CN114605442A - Multi-sulfur-based boron trifluoride salt electrolyte and preparation method and application thereof - Google Patents
Multi-sulfur-based boron trifluoride salt electrolyte and preparation method and application thereof Download PDFInfo
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- CN114605442A CN114605442A CN202011418823.8A CN202011418823A CN114605442A CN 114605442 A CN114605442 A CN 114605442A CN 202011418823 A CN202011418823 A CN 202011418823A CN 114605442 A CN114605442 A CN 114605442A
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- ring
- unsaturated
- saturated
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- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical class FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 238000002360 preparation method Methods 0.000 title claims abstract description 66
- 239000003792 electrolyte Substances 0.000 title claims abstract description 64
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 56
- 239000011593 sulfur Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 58
- 150000003839 salts Chemical class 0.000 claims abstract description 55
- 239000000654 additive Substances 0.000 claims abstract description 41
- 239000007787 solid Substances 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000005842 heteroatom Chemical group 0.000 claims description 92
- -1 heteroalkenyl groups Chemical group 0.000 claims description 79
- 125000004429 atom Chemical group 0.000 claims description 73
- 125000001424 substituent group Chemical group 0.000 claims description 67
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 64
- 229920006395 saturated elastomer Polymers 0.000 claims description 57
- 125000000623 heterocyclic group Chemical group 0.000 claims description 52
- 239000011244 liquid electrolyte Substances 0.000 claims description 43
- 125000003367 polycyclic group Chemical group 0.000 claims description 40
- 125000002837 carbocyclic group Chemical group 0.000 claims description 39
- 125000002950 monocyclic group Chemical group 0.000 claims description 36
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 25
- 125000005843 halogen group Chemical group 0.000 claims description 23
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 22
- 229910015900 BF3 Inorganic materials 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 20
- 239000007784 solid electrolyte Substances 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 125000003342 alkenyl group Chemical group 0.000 claims description 16
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 16
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 13
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 12
- 125000000304 alkynyl group Chemical group 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 12
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 12
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 125000004185 ester group Chemical group 0.000 claims description 10
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 150000001408 amides Chemical class 0.000 claims description 8
- 150000001768 cations Chemical class 0.000 claims description 8
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 8
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 8
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 8
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 150000003254 radicals Chemical class 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- CXWGKAYMVASWDQ-UHFFFAOYSA-N 1,2-dithiane Chemical compound C1CCSSC1 CXWGKAYMVASWDQ-UHFFFAOYSA-N 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 6
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 claims description 6
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims description 6
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- 125000003003 spiro group Chemical group 0.000 claims description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- WYNCHZVNFNFDNH-UHFFFAOYSA-N Oxazolidine Chemical compound C1COCN1 WYNCHZVNFNFDNH-UHFFFAOYSA-N 0.000 claims description 5
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 5
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical compound C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 claims description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 5
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 4
- YNGDWRXWKFWCJY-UHFFFAOYSA-N 1,4-Dihydropyridine Chemical compound C1C=CNC=C1 YNGDWRXWKFWCJY-UHFFFAOYSA-N 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- ARGCQEVBJHPOGB-UHFFFAOYSA-N 2,5-dihydrofuran Chemical compound C1OCC=C1 ARGCQEVBJHPOGB-UHFFFAOYSA-N 0.000 claims description 4
- VSWICNJIUPRZIK-UHFFFAOYSA-N 2-piperideine Chemical compound C1CNC=CC1 VSWICNJIUPRZIK-UHFFFAOYSA-N 0.000 claims description 4
- MGADZUXDNSDTHW-UHFFFAOYSA-N 2H-pyran Chemical compound C1OC=CC=C1 MGADZUXDNSDTHW-UHFFFAOYSA-N 0.000 claims description 4
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 claims description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 4
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 claims description 4
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 4
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 claims description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000003172 aldehyde group Chemical group 0.000 claims description 4
- 125000006193 alkinyl group Chemical group 0.000 claims description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 4
- 150000007942 carboxylates Chemical class 0.000 claims description 4
- ZXIJMRYMVAMXQP-UHFFFAOYSA-N cycloheptene Chemical compound C1CCC=CCC1 ZXIJMRYMVAMXQP-UHFFFAOYSA-N 0.000 claims description 4
- UVJHQYIOXKWHFD-UHFFFAOYSA-N cyclohexa-1,4-diene Chemical compound C1C=CCC=C1 UVJHQYIOXKWHFD-UHFFFAOYSA-N 0.000 claims description 4
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 claims description 4
- OOXWYYGXTJLWHA-UHFFFAOYSA-N cyclopropene Chemical compound C1C=C1 OOXWYYGXTJLWHA-UHFFFAOYSA-N 0.000 claims description 4
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 claims description 4
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 4
- 239000011245 gel electrolyte Substances 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 claims description 4
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 claims description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 4
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 4
- RPMXALUWKZHYOV-UHFFFAOYSA-N nitroethene Chemical group [O-][N+](=O)C=C RPMXALUWKZHYOV-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- OSFBJERFMQCEQY-UHFFFAOYSA-N propylidene Chemical compound [CH]CC OSFBJERFMQCEQY-UHFFFAOYSA-N 0.000 claims description 4
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 claims description 4
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 238000007363 ring formation reaction Methods 0.000 claims description 4
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 4
- 125000000565 sulfonamide group Chemical group 0.000 claims description 4
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 4
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 claims description 4
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- OXBLVCZKDOZZOJ-UHFFFAOYSA-N 2,3-Dihydrothiophene Chemical compound C1CC=CS1 OXBLVCZKDOZZOJ-UHFFFAOYSA-N 0.000 claims description 3
- ATVJJNGVPSKBGO-UHFFFAOYSA-N 3,4-dihydro-2h-thiopyran Chemical compound C1CSC=CC1 ATVJJNGVPSKBGO-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- BUDQDWGNQVEFAC-UHFFFAOYSA-N Dihydropyran Chemical compound C1COC=CC1 BUDQDWGNQVEFAC-UHFFFAOYSA-N 0.000 claims description 3
- YPWFISCTZQNZAU-UHFFFAOYSA-N Thiane Chemical compound C1CCSCC1 YPWFISCTZQNZAU-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- LOZWAPSEEHRYPG-UHFFFAOYSA-N dithiane Natural products C1CSCCS1 LOZWAPSEEHRYPG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- OTPDWCMLUKMQNO-UHFFFAOYSA-N 1,2,3,4-tetrahydropyrimidine Chemical compound C1NCC=CN1 OTPDWCMLUKMQNO-UHFFFAOYSA-N 0.000 claims description 2
- WCFAPJDPAPDDAQ-UHFFFAOYSA-N 1,2-dihydropyrimidine Chemical compound C1NC=CC=N1 WCFAPJDPAPDDAQ-UHFFFAOYSA-N 0.000 claims description 2
- CZSRXHJVZUBEGW-UHFFFAOYSA-N 1,2-thiazolidine Chemical compound C1CNSC1 CZSRXHJVZUBEGW-UHFFFAOYSA-N 0.000 claims description 2
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 claims description 2
- DKYBVKMIZODYKL-UHFFFAOYSA-N 1,3-diazinane Chemical class C1CNCNC1 DKYBVKMIZODYKL-UHFFFAOYSA-N 0.000 claims description 2
- OGYGFUAIIOPWQD-UHFFFAOYSA-N 1,3-thiazolidine Chemical compound C1CSCN1 OGYGFUAIIOPWQD-UHFFFAOYSA-N 0.000 claims description 2
- VQFZKDXSJZVGDA-UHFFFAOYSA-N 1,5,9-triazacyclododecane Chemical compound C1CNCCCNCCCNC1 VQFZKDXSJZVGDA-UHFFFAOYSA-N 0.000 claims description 2
- UUFQTNFCRMXOAE-UHFFFAOYSA-N 1-methylmethylene Chemical compound C[CH] UUFQTNFCRMXOAE-UHFFFAOYSA-N 0.000 claims description 2
- 125000006017 1-propenyl group Chemical group 0.000 claims description 2
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 claims description 2
- 125000004398 2-methyl-2-butyl group Chemical group CC(C)(CC)* 0.000 claims description 2
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
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- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 claims description 2
- 101150065749 Churc1 gene Proteins 0.000 claims description 2
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- 125000000480 butynyl group Chemical group [*]C#CC([H])([H])C([H])([H])[H] 0.000 claims description 2
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- 125000000582 cycloheptyl group Chemical class [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
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- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 claims description 2
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- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 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
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
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Abstract
The application provides a multi-element sulfur-based boron trifluoride salt electrolyte and a preparation method and application thereof. The multi-sulfur-based boron trifluoride salt electrolyte includes a boron trifluoride salt represented by the following general formula I. Wherein the multi-sulfur-based boron trifluoride salt can be used as an additive and a salt in an electrolyte. When used as an electrolyte additive, can be remarkably improvedFirst-pass and cycle performance of the battery; when used as salt in electrolyte, the electrolyte has better ion transmission and stable electrochemical performance. The boron trifluoride salt provided by the application can be applied to liquid batteries, solid-liquid hybrid batteries, semi-solid batteries, gel batteries, quasi-solid batteries and all-solid batteries, and is beneficial to improving the energy density, the cycling stability and the service life of the batteries. And the raw materials are low in price, the synthesis process is simple, and the method has good economic benefit.
Description
Technical Field
The application relates to the technical field of batteries, in particular to a multi-element sulfur-based boron trifluoride salt electrolyte and a preparation method and application thereof.
Background
With the rapid development of society, the demand for sustainable energy is increasing day by day. The secondary battery is an energy storage/conversion system, and can store renewable energy sources such as wind energy, water energy and solar energy, and can store electric energy when the electric quantity of a power grid is excessive. More importantly, it can release energy according to the needs at any time and any place. In addition, as the social development is promoted, further improvement of energy density, cycle stability and safety of the secondary battery is urgently required.
In order to increase the energy density of a lithium battery, for example, a high-voltage high-specific-volume positive electrode material and a low-voltage high-capacity negative electrode material, such as a high-voltage Lithium Cobaltate (LCO), a high-nickel multi-element (NCM811, NCM622, NCM532, and NCA), a Lithium Nickel Manganese Oxide (LNMO), and the like, and a negative electrode material, such as metallic lithium, graphite, silicon oxycarbon, and the like, need to be used. And simultaneously, the electrolyte with wide electrochemical window is matched or a stable passivation layer is formed on the surface of an electrode so as to improve the cycling stability of the battery.
The electrolyte can be divided into a liquid electrolyte and a solid electrolyte according to states, and the liquid electrolyte has the remarkable advantages of high conductivity and good wettability to the inside of the electrode. However, the organic solvent in the liquid electrolyte is flammable and is easy to have a risk of thermal runaway, the liquid electrolyte is easy to generate uncontrollable side reactions, and the electrode interface is unstable, so that the capacity is seriously declined, and therefore, the battery safety is poor and the cycle life is short. The above problems can be significantly improved by using a non-flammable solid electrolyte, and further, it has been proposed to suppress the growth of lithium dendrites in a metallic lithium negative electrode using a solid electrolyte. Solid electrolytes can be divided into two broad categories, organic polymer electrolytes and inorganic (sulfide and oxide) electrolytes. The polymer has better flexibility and easy useThe method is easy to process and contact with the interface of an electrode, but has lower ionic conductivity at room temperature, limited thermal stability and narrower electrochemical window; sulfide has high ionic conductivity and good processing capacity, but most sulfides are unstable in air and generate toxic H with water molecules2S gas, and therefore requires a very harsh processing environment; the oxide has excellent chemical and thermal stability, high voltage resistance, high ionic conductivity, poor flexibility and large interface resistance. Therefore, liquid electrolytes are still mainly used, and various functional additives, such as FEC (fluoroethylene carbonate), VC (vinylene carbonate), VEC (vinylene carbonate), DTD (vinyl sulfate), and the like, need to be added to the liquid electrolytes in order to improve the cycle stability of liquid batteries. Wherein the SEI passive film formed on the surface of the negative electrode contains various inorganic components Li as main component2CO3、LiF、Li2O, LiOH, and various organic components such as ROCOOLi, ROLi, ROCOOLi, etc., and conventional functional electrolyte additives contain no dissociable ions and only consume ions of the positive electrode to form a surface passivation layer, so the first effect and specific discharge capacity are relatively low. If the added additive can form a passivation layer which is conductive to ions and good in stability on the surface of the electrode, and meanwhile, the ions from the electrode are less consumed, the oxidation/reduction decomposition of the anode and cathode materials to the electrolyte can be effectively prevented, so that the liquid electrolyte and the polymer electrolyte with narrow electrochemical windows can be applied to a high-voltage battery system, and the energy density and the cycle life of the battery are effectively improved. In addition, the salt synthesis/purification process of the current commercial electrolyte is complex and has high price, so that the cost of the whole battery is higher, and if the salt synthesis/purification process of a new electrolyte is simple and has low price, the salt synthesis/purification process can partially or completely replace the salt of the electrolyte in the prior art, so that the excellent performance and the lower cost can be both considered.
One of the groups of the Applicant has been working on compositions containing-SBF obtained after substitution by an-SH3Compounds of the M group were studied. Due to-SBF3Is a strongly polar group capable of forming a salt structure with a cation, thus, -SBF3M has a strong sense of presence in one molecular structure, which may change the properties of the entire molecular structure. In the prior art, BF-containing samples were also only investigated by very individual researchers3The compounds of the group were studied sporadically.
Patent No. CN105789701A discloses an electrolyte additive comprising a hydrogenated thiophene-boron trifluoride complex compound and lithium fluorophosphate, wherein the hydrogenated thiophene-boron trifluoride complex compound is at least one selected from compounds having a structural formula shown in formula (1): wherein R1, R2, R3 and R4 are respectively and independently selected from a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted C1-20 alkyl group, a substituted or unsubstituted C2-20 alkenyl group and a substituted or unsubstituted C6-26 aryl group; the substituent is selected from halogen and cyano. However, the compound is a complex compound, is not a sulfenyl salt, and does not have much research result at present and industrial application result.
In the prior art, the rare target is-S-BF3The M group was not studied, let alone for the multiple-SBF3Studies of the M group are published. This is because-SBF3M is strongly sensitive to the presence of-SBF if added to the molecule3The number of M may vary unpredictably in the overall properties of the overall molecular structure, and thus research teams may be conducting a system containing multiple-SBF3M research results show that resistance is greatly increased, time cost and economic cost are extremely high, and results are not well predicted, so that the research team only always contains one-SBF3M was studied.
