KR20230080622A - Electrolyte for secondary battery and secondary battery comprising the same - Google Patents
Electrolyte for secondary battery and secondary battery comprising the same Download PDFInfo
- Publication number
- KR20230080622A KR20230080622A KR1020210167969A KR20210167969A KR20230080622A KR 20230080622 A KR20230080622 A KR 20230080622A KR 1020210167969 A KR1020210167969 A KR 1020210167969A KR 20210167969 A KR20210167969 A KR 20210167969A KR 20230080622 A KR20230080622 A KR 20230080622A
- Authority
- KR
- South Korea
- Prior art keywords
- group
- electrolyte
- alkyl
- secondary battery
- substituted
- Prior art date
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 30
- -1 aminophosphine compound Chemical class 0.000 claims abstract description 43
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 24
- 150000003839 salts Chemical class 0.000 claims abstract description 24
- 125000002837 carbocyclic group Chemical group 0.000 claims abstract description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000003118 aryl group Chemical group 0.000 claims abstract description 16
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 15
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 13
- 125000004446 heteroarylalkyl group Chemical group 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 13
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 12
- 125000000304 alkynyl group Chemical group 0.000 claims abstract description 12
- 125000005343 heterocyclic alkyl group Chemical group 0.000 claims abstract description 12
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 12
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 11
- 150000002367 halogens Chemical class 0.000 claims abstract description 11
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 10
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000004104 aryloxy group Chemical group 0.000 claims abstract description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 9
- 125000002560 nitrile group Chemical group 0.000 claims abstract description 9
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 9
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims abstract description 9
- 125000003396 thiol group Chemical class [H]S* 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-VVKOMZTBSA-N Dideuterium Chemical compound [2H][2H] UFHFLCQGNIYNRP-VVKOMZTBSA-N 0.000 claims abstract description 8
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000003172 aldehyde group Chemical group 0.000 claims abstract description 8
- 125000005377 alkyl thioxy group Chemical group 0.000 claims abstract description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 8
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 claims abstract description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 8
- 125000004185 ester group Chemical group 0.000 claims abstract description 8
- 125000005553 heteroaryloxy group Chemical group 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 8
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims abstract description 8
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000003368 amide group Chemical group 0.000 claims abstract description 5
- 125000003277 amino group Chemical group 0.000 claims abstract description 5
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical group [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 claims abstract description 5
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 20
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 18
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 claims description 17
- 239000003125 aqueous solvent Substances 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 9
- 229910003002 lithium salt Inorganic materials 0.000 claims description 9
- 159000000002 lithium salts Chemical class 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 description 22
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 18
- 239000002904 solvent Substances 0.000 description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 11
- 229910001416 lithium ion Inorganic materials 0.000 description 11
- 239000003960 organic solvent Substances 0.000 description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 10
- 239000004020 conductor Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 8
- 239000003660 carbonate based solvent Substances 0.000 description 8
- 150000005676 cyclic carbonates Chemical class 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 102100028667 C-type lectin domain family 4 member A Human genes 0.000 description 7
- 101000766908 Homo sapiens C-type lectin domain family 4 member A Proteins 0.000 description 7
- 229910013872 LiPF Inorganic materials 0.000 description 7
- 101150058243 Lipf gene Proteins 0.000 description 7
- 239000008151 electrolyte solution Substances 0.000 description 7
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000011255 nonaqueous electrolyte Substances 0.000 description 7
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
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- 229910013075 LiBF Inorganic materials 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 239000006182 cathode active material Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000011149 active material Substances 0.000 description 4
- 239000006183 anode active material Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000009830 intercalation Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 125000005587 carbonate group Chemical group 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 238000009831 deintercalation Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XQJHRCVXRAJIDY-UHFFFAOYSA-N aminophosphine Chemical compound PN XQJHRCVXRAJIDY-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 229940105329 carboxymethylcellulose Drugs 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 2
- CYEDOLFRAIXARV-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound CCCOC(=O)OCC CYEDOLFRAIXARV-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 2
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 150000008053 sultones Chemical class 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- LWLOKSXSAUHTJO-UHFFFAOYSA-N 4,5-dimethyl-1,3-dioxolan-2-one Chemical compound CC1OC(=O)OC1C LWLOKSXSAUHTJO-UHFFFAOYSA-N 0.000 description 1
- LSUWCXHZPFTZSF-UHFFFAOYSA-N 4-ethyl-5-methyl-1,3-dioxolan-2-one Chemical compound CCC1OC(=O)OC1C LSUWCXHZPFTZSF-UHFFFAOYSA-N 0.000 description 1
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 1
- AUXJVUDWWLIGRU-UHFFFAOYSA-N 4-propyl-1,3-dioxolan-2-one Chemical compound CCCC1COC(=O)O1 AUXJVUDWWLIGRU-UHFFFAOYSA-N 0.000 description 1
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- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
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- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
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- 230000002441 reversible effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- QUBMWJKTLKIJNN-UHFFFAOYSA-B tin(4+);tetraphosphate Chemical compound [Sn+4].[Sn+4].[Sn+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QUBMWJKTLKIJNN-UHFFFAOYSA-B 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
-
- 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
Abstract
본 발명의 이차전지용 전해질은 하기 화학식 1 내지 3 중 어느 하나로 표시되는 아미노포스핀(aminophosphine) 화합물을 포함한다:
[화학식 1]
[화학식 2]
[화학식 3]
상기 화학식 1 내지 3에서 Rn1, Rn2, Rn3, Rn4, Rn5 및 Rn6은 서로 동일하거나 상이하며, 각각 독립적으로,
수소; 중수소; 할로겐; 치환 또는 비치환된 탄소수 30 이하의 알킬기, 알케닐기, 알카이닐기, 아릴기, 헤테로아릴기, 아릴알킬기, 헤테로아릴알킬기, 탄소고리기, 탄소고리알킬기, 헤테로고리기, 헤테로고리알킬기; 치환 또는 비치환된 탄소수 30 이하의 알콕시기, 아릴옥시기, 헤테로아릴옥시기; 나이트릴기; 하이드록시기; 알킬티옥시기; 붕소기; 포스핀기, 포스핀옥사이드기; 니트로기; 티올; 포스포네이트; 실릴기; 알데하이드기; 에스테르기; 카르복실기나 그의 염; 술포닐기; 설파모일(sulfamoyl)기; 술폰산기나 그의 염; 및 인산이나 그의 염 중에서 선택되고,
Rp1 및 Rp2는 서로 동일하거나 상이하며, 각각 독립적으로,
수소; 중수소; 할로겐; 치환 또는 비치환된 탄소수 30 이하의 알킬기, 알케닐기, 알카이닐기, 아릴기, 헤테로아릴기, 아릴알킬기, 헤테로아릴알킬기, 탄소고리기, 탄소고리알킬기, 헤테로고리기, 헤테로고리알킬기; 치환 또는 비치환된 탄소수 30 이하의 알콕시기, 아릴옥시기, 헤테로아릴옥시기; 나이트릴기; 하이드록시기; 알킬티옥시기; 붕소기; 아미노기; 히드라진; 아미드기; 니트로기; 티올; 포스포네이트; 실릴기; 알데하이드기; 에스테르기; 카르복실기나 그의 염; 술포닐기; 설파모일(sulfamoyl)기; 술폰산기나 그의 염; 및 인산이나 그의 염 중에서 선택된다. The electrolyte for a secondary battery of the present invention includes an aminophosphine compound represented by any one of Formulas 1 to 3 below:
[Formula 1]
[Formula 2]
[Formula 3]
In Chemical Formulas 1 to 3, Rn 1 , Rn 2 , Rn 3 , Rn 4 , Rn 5 and Rn 6 are the same as or different from each other, and each independently,
hydrogen; heavy hydrogen; halogen; A substituted or unsubstituted alkyl group having 30 or less carbon atoms, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an arylalkyl group, a heteroarylalkyl group, a carbocyclic group, a carbocyclic alkyl group, a heterocyclic group, a heterocyclic alkyl group; A substituted or unsubstituted alkoxy group having 30 or less carbon atoms, an aryloxy group, or a heteroaryloxy group; nitrile group; hydroxy group; Alkyl thioxy group; boron group; A phosphine group, a phosphine oxide group; nitro group; thiol; phosphonates; silyl group; aldehyde group; ester group; carboxyl groups or salts thereof; sulfonyl group; Sulfamoyl group; sulfonic acid groups or salts thereof; And it is selected from phosphoric acid or a salt thereof,
Rp 1 and Rp 2 are the same as or different from each other, and each independently,
hydrogen; heavy hydrogen; halogen; A substituted or unsubstituted alkyl group having 30 or less carbon atoms, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an arylalkyl group, a heteroarylalkyl group, a carbocyclic group, a carbocyclic alkyl group, a heterocyclic group, a heterocyclic alkyl group; A substituted or unsubstituted alkoxy group having 30 or less carbon atoms, an aryloxy group, or a heteroaryloxy group; nitrile group; hydroxy group; Alkyl thioxy group; boron group; amino group; hydrazine; amide group; nitro group; thiol; phosphonates; silyl group; aldehyde group; ester group; carboxyl groups or salts thereof; sulfonyl group; Sulfamoyl group; sulfonic acid groups or salts thereof; and phosphoric acid or a salt thereof.
