fig. 1 is compound 11H-NMR nuclear-magnetism identifies map；
Fig. 2 is compound 119F-NMR nuclear-magnetism identifies map.
Specific embodiment
The following detailed description of the electrolyte and electrochemical energy storage device according to the application.
Illustrate the electrolyte according to the application first aspect first.
Electrolyte according to the application first aspect includes additive, and the additive is phosphoric acid ester quat.The phosphorus
Ester quat is selected from one or more of 1 compound represented of formula.Wherein, the phosphoric acid ester quat includes anion base
Group (corresponds to) and cation group (removingExcept part).
In formula 1, R1、R2Be each independently selected from substituted or unsubstituted carbon atom number be 1~6 alkyl, replace or not
One of the monocyclic aryl that substituted carbon atom number is 6~16；R3It is 1~12 selected from substituted or unsubstituted carbon atom number
One of alkylidene；R4One of the alkyl for being 1~6 selected from substituted or unsubstituted carbon atom number；R5Selected from substitution or not
One of the alkylidene that substituted carbon atom number is 1~3；Alkyl that substituent group is 1~3 selected from carbon atom number, in halogen
It is one or more of.
In formula 1,Indicate anion,Selected from F-、[PF6]-、[AsF6]-、[BF4]-、[NO3]-、[ClO4]-、 One of.
In the electrolyte according to the application first aspect, the electrolyte can be poly- for liquid electrolyte, solid-state
Polymer electrolyte or gel polymer electrolytes can be selected according to actual needs.
In the electrolyte according to the application first aspect, the cation group of the phosphoric acid ester quat has spy
Different structure, i.e., the cation group part of the described phosphoric acid ester quat is by the cyclic quaternary head of tape unit positive charge and function
Property phosphate tail portion formed by intermediate organic carbon chain link.The cyclic quaternary head of tape unit positive charge can be in electrification
Under the internal electric field effect formed when energy storage device chemical conversion, entire cation group is driven actively preferentially to be gone back close to cathode
Original decomposes fracture, and releases functional phosphate tail portion, can establish one layer by alkyl phosphoric acid metal in negative terminal surface
Salt (XOP (=O) (OR)2) etc. material compositions solid electrolyte interface film (SEI film), due to alkyl phosphoric acid metal salt have compared with
High intrinsic ionic conductivity, and there is very high thermal stability, therefore the SEI film being consequently formed has internal structure fine and close and equal
The features such as even, impedance low and high temperature is had excellent performance is very suitable to the electrode slice design of high-pressure solid and thick coating, so as to improve electricity
First charge-discharge efficiency, high temperature cyclic performance, high-temperature storage performance and the high rate performance of chemical energy storage device.
In addition, since phosphate tail portion is in hydrophily, and cyclic quaternary head is in oleophylic for liquid electrolyte
Property, the surface tension for reducing liquid electrolyte is also helped in oleophylic and hydrophilic amphiphilic structure respectively end to end so this,
Enable liquid electrolyte quickly and uniformly to infiltrate through each interstitial site between positive and negative electrode on piece active material particle, mentions
High wellability of the liquid electrolyte to the positive and negative plate of high-pressure solid and thick coating.
In the electrolyte according to the application first aspect, the cation group of the phosphoric acid ester quat be can be selected from One of.
In the electrolyte according to the application first aspect, specifically, the phosphoric acid ester quat can be selected from following
One or more of compound, but the application is not limited only to this；
In the electrolyte according to the application first aspect, due to liquid electrolyte and solid polymer electrolyte,
The mechanism of action of gel polymer electrolytes is similar, therefore is only illustrated by taking liquid electrolyte as an example in this application, i.e., under
State the electrolyte in bright generation refer to liquid electrolyte.
In the electrolyte according to the application first aspect, the content of the phosphoric acid ester quat can be the electrolysis
The 0.01%~10% of liquid gross mass proposes electrolyte wellability when the content of phosphoric acid ester quat is less than 0.01%
It rises and unobvious in the film modified effect of SEI of negative terminal surface, and when the content of phosphoric acid ester quat is greater than 10%, excessive phosphorus
Ester quat cannot be completely dissolved and will lead to the viscosity of electrolyte and dramatically increase, while it is significant to also result in ionic conductivity
It reduces, and then sharply deteriorates the dynamic performance of electrochemical energy storage device.Preferably, the content of the phosphoric acid ester quat is institute
State the 0.05%~1% of electrolyte gross mass.Similarly, in solid polymer electrolyte, gel polymer electrolytes, phosphoric acid
The content of ester quat is too low unobvious to the modification effect of cathode SEI film, and content is excessively easy to cause electrolyte ion to migrate
The decline of several and ionic conductivity.It is understood that being required in relatively low or more secondary use demand for some, phosphoric acid
When the content of ester quat exceeds this range, it can still improve the electrochemistry of electrochemical energy storage device to a certain extent
Energy.
