CN101632198A - Nitroxides for lithium-ion batteries - Google Patents
Nitroxides for lithium-ion batteries Download PDFInfo
- Publication number
- CN101632198A CN101632198A CN200880007674A CN200880007674A CN101632198A CN 101632198 A CN101632198 A CN 101632198A CN 200880007674 A CN200880007674 A CN 200880007674A CN 200880007674 A CN200880007674 A CN 200880007674A CN 101632198 A CN101632198 A CN 101632198A
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- Prior art keywords
- alkyl
- cycloalkyl
- compound
- independently
- aryl
- Prior art date
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 48
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 41
- -1 Nitroxides Chemical class 0.000 title claims description 34
- 150000001875 compounds Chemical class 0.000 claims abstract description 104
- 239000003792 electrolyte Substances 0.000 claims abstract description 34
- 125000000217 alkyl group Chemical group 0.000 claims description 41
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 35
- 229910052744 lithium Inorganic materials 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 32
- 229910052799 carbon Inorganic materials 0.000 claims description 29
- 125000005842 heteroatom Chemical group 0.000 claims description 29
- 229910052760 oxygen Inorganic materials 0.000 claims description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims description 25
- 230000033116 oxidation-reduction process Effects 0.000 claims description 19
- 150000001721 carbon Chemical group 0.000 claims description 18
- 230000001590 oxidative effect Effects 0.000 claims description 17
- 230000004087 circulation Effects 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 14
- 229910052700 potassium Inorganic materials 0.000 claims description 14
- 229910052708 sodium Inorganic materials 0.000 claims description 14
- 229910052731 fluorine Inorganic materials 0.000 claims description 13
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 13
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 12
- 159000000002 lithium salts Chemical class 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
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- 125000003342 alkenyl group Chemical group 0.000 claims description 9
- 125000000304 alkynyl group Chemical group 0.000 claims description 9
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 230000001681 protective effect Effects 0.000 claims description 9
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 229910003002 lithium salt Inorganic materials 0.000 claims description 8
- 229910013872 LiPF Inorganic materials 0.000 claims description 7
- 101150058243 Lipf gene Proteins 0.000 claims description 7
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 7
- 125000001072 heteroaryl group Chemical group 0.000 claims description 7
- 229910015015 LiAsF 6 Inorganic materials 0.000 claims description 6
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- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 6
- 229910012513 LiSbF 6 Inorganic materials 0.000 claims description 6
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
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- 239000001989 lithium alloy Substances 0.000 claims description 5
- 125000000962 organic group Chemical group 0.000 claims description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 150000002367 halogens Chemical class 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
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- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 3
- YMOIGAJEKSCMNY-UHFFFAOYSA-N C(C)C(C(OC)(OC)F)F Chemical compound C(C)C(C(OC)(OC)F)F YMOIGAJEKSCMNY-UHFFFAOYSA-N 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 3
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- 229910015726 LiMn0.3Co0.3Ni0.3O2 Inorganic materials 0.000 claims description 3
- 229910016087 LiMn0.5Ni0.5O2 Inorganic materials 0.000 claims description 3
- 229910013716 LiNi Inorganic materials 0.000 claims description 3
- 229910013290 LiNiO 2 Inorganic materials 0.000 claims description 3
- 229910013086 LiNiPO Inorganic materials 0.000 claims description 3
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 3
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- 239000002178 crystalline material Substances 0.000 claims description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical class COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 3
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- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
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- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 3
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- 238000010276 construction Methods 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- CSSYKHYGURSRAZ-UHFFFAOYSA-N methyl 2,2-difluoroacetate Chemical class COC(=O)C(F)F CSSYKHYGURSRAZ-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 24
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical class O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 abstract description 4
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- 238000002360 preparation method Methods 0.000 description 19
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 13
- 238000005259 measurement Methods 0.000 description 13
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- 239000000463 material Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 11
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- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000480 butynyl group Chemical group [*]C#CC([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000005779 cell damage Effects 0.000 description 1
- 208000037887 cell injury Diseases 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000001047 cyclobutenyl group Chemical group C1(=CCC1)* 0.000 description 1
- 238000006210 cyclodehydration reaction Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 125000002704 decyl group Chemical group [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])* 0.000 description 1
- 125000005070 decynyl group Chemical group [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#C* 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- LGTLXDJOAJDFLR-UHFFFAOYSA-N diethyl chlorophosphate Chemical compound CCOP(Cl)(=O)OCC LGTLXDJOAJDFLR-UHFFFAOYSA-N 0.000 description 1
- GLUUGHFHXGJENI-UHFFFAOYSA-N diethylenediamine Natural products C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- ZVDBUOGYYYNMQI-UHFFFAOYSA-N dodec-1-yne Chemical compound CCCCCCCCCCC#C ZVDBUOGYYYNMQI-UHFFFAOYSA-N 0.000 description 1
- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 0.000 description 1
- 125000003438 dodecyl group Chemical group [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])C([H])([H])C([H])([H])* 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 239000011263 electroactive material Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000003818 flash chromatography Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- YVXHZKKCZYLQOP-UHFFFAOYSA-N hept-1-yne Chemical compound CCCCCC#C YVXHZKKCZYLQOP-UHFFFAOYSA-N 0.000 description 1
- RBBOWEDMXHTEPA-UHFFFAOYSA-N hexane;toluene Chemical compound CCCCCC.CC1=CC=CC=C1 RBBOWEDMXHTEPA-UHFFFAOYSA-N 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- YVJRCWCFDJYONJ-UHFFFAOYSA-N hydroperoxymethylbenzene Chemical compound OOCC1=CC=CC=C1 YVJRCWCFDJYONJ-UHFFFAOYSA-N 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Substances C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- OSSQSXOTMIGBCF-UHFFFAOYSA-N non-1-yne Chemical group CCCCCCCC#C OSSQSXOTMIGBCF-UHFFFAOYSA-N 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 125000001400 nonyl 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])[H] 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000005981 pentynyl group Chemical group 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- UNQNIRQQBJCMQR-UHFFFAOYSA-N phosphorine Chemical compound C1=CC=PC=C1 UNQNIRQQBJCMQR-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- JTHRRMFZHSDGNJ-UHFFFAOYSA-N piperazine-2,3-dione Chemical compound O=C1NCCNC1=O JTHRRMFZHSDGNJ-UHFFFAOYSA-N 0.000 description 1
- 125000005936 piperidyl group Chemical group 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001844 prenyl group Chemical group [H]C([*])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YORCIIVHUBAYBQ-UHFFFAOYSA-N propargyl bromide Chemical compound BrCC#C YORCIIVHUBAYBQ-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 150000003235 pyrrolidines Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- NBRKLOOSMBRFMH-UHFFFAOYSA-N tert-butyl chloride Chemical compound CC(C)(C)Cl NBRKLOOSMBRFMH-UHFFFAOYSA-N 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 125000005065 undecenyl group Chemical group C(=CCCCCCCCCC)* 0.000 description 1
- 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 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
- C07D241/06—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having one or two double bonds between ring members or between ring members and non-ring members
- C07D241/08—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having one or two double bonds between ring members or between ring members and non-ring members with oxygen atoms directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/30—Oxygen or sulfur atoms
- C07D233/32—One oxygen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/28—1,4-Oxazines; Hydrogenated 1,4-oxazines
- C07D265/30—1,4-Oxazines; Hydrogenated 1,4-oxazines not condensed with other rings
- C07D265/32—1,4-Oxazines; Hydrogenated 1,4-oxazines not condensed with other rings with oxygen atoms directly attached to ring carbon atoms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Secondary Cells (AREA)
Abstract
This invention relates to overcharge protection and molecular redox shuttles in rechargeable lithium-ion cells. For this, specific nitroxyls or oxoammonium salts are used in the electrolyte. This invention also relates to a method of producing such lithium-ion cells and to a method of recharging such lithium-ion cells. This invention also pertains to some nitroxyls compounds and oxoammonium salts.
Description
The present invention relates to over-charge protective and molecular oxidation reduction shuttle (redox shuttle) in the rechargeable lithium ion battery.For this reason, in electrolyte, use specific nitroxyl or oxo ammonium salt.The invention still further relates to the method for making this class lithium ion battery and with the method for this class lithium-ion electric battery recharge.The invention still further relates to some nitroxyl compound and oxo ammonium salt.
WO-A-2006/124389 has described the alicyclic N-oxide as the used redox shuttle of rechargeable lithium ion battery (that is over-charge protective).This alicyclic N-oxide comprises piperidyl or pyrrolidines basic ring.
EP-A-1843426 and WO2007/116363 have described the alicyclic N-oxide as the redox active compound in the electrolyte that is dissolved in rechargeable lithium ion battery especially.
People such as Q.Wang, Angew.Chem.Int.Ed.2006,45,8197-8200 has described the molecular oxidation reduction shuttle that is used for rechargeable lithium ion battery.Use osmium complex as this quasi-molecule redox shuttle.
JP-A-2002-268861 has described to have and has contained 2,2,6,6-four replacement-piperidines-N-oxide or 2,2,5, the secondary cell of the nonaqueous electrolyte of 5-four replacement-pyrrolidines-N-oxide.
EP-A-1381100 has described has anodal charge storage device, and wherein positive pole comprises 2,2, and 6,6-four replacement-piperidines-N-oxo ammonium cation, 2,2,5,5-four replacement-pyrrolidines-N-oxo ammonium cation or 2,2,5,5-four replacement-3-pyrrolin-N-oxo ammonium cation.
US3532703 has described as 2,2,5 of polyolefinic anti-photic deterioration stabilizer, 5-four replacement-4-oxo-imidazole alkane-1-oxides.
WO-A-01/23435 has described the 2-oxo-3,3,5 as polymerization regulator, 5-four replacement-morpholines-N-oxide.
When design with construct when correct, rechargeable lithium ion battery can show excellent charge-discharge cycle life, have little or no memory effect and high specific energy and volume energy.But lithium ion battery has some shortcomings really, comprises can not allowing in cycle life and not recharging to the current potential of the charging potential limit that is higher than manufacturer recommendation under the situation of variation; Recharge overheated, the danger of catching fire or exploding to the battery of the current potential of the charging potential limit that is higher than recommendation; Be difficult to make be used for consumer applications to electricity and the macrocell of mechanical damage with sufficient tolerance.Singlely comprise electric charge control electronic device usually with the lithium ion battery that is connected (for example series connection) and surpass the charging potential limit of recommending to prevent each battery.Sort circuit has increased cost and complexity, and hinders lithium ion battery in the electricity of low-cost mass selling and the application in the electronic device (for example photoflash lamp, radio device, CD Player etc.).The ground that replaces, these low-cost devices are usually with rechargeable battery not, as the alkaline battery energy supply.
All cpds has been proposed to give rechargeable lithium ion battery over-charge protective.Be known as " redox shuttle " or " shuttle " in case compound can provide in theory charging potential reach desirable value just can be between negative electrode and positive electrode oxidable and reducible charge transport materials of transmission charge repeatedly.
But the necessary electrochemistry addressing of the electroactive material in the lithium ion battery is with their capacity of abundant exploitation.Because electrode material lacks electron conduction, a large amount of conductive additives (for example carbon black or graphite) must be mixed in the electrode, to be formed for the continuous conduction network of electron-osmosis.Therefore, the existence of a large amount of non-activity conductive agents has greatly reduced the energy density of battery.Help to overcome the insulation of lithium-insertion material or the problem of difference conduction by the molecular oxidation reduction target-seeking (redox targeting) that freely spreads the realization of relaying molecule.
Term " positive pole " is meant one of a pair of rechargable lithium ion cell electrode, and they under normal circumstances and have a maximum potential when battery charges fully.We are shown in same physical electrode under all battery operated conditions with this nomenclature all the time, even this class electrode temporary transient (for example because battery overcharge) is driven to or shows the current potential that is lower than another electrode (negative pole).
Term " negative pole " is meant one of a pair of rechargable lithium ion cell electrode, and they under normal circumstances and have a potential minimum when battery charges fully.We are shown in same physical electrode under all battery operated conditions with this nomenclature all the time, even this class electrode temporary transient (for example because battery overcharge) is driven to or shows the current potential that is higher than another electrode (positive pole).
Term " redox chemistry shuttle " is meant the electrochemical reversible material, and it is oxidized at the positive pole place in the lithium ion cell charging process, move to negative pole, be reduced at the negative pole place to form the material and move back positive pole of shuttling back and forth of not oxidation (or than suboxides) again.