Description
본 발명은 이차전지용 전해질 및 이를 포함하는 이차전지에 관한 것으로, 더욱 상세하게는 전지의 고온저장 성능의 열화 없이 고온 수명 특성을 향상시킬 수 있는 리튬 이차전지용 전해질 및 이를 포함하는 리튬 이차전지에 관한 것이다. The present invention relates to an electrolyte for a secondary battery and a secondary battery including the same, and more particularly, to an electrolyte for a lithium secondary battery capable of improving high-temperature lifespan characteristics without deterioration of high-temperature storage performance of the battery and a lithium secondary battery including the same. .
리튬 이차전지는 휴대폰, 디지털카메라, 노트북 컴퓨터 및 전동공구 뿐만 아니라 전기자전거, 전기자동차 및 에너지저장장치까지 적용 분야가 확대되면서 에너지 전자 기기의 전원으로 사용되는 전지의 고에너지밀도화 및 고안전성에 대한 요구가 높아지고 있다. As lithium secondary batteries expand their applications to not only mobile phones, digital cameras, laptop computers and power tools, but also electric bicycles, electric vehicles and energy storage devices, there is a growing interest in the high energy density and high safety of batteries used as power sources for energy electronic devices. Demand is rising.
일 예로서, 리튬이온 이차전지는 이러한 요구를 가장 잘 충족시킬 수 있는 전지로서 이에 대한 연구가 활발히 진행되고 있다. 리튬이온 이차전지는 리튬이온의 삽입 및 탈리가 가능한 탄소재 등의 음극, 리튬 함유 산화물 등으로 이루어진 양극, 두 전극 사이에 다공성 분리막 및 혼합 유기용매에 리튬이 용해된 비수전해액으로 주요 구성되어 있다. 비수 전해액으로는 프로필렌카보네이트, 에틸카보네이트, 디메틸카보네이트, 디에틸카보네이트 등의 비수성 용매에 LiPF6 등 리튬염이 용해된 것을 사용하고 있다. As an example, a lithium ion secondary battery is a battery that can best satisfy these demands, and research on this is being actively conducted. A lithium ion secondary battery is mainly composed of a negative electrode made of a carbon material capable of intercalating and deintercalating lithium ions, a positive electrode made of lithium-containing oxide, a porous separator between the two electrodes, and a non-aqueous electrolyte in which lithium is dissolved in a mixed organic solvent. As the non-aqueous electrolyte, a lithium salt such as LiPF 6 dissolved in a non-aqueous solvent such as propylene carbonate, ethyl carbonate, dimethyl carbonate, or diethyl carbonate is used.
그러나 이러한 유기용매는 일반적으로 고온에서 장시간 보관할 경우 전해액의 산화로 기체 발생되어 전지가 발화, 폭발되는 문제를 야기할 수 있다. 최근 이러한 문제를 해결하기 위해 첨가제를 포함하는 새로운 조성의 전해액을 개발하려는 연구가 다양하게 시도되고 있다. 그러나 카보네이트계 유기용매의 분해로 인하여 전지 내부에 가스가 발생하는 문제점이 있다.However, when such an organic solvent is generally stored at a high temperature for a long time, gas is generated due to oxidation of the electrolyte solution, which may cause ignition or explosion of the battery. Recently, in order to solve this problem, various attempts have been made to develop an electrolyte solution having a new composition including an additive. However, there is a problem in that gas is generated inside the battery due to decomposition of the carbonate-based organic solvent.
카보네이트계 유기용매를 사용하는 전지에서는 부동태막(passivation layer) 형성 반응 중 카보네이트계 유기용매의 분해로 인하여 전지 내부에 가스가 발생하는 문제점이 있다. 이러한 가스로는 비수성 유기 용매와 전극 활물질의 종류에 따라 H2, CO, CO2, CH4 등이 될 수 있다. 전지 내부의 가스 발생으로 인하여 충전시 전지의 두께가 팽창되고, 또한 만충전 상태에서의 고온방치 시(예: 4.2V 100% 충전 후, 60℃, 4주 방치) SEI 필름은 시간이 경과함에 따라 증가된 전기화학적 에너지와 열에너지에 의해 서서히 붕괴되어, 주위의 전해질이 노출된 새로운 음극 표면과 반응하는 부반응을 지속적으로 일으키게 된다. 이때의 계속적인 가스발생으로 인하여 전지의 내부 압력이 상승하고, 전지의 부피팽창 등으로 인해 고온에서 전지의 성능 등 열화가 일어난다.In a battery using a carbonate-based organic solvent, there is a problem in that gas is generated inside the battery due to decomposition of the carbonate-based organic solvent during a passivation layer formation reaction. Such a gas may be H 2 , CO, CO 2 , CH 4 , or the like, depending on the type of non-aqueous organic solvent and electrode active material. Due to gas generation inside the battery, the thickness of the battery expands during charging, and when left at high temperature in a fully charged state (e.g., after charging 4.2V 100%, left at 60°C for 4 weeks), the SEI film deteriorates over time. It is gradually disintegrated by the increased electrochemical energy and thermal energy, continuously causing a side reaction in which the surrounding electrolyte reacts with the exposed new cathode surface. At this time, due to the continuous gas generation, the internal pressure of the battery rises, and the performance of the battery deteriorates at high temperatures due to volume expansion of the battery.
따라서, 리튬이차전지의 수명특성 및 저장특성 등의 성능을 개선하기 위해 전해액과 전극의 계면 반응을 효과적으로 제어할 수 있는 기술 개발이 요구되고 있다.Therefore, in order to improve the performance of lithium secondary batteries, such as life characteristics and storage characteristics, there is a need for the development of technology capable of effectively controlling the interfacial reaction between the electrolyte and the electrode.
본 발명은 이차전지의 고온저장 특성과 고온수명 특성을 향상시킬 수 있는 이차전지용 전해질 및 이를 포함하는 이차전지를 제공하고자 한다. An object of the present invention is to provide an electrolyte for a secondary battery capable of improving high-temperature storage characteristics and high-temperature lifespan characteristics of the secondary battery and a secondary battery including the same.
본 발명의 이차전지용 전해질은 하기 화학식 1 내지 3 중 어느 하나로 표시되는 아미노포스핀(aminophosphine) 화합물을 포함한다. The electrolyte for a secondary battery of the present invention includes an aminophosphine compound represented by any one of Chemical Formulas 1 to 3 below.
[화학식 1][Formula 1]
[화학식 2][Formula 2]
[화학식 3][Formula 3]
상기 화학식 1 내지 3에서, Rn1, Rn2, Rn3, Rn4, Rn5 및 Rn6은 서로 동일하거나 상이하며, 각각 독립적으로, 수소; 중수소; 할로겐; 치환 또는 비치환된 탄소수 30 이하의 알킬기, 알케닐기, 알카이닐기, 아릴기, 헤테로아릴기, 아릴알킬기, 헤테로아릴알킬기, 탄소고리기, 탄소고리알킬기, 헤테로고리기, 헤테로고리알킬기; 치환 또는 비치환된 탄소수 30 이하의 알콕시기, 아릴옥시기, 헤테로아릴옥시기; 나이트릴기; 하이드록시기; 알킬티옥시기; 붕소기; 포스핀기, 포스핀옥사이드기; 니트로기; 티올; 포스포네이트; 실릴기; 알데하이드기; 에스테르기; 카르복실기나 그의 염; 술포닐기; 설파모일(sulfamoyl)기; 술폰산기나 그의 염; 및 인산이나 그의 염 중에서 선택된다. In Chemical Formulas 1 to 3, Rn 1 , Rn 2 , Rn 3 , Rn 4 , Rn 5 and Rn 6 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; halogen; A substituted or unsubstituted alkyl group having 30 or less carbon atoms, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an arylalkyl group, a heteroarylalkyl group, a carbocyclic group, a carbocyclic alkyl group, a heterocyclic group, a heterocyclic alkyl group; A substituted or unsubstituted alkoxy group having 30 or less carbon atoms, an aryloxy group, or a heteroaryloxy group; nitrile group; hydroxy group; Alkyl thioxy group; boron group; A phosphine group, a phosphine oxide group; nitro group; thiol; phosphonates; silyl group; aldehyde group; ester group; carboxyl groups or salts thereof; sulfonyl group; Sulfamoyl group; sulfonic acid groups or salts thereof; and phosphoric acid or a salt thereof.
또한, 상기 화학식 1 내지 3에서, Rp1 및 Rp2는 서로 동일하거나 상이하며, 각각 독립적으로, 수소; 중수소; 할로겐; 치환 또는 비치환된 탄소수 30 이하의 알킬기, 알케닐기, 알카이닐기, 아릴기, 헤테로아릴기, 아릴알킬기, 헤테로아릴알킬기, 탄소고리기, 탄소고리알킬기, 헤테로고리기, 헤테로고리알킬기; 치환 또는 비치환된 탄소수 30 이하의 알콕시기, 아릴옥시기, 헤테로아릴옥시기; 나이트릴기; 하이드록시기; 알킬티옥시기; 붕소기; 아미노기; 히드라진; 아미드기; 니트로기; 티올; 포스포네이트; 실릴기; 알데하이드기; 에스테르기; 카르복실기나 그의 염; 술포닐기; 설파모일(sulfamoyl)기; 술폰산기나 그의 염; 및 인산이나 그의 염 중에서 선택된다. In addition, in Chemical Formulas 1 to 3, Rp 1 and Rp 2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; A substituted or unsubstituted alkyl group having 30 or less carbon atoms, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an arylalkyl group, a heteroarylalkyl group, a carbocyclic group, a carbocyclic alkyl group, a heterocyclic group, a heterocyclic alkyl group; A substituted or unsubstituted alkoxy group having 30 or less carbon atoms, an aryloxy group, or a heteroaryloxy group; nitrile group; hydroxy group; Alkyl thioxy group; boron group; amino group; hydrazine; amide group; nitro group; thiol; phosphonates; silyl group; aldehyde group; ester group; carboxyl groups or salts thereof; sulfonyl group; Sulfamoyl group; sulfonic acid groups or salts thereof; and phosphoric acid or a salt thereof.