In the electrolyte according to the application first aspect, the electrolyte further includes organic solvent, described organic
The type of solvent can be selected according to actual needs there is no specific limitation.Preferably, using non-aqueous organic solvent.Institute
Stating non-aqueous organic solvent can be selected from ethylene carbonate, propene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, carbon
Sour first propyl ester, gamma-butyrolacton, δ-valerolactone, methyl formate, Ethyl formate, methyl acetate, ethyl acetate, propyl acetate, propionic acid
Ethyl ester, methyl butyrate, butyl formate, propyl propionate, ethyl butyrate, butyl acetate, methyl valerate, amyl formate, sulfuric acid ethylene
Ester, sulfuric acid acrylic ester, dimethyl suflfate, sulfuric acid methyl ethyl ester, dithyl sulfate, tetrahydrofuran, 1,3- dioxolanes, 1,3- dioxy
Own ring, dimethoxymethane, diethoxymethane, 1,2- dimethoxy-ethane, 1,2- diethoxyethane, sulfolane, ring penta
One of sulfone, dimethyl sulfone, the first and second sulfones, diethyl sulfone, ring fourth sulfoxide, penta sulfoxide of ring, dimethyl sulfoxide, the first and second sulfoxides, ethyl-sulfoxide
Or it is several.Consider from using and being commercialized angle, it is further preferred that the non-aqueous organic solvent uses carbonic ester and carboxylic acid
Ester.
In the electrolyte according to the application first aspect, the electrolyte further includes film for additive, and film forming adds
Agent is added to can be selected from vinylene carbonate (VC), vinylethylene carbonate (VEC), 1- propylene -1,3- sultone (PS), sulfuric acid Asia second
One or more of enester (DTD), fluorinated ethylene carbonate (FEC), above-mentioned substance and phosphoric acid ester quat are used in combination can
Further improve the chemical property of electrochemical energy storage device.Wherein, the content of the film for additive is smaller than equal to described
The 3% of electrolyte gross mass.
In the electrolyte according to the application first aspect, the electrolytic salt in the electrolyte can be selected from lithium salts or
Sodium salt.
In the electrolyte according to the application first aspect, the concentration of the electrolytic salt is not limited specifically,
It can be selected according to actual needs.Specifically, the concentration of the electrolytic salt can be 0.5mol/L~2.5mol/L, if electrolysis
The concentration of matter salt is too low, then the ionic conductivity of corresponding electrolyte is too low, if the excessive concentration of electrolytic salt, corresponding electricity
The viscosity of solution liquid can rise, and the ionic conductivity that this also results in electrolyte is too low.Preferably, the concentration of the electrolytic salt
Upper limit value is 2.0mol/L, it is further preferred that the upper limit value of the concentration of the electrolytic salt is 1.5mol/L.Preferably, institute
The lower limit value for stating the concentration of electrolytic salt is 0.7mol/L, it is further preferred that the lower limit value of the concentration of the electrolytic salt is
0.9mol/L.Similarly, in solid polymer electrolyte, gel polymer electrolytes, the content of electrolytic salt can be according to reality
Border demand is selected.
In the electrolyte according to the application first aspect, the type of the lithium salts is not limited specifically, can root
It is selected according to actual demand.Specifically, the lithium salts can be selected from lithium hexafluoro phosphate (LiPF6), LiBF4 (LiBF4), it is high
Lithium chlorate (LiClO4), hexafluoroarsenate lithium (LiAsF6), hexafluoro-antimonic acid lithium (LiSbF6), bis- (oxalic acid) lithium borate [LiB (C2O4)2
Or LiBOB], difluoro (oxalic acid) lithium borate [LiBF2(C2O4) or LiDFOB], bis- (fluorine sulphonyl) imine lithium [LiN (SO2F)2Or
LiFSI], bis- (trifluoro methylsulfonyl) imine lithium [LiN (SO2CF3)2LiTFSI], difluorophosphate (LiPO2F2), difluoro it is bis- (grass
Acid) lithium phosphate [LiPF2(C2O4)2], tetrafluoro (oxalic acid) lithium phosphate [LiPF4(C2O4One or more of)].From using and quotient
Industry angle considers, it is preferable that the lithium salts is selected from LiPF6Or other lithium salts and LiPF6The lithium salts being mixed to form with arbitrary proportion
One or more of.