Even if the pair contains one-SBF3M is studied, and because the prior art is very few, the reference value is very small, and the research on a plurality of groups does not have any reference source, and the research team also unexpectedly finds that the group contains the multi-SBF in the accidental research3The M-substituted organic substance can be used in liquid electrolyte and solid electrolyte, and the above electrolyte is preparedThe battery is surprisingly tested to have excellent performance, so that a special establishment team carries out special research on the multi-substituted-SBF3M, and obtains better research results.
Disclosure of Invention
In view of this, the embodiments of the present application provide a multi-sulfur-based boron trifluoride electrolyte, and a preparation method and an application thereof, so as to solve technical defects in the prior art.
Provided is a multi-sulfur-based boron trifluoride salt electrolyte including a boron trifluoride salt represented by the following general formula I:
in the above formula I, Q1represents-SBF3M, M is a metal cation; r, R1、R2、R3、R4、R5Independently is nothing, a first ring or a first chain containing at least one atom, and R, R1～R5Not both can be H or none;
R、R1、R2、R3、R4、R5to any one, two or more atoms of which 3 to 7-SBFs are attached3M, and each-SBF3Each M is independently attached through E ', and E' are independently absent, a second ring, or a second chain containing at least one atom;
R、R1、R2、R3、R4、R5and R6May be independently attached with a first substituent;
the first and second rings may be independently a carbocyclic ring consisting of only C atoms or a heterocyclic ring containing at least one heteroatom;
the first and second chains may independently be carbon chains consisting of only C atoms or hetero chains containing at least one heteroatom, the first and second chains independently comprising saturated chains and chains containing unsaturated bonds comprising double and/or triple bonds.
Further, in the general formula I, the hetero atom includes S, N, O, P, Se, Ca, Al, B or Si;
the first ring and the second ring can be any one of three-membered to twenty-membered rings independently, and the rings include saturated carbocycle, saturated heterocycle, unsaturated carbocycle, unsaturated heterocycle or aromatic ring;
the first and second chains may independently be chains of 1 to 30 atoms.
Further, the heteroatoms include ring-located heteroatoms including P, S, Si, N or O and chain-located heteroatoms including S, N, O, P, B, Ca or Si.
Further, in the formula I, with-SBF3The atom to which M is attached is a carbon atom C.
Further, the first substituent may be independently selected from H, a chain substituent or a cyclic substituent; the chain substituents include halogen atoms, ether oxygen groups, ether sulfur groups, nitro groups, cyano groups, amides, sulfonamide groups, sulfo groups, sulfonic acid groups, sulfonic ester groups, C ═ O-containing substituents, N-containing substituents, alkyl groups, heteroalkyl groups, alkenyl groups, heteroalkenyl groups, alkynyl groups, heteroalkynyl groups, alkinyl groups, salt-type substituents, ═ O, ═ S, nitro groups, cyano groups, amides, sulfonamide groups, sulfo groups, sulfonic acid groups, sulfonic ester groups, C ═ O-containing substituents, N-containing substituents, alkyl groups, heteroalkyl groups, alkenyl groups, heteroalkenyl groups, alkynyl groups, heteroalkynyl groups, alkinyl groups, salt-type substituents,
Or ═ N-R7(ii) a The cyclic substituent comprises a three-membered ring, a four-membered ring, a five-membered ring, a six-membered ring, a seven-membered ring and a polycyclic substituent containing two or more than two ring structures simultaneously, and any hydrogen H in the chain substituent or the cyclic substituent can be substituted by halogen atoms;
wherein R is5、R6And R7Independently H, alkyl, heteroalkyl, fluoroalkyl, fluoroheteroalkyl, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, or ring, preferably R7In a structure other than H, the salt substituent includes, but is not limited to, sulfate, phosphate, carboxylate, sulfonate, sulfonimide, carbonate, ether, ammonium, silicate, phosphate, hydrochloride, nitrate, azideSalt;
the above substituents may be optionally bonded to an atom.
Further, the first and second rings may be independently monocyclic, polycyclic, or complex rings;
the monocyclic ring includes a saturated carbocyclic ring, a saturated heterocyclic ring, an unsaturated carbocyclic ring, an unsaturated heterocyclic ring, an aromatic carbocyclic ring and an aromatic heterocyclic ring; the single ring is a three-to eighteen-membered ring;
the polycyclic ring is composed of two or more monocyclic rings; the polycyclic rings include linked, fused, bridged or spiro rings; the interlinkage is formed by a plurality of single rings, and two adjacent single rings are connected together through a single bond; the fused ring is formed by combining more than 2 single rings, and two adjacent rings share atoms on two rings; the bridge ring is a polycyclic structure sharing more than two atoms; the spiro ring is a ring sharing one atom by two adjacent monocyclic rings;
the composite ring comprises a direct ring and a sleeving ring; the direct cyclization is a ring formed by connecting multiple rings or between multiple rings and a single ring through a single bond, a chain connection containing at least one atom or a common atom; the nested ring is a ring in which at least 2 monocyclic and/or polycyclic rings are connected into a whole by a single bond or a chain of at least one atom;
the first substituent may be independently attached to any one of the monocyclic, polycyclic or complex rings.
Further, the monocyclic ring includes a ring represented by not limited to any one of:
m in each ring structure0-M17Each independently can be C, O, N, P, Si, Se or S, and the ring can be connected with the first substituent;
the interlinkage in the rings is formed by 2,3, 4 or 5 single rings, and two adjacent single rings are connected together through a single bond; merging rings in the rings are 2-7 single rings, and two adjacent rings share atoms on the two rings; the bridge ring in the polycyclic structure is a polycyclic structure sharing more than two atoms, and the number of ring-forming rings is 2 or 3 monocyclic rings; spiro rings in the polycyclic rings share one atom for two monocyclic rings; the composite ring is formed by 2-4 polycyclic rings or polycyclic rings and monocyclic rings, or 2-6 monocyclic rings are fused together.
Further, in the general formula i, the monocyclic ring in the first ring or the second ring includes a saturated carbocyclic ring, a saturated heterocyclic ring, an unsaturated carbocyclic ring and an unsaturated heterocyclic ring, the monocyclic ring in the first ring is a three-to ten-membered ring, a twelve-membered ring, a fourteen-membered ring, a sixteen-membered ring or an eighteen-membered ring, and the monocyclic ring in the second ring is a three-to eight-membered ring;
in the above first ring or second ring, the three-membered unsaturated carbocyclic ring includes a carbocyclic ring of 1 double bond; a ternary saturated heterocycle includes a saturated ring containing 1 or 2 heteroatoms; the ternary unsaturated heterocycle comprises 1 double bond and simultaneously contains 1 or 2 heteroatoms;
the quaternary unsaturated carbocycle includes carbocycles containing 1 double bond or 2 double bonds, and if 2 double bonds, they are not adjacently disposed; a quaternary saturated heterocycle includes a saturated ring containing 1 or 2 heteroatoms; the quaternary unsaturated heterocycle is a four-membered ring which contains 1 or 2 double bonds and simultaneously contains 1 or 2 heteroatoms;
five-membered unsaturated carbocycles include carbocycles containing 1 double bond or 2 double bonds, and if 2 double bonds, they are not disposed adjacent; a five-membered saturated heterocycle includes a saturated ring containing 1,2, 3, or 4 heteroatoms; the five-membered unsaturated heterocycle is a five-membered ring which contains 1 or 2 double bonds and simultaneously contains 1,2, 3 or 4 heteroatoms;
the six-membered unsaturated carbocyclic ring comprises a carbocyclic ring containing 1,2 or 3 double bonds, and if 2 or 3 double bonds are contained, the two carbocyclic rings are arranged non-adjacently; six membered saturated heterocyclic rings include saturated rings containing 1,2, 3, 4, 5 or 6 heteroatoms; the six-membered unsaturated heterocycle is a six-membered ring which contains 1,2 or 3 double bonds and simultaneously contains 1,2, 3, 4, 5 or 6 heteroatoms;
the seven-membered unsaturated carbocyclic ring comprises a carbocyclic ring containing 1,2 or 3 double bonds, and if 2 or 3 double bonds are contained, the two carbocyclic rings are arranged non-adjacently; a seven membered saturated heterocyclic ring includes a saturated ring containing 1,2, 3 or 4 heteroatoms; the seven-membered unsaturated heterocycle is a seven-membered ring which contains 1,2 or 3 double bonds and simultaneously contains 1,2, 3 or 4 heteroatoms;
the eight-membered unsaturated carbocyclic ring comprises a carbocyclic ring containing 1,2, 3 or 4 double bonds, and if 2 or more double bonds are present, the two double bonds are not adjacent to each other; an eight membered saturated heterocyclic ring includes a saturated ring containing 1,2, 3 or 4 heteroatoms; an eight-membered unsaturated heterocycle is an eight-membered ring containing 1,2, 3 or 4 double bonds and simultaneously 1,2, 3 or 4 heteroatoms;
the nine-membered unsaturated carbocyclic ring comprises a carbocyclic ring containing 1,2, 3 or 4 double bonds, and if 2 or more double bonds are present, the two double bonds are not adjacent to each other; a nine membered saturated heterocyclic ring includes a saturated ring containing 1,2, 3 or 4 heteroatoms; the nine-membered unsaturated heterocycle is a nine-membered ring which contains 1,2, 3 or 4 double bonds and simultaneously contains 1,2, 3 or 4 heteroatoms;
the ten-membered unsaturated carbocyclic ring comprises a carbocyclic ring containing 1,2, 3 or 4 double bonds, and if 2 or more double bonds are present, the two are arranged non-adjacently; a ten-membered saturated heterocyclic ring includes a saturated ring containing 1,2, 3, or 4 heteroatoms; the ten-membered unsaturated heterocycle is a ten-membered ring containing 1,2, 3 or 4 double bonds and simultaneously containing 1,2, 3 or 4 heteroatoms;
the twelve-membered ring, the fourteen-membered ring, the sixteen-membered ring and the eighteenth-membered ring respectively and independently comprise a saturated carbon ring, a saturated heterocyclic ring containing 1,2, 3, 4, 5 or 6 heteroatoms and an unsaturated heterocyclic ring, wherein the unsaturated heterocyclic ring is a ring containing 1,2, 3, 4, 5 or 6 heteroatoms and simultaneously containing 1,2, 3, 4, 5 or 6 unsaturated bonds;
the polycyclic ring is formed by combining more than 2-5 single rings.
Further, in the general formula I, the first chain and the second chain are independently a saturated carbon chain, an unsaturated carbon chain, a saturated hetero chain or an unsaturated hetero chain, and the first chain and the second chain are independently a chain of 1 to 25 atoms;
wherein, for a 1 atom chain: if the chain is the first chain, the chain can be a carbon chain or a miscellaneous chain of 1 atom, and if the chain is the second chain, the chain is a carbon chain of 1 atom;
for a 2 atom chain, it is a saturated carbon chain, a saturated heterochain containing 1 heteroatom, an unsaturated carbon chain containing 1 double bond, or an unsaturated heterochain containing both 1 unsaturated bond and 1 heteroatom;
for a 3 atom chain, it includes a saturated carbon chain, an unsaturated carbon chain containing 1 unsaturated bond, a saturated heterochain containing 1 heteroatom, or an unsaturated heterochain containing both 1 unsaturated bond and 1 heteroatom;
for a 4 atom chain, it includes a saturated carbon chain, an unsaturated carbon chain containing 1 unsaturated bond, a saturated heterochain, or an unsaturated heterochain; the saturated heterochain contains 1 or 2 heteroatoms, and the unsaturated heterochain simultaneously contains 1 unsaturated bond and 1 or 2 heteroatoms;
for a 5 atom chain, it includes a saturated carbon chain, an unsaturated carbon chain containing 1 or 2 unsaturated bonds, a saturated heterochain, or an unsaturated heterochain; the saturated heterochain contains 1,2, 3, 4 or 5 heteroatoms, and the unsaturated heterochain contains 1 unsaturated bond and simultaneously contains 1,2, 3, 4 or 5 heteroatoms;
for a 6 atom chain, it includes a saturated carbon chain, an unsaturated carbon chain containing 1 or 2 unsaturated bonds, a saturated heterochain, or an unsaturated heterochain; the saturated heterochain contains 1,2 or 3 heteroatoms, and the unsaturated heterochain contains 1 or 2 unsaturated bonds and also contains 1,2 or 3 heteroatoms;
for a 7 atom chain, it includes a saturated carbon chain, an unsaturated carbon chain containing 1 or 2 unsaturated bonds, a saturated heterochain, or an unsaturated heterochain; the saturated heterochain contains 1,2 or 3 heteroatoms, and the unsaturated heterochain contains 1 or 2 unsaturated bonds and 1,2 or 3 heteroatoms;
for a chain of 8 atoms, it includes a saturated carbon chain, an unsaturated carbon chain, a saturated heterochain, or an unsaturated heterochain; the unsaturated carbon chain contains 1,2 or 3 unsaturated bonds, the saturated heterochain contains 1,2 or 3 heteroatoms, and the unsaturated heterochain contains 1,2 or 3 unsaturated bonds and simultaneously contains 1,2 or 3 heteroatoms;
for a 9 atom chain, it includes a saturated carbon chain, an unsaturated carbon chain, a saturated heterochain, or an unsaturated heterochain; wherein the unsaturated carbon chain contains 1,2, 3 or 4 unsaturated bonds, the saturated heterochain contains 1,2, 3 or 4 heteroatoms, and the unsaturated heterochain contains 1,2 or 3 unsaturated bonds and simultaneously contains 1,2 or 3 heteroatoms;
for a 10, 11, 12, 13, 14, or 15 atom chain, it includes a saturated carbon chain, an unsaturated carbon chain, a saturated heterochain, or an unsaturated heterochain; the unsaturated carbon chain contains 1,2, 3 or 4 unsaturated bonds, the saturated heterochain contains 1,2, 3 or 4 heteroatoms, and the unsaturated heterochain contains 1,2 or 3 unsaturated bonds and simultaneously contains 1,2 or 3 heteroatoms;
for a chain of 16-25 atoms, the chain comprises a saturated carbon chain, an unsaturated carbon chain, a saturated heterochain or an unsaturated heterochain; the unsaturated carbon chain comprises 1 to 7 unsaturated bonds, the saturated heterochain comprises 1 to 7 heteroatoms, and the unsaturated heterochain contains 1 to 7 unsaturated bonds and 1 to 7 heteroatoms;
the first substituent may be attached to any one of the first chains.