일 구현예로서, 상기 화학식 1 내지 3에서 Rn1, Rn2, Rn3, Rn4, Rn5 및 Rn6은 서로 동일하거나 상이하며, 각각 독립적으로, 치환 또는 비치환된 탄소수 30 이하의 알킬기, 알케닐기, 알카이닐기, 아릴기, 헤테로아릴기, 아릴알킬기, 헤테로아릴알킬기, 탄소고리기, 탄소고리알킬기, 헤테로고리기 및 헤테로고리알킬기 중에서 선택될 수 있다. As an embodiment, in Chemical Formulas 1 to 3, Rn 1 , Rn 2 , Rn 3 , Rn 4 , Rn 5 and Rn 6 are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group having 30 or less carbon atoms; It may be selected from an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an arylalkyl group, a heteroarylalkyl group, a carbocyclic group, a carbocyclic alkyl group, a heterocyclic group, and a heterocyclic alkyl group.
일 구현예로서, 상기 Rn1, Rn2, Rn3, Rn4, Rn5 및 Rn6은 서로 동일하거나 상이하며, 각각 독립적으로, 치환 또는 비치환된 아릴기, 헤테로아릴기, 아릴알킬기 및 헤테로아릴알킬기 중에서 선택될 수 있다. In one embodiment, Rn 1 , Rn 2 , Rn 3 , Rn 4 , Rn 5 and Rn 6 are the same as or different from each other, and are each independently a substituted or unsubstituted aryl group, a heteroaryl group, an arylalkyl group and a hetero group. It may be selected from arylalkyl groups.
일 구현예로서, 상기 Rp1 및 Rp2 중 어느 하나, 또는 Rp1 및 Rp2 은 할로겐일 수 있다. In one embodiment, any one of Rp 1 and Rp 2 , or Rp 1 and Rp 2 is may be halogen.
일 구현예로서, 상기 아미노포스핀(aminophosphine) 화합물은 하기 화학식 1-1로 표시되는 화합물일 수 있다. As an embodiment, the aminophosphine compound may be a compound represented by Formula 1-1 below.
[화학식 1-1][Formula 1-1]
일 구현예로서, 상기 화학식 1로 표시되는 아미노포스핀(aminophosphine) 화합물은 이차전지용 전해질 전체 대비 0.05 내지 20중량%로 첨가될 수 있다. As an embodiment, the aminophosphine compound represented by Chemical Formula 1 may be added in an amount of 0.05 to 20% by weight based on the total weight of the secondary battery electrolyte.
일 구현예로서, 상기 화학식 1로 표시되는 아미노포스핀(aminophosphine) 화합물 이외에도, 첨가제로서 비닐렌카보네이트(vinylidene carbonate, VC), 프로판설톤(propanesultone, PS) 및 에틸렌설페이트(ethylene sulfate, ESA) 중에서 선택되는 어느 하나 이상의 화합물을 더 포함할 수 있다. As an embodiment, in addition to the aminophosphine compound represented by Formula 1, vinylene carbonate (VC), propanesultone (PS) and ethylene sulfate (ESA) are selected as additives Any one or more compounds may be further included.
본 발명의 일 실시예에 의한 이차전지용 전해질은 비수계 용매; 및 리튬염;을 더 포함할 수 있다. An electrolyte for a secondary battery according to an embodiment of the present invention includes a non-aqueous solvent; And a lithium salt; may further include.
본 발명의 일 실시예에 의한 이차전지는 양극; 음극; 및 상기 이차전지용 전해질;을 포함한다. A secondary battery according to an embodiment of the present invention includes a cathode; cathode; and the electrolyte for the secondary battery.
본 발명은 전지의 고온저장시 두께변화율 감소 및 DCIR 변화율 감소로 인하여 전지의 고온저장 특성과 고온수명 특성을 현저히 개선시킬 수 있다. The present invention can remarkably improve the high-temperature storage characteristics and high-temperature lifespan characteristics of the battery due to the decrease in the thickness change rate and the DCIR change rate during high-temperature storage of the battery.
본 명세서에서 사용되는 "포함하는"과 같은 표현은, 다른 실시예를 포함할 가능성을 내포하는 개방형 용어(open-ended terms)로 이해되어야 한다.Expressions such as "comprising" used herein should be understood as open-ended terms that connote the possibility of including other embodiments.
본 명세서에서 사용되는 "바람직한" 및 "바람직하게"는 소정 환경 하에서 소정의 이점을 제공할 수 있는 본 발명의 실시 형태를 지칭한다. 그러나, 동일한 환경 또는 다른 환경 하에서, 다른 실시 형태가 또한 바람직할 수 있다. 추가로, 하나 이상의 바람직한 실시 형태의 언급은 다른 실시 형태가 유용하지 않다는 것을 의미하지 않으며, 본 발명의 범주로부터 다른 실시 형태를 배제하고자 하는 것은 아니다.As used herein, “preferred” and “preferably” refer to embodiments of the invention that may provide certain advantages under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Additionally, the recitation of one or more preferred embodiments does not imply that the other embodiments are not useful, nor is it intended to exclude the other embodiments from the scope of the present invention.
본 발명의 이차전지용 전해질은 이차전지의 고온저장시 두께변화율 감소 및 DCIR 변화율 감소로 인하여 전지의 고온저장 특성과 고온수명 특성을 현저히 개선시키고자, 하기 화학식 1 내지 3 중 어느 하나로 표시되는 아미노포스핀(aminophosphine) 화합물을 포함한다. The electrolyte for a secondary battery of the present invention is aminophosphine represented by any one of the following formulas 1 to 3 in order to significantly improve the high-temperature storage characteristics and high-temperature lifespan characteristics of a secondary battery due to a decrease in the thickness change rate and DCIR change rate during high-temperature storage of the secondary battery (aminophosphine) compounds.
[화학식 1][Formula 1]
[화학식 2][Formula 2]
[화학식 3][Formula 3]
상기 화학식 1 내지 3에서, Rn1, Rn2, Rn3, Rn4, Rn5 및 Rn6은 질소(N) 원자에 결합된 작용기를 의미하며, 각각 독립적으로, 수소; 중수소; 할로겐; 치환 또는 비치환된 탄소수 30 이하의 알킬기, 알케닐기, 알카이닐기, 아릴기, 헤테로아릴기, 아릴알킬기, 헤테로아릴알킬기, 탄소고리기, 탄소고리알킬기, 헤테로고리기, 헤테로고리알킬기; 치환 또는 비치환된 탄소수 30 이하의 알콕시기, 아릴옥시기, 헤테로아릴옥시기; 나이트릴기; 하이드록시기; 알킬티옥시기; 붕소기; 포스핀기, 포스핀옥사이드기; 니트로기; 티올; 포스포네이트; 실릴기; 알데하이드기; 에스테르기; 카르복실기나 그의 염; 술포닐기; 설파모일(sulfamoyl)기; 술폰산기나 그의 염; 및 인산이나 그의 염 중에서 선택된다. In Chemical Formulas 1 to 3, Rn 1 , Rn 2 , Rn 3 , Rn 4 , Rn 5 and Rn 6 denote functional groups bonded to nitrogen (N) atoms, and each independently represent hydrogen; heavy hydrogen; halogen; A substituted or unsubstituted alkyl group having 30 or less carbon atoms, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an arylalkyl group, a heteroarylalkyl group, a carbocyclic group, a carbocyclic alkyl group, a heterocyclic group, a heterocyclic alkyl group; A substituted or unsubstituted alkoxy group having 30 or less carbon atoms, an aryloxy group, or a heteroaryloxy group; nitrile group; hydroxy group; Alkyl thioxy group; boron group; A phosphine group, a phosphine oxide group; nitro group; thiol; phosphonates; silyl group; aldehyde group; ester group; carboxyl groups or salts thereof; sulfonyl group; Sulfamoyl group; sulfonic acid groups or salts thereof; and phosphoric acid or a salt thereof.
상기 화학식 1 내지 3에서, Rp1 및 Rp2는 인(P) 원자에 결합된 작용기를 의미하며, 각각 독립적으로, 수소; 중수소; 할로겐; 치환 또는 비치환된 탄소수 30 이하의 알킬기, 알케닐기, 알카이닐기, 아릴기, 헤테로아릴기, 아릴알킬기, 헤테로아릴알킬기, 탄소고리기, 탄소고리알킬기, 헤테로고리기, 헤테로고리알킬기; 치환 또는 비치환된 탄소수 30 이하의 알콕시기, 아릴옥시기, 헤테로아릴옥시기; 나이트릴기; 하이드록시기; 알킬티옥시기; 붕소기; 아미노기; 히드라진; 아미드기; 니트로기; 티올; 포스포네이트; 실릴기; 알데하이드기; 에스테르기; 카르복실기나 그의 염; 술포닐기; 설파모일(sulfamoyl)기; 술폰산기나 그의 염; 및 인산이나 그의 염 중에서 선택된다. In Chemical Formulas 1 to 3, Rp 1 and Rp 2 mean a functional group bonded to a phosphorus (P) atom, and each independently hydrogen; heavy hydrogen; halogen; A substituted or unsubstituted alkyl group having 30 or less carbon atoms, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an arylalkyl group, a heteroarylalkyl group, a carbocyclic group, a carbocyclic alkyl group, a heterocyclic group, a heterocyclic alkyl group; A substituted or unsubstituted alkoxy group having 30 or less carbon atoms, an aryloxy group, or a heteroaryloxy group; nitrile group; hydroxy group; Alkyl thioxy group; boron group; amino group; hydrazine; amide group; nitro group; thiol; phosphonates; silyl group; aldehyde group; ester group; carboxyl groups or salts thereof; sulfonyl group; Sulfamoyl group; sulfonic acid groups or salts thereof; and phosphoric acid or a salt thereof.