In the electrolyte according to the application first aspect, the type of the sodium salt is not limited specifically, can root
It is selected according to actual demand.Specifically, the sodium salt can be selected from sodium hexafluoro phosphate (NaPF6), sodium tetrafluoroborate (NaBF4), it is high
Sodium chlorate (NaClO4), hexafluoroarsenate sodium (NaAsF6), trifluoromethanesulfonic acid sodium (NaCF3SO3), double trifluoromethanesulfonimide sodium
[NaN(CF3SO2)2], double pentafluoroethane sulfimide sodium [NaN (C2F5SO2)2], bis- (fluorine sulphonyl) imines sodium [NaN (FSO2)2]
One or more of.
Secondly illustrate the electrochemical energy storage device according to the application second aspect.
It include the electricity according to the application first aspect according to electrochemical energy storage device described in the application second aspect
Solve liquid.
In the electrochemical energy storage device according to the application second aspect, the electrochemical energy storage device further includes just
Pole piece, negative electrode tab and pack case etc..
In the electrochemical energy storage device according to the application second aspect, it should be noted that the electrochemistry storage
Energy device can be lithium ion battery, sodium-ion battery, lithium metal battery, solid lithium battery, all solid state sode cell or super electricity
Container.In embodiments herein, the embodiment that electrochemical energy storage device is lithium ion battery is only shown, but the application is unlimited
In this.
In lithium ion battery, positive plate includes plus plate current-collecting body and the positive diaphragm that is set on plus plate current-collecting body.Institute
Stating plus plate current-collecting body is aluminium foil.Positive electrode active materials can be selected from cobalt acid lithium (LiCoO2), LiFePO4 (LiFePO4)、LiNiO2、
LiMn2O4 (LiMn2O4), nickel manganese cobalt ternary material (LiNixCoyMn1-x-yO2(0≤x≤1,0≤y≤1)) one of or it is several
Kind, wherein specifically, the nickel manganese cobalt ternary material can be selected from LiNi1/3Co1/3Mn1/3O2、LiNi0.5Co0.2Mn0.3O2、
LiNi0.6Co0.2Mn0.2O2、LiNi0.7Co0.15Mn0.15O2、LiNi0.8Co0.1Mn0.1O2.The positive conductive agent be selected from acetylene black,
One or more of conductive black, carbon fiber (VGCF), carbon nanotube (CNT), Ketjen black.The type of positive electrode binder does not have
The limitation of body can be selected according to actual needs.
In lithium ion battery, negative electrode tab includes negative current collector and the cathode membrane that is set on negative current collector.Institute
Stating negative current collector is copper foil.Negative electrode active material can be selected from artificial graphite, natural graphite, silicon, silicon oxide compound, silicon-base alloy
One or more of.The cathode conductive agent is selected from acetylene black, conductive black (Super P, Super S, 350G), carbon fiber
(VGCF), one or more of carbon nanotube (CNT), Ketjen black.
In lithium ion battery, the type of the isolation film is not specifically limited, and can be selected according to actual needs, tool
Body, the isolation film can be selected from polyethylene film, polypropylene screen, polyvinylidene fluoride film and their multilayer complex films.
Below with reference to embodiment, the application is further described.It should be understood that these embodiments be merely to illustrate the application without
For limiting scope of the present application.The case where electrochemical energy storage device is lithium ion battery, but this Shen are only shown in embodiment
It please be without being limited thereto.
In the following embodiments, reagent, material and the instrument used such as not special explanation, it is commercially available to obtain
?.