Further, when the general formula i is a ring structure, it includes:
A) r is a first ring, R1、R2、R3、R4、R5Are all H or nothing, and are denoted as R-E-Q1Wherein, R is also connected with 3-5-E' -SBF3M; any ring atom on the first ring R may be directly or indirectly linked to 1 or 2-SBF3M；
B) R is a first ring to which R is not directly attached-SBF3M，R1Is a first chain, R2、R3、R4、R5All are nothing (or H) or the first chain, noted
R1、R2、R3、R4、R5Is connected with 3-6-E' -SBFs3M, and R4、R5Independently attached-E' -SBF3The number of M is 0 or 2;
C) r is a first ring, R1Is a first chain, R2、R3、R4Independently is nothing or a first chain, R5All are H or nothing, and are marked as
Wherein R is linked to at least 1-E' -SBF3M，R1、R2、R3、R4To which 1-4-E' -SBF groups are attached3M；
D) R is nothing, a first ring or a first chain, R1And R4Is a first ring, R3、R5All are H or nothing, and are marked as
Wherein R is4To which at least 1-E' -SBF is attached3M，R、R1、R2Independently connected with 0-3-E' -SBF3M；
R, R in A) -D)1、R2、R3、R4Or R5Each of which is independently attached to the first substituent.
23. The multi-sulfur-based boron trifluoride salt electrolyte of claim 10, wherein: when formula I is a chain structure, it includes:
E)R、R1、R2、R3、R4、R5independently is a first chain containing no or at least one atom, and R,R1～R5Not all of them being simultaneously H or none, is denoted
F) When the general formula I is a chain structure, R is a ring, R5Is absent, R1、R2、R3、R4Independently is nothing or a first strand; r1、R2、R3To which 4-5-SBF are attached3M，R4To which 0-2-SBF are attached3M, is marked as
R, R in E) to F)1、R2、R3、R4Or R5Each of which is independently attached to the first substituent.
Further, in a) -F), said first ring comprises said monocyclic, polycyclic or composite ring; the monocyclic ring is selected from the following rings: cyclopropane, cyclopropene, ethylene oxide, thiirane, cycloazethane, cyclobutane,
Cyclobutene, cyclopentyl, cyclopentene, cyclopentadiene, pyrrole, dihydropyrrole
Tetrahydropyrrole, furan, dihydrofuran
Tetrahydrofuran, thiophene, dihydrothiophene
Tetrahydrothiophene, imidazole, pyrazole, thiazole
Dihydrothiazoles, tetrahydrothiazoles, isothiazoles
Dihydroisothiazoles
Tetrahydroisothiazole, oxazole
Dihydrooxazole and tetrahydrooxazole
Isoxazoles
Dihydroisoxazole
Triazole compounds
Dihydrotriazoltetrazolyl, phenyl, pyridine, dihydropyridine, tetrahydropyridine, pyrimidine, pyrazine, pyridazine, p-diazabenzene, triazine
Cyclohexane and dioxane
Cyclohexene, 1, 3-cyclohexadiene, 1, 4-cyclohexadiene, piperidine, pyran, dihydropyran
Tetrahydropyran, dihydrothiopyran
Tetrahydrothiopyrans, dithianes
1, 2-dithianes
[1,3]Oxazolidines, morpholines, piperazines, pyrones, dihydropyrimidines, tetrahydropyrimidines, hexahydropyrimidines, cycloheptanes, [1,4 ]]Dioxepane, cyclohexene oxide, cycloheptene, 1, 3-cycloheptene, cyclooctane, cyclononane triene, cyclododecane, 1,5, 9-triazacyclododecane,
Or 18-crown ethers;
the polycyclic ring is composed of the above-mentioned monocyclic ring; in the composite ring, the direct ring formation is a composite ring formed by connecting at least two polycyclic rings or at least one polycyclic ring and at least one monocyclic ring through a single bond, a chain containing at least one atom or a common atom, and the composite ring includes, but is not limited to, the following rings:
wherein A is11、A12、A13、A14Independently is-CH2-、-S-、-SO2-；
In the above rings, H on N is replaced by a covalent bond or a metal cation.
Further, E or E' is selected from the group consisting of absent, carbonyl, ester, alkyl, heteroalkyl, alkenyl, heteroalkenyl, etheroxy, etherthio, a group containing a cyclic structure, ═ CH-R8-、＝N-R4-or a group obtained after any one of these structures H is substituted by halogen;
the heteroalkenyl group includes a structure containing a carbon-carbon double bond C ═ C and a structure containing a carbon-carbon double bond C ═ N, wherein R is4And R8Independently isAlkyl, heteroalkyl, alkenyl, heteroalkenyl or a ring structure, R8Or none.
Further, the general formula I as described for A) includes the following compounds:
the general formula I described for B) includes the following compounds:
the general formula I mentioned for C) includes the following compounds:
the general formula I as described for D) includes the following compounds:
in the above structure, Q0～Q6All represent-SBF3M; e in each ring structure1～E12Are each independently a group, a ring-containing structure or a chain structure containing at least one atom, and E0～E6May be absent; a in each ring structure1～A7Are each independently absent or a second substituent in accordance with the definition of the first substituent; any one H on each ring can be replaced by A1、A2、A3、A4、A5、A6Or A7And two or more of H may be substituted by one H, and if two or more of H are substituted, the substituents may be the same or different.
Further, the second substituents are each independently selected from H, a halogen atom, a carbonyl group, an ester group, an aldehyde group, an ether oxygen bond/group, an ether sulfur bond/group, ═ O, ═ S, ═ CH2Nitro, cyano, disubstituted amino, amide, sulfonamide, sulfoalkane, sulfonate, sulfate, sulfonate, phosphate, hydrochloride, nitrate, diazo, azide, sulfonimide, carbonic acidSalts, carboxylates, thioether salts, oxoether salts, ammonium salts, -OCF3Alkyl, heteroalkyl, alkenyl, heteroalkenyl, alkynyl, alkenylalkynyl, cyclopropyl, aryl, cyclopentyl, cyclohexyl, polycyclic and any H of these second substituents may be independently substituted with a halogen atom to provide a halo substituent.
Further, the halogen atoms include F, Cl, Br, I;
the carbonyl group is
The ester group is
Or
Sulfonic acid ester
Disubstituted amino is
Amide is
Or
The sulfoalkane is
The ether oxygen bond/radical being-O-R35or-R31OR32The etherthio group/radical being-S-R35or-R31SR32Wherein R is22、R23、R24、R25、R46、R50、R51、R52、R53、R54、R55、R56、R79、R80Independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopreneA radical, s-pentyl, neopentyl, hexyl or heptyl, and R22、R24、R31、R50、R55May be absent; wherein the ester group can also be selected from-COOCH2(CH2)6CH3、-COOCH2(CH2)10CH3、-COOCH2(CH2)14CH3Or, -COOCH2(CH2)16CH3(ii) a The ether oxy group can also be selected from-CH2(CH2)5OEt、-OCH2(CH2)8CH3、-OCH(CH3)Et、-OCH(CH3)CH2CH(CH3)2、-OCH(CH3)CH2CH2CH(CH3)2；R79、R80And can also be selected from methoxy, ethoxy independently;
cyano radicals selected from-CN, -CH2CN、-CH＝C(CN)2or-CH2CH2CN。
The alkyl group includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, n-hexyl, isohexyl, sec-hexyl, neohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, -C (CH)3)3、-CH2C(CH3)3、-C(CH3)2CH2CH3、-CH2CH2C(CH3)3；
The heteroalkyl group is selected from: -OCH2CH2Si(CH3)3、-CH2CH(SCH2CH3)2、-CH(SCH2CH3)2、-CH2S-S-CH3、-S-S-CH3、-OCF3、-CH2Z1CH3、-O(CH2CH3)2、-CH2Z1CH(CH3)2、
The alkenyl group includes: ethenyl, 1-propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, 1, 3-hexadienyl, -C (CH)3)＝CH2、-OCH2CH＝CH2、-C(CH3)＝CHCH3、-CH2CH＝C(CH3)2、
-C(CH3)＝CH2、
Heteroalkenyl: -COCH ═ CH2、＝NCH2CH2CH3、-CH2OCHO、-CO(CH2)2C(CH3)3、-OCOCH(CH3)Et、-CH2(CH2)3CH(CH3)COCH3、-N＝CHCH3、-C(CH3)＝CHCOCH3、-COCH＝CHCH2CH3、-CH2-CH＝CH-Z1CH3、
Alkynyl is selected from ethynyl, propynyl, butynyl, pentynyl or-C.ident.C-Si (CH)3)3；
Alkenylalkynyl is selected from: -C ≡ CCH ═ CHCH3；
The cyclopropyl group is selected from the group consisting of cyclopropane
Ethylene oxide radical
Or cyclopropene;
aryl is selected from benzene ring, pyridine, pyrimidine, pyrazine, pyridazine, p-diAzabenzene, triazine,
Cyclopentyl is selected from cyclopentyl, cyclopentenyl, cyclopentadienyl, dihydropyridine, tetrahydropyridine, pyrrolyl, dihydropyrrolyl, tetrahydropyrrolyl, furyl, dihydrofuryl, tetrahydrofuryl, 2, 5-dihydrofuran, thienyl, dihydrothiophene, tetrahydrothiophene, imidazolyl, thiazolyl, 2, 3-dihydrothiazolyl, pyrazolyl, oxazole, isoxazole, triazolyl, pyridyl, etc,
The cyclohexyl is selected from: cyclohexane, cyclohexenyl, 1, 3-cyclohexadiene, 1, 4-cyclohexadiene, piperidine, pyran, dihydropyran, (3, 6-dihydro-2H-pyran), tetrahydropyran, morpholine, piperazine, pyrone, dihydropyrimidine, tetrahydropyrimidine, dioxane, dihydrothiopyran, tetrahydrothiopyran, dithiane or oxazolidine;
the polycyclic ring is selected from: naphthyl, anthryl, phenanthryl, quinonyl, pyrenyl, acenaphthenyl, carbazolyl, indolyl, isoindolyl, quinolyl, purinyl, nucleobase, benzoxazole,
The halogenated substituent comprises a substituent obtained after any H in alkyl, heteroalkyl, alkenyl, heteroalkenyl, alkynyl and alkenylalkynyl is independently substituted by halogen atoms;
in the above ring, R20is-CH2-or-CO-;
any one of the cyclopropyl, the aryl, the cyclopentyl, the cyclohexyl and the polycyclic can pass through a single bond, -O-, -S-、-CH2-、-OCH2-、-CH2CH2-、-CH2OCH2-、-C(CH3)2-、-COO-、-COOCH2-、-N＝C-、-COON(CH3)-、-ON(CH3)2-C＝C-C＝、-OCOOCH2-、-O-COO-、-CO-CH＝CH-、
-N＝N-、-OCH2CH2-or the amide is linked to a substituted structure wherein H on N of the amide is replaced by an alkyl or a metal cation;
any H on any one of said cyclopropyl, aryl, cyclopentyl, cyclohexyl, or polycyclic rings can be independently substituted with said third substituent comprising a halogen atom, methyl, ethyl, -COCH3、＝O、＝S、-COOCH3Methoxy, trifluoromethyl, nitro, nitrate, -SO2N(CH2CH2CH3)2-CN or
And all hydrogens H on the nitrogen atom N are substituted with said third substituent.
Further, E0、E1、E2、E3、E4、E5、E6Independently selected from the group consisting of none, carbonyl-CO-, -CH2-, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, sec-heptyl, n-octyl, isooctyl, sec-octyl, n-nonyl, isononyl, sec-nonyl, n-decyl, isodecyl, sec-decyl, ethenyl, propenyl, butenyl, ethynyl, propynyl, undecyl, -OCH2-、-OCH2CH2-、-CH2OCH2-、CH2SCH2-、CH2SSCH2-、CH2SCH2CH2-、CH2SSCH2CH2-、-SCH2CH2-、-SSCH2CH2-、-CH2CO-、-CH2CH2CO-、-CH(CH3)CO-、-CH(CH3)-、-CH＝CHCH(CH3)-、-N＝C(CH3)-、-C(CH3)2-、-CH(CH2Cl)-、-CH(OCH3)-、-CH2CH(CH3)-、-OCH2CH＝、-CH(CHO)-、-CH2C(CH3)2-、-C(CH3)2CH2CH2-、-N＝C(CF3)-、-CH(CH3)CH2CH2-、-CH(CH3)CH2CH2CH2-、-COCH2N＝、-CH＝CH-CO-、-CH2CH(CH3)-、-C(CF3)2-、-CH(CF3)-、-CH2C(CH3)2-、-CH2CH(Et)-、-CH2CH2CH(CH3)-、-C(CH3)2CH2CH2-、-CH(CH2CH3)-、-CH(CH2CH2CH3)-、-OCH2CH2CH2CO-、-COOCH2CH2-、
Phenyl, phenyl,
E7、E9、E10And E11Independently selected from,
E8Selected from among,
-COCH2CH2-、-COOCH2-、
And
E12is selected from
Or
In the above-mentioned E0～E6In the formula, n is any integer of 0-10; in the above-mentioned E0～E11Wherein each ring may be independently attached to a substituent group which is null, -CH3Ethyl, propyl, halogen atoms, nitro, ethylene or methoxy, R10is-CH3Ethyl, propyl, nitro, ethylene or cyclo.
Further, for formula I as described in E), it includes any one of the following structures:
for formula I as described in F), it includes any one of the following structures:
in E) and F), Q1-Q6Independently is-SBF3M，Z0-Z25Independently is H or a fourth substituent,
each of the radicals and Z0-Z25Any H on the attached atoms may be independently substituted with H or a fourth substituent; the fourth substituent is selected from O, methyl, ethyl, halogen atom, CH2Methoxy, aldehyde group,
Vinyl, -SCH2CH3Or ═ CHCH2CH3(ii) a In E), Z0-Z25And can also independently be:
the ring structure of the fourth substituent may be bonded to a methyl group, an ethyl group, a halogen group, a nitro group, an ═ O group, a methoxy group, a cyano group, a hydroxy groups, a hydroxy group, a hydroxy groups, and the like,
And the like; r9Is an alkyl group.
Further, the general formula I is boron trifluoride salt obtained by replacing all or part of H on all C in any one general formula I by halogen, preferably by F;
and/or said formula I is a boron trifluoride salt in any one of the formulae I as claimed in any of claims 1 to 8, in which all or part of the oxygen atoms are independently replaced by sulfur atoms.
Further, M of the general formula I includes Na+、K+、Li+、Mg2+Or Ca2+Preferably Na+、K+Or Li+。
The present application also provides a method of preparing a multi-sulfur-based boron trifluoride salt electrolyte as described in any of the above paragraphs by reacting a multi-structure containing a plurality of-SH groups, a boron trifluoride-based compound, and a source of M to obtain a product containing a plurality of-SBFs3The boron trifluoride salt structure of M.