Term " the molecular oxidation reduction shuttle that is used for redox target-seeking (redox targeting) " or " molecular oxidation reduction shuttle " are meant the electrochemical reversible material.In charging process, the molecular oxidation reduction shuttle (S) that is used for the redox target-seeking is oxidized at the collector body place.Oxidized material (S+) flows to active electrode material (LiFePO for example by body diffusion with positive charge
4) corresponding particle, and be reduced back S.On the contrary, in discharge process, S+ is reduced into S at the collector body place, and it gives the oxidation active electrode material with electron transport again.Use the advantage of free diffusible oxydation reduction shuttle to be that it can make charge transfer carry out with faster speed, greatly improve the power output of battery thus.Therefore, for example, can reduce the response time of electrode.For example, can reduce or omit the amount of conductive additive in the electrode (for example carbon black or graphite).
When contact is anodal when using, term " recharge current potential " and be meant as described below record with respect to Li/Li
+Value E
Cp: structure contains positive pole, lithium metal negative pole and electrolyte but does not contain compound battery (iii), carry out charge/discharge cycle test, and observe anodal current potential when in first charging cycle, taking off lithium (delithiated) at least 90% the lithium content that is equivalent to available storage battery capacity.For some positive pole (LiFePO for example
4), this lithium content may be equivalent to roughly to take off lithium fully and (for example, become Li
0FePO
4).For other positive poles (for example, having some electrodes that layering contains the lithium structure), this lithium content may be equivalent to part and take off lithium.
When contact redox chemistry shuttle uses; word " capable of circulation " is meant following material: with this material oxidation (for example be enough to when being exposed to; be oxidized to cationic form from neutrality; or from being oxidized to higher oxidation state than low-oxidation-state) charging voltage the time and flow down at 100% the electric charge that overcharges that equals battery capacity, this material provides the over-charge protective of at least two circulations for the battery that contains selecteed positive pole.
Term " phase " is meant the uniform liquid part that existence maybe can form in liquid system.Term " a plurality of phase " is meant in inhomogeneous liquid system and exists more than a phase.When contact redox chemistry shuttle and the use of electrolytical mixture; term " dissolving " and " solubilized " be meant when being present in electrolyte or add in the electrolyte and form the shuttle that maybe can form single phase soln, described single phase soln be enough under the following charging current speed/provide the amount of over-charge protective to contain removable load material: this charging current speed is enough to will to contain selecteed positive pole, negative pole and electrolytical lithium ion battery in 10 hours or shorter time and charges fully.
When contact redox chemistry shuttle uses, term " oxidizing potential " value of being meant E
CvE
CvCan followingly measure: this shuttle is dissolved in the electrolyte of selection, uses cyclic voltammetry and platinum or vitreous carbon work electrode, copper that electrode and non-water Ag/AgCl reference electrode are measured the relation of electric current and voltage, and measure current potential V
Upwards(promptly in scanning in the process of high normal potential more) and V
Downwards(promptly in scanning in the process of negative potential more) observes peak current at this.E
CvBe V
UpwardsAnd V
DownwardsMean value.Can the following accurate estimation shuttle oxidizing potential (value of providing E
Calc): structure contain this shuttle battery, carry out charge/discharge cycle test, and the current potential when in the charge sequence process, observing the voltage platform that shows shuttle oxidation and reduction and occurring.Can interrelate by oxidizing potential and lithium ion battery performance, use modeling software (for example from the GAUSSIAN 03 of Gaussian Inc. with the compound of model ionization potential and measurement
TM) oxidizing potential that shuttles back and forth (with the value of providing " Ecajc ") is provided, thus the prediction oxidizing potential is (for example, for E
CvUnknown compound).
Accompanying drawing is described
The Reversible Cycle voltammogram of Fig. 1: Cmpd 1
The Reversible Cycle voltammogram of Fig. 2: Cmpd 9
The Reversible Cycle voltammogram of Fig. 3: Cmpd 16
The Reversible Cycle voltammogram of Fig. 4: Cmpd 20
The Reversible Cycle voltammogram of Fig. 5: Cmpd 25
The Reversible Cycle voltammogram of Fig. 6: Cmpd 26
The Reversible Cycle voltammogram of Fig. 7: Cmpd 39
Fig. 8: the figure of the cell potential described in the embodiment of demonstration use Cmpd 31 in the continuous charge-discharge cyclic process of battery.
Rechargeable lithium ion battery is provided among the present invention in one aspect, and it comprises:
(a) anodal (for example, having the current potential of recharging),
(b) negative pole and
(c) electrolyte, this electrolyte comprises
(i) lithium salts,
(ii) polar non-solute and
The (iii) at least a compound that selects the group of free style (d1) to (d6) composition
Wherein
G is
Or
Preferably, G is
X is O or S;
If X is O, then R
6And R
7It is duplet;
If X is S, then R
6And R
7Be independently duplet or=O;
Y is-CH
2-O-CH
2-,-CH
2-S-CH
2-,-CH
2-S (=O)-CH
2-,-CH
2-S (=O)
2-CH
2-,
-CH
2-NR
5-CH
2-,
Or
Preferably-CH
2-S (=O)
2-CH
2-;
A
-And D
-Be the anion of organic or inorganic acid independently, be preferably LiPF
6, LiClO
4, LiBF
4, LiO
3SCF
3, LiN (C
2F
5SO
2)
2, LiC (CF
3SO
2)
3, LiC (C
2F
5SO
2)
3, LiB (C
2O
4)
2, LiB (C
6H
5)
4, LiB (C
6F
5)
4, LiSbF
6, LiAsF
6, LiBr, LiBF
3C
2F
5Or LiPF
3(CF
2CF
3)
3Anion, D for example
-Be I
-, D for example
-Be ClO
4 -,
*Be meant free valency;
R
1, R
2, R
3And R
4Be C independently
1-C
18Alkyl, C
6-C
10Aryl, C
5-C
8Heteroaryl, C
7-C
11Aralkyl or C
5-C
6Cycloalkyl; Or the described group that is replaced by one or more F; Or by one or more heteroatom groups insertions, preferably by O, NR
16, Si (R
16) (R
17), PR
16Or S inserts, most preferably by O or NR
16Described alkyl and/or the cycloalkyl inserted; Or by one or more heteroatom groups replace, preferably by Cl ,-COOR
12,-CONHR
16,-CON (R
16) (R
17), OR
12,-OC (O) R
12,-OC (O) OR
12,-OC (O) NHR
16,-OC (O) N (R
16) (R
17) ,-NHC (O) R
16,-NR
16C (O) R
17,-NCO ,-N
3, NHC (O) NHR
16,-NR
18C (O) N (R
16) (R
17) ,-NHCOOR
12,-N (R
16) (R
17) ,-NR
16COOR
12,-N
+(R
16) (R
17) (R
18) A
-, S
+(R
16) (R
17) A
-Or P
+(R
16) (R
17) (R
18) A
-The described alkyl and/or the cycloalkyl that replace; Or described alkyl and/or the cycloalkyl being inserted and replace by one or more heteroatom groups (for example as defined above those); Or by 1 to 4 C
1-C
4Described aryl, heteroaryl and/or aralkyl that alkyl replaces; Or
R
1With R
2And/or R
3With R
4Form the C that is not substituted or is replaced by F with connecting carbon atom
4-C
13The cycloalkyl double-basis;
R for example
1-R
4Be CH
3:
R
5Be H, OH, C
1-C
18Alkyl, C
6-C
10Aryl, C
7-C
11Aralkyl, C
2-C
18Alkenyl, C
2-C
18Alkynyl, C
5-C
6Cycloalkyl, glycidyl ,-CO-R
16,-CO-NH-R
16,-CON (R
16) (R
17) ,-O-CO-R
16, CO-OR
12,-PO (OR
12) (OR
13) ,-S (=O)
2OR
12,-SR
12,-S (=O) R
12,-S (=O)
2R
12,-S-OR
12,-S (=O)-OR
12,-SiR
16R
17R
18,-CN or halogen; Or the described group that is replaced by one or more F; Or by one or more heteroatom groups insertions, preferably by O, NR
16, Si (R
16) (R
17), PR
16Or S, most preferably by O or NR
16Described alkyl, alkenyl, alkynyl or the cycloalkyl inserted; Or by one or more heteroatom groups replace, preferably by Cl ,-COOR
12,-CONHR
16,-CON (R
16) (R
17), OR
12,-OC (O) R
16,-OC (O) OR
12,-OC (O) NHR
16,-OC (O) N (R
16) (R
17) ,-NHC (O) R
16,-NR
16C (O) R
17,-NCO ,-N
3, NHC (O) NHR
16,-NR
18C (O) N (R
16) (R
17) ,-NHCOOR
12,-N (R
16) (R
17) ,-NR
16COOR
12,-N
+(R
16) (R
17) (R
18) A
-, S
+(R
16) (R
17) A
-Or P
+(R
16) (R
17) (R
18) A
-Replace, more preferably by-O-CO-R
16, CO-OR
16Or OR
12The described alkyl, alkenyl, alkynyl or the cycloalkyl that replace, are most preferably replaced by OH; Or described alkyl and/or the cycloalkyl being inserted and replace by one or more heteroatom groups (for example as defined above those); Or by 1 to 4 C
1-C
4The described aryl or aralkyl that alkyl replaces; Or R
5Be to connect more than a construction unit (d1) to (d4) or the nuclear of multivalence (d6), this multivalence nuclear is preferably C
2-C
20Many acyl groups (be selected from two-, three-, four-, five-or six-carboxylic acid), C
2-C
20Alkyl, C
6-C
10Aryl, C
3-C
8Heteroaryl, C
4-C
24Two-, three-or four-aryl or C
4-C
24Two-, three-or four-heteroaryl, wherein said group be unsubstituted or replaced by F and/or described many acyl groups or described alkyl be not inserted into or inserted by one or more heteroatom groups, preferably by O, NR
16, Si (R
16) (R
17), PR
16Or the S insertion, most preferably by O or NR
16Insert, and/or described many acyl groups or described alkyl be unsubstituted or replaced by one or more heteroatom groups, preferably by Cl ,-COOR
12,-CONHR
16,-CON (R
16) (R
17), OR
12,-OC (O) R
16,-OC (O) OR
12,-OC (O) NHR
16,-OC (O) N (R
16) (R
17) ,-NHC (O) R
16,-NR
16C (O) R
17,-NCO ,-N
3, NHC (O) NHR
16,-NR
18C (O) N (R
16) (R
17) ,-NHCOOR
12,-N (R
16) (R
17) ,-NR
16COOR
12,-N
+(R
16) (R
17) (R
18) A
-, S
+(R
16) (R
17) A
-Or P
+(R
16) (R
17) (R
18) A
-Replace, most preferably replaced by OH;
R
8And R
9Be independently-CH
2O-CO-C
1-C
18Alkyl ,-CH
2-NH-CO-C
1-C
18Alkyl or as to R
1Define;
Or R
8And R
9Form with connecting carbon atom
Group;
R
10And R
11Be H or CH independently
3
R
12And R
13Be H, NH independently
4, Li, Na, K or as to R
16Define;
R
14, R
15Be H or C independently
1-C
8Alkyl;
Or R
14And R
15Form C with connecting carbon atom
4-C
13The cycloalkyl double-basis;
R
16, R
17And R
18Be C independently
1-C
18Alkyl, C
2-C
18Alkenyl, C
6-C
10Aryl, C
5-C
8Heteroaryl, C
7-C
11Aralkyl or C
5-C
6Cycloalkyl; Or the described group that is replaced by one or more F; Or by one or more heteroatom groups insertions, preferably by O, NR
20, Si (R
20) (R
21), PR
20Or S inserts, most preferably by O or NR
20Described alkyl and/or the cycloalkyl inserted; Or by one or more heteroatom groups replace, preferably by Cl ,-COOR
23,-CONHR
20,-CON (R
20) (R
21), OR
23,-OC (O) R
20,-OC (O) OR
23,-OC (O) NHR
20,-OC (O) N (R
20) (R
21) ,-NHC (O) R
20,-NR
20C (O) R
21,-NCO ,-N
3, NHC (O) NHR
20,-NR
20C (O) N (R
21) (R
22) ,-NHCOOR
23,-N (R
20) (R
21) ,-NR
20COOR
23,-N
+(R
20) (R
21) (R
22) A
-, S
+(R
20) (R
21) A
-Or P
+(R
20) (R
21) (R
22) A
-The described alkyl and/or the cycloalkyl that replace; Or described alkyl and/or the cycloalkyl being inserted and replace by one or more heteroatom groups (for example as defined above those); Or by 1 to 4 C
1-C
4Described aryl, heteroaryl and/or aralkyl that alkyl replaces;
R
20, R
21And R
22Be C independently
1-C
18Alkyl, C
2-C
18Alkenyl, C
6-C
10Aryl, C
5-C
8Heteroaryl, C
7-C
11Aralkyl or C
5-C
6Cycloalkyl is preferably C
1-C
18Alkyl; Or the described group that is replaced by one or more F;
R
23Be H, NH
4, Li, Na, K or as to R
20Define, be preferably H or C
1-C
18Alkyl;
R
24Be C
1-C
18Alkyl, C
6-C
10Aryl, C
5-C
8Heteroaryl, C
7-C
11Aralkyl, C
2-C
18Alkenyl, C
2-C
18Alkynyl, C
5-C
6Cycloalkyl or glycidyl;
R
25And R
26Be H, C independently
1-C
18Alkyl, C
6-C
10Aryl, C
7-C
11Aralkyl, C
2-C
18Alkenyl, C
2-C
18Alkynyl, C
5-C
6Cycloalkyl or glycidyl;
R
27Be C
1-C
18Alkyl, C
6-C
10Aryl or-O-C
1-C
18Alkyl or-O-C
6-C
10Aryl;
R
28Be H ,-OH, C
1-C
18Alkyl, C
6-C
10Aryl, C
7-C
11Aralkyl, C
5-C
6Cycloalkyl ,-O-C
1-C
18Alkyl ,-O-C
6-C
10Aryl or-OQ, wherein Q is NH
4, Li, Na or K.