In embodiment and comparative example, used phosphoric acid ester quat can be prepared as follows:
The synthesis of compound 1:
First step reaction:
Second step reaction:
Third step reaction:
Four-step reaction:
Operating procedure:
Ethylene bromohyrin (3g, 24mmol) is added in the twoport flask containing anhydrous acetonitrile (80mL), 0 DEG C is cooled to, adds
Enter piperidines (2.04g, 24mmol) and potassium carbonate (13g, 96mmol), temperature rising reflux 8 hours.It is cooled to room temperature and carries out vacuum mistake
Filter removes organic solvent with Rotary Evaporators.Residue is purified into (chloroform: methanol=10:1) through flash chromatography silicagel column
Obtain colorless oil (compound 1-1,0.9g, yield 30%).Wherein, the Structural Identification data of compound 1-1 are1H-NMR
(400MHz,CDCl3): δ=3.55 (dd, J=13.1,5.4Hz, 2H)；δ=2.48-2.27 (m, 6H)；δ=1.58-1.46
(m,4H)；δ=1.38 (t, 2H).
Compound 1-1 (6.45g, 50mmol) and triethylamine (12.6g, 2.5eq) are dissolved in methylene chloride 50mL,
It is slowly added dropwise at -20 DEG C into the methylene chloride containing solutions of dimethyl phosphoryl chlorine (2.1mL) (40mL).It is small to be warmed to room temperature stirring 5
When, it is cooled to 0 DEG C of filtering, filtrate removes organic solvent through Rotary Evaporators.Residue is carried out through flash chromatography silicagel column
Purifying (chloroform: methanol=10:1) obtains brown oil liquid (compound 1-2,7.1g, yield 60%).Wherein, compound 1-2
Structural Identification data be 1H-NMR (400MHz, CDCl3): δ=4.19-4.08 (m, 2H)；δ=3.76 (s, 3H)；δ=3.73
(s,3H)；δ=2.61 (t, J=6.0Hz, 2H), δ=2.42 (t, 4H), δ=1.55 (dt, J=11.1,5.6Hz, 4H)；δ=
1.40 (dd, J=10.8,5.9Hz, 2H).
Compound 1-2 (2.37g, 10mmol) is dissolved in anhydrous ether (30mL), excessive iodomethane is added, is stirred
Overnight, salt iodide are obtained, obtain 3.4g substance (i.e. compound 1-3), yield 90% by filtration and recrystallization.Wherein, change
Close object 1-3 Structural Identification data be1H-NMR(400MHz,D2O): δ=4.49 (t, 2H)；δ=3.75 (s, 3H)；δ=3.72
(s,3H)；δ=3.68 (t, J=3.0Hz, 2H)；δ=3.34 (t, J=5.4Hz, 4H)；δ=3.05 (s, 3H)；δ=1.80
(dt,4H)；δ=1.62-1.52 (dd, 2H).
The compound 1-3 (1g, 2.635mmol) that upper step obtains is added in anhydrous propanone (10mL), is slow added into
Contain KPF6The acetone soln of (1.9g, 10.5mmol).Lower 40 DEG C of nitrogen protection are stirred 30 hours.It is removed using Rotary Evaporators
Organic solvent in methylene chloride by residue dissolution is filtered to remove insoluble matter, and methylene chloride, solid product warp is removed in vacuum
Ethyl acetate and ether elute to obtain compound 1 (0.1g, yield 10%).
Compound 11H-NMR and19F-NMR nuclear-magnetism appraising datum:
1H-NMR(400MHz,CDCl3): δ=4.55 (dd, J=9.0,6.9Hz, 2H)；δ=4.07-4.02 (m, 2H)；δ
=3.83 (s, 3H)；δ=3.81 (s, 3H)；δ=3.71-3.63 (m, 4H)；δ=3.35 (s, 3H)；δ=1.96 (dd, J=
11.3,5.7Hz,4H)；δ=1.83-1.73 (m, 2H) (specifically can refer to Fig. 1).
19F-NMR(376MHz,CDCl3)；δ=- 70.57；δ=- 72.46 (specifically can refer to Fig. 2).
The synthesis of compound 2 to compound 8 is similar with compound 1, it is only necessary to feed change (such as change reaction substrate salt
Deng) and response parameter, this is no longer going to repeat them.