상기 "치환 또는 비치환"은 알킬기 또는 알콕시기의 수소 원자가 할로겐 원자, 니트릴기, 니트로기, 하이드록시기, 카보닐기, 아미드기, 아미노기, 포스핀기, 포스핀옥사이드기, 티올기, 티옥시기, 알콕시기, 아릴옥시기, 알킬티옥시기, 아릴티옥시기, 알킬술폭시기, 아릴술폭시기, 실릴기, 붕소기, 알킬기, 알케닐기, 알카이닐기, 아릴기, 헤테로고리기, 및 헤테로고리알킬기로 이루어진 군에서 선택된 1개 이상의 치환기로 치환 또는 비치환된 것을 의미한다. The "substituted or unsubstituted" means that the hydrogen atom of the alkyl or alkoxy group is a halogen atom, a nitrile group, a nitro group, a hydroxyl group, a carbonyl group, an amide group, an amino group, a phosphine group, a phosphine oxide group, a thiol group, a thioxyl group, consisting of an alkoxy group, an aryloxy group, an alkylthiooxy group, an arylthiooxy group, an alkylsulfoxyl group, an arylsulfoxyl group, a silyl group, a boron group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, and a heterocyclic alkyl group It means substituted or unsubstituted with one or more substituents selected from the group.
상기 아미노포스핀(aminophosphine) 화합물은 이차전지용 전해질의 첨가제로서 첨가되는 화합물일 수 있다. The aminophosphine compound may be a compound added as an additive to an electrolyte for a secondary battery.
일 구현예로서, 상기 화학식 1 내지 3에서 Rn1, Rn2, Rn3, Rn4, Rn5 및 Rn6은 서로 동일하거나 상이하며, 각각 독립적으로, 치환 또는 비치환된 탄소수 30 이하의 알킬기, 알케닐기, 알카이닐기, 아릴기, 헤테로아릴기, 아릴알킬기, 헤테로아릴알킬기, 탄소고리기, 탄소고리알킬기, 헤테로고리기 및 헤테로고리알킬기 중에서 선택될 수 있다. As an embodiment, in Chemical Formulas 1 to 3, Rn 1 , Rn 2 , Rn 3 , Rn 4 , Rn 5 and Rn 6 are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group having 30 or less carbon atoms; It may be selected from an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an arylalkyl group, a heteroarylalkyl group, a carbocyclic group, a carbocyclic alkyl group, a heterocyclic group, and a heterocyclic alkyl group.
또한, 일 구현예로서, 상기 화학식 1 내지 3에서 Rn1, Rn2, Rn3, Rn4, Rn5 및 Rn6은 서로 동일하거나 상이하며, 각각 독립적으로, 치환 또는 비치환된 아릴기, 헤테로아릴기, 아릴알킬기 및 헤테로아릴알킬기 중에서 선택될 수 있다. In addition, as an embodiment, Rn 1 , Rn 2 , Rn 3 , Rn 4 , Rn 5 and Rn 6 in Formulas 1 to 3 are the same as or different from each other, and each independently represent a substituted or unsubstituted aryl group, a hetero group, It may be selected from an aryl group, an arylalkyl group and a heteroarylalkyl group.
보다 바람직하게는, R1 및/또는 R2는 모두 페닐기일 수 있다. More preferably, both R1 and/or R2 may be a phenyl group.
일 구현예로서, 상기 화학식 1 내지 3에서 Rp1 및 Rp2 중 어느 하나, 또는 Rp1 및 Rp2 은 할로겐일 수 있다. As an embodiment, any one of Rp 1 and Rp 2 in Formulas 1 to 3, or Rp 1 and Rp 2 may be halogen.
보다 바람직하게는, Rp1 및 Rp2 중 어느 하나, 또는 Rp1 및 Rp2 은 불소일 수 있다. More preferably, any one of Rp 1 and Rp 2 or Rp 1 and Rp 2 is may be fluorine.
가장 바람직하게는 Rp1 및 Rp2 모두 불소일 수 있다. Most preferably both Rp 1 and Rp 2 may be fluorine.
일 예로서, 본 발명의 아미노포스핀(aminophosphine) 화합물은 하기와 같을 수 있다. As an example, the aminophosphine compound of the present invention may be as follows.
가장 바람직한 일 구현예로서, 상기 아미노포스핀(aminophosphine) 화합물은 하기 화학식 1-1로 표시되는 디플로로 디페닐아미노 포스핀(Difluoro(diphenylamino)phosphine) 일 수 있다. As a most preferred embodiment, the aminophosphine compound may be difluoro(diphenylamino)phosphine represented by Formula 1-1 below.
[화학식 1-1][Formula 1-1]
일 구현예로서, 상기 화학식 1로 표시되는 아미노포스핀(aminophosphine) 화합물은 이차전지용 전해질 전체 대비 0.05 내지 20중량%, 0.1 내지 10중량%, 보다 0.1 내지 5중량%, 또는 0.1 내지 1중량%로 첨가될 수 있다. 상기 화학식의 아미노포스핀(aminophosphine) 화합물이 0.05중량% 미만으로 포함되는 경우 전지 특성 및 포스핀 화합물 특성이 나타나지 않는 문제점이 있고, 20중량% 초과하여 포함되면, 저항 증가, 용량 저하 등의 전지 특성이 저하되는 문제점이 있다. As an embodiment, the aminophosphine compound represented by Formula 1 is 0.05 to 20% by weight, 0.1 to 10% by weight, 0.1 to 5% by weight, or 0.1 to 1% by weight relative to the total electrolyte for a secondary battery. may be added. When the aminophosphine compound of the above formula is included in less than 0.05% by weight, there is a problem in that battery characteristics and phosphine compound characteristics do not appear, and when it is included in more than 20% by weight, battery characteristics such as resistance increase and capacity decrease There is a problem with this degradation.
일 구현예로서, 상기 화학식 1로 표시되는 아미노포스핀(aminophosphine) 화합물 이외에도, 첨가제로서 카보네이트 계열의 화합물, 설톤 계열의 화합물, 설페이트 계열의 화합물, 포스파젠 계열의 화합물 중에서 선택되는 어느 하나 이상의 첨가제를 더 포함할 수 있다. In one embodiment, in addition to the aminophosphine compound represented by Formula 1, one or more additives selected from carbonate-based compounds, sultone-based compounds, sulfate-based compounds, and phosphazene-based compounds are used as additives. can include more.
보다 바람직한 일 예로서, 상기 화학식 1로 표시되는 아미노포스핀(aminophosphine) 화합물 이외에도, 첨가제로서 비닐렌카보네이트(vinylidene carbonate, VC), 프로판설톤(propanesultone, PS) 및 에틸렌설페이트(ethylene sulfate, ESA) 중에서 선택되는 어느 하나 이상의 화합물을 더 포함할 수 있다. As a more preferred example, in addition to the aminophosphine compound represented by Formula 1, among vinylene carbonate (VC), propanesultone (PS) and ethylene sulfate (ESA) as additives Any one or more selected compounds may be further included.
특히, 본 발명은 화학식 1로 표시되는 아미노포스핀(aminophosphine) 화합물 이외에도, 카보네이트 계열의 화합물, 설톤 계열의 화합물 및 설페이트 계열의 화합물을 모두 포함하는 경우에 보다 고온저장 특성과 고온수명 특성이 향상되는 것을 실험을 통해 확인할 수 있다. In particular, the present invention is a case in which, in addition to the aminophosphine compound represented by Formula 1, a carbonate-based compound, a sultone-based compound, and a sulfate-based compound are all included, high-temperature storage characteristics and high-temperature lifespan characteristics are improved. This can be verified through experimentation.
특히, 본 발명은 상기 화학식 1로 표시되는 아미노포스핀(aminophosphine) 화합물 이외에도, 비닐렌카보네이트, 프로판설톤 및 에틸렌설페이트 모두를 더 포함할 수 있다. 이와 같이 본 발명의 아미노포스핀(aminophosphine) 화합물, 비닐렌카보네이트, 프로판설톤 및 에틸렌설페이트 모두가 첨가제로서 사용되는 경우에는 보다 고온저장 특성과 고온수명 특성이 향상되는 것을 확인할 수 있다. In particular, the present invention may further include all of vinylene carbonate, propanesultone, and ethylene sulfate in addition to the aminophosphine compound represented by Formula 1 above. As such, it can be seen that when all of the aminophosphine compound, vinylene carbonate, propanesultone and ethylene sulfate of the present invention are used as additives, the high temperature storage characteristics and high temperature life characteristics are improved.