In compound of the present invention, also can there be different types of group-G-simultaneously.In other words, some group-G-can be used as nitroxide group＞N-O and exist, and some are as oxo ammonium salt＞N
+=O exists, and some in addition exist as amine＞N-H or azanol＞N-OH.
Can in disclosed lithium ion battery, use various positive poles.Some positive poles can use with the compound of the formula (d1) to (d6) of wide region, and other have the higher relatively positive electrode that recharges current potential and can only use with the compound of more among a small circle the formula with suitable higher oxidizing potential (d1) to (d6).
For example, positive pole comprises and is selected from by organic group (for example nitroxyl), LiFePO
4, Li
2FeSiO
4, Li
wMnO
2, MnO
2, Li
4Ti
5O
12, LiMnPO
4, LiCoO
2, LiNiO
2, LiNi
1-xCo
yMet
zO
2, LiMn
0.5Ni
0.5O
2, LiMn
0.3Co
0.3Ni
0.3O
2, LiFeO
2, LiMet
0.5Mn
1.5O
4, vanadium oxide, Li
1+xMn
2-zMet
yO
4-mX
n, FeS
2, LiCoPO
4, Li
2FeS
2, Li
2FeSiO
4, LiMn
2O
4, LiNiPO
4, LiV
3O
4, LiV
6O
13, LiVOPO
4, LiVOPO
4F, Li
3V
2(PO
4)
3, MoS
3, sulphur, TiS
2, TiS
3And the compound of the group formed of combination, 0＜m＜0.5,0＜n＜0.5,0.3≤w≤0.4,0＜x＜0.3,0＜z＜0.5,0＜y＜0.5 wherein, Met is Al, Mg, Ti, B, Ga, Si, Ni or Co, and X is S or F.The example of this class organic group is listed among the EP1128453.More particularly, this organic group in EP1128453 with chemical formula (A1) to (A11), especially with chemical formula (A2) with (A7) to (A10), particularly represent with chemical formula (A7)-(A10).Other example of this class organic group is the compound in the Table A 23-57 page or leaf of the compound of the cross-linked polymer that can obtain according to the method for WO-A-2007/115939 and formula (c1)-(c7), (d1) to (d7), (e1) to (e7) and WO-A-2007/107468.
In the positive pole that forms, can comprise powdery lithium (for example, LECTRO
TMThe MAX stabilized lithium metal, from FMC Corp., Gastonia, NC).Lithium also can mix in the negative pole, so as in the initial discharge process, to have can extract lithium can be for mixing in the positive pole.Some positive electrodes can according to they structure or form and under many voltages, to charge, if therefore select suitable form and suitable battery operated condition then can be used as positive pole.By LiFePO
4, Li
2FeSiO
4, Li
xMnO
2(wherein x is about 0.3 to about 0.4, and for example be heated to about 300 to about 400 ℃ make) or MnO by stoichiometric mixture with electrolytic manganese dioxide and LiOH
2The electrode that (for example making by electrolytic manganese dioxide being heat-treated to about 350 ℃) makes can be provided in the battery that has especially desirable performance characteristic when compound with formula (d1) to (d6) uses.This positive pole can contain the additive that those skilled in the art are familiar with, for example carbon black, flake graphite etc.For example, this positive pole can be any form easily, comprises paper tinsel, plate, bar, paste, or by on conduction collector body or other suitable carriers, forming the composite material that the positive electrode coating is made.
For example, negative pole comprise graphitic carbon, lithium metal, lithium alloy (for example Li/Sn alloy or Li/Co alloy), based on non-crystalline material or its combination of Sn and Co.
Graphitic carbon is for example to have
(002) interplanar distance d
002And the graphitic carbon that exists with powder, thin slice, fiber or spheroid (for example in the middle of phase microballoon) form; Lithium alloy is for example as United States Patent (USP) 6,203,944 and WO 00/103444 described in, Li for example
4/3Ti
5/3O
4Sn-Co base amorphous negative pole is (for example, from the NEXELION of Sony Corp.
TMNegative pole in the composite lithium ion cell); And combination.Can use to contain the negative pole that can extract lithium (for example metal lithium electrode, can extract lithium alloy electrode or contain the electrode of powdery lithium), in the initial discharge process, mix in the positive pole so that can extract lithium.Negative pole can contain the additive that those skilled in the art are familiar with, for example carbon black.Negative pole can be any form easily, comprises paper tinsel, plate, bar, paste or the composite material of making by formation negative material coating on conduction collector body or other suitable carriers.
Electrolyte (c) provide load path between positive pole and negative pole.This electrolyte except that component (i), (ii) and can also comprise other additive that those skilled in the art are familiar with (iii).This electrolyte can be any form easily, comprises liquid and gel.
Lithium salts (i) is preferably selected from by LiPF
6, LiClO
4, LiBF
4, LiO
3SCF
3, LiN (C
2F
5SO
2)
2, LiC (CF
3SO
2)
3, LiC (C
2F
5SO
2)
3Or LiB (C
2O
4)
2, LiB (C
6H
5)
4, LiB (C
6F
5)
4, LiSbF
6, LiAsF
6, LiBr, LiBF
3C
2F
5, LiPF
3(CF
2CF
3)
3And the group of combination composition.
In electrolyte, can use various polar non-solutes (ii).Exemplary polar non-solute (ii) is to dissolve capacity lithium salts (i) and formula (d1) liquid or the gel to the compound of (d6), so that an amount of electric charge can be transferred to negative pole from positive pole.Exemplary polar non-solute (ii) can for example approximately-30 ℃ to about 70 ℃ wide temperature range, under the situation of not freezing or boiling, use, and in the electrochemistry scope of the compound work of battery electrode and formula (d1) to (d6), stablize.
Preferably, this polar non-solute (ii) is selected from by the inferior propyl ester of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, gamma-butyrolacton, oxolane, dioxolanes, sulfolane, dimethyl formamide, dimethylacetylamide, N-N-methyl-2-2-pyrrolidone N-, butylene carbonate, vinylene carbonate, carbonic acid fluoro ethyl, carbonic acid fluoro, difluoroacetic acid methyl esters, ethyl difluoro, dimethoxy-ethane, two (2-methoxy ethyl) ether and the group formed thereof.
The component that electrolyte also contains dissolving easily (iii), i.e. the compound of formula (d1) to (d6).This electrolyte can be prepared under no component situation (iii), incorporating its negative or positive electrode again into contains in the solubilized component battery (iii), this solubilized component (iii) can or be dissolved in this electrolyte in the first charge-discharge cyclic process in battery assembling back, so that this battery is once coming into operation, the component that this electrolyte just contains dissolving (iii).
For example, component (iii) is formula (d1) or compound (d3), wherein
X is O;
R
1-R
4Be CH
3
R
5Be C
1-C
18Alkyl, C
5-C
6Cycloalkyl ,-CO-R
16,-CON (R
16) (R
17), CO-OR
12,-PO (OR
12) (OR
13) ,-S (=O)
2R
12Or the described group that is replaced by one or more F; Or by one or more heteroatom groups insertions, preferably by O, NR
16Described alkyl, alkenyl, alkynyl or the cycloalkyl inserted; Or by one or more heteroatom groups replace, preferably by-COOR
12,-CON (R
16) (R
17), OR
12,-OC (O) R
16,-OC (O) OR
12,-OC (O) N (R
16) (R
17) ,-NR
16C (O) R
17,-N
3,-NR
18C (O) N (R
16) (R
17) ,-N (R
16) (R
17) ,-NR
16COOR
12Replace, more preferably by-O-CO-R
16, CO-OR
16Or OR
12The described alkyl, alkenyl, alkynyl or the cycloalkyl that replace; Or described alkyl and/or the cycloalkyl being inserted and replace by one or more heteroatom groups (for example as defined above those); Or by 1 to 4 C
1-C
4The described aryl or aralkyl that alkyl replaces;
R
12And R
13Be H, NH independently
4, Li, Na, K or as to R
16Define;
R
16, R
17And R
18Be C independently
1-C
18Alkyl, C
2-C
18Alkenyl, C
6-C
10Aryl, C
5-C
8Heteroaryl, C
7-C
11Aralkyl or C
5-C
6Cycloalkyl; Or the described group that is replaced by one or more F; Or by one or more heteroatom groups insertions, preferably by O, NR
20, PR
20Or S inserts, most preferably by O or NR
20Described alkyl and/or the cycloalkyl inserted; Or by one or more heteroatom groups replace, preferably by Cl ,-COOR
23,-CON (R
20) (R
21), OR
23,-OC (O) R
20,-OC (O) OR
23,-OC (O) N (R
20) (R
21) ,-NR
20C (O) R
21,-NCO ,-N
3,-NR
20C (O) N (R
21) (R
22) ,-N (R
20) (R
21) ,-NR
20COOR
23The described alkyl and/or the cycloalkyl that replace; Or described alkyl and/or the cycloalkyl being inserted and replace by one or more heteroatom groups (for example as defined above those); Or by 1 to 4 C
1-C
4Described aryl, heteroaryl and/or aralkyl that alkyl replaces;
R
20, R
21And R
22Be C independently
1-C
18Alkyl, C
2-C
18Alkenyl, C
6-C
10Aryl, C
5-C
8Heteroaryl, C
7-C
11Aralkyl or C
5-C
6Cycloalkyl, preferred C
1-C
18Alkyl; Or the described group that is replaced by one or more F;
R
23Be H, NH
4, Li, Na, K or as to R
20Define, be preferably H or C
1-C
18Alkyl.
As component (iii), the compound of formula (d1) to (d6) preferably, wherein
For the compound of formula (d1), X is O;
For the compound of formula (d2), X is S;
Y is-CH
2-O-CH
2-,-CH
2-S-CH
2-,-CH
2-S (=O)-CH
2-,-CH
2-S (=O)
2-CH
2-,-CH
2-NR
5-CH
2-,
Or
D
-Be I
-Or LiPF
6, LiClO
4, LiBF
4, LiO
3SCF
3, LiN (C
2F
5SO
2)
2, LiC (CF
3SO
2)
3, LiC (C
2F
5SO
2)
3, LiB (C
2O
4)
2, LiB (C
6H
5)
4, LiB (C
6F
5)
4, LiSbF
6, LiAsF
6, LiBr, LiBF
3C
2F
5Or LiPF
3(CF
2CF
3)
3Anion, be preferably I
-Or ClO
4 -
R
1, R
2, R
3And R
4Be C independently
1-C
18Alkyl or C
6-C
10Aryl; Or the described group that is replaced by one or more F; Or
R
1And R
2And/or R
3And R
4Form the C that is not substituted or is replaced by F with connecting carbon atom
4-C
13The cycloalkyl double-basis;
R
5Be H, OH, C
1-C
18Alkyl, C
6-C
10Aryl, C
7-C
11Aralkyl, C
3-C
18Alkenyl, C
3-C
18Alkynyl, C
5-C
6Cycloalkyl, glycidyl ,-CO-R
16,-CO-NH-R
16,-CON (R
16) (R
17) ,-O-CO-R
16,-CO-OR
12,-(CH
2)
qCOOR
12Or-PO (OR
12) (OR
13); Or the described group that is replaced by one or more F; Or the described alkyl that is replaced by one or more OH;
R
6And R
7Be independently duplet or=O;
R
8And R
9Be independently-CH
2O-CO-C
1-C
18Alkyl ,-CH
2-NH-CO-C
1-C
18Alkyl or as to R
1Define;
Or R
8And R
9Form with connecting carbon atom
Group;
R
10And R
11Be H or CH independently
3
R
12And R
13Be H, NH independently
4, Li, Na, K or as to R
16Define, and
R
16And R
17Be C independently
1-C
18Alkyl, C
3-C
18Alkenyl, C
6-C
10Aryl or C
7-C
11Aralkyl; Or the described group that is replaced by one or more F;
R
25And R
26Be H, C independently
1-C
18Alkyl, C
6-C
10Aryl, C
7-C
11Aralkyl, C
2-C
18Alkenyl, C
2-C
18Alkynyl, C
5-C
6Cycloalkyl or glycidyl;
R
28Be H ,-OH, C
1-C
18Alkyl, C
6-C
10Aryl, C
7-C
11Aralkyl, C
5-C
6Cycloalkyl ,-O-C
1-C
18Alkyl ,-O-C
6-C
10Aryl or-OQ, wherein Q is NH
4, Li, Na or K;
And
Q is 1 to 6 integer.