Lithium ion battery in embodiment 1-19 and comparative example 1-6 is prepared by the following method:
(1) preparation of positive plate
By positive electrode active materials LiNi0.5Co0.2Mn0.3O2, conductive agent Super P, binder polyvinylidene fluoride (PVDF)
It being uniformly mixed in N-Methyl pyrrolidone (NMP), anode sizing agent is made, wherein the solid content of anode sizing agent is 77wt%,
Positive electrode active materials LiNi0.5Co0.2Mn0.3O2, conductive agent Super P and binder PVDF mass ratio be 97:1.4:1.6；It connects
Anode sizing agent is coated on the plus plate current-collecting body aluminium foil with a thickness of 14 μm and is dried at 85 DEG C, then be cold-pressed；Then
After carrying out trimming, cut-parts, slitting, 4h is dried under 85 DEG C of vacuum condition, positive plate is made.
(2) preparation of negative electrode tab
By negative electrode active material graphite, conductive agent Super P, thickener CMC, bonding agent butadiene-styrene rubber (SBR) go from
In sub- water be uniformly mixed, negative electrode slurry is made, wherein the solid content of negative electrode slurry be 54wt%, negative electrode active material graphite,
The mass ratio of conductive agent Super P, thickener CMC and bonding agent SBR are 96.4:1.5:0.5:1.6；Negative electrode slurry is coated on
It dries, then is cold-pressed with a thickness of on 8 μm of negative current collector copper foil and at 85 DEG C；Then trimming, cut-parts, slitting are carried out
Afterwards, 12h is dried under 120 DEG C of vacuum conditions, negative electrode tab is made.
(3) preparation of electrolyte
In the glove box full of argon gas, by ethylene carbonate (EC), diethyl carbonate (DEC) and methyl ethyl carbonate
(EMC) it is mixed in mass ratio for EC:DEC:EMC=3:2:5, concentration is then slowly added into mixed solution again is
The LiPF of 1.0mol/L6, it is eventually adding additive, obtains electrolyte after mixing evenly.Wherein, the specific type of additive and its
Content is shown in table 1.In table 1, the content of additive is the quality percentage that the gross mass based on electrolyte is calculated
Number.
(4) preparation of isolation film
Using the polyethylene film (PE) with a thickness of 12 μm as isolation film
(5) preparation of lithium ion battery
Positive plate, isolation film, negative electrode tab are folded in order, isolation film is made to be in the middle position of positive and negative plate, is wound
Obtain naked battery core；Soldering polar ear；Naked battery core is placed in outer packing, after each electrolyte in table 1 is implanted sequentially drying
In dry battery core, encapsulation, stand, chemical conversion (with 0.02C multiplying power constant-current charge to 3.3V, then is arrived with 0.1C multiplying power constant-current charge
3.6V), the preparation of lithium ion battery is completed in shaping, volume test.
The parameter of table 1 embodiment 1-19 and comparative example 1-6
The test process of lithium ion battery will be illustrated next.
(1) first charge-discharge efficiency is tested
It with 0.5C multiplying power constant-current charge to voltage is 4.3V with lithium ion battery, then with 4.3V constant-voltage charge at 25 DEG C
It is 0.05C to electric current, this is the first time charging process of lithium ion battery, and the total capacity after charging is denoted as C0；Stand 5 minutes
It afterwards, then with 0.5C multiplying power constant-current discharge to voltage is 2.8V, this is the first time discharge process of lithium ion battery, total after electric discharge
Capacity is denoted as D0。
First charge-discharge efficiency (%)=D of lithium ion battery0/C0× 100%.
(2) high temperature cyclic performance test of the lithium from battery
It with 1C multiplying power constant-current charge to voltage is 4.3V by lithium ion battery, then extremely with 4.3V constant-voltage charge at 45 DEG C
Electric current is 0.05C, stand after five minutes, be 2.8V with 1C multiplying power constant-current discharge to voltage, then stand 5 minutes again, this for lithium from
One charge and discharge cycles of sub- battery, the discharge capacity for the first time of lithium ion battery are denoted as D1, in a manner described by lithium ion battery
Multiple cyclic charging and discharging test is carried out, the discharge capacity of the 200th circulation is denoted as D200。