일 예로서, 첨가제로서 비닐렌카보네이트, 프로판설톤 및 에틸렌설페이트 중에서 선택되는 어느 하나 이상의 화합물이 더 포함되는 경우, 상기 비닐렌카보네이트, 프로판설톤 및 에틸렌설페이트 중에서 선택되는 어느 하나 이상의 화합물은 이차전지용 전해질 전체 대비 0.01 내지 20중량%, 0.1 내지 10중량%, 또는 0.1 내지 5중량%로 첨가될 수 있다. As an example, when any one or more compounds selected from vinylene carbonate, propanesultone, and ethylene sulfate are further included as an additive, any one or more compounds selected from vinylene carbonate, propanesultone, and ethylene sulfate may be used as the entire secondary battery electrolyte It may be added at 0.01 to 20% by weight, 0.1 to 10% by weight, or 0.1 to 5% by weight.
만약, 일 예로서, 상기 화학식 1로 표시되는 아미노포스핀(aminophosphine) 화합물 이외에도, 비닐렌카보네이트, 프로판설톤 및 에틸렌설페이트 모두 포함하는 경우, 상기 아미노포스핀(aminophosphine) 화합물은 비닐렌카보네이트, 프로판설톤 및 에틸렌설페이트를 모두 합한 전체 대비 0.05 중량%이상, 5중량% 이상, 10중량% 이상, 90중량%이하, 70중량%이하, 50중량%이하, 또는 30중량%이하일 수 있다. If, as an example, in addition to the aminophosphine compound represented by Formula 1, when all of vinylene carbonate, propanesultone and ethylene sulfate are included, the aminophosphine compound is vinylene carbonate, propanesultone and ethylene sulfate may be 0.05% by weight or more, 5% by weight or more, 10% by weight or more, 90% by weight or less, 70% by weight or less, 50% by weight or less, or 30% by weight or less based on the total amount of ethylene sulfate.
본 발명의 일 실시예에 의한 이차전지용 전해질은 비수계 용매; 및 리튬염;을 더 포함할 수 있다. An electrolyte for a secondary battery according to an embodiment of the present invention includes a non-aqueous solvent; And a lithium salt; may further include.
본 발명의 이차전지용 전해질에 포함되는 상기 비수계 용매는 선형 또는 환형의 카보네이트, 에스테르 및 에테르 중에서 선택되는 어느 하나 이상을 더 포함할 수 있으나, 이에 특별히 한정되는 것은 아니다. The non-aqueous solvent included in the electrolyte for a secondary battery of the present invention may further include at least one selected from linear or cyclic carbonates, esters, and ethers, but is not particularly limited thereto.
보다 바람직한 일 예로서, 상기 비수계 용매는 선형 카보네이트계 용매, 환형 카보네이트계 용매 또는 이들의 혼합용매로부터 선택될 수 있으며, 상기 선형 카보네이트계 용매는 디메틸카보네이트(DMC), 디에틸카보네이트(DEC), 디프로필카보네이트(DPC), 에틸프로필카보네이트(EPC), 에틸메틸카보네이트(EMC) 및 메틸프로필카보네이트(MPC)로 이루어진 군에서 선택될 수 있고, 환형 카보네이트계 용매는 에틸렌카보네이트(EC), 프로필렌카보네이트(PC), 1,2-부틸렌카보네이트(BC), 2,3-부틸렌카보네이트, 1,2-펜틸렌 카보네이트, 2,3-펜틸렌카보네이트, 비닐렌카보네이트(VC) 및 플루오르에틸렌카보네이트(FEC), 이루어진 군에서 선택될 수 있다. As a more preferable example, the non-aqueous solvent may be selected from a linear carbonate-based solvent, a cyclic carbonate-based solvent, or a mixed solvent thereof, and the linear carbonate-based solvent may include dimethyl carbonate (DMC), diethyl carbonate (DEC), It may be selected from the group consisting of dipropyl carbonate (DPC), ethyl propyl carbonate (EPC), ethyl methyl carbonate (EMC) and methyl propyl carbonate (MPC), and the cyclic carbonate-based solvent is ethylene carbonate (EC), propylene carbonate ( PC), 1,2-butylene carbonate (BC), 2,3-butylene carbonate, 1,2-pentylene carbonate, 2,3-pentylene carbonate, vinylene carbonate (VC) and fluoroethylene carbonate (FEC ), can be selected from the group consisting of.
보다 바람직하게는, 상기 카보네이트계 유기용매 중에서도 전지의 충방전 성능을 높일 수 있는 높은 이온전도도를 갖는 고유전율의 카보네이트계 유기용매와 상기 고유전율의 유기용매의 점도를 적절하게 조절할 수 있는 점도가 낮은 카보네이트계 유기용매를 혼합하여 사용하는 것이 바람직할 수 있다. 구체적으로 프로필렌 카보네이트, 에틸렌 카보네이트 및 이들의 혼합물로 이루어진 군에서 선택되는 고유전율의 유기용매와, 디에틸 카보네이트, 에틸 메틸 카보네이트, 미케틸 카보네이트 및 이들의 혼합물로 이루어진 군에서 선택되는 저점도의 유기용매를 혼합하여 사용할 수 있다.More preferably, among the carbonate-based organic solvents, a carbonate-based organic solvent having a high dielectric constant having a high ion conductivity capable of increasing the charge and discharge performance of a battery and a low viscosity capable of appropriately adjusting the viscosity of the high dielectric constant organic solvent It may be preferable to use a mixture of carbonate-based organic solvents. Specifically, a high permittivity organic solvent selected from the group consisting of propylene carbonate, ethylene carbonate and mixtures thereof, and a low viscosity organic solvent selected from the group consisting of diethyl carbonate, ethyl methyl carbonate, miketyl carbonate and mixtures thereof can be used in combination.
환형 카보네이트 용매는 극성이 커서 리튬 이온을 충분히 해리시킬 수 있는 반면, 점도가 커서 이온 전도도가 작은 단점이 있기 때문에, 상기 환형 카보네이트 용매에 극성은 작지만 점도가 낮은 선형 카보네이트 용매를 혼합하여 사용함으로써 리튬 이차 전지의 특성을 최적화할 수 있다. 따라서, 상기 비수계 용매로 환형 카보네이트 용매에서 선택되는 하나 이상의 용매와 선형 카보네이트 용매에서 선택되는 하나 이상의 용매를 혼합하여 사용하는 것이 바람직하다. 이때, 환형 카보네이트계 용매와 사슬형 카보네이트계 용매는 부피비를 기준으로 9:1 내지 1:9의 비율로 혼합하고, 보다 바람직하게는 2:8 내지 8:2의 부피비율로 혼합하여 사용하는 것이 전지의 수명특성과 저장특성 측면에서 가장 바람직하다.Since the cyclic carbonate solvent has a high polarity and can sufficiently dissociate lithium ions, but has a low ionic conductivity due to a high viscosity, the lithium secondary carbonate solvent is mixed with a linear carbonate solvent having a low polarity but low viscosity to the cyclic carbonate solvent. Battery characteristics can be optimized. Therefore, it is preferable to use a mixture of one or more solvents selected from cyclic carbonate solvents and one or more solvents selected from linear carbonate solvents as the non-aqueous solvent. At this time, the cyclic carbonate-based solvent and the chain-shaped carbonate-based solvent are mixed at a volume ratio of 9:1 to 1:9, and more preferably at a volume ratio of 2:8 to 8:2. It is most preferable in terms of life characteristics and storage characteristics of the battery.
특히, 환형 카보네이트계 용매 중에서는 유전율이 높은 에틸렌 카보네이트와 프로필렌 카보네이트를 사용하고, 음극 활물질로 천연흑연이 사용되는 경우에는 에틸렌 카보네이트를 사용하는 것이 바람직하며, 사슬형 카보네이트계 용매 중에서는 점도가 낮은 디메틸 카보네이트, 에틸메틸 카보네이트, 디에틸 카보네이트를 사용하는 것이 바람직하다.In particular, among cyclic carbonate-based solvents, ethylene carbonate and propylene carbonate with high permittivity are used, and when natural graphite is used as an anode active material, it is preferable to use ethylene carbonate. Among chain carbonate-based solvents, dimethyl with low viscosity is used. It is preferable to use carbonate, ethylmethyl carbonate, or diethyl carbonate.