Y is more preferably-CH
2-S (=O)
2-CH
2-,
Or
Especially-CH
2-S (=O)
2-CH
2-;
D
-Be I
-Or ClO
4 -
R
1, R
2, R
3And R
4Be methyl, ethyl or propyl group independently; Or
R
1And R
2And/or R
3And R
4Form C with connecting carbon atom
6-C
7The cycloalkyl double-basis;
R
5Be H, OH, C
1-C
8Alkyl, phenyl, benzyl, C
3-C
6Alkynyl, C
5-C
6Cycloalkyl, glycidyl ,-CO-R
16,-CO-C
1-C
5Perfluoroalkyl ,-CO-NH-R
16,-CO-OR
16Or-PO (OR
12) (OR
13); Or by the described alkyl of an OH replacement;
R
6And R
7Be independently duplet or=O;
R
8And R
9Be independently-CH
2O-CO-C
1-C
4Alkyl ,-CH
2-NH-CO-C
1-C
4Alkyl or as to R
1Define;
Or R
8And R
9Form with connecting carbon atom
Group;
R
10And R
11Be H or CH independently
3
R
12And R
13Be H, NH independently
4, Li, Na, K or as to R
16Define; And
R
16Be C
1-C
8Alkyl, C
3-C
6Alkenyl, phenyl or benzyl;
R
25And R
26Be C
1-C
8Alkyl or phenyl; And
R
28It is phenyl;
Condition is if R
6And R
7All be=O, then R
5Can only be OH.
Y most preferably is-CH
2-S (=O)
2-CH
2-,
Especially-CH
2-S (=O)
2-CH
2-;
D
-Be I
-Or ClO
4 -
R
1, R
2, R
3And R
4Be methyl, ethyl or propyl group independently; Or
R
1And R
2And/or R
3And R
4Form C with connecting carbon atom
6-C
7The cycloalkyl double-basis;
R
5Be H, C
1-C
8Alkyl, phenyl, benzyl, C
3-C
6Alkynyl, glycidyl ,-CO-R
16,-CO-NH-R
16, CO-OR
16Or-PO (OR
12) (OR
13); Or by the described alkyl of an OH replacement;
R
6And R
7Be independently duplet or=O;
R
8And R
9Be independently-CH
2O-CO-C
1-C
4Alkyl or as to R
1Define;
R
10And R
11Be H or CH independently
3
R
12And R
13Independently as to R
16Define R
12And R
13Be preferably C
1-C
8Alkyl, most preferably C
1-C
4Alkyl;
R
16Be C
1-C
8Alkyl, C
3-C
6Alkenyl, phenyl or benzyl;
R
25, R
26Be C
1-C
4Alkyl or phenyl, preferable methyl or phenyl;
R
28It is phenyl; And
R
29Be H, C
1-C
4Alkyl or-CO-O-C
1-C
8Alkyl, preferred H, methyl or-the CO-O-tert-butyl group.
Be suitable as component (iii) be for example following nitroxide:
Preferably, compound (iii) is dissolved in the electrolyte.
Preferred embodiment is rechargeable lithium ion battery, and it comprises:
(a) anodal (for example having the current potential of recharging), it comprises and is selected from by LiFePO
4, Li
2FeSiO
4, Li
wMnO
2, MnO
2, Li
4Ti
5O
12, LiMnPO
4, LiCoO
2, LiNiO
2, LiNi
1-xCo
yMet
zO
2, LiMn
0.5Ni
0.5O
2, LiMn
0.3Co
0.3Ni
0.3O
2, LiFeO
2, LiMet
0.5Mn
1.5O
4, vanadium oxide, Li
1+xMn
2-zMet
yO
4-mX
n, FeS
2, LiCoPO
4, Li
2FeS
2, Li
2FeSiO
4, LiMn
2O
4, LiNiPO
4, LiV
3O
4, LiV
6O
13, LiVOPO
4, LiVOPO
4F, Li
3V
2(PO
4)
3, MoS
3, sulphur, TiS
2, TiS
3And the compound of the group formed of combination, 0＜m＜0.5,0＜n＜0.5,0.3≤w≤0.4,0＜x＜0.3,0＜z＜0.5,0＜y＜0.5 wherein, Met is Al, Mg, Ti, B, Ga, Si, Ni or Co, and X is S or F;
(b) negative pole, it comprises graphitic carbon, lithium metal, lithium alloy (for example Li/Sn alloy or Li/Co alloy), based on non-crystalline material or its combination of Sn and Co; With
(c) electrolyte, it comprises:
(i) lithium salts is selected from by LiPF
6, LiClO
4, LiBF
4, LiO
3SCF
3, LiN (C
2F
5SO
2)
2, LiC (CF
3SO
2)
3, LiC (C
2F
5SO
2)
3Or LiB (C
2O
4)
2, LiB (C
6H
5)
4, LiB (C
6F
5)
4, LiSbF
6, LiAsF
6, LiBr, LiBF
3C
2F
5, LiPF
3(CF
2CF
3)
3And the group of combination composition;
(ii) polar non-solute is selected from by ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, gamma-butyrolacton, oxolane, dioxolanes, sulfolane, dimethyl formamide, dimethylacetylamide, N-N-methyl-2-2-pyrrolidone N-, butylene carbonate, vinylene carbonate, carbonic acid fluoro ethyl, the inferior propyl ester of carbonic acid fluoro, difluoroacetic acid methyl esters, ethyl difluoro, dimethoxy-ethane, two (2-methoxy ethyl) ether and combination thereof; With
(iii) be dissolved at least a in the electrolyte and be selected from the compound of the group of forming by formula (d1) to (d6) as defined above.
For example, by weight, amount (i) is 1-50% (ii), preferred 5-30%, most preferably 10-25%.
For example, by weight, amount (iii) is 0.1-50% (ii), preferred 1-20%, most preferably 2-10%.
Embodiment is to make the method for rechargeable lithium ion sealed cell, comprises with any order with the following substances assembling be encapsulated in step in the suitable shell:
(a) anodal (for example having the current potential of recharging);
(b) negative pole; With
(c) electrolyte, it comprises
(i) lithium salts,
(ii) polar non-solute and
The (iii) at least a compound that is selected from the group of forming by formula (d1) to (d6) as defined above.
Described in the layout of lithium ion battery such as the WO 2006/124389.
Described lithium ion battery can comprise the porous battery separator, and it is between positive pole and negative pole, and load material (comprising that compound (iii)) can therefrom pass.Suitable dividing plate is that those skilled in the art are familiar with.Disclosed battery can be sealed in the suitable shell, for example, as the button cell that those skilled in the art are familiar with the engagement cylindrical metal shell in, in elongated cylindrical AAA, AA, C or D battery case or replaceable battery group.Described battery can be used in the multiple device, comprises portable computer, console display, personal digital assistant, mobile phone, motorization device (for example individual or home appliances and vehicle), instrument, lighting device (for example photoflash lamp) and heater.Disclosed battery can be used in the electricity and electronic device (for example photoflash lamp, radio device, CD Player etc.) of low-cost mass selling especially, and they are before this usually with not rechargeable battery (for example alkaline battery) energy supply.About the structure of rechargeable lithium ion battery and the further details of application is that those skilled in the art are familiar with.
An embodiment is rechargeable lithium ion battery, and wherein compound (iii) is dissolving or may be dissolved in the electrolyte and have the redox chemistry shuttle capable of circulation that is higher than the anodal oxidizing potential that recharges current potential.
(compound (iii) being higher than this redox chemistry shuttle capable of circulation when attempting, be the compound of formula (d1) to (d6)) oxidizing potential during with battery charge, the redox chemistry shuttle capable of circulation load of this oxidation and the suitable quantity of electric charge of charging current that is applied on the negative pole have prevented over-charging of battery thus.
This compound (iii) has usually and recharges current potential height (promptly more positive) oxidizing potential than positive pole.For example, compound oxidizing potential (iii) is only a little more than the current potential that recharges of positive pole, and is lower than the current potential when the irreversible cell damage may take place, and desirably is lower than the current potential when excessive battery heating or outgas may take place.
Preferably have (iii) than the compound that recharges the high 0.3V to 5V of current potential, preferred 0.3 to 0.6V oxidizing potential of positive pole.
For example, compound (iii) at least 30 under the following conditions charge-discharges circulation back, preferably at least 80 charge-discharges circulation backs, after at least 100 charge-discharges circulations, provide over-charge protective especially: (iii) (wherein G is with compound being enough to
) under the charging voltage of oxidation, each cycle period flows down at 100% the electric charge that overcharges that equals battery capacity.
Also can use two or more compounds mixture (iii) with different electrochemical potentialses.For example, effective first compound effective second compound (iii) and under high voltage (iii) all can be used in the monocell under low voltage.If first compound is (iii) degraded and is lost its effectiveness after many charge, second compound (iii) (it can be (iii) effectively simultaneously not oxidized at first compound) can be taken over, and provides further (though higher E at overcharging to destroy
Cv) margin of safety.Compound (iii) also can provide over for battery or series battery; This over can obtain similarly with WO 2005/099025.
Embodiment is the method that the battery that lithium-ion electric battery recharge and chemical restriction cause by overcharging is damaged, be included between the positive pole of the Lithuim rechargeable battery that contains electrolyte (c) and the negative pole and supply charging current, this electrolyte (c) comprise lithium salts (i), polar non-solute (ii) with redox chemistry shuttle capable of circulation, this redox chemistry shuttle capable of circulation comprise be dissolved in the electrolyte and have be higher than the anodal oxidizing potential that recharges current potential compound as defined above (iii).
Preferably use as defined above compound (iii) as the redox chemistry shuttle in the rechargeable lithium ion battery.
An embodiment is rechargeable lithium ion battery, and wherein compound (iii) is the molecular oxidation reduction shuttle that is used for the redox target-seeking.
For example, this molecular oxidation reduction shuttle (be compound (iii)) is dissolved in the electrolyte of negative or positive electrode, especially in the Zheng Ji electrolyte.
In charging process, molecular oxidation reduction shuttle (S) is oxidized to molecular oxidation reduction shuttle, and (that is, G is at the collector body place
The compound of formula (d1) to (d6)) cation (S
+), it gives electrode by the body diffusion with charge transport.S
+(that is, G is to be reduced back S by the injection of the hole in the electrode particle
The compound of formula (d1) to (d6)).In discharge process, S
+The place is reduced into S at collector body, and it gives the oxidizing electrode particle with electron transport again.Using the advantage that freely spreads molecular oxidation reduction shuttle is that it allows to carry out fast charge transfer, so the output of the power of this battery is huge.Usually, active electrode material contacts with the collector body electronics.Electrode material is usually with conductive additive preparation, is attached to electrode slice on the metallic carrier with formation.For example, in the presence of described molecular oxidation reduction shuttle, do not need or only need the conductive additive of low amount, and greatly improved the energy density of electrode.
Equally preferably use compound as defined above (iii) as the molecular oxidation reduction shuttle that is used for the redox target-seeking.