45 DEG C of lithium ion battery circulation 200 times after capacity retention ratio (%)=D200/D1× 100%.
(3) the high-temperature storage performance test of lithium ion battery
It with 1C multiplying power constant-current charge to voltage is 4.3V by lithium ion battery, then extremely with 4.3V constant-voltage charge at 25 DEG C
Electric current is 0.05C, stands after five minutes, is 2.8V with 1C multiplying power constant-current discharge to voltage, then stands 5 minutes again, with 1C multiplying power
Constant-current charge is 0.05C to voltage 4.3V, then with 4.3V constant-voltage charge to electric current, and lithium ion battery is in fully charged state at this time,
The discharge capacity of corresponding lithium ion battery during this is denoted as D1.Then, lithium ion battery is put into 60 DEG C of insulating box
In, it is 2.8V with 1C multiplying power constant-current discharge to voltage that heat preservation, which is taken out after 90 days and is placed in 25 DEG C of environment, will be corresponding during this
Discharge capacity of lithium ion battery be denoted as D90。
60 DEG C of lithium ion battery storage 90 days after capacity retention ratio (%)=D90/D1× 100%.
(4) the high rate performance test of lithium ion battery
It with 0.2C multiplying power constant-current charge to voltage is 4.3V by lithium ion battery, then with 4.3V constant-voltage charge at 25 DEG C
Be 0.05C to electric current, stand after five minutes, then with 0.2C multiplying power constant-current discharge to voltage 2.8V, by corresponding lithium during this from
The discharge capacity of sub- battery is denoted as D0.2C；It stands after five minutes, is 4.3V with 0.2C multiplying power constant-current charge to voltage, then with 4.3V
Constant-voltage charge to electric current is 0.05C, is stood after five minutes, then with 2C multiplying power constant-current discharge to voltage be 2.8V, will be right during this
The discharge capacity for the lithium ion battery answered is denoted as D2C。
High rate performance (%)=D of lithium ion battery 2C/0.2C2C/D0.2C× 100%.
The performance test results of table 2 embodiment 1-19 and comparative example 1-6
From the Correlative data analysis in above-mentioned table 2 it is found that in comparative example 1, any additive is not added in electrolyte, it is non-aqueous
Organic solvent can generate more side reaction in pole piece, lead to first charge-discharge efficiency, the high temperature circulation of lithium ion battery
Capacity retention ratio, high temperature storage capacity retention ratio and high rate performance are poor.In Examples 1 to 8, although additive phosphoric acid
The type of ester quat is different, but promotes the first charge-discharge efficiency of lithium ion battery with can dramatically, this illustrates phosphate season
Limited active lithium money consumed by SEI film is established in negative terminal surface when ammonium salt can be effectively reduced for lithium ion battery chemical conversion
Source；In addition, after phosphoric acid ester quat is added, the high temperature circulation capacity retention ratio and high temperature storage capacity retention ratio of lithium ion battery
It is obviously improved, it is very fine and close and steady that this explanation by phosphoric acid ester quat participates in the SEI film formed in negative terminal surface
It is fixed, it can keep basicly stable without gradually being dissolved by electrolyte in prolonged high temperature circulation and high temperature storage；Add simultaneously
After entering phosphoric acid ester quat, the high rate performance of lithium ion battery is also obviously improved, this explanation is existed by phosphoric acid ester quat
Negative terminal surface participates in the SEI film to be formed with relatively low lithium ion transport impedance.
Analysis is it is found that the content of phosphoric acid ester quat is got in electrolyte in embodiment 1, embodiment 9~14 and comparative example 1
Greatly, to the first charge-discharge efficiency of lithium ion battery, high temperature circulation capacity retention ratio, high temperature storage capacity retention ratio and forthright again
The improvement of energy is more significant, and when the content of phosphoric acid ester quat is less, the chemical property of lithium ion battery can be certain
Improved in degree, but improved amplitude is smaller, when the content of phosphoric acid ester quat is stepped up from 0.05% to 1%,
It is larger that the chemical property of lithium ion battery improves amplitude, but when the content of phosphoric acid ester quat increases to 5% from 1%, lithium
The improved amplitude of the chemical property of ion battery is begun to decline, after the content of phosphoric acid ester quat increases to 10%, if
Continue the content of increase phosphoric acid ester quat, then phosphoric acid ester quat can not be completely dissolved, this will affect the electricity of lithium ion battery
The improvement of chemical property.
The analysis in embodiment 15~19 and comparative example 2~6 is it is found that phosphoric acid ester quat can also add with conventional film forming
Agent is added to be used in combination, further to improve the chemical property of lithium ion battery.When phosphoric acid ester quat and FEC, PS, VC,
When VEC, DTD are used in combination, compared with the lithium ion battery only containing FEC, PS, VC, VEC, DTD, electrochemical energy obtain into
The optimization of one step.The reason is that by phosphoric acid ester quat negative terminal surface participate in the SEI film ratio formed by FEC, PS, VC,
Traditional SEI film that VEC, DTD are formed is more form compact and stable and has lower lithium ion transport impedance, therefore can be further
Improve the chemical property of lithium ion battery.