본 발명의 이차전지용 전해질에 포함되는 상기 리튬염은 LiPF6, LiBF4, LiB12F12, LiAsF6, LiFSO3, Li2SiF6, LiCF3CO2, LiCH3CO2, LiCF3SO3, LiC4F9SO3, LiCF3CF2SO3, LiCF3(CF2)7SO3, LiCF3CF2(CF3)2CO, Li(CF3SO2)2CH, LiNO3, LiN(CN)2, LiN(FSO2)2, LiN(F2SO2)2, LiN(CF3SO2)2, LiN(C2F5SO2)2, LiC(CF3SO2)3, LiP(CF3)6, LiPF(CF3)5, LiPF2(CF3)4, LiPF3(CF3)3, LiPF4(CF3)2, LiPF4(C2F5)2, LiPF4(CF3SO2)2, LiPF4(C2F5SO2)2, LiBF2C2O4, LiBC4O8, LiBF2(CF3)2, LiBF2(C2F5)2, LiBF2(CF3SO2)2, LiBF2(C2F5SO2)2, LiSbF6, LiAlO4, LiAlF4, LiSCN, LiClO4, LiCl, LiF, LiBr, LiI, LiAlCl4 중에서 선택되는 어느 하나 이상일 수 있으나, 이에 한정되는 것은 아니다. The lithium salt included in the secondary battery electrolyte of the present invention is LiPF 6 , LiBF 4 , LiB 12 F 12 , LiAsF 6 , LiFSO 3 , Li 2 SiF 6 , LiCF 3 CO 2 , LiCH 3 CO 2 , LiCF 3 SO 3 , LiC 4 F 9 SO 3 , LiCF 3 CF 2 SO 3 , LiCF 3 (CF 2 ) 7 SO 3 , LiCF 3 CF 2 (CF 3 ) 2 CO, Li(CF 3 SO 2 ) 2 CH, LiNO 3 , LiN( CN) 2 , LiN(FSO 2 ) 2 , LiN(F 2 SO 2 ) 2 , LiN(CF 3 SO 2 ) 2 , LiN(C 2 F 5 SO 2 ) 2 , LiC(CF 3 SO 2 ) 3 , LiP (CF 3 ) 6 , LiPF(CF 3 ) 5 , LiPF 2 (CF 3 ) 4 , LiPF 3 (CF 3 ) 3 , LiPF 4 (CF 3 ) 2 , LiPF 4 (C 2 F 5 ) 2 , LiPF 4 ( CF 3 SO 2 ) 2 , LiPF 4 (C 2 F 5 SO 2 ) 2 , LiBF 2 C 2 O 4 , LiBC 4 O 8 , LiBF 2 (CF 3 ) 2 , LiBF 2 (C 2 F 5 ) 2 , LiBF 2 (CF 3 SO 2 ) 2 , LiBF 2 (C 2 F 5 SO 2 ) 2 , LiSbF 6 , LiAlO 4 , LiAlF 4 , LiSCN, LiClO 4 , LiCl, LiF, LiBr, LiI, LiAlCl 4 It may be more than one, but is not limited thereto.
본 발명의 실시예에 따른 이차전지용 비수성 전해액에서, 리튬염은 격자에너지가 해리도가 커서 이온전도도가 우수하고, 열 안정성 및 내산화성이 우수한 것을 사용하는 것이 바람직하다. 상기 리튬염은 전지 내에서 리튬 이온의 공급원으로 작용하여 기본적인 리튬전지의 작동을 가능하게 한다. In the non-aqueous electrolyte solution for a secondary battery according to an embodiment of the present invention, it is preferable to use a lithium salt having a high dissociation degree of lattice energy, excellent ion conductivity, excellent thermal stability and oxidation resistance. The lithium salt serves as a source of lithium ions in the battery, enabling basic operation of the lithium battery.
상기 리튬염의 용매는 그 농도가 전체 전해액 내에서 0.3 내지 2.0M일 수 있다. 전기전도도와 관련된 성질 및 리튬이온의 이동성과 관련된 점도를 고려할 때 0.7 내지 1.6M의 범위가 되도록 해주는 것이 바람직하다. 만일 리튬염의 농도가 0.3M 미만이면 전해액의 전기 전도도가 낮아져서 리튬 이차 전지의 양극과 음극 사이에서 빠른 속도로 이온을 전달하는 비수성 전해액의 성능이 떨어지고, 2.0M을 초과하는 경우에는 전해질의 점도가 증가하여 리튬이온의 이동성이 감소하고 저온성능도 저하되는 문제점이 있다.The solvent of the lithium salt may have a concentration of 0.3 to 2.0 M in the entire electrolyte solution. Considering the properties related to electrical conductivity and the viscosity related to the mobility of lithium ions, it is preferable to make it in the range of 0.7 to 1.6M. If the concentration of the lithium salt is less than 0.3M, the electrical conductivity of the electrolyte is lowered, and the performance of the non-aqueous electrolyte solution that transfers ions at a high speed between the positive and negative electrodes of the lithium secondary battery is deteriorated. There is a problem that the mobility of lithium ions decreases and low-temperature performance also deteriorates.
본 발명의 이차전지용 비수성 전해액은 통상 -10 내지 60℃의 온도 범위에서 보존특성이 우수하고 장시간의 수명을 유지할 수 있으며, 리튬 이차 전지의 안전성과 신뢰성을 향상시킨다.The non-aqueous electrolyte for a secondary battery of the present invention has excellent storage characteristics and can maintain a long lifespan in a temperature range of -10 to 60 ° C., and improves the safety and reliability of a lithium secondary battery.
본 발명의 일 실시예에 의한 이차전지는 양극; 음극; 및 상기 이차전지용 전해질;을 포함한다. A secondary battery according to an embodiment of the present invention includes a cathode; cathode; and the electrolyte for the secondary battery.
상기 이차전지의 비제한적인 예로는 리튬금속 이차전지, 리튬이온 이차전지, 리튬폴리머 이차전지, 리튬이온 폴리머 이차전지 또는 리튬황 이차전지 등이 있다.Non-limiting examples of the secondary battery include a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery, a lithium ion polymer secondary battery, or a lithium sulfur secondary battery.
상기 양극 및/또는 음극은 전극활물질, 바인더 및 도전재, 필요한 경우 증점제를 용매에 분산시켜 전극 슬러리 조성물을 제조하고, 이 슬러리 조성물을 전극 집전체에 도포하여 제조될 수 있다. 양극 집전체로는 흔히 알루미늄 또는 알루미늄 합금 등을 사용할 수 있고, 음극 집전체로는 흔히 구리 또는 구리 합금 등을 사용할 수 있다. 상기 양극 집전체 및 음극 집전체의 형태로는 포일이나 메시 형태를 들 수 있다.The positive electrode and/or negative electrode may be prepared by dispersing an electrode active material, a binder and a conductive material, and, if necessary, a thickener in a solvent to prepare an electrode slurry composition, and applying the slurry composition to an electrode current collector. Aluminum or an aluminum alloy may be commonly used as the anode current collector, and copper or copper alloy may be commonly used as the anode current collector. The positive and negative current collectors may be in the form of foil or mesh.
상기 양극활물질로는 리튬의 가역적인 인터칼레이션 및 디인터칼레이션이 가능한 화합물로서, LiCoO2, LiMnO2, LiMn2O4, LiNiO2 또는 LiNi1-x-yCoxMyO2(0≤x≤1, 0≤y≤1, 0≤x+y≤1, M은 Al, Sr, Mg, Mn 또는 La) 등의 리튬금속산화물 또는 리튬 칼코게나이드 화합물과 같은 리튬 인터칼레이션 화합물을 사용할 수 있으며, 이에 제한되지 않고 리튬 2차 전지에서 양전극 활물질로서 사용가능한 임의의 물질을 사용할 수 있다. 상기 양극활물질은 코발트, 망간, 니켈에서 선택되는 최소한 1종 및 리튬과의 복합 금속 산화물인 것이 바람직하나, 이에 한정되는 것은 아니다. 금속 사이의 고용율은 다양하게 이루어질 수 있으며, 이들 금속 외에 Mg, Al, Co, K, Na, Ca, Si, Ti, Sn, V, Ge, Ga, B, As, Zr, Mn, Cr, Fe, Sr, V 및 희토류 원소로 이루어진 군에서 선택되는 원소가 더 포함될 수 있다. 상기 양극 활물질의 구체적인 예로는 하기 화학식 중 어느 하나로 표현되는 화합물을 사용할 수 있다:The cathode active material is a compound capable of reversible intercalation and deintercalation of lithium, LiCoO 2 , LiMnO 2 , LiMn 2 O 4 , LiNiO 2 or LiNi 1-xy Co x M y O 2 (0≤x ≤1, 0≤y≤1, 0≤x+y≤1, where M is Al, Sr, Mg, Mn or La), etc., or a lithium intercalation compound such as a lithium chalcogenide compound may be used. However, it is not limited thereto, and any material usable as a positive electrode active material in a lithium secondary battery may be used. The cathode active material is preferably a composite metal oxide of at least one selected from cobalt, manganese, and nickel and lithium, but is not limited thereto. The solid solution ratio between metals can be made in various ways, and in addition to these metals, Mg, Al, Co, K, Na, Ca, Si, Ti, Sn, V, Ge, Ga, B, As, Zr, Mn, Cr, Fe, An element selected from the group consisting of Sr, V and rare earth elements may be further included. As a specific example of the cathode active material, a compound represented by any one of the following formulas may be used:
상기 음극활물질로는 리튬 이온을 가역적으로 인터칼레이션 및 디인터칼레이션할 수 있는 물질로 결정질 탄소, 비정질 탄소, 탄소 복합체, 탄소 섬유, 리튬금속, 리튬 합금 또는 탄소-금속복합체 등을 사용할 수 있으며, 이에 제한되지 않고 이차전지에서 음극 활물질로서 사용가능한 임의의 물질을 사용할 수 있다.As the anode active material, as a material capable of reversibly intercalating and deintercalating lithium ions, crystalline carbon, amorphous carbon, carbon composite, carbon fiber, lithium metal, lithium alloy, or carbon-metal composite may be used. , but not limited thereto, and any material usable as an anode active material in a secondary battery may be used.