Another embodiment be as defined above compound (d1) to (d6),
Wherein
G is
Or
When G is
The time,
This compound is formula (d1), (d3) or compound (d4), and
R
5Be-CO-R
16,-CO-NH-R
16,-CON (R
16) (R
17), CO-OR
16,-O-CO-R
16,-(CH
2)
qCOOR
12,-PO (OR
12) (OR
13) ,-S (=O)
2OR
12,-SR
12,-S (=O) R
12,-S (=O)
2R
12,-S-OR
12,-S (=O)-OR
12,-SiR
16R
17R
18,-CN or-halogen; R
5Preferably-CO-R
16,-CO-NH-R
16, CO-OR
16,-(CH
2)
qCOOR
12,-PO (OR
12) (OR
13) ,-S (=O)
2OR
12,-SiR
16R
17R
18,-CN or-halogen; R
5Most preferably be-CO-R
16,-CO-NH-R
16, CO-OR
16,-PO (OR
12) (OR
13) ,-S (=O)
2OR
12,-SiR
16R
17R
18,-CN or-halogen;
Q is 1 to 6 integer;
Condition is
For the compound of formula (d1), R
5Be-PO (OR
12) (OR
13) ,-S (=O)
2OR
12,-SR
12The R of ,-S)
12,-S (=O)
2R
12,-S-OR
12,-S (=O)-OR
12Or-SiR
16R
17R
18And
Get rid of compound
With
For example, for these compounds, be suitable for rechargeable battery in compound (iii) identical preferably.
Formula (d1) to the precursor compound of the compound of (d6) is known substantially and partly can buys.They can prepare by known method.Their preparation is disclosed in for example people such as A.Khalaj, Monatshefte f ü r Chemie, 1997,128,395-398; People such as S.D.Worley, Biotechnol.Prog., 1991,7,60-66; People such as T.Toda, Bull.Chem.Soc.Jap., 1972,45, among the 557-561.
Can use hydrogen peroxide and US 5,654, the 4-hydroxyl-2,2,6 described in 434, the oxidation of 6-tetramethyl piperidine is oxidized to nitroxide with nitrogenous (aminic) precursor similarly.Another same suitable oxidizing process is described in the WO 00/40550 that uses peracetic acid.
The limit of nitroxide chemistry is described and is found in for example L.B.Volodarsky, V.A.Reznikov, V.I.Ovcharenko.: " Synthetic Chemistry of Stable Nitroxides ", CRC Press, 1994.
Y is-CH 2 -O-CH 2 -compoundJ.T.Lai:Synthesis 122-123 for example, (1984) described cyclodehydration preparation by corresponding aminodiol.
Y is-CH 2 -S (=O) 2 -CH 2 -compoundCan be by the cyclisation of dimethyl-allyl sulfone being prepared described in DE 2 351 865 with ammonia.This patent has also been reported the preparation of corresponding nitroxide.
Y is-CH 2 -S (=O)-CH 2 -compoundCan be as for example Still, Ian W.J.; Szilagyi, Sandor:Synthetic Communications (1979), 9 (10), 923-30 is described to be removed an oxygen atom by reproducibility and prepares
Y is-CH 2 -S-CH 2 -compoundCan be as Akgun, Eyup; Mahmood, Khalid; Mathis, Chester:Journal of the Chemical Society, ChemicalCommunications (1994), (6), 761-2 is described to be removed two oxygen atoms by reproducibility and prepares.
Y is
Compound can be by the multiple known method preparation of preparation sulfonium salt.
Y is
Or-CH
2-NR
5-CH
2-compound can be by using LiAlH
4Reducing corresponding piperazinedione or piperazine ketone prepares, as Kaliska, and Viera; Toma, Stefan; Lesko, Jan.:Collection of Czechoslovak Chemical Communications (1987), 52 (9), 2266-73 is described.
The gained compound can be further functionalized via alkylation, acyl groupization etc. (they are known standard reactions) on the N-atom.
Y is
Or
Compound can by the cyclisation of dimethyl Xi Bing Ji phosphonium salt and randomly subsequently from phosphorus hydrolysis remove a group and prepare, as Skolimowski, J.; Skowronski, R.; Simalty, M.:Tetrahedron Letters 4833-4 (1974) is described.
Z=CH
2-CH
2-or-CH
2-CO-and Q=-CH
2-compound can be as Ramasseul, R.; Rassat A.; Rey prepares described in the works of P.:Tetrahedron Letters 839 (1975) or with it similarly.
Y is
Or
Compound can prepare described in the 353B2 as US 6,664.
Y is
Or
Compound can be as Rozantsev, E.G.; Chudinov, A.V.; Sholle, V.D.:Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya (1980), (9), the described preparation of 2114-17.
The method of describing among the WO 2004/031150 can be used for preparing the oxo ammonium salt.
The term alkyl comprises for example methyl, ethyl, propyl group, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, 2-ethyl-butyl, n-pentyl, isopentyl, 1-methyl amyl, 1 in given carbon atom limit, 3-dimethylbutyl, n-hexyl, 1-methyl hexyl, n-heptyl, 2-methylheptyl, 1,1,3,3-tetramethyl butyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethyl hexyl, 1,1,3,3-tetramethyl amyl group, nonyl, decyl, undecyl, 1-methyl undecyl or dodecyl.
The alkyl that is inserted by one or more heteroatom groups comprises at least two carbon atoms.
The alkenyl and the alkynyl that are inserted by one or more heteroatom groups comprise at least three carbon atoms.
For example, heteroaryl contains 1 or 2 hetero-atom, especially O, N, P, S or its combination.
The example of heteroaryl is furans, pyrroles, thiophene, pyridine, imidazoles, oxazole, thiazole, triazole, pyridine, pyridazine, pyrimidine or pyrazine.
Non-limiting examples of alkenyls in given carbon atom limit is vinyl, pi-allyl, and the side chain of cyclobutenyl, pentenyl, hexenyl, heptenyl, octenyl, nonene base, decene base, undecenyl and dodecenyl succinic and straight chain isomers.But the term alkenyl also comprises the residue that has more than a conjugation or unconjugated pair of key, for example can comprise a two key.
The example of the alkynyl in given carbon atom limit is acetenyl, propinyl, and the side chain of butynyl, pentynyl, hexin base, heptyne base, octyne base, n-heptylacetylene base, decynyl, hendecyne base and dodecyne base and straight chain isomers.But the term alkynyl also comprises the residue and the residue with at least one triple bond and at least one two key that has more than a conjugation or unconjugated triple bond, for example comprises the residue with a triple bond.
Some examples of cycloalkyl are cyclopenta, cyclohexyl, methylcyclopentyl or dimethylcyclopentyl, especially cyclopenta or cyclohexyl, particularly cyclohexyl.
Some examples of cycloalkyl double-basis are 1,1-cyclopenta double-basis, 1,1-cyclohexyl double-basis or 1,1-suberyl double-basis, especially 1,1-cyclohexyl double-basis or 1,1-suberyl double-basis.
Aryl is a phenyl for example.
Aralkyl is for example benzyl or α, α-Er Jiajibianji.
Term halogen can comprise fluorine, chlorine, bromine and iodine; For example halogen is a fluorine.
The group that is replaced by one or more F can be fluoridized (especially, all hydrogen atoms of described group is substituted by F).
Unless indicate separately, percentage is weight %, and ratio is a ratio by weight.
Abbreviation
The cmpd compound
The CV cyclic voltammetry
The DMF dimethyl formamide
The EDTA ethylenediamine tetra-acetic acid
The MS mass spectrography
The NMR nulcear magnetic resonance (NMR)
Sat ' d is saturated
Satd is saturated
TEMPO 2,2,6,6-tetramethyl piperidine-N-oxygen base
The THF oxolane
Synthesis example
Embodiment 1 (Cmpd 1):
Slowly add hydrogen peroxide (water-based, 30%, 2.5 gram, 22 mMs) to 2,2,3,5,5-pentamethyl-imidazolidine-4-ketone (1.85 grams, 10 mMs) is containing EDTA (0.0497 gram, 0.17 mM) and Na
2WO
4* 2H
2In the solution in the acetate (15 milliliters) of O (0.0495 gram, 0.15 mM), and the gained light yellow suspension stirred down in room temperature (25 ℃) spend the night.Append hydrogen peroxide (2.4 grams, 21 mMs), and this orange solution was stirred 2 days again.Make reactant mixture reach pH 7 (the NaOH aqueous solution, 30%), and with gained orange suspension CH
2Cl
2(2 * 40 milliliters) extraction.With organic facies salt water washing, through MgSO
4Drying also distillates solvent to stay reddish oil on rotary evaporator, it solidifies when leaving standstill.Purify by chromatography (silica gel, hexane/ethyl acetate 4/6), produce the title compound of the orange lenticular of 0.4 gram, mp.67-69 ℃.MS: to C
8H
15N
2O
2(171.22), actual measurement M
+=171.
Intermediate:
A) 2,2,5,5-tetramethyl-imidazolidine-4-ketone
As EP1283240 (2003; Authorize people such as D.Lazzari, Ciba Specialty ChemicalsHolding Inc.; CAN 138:154404) preparation described in.
B) 2,2,3,5,5-pentamethyl-imidazolidine-4-ketone
Slowly add methyl iodide (3.6 grams, 25 mMs) to 2,2,5,5-tetramethyl-imidazolidine-4-ketone (3.55 grams, 25 mMs) is in the ice-cold suspension in the toluene (10 milliliters) that contains potassium tert-butoxide (2.9 grams, 25 mMs).Remove ice bath and reactant mixture stirred and spend the night.Filter and on rotary evaporator evaporating solvent, stay yellow oil.The fractionation short-path vacuum distillation of use Kugelrohr stove provides the title compound of 2 gram colourless liquid shapes.MS: to C
8H
16N
2O (156.23), actual measurement M
+=156.
1H-NMR(300MHz，CDCl
3)，δ(ppm).2.81(s，3H)，1.78(br?s，1H)，1.39(s，6H)，1.33(s，6H)。
Embodiment 2 (Cmpd 2):
As Toda, Toshimasa; Morimura, Syoji; Mori, Eiko; Horiuchi, Hideo; Murayama, Keisuke:Bulletin of the Chemical Society of Japan (1971), 44 (12), prepare described in the 3445-50.
Embodiment 3 (Cmpd 3):
With 2,2,5,5-tetramethyl-imidazolidine-4-ketone-1-N-oxygen base (Cmpd 2) (23.6 grams, 0.15 mole) is dissolved in the dry DMF (100 milliliters), and slowly adds sodium hydride (0.157 mole, 55% dispersion of 6.9 grams in paraffin oil).This mixture was stirred 2 hours down at 40 ℃, be cooled to 3 ℃ then.Added propargyl bromide (19.6 grams, 0.165 mole) then through 45 minutes, temperature is remained on 3-8 ℃ simultaneously.This mixture was at room temperature stirred 15 hours again water (1000 milliliters) dilution then.Leach solid and on silicagel column, use carrene-ethyl acetate (4: 1) chromatographic isolation, so that 22.8 gram red crystals, mp.119-121 ℃ to be provided.
Embodiment 4 (Cmpd 4):
With 2,2,5,5-tetramethyl-imidazolidine-4-ketone-1-N-oxygen base (Cmpd 2) (1.73 grams, 0.011 mole), triethylamine (1.7 milliliters, 0.012 mole) and 4-dimethylaminopyridine (67 milligrams) are dissolved in the carrene (12 milliliters).In this agitating solution, slowly add methacrylic chloride (1.27 grams, 0.012 mole), make temperature remain on 3-8 ℃ simultaneously.This mixture was at room temperature stirred 2 hours, wash (3 * 5 milliliters) and evaporation then with water.Solid residue from methyl alcohol recrystallization with provide 2.08 the gram red crystals, mp.94-96 ℃.
Embodiment 5 (Cmpd 5):
As Toda, Toshimasa; Morimura, Syoji; Mori, Eiko; Horiuchi, Hideo; Murayama, Keisuke:Bulletin of the Chemical Society of Japan (1971), 44 (12), prepare described in the 3445-50.
As Nesvadba, P., Kramer, A., Zink, M.-O.:US 6,479,608B1, (2002), (US 6 for cmpd 6,479, the embodiment A 4 of 608B1), (US 6,479 for cmpd 12, the Embodiment B 34 of 608B1), cmpd 13 (US 6,479, the Embodiment B 68 of 608B1), cmpd 15 (US6,479, the Embodiment B 30 of 608B1), (US 6,479 for cmpd 16, the Embodiment B 57 of 608B1), cmpd 17 (US 6,479, the Embodiment B 77 of 608B1), (US 6 for cmpd 18,479, the Embodiment B 37 of 608B1), (US 6,479 for cmpd 19, the Embodiment B 26 of 608B1), cmpd 20 (US 6,479, the Embodiment B 88 of 608B1), (US 6 for cmpd 21,479, the Embodiment B 74 of 608B1), cmpd 22 (US 6,479, the Embodiment B 62 of 608B1), (US 6 for cmpd 24,479, the Embodiment B 1 of 608B1), cmpd 25 (US 6,479, the Embodiment B 5 of 608B1), (US 6 for cmpd 26,479, the Embodiment B 11 of 608B1) preparation described in.