The present application also provides a use of a multi-sulfur-based boron trifluoride salt electrolyte as described in any of the above paragraphs in a secondary battery cell, the use comprising: the multi-sulfur-based boron trifluoride salts can be used both as salts and as additives;
preferably, the applications include applications in liquid electrolytes, gel electrolytes, mixed solid-liquid electrolytes, quasi-solid electrolytes, all-solid electrolytes, each independently including a multi-sulfur-based boron trifluoride salt electrolyte as described in any of the above paragraphs;
preferably, the application also includes application as a battery or battery pack, the battery comprising a multi-sulfur-based boron trifluoride salt electrolyte as described in any of the above paragraphs, and a positive electrode, a negative electrode, and a package housing; the liquid electrolyte, the gel electrolyte, the mixed solid-liquid electrolyte, the quasi-solid electrolyte and the all-solid electrolyte can be applied to liquid batteries, mixed solid-liquid batteries, semi-solid batteries, gel batteries, quasi-solid batteries and all-solid batteries, and the battery pack comprises the batteries.
The technical effects of this application do:
the electrolyte provided by the application creatively combines a plurality of SBFs3M is combined in a structure to form a structure containing multiple-SBFs3A sulfur-based boron trifluoride salt of the structure M,the structure effect protected by the invention is more prominent.
1. The sulfur-based boron trifluoride salt can be used as an additive in a battery, can form a stable and compact passivation film on the surface of an electrode of the battery, prevents direct contact between an electrolyte and an electrode active substance, inhibits decomposition of each component of the electrolyte, widens the electrochemical window of the whole electrolyte system, and can remarkably improve the discharge specific capacity, the coulombic efficiency and the cycle performance of the battery; in addition, the sulfur-based boron trifluoride is an ion conductor, and as an additive, the sulfur-based boron trifluoride is capable of forming a passivation layer on the surface of an electrode and simultaneously consuming less active ions coming out of the positive electrode, so that the first coulombic efficiency and the first cycle discharge specific capacity of the battery can be obviously improved. And when the electrolyte containing the sulfenyl boron trifluoride salt, the conventional high-voltage high-specific-volume positive electrode material and the conventional low-voltage high-specific-volume negative electrode material are compounded into a battery, the electrochemical performance of the battery is improved. In addition, the structure of the application can be mixed with conventional additives for use, namely, a double additive or a multi-additive, and the battery using the double additive or the multi-additive shows more excellent electrochemical performance.
In addition, when the structure in the application is used in an electrolyte, the structure can act synergistically as an additive property and a main salt property, so that the electrolyte has an excellent effect superior to that of a traditional additive/main salt, for example, when the structure is used as an additive or a main salt, a stable passivation layer can be formed on the surface of an electrode in the battery cycling process, and components with narrow electrochemical window (such as PEO or other components and the like) are prevented from being further decomposed by the electrode, so that the electrochemical window of the whole electrolyte system is widened, and the structure also has good ion transmission performance, so that the battery has more excellent long-cycle stability and comprehensive effect.
2. The boron trifluoride salt has the advantages of rich raw material source, wide raw material selectivity, low cost, simple preparation process, simple reaction, mild conditions and excellent industrial application prospect.
3. The method can also adopt metals such as sodium and potassium except traditional lithium to form salts, so that more possibilities are provided for later application, cost control or raw material selection, and the like, and the method has great significance.
Therefore, the electrolyte provided by the application can be applied to liquid batteries, mixed solid-liquid batteries, semi-solid batteries, gel batteries, quasi-solid batteries and all-solid batteries, can improve the electrochemical performance of the batteries, including improving the energy density of the batteries, improving the cycle stability and prolonging the service life of the batteries, and has the advantages of simple synthesis process, low raw material price and good economic benefit.
Drawings
FIGS. 1 to 2 are nuclear magnetic hydrogen spectra of products shown in examples 1 to 2 of the present application; FIGS. 3 to 4 are nuclear magnetic hydrogen spectra of the products of examples 6 to 7 of the present application; FIG. 5 is a nuclear magnetic hydrogen spectrum of the product shown in example 10 of the present application; FIGS. 6 to 10 are nuclear magnetic hydrogen spectra of products shown in examples 12 to 16 of the present application; FIG. 11 is a nuclear magnetic hydrogen spectrum of a product shown in example 19 of the present application; FIGS. 12 to 13 are nuclear magnetic hydrogen spectra of products shown in examples 26 to 27 of the present application; FIG. 14 is a nuclear magnetic hydrogen spectrum of a product shown in example 32 of the present application; FIG. 15 is a nuclear magnetic hydrogen spectrum of a product shown in example 36 of the present application; FIG. 16 is a nuclear magnetic hydrogen spectrum of a product shown in example 40 of the present application; FIG. 17 is a nuclear magnetic hydrogen spectrum of a product shown in example 45 of the present application;
FIGS. 18-21 are graphs comparing the performance of battery 7/14/26/45 made with example 7/14/26/45 as an electrolyte additive to a corresponding comparative battery 7/14/26/45 that did not contain example 7/14/26/45 of the present invention;
FIGS. 22-23 are graphs comparing the effect of cell 2/12 made in accordance with example 2/12 as a liquid electrolyte salt with a corresponding comparative cell 2/12 that did not contain example 2/12 in accordance with the present invention;
fig. 24 is a graph comparing the effect of example 39 made as a battery 39 made with salt in solid electrolyte with a comparative battery 2 made with LiTFSI as the salt.
Detailed Description
The following description of specific embodiments of the present application refers to the accompanying drawings.
In the present invention, unless otherwise specified, scientific and technical terms used herein have the meanings that are commonly understood by those skilled in the art. Also, the reagents, materials and procedures used herein are those that are widely used in the corresponding fields. Meanwhile, in order to better understand the present invention, the following provides definitions and explanations of related terms.
In the present invention, if a group is desired to be attached to a two-part structure, it has two linkages to be attached, and if it is not specified which two atoms are attached to the attached part, any one of the atoms containing H may be attached.
In the context of the present invention, a chemical bond is not drawn on an atom, but on a position where it intersects the bond, e.g. on the surface of a metal
Represents that any H on cyclohexane can be substituted by a substituent R04And two or more H can be replaced by one H, and the substituents can be same or different. If a certain C of cyclohexane contains two H, the two H may be substituted by all substituents or only 1, for example both H may be substituted by methyl, or one may be substituted by methyl and one by ethyl. In addition, substituents may also be attached to the ring via a double bond. For example, in this structure, if R04Is methyl, ═ O, F, the structure can be
Or
In the structural formulae of the present invention, when a group in the parentheses "()" is contained after a certain atom, it means that the group in the parentheses is connected to the atom before it. Such as-C (CH)3)2-is of
-CH(CH3) -is of
In the title and description of the invention, -SBF3M in M may be a monovalent, divalent, trivalent or polyvalent metal cation, if it is a non-monovalent ion, then-SBF3The number of (c) is increased correspondingly so that it exactly matches the valence of M.
The "boron trifluoride-based compound" refers to boron trifluoride, a compound containing boron trifluoride, a boron trifluoride complex or the like. The "Et" is ethyl and the "Ph" is phenyl.
The invention provides a polybasic organic boron trifluoride salt which can be used as an electrolyte additive and an electrolyte salt, namely, the organic matter contains a plurality of-SBFs3M is a group in which M is Li+Or Na+And the like. The multi-element boron trifluoride salt can be applied to liquid batteries, mixed solid-liquid batteries, semi-solid batteries, gel batteries, quasi-solid batteries and all-solid batteries. The preparation method of the compound is simple and ingenious, and the yield is high. Namely, the boron trifluoride compound is obtained by reacting a raw material, a boron trifluoride compound and an M source, specifically, -SH in the raw material participates in the reaction, and other structures do not participate in the reaction. The specific preparation method mainly comprises two methods:
adding an M source and a raw material into a solvent under the atmosphere of nitrogen/argon, mixing, reacting at 5-60 ℃ for 5-24 hours, and drying the obtained mixed solution under reduced pressure at 20-80 ℃ and the vacuum degree of about-0.1 MPa to remove the solvent to obtain an intermediate; adding boron trifluoride compounds, stirring and reacting at 5-60 ℃ for 6-24 hours, drying the obtained mixed solution under reduced pressure at 20-80 ℃ and under the vacuum degree of about-0.1 MPa to obtain a crude product, washing, filtering and drying the crude product to obtain a final product, namely the polynary boron trifluoride organic salt, wherein the yield is 74-95%.
Secondly, under the atmosphere of nitrogen/argon, adding the raw materials and boron trifluoride compounds into a solvent, uniformly mixing, reacting for 6-24 hours at the temperature of 5-60 ℃, decompressing and drying the obtained mixed solution at the temperature of 20-80 ℃ and the vacuum degree of about-0.1 MPa to remove the solvent, and reacting to obtain an intermediate; adding an M source into a solvent, adding the solvent containing the M source into the intermediate, stirring at 5-60 ℃ for reaction for 5-24 hours to obtain a crude product, directly washing the crude product or washing the crude product after drying under reduced pressure, and then filtering and drying to obtain a final product, namely the polynary boron trifluoride organic salt, wherein the yield is 74-95%.
In the above two specific preparation methods, the boron trifluoride compounds may include boron trifluoride diethyl etherate complex, boron trifluoride tetrahydrofuran complex, boron trifluoride dibutyl etherate complex, boron trifluoride acetic acid complex, boron trifluoride monoethyl amine complex, boron trifluoride phosphoric acid complex, and the like. M sources include lithium/sodium metal tablets, lithium/sodium methoxide, lithium/sodium hydroxide, lithium/sodium ethoxide, butyl lithium/sodium, lithium/sodium acetate, and the like. The solvent is independently alcohol (some liquid alcohol can be used as solvent), ethyl acetate, DMF, acetone, hexane, dichloromethane, tetrahydrofuran, ethylene glycol dimethyl ether, etc. The washing may be carried out with diethyl ether, n-butyl ether, cyclohexane, diphenyl ether, etc.
Example 1
Starting materials
Wherein Q represents
The preparation method comprises the following steps: 0.01mol of the starting material and boron trifluoride tetrahydrofuran complex (5.6g, 0.04mol) were mixed uniformly in 15ml of ethylene glycol dimethyl ether in a nitrogen atmosphere, and reacted at room temperature for 12 hours. The obtained mixed solution is decompressed and dried at 40 ℃ and under the vacuum degree of about-0.1 MPa to remove the solvent, and an intermediate is obtained. Lithium ethoxide (2.08g, 0.04mol) is dissolved in 10ml of ethanol and slowly added into the intermediate, the mixture is stirred and reacted for 8 hours at 45 ℃, the obtained mixed solution is dried under reduced pressure at 45 ℃ and the vacuum degree of about-0.1 MPa, the obtained solid is washed with n-butyl ether for three times, and the product M1 is obtained after filtration and drying, the yield is 94%, and nuclear magnetism is shown in figure 1.
Example 2
Raw materials
Wherein Q represents
The preparation method comprises the following steps: 0.01mol of the starting material and boron trifluoride diethyl etherate (5.68g, 0.04mol) were mixed uniformly in 15ml of THF (tetrahydrofuran) under an argon atmosphere, and reacted at room temperature for 12 hours. The obtained mixed solution is decompressed and dried at 30 ℃ and the vacuum degree of about-0.1 MPa to remove the solvent, and an intermediate is obtained. 25ml of butyllithium in hexane (c 1.6mol/L) was added to the intermediate, the reaction was stirred at room temperature for 6 hours, the resulting mixture was dried under reduced pressure at 40 ℃ under a vacuum of about-0.1 MPa, and the resulting crude product was washed with cyclohexane 3 times, filtered and dried to obtain a product M2 with a yield of 90%, and nuclear magnetic resonance was as shown in FIG. 2.
Example 3
Raw materials
Wherein Q represents
The preparation method comprises the following steps: 0.01mol of the starting material and lithium methoxide (1.52g,0.04mol) were mixed uniformly with 20ml of methanol under a nitrogen atmosphere and reacted at room temperature for 8 hours. The obtained mixed solution is decompressed and dried at 40 ℃ and under the vacuum degree of about-0.1 MPa to remove the solvent, and an intermediate is obtained. Boron trifluoride tetrahydrofuran complex (5.58g, 0.04mol) and 15ml THF (tetrahydrofuran) were added to the intermediate, the reaction was stirred at room temperature for 16 hours, the resulting mixture was dried under reduced pressure at 40 ℃ under a vacuum degree of about-0.1 MPa, and the resulting solid was washed three times with isopropyl ether, filtered, and dried to give product M3 in 87% yield.
Example 4
Raw materials
Wherein Q represents
The preparation method comprises the following steps: in a glove box, 0.01mol of the starting material and boron trifluoride diethyl etherate (5.96g, 0.042mol) were mixed uniformly in 15ml of ethylene glycol dimethyl ether, and reacted at room temperature for 12 hours. And drying the obtained mixed solution under reduced pressure at room temperature and under the vacuum degree of about-0.1 MPa to remove the solvent to obtain an intermediate. Dissolving lithium ethoxide (2.08g, 0.04mol) in 10ml ethanol, adding the mixture into the intermediate, stirring at room temperature for reaction for 12 hours, drying the obtained mixed solution under reduced pressure at 40 ℃ and under the vacuum degree of-0.1 MPa, washing the obtained solid with isopropyl ether three times, filtering and drying to obtain a product M4, wherein the yield is 82%.
Example 5
Raw materials
Wherein Q represents
The preparation method comprises the following steps: 0.01mol of the starting material and boron trifluoride acetic acid complex (9.40g, 0.05mol) were mixed uniformly in 15ml of THF (tetrahydrofuran) under an argon atmosphere, reacted at room temperature for 12 hours, and the resulting mixed solution was dried under reduced pressure at 40 ℃ and a vacuum degree of about-0.1 MPa to remove the solvent, to obtain an intermediate. Lithium acetate (3.30g, 0.05mol) was dissolved in 10ml of N, N-dimethylformamide and added to the intermediate, and the reaction was stirred at 50 ℃ for 8 hours, and the resulting mixture was dried under reduced pressure at 80 ℃ under a vacuum degree of about-0.1 MPa, and the resulting solid was washed three times with diphenyl ether, filtered, and dried to give a product M5 with a yield of 84%.