상기 바인더는 활물질의 페이스트화, 활물질의 상호 접착, 집전체와의 접착, 활물질 팽창 및 수축에 대한 완충 효과 등의 역할을 하는 물질로서, 통상의 당업자에 의해 사용될 수 있는 것이면 모두 가능하다. 예를 들면, 폴리비닐알코올, 카르복시메틸셀룰로오스, 히드록시프로필셀룰로오스, 디아세틸셀룰로오스, 폴리비닐클로라이드, 카르복실화된 폴리비닐클로라이드, 폴리비닐플루오라이드, 폴리에틸렌옥사이드, 폴리비닐피롤리돈, 폴리우레탄, 폴리테트라플루오로에틸렌, 리비닐리덴플루오라이드(PVdF), 폴리헥사플루오로프로필렌-폴리비닐리덴플루오라이드의 공중합체(PVdF/HFP)), 폴리(비닐아세테이트), 알킬레이티드폴리에틸렌옥사이드, 폴리비닐에테르, 폴리(메틸메타크릴레이트), 폴리(에틸아크릴레이트), 폴리아크릴로니트릴, 폴리비닐피리딘, 폴리에틸렌, 폴리프로필렌, 스티렌-부타디엔 고무, 아크릴레이티드 스티렌-부타디엔 고무, 아크릴로니트릴-부타디엔 고무, 에폭시수지, 나일론 등을 사용할 수 있으나, 이에 한정되는 것은 아니다.The binder is a material that acts as a paste of active materials, mutual adhesion of active materials, adhesion to a current collector, and a buffering effect on expansion and contraction of active materials, and any material that can be used by those skilled in the art is possible. For example, polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, polyethylene oxide, polyvinylpyrrolidone, polyurethane, Polytetrafluoroethylene, livinylidene fluoride (PVdF), polyhexafluoropropylene-polyvinylidene fluoride copolymer (PVdF/HFP)), poly(vinyl acetate), alkylated polyethylene oxide, polyvinyl Ether, poly(methyl methacrylate), poly(ethyl acrylate), polyacrylonitrile, polyvinylpyridine, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, acrylonitrile-butadiene rubber , epoxy resin, nylon, etc. may be used, but is not limited thereto.
상기 도전재는 전극에 도전성을 부여하기 위해 사용되는 것으로서, 구성되는 전지에 있어서, 화학변화를 야기하지 않고 전자 전도성 재료이면 어떠한 것도 사용가능하다. 도전재로는 흑연계 도전재, 카본 블랙계 도전재, 금속 또는 금속 화합물계 도전재로 이루어진 군에서 선택되는 적어도 하나를 사용할 수 있다. 상기 흑연계 도전재의 예로는 인조흑연, 천연 흑연 등이 있으며, 카본 블랙계 도전재의 예로는 아세틸렌 블랙, 케첸 블랙(ketjen black), 덴카 블랙(denkablack), 써멀 블랙(thermal black), 채널 블랙(channel black) 등이 있으며, 금속계 또는 금속 화합물계 도전제의 예로는 주석, 산화주석, 인산주석(SnPO4), 산화티타늄, 티탄산칼륨, LaSrCoO3, LaSrMnO3와 같은 페로브스카이트(perovskite) 물질이 있다. 그러나 상기 열거된 도전재에 한정되는 것은 아니다.The conductive material is used to impart conductivity to the electrode, and any material that does not cause chemical change and conducts electrons can be used in the battery. As the conductive material, at least one selected from the group consisting of a graphite-based conductive material, a carbon black-based conductive material, and a metal or metal compound-based conductive material may be used. Examples of the graphite-based conductive material include artificial graphite and natural graphite, and examples of the carbon black-based conductive material include acetylene black, ketjen black, denka black, thermal black, and channel black black), etc., and examples of the metal-based or metal compound-based conductive agent include perovskite materials such as tin, tin oxide, tin phosphate (SnPO4), titanium oxide, potassium titanate, LaSrCoO3, and LaSrMnO3. However, it is not limited to the above-listed conductive materials.
상기 증점제는 활물질 슬러리 점도조절의 역할을 할 수 있는 것이라면 특별히 한정되지 않으나, 예를 들면 카르복시 메틸 셀룰로오스, 하이드록시메틸 셀룰로오스, 하이드록시에틸 셀룰로오스, 하이드록시프로필 셀룰로오스 등이 사용될 수 있다.The thickener is not particularly limited as long as it can play a role of adjusting the viscosity of the active material slurry, but for example, carboxy methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and the like may be used.
전극활물질, 바인더, 도전재 등이 분산되는 용매로는 비수용매 또는 수계용매가 사용된다. 비수용매로는 N-메틸-2-피롤디돈(NMP), 디메틸포름아미드, 디메틸아세트아미드, N,N-디메틸아미노프로필아민, 에틸렌옥사이드, 테트라히드로퓨란 등을 들 수 있으나, 이에 한정되는 것은 아니다. A non-aqueous solvent or an aqueous solvent is used as a solvent in which the electrode active material, binder, and conductive material are dispersed. Non-aqueous solvents include, but are not limited to, N-methyl-2-pyrroldidone (NMP), dimethylformamide, dimethylacetamide, N,N-dimethylaminopropylamine, ethylene oxide, and tetrahydrofuran. .
본 발명의 이차전지는 양극 및 음극 사이에 단락을 방지하고 리튬 이온의 이동통로를 제공하는 세퍼레이터를 더 포함할 수 있으며, 이러한 세퍼레이터로는 폴리프로필렌, 폴리에틸렌, 폴리에틸렌/폴리프로필렌, 폴리에틸렌/폴리프로필렌/폴리에틸렌, 폴리프로필렌/폴리에틸렌/폴리프로필렌 등의 폴리올레핀계 고분자막 또는 이들의 다중막, 미세다공성 필름, 직포 및 부직포를 사용할 수 있다. 또한 다공성의 폴리올레핀 필름에 안정성이 우수한 수지가 코팅된 필름을 사용할 수도 있으나, 이에 한정되는 것은 아니다. The secondary battery of the present invention may further include a separator preventing a short circuit between the positive electrode and the negative electrode and providing a lithium ion movement path. Such separators include polypropylene, polyethylene, polyethylene/polypropylene, polyethylene/polypropylene/ Polyolefin-based polymer films such as polyethylene, polypropylene/polyethylene/polypropylene, or multilayers thereof, microporous films, woven fabrics, and non-woven fabrics may be used. In addition, a porous polyolefin film coated with a resin having excellent stability may be used, but is not limited thereto.
본 발명의 리튬 이차전지는 각형 외에 원통형, 파우치형 등 다른 형상으로 이루어질 수 있다.The lithium secondary battery of the present invention may be formed in other shapes such as a cylindrical shape and a pouch shape in addition to a prismatic shape.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시한다. 그러나 하기의 실시 예는 본 발명을 보다 쉽게 이해하기 위하여 제공되는 것일 뿐, 하기 실시예는 단지 예시적인 것이지 본 발명의 범위를 어떤 식으로든 제한하기 위한 것은 아니다.Hereinafter, a preferred embodiment is presented to aid understanding of the present invention. However, the following examples are provided to more easily understand the present invention, and the following examples are merely illustrative and are not intended to limit the scope of the present invention in any way.
이차전지용 전해액의 제조Manufacture of electrolyte solution for secondary battery
[실시예][Example]
에틸렌 카보네이트(EC), 에틸메틸카보네이트(EMC)의 혼합용매(EC/EMC=25/75의 혼합 부피비)에 LiPF6 1.0M이 되도록 용해한 후, 이 혼합용액에 1.0 중량%의 비닐렌카보네이트(VC), 1.0 중량%의 프로판설톤(PS) 에틸렌설페이트(ESA) 및 디플로로 디페닐아미노 포스핀(Difluoro(diphenylamino)phosphine) 0.5 중량%를 첨가하여 전해액을 제조하였다.After dissolving LiPF 6 in a mixed solvent of ethylene carbonate (EC) and ethyl methyl carbonate (EMC) (mixed volume ratio of EC/EMC = 25/75) to 1.0M, 1.0% by weight of vinylene carbonate (VC) was added to the mixed solution. ), 1.0 wt% of propanesultone (PS), ethylene sulfate (ESA), and 0.5 wt% of difluoro(diphenylamino)phosphine were added to prepare an electrolyte solution.
[비교예][Comparative example]
상기 실시예 1에서 디플로로 디페닐아미노 포스핀(Difluoro(diphenylamino)phosphine)를 제외하고, 상기 실시예 1과 동일하게 전해액을 제조하였다. An electrolyte solution was prepared in the same manner as in Example 1 except for difluoro(diphenylamino)phosphine in Example 1.
리튬 이차전지의 제조Manufacture of lithium secondary battery
Li[NixCo1-x-yMny]O2 (0<x<0.5, 0<y<0.5)를 포함하는 NCM계 양극활물질 96 중량%, 도전제로 카본블랙 2 중량%, 바인더로 폴리비닐리덴 플로라이드(PVdF) 2 량%를 용매인 N-methyl 2-pyrrolidinone(NMP) 용매에 첨가하여 양극활물질 슬러리를 제조하였다. 상기 양극 활물질 슬러리를 집전체인 알루미늄 박막에 도포 및 건조하여 양극을 제조한 다음 롤프레스로 압연하여 양극을 준비하였다. 96% by weight of NCM-based cathode active material including Li[Ni x Co 1-xy Mn y ]O 2 (0<x<0.5, 0<y<0.5), 2% by weight of carbon black as a conductive agent, and polyvinylidene as a binder A cathode active material slurry was prepared by adding 2% by weight of fluoride (PVdF) to N-methyl 2-pyrrolidinone (NMP) as a solvent. The positive electrode active material slurry was applied to an aluminum thin film as a current collector and dried to prepare a positive electrode, and then rolled using a roll press to prepare a positive electrode.