Embodiment 7 (Cmpd 7):
As Toda, Toshimasa; Morimura, Syoji; Mori, Eiko; Horiuchi, Hideo; Murayama, Keisuke:Bulletin of the Chemical Society of Japan (1971), 44 (12), prepare described in the 3445-50.
Embodiment 8 (Cmpd 8):
As Chalmers, Alexander M.:(Ciba-Geigy), Ger.Offen. (1975), DE2500313, preparation described in the embodiment 14.
Embodiment 9 (Cmpd 9):
With Ramey, Chester E.; Luzzi, the embodiment 7 of John J.US3936456 (1976) prepares similarly.Red crystals, mp.=52-54 ℃.
Embodiment 10 (Cmpd 10):
As Yoshioka, Takao; Mori, Eiko; Murayama, Keisuke:Bulletin ofthe Chemical Society of Japan (1972), 45 (6), prepare described in the 1855-60.
Embodiment 11 (Cmpd 11):
As Yoshioka, Takao; Mori, Eiko; Murayama, Keisuke:Bulletin ofthe Chemical Society of Japan (1972), 45 (6), prepare described in the 1855-60.
Embodiment 14 (Cmpd 14):
As Lai, John T.Synthesis (1981), (1) prepares described in the 40-2.
Embodiment 23 (Cmpd 23):
As Lai, John Ta-yuan; Filla, Deborah S.WO 2001023435A1, preparation described in the embodiment 2.
Embodiment 27,28 (Cmpds 27,28):
As Lai, John Ta-yuan; Masler, William F.; Nicholas, Paul Peter; Pourahmady, Naser; Puts, Rutger D.; Tahiliani, Shonali, EP 869137A1, preparation described in the embodiment 5 and 6.
Embodiment 29 (Cmpd 29): 3-(2,2-dimethyl-propiono)-2,2,5,5-tetramethyl-imidazolidine-4-ketone-1-N-oxygen base
With 2,2,5,5-tetramethyl-imidazolidine-4-ketone-1-N-oxygen base (Cmpd 2) (1.73 grams, 0.011 mole), triethylamine (1.7 milliliters, 0.012 mole) and 4-dimethylaminopyridine (67 milligrams) are dissolved in the carrene (12 milliliters).In this agitating solution, slowly add pivalyl chloride (1.46 grams, 0.012 mole), make temperature remain on 3-8 ℃ simultaneously.This mixture was at room temperature stirred 2 hours, wash (3 * 5 milliliters) and evaporation then with water.Through silica gel (hexane-ethyl acetate 3: 1) with the solid residue chromatographic isolation, and from hexane recrystallization with provide 1.85 the gram red crystals, mp.69-71 ℃.MS: to C
12H
21N
2O
3(241.3), actual measurement M
+=241.
Embodiment 30 (Cmpd 30): (2,2,4,4-tetramethyl-5-oxo-imidazolidine-3-N-Oxy-1-yl)-diethyl phosphonate
With 2,2,5,5-tetramethyl-imidazolidine-4-ketone-1-N-oxygen base (Cmpd 2) (1.60 grams, 0.01 mole) is dissolved in the dimethyl formamide (13 milliliters).Add sodium hydride (0.48 gram, 0.011 mole, 55% in paraffin oil) then, and this mixture was stirred 60 minutes down at 50 ℃.Then this mixture is cooled to 2 ℃ and added diethyl chloro-phosphate (1.97 grams, 0.011 mole) through 5 minutes.At room temperature stir and add entry (150 milliliters) after 17 hours, and with this mixture of dichloromethane extraction (3 * 30 milliliters).With the extract evaporation that merges, and through silica gel (hexane-ethyl acetate 1: 1) with the residue chromatographic isolation, and from carrene-hexane recrystallization so that 2.1 gram red crystals, mp.78-80 ℃ to be provided.MS: to C
11H
22N
2O
5P (293.3), actual measurement M
+=293.
Embodiment 31 (Cmpd 31): 2,2,4,4-tetramethyl-5-oxo-imidazolidine-3-N-Oxy-1-methyl formate
With 2,2,5,5-tetramethyl-imidazolidine-4-ketone-1-N-oxygen base (Cmpd 2) (1.73 grams, 0.011 mole), triethylamine (1.7 milliliters, 0.012 mole) and 4-dimethylaminopyridine (67 milligrams) are dissolved in the carrene (15 milliliters).In this agitating solution, slowly add methylchloroformate (1.14 grams, 0.012 mole), make temperature remain on 3-8 ℃ simultaneously.This mixture was at room temperature stirred 4 hours.Add more 4-dimethylaminopyridines (50 milligrams), triethylamine (0.85 milliliter) and methylchloroformate (0.5 milliliter) then, and this mixture was stirred 3 hours again, wash (3 * 10 milliliters) and evaporation then with water.Through silica gel (carrene-ethyl acetate 25: 1) with the solid residue chromatographic isolation, and from carrene-hexane recrystallization with provide 1.4 the gram red crystals, mp.82-86 ℃.MS: to C
9H
15N
2O
4(215.2), actual measurement M
+=215.
Embodiment 32 (Cmpd 32): 4-dibenzylsulfide alkyl-2,5-diethyl-2,5-dimethyl-2,5-dihydro-1H-imidazoles-1-N-oxygen base
A) 4-dibenzylsulfide alkyl-2,5-diethyl-2,5-dimethyl-2,5-dihydro-1H-imidazoles
With 2,2,5,5-tetramethyl-imidazolidine-4-thioketones (33.5 grams, 0.18 mole), acetone (300 milliliters), potash (26.1 grams, 0.189 mole) and benzyl bromide a-bromotoluene (32.3 grams, 0.189 mole) stirred 5 hours under refluxing.Leach solid then and wash with acetone.Filtrate is evaporated so that the title compound of 50 gram thickness yellow oilies to be provided.
B) oxidation
With 4-dibenzylsulfide alkyl-2,5-diethyl-2,5-dimethyl-2,5-dihydro-1H-imidazoles (48.1 grams, 0.174 mole) is dissolved in the ethyl acetate (400 milliliters).Then between adding in 30 minutes-chlorine benzylhydroperoxide (64.35 grams, 0.26 mole, 70% content), make temperature remain on 10-15 ℃ simultaneously.This mixture is at room temperature stirred 2 hours, and append 20 the gram between-the chlorine benzylhydroperoxide.After stirring 2 hours, add again between 20 grams-the chlorine benzylhydroperoxide, and this mixture was at room temperature stirred 16 hours, use 1M-NaHCO then
3(3 * 300 milliliters) washing and evaporation.Use hexane-ethyl acetate (9: 1 to 6: 1) with the residue chromatographic isolation through silica gel, so that the title compound of the red oily of 9.5 grams to be provided.To C
16H
23N
2OS (291.44) calculates C 65.94%, and H 7.95%, and N 9.61%, actual measurement C65.89%, and H 7.95%, and N 9.53%.
Embodiment 33 (Cmpd 33): 2,5-diethyl-2,5-dimethyl-4-phenyl methanesulfonamide acyl group-2,5-dihydro-1H-imidazoles-1-N-oxygen base
By polarity cut recrystallization from hexane that will in the chromatogram purification process of Cmpd 32, obtain, obtain this compound of orange solids shape, 8.1 grams, 66-72 ℃.MS: to C
16H
23N
2O
3S (323.4), actual measurement M
+=323.
Embodiment 34 (Cmpd 34): 3,3-diethyl-5,5-dimethyl-piperazine-2-ketone-4-N-oxygen base
A) 3,3-diethyl-5,5-dimethyl-piperazine-2-ketone
With the 1-tert-butyl group-3,3-diethyl-5,5-dimethyl-piperazine-2-ketone (315.7 grams, 1.3 moles, as Nesvadba, Peter; Kramer, Andreas; Zink, Marie-odile.Ger.Offen. (2000) prepares described in the DE-A-19949352) slowly add (316 milliliters of hydrochloric acid to, 37%) in, and, pour into then in the cold soln of NaOH (151 grams, 3.775 moles) in 500 ml waters this mixture backflow 24 hours.Throw aside organic layer (tertiary butyl chloride), and with water layer with the tert-butyl group-methyl ether (5 * 100 milliliters) extraction.Through MgSO
4With the extract drying that merges, and the rough title compound (256 gram) of evaporation so that the yellow liquid shape to be provided.
B) oxidation
To 3,3-diethyl-5 slowly adds peracetic acid (15.8 grams, 0.083 mole, 40% in acetate) in the solution of 5-dimethyl-piperazine-2-ketone (9.21 grams, 0.05 mole) in ethyl acetate (25 milliliters), and this mixture was at room temperature stirred 8 hours.Add entry (100 milliliters) then, and this mixture is extracted with the tert-butyl group-methyl ether (6 * 35 milliliters).Extract is with 5%NaOH (100 milliliters) washing, through MgSO
4Dry also evaporation.With residue recrystallization from toluene-hexane, so that the title compound of 6.56 gram yellow crystals shapes, mp.126-129 ℃ to be provided.To C
10H
19N
2O
2(199.27), calculate C 60.27%, H 9.61%, and N 14.05%, actual measurement C 60.37%, and H 9.67%, and N 13.93%.
Embodiment 35 (Cmpd 35): 1-(2,2-dimethyl-propiono)-3,3,5,5-tetramethyl-piperazine-2,6-diketone-4-N-oxygen base
A) 1-(2,2-dimethyl-propiono)-3,3,5,5-tetramethyl-piperazine-2,6-diketone
With 3,3,5,5-tetramethyl-piperazine-2,6-diketone (1.7 grams, 0.01 mole, according to Bulletin ofthe Chemical Society of Japan (1972), 45 (6), 1855) make), triethylamine (1.6 milliliters, 0.011 mole) and 4-dimethylaminopyridine (55 milligrams) be dissolved in the carrene (20 milliliters).Added pivalyl chloride (1.33 grams, 0.011 mole) then through 3 minutes, and this mixture was at room temperature stirred 20 hours.Add carrene (50 milliliters) and water (50 milliliters) then, separate organic layer, and through silica gel carrene-ethyl acetate (4: 1) chromatographic isolation, so that the title compound of 2.42 gram colorless solid shapes, mp.100-102 ℃ to be provided.MS: to C
16H
23N
2O
3S (323.4), actual measurement M
+=323.
B) oxidation
To 1-(2,2-dimethyl-propiono)-3,3,5,5-tetramethyl-piperazine-2,6-diketone (1.75 grams, 6.88 mMs), NaHCO
3Slowly add peracetic acid (2.1 restrain, 11 mMs, 40% in acetate) in the stirring the mixture of (1.8 gram, 21.4 mMs), carrene (20 milliliters) and water (3 milliliters), and this mixture was at room temperature stirred 17 hours.Append 0.33 gram peracetic acid, and continue to stir 2 hours.Separate organic layer then, use 2M Na
2CO
3(2 * 10 milliliters) washing and evaporation.Through silica gel with carrene with the residue chromatographic isolation, and from hexane crystallization so that the title compound of 0.78 gram red crystals shape, mp.115-117 ℃ to be provided.MS: to C
13H
21N
2O
4(269.3), actual measurement M
+=269.
Embodiment 36 (Cmpd 36): 1-(2,2-dimethyl-propiono)-3,3-diethyl-5,5-dimethyl-piperazine-2-ketone-4-N-oxygen base
With 3,3-diethyl-5,5-dimethyl-piperazine-2-ketone-4-N-oxygen base (Cmpd 34) (1.99 grams, 0.01 mole), triethylamine (1.6 milliliters, 0.011 mole) and 4-dimethylaminopyridine (56 milligrams) are dissolved in the carrene (12 milliliters).In this agitating solution, slowly add pivalyl chloride (1.32 grams, 0.011 mole), make temperature remain on 3-8 ℃ simultaneously.Then this mixture was at room temperature stirred 3 hours, wash (2 * 10 milliliters) and evaporation then with water.Through silica gel (hexane-ethyl acetate 3: 1) with the solid residue chromatographic isolation, with provide 2.65 the gram red oily title compound.MS: to C
15H
27N
2O
3(283.4), actual measurement M
+=283.