Example 6
Raw materials
Wherein Q represents
The preparation method comprises the following steps: 0.01mol of the starting material and lithium hydroxide (1.20g, 0.05mol) were mixed uniformly with 10ml of a methanol solution under a nitrogen atmosphere, and reacted at room temperature for 8 hours. The obtained mixed solution is decompressed and dried at 40 ℃ and under the vacuum degree of about-0.1 MPa to remove the solvent, and an intermediate is obtained. Boron trifluoride phosphate complex (8.29g, 0.05mol) and 15ml THF are added into the intermediate, the mixture is stirred and reacted for 6 hours at 45 ℃, the obtained mixed solution is decompressed and dried at 60 ℃ and the vacuum degree of about-0.1 MPa, and the obtained crude product is filtered and dried by dichloromethane to obtain a product M6. The yield was 83%, and the nuclear magnetization is shown in FIG. 3.
Example 7
Raw materials
Wherein Q represents
The preparation method comprises the following steps: in an argon atmosphere, lithium methoxide (2.28g, 0.06mol) was dissolved in 15ml of methanol, and after uniform mixing, the mixture was added to the raw material (0.01mol) and uniformly mixed, and reacted at 45 ℃ for 12 hours, and the resulting mixed solution was dried under reduced pressure at 45 ℃ and a vacuum degree of about-0.1 MPa to remove the solvent, thereby obtaining an intermediate. Boron trifluoride diethyl etherate (8.94g, 0.063mol) and 15ml THF were added to the intermediate, stirred at room temperature for 24 hours, the resulting mixture was dried under reduced pressure at 40 ℃ under a vacuum degree of about-0.1 MPa, and the resulting solid was washed three times with methylene chloride, filtered and dried to obtain a product M7. The yield was 91%, and the nuclear magnetization is shown in FIG. 4.
Example 8
Raw materials
Wherein Q represents
The preparation method comprises the following steps: under a nitrogen atmosphere, the raw material (0.01mol) and lithium hydroxide (1.44g, 0.06mol) were mixed uniformly with 10ml of a methanol solution and reacted at 10 ℃ for 8 hours. The obtained mixed solution is decompressed and dried at 40 ℃ and under the vacuum degree of about-0.1 MPa to remove the solvent, and an intermediate is obtained. Boron trifluoride diethyl etherate (8.94g, 0.063mol) is added into the intermediate, 10ml of ethylene glycol dimethyl ether solvent is added, stirring is carried out for 24 hours at room temperature, the obtained mixed solution is decompressed and dried under the conditions of 40 ℃ and vacuum degree of about-0.1 MPa, the obtained solid is washed three times by dichloromethane, and the product M8 is obtained after filtration and drying. The yield was 90%.
Example 9
Raw materials
Wherein Q represents
The preparation method comprises the following steps: under a nitrogen atmosphere, the raw materials (0.01mol) and sodium hydroxide (1.60g, 0.04mol) were mixed uniformly with 10ml of a methanol solution and reacted at 10 ℃ for 8 hours. The obtained mixed solution is decompressed and dried at 40 ℃ and under the vacuum degree of about-0.1 MPa to remove the solvent, and an intermediate is obtained. Boron trifluoride diethyl etherate (5.96g, 0.042mol) is added into the intermediate, 10ml of ethylene glycol dimethyl ether solvent is added, the mixture is stirred for 24 hours at room temperature, the obtained mixed solution is decompressed and dried at 40 ℃ and the vacuum degree of about-0.1 MPa, the obtained solid is washed three times by dichloromethane, and the product M9 is obtained after filtration and drying, and the yield is 85%.
Example 10
Starting materials
Wherein Q represents
The preparation method comprises the following steps: the product M10 was prepared from the starting material by the method of example 4. Yield 85% and nuclear magnetization are shown in figure 5.
Example 11
Starting materials
Wherein Q represents
The preparation method comprises the following steps: the product M11 was prepared from the starting material by the method of example 3. The yield was 86%.
Example 12
Raw materials
Wherein Q represents
The preparation method comprises the following steps: the product M12 was prepared from the starting material by the method of example 2. Yield 92% and nuclear magnetization are shown in figure 6.
Example 13
Raw materials
Wherein Q represents
The preparation method comprises the following steps: the product M13 was prepared from the starting material by the method of example 1. Yield 90% and nuclear magnetization are shown in figure 7.
Example 14
Raw materials
Wherein Q represents
The preparation method comprises the following steps: the product M14 was prepared from the starting material by the method of example 3. Yield 83%, nuclear magnetization is shown in fig. 8.
Example 15
Raw materials
Wherein Q represents
The preparation method comprises the following steps: the product M15 was prepared from the starting material by the method of example 4. Yield 82%, nmr is shown in figure 9.
Example 16
Raw materials
Wherein Q represents
The preparation method comprises the following steps: the product M16 was prepared from the starting material by the method of example 2. Yield 85%, nuclear magnetization is shown in fig. 10.
Example 17
Starting materials
Wherein Q represents
The preparation method comprises the following steps: the product M17 was prepared from the starting material by the method of example 1. The yield was 84%.
Example 18
Raw materials
Wherein Q represents
The preparation method comprises the following steps: the product M18 was prepared from the starting material by the method of example 5. The yield was 85%.
Example 19
Raw materials
Wherein Q represents
The preparation method comprises the following steps: the product M19 was prepared from the starting material by the method of example 4 in 87% yield with nuclear magnetism as shown in figure 11.
Example 20
Raw materials
Wherein Q represents
The preparation method comprises the following steps: the product M20 was prepared from the starting material by the method of example 6 in 83% yield.
Example 21
Starting materials
Wherein Q represents
The preparation method comprises the following steps: the product M21 was prepared from the starting material by the method of example 8 in 82% yield.
Example 22
Raw materials
Wherein Q represents
The preparation method comprises the following steps: the product M22 was prepared from the starting material by the method of example 4 in 90% yield.
Example 23
Raw materials
Wherein Q represents
The preparation method comprises the following steps: the product M23 was prepared from the starting material by the method of example 1 in 87% yield.
Example 24
Raw materials
Wherein Q represents
The preparation method comprises the following steps: the product M24 was prepared from the starting material by the method of example 7 in 85% yield.
Example 25
Raw materials
Wherein Q represents
The preparation method comprises the following steps: the product M25 was prepared from the starting material by the method of example 4 in 83% yield.
Example 26
Starting materials
Wherein Q represents
The preparation method comprises the following steps: the product M26 was prepared from the starting material by the method of example 5 in 84% yield with nuclear magnetization as shown in figure 12.
Example 27
Raw materials
Wherein Q represents
The preparation method comprises the following steps: the product M27 was prepared from the starting material by the method of example 3 in 82% yield with a nuclear magnetism as shown in figure 13.
Example 28
Raw materials
Wherein Q represents
The preparation method comprises the following steps: the product M28 was prepared from the starting material by the method of example 2 in 85% yield.
Example 29
Raw materials
Wherein Q represents
The preparation method comprises the following steps: the product M29 was prepared from the starting material by the method of example 4 in 83% yield.
Example 30
Raw materials
Wherein Q represents
The preparation method comprises the following steps: the product M30 was prepared from the starting material by the method of example 1 in 87% yield.
Example 31
Raw materials
Wherein Q represents
The preparation method comprises the following steps: the product M31 was prepared from the starting material by the method of example 2 in 85% yield.
Example 32
Raw materials
Wherein Q represents
The preparation method comprises the following steps: the product M32 was prepared from the starting material by the method of example 3 in 86% yield with nuclear magnetism as shown in figure 14.
Example 33
Raw materials
Wherein Q represents
The preparation method comprises the following steps: the product M33 was prepared from the starting material by the method of example 1 in 87% yield.
Example 34
Raw materials
Wherein Q represents
The preparation method comprises the following steps: the product M34 was prepared from the starting material by the method of example 4 in 85% yield.
Example 35
Raw materials
Wherein Q represents
The preparation method comprises the following steps: the product M35 was prepared from the starting material by the method of example 2 in 88% yield.
Example 36
Raw materials
Wherein Q represents
The preparation method comprises the following steps: the product M36 was prepared from the starting material by the method of example 3 in 86% yield with nuclear magnetization as shown in figure 15.
Example 37
Raw materials
Wherein Q represents
The preparation method comprises the following steps: the product M37 was prepared from the starting material by the method of example 1 in 85% yield.
Example 38
Starting materials
Wherein Q represents
The preparation method comprises the following steps: the product M38 was prepared from the starting material by the method of example 4 in 84% yield.
Example 39
Raw materials
Wherein Q represents
The preparation method comprises the following steps: the product M39 was prepared from the starting material by the method of example 2 in 86% yield.
Example 40
Raw materials
Wherein Q represents
The preparation method comprises the following steps: the product M40 was prepared from the starting material by the method of example 3 in 89% yield with nuclear magnetization as shown in figure 16.
EXAMPLE 41
Raw materials
Wherein Q represents
The preparation method comprises the following steps: the product M41 was prepared from the starting material by the method of example 4 in 90% yield.
Example 42
Raw materials
Wherein Q represents
The preparation method comprises the following steps: the product M42 was prepared from the starting material by the method of example 8 in 84% yield.
Example 43
Raw materials
Wherein Q represents
The preparation method comprises the following steps: the product M43 was prepared from the starting material by the method of example 7 in 87% yield.
Example 44
Raw materials
Wherein Q represents
The preparation method comprises the following steps: the product M44 was prepared from the starting material by the method of example 5 in 85% yield.
Example 45
Raw materials
Wherein Q represents
The preparation method comprises the following steps: the product M45 was prepared from the starting material by the method of example 6 in 89% yield with nuclear magnetization as shown in figure 17.
Example 46
Raw materials
Wherein Q represents
The preparation method comprises the following steps: the product M46 was prepared from the starting material by the method of example 5 in 84% yield.
Example 47
Raw materials
Wherein Q represents
The preparation method comprises the following steps: the product M47 was prepared from the starting material by the method of example 6 in 82% yield.
Example 48
Raw materials
Wherein Q represents
The preparation method comprises the following steps: the product M48 was prepared from the starting material by the method of example 9 in 85% yield.
Example 49
Raw materials
Wherein Q represents
The preparation method comprises the following steps: the product M49 was prepared from the starting material by the method of example 9 in 87% yield.
Example 50
Raw materials
Wherein Q represents
The preparation method comprises the following steps: the product M50 was prepared from the starting material by the method of example 9 in 84% yield.
Example 51
The multi-sulfur-based boron trifluoride organic salt protected by the invention is mainly used as an additive and a main salt in a battery (including liquid and solid batteries), the additive mainly plays a role in generating a passivation layer, and ions can be dissociated per se to play a role in supplementing consumed ions, so that the first-cycle efficiency, the first-cycle discharge specific capacity, the long-cycle stability and the rate capability of the battery are greatly improved; the salt serving as electrolyte mainly plays a role in providing ion transmission and passivating an electrode, and is matched with the traditional salt to be used as double salt, so that the effect is good. The performance of the present application is described below by way of tests.
As additive in liquid electrolyte
(1) Positive pole piece
Adding the active substance of the main anode material, the electronic conductive additive and the binder into a solvent according to the mass ratio of 95:2:3, wherein the solvent accounts for 65% of the total slurry by mass percent, and uniformly mixing and stirring to obtain anode slurry with certain fluidity; and coating the anode slurry on an aluminum foil, drying, compacting and cutting to obtain the usable anode piece. Lithium cobaltate (LiCoO) is selected as the active material2LCO for short), lithium nickel cobalt manganese oxide (NCM811 for selection), lithium nickel cobalt aluminate (LiNi)0.8Co0.15Al0.05O2Abbreviated NCA) and lithium nickel manganese oxide (LiNi)0.5Mn1.5O4Abbreviated LNMO), Na0.9[Cu0.22Fe0.3Mn0.48]O2(NCFMO for short), Carbon Nanotubes (CNT) and Super P are selected as the electron conductive additive, polyvinylidene fluoride (PVDF) is used as the binder, and N-methylpyrrolidone (NMP) is used as the solvent.
(2) Negative pole piece
Adding a main negative material active substance (except metal Li), an electronic conductive additive and a binder into solvent deionized water according to a ratio of 95:2.5:2.5, wherein the solvent accounts for 42% of the total slurry, and uniformly mixing and stirring to obtain negative slurry with certain fluidity; and coating the negative electrode slurry on copper foil, drying and compacting to obtain the usable negative electrode piece. Graphite (C), silicon oxygen carbon (SiOC450), metal lithium (Li) and Soft Carbon (SC) are selected as the active materials, CNT and Super P are used as the conductive agents, and carboxymethyl cellulose (CMC) and Styrene Butadiene Rubber (SBR) are used as the binders.
The anode and cathode systems selected by the invention are shown in table 1:
TABLE 1 Positive and negative electrode systems
| Positive and negative electrode system of battery | Positive electrode main material | Negative electrode main material |
| A1 | LCO | SiOC450 |
| A2 | NCM811 | SiOC450 |
| A3 | NCM811 | Li |
| A4 | NCA | C |
| A5 | LNMO | C |
| A6 | LCO | Li |
| A7 | NCFMO | SC |
(3) Preparing liquid electrolyte
M1-M50, organic solvent, conventional salt and conventional additives are mixed uniformly to obtain series of liquid electrolytes E1-E50, wherein the organic solvent is methyl ethyl carbonate (EMC), dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethylene Carbonate (EC), carbonAcrylic acid (PC). Conventional additives are fluoroethylene carbonate (FEC), Vinylene Carbonate (VC), trimethyl phosphate (TMP), ethoxypentafluorocyclotriphosphazene (PFPN), vinyl sulfate (DTD); conventional salts are lithium bis (oxalato) borate (LiBOB), lithium difluoro (oxalato) borate (LiODFB), lithium bis (fluorosulfonylimide) (LiFSI), lithium hexafluorophosphate (LiPF)6) Lithium bis (trifluoromethyl) sulfonimide (LiTFSI), lithium perchlorate (LiClO)4) Lithium tetrafluoroborate (LiBF)4) Sodium hexafluorophosphate (NaPF)6). The specific components and ratios are shown in table 2.
TABLE 2 liquid electrolytes E1 to E50 formulated with M1 to M50 as additives
Note: 1M means 1 mol/L.
Comparison sample: and (3) replacing M1-M50 with blanks according to the proportion of E1-E50 (namely, not adding M1-M50), thus obtaining corresponding conventional liquid electrolyte comparison samples L1-L50.