In conclusion the cation group structure special due to phosphoric acid ester quat, so that the ring-type of tape unit positive charge
Under the internal electric field effect that quaternary ammonium head can be formed when lithium ion battery is melted into, drive entire cation group actively close to negative
Pole and be broken by preferential reduction decomposition, and release functional phosphate tail portion, for negative terminal surface establish one layer it is main
By alkyl phosphoric acid lithium (LiOP (=O) (OR)2) etc. thing liquids composition SEI film.Due to alkyl phosphoric acid lithium intrinsic lithium with higher
Ionic conductivity, and there is very high thermal stability, so the SEI film being consequently formed has internal structure fine and close, impedance is low
The excellent feature with high temperature resistant etc. is suitble to the electrode slice design of high-pressure solid and thick coating.
Claims (10)
1. a kind of electrolyte, which is characterized in that the electrolyte includes additive, and the additive is phosphoric acid ester quat, institute
It states phosphoric acid ester quat and is selected from one or more of 1 compound represented of formula；
In formula 1, R1、R2It is each independently selected from the alkyl, substituted or unsubstituted that substituted or unsubstituted carbon atom number is 1~6
Carbon atom number be 6~16 one of monocyclic aryl, R3The alkylene for being 1~12 selected from substituted or unsubstituted carbon atom number
One of base, R4One of the alkyl for being 1~6 selected from substituted or unsubstituted carbon atom number, R5Selected from substituted or unsubstituted
Carbon atom number be 1~3 one of alkylidene, substituent group is selected from alkyl, one of halogen that carbon atom number is 1~3
Or it is several；
Indicate anion,Selected from F-、[PF6]-、[AsF6]-、[BF4]-、[NO3]-、[ClO4]-、
One of.
2. electrolyte according to claim 1, which is characterized in that the cation group of the phosphoric acid ester quat is selected from
One of.
3. electrolyte according to claim 2, which is characterized in that the phosphoric acid ester quat is in following compounds
It is one or more of；
4. electrolyte according to claim 1, which is characterized in that the content of the phosphoric acid ester quat is the electrolyte
The 0.01%~10% of gross mass.
5. electrolyte according to claim 1, which is characterized in that the electrolyte further includes film for additive, and film forming adds
Agent is added to be selected from vinylene carbonate, vinylethylene carbonate, 1- propylene -1,3- sultone, sulfuric acid vinylene, fluoro carbonic acid second
One or more of enester.
6. electrolyte according to claim 5, which is characterized in that the content of the film for additive is less than or equal to the electricity
Solve the 3% of liquid gross mass.
7. electrolyte according to claim 1, which is characterized in that the electrolyte is liquid electrolyte, solid polymer
Electrolyte or gel polymer electrolytes.
8. electrolyte according to claim 1, which is characterized in that the electrolytic salt in the electrolyte is selected from lithium salts or sodium
Salt.
9. electrolyte according to claim 8, which is characterized in that
The lithium salts is selected from lithium hexafluoro phosphate, LiBF4, lithium perchlorate, hexafluoroarsenate lithium, hexafluoro-antimonic acid lithium, bis- (oxalic acid)
Lithium borate, difluoro (oxalic acid) lithium borate, bis- (fluorine sulphonyl) imine lithiums, bis- (trifluoro methylsulfonyl) imine lithiums, difluorophosphate, difluoro
One or more of bis- (oxalic acid) lithium phosphates, tetrafluoro (oxalic acid) lithium phosphate；
The sodium salt is selected from sodium hexafluoro phosphate, sodium tetrafluoroborate, sodium perchlorate, hexafluoroarsenate sodium, trifluoromethanesulfonic acid sodium, double trifluoros
One or more of methane Huang acid imide sodium, double pentafluoroethane sulfimide sodium, bis- (fluorine sulphonyl) imines sodium.
10. a kind of electrochemical energy storage device, which is characterized in that including electrolyte according to claim 1 to 9.
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| KR20230059227A (en) * | 2021-10-26 | 2023-05-03 | 에스케이온 주식회사 | Ionic liquids, electrolyte for secondary battery including the ionic liquids and secondary battery including the same |
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