Embodiment 37 (Cmpd 37): 2,2,5,5-tetramethyl-3-oxiranylmethyl radical-imidazolidine-4-ketone-N-oxygen base
With 2,2,5,5-tetramethyl-imidazolidine-4-ketone-1-N-oxygen base (Cmpd 2) (7.0 grams, 0.045 mole) is dissolved among the THF (48 milliliters).At room temperature by a part adding sodium hydride (1.23 grams, 0.051 mole).This mixture is heated to 30 ℃ and stirred 4 hours, then removal of solvent under reduced pressure.Add chloropropylene oxide (42 milliliters), and suspension was stirred 18 hours down at 60 ℃.Removal of solvent under reduced pressure, and with residue by at SiO
2On flash chromatography purify so that 7.19 gram orange solids, mp.64-75 ℃ to be provided.
Embodiment 38 (Cmpd 38): as Vanifatova, N.G.; Evstiferov, M.V.; Martin, V.V.; Petrukhin, O.M.; Volodarskii, L.B.; Zolotov, Y u.A.ZhurnalAnaliticheskoi Khimii (1988), 43 (3), prepare described in the 435-40.
Embodiment 39 (Cmpd 39): 3,3,5,5-tetramethyl-thiomorpholine 1,1-dioxide-N-oxygen base
As DE 2 351 865, the 49th page, this compound of preparation described in the embodiment 6.
Embodiment 40 (Cmpd 40): 2,2,7,7-tetramethyl-1,4-diazacyclo heptan-5-ketone 1-N-oxygen base
As Rozantsev, E.G.; Chudinov, A.V.; Sholle, V.D.:lzvestiyaAkademii Nauk SSSR, Seriya Khimicheskaya (1980), (9), this compound of the described preparation of 2114-17.
Embodiment 41 (Cmpd 41): 2,2,4,7,7-pentamethyl-1,4-diazacyclo heptan-5-ketone 1-N-oxygen base
With 2,2,7,7-tetramethyl-1,4-diazacyclo heptan-5-ketone 1-N-oxygen base, (1.3 grams, the 7 mMs) solution in methyl iodide (2 milliliters) at room temperature stirred 1 hour together with sodium hydrate aqueous solution (2 milliliters, 50% solution) and bromination tetrabutylammonium (0.1 restrains).Separate organic layer, wash with water and evaporate.Through silica gel CH
2Cl
2So that the title compound of the red oily of 0.79 gram to be provided, it slowly solidified when leaving standstill-ethyl acetate-methyl alcohol with the residue chromatographic isolation in 5: 4: 1.C
10H
19N
2O
2MS (199.27) actual measurement M
+=199.
Embodiment 42 (Cmpd 42): 1,1,3,3,5,5-hexamethyl-perhydro--carotene 1,4-diaza
-1-iodide-4-N-oxygen base
As Ramasseul, R.; Rassat A.; Rey, P.:Tetrahedron Letters 839 (1975) these compounds of described preparation.
Embodiment 43 (Cmpd 43): 2,7-diethyl-2,3,7-trimethyl-1,4-diazacyclo heptan-5-ketone 1-N-oxygen base
As US 6,479,608B1, this compound of preparation described in the Embodiment C 3.
Embodiment 44 (Cmpd 44): 3,5-diethyl-2,3,5-trimethyl-7-oxo-perhydro--carotene 1,4-diaza
-1-formic acid-tertiary butyl ester-4-N-oxygen base
As US 6,479,608B1, this compound of preparation described in the Embodiment C 8.
Embodiment 45 (Cmpd 45): 2,2,6,6-tetramethyl-4-phenyl-perhydro--carotene 1,4-azepine phosphorine4-oxide-N-oxygen base
As Skolimowski, J.; Skowronski, R.; Simalty, this compound of the described preparation of M.:Tetrahedron Letters4833-4 (1974).
Embodiment 46 (Cmpd 46): 2,2,6,6-tetramethyl-4,4-diphenyl-1,4-azepine tetrahydrochysene phosphorinium perchlorate-N-oxygen base
As Skolimowski, J.; Skowronski, R.; Simalty, this compound of the described preparation of M.:Tetrahedron Letters4833-4 (1974).
The oxidation-reduction potential data of several compounds:
| Compound number | ??E 0(V) |
| ??TEMPO | ??0.695 |
| ??1 | ??1.181 |
| ??9 | ??1.142 |
| ??15 | ??0.901 |
| ??16 | ??0.871 |
| ??20 | ??0.969 |
| ??25 | ??1.099 |
| ??26 | ??1.188 |
| ??29 | ??1.265 |
| ??30 | ??1.255 |
| ??31 | ??1.273 |
| ??32 | ??1.032 |
| ??34 | ??0.931 |
| ??35 | ??1.231 |
| ??36 | ??1.061 |
| ??37 | ??1.186 |
| ??39 | ??1.039 |
| ??40 | ??0.791 |
| ??41 | ??0.789 |
| ??43 | ??0.783 |
Can know and find out that compound of the present invention has the oxidizing potential of the compound TEMPO (2,2,6,6-tetramethyl piperidine-N-oxygen base) apparently higher than prior art.
The experimental detail that oxidation-reduction potential is measured and the record of cyclic voltammogram
Use has work electrode, the three electrode glass batteries and the computer-controlled potentiostat of electrode and reference electrode is carried out cyclic voltammetry (CV), apply linear potential scanning (referring to people such as for example B.Schoellhorn, New Journal of Chemistry, 2006,30,430-434; CAN144:441363).Write down a plurality of CV-scannings of every kind of compound used therefor, and obtain the mean value of spike potential.
The CV-experiment condition
Potentiostat: VersaStat II (EG﹠amp; G Instruments), 0.1M Bu
4NBF
4, 2.7E-3M nitroxide, MeCN
-Pt coils d=5mm (WE), Pt line (CE), the saturated (RE of Ag/AgCl/NaCl; + 0.194V is with respect to NHE)
15-0-1.2V(TEMPO)，0-2.0V，0.1V/s，25℃。
According to E
0=0.5 (E
Pa+ E
Pc) calculating oxidation-reduction potential E
0
(E
Pa=anode spike potential, E
Pc=negative electrode spike potential)
Confirmed the character of the completely reversibility of aforesaid oxidation-reduction method by the Reversible Cycle voltammogram shown in Fig. 1-7.
Use the charge-discharge of compound 31 and the experimental detail of circulation experiment
Use has LiFePO
4Work electrode, Li carry out the charge-discharge test (referring to people such as for example J.K.Feng, ElectrochemistryCommunications, 2007,9,25-30 to the three-electrode battery of electrode and Li reference electrode; CAN147:146607).
LiFePO
4Positive electrode is by 60%LiFePO
4(Phostech), 20%Super P (Timcal) and 20%PVDF adhesive constitute, and prepare by being applied on the aluminium foil.Use the lithium paper tinsel as negative pole.Electrolyte is the 1M LiPF in the EC/DMC that contains 0.1M compound 31 1: 1
6
For the constant current experiment, this battery is charged to 160% of nominal charging capacity repeatedly under constant current, be discharged to 2.80V then.
Confirmed with the Li/LiFePO of compound 31 by the charge-discharge curve shown in Fig. 8 as additive agent electrolyte
4Effective over-charge protective of battery.At LiFePO
4After charging fully under 3.4V, voltage rises to rapidly and is higher than 4V, begins at this over-charge protective of realizing by the redox shuttle of compound 31, causes the constant charge platform at 4.1V.This effect is kept 10 charge-discharge circulations repeatedly under the situation of no deterioration.
Claims (16)
1. rechargeable lithium ion battery, it comprises:
(a) positive pole,
(b) negative pole and
(c) electrolyte, this electrolyte comprises
(i) lithium salts,
(ii) polar non-solute and
The (iii) at least a compound that selects the group of free style (d1) to (d6) composition
Wherein
G is
Or
Preferably, G is
X is O or S;
If X is O, then R
6And R
7It is duplet;
If X is S, then R
6And R
7Be independently duplet or=O;
Y is-CH
2-O-CH
2-,-CH
2-S-CH
2-,-CH
2-S (=O)-CH
2-,-CH
2-S (=O)
2-CH
2-,
-CH
2-NR
5-CH
2-,
Or
A
-And D
-Be the anion of organic or inorganic acid independently;
*Refer to free valency;
R
1, R
2, R
3And R
4Be C independently
1-C
18Alkyl, C
6-C
10Aryl, C
5-C
8Heteroaryl, C
7-C
11Aralkyl or C
5-C
6Cycloalkyl; Or the described group that is replaced by one or more F; Or described alkyl and/or the cycloalkyl inserted by one or more heteroatom groups; Or the described alkyl and/or the cycloalkyl that are replaced by one or more heteroatom groups; Or described alkyl and/or the cycloalkyl being inserted and replace by one or more heteroatom groups; Or by 1 to 4 C
1-C
4Described aryl, heteroaryl and/or aralkyl that alkyl replaces; Or
R
1And R
2And/or R
3And R
4Form the C that is not substituted or is replaced by F with connecting carbon atom
4-C
13The cycloalkyl double-basis;
R
5Be H, OH, C
1-C
18Alkyl, C
6-C
10Aryl, C
7-C
11Aralkyl, C
2-C
18Alkenyl, C
2-C
18Alkynyl, C
5-C
6Cycloalkyl, glycidyl ,-CO-R
16,-CO-NH-R
16,-CON (R
16) (R
17) ,-O-CO-R
16, CO-OR
12,-PO (OR
12) (OR
13) ,-S (=O)
2OR
12,-SR
12,-S (=O) R
12,-S (=O)
2R
12,-S-OR
12,-S (=O)-OR
12,-SiR
16R
17R
18,-CN or halogen; Or the described group that is replaced by one or more F; Or described alkyl, alkenyl, alkynyl or the cycloalkyl inserted by one or more heteroatom groups; Or the described alkyl, alkenyl, alkynyl or the cycloalkyl that are replaced by one or more heteroatom groups; Or described alkyl and/or the cycloalkyl being inserted and replace by one or more heteroatom groups; Or by 1 to 4 C
1-C
4The described aryl or aralkyl that alkyl replaces; Or R
5Be construction unit (d1)-(d4) or the nuclear of multivalence (d6) that is connecting more than one;
R
8And R
9Be independently-CH
2O-CO-C
1-C
18Alkyl ,-CH
2-NH-CO-C
1-C
18Alkyl or as to R
1Define;
Or R
8And R
9Form with connecting carbon atom
Group;
R
10And R
11Be H or CH independently
3
R
12And R
13Be H, NH independently
4, Li, Na, K or as to R
16Define;
R
14, R
15Be H or C independently
1-C
8Alkyl;
Or R
14And R
15Form C with connecting carbon atom
4-C
13The cycloalkyl double-basis;
R
16, R
17And R
18Be C independently
1-C
18Alkyl, C
2-C
18Alkenyl, C
6-C
10Aryl, C
5-C
8Heteroaryl, C
7-C
11Aralkyl or C
5-C
6Cycloalkyl; Or the described group that is replaced by one or more F; Or described alkyl and/or the cycloalkyl inserted by one or more heteroatom groups; Or the described alkyl and/or the cycloalkyl that are replaced by one or more heteroatom groups; Or described alkyl and/or the cycloalkyl being inserted and replace by one or more heteroatom groups; Or by 1 to 4 C
1-C
4Described aryl, heteroaryl and/or aralkyl that alkyl replaces;
R
20, R
21And R
22Be C independently
1-C
18Alkyl, C
2-C
18Alkenyl, C
6-C
10Aryl, C
5-C
8Heteroaryl, C
7-C
11Aralkyl or C
5-C
6Cycloalkyl; Or the described group that is replaced by one or more F; And
R
23Be H, NH
4, Li, Na, K or as to R
20Define, be preferably H or C
1-C
18Alkyl;
R
24Be C
1-C
18Alkyl, C
6-C
10Aryl, C
5-C
8Heteroaryl, C
7-C
11Aralkyl, C
2-C
18Alkenyl, C
2-C
18Alkynyl, C
5-C
6Cycloalkyl or glycidyl;
R
25And R
26Be H, C independently
1-C
18Alkyl, C
6-C
10Aryl, C
7-C
11Aralkyl, C
2-C
18Alkenyl, C
2-C
18Alkynyl, C
5-C
6Cycloalkyl or glycidyl;
R
27Be C
1-C
18Alkyl, C
6-C
10Aryl or-O-C
1-C
18Alkyl or-O-C
6-C
10Aryl;
R
28Be H ,-OH, C
1-C
18Alkyl, C
6-C
10Aryl, C
7-C
11Aralkyl, C
5-C
6Cycloalkyl ,-O-C
1-C
18Alkyl ,-O-C
6-C
10Aryl or-OQ, wherein Q is NH
4, Li, Na or K.