(4) Button cell assembly
The liquid electrolyte series E1-E50 containing the structure of the embodiment as an additive and the conventional liquid electrolytes L1-L50 are assembled into a button cell in a comparative way, and the details are as follows: negative electrode shell, negative electrode pole piece, PE/Al2O3A button cell is assembled by a diaphragm, an electrolyte, a positive pole piece, a stainless steel sheet, a spring piece and a positive shell, and a long circulation test is carried out at room temperature, wherein the circulation modes are 0.1C/0.1C 1 week, 0.2C/0.2C 5 week and 1C/1C 44 week (C represents multiplying power), the positive pole piece is a circular sheet with the diameter of 12mm, the negative pole piece is a circular sheet with the diameter of 14mm, the diaphragm is a circular sheet with the diameter of 16.2mm, and is a commercial Al circular sheet2O3a/PE porous separator.
The battery systems prepared from E1 to E50 were batteries 1 to 50, respectively, and the battery systems prepared from L1 to L50 were comparative batteries 1 to 50, respectively. Specific configurations and voltage ranges of the batteries are shown in table 3, and results of specific discharge capacity at first cycle, first cycle efficiency and capacity retention rate at cycle 50 cycle of the batteries 1 to 50 and comparative batteries 1 to 50 at room temperature are shown in table 4.
TABLE 3 arrangement and test mode for batteries 1-50 and comparative batteries 1-50
TABLE 4 comparison of test results between batteries 1-50 and comparative batteries 1-50
From the test results of the battery and the comparative battery, in the button battery, when the positive and negative electrode systems are the same, the first-cycle efficiency, the specific discharge capacity and the capacity retention rate of the battery using the structure M1-M50 as the liquid electrolyte additive are much better than those of the battery without the additive, and the performance of the battery is superior to that of the conventional additive at present. In addition, the use of the boron salt-containing additive of the present invention shows a synergistic effect in the presence of conventional additives, and the battery shows more excellent cycle performance.
Secondly, as a salt in a liquid electrolyte
(1) Preparing liquid electrolyte
M2, M6, M10, M12, M19, M27, M32, M36, M39, M45, organic solvent, conventional additive and conventional salt are mixed uniformly to obtain a series of liquid electrolytes R2, R6, R10, R12, R19, R27, R32, R36, R39 and R45, and conventional salt, organic solvent and conventional additive are mixed uniformly to obtain a series of conventional liquid electrolytes Q2, Q6, Q10, Q12, Q19, Q27, Q32, Q36, Q39 and Q45, and the used solvent and functional additive all comprise the solvent and functional additive described in the "one" of the present examples. The specific components and ratios of the liquid electrolyte are shown in table 5.
Table 5 synthesis of liquid electrolytes formulated with boron containing organics as salts
(2) Battery assembly
The obtained series of liquid electrolytes R (shown in table 5) and the conventional liquid electrolyte Q (shown in table 5) were assembled into a button cell, and the positive and negative electrodes, the size of the separator, the assembly method, and the cycling manner of the cell were the same as those of the button cell shown in "one" of this example, i.e., cells 2, 6, 10, 12, 19, 27, 32, 36, 39, 45 and the corresponding comparative cells, respectively. Specific configurations, cycling modes and voltage ranges of the batteries are shown in table 6, and specific first-cycle discharge capacity, first-cycle efficiency and 50-cycle capacity retention rate results of the batteries and comparative batteries at room temperature are shown in table 7.
Table 6 arrangement and test mode of example and comparative example cells
Table 7 comparison of test results for example and comparative batteries shown in table 6
In conclusion, the boron-containing salt provided by the invention is independently used as a salt or forms a double salt with a conventional salt in a non-aqueous solvent, ions are easily solvated, higher ionic conductivity is provided for a battery, the stability is high, and the comprehensive performance is excellent.
Thirdly, as a salt in a solid electrolyte
(1) Preparation of Polymer electrolyte Membrane
In an environment with a dew point lower than minus 60 ℃, salt, polymer and inorganic filler are blended, melt extruded and pressed into a film according to the proportion to obtain polymer electrolyte membranes G7, G12, G27, G32, G39 and G45 and polymer comparison electrolyte membranes G '1-G' 2. The specific components and ratios are shown in Table 8. Wherein the polymer is polyethylene oxide (PEO, molecular weight is 100 ten thousand), the inorganic filler is LLZO of 160nm, i.e. crystal form of Li with median particle diameter of 160nm as cubic phase7La3Zr2O12An inorganic oxide solid electrolyte.
TABLE 8 concrete composition and compounding ratio of Polymer electrolyte Membrane
| Polymer electrolyte membrane | Polymer and method of making same | Salt (salt) | Inorganic filler | The former mass ratio |
| G7 | PEO100 ten thousand | M7 | 160nmLLZO | 4.2：1：0.8 |
| G12 | PEO100 ten thousand | M12 | / | 4.2：1 |
| G27 | PEO100 ten thousand | M27 | / | 4.2：1 |
| G32 | PEO100 ten thousand | M32 | 160nmLLZO | 4.2：1：0.8 |
| G39 | PEO100 ten thousand | M39 | / | 4.2：1 |
| G45 | PEO100 ten thousand | M45 | / | 4.2：1 |
| G’1 | PEO100 ten thousand | LiTFSI | 160nmLLZO | 4.2：1：0.8 |
| G’2 | PEO100 ten thousand | LiTFSI | / | 4.2：1 |
(2) Preparation of positive and negative pole pieces
In an environment with a dew point lower than-60 ℃, mixing a positive electrode main material active substance, a polymer + salt (the proportion is the same as that of a polymer electrolyte membrane), an electronic conductive additive and a binder according to a mass ratio of 91.3: 4.8: 2.1: 1.8, obtaining the all-solid-state positive pole piece by blending, melt extrusion and compression molding on an aluminum foil. Lithium cobaltate (LiCoO) is selected as the active material2LCO for short), nickel cobalt lithium manganate (NCM811 for choice), Super P for the electron conductive additive, and polyvinylidene fluoride (PVDF) for the binder.
And pressing metal lithium sheets with the thickness of 50 mu m on two sides of the copper foil to be used as negative pole pieces.
(3) Battery assembly and testing
And (3) cutting the polymer electrolyte membrane and the positive and negative pole pieces, assembling into a 1Ah all-solid-state soft package battery, and carrying out 50-DEG C long cycle test on the battery in a cycle mode of 0.1C/0.1C 2 cycle and 0.3/0.3C 48 cycle. Specific assembly systems and test methods of the batteries are shown in table 9, and test results are shown in table 10.
Table 9 configuration and test mode for example and comparative batteries
TABLE 10 comparison of test results for cells and comparative cells in TABLE 9
From the data in tables 9 and 10, it can be seen that the batteries prepared by the present application M7, M12, M27, M32, M39, M45 have excellent long-cycle stability and the performance is superior to that of the battery corresponding to LiTFSI. Probably because the boron trifluoride salt has excellent ion transmission performance, a layer of more compact and stable passivation layer can be formed on the surface of the positive electrode, and the catalytic decomposition of the positive electrode active material on each component of electrolyte is prevented, and in addition, the boron trifluoride salt does not corrode a current collector, so that the electrochemical performance of the boron trifluoride salt is superior to that of the traditional salt.
In addition, the attached figure part selects a plurality of polybasic sulfur-based boron trifluoride salts as additives, and a battery test effect graph of the salts is used as an illustration. FIGS. 18-21 are graphs comparing the performance of cell 7/14/26/45 made in accordance with example 7/14/26/45 as a liquid electrolyte additive to a corresponding comparative cell 7/14/26/45 that did not contain example 7/14/26/45 of the present invention. FIGS. 22-23 are graphs comparing the performance of cell 2/12 made in accordance with example 2/12 as a liquid electrolyte salt with a corresponding comparative cell 2/12 that did not contain example 2/12 of the present invention. Fig. 24 is a graph comparing the effect of example 39 made as a battery 39 made with salt in solid electrolyte with a comparative battery 2 made with LiTFSI as the salt. From fig. 18 to 24, it can be seen that the structure of the present invention has excellent effects.
In summary, the first cycle efficiency, specific discharge capacity, capacity retention rate, and other properties have a direct and significant impact on the overall performance of the battery, which directly determines whether the battery can be used. Therefore, it is the goal or direction of many researchers in this field to improve these properties, but in this field, the improvement of these properties is very difficult, and generally about 3-5% improvement is a great progress. In the previous experimental data, the data are surprisingly found to be greatly improved compared with the conventional data, particularly the performance of the liquid electrolyte additive is improved by about 5-30%, and the additive and the conventional additive in the application also show better effect. The examples section shows only additives as liquid electrolytes, while the multi-sulfur-based boron trifluoride salts in the present application are also additives as solid electrolytes, and also show excellent electrochemical properties, which are not necessarily shown here for reasons of space. Further, the structure in the present application can be applied to a solid electrolyte for use as a main salt, and exhibits excellent effects. More importantly, the structural type of the application is greatly different from the conventional structure, a new direction and thought are provided for the research and development in the field, a large space is brought for further research, and the application can be used for multiple purposes and has great significance.
Example 52
1. As liquid electrolyte additive
For further study and understanding of the structural properties in the present application, the applicant evaluated the effect of the following 2 structures as liquid electrolyte additives on the long cycle performance of the battery at room temperature. The structures of examples 19 and 32 (i.e., M19 and M32) were selected for the structure of the present application, and the following 2 comparative example structures were structures W1 and W2, respectively.
(1) Liquid electrolyte preparation
The D0 group in the table above was used as a control without any additives.
(2) Button cell configuration
The obtained liquid electrolytes D0 to D2, D19 and D32 were assembled into a button cell, and the positive and negative electrodes, the size of the separator, the arrangement method, and the battery cycle were the same as those of the button cell shown in example 51, i.e., batteries Y0 to Y2, Y19, and Y32, respectively. The specific configuration, cycling profile and voltage range of the cell are shown in table 12 and the test results are shown in table 13.
Configuration and test mode of watch 12 button cell
TABLE 13 test results for batteries
| Battery with a battery cell | Specific capacity of first cycle discharge (mAh/g) | First week efficiency (%) | Capacity retention (%) at 50 weeks of circulation |
| Y0 | 141.3 | 75.4 | 77.4 |
| Y1 | 157.1 | 80.5 | 84.2 |
| Y2 | 156.5 | 80.2 | 83.6 |
| Y19 | 172.0 | 84.0 | 89.7 |
| Y32 | 172.1 | 83.9 | 89.8 |
The test results of the batteries Y0-Y2, Y19 and Y32 show that the batteries W1-W2, M19 and M32 as liquid electrolyte additives can improve the first efficiency, the specific discharge capacity of 1-50 weeks and the capacity retention rate of the batteries. However, compared with W1-W2, the first effect and the first peripheral discharge specific capacity of the battery are improved more obviously by M19 and M32. The reason for this is probably that W1 and W2 are non-salt complexes, which are greatly different from the structure of the present application and do not contain-SBF3When Li, as an additive, accounts for 1% by mass of the salt, a good passivation layer cannot be formed in the positive and negative electrodes. And contains a plurality of-SBFs3The Li M19 and M32 contain lithium sources, and lithium ions coming out from the positive electrode are less consumed in the process of forming a good passivation layer, so that the first efficiency, the first-cycle discharge specific capacity and the capacity retention rate of the battery are improved.
That is, the boron trifluoride organic salt in the present application can be used as both additive and salt in the electrolyte, such as M19 and M32, and the dual application of the boron trifluoride organic salt in the electrolyte can play a synergistic role, so that the effect is better than that of other components. The applicant is still in further research with a clearer and more clear mechanism. However, in any case, it is certain that the SBF is3The presence and amount of M has a substantial effect on battery performance.
In summary, in the present invention, the structures in examples 1 to 50 were selected as representative to explain the production method and effects of the present application. Other structures not specifiedCan be produced by the method described in any one of examples 1 to 9. The preparation method is that the raw material, boron trifluoride compounds and M source react to obtain the product boron trifluoride organic salt, namely-SH in the raw material is changed into-SBF3M, M may be Li+、Na+Etc., and the other structures are not changed. In addition, many structures have been tested in series, and the results are similar to those of the above embodiments, but only some of the structures are described in space.
In the present invention, only a part of the structures are selected as representative examples to explain the production method, effects, and the like of the present application, and other structures not listed have similar effects. For example:
The raw materials used in the examples can be purchased or simply prepared, and the preparation processes are also prior art, so the detailed description is not provided in the specification.
It should be noted that, the applicant has performed a great number of tests on the series of structures, and sometimes, for better comparison with the existing system, there are cases where the same structure and system are tested more than once, and therefore, there may be some error in the tests performed at different times.
Finally, it should be noted that: the above-mentioned embodiments are only used for illustrating the technical solution of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (22)
1. A multi-sulfur-based boron trifluoride salt electrolyte, characterized by: the multi-sulfur-based boron trifluoride salt electrolyte includes a boron trifluoride salt represented by the following general formula I:
in the above formula I, Q1represents-SBF3M, M is a metal cation; r, R1、R2、R3、R4、R5Independently is nothing, a first ring or a first chain containing at least one atom, and R, R1～R5Not both can be H or none;
R、R1、R2、R3、R4、R5to any one, two or more atoms of which 3 to 7-SBFs are attached3M, and each-SBF3Each M may independently be linked by E ', E and E' are independently absent, a second ring, or a second chain containing at least one atom;
R、R1、R2、R3、R4、R5and R6May be independently attached with a first substituent;
the first and second rings may be independently a carbocyclic ring consisting of only C atoms or a heterocyclic ring containing at least one heteroatom;
the first and second chains may independently be carbon chains consisting of only C atoms or hetero chains containing at least one heteroatom, the first and second chains independently comprising saturated chains and chains containing unsaturated bonds comprising double and/or triple bonds.
2. The multi-sulfur based boron trifluoride salt electrolyte of claim 1, wherein: in the general formula I, the compound has the following structure,
the heteroatom comprises S, N, O, P, Se, Ca, Al, B or Si;
the first ring and the second ring can be any one of three-membered to twenty-membered rings independently, and the rings include saturated carbocycle, saturated heterocycle, unsaturated carbocycle, unsaturated heterocycle or aromatic ring;
the first and second chains may independently be chains of 1 to 30 atoms.
3. The multi-sulfur based boron trifluoride salt electrolyte of claim 1, wherein: the heteroatoms include ring-located heteroatoms including P, S, Si, N or O and chain-located heteroatoms including S, N, O, P, B, Ca or Si.
4. The multi-sulfur based boron trifluoride salt electrolyte of claim 1, wherein: in the general formula I, with-SBF3The atom to which M is attached is a carbon atom C.