또한 음극활물질로는 흑연, 바인더로 CMC, SBR, 도전제로 카본블랙을 각각 97.1 중량%, 1 중량% ,1 중량% 및 0.9 중량%로 하여 용매 H2O에 첨가하여 음극활물질 슬러리를 제조하였다. 상기 음극 혼합물을 음극 집전체인 구리 박막에 도포 및 건조하여 음극을 준비하였다. In addition, 97.1% by weight, 1% by weight, 1% by weight, and 0.9% by weight of graphite as an anode active material, CMC and SBR as a binder, and carbon black as a conductive agent were added to solvent H 2 O to prepare a negative electrode active material slurry. An anode was prepared by applying the anode mixture to a copper thin film as an anode current collector and drying it.
또한 상기와 같이 제조된 양극 및 음극을 준비하고, 그사이에 분리막을 개제시켰으며, 기준용량을 720mAh를 기준으로 제작하였으며, 각 전지당 초기 용량의 편차는 ±20mAh의 차이를 보일 수 있다. 여기에 상기 실시예 및 비교예에서 제조한 전해액을 주입하여 알루미늄 파우치 형태(Al-Pouch type) 리튬이차전지를 제조하였다.In addition, the positive and negative electrodes prepared as described above were prepared, a separator was interposed therebetween, and the standard capacity was manufactured based on 720mAh, and the deviation of the initial capacity for each battery may show a difference of ±20mAh. Here, an aluminum pouch type (Al-Pouch type) lithium secondary battery was prepared by injecting the electrolyte solution prepared in the above Examples and Comparative Examples.
[실험예 1] 고온(45℃) 수명 특성 평가[Experimental Example 1] Evaluation of life characteristics at high temperature (45 ° C)
상기 실시예 및 비교예의 비수전해액을 사용하여 제조된 각 전지를 고온(45℃에서 1C-rate로 4.2V까지 충전 후 10분의 휴지 시간을 갖고, 1C-rate로 2.7V까지 방전 후, 다시 10분의 휴지시간을 가졌다. 이 과정을 300회 반복하여 전지 용량(mAh) 및 용량유지율(%)을 측정하였으며, 하기 표 1에 측정된 용량 및 용량유지율을 나타내었다.Each battery manufactured using the non-aqueous electrolytes of Examples and Comparative Examples was charged to 4.2V at a high temperature (45 ° C. at a 1C-rate, followed by a rest time of 10 minutes, discharged to 2.7V at a 1C-rate, and then charged to 4.2V at a 1C-rate. This process was repeated 300 times to measure battery capacity (mAh) and capacity retention rate (%), and the measured capacity and capacity retention rate are shown in Table 1 below.
상기 표 1의 고온 수명 특성 평가 결과, 본 발명의 실시예는 비교예 보다 고온에서 용량유지율이 더 우수한 것을 확인할 수 있다.As a result of evaluating the lifespan characteristics at high temperatures in Table 1, it can be seen that the examples of the present invention have better capacity retention rates at high temperatures than the comparative examples.
[실험예 2] 만충전 후 고온(60℃에서 4주 방치 후 두께 변화율, 용량유지율, 용량회복율 및 DCIR 변화율 평가[Experimental Example 2] Evaluation of thickness change rate, capacity retention rate, capacity recovery rate and DCIR change rate after leaving at high temperature (60 ° C. for 4 weeks after full charge)
상기 실시예 및 비교예의 비수전해액을 사용하여 제작한 파우치 타입 전지를 고온(60℃에서 충전 후 4주간 방치 후 전지두께, 용량유지율, 용량회복율, DCIR 변화율변화율을 측정하였으며 하기 표 2에 측정된 결과를 나타내었다.After charging the pouch-type batteries prepared using the non-aqueous electrolytes of Examples and Comparative Examples at a high temperature (60 ° C.) and leaving them for 4 weeks, the battery thickness, capacity retention rate, capacity recovery rate, and DCIR change rate were measured, and the results measured in Table 2 below showed
상기 표 2에서 보는 바와 같이, 실시예는 비교예 보다 고온(60℃에서 충전 후 4주간 방치 후 전지 두께, 용량유지율, 용량회복율 및 DCIR 변화율에서 우수한 전지 특성을 가지는 것을 확인할 수 있다. As shown in Table 2, it can be seen that the example has excellent battery characteristics in battery thickness, capacity retention rate, capacity recovery rate and DCIR change rate after being left for 4 weeks after charging at a high temperature (60 ° C.) than the comparative example.
실시예 및 비교예 비교 결과, 첨가제 1.0 중량%의 비닐렌카보네이트(VC), 1.0 중량%의 프로판설톤(PS) 에틸렌설페이트(ESA)을 포함한 비교예 경우에 비해 첨가제 1.0 중량%의 비닐렌카보네이트(VC), 1.0 중량%의 프로판설톤(PS) 에틸렌설페이트(ESA) 및 상기 화학식 1로 표시되는 아미노포스핀 화합물을 포함하는 경우, 고온(45℃수명특성과 고온(60℃저장시 전지의 두께 및 DCIR 변화율이 감소하였고, 용량유지율 및 용량회복율의 성능이 우수함을 확인할 수 있다. As a result of comparison of Examples and Comparative Examples, 1.0% by weight of vinylene carbonate (VC), 1.0% by weight of propanesultone (PS), and 1.0% by weight of vinylene carbonate ( VC), 1.0% by weight of propanesultone (PS) ethylene sulfate (ESA) and the aminophosphine compound represented by Formula 1, high temperature (45 ℃ life characteristics and high temperature (60 ℃ storage thickness and It can be seen that the DCIR change rate decreased, and the performance of capacity retention rate and capacity recovery rate was excellent.
Claims (9)
이차전지용 전해질:
[화학식 1]
[화학식 2]
[화학식 3]
상기 화학식 1 내지 3에서 Rn1, Rn2, Rn3, Rn4, Rn5 및 Rn6은 서로 동일하거나 상이하며, 각각 독립적으로,
수소; 중수소; 할로겐; 치환 또는 비치환된 탄소수 30 이하의 알킬기, 알케닐기, 알카이닐기, 아릴기, 헤테로아릴기, 아릴알킬기, 헤테로아릴알킬기, 탄소고리기, 탄소고리알킬기, 헤테로고리기, 헤테로고리알킬기; 치환 또는 비치환된 탄소수 30 이하의 알콕시기, 아릴옥시기, 헤테로아릴옥시기; 나이트릴기; 하이드록시기; 알킬티옥시기; 붕소기; 포스핀기, 포스핀옥사이드기; 니트로기; 티올; 포스포네이트; 실릴기; 알데하이드기; 에스테르기; 카르복실기나 그의 염; 술포닐기; 설파모일(sulfamoyl)기; 술폰산기나 그의 염; 및 인산이나 그의 염 중에서 선택되고,
Rp1 및 Rp2는 서로 동일하거나 상이하며, 각각 독립적으로,
수소; 중수소; 할로겐; 치환 또는 비치환된 탄소수 30 이하의 알킬기, 알케닐기, 알카이닐기, 아릴기, 헤테로아릴기, 아릴알킬기, 헤테로아릴알킬기, 탄소고리기, 탄소고리알킬기, 헤테로고리기, 헤테로고리알킬기; 치환 또는 비치환된 탄소수 30 이하의 알콕시기, 아릴옥시기, 헤테로아릴옥시기; 나이트릴기; 하이드록시기; 알킬티옥시기; 붕소기; 아미노기; 히드라진; 아미드기; 니트로기; 티올; 포스포네이트; 실릴기; 알데하이드기; 에스테르기; 카르복실기나 그의 염; 술포닐기; 설파모일(sulfamoyl)기; 술폰산기나 그의 염; 및 인산이나 그의 염 중에서 선택된다.
Including an aminophosphine compound represented by any one of the following formulas 1 to 3,
Electrolyte for secondary battery:
[Formula 1]
[Formula 2]
[Formula 3]
In Chemical Formulas 1 to 3, Rn 1 , Rn 2 , Rn 3 , Rn 4 , Rn 5 and Rn 6 are the same as or different from each other, and each independently,
hydrogen; heavy hydrogen; halogen; A substituted or unsubstituted alkyl group having 30 or less carbon atoms, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an arylalkyl group, a heteroarylalkyl group, a carbocyclic group, a carbocyclic alkyl group, a heterocyclic group, a heterocyclic alkyl group; A substituted or unsubstituted alkoxy group having 30 or less carbon atoms, an aryloxy group, or a heteroaryloxy group; nitrile group; hydroxy group; Alkyl thioxy group; boron group; A phosphine group, a phosphine oxide group; nitro group; thiol; phosphonates; silyl group; aldehyde group; ester group; carboxyl groups or salts thereof; sulfonyl group; Sulfamoyl group; sulfonic acid groups or salts thereof; And it is selected from phosphoric acid or a salt thereof,
Rp 1 and Rp 2 are the same as or different from each other, and each independently,
hydrogen; heavy hydrogen; halogen; A substituted or unsubstituted alkyl group having 30 or less carbon atoms, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an arylalkyl group, a heteroarylalkyl group, a carbocyclic group, a carbocyclic alkyl group, a heterocyclic group, a heterocyclic alkyl group; A substituted or unsubstituted alkoxy group having 30 or less carbon atoms, an aryloxy group, or a heteroaryloxy group