2. according to the rechargeable lithium ion battery of claim 1, wherein
For the compound of formula (d1), X is O;
For the compound of formula (d2), X is S;
Y is-CH
2-O-CH
2-,-CH
2-S-CH
2-,-CH
2-S (=O)-CH
2-,-CH
2-S (=O)
2-CH
2-,-CH
2-NR
5-CH
2-,
Or
D
-Be I
-Or LiPF
6, LiClO
4, LiBF
4, LiO
3SCF
3, LiN (C
2F
5SO
2)
2, LiC (CF
3SO
2)
3, LiC (C
2F
5SO
2)
3, LiB (C
2O
4)
2, LiB (C
6H
5)
4, LiB (C
6F
5)
4, LiSbF
6, LiAsF
6, LiBr, LiBF
3C
2F
5Or LiPF
3(CF
2CF
3)
3Anion;
R
1, R
2, R
3And R
4Be C independently
1-C
18Alkyl or C
6-C
10Aryl; Or the described group that is replaced by one or more F; Or
R
1And R
2And/or R
3And R
4Form the C that is not substituted or is replaced by F with connecting carbon atom
4-C
13The cycloalkyl double-basis;
R
5Be H, OH, C
1-C
18Alkyl, C
6-C
10Aryl, C
7-C
11Aralkyl, C
3-C
18Alkenyl, C
3-C
18Alkynyl, C
5-C
6Cycloalkyl, glycidyl ,-CO-R
16,-CO-NH-R
16,-CON (R
16) (R
17) ,-O-CO-R
16,-CO-OR
12,-(CH
2)
qCOOR
12Or-PO (OR
12) (OR
13); Or the described group that is replaced by one or more F; Or the described alkyl that is replaced by one or more OH;
R
6And R
7Be independently duplet or=O;
R
8And R
9Be independently-CH
2O-CO-C
1-C
18Alkyl ,-CH
2-NH-CO-C
1-C
18Alkyl or as to R
1Define;
Or R
8And R
9Form with connecting carbon atom
Group;
R
10And R
11Be H or CH independently
3
R
12And R
13Be H, NH independently
4, Li, Na, K or as to R
16Define, and
R
16And R
17Be C independently
1-C
18Alkyl, C
3-C
18Alkenyl, C
6-C
10Aryl or C
7-C
11Aralkyl; Or the described group that is replaced by one or more F;
R
25And R
26Be H, C independently
1-C
18Alkyl, C
6-C
10Aryl, C
7-C
11Aralkyl, C
2-C
18Alkenyl, C
2-C
18Alkynyl, C
5-C
6Cycloalkyl or glycidyl;
R
28Be H ,-OH, C
1-C
18Alkyl, C
6-C
10Aryl, C
7-C
11Aralkyl, C
5-C
6Cycloalkyl ,-O-C
1-C
18Alkyl ,-O-C
6-C
10Aryl or-OQ, wherein Q is NH
4, Li, Na or K;
And
Q is 1 to 6 integer.
3. according to the rechargeable lithium ion battery of claim 2, wherein
Y is-CH
2-S (=O)
2-CH
2-,
Or
D
-Be I
-Or ClO
4 -
R
1, R
2, R
3And R
4Be methyl, ethyl or propyl group independently; Or
R
1And R
2And/or R
3And R
4Form C with connecting carbon atom
6-C
7The cycloalkyl double-basis;
R
5Be H, OH, C
1-C
8Alkyl, phenyl, benzyl, C
3-C
6Alkynyl, C
5-C
6Cycloalkyl, glycidyl ,-CO-R
16,-CO-C
1-C
5Perfluoroalkyl ,-CO-NH-R
16, CO-OR
16Or-PO (OR
12) (OR
13); Or by the described alkyl of an OH replacement;
R
6And R
7Be independently duplet or=O;
R
8And R
9Be independently-CH
2O-CO-C
1-C
4Alkyl ,-CH
2-NH-CO-C
1-C
4Alkyl or as to R
1Define;
Or R
8And R
9Form with connecting carbon atom
Group;
R
10And R
11Be H or CH independently
3
R
12And R
13Be H, NH independently
4, Li, Na, K or as to R
16Define; And
R
16Be C
1-C
8Alkyl, C
3-C
6Alkenyl, phenyl or benzyl;
R
25And R
26Be C
1-C
8Alkyl or phenyl; And
R
28It is phenyl;
Condition is if R
6And R
7All be=O, then R
5Can only be OH.
4. according to each rechargeable lithium ion battery of claim 1 to 3, wherein compound
(iii) be dissolved in the electrolyte.
5. according to each rechargeable lithium ion battery of claim 1 to 4, wherein positive pole comprises and is selected from by organic group, LiFePO
4, Li
2FeSiO
4, Li
wMnO
2, MnO
2, Li
4Ti
5O
12, LiMnPO
4, LiCoO
2, LiNiO
2, LiNi
1-xCo
yMet
zO
2, LiMn
0.5Ni
0.5O
2, LiMn
0.3Co
0.3Ni
0.3O
2, LiFeO
2, LiMet
0.5Mn
1.5O
4, vanadium oxide, Li
1+xMn
2-zMet
yO
4-mX
n, FeS
2, LiCoPO
4, Li
2FeS
2, Li
2FeSiO
4, LiMn
2O
4, LiNiPO
4, LiV
3O
4, LiV
6O
13, LiVOPO
4, LiVOPO
4F, Li
3V
2(PO
4)
3, MoS
3, sulphur, TiS
2, TiS
3And the compound of the group of combination composition,
0＜m＜0.5,0＜n＜0.5,0.3≤w≤0.4,0＜x＜0.3,0＜z＜0.5,0＜y＜0.5 wherein, Met is Al, Mg, Ti, B, Ga, Si, Ni or Co, and X is S or F.
6. according to each rechargeable lithium ion battery of claim 1 to 5, wherein negative pole comprise graphitic carbon, lithium metal, lithium alloy, based on the non-crystalline material of Sn and Co or their combination.
7. according to each rechargeable lithium ion battery of claim 1 to 6, wherein lithium salts (i) is selected from by LiPF
6, LiClO
4, LiBF
4, LiO
3SCF
3, LiN (C
2F
5SO
2)
2, LiC (CF
3SO
2)
3, LiC (C
2F
5SO
2)
3Or LiB (C
2O
4)
2, LiB (C
6H
5)
4, LiB (C
6F
5)
4, LiSbF
6, LiAsF
6, LiBr, LiBF
3C
2F
5, LiPF
3(CF
2CF
3)
3And the group of combination composition.
8. according to each rechargeable lithium ion battery of claim 1 to 7, wherein polar non-solute (ii) is selected from by ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, gamma-butyrolacton, oxolane, dioxolanes, sulfolane, dimethyl formamide, dimethylacetylamide, the N-N-methyl-2-2-pyrrolidone N-, butylene carbonate, vinylene carbonate, carbonic acid fluoro ethyl, the inferior propyl ester of carbonic acid fluoro, the difluoroacetic acid methyl esters, ethyl difluoro, dimethoxy-ethane, the group that two (2-methoxy ethyl) ethers and combination thereof are formed.
9. according to each rechargeable lithium ion battery of claim 1 to 8, wherein compound (iii) is following redox chemistry shuttle capable of circulation: it is dissolved in or may be dissolved in the electrolyte, and has and be higher than the anodal oxidizing potential that recharges current potential.
10. according to the rechargeable lithium ion battery of claim 9, wherein compound (iii) has the oxidizing potential that recharges the high 0.3V to 5V of current potential than positive pole.
11. according to the rechargeable lithium ion battery of claim 9 or 10, wherein compound (iii) provides over-charge protective after the charge-discharge under at least 30 following conditions circulation: being enough to be with G wherein
Compound (iii) under the charging voltage of oxidation, each cycle period flows down at 100% the electric charge that overcharges that equals battery capacity.
12. according to each rechargeable lithium ion battery of claim 1 to 8, wherein compound (iii) is the molecular oxidation reduction shuttle that is used for the redox target-seeking.
13. according to the rechargeable lithium ion battery of claim 12, wherein compound (iii) is dissolved in the anodal electrolyte.
14. as each described compound of claim 1 to 3 purposes (iii), as the redox chemistry shuttle capable of circulation in the rechargeable lithium ion battery.
15. as each described compound of claim 1 to 3 purposes (iii), with the molecular oxidation reduction shuttle that acts on the redox target-seeking.
16. as each described compound (d1) of claim 1 to 3 to (d6), wherein
G is
Or
When G is
The time,
This compound is formula (d1), (d3) or compound (d4), and
R
5Be-CO-R
16,-CO-NH-R
16,-CON (R
16) (R
17), CO-OR
16,-O-CO-R
16,-(CH
2)
qCOOR
12,-PO (OR
12) (OR
13) ,-S (=O)
2OR
12,-SR
12,-S (=O) R
12,-S (=O)
2R
12,-S-OR
12,-S (=O)-OR
12,-SiR
16R
17R
18,-CN or-halogen;
Q is 1 to 6 integer;
Condition is
For the compound of formula (d1), R
5Be-PO (OR
12) (OR
13) ,-S (=O)
2OR
12,-SR
12,-S (=O) R
12,-S (=O)
2R
12,-S-OR
12,-S (=O)-OR
12Or-SiR
16R
17R
18And
Get rid of compound
With
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP07103869 | 2007-03-09 | ||
| EP07103869.9 | 2007-03-09 | ||
| EP07119346.0 | 2007-10-26 |
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| Publication Number | Publication Date |
|---|---|
| CN101632198A true CN101632198A (en) | 2010-01-20 |
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ID=38659884
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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|---|---|---|---|---|
| CN103765664A (en) * | 2011-09-29 | 2014-04-30 | 三洋电机株式会社 | Nonaqueous electrolyte and nonaqueous electrolyte secondary cell |
| CN106133984A (en) * | 2014-03-28 | 2016-11-16 | 住友精化株式会社 | Addition agent of non-aqueous electrolyte, nonaqueous electrolytic solution and electrical storage device |
| CN107531830A (en) * | 2015-08-26 | 2018-01-02 | 赢创德固赛有限公司 | Purposes of some polymer as charge accumulator |
| US10756348B2 (en) | 2015-08-26 | 2020-08-25 | Evonik Operations Gmbh | Use of certain polymers as a charge store |
| US10844145B2 (en) | 2016-06-02 | 2020-11-24 | Evonik Operations Gmbh | Method for producing an electrode material |
| CN112010894A (en) * | 2020-08-17 | 2020-12-01 | 湖州师范学院 | Sulfur phosphate compound, nonaqueous lithium ion battery electrolyte containing sulfur phosphate compound and lithium ion battery |
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2008
- 2008-02-29 CN CN200880007674A patent/CN101632198A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103765664A (en) * | 2011-09-29 | 2014-04-30 | 三洋电机株式会社 | Nonaqueous electrolyte and nonaqueous electrolyte secondary cell |
| CN103765664B (en) * | 2011-09-29 | 2015-12-09 | 三洋电机株式会社 | Nonaqueous electrolyte and rechargeable nonaqueous electrolytic battery |
| CN106133984A (en) * | 2014-03-28 | 2016-11-16 | 住友精化株式会社 | Addition agent of non-aqueous electrolyte, nonaqueous electrolytic solution and electrical storage device |
| CN107531830A (en) * | 2015-08-26 | 2018-01-02 | 赢创德固赛有限公司 | Purposes of some polymer as charge accumulator |
| CN107531830B (en) * | 2015-08-26 | 2019-06-28 | 赢创德固赛有限公司 | Purposes of certain polymer as charge accumulator |
| US10756348B2 (en) | 2015-08-26 | 2020-08-25 | Evonik Operations Gmbh | Use of certain polymers as a charge store |
| US10844145B2 (en) | 2016-06-02 | 2020-11-24 | Evonik Operations Gmbh | Method for producing an electrode material |
| US11001659B1 (en) | 2016-09-06 | 2021-05-11 | Evonik Operations Gmbh | Method for the improved oxidation of secondary amine groups |
| CN112010894A (en) * | 2020-08-17 | 2020-12-01 | 湖州师范学院 | Sulfur phosphate compound, nonaqueous lithium ion battery electrolyte containing sulfur phosphate compound and lithium ion battery |
| CN112010894B (en) * | 2020-08-17 | 2023-08-11 | 湖州师范学院 | Phosphorothioate compound, nonaqueous lithium ion battery electrolyte containing phosphorothioate compound and lithium ion battery |
| CN114583263A (en) * | 2020-11-30 | 2022-06-03 | 比亚迪股份有限公司 | Electrolyte, positive electrode, lithium ion battery and vehicle |
| CN114583263B (en) * | 2020-11-30 | 2023-11-14 | 比亚迪股份有限公司 | Electrolyte, positive electrode, lithium ion battery and vehicle |
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