5. The multi-sulfur based boron trifluoride salt electrolyte of claim 1, wherein: the first substituent may be independently selected from H, a chain substituent or a cyclic substituent; the chain substituents include halogen atoms, ether oxygen groups, ether sulfur groups, nitro groups, cyano groups, amides, sulfonamide groups, sulfo groups, sulfonic acid groups, sulfonic ester groups, C ═ O-containing substituents, N-containing substituents, alkyl groups, heteroalkyl groups, alkenyl groups, heteroalkenyl groups, alkynyl groups, heteroalkynyl groups, alkinyl groups, salt-type substituents, ═ O, ═ S, nitro groups, cyano groups, amides, sulfonamide groups, sulfo groups, sulfonic acid groups, sulfonic ester groups, C ═ O-containing substituents, N-containing substituents, alkyl groups, heteroalkyl groups, alkenyl groups, heteroalkenyl groups, alkynyl groups, heteroalkynyl groups, alkinyl groups, salt-type substituents,
Or ═ N-R7(ii) a The cyclic substituent comprises a three-membered ring, a four-membered ring, a five-membered ring, a six-membered ring, a seven-membered ring and a polycyclic substituent containing two or more than two ring structures simultaneously, and any hydrogen H in the chain substituent or the cyclic substituent can be substituted by halogen atoms;
wherein R is5、R6And R7Independently H, alkyl, heteroalkyl, fluoroalkyl, fluoroheteroalkyl, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, or ring, preferably R7In a non-H structure, the salt substituents include, but are not limited to, sulfate, phosphate, carboxylate, sulfonate, sulfonimide, carbonate, ether, ammonium, silicate, phosphate, hydrochloride, nitrate, azide;
the above substituents may be optionally bonded to an atom.
6. The multi-sulfur based boron trifluoride salt electrolyte of claim 1, wherein: the first and second rings can be independently monocyclic, polycyclic, or complex rings;
the monocyclic ring includes a saturated carbocyclic ring, a saturated heterocyclic ring, an unsaturated carbocyclic ring, an unsaturated heterocyclic ring, an aromatic carbocyclic ring and an aromatic heterocyclic ring; the single ring is a three-to eighteen-membered ring;
the polycyclic ring is composed of two or more monocyclic rings; the polycyclic rings include linked, fused, bridged or spiro rings; the interlinkage is formed by a plurality of single rings, and two adjacent single rings are connected together through a single bond; the fused ring is formed by combining more than 2 single rings, and two adjacent rings share atoms on two rings; the bridge ring is a polycyclic structure sharing more than two atoms; the spiro ring is a ring sharing one atom by two adjacent monocyclic rings;
the composite ring comprises a direct ring and a sleeving ring; the direct cyclization is a ring formed by connecting multiple rings or between multiple rings and a single ring through a single bond, a chain connection containing at least one atom or a common atom; the nested ring is a ring in which at least 2 monocyclic and/or polycyclic rings are connected into a whole by a single bond or a chain of at least one atom;
the first substituent may be independently attached to any one of the monocyclic, polycyclic or complex rings.
7. The multi-sulfur based boron trifluoride salt electrolyte of claim 6, wherein: the monocyclic ring includes, but is not limited to, rings represented by any one of:
m in each ring structure0-M17Each independently can be C, O, N, P, Si, Se or S, and the ring can be connected with the first substituent;
the interlinkage in the rings is formed by 2,3, 4 or 5 single rings, and two adjacent single rings are connected together through a single bond; merging rings in the rings are 2-7 single rings, and two adjacent rings share atoms on the two rings; the bridge ring in the polycyclic structure is a polycyclic structure sharing more than two atoms, and the number of ring-forming rings is 2 or 3 monocyclic rings; spiro rings in the polycyclic rings share one atom for two monocyclic rings; the composite ring is formed by 2-4 polycyclic rings or polycyclic rings and monocyclic rings, or 2-6 monocyclic rings are fused together.
8. The multi-sulfur based boron trifluoride salt electrolyte according to claim 7, wherein:
in the general formula I, the monocyclic ring in the first ring or the second ring comprises a saturated carbocyclic ring, a saturated heterocyclic ring, an unsaturated carbocyclic ring and an unsaturated heterocyclic ring, the monocyclic ring in the first ring is a three-to-ten-membered ring, a twelve-membered ring, a fourteen-membered ring, a sixteen-membered ring or an eighteen-membered ring, and the monocyclic ring in the second ring is a three-to-eight-membered ring;
in the above first ring or second ring, the three-membered unsaturated carbocyclic ring includes a carbocyclic ring of 1 double bond; a ternary saturated heterocycle includes a saturated ring containing 1 or 2 heteroatoms; the ternary unsaturated heterocycle comprises 1 double bond and simultaneously contains 1 or 2 heteroatoms;
the quaternary unsaturated carbocycle includes carbocycles containing 1 double bond or 2 double bonds, and if 2 double bonds, they are not adjacently disposed; a quaternary saturated heterocycle includes a saturated ring containing 1 or 2 heteroatoms; the quaternary unsaturated heterocycle is a four-membered ring which contains 1 or 2 double bonds and simultaneously contains 1 or 2 heteroatoms;
five-membered unsaturated carbocycles include carbocycles containing 1 double bond or 2 double bonds, and if 2 double bonds, they are not disposed adjacent; a five-membered saturated heterocycle includes a saturated ring containing 1,2, 3, or 4 heteroatoms; the five-membered unsaturated heterocycle is a five-membered ring which contains 1 or 2 double bonds and simultaneously contains 1,2, 3 or 4 heteroatoms;
the six-membered unsaturated carbocyclic ring comprises a carbocyclic ring containing 1,2 or 3 double bonds, and if 2 or 3 double bonds are contained, the two carbocyclic rings are arranged non-adjacently; six membered saturated heterocyclic rings include saturated rings containing 1,2, 3, 4, 5 or 6 heteroatoms; the six-membered unsaturated heterocycle is a six-membered ring which contains 1,2 or 3 double bonds and simultaneously contains 1,2, 3, 4, 5 or 6 heteroatoms;
the seven-membered unsaturated carbocyclic ring comprises a carbocyclic ring containing 1,2 or 3 double bonds, and if 2 or 3 double bonds are contained, the two carbocyclic rings are arranged non-adjacently; a seven membered saturated heterocyclic ring includes a saturated ring containing 1,2, 3 or 4 heteroatoms; the seven-membered unsaturated heterocycle is a seven-membered ring which contains 1,2 or 3 double bonds and simultaneously contains 1,2, 3 or 4 heteroatoms;
the eight-membered unsaturated carbocyclic ring comprises a carbocyclic ring containing 1,2, 3 or 4 double bonds, and if 2 or more double bonds are present, the two double bonds are not adjacent to each other; an eight membered saturated heterocyclic ring includes a saturated ring containing 1,2, 3 or 4 heteroatoms; an eight-membered unsaturated heterocycle is an eight-membered ring containing 1,2, 3 or 4 double bonds and simultaneously 1,2, 3 or 4 heteroatoms;
the nine-membered unsaturated carbocyclic ring includes a carbocyclic ring containing 1,2, 3 or 4 double bonds, and if 2 or more double bonds are present, they are not adjacently disposed; a nine membered saturated heterocyclic ring includes a saturated ring containing 1,2, 3 or 4 heteroatoms; the nine-membered unsaturated heterocycle is a nine-membered ring which contains 1,2, 3 or 4 double bonds and simultaneously contains 1,2, 3 or 4 heteroatoms;
the ten-membered unsaturated carbocyclic ring comprises a carbocyclic ring containing 1,2, 3 or 4 double bonds, and if 2 or more double bonds are present, the two are arranged non-adjacently; a ten-membered saturated heterocyclic ring includes a saturated ring containing 1,2, 3, or 4 heteroatoms; the ten-membered unsaturated heterocycle is a ten-membered ring containing 1,2, 3 or 4 double bonds and simultaneously containing 1,2, 3 or 4 heteroatoms;
the twelve-membered ring, the fourteen-membered ring, the sixteen-membered ring and the eighteenth-membered ring independently comprise a saturated carbocyclic ring, a saturated heterocyclic ring containing 1,2, 3, 4, 5 or 6 heteroatoms and an unsaturated heterocyclic ring, and the unsaturated heterocyclic ring is a ring containing 1,2, 3, 4, 5 or 6 heteroatoms and simultaneously containing 1,2, 3, 4, 5 or 6 unsaturated bonds;
the polycyclic ring is formed by combining more than 2-5 single rings.
9. The multi-sulfur based boron trifluoride salt electrolyte of claim 8, wherein: in formula I, the first and second chains are independently a saturated carbon chain, an unsaturated carbon chain, a saturated heterochain, or an unsaturated heterochain, and the first and second chains are independently a chain of 1-25 atoms;
wherein, for a 1 atom chain: if the chain is the first chain, the chain can be a carbon chain or a miscellaneous chain of 1 atom, and if the chain is the second chain, the chain is a carbon chain of 1 atom;
for a 2 atom chain, it is a saturated carbon chain, a saturated heterochain containing 1 heteroatom, an unsaturated carbon chain containing 1 double bond, or an unsaturated heterochain containing both 1 unsaturated bond and 1 heteroatom;
for a 3 atom chain, it includes a saturated carbon chain, an unsaturated carbon chain containing 1 unsaturated bond, a saturated heterochain containing 1 heteroatom, or an unsaturated heterochain containing both 1 unsaturated bond and 1 heteroatom;
for a 4 atom chain, it includes a saturated carbon chain, an unsaturated carbon chain containing 1 unsaturated bond, a saturated heterochain, or an unsaturated heterochain; the saturated heterochain contains 1 or 2 heteroatoms, and the unsaturated heterochain simultaneously contains 1 unsaturated bond and 1 or 2 heteroatoms;
for a 5 atom chain, it includes a saturated carbon chain, an unsaturated carbon chain containing 1 or 2 unsaturated bonds, a saturated heterochain, or an unsaturated heterochain; the saturated heterochain contains 1,2, 3, 4 or 5 heteroatoms, and the unsaturated heterochain contains 1 unsaturated bond and simultaneously contains 1,2, 3, 4 or 5 heteroatoms;
for a 6 atom chain, it includes a saturated carbon chain, an unsaturated carbon chain containing 1 or 2 unsaturated bonds, a saturated heterochain, or an unsaturated heterochain; the saturated heterochain contains 1,2 or 3 heteroatoms, and the unsaturated heterochain contains 1 or 2 unsaturated bonds and also contains 1,2 or 3 heteroatoms;
for a 7 atom chain, it includes a saturated carbon chain, an unsaturated carbon chain containing 1 or 2 unsaturated bonds, a saturated heterochain, or an unsaturated heterochain; the saturated heterochain contains 1,2 or 3 heteroatoms, and the unsaturated heterochain contains 1 or 2 unsaturated bonds and also contains 1,2 or 3 heteroatoms;
for a chain of 8 atoms, it includes a saturated carbon chain, an unsaturated carbon chain, a saturated heterochain, or an unsaturated heterochain; the unsaturated carbon chain contains 1,2 or 3 unsaturated bonds, the saturated heterochain contains 1,2 or 3 heteroatoms, and the unsaturated heterochain contains 1,2 or 3 unsaturated bonds and simultaneously contains 1,2 or 3 heteroatoms;
for a 9 atom chain, it includes a saturated carbon chain, an unsaturated carbon chain, a saturated heterochain, or an unsaturated heterochain; wherein the unsaturated carbon chain contains 1,2, 3 or 4 unsaturated bonds, the saturated heterochain contains 1,2, 3 or 4 heteroatoms, and the unsaturated heterochain contains 1,2 or 3 unsaturated bonds and simultaneously contains 1,2 or 3 heteroatoms;
for a 10, 11, 12, 13, 14, or 15 atom chain, it includes a saturated carbon chain, an unsaturated carbon chain, a saturated heterochain, or an unsaturated heterochain; the unsaturated carbon chain contains 1,2, 3 or 4 unsaturated bonds, the saturated heterochain contains 1,2, 3 or 4 heteroatoms, and the unsaturated heterochain contains 1,2 or 3 unsaturated bonds and simultaneously contains 1,2 or 3 heteroatoms;
for a chain of 16-25 atoms, the chain comprises a saturated carbon chain, an unsaturated carbon chain, a saturated heterochain or an unsaturated heterochain; the unsaturated carbon chain comprises 1 to 7 unsaturated bonds, the saturated heterochain comprises 1 to 7 heteroatoms, and the unsaturated heterochain contains 1 to 7 unsaturated bonds and 1 to 7 heteroatoms;
the first substituent may be attached to any one of the first chains.
10. The multi-sulfur-based boron trifluoride salt electrolyte according to any one of claim 9, wherein: when the general formula I is a ring structure, it includes:
A) r is a first ring, R1、R2、R3、R4、R5Are all H or nothing, and are denoted as R-E-Q1Wherein, R is also connected with 3-5-E' -SBF3M; first of allAny ring atom on the ring R can be directly or indirectly connected with 1 or 2-SBF3M；
B) R is a first ring to which-SBF is not directly attached3M，R1Is a first chain, R2、R3、R4、R5All are nothing (or H) or the first chain, noted
R1、R2、R3、R4、R5Is connected with 3-6-E' -SBF3M, and R4、R5Independently attached-E' -SBF3The number of M is 0 or 2;
C) r is a first ring, R1Is a first chain, R2、R3、R4Independently is nothing or a first chain, R5All are H or nothing, and are marked as
Wherein R is linked to at least 1-E' -SBF3M，R1、R2、R3、R4To which 1-4-E '-SBF's are attached3M；
D) R is nothing, a first ring or a first chain, R1And R4Is a first ring, R3、R5Are all H or none, and are marked
Wherein R is4To which at least 1-E' -SBF is attached3M，R、R1、R2Independently connected with 0-3-E' -SBF3M；
R, R in A) -D)1、R2、R3、R4Or R5Each of which may be independently attached to said first substituent.
11. The multi-sulfur-based boron trifluoride salt electrolyte of claim 10, wherein: when formula I is a chain structure, it includes:
E)R、R1、R2、R3、R4、R5independently a first chain without or containing at least one atom, and R, R1～R5Not all of them being simultaneously H or none, is denoted
F) When the general formula I is a chain structure, R is a ring, R5Is absent, R1、R2、R3、R4Independently is nothing or a first strand; r is1、R2、R3To which 4-5-SBF are attached3M，R4To which 0-2-SBF are attached3M, is marked as
R, R in E) to F)1、R2、R3、R4Or R5Each of which may be independently attached to said first substituent.
12. The multi-sulfur-based boron trifluoride salt electrolyte of claim 11, wherein: A) -F), said first ring comprises said monocyclic, polycyclic or composite ring; the monocyclic ring is selected from the following rings: cyclopropane, cyclopropene, ethylene oxide, thiirane, cycloazethane, cyclobutane,
Cyclobutene, cyclopentyl, cyclopentene, cyclopentadiene, pyrrole, dihydropyrrole, tetrahydropyrrole, furan, dihydrofuran, tetrahydrofuran, thiophene, dihydrothiophene, tetrahydrothiophene, imidazole, pyrazole, thiazole, dihydrothiazole, thiazolidine, isothiazole, dihydroisothiazole, tetrahydroisothiazole, oxazole, dihydrooxazole, tetrahydrooxazole, isoxazole, dihydroisoxazole, triazole, dihydrotriazoltetrazolyl, benzene ring, pyridine, dihydropyridine, tetrahydropyridine, pyrimidine, pyrazine, pyridazine, p-diazabenzene, triazine, cyclohexane, dioxane, cyclohexene, 1, 3-ringHexadiene, 1, 4-cyclohexadiene, piperidine, pyran, dihydropyran, tetrahydropyran, dihydrothiopyran, tetrahydrothiopyran, dithiane, 1, 2-dithiane, [1,3 ] -dithiane]Oxazolidines, morpholines, piperazines, pyrones, dihydropyrimidines, tetrahydropyrimidines, hexahydropyrimidines, cycloheptanes, [1,4 ]]Dioxepane, cyclohexene oxide, cycloheptene, 1, 3-cycloheptene, cyclooctane, cyclononane triene, cyclododecane, 1,5, 9-triazacyclododecane,
Or 18-crown ethers;
the polycyclic ring is composed of the above monocyclic ring; in the composite ring, the direct ring formation is a composite ring formed by connecting at least two polycyclic rings or at least one polycyclic ring and at least one monocyclic ring through a single bond, a chain containing at least one atom or a common atom, and the composite ring includes, but is not limited to, the following rings:
wherein A is11、A12、A13、A14Independently is-CH2-、-S-、-SO2-；
In the above rings, H on N is replaced by a covalent bond or a metal cation.
13. The multi-sulfur based boron trifluoride salt electrolyte of claim 12, wherein: e or E' is selected from the group consisting of alkyl, heteroalkyl, alkenyl, heteroalkenyl, etheroxy, etherthio, cyclic structure-containing groups, ═ CH-R8-、＝N-R4-or obtained by substitution of any one of these structures by halogenA group;
the heteroalkenyl group includes a structure containing a carbon-carbon double bond C ═ C and a structure containing a carbon-carbon double bond C ═ N, wherein R is4And R8Independently an alkyl, heteroalkyl, alkenyl, heteroalkenyl or ring structure, R8Or none.
14. The multi-sulfur based boron trifluoride salt electrolyte of claim 12, wherein: the general formula I as described for A) includes the following compounds:
the general formula I described for B) includes the following compounds:
the general formula I as described for C) includes the following compounds:
the general formula I as described for D) includes the following compounds:
in the above structure, Q0～Q6All represent-SBF3M; e in each ring structure1～E12Are each independently a group, a ring-containing structure orA chain structure containing at least one atom, and E0～E6May be absent; a in each ring structure1～A7Are each independently absent or a second substituent in accordance with the definition of the first substituent; any one H on each ring can be replaced by A1、A2、A3、A4、A5、A6Or A7And two or more of H may be substituted by one H, and if two or more of H are substituted, the substituents may be the same or different.
15. The multi-sulfur based boron trifluoride salt electrolyte of claim 14, wherein: the second substituent is independently selected from H, halogen atom, carbonyl, ester group, aldehyde group, ether oxygen bond/group, ether sulfur bond/group, ═ O, ═ S and ═ CH2Nitro, cyano, disubstituted amino, amide, sulfonamide, sulfoalkane, sulfonate, sulfate, sulfonate, phosphate, hydrochloride, nitrate, diazo, azide, sulfonimide, carbonate, carboxylate, thioether, oxoether, ammonium, -OCF3Alkyl, heteroalkyl, alkenyl, heteroalkenyl, alkynyl, alkenylalkynyl, cyclopropyl, aryl, cyclopentyl, cyclohexyl, polycyclic and any H of these second substituents may be independently substituted with a halogen atom to provide a halo substituent.
16. The multi-sulfur-based boron trifluoride salt electrolyte of claim 15, wherein: the halogen atoms comprise F, Cl, Br and I;
the carbonyl group is
The ester group is
Sulfonic acid ester
Disubstituted amino is
Amide is
The sulfoalkane is
The ether oxygen bond/radical being-O-R35or-R31OR32The etherthio group/radical being-S-R35or-R31SR32Wherein R is22、R23、R24、R25、R46、R50、R51、R52、R53、R54、R55、R56、R79、R80Independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, hexyl or heptyl, and R22、R24、R31、R50、R55May be absent; wherein the ester group can also be selected from-COOCH2(CH2)6CH3、-COOCH2(CH2)10CH3、-COOCH2(CH2)14CH3or-COOCH2(CH2)16CH3(ii) a The ether oxy group can also be selected from-CH2(CH2)5OEt、-OCH2(CH2)8CH3、-OCH(CH3)Et、-OCH(CH3)CH2CH(CH3)2、-OCH(CH3)CH2CH2CH(CH3)2；R79、R80And can also be selected from methoxy, ethoxy independently;
cyano radicals selected from-CN, -CH2CN、-CH＝C(CN)2or-CH2CH2CN；
The alkyl group includes methyl, ethyl, n-propyl, isopropyl, n-butyl, n-,Isobutyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, n-hexyl, isohexyl, sec-hexyl, neohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, -C (CH)3)3、-CH2C(CH3)3、-C(CH3)2CH2CH3、-CH2CH2C(CH3)3；
The heteroalkyl group is selected from: -OCH2CH2Si(CH3)3、-CH2CH(SCH2CH3)2、-CH(SCH2CH3)2、-CH2S-S-CH3、-S-S-CH3、-OCF3、-CH2Z1CH3、-O(CH2CH3)2、-CH2Z1CH(CH3)2、
The alkenyl group includes: ethenyl, 1-propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, 1, 3-hexadienyl, -C (CH)3)＝CH2、-OCH2CH＝CH2、-C(CH3)＝CHCH3、-CH2CH＝C(CH3)2、
-C(CH3)＝CH2、
A heteroalkenyl group: -COCH ═ CH2、＝NCH2CH2CH3、-CH2OCHO、-CO(CH2)2C(CH3)3、-OCOCH(CH3)Et、-CH2(CH2)3CH(CH3)COCH3、-N＝CHCH3、-C(CH3)＝CHCOCH3、-COCH＝CHCH2CH3、-CH2-CH＝CH-Z1CH3、
Alkynyl is selected from ethynyl, propynyl, butynyl, pentynyl or-C.ident.C-Si (CH)3)3；
Alkenylalkynyl is selected from: -C ≡ CCH ═ CHCH3；
The cyclopropyl group is selected from the group consisting of cyclopropane
Ethylene oxide radical
Or cyclopropene;
the aryl group is selected from benzene ring, pyridine, pyrimidine, pyrazine, pyridazine, p-diazabenzene, triazine,
Cyclopentyl is selected from cyclopentyl, cyclopentenyl, cyclopentadienyl, dihydropyridine, tetrahydropyridine, pyrrolyl, dihydropyrrolyl, tetrahydropyrrolyl, furyl, dihydrofuryl, tetrahydrofuryl, 2, 5-dihydrofuran, thienyl, dihydrothiophene, tetrahydrothiophene, imidazolyl, thiazolyl, 2, 3-dihydrothiazolyl, pyrazolyl, oxazole, isoxazole, triazolyl, pyridyl, etc,
The cyclohexyl is selected from: cyclohexane, cyclohexenyl, 1, 3-cyclohexadiene, 1, 4-cyclohexadiene, piperidine, pyran, dihydropyran, tetrahydropyran, morpholine, piperazine, pyrone, dihydropyrimidine, tetrahydropyrimidine, dioxane, dihydrothiopyran, tetrahydrothiopyran, dithiane, or oxazolidine;
the polycyclic ring is selected from: naphthyl, anthryl, phenanthryl, quinonyl, pyrenyl, acenaphthenyl, carbazolyl, indolyl, isoindolyl, quinolyl, purinyl, nucleobase, benzoxazole,
The halogenated substituent comprises a substituent obtained after any H in alkyl, heteroalkyl, alkenyl, heteroalkenyl, alkynyl and alkenylalkynyl is independently substituted by halogen atoms;
in the above ring, R20is-CH2-or-CO-;
any one of the cyclopropyl, aryl, cyclopentyl, cyclohexyl and polycyclic rings can be replaced by single bond, -O-, -S-S-, -CH2-、-OCH2-、-CH2CH2-、-CH2OCH2-、-C(CH3)2-、-COO-、-COOCH2-、-N＝C-、-COON(CH3)-、-ON(CH3)2-C＝C-C＝、-OCOOCH2-、-O-COO-、-CO-CH＝CH-、
-N＝N-、-OCH2CH2-or amides linked to substituted structures, wherein H on N in the amide is replaced by an alkyl or metal cation;
any H on any one of said cyclopropyl, aryl, cyclopentyl, cyclohexyl, or polycyclic rings can be independently substituted with said third substituent comprising a halogen atom, methyl, ethyl, -COCH3、＝O、＝S、-COOCH3Methoxy, trifluoromethyl, nitro, nitrate, -SO2N(CH2CH2CH3)2-CN or
And all hydrogens H on the nitrogen atom N are substituted with said third substituent.
17. The multi-sulfur based boron trifluoride salt electrolyte of claim 14, wherein: e0、E1、E2、E3、E4、E5、E6Independently selected from the group consisting of none, carbonyl-CO-, -CH2-, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, sec-heptyl, n-octyl, isooctyl, sec-octyl, n-nonyl, isononyl, sec-nonyl, n-decyl, isodecyl, sec-decyl, ethenyl, propenyl, butenyl, ethynyl, propynyl, undecyl, -OCH2-、-OCH2CH2-、-CH2OCH2-、CH2SCH2-、CH2SSCH2-、CH2SCH2CH2-、CH2SSCH2CH2-、-SCH2CH2-、-SSCH2CH2-、-CH2CO-、-CH2CH2CO-、-CH(CH3)CO-、-CH(CH3)-、-CH＝CHCH(CH3)-、-N＝C(CH3)-、-C(CH3)2-、-CH(CH2Cl)-、-CH(OCH3)-、-CH2CH(CH3)-、-OCH2CH＝、-CH(CHO)-、-CH2C(CH3)2-、-C(CH3)2CH2CH2-、-N＝C(CF3)-、-CH(CH3)CH2CH2-、-CH(CH3)CH2CH2CH2-、-COCH2N＝、-CH＝CH-CO-、-CH2CH(CH3)-、-C(CF3)2-、-CH(CF3)-、-CH2C(CH3)2-、-CH2CH(Et)-、-CH2CH2CH(CH3)-、-C(CH3)2CH2CH2-、-CH(CH2CH3)-、-CH(CH2CH2CH3)-、-OCH2CH2CH2CO-、-COOCH2CH2-、
Phenyl group,
E7、E9、E10And E11Independently selected from,
E8Selected from,
-CH2-、-O-、-S-S-、
-COCH2CH2-、-COOCH2-、
E12Is selected from
In the above-mentioned E0～E6Wherein n is any integer of 0-10; in the above-mentioned E0～E11Wherein each ring may be independently attached to a substituent group which is null, -CH3Ethyl, propyl, halogen atoms, nitro, ethylene or methoxy, R10is-CH3Ethyl, propyl, nitro, ethylene or cyclo.
18. The multi-sulfur-based boron trifluoride salt electrolyte of claim 11, wherein: for formula I as described in E), including any one of the following structures:
for formula I as described in F), it includes any one of the following structures:
in E) and F), Q1-Q6Independently is-SBF3M，Z0-Z25Independently is H or a fourth substituent;
each of the radicals and Z0-Z25Any H on the attached atoms may be independently substituted with H or a fourth substituent; the fourth substituent is selected from O, methyl, ethyl, halogen atom, CH2Methoxy, aldehyde group,
Vinyl, -SCH2CH3Or ═ CHCH2CH3(ii) a In E), Z0-Z25And can also independently be:
the ring structure of the fourth substituent may be bonded to a methyl group, an ethyl group, a halogen group, a nitro group, an ═ O group, a methoxy group, a cyano group, a hydroxy groups, a hydroxy group, a hydroxy groups, and the like,
And the like; r9Is an alkyl group.
19. The multi-sulfur based boron trifluoride salt electrolyte according to any one of claims 1 to 18, wherein: the compound of formula i is a boron trifluoride salt in which all H on C are substituted, in whole or in part, by halogen, preferably by F, according to any one of claims 1 to 18;
and/or said formula I is a boron trifluoride salt in any one of the formulae I as claimed in any of claims 1 to 8, in which all or part of the oxygen atoms are independently replaced by sulfur atoms.
20. The multi-sulfur based boron trifluoride salt electrolyte of claim 1, wherein: m of the formula I comprises Na+、K+、Li+、Mg2+Or Ca2+Preferably Na+、K+Or Li+。
21. A plurality according to any one of claims 1 to 20The preparation method of the sulfur-based boron trifluoride salt electrolyte is characterized by comprising the following steps: the method comprises the step of reacting a multi-element structure containing a plurality of-SH groups, a boron trifluoride compound and an M source to obtain a product, namely the product containing a plurality of-SBF groups3M is boron trifluoride salt structure.
22. Use of the multi-sulfur based boron trifluoride salt electrolyte according to any one of claims 1 to 20 in a secondary battery, wherein: the application is as follows: the multi-sulfur-based boron trifluoride salts can be used both as salts and as additives;
preferably, the applications include applications in liquid electrolytes, gel electrolytes, mixed solid-liquid electrolytes, quasi-solid electrolytes, all-solid electrolytes, each independently comprising a multi-sulfur-based boron trifluoride salt electrolyte according to any one of claims 1 to 20;
preferably, the use further comprises use as a battery or battery, the battery comprising the polysulfido boron trifluoride electrolyte of any of claims 1 to 20 and a positive electrode, a negative electrode and an encapsulating housing; the liquid electrolyte, the gel electrolyte, the mixed solid-liquid electrolyte, the quasi-solid electrolyte and the all-solid electrolyte can be applied to liquid batteries, mixed solid-liquid batteries, semi-solid batteries, gel batteries, quasi-solid batteries and all-solid batteries, and the battery pack comprises the batteries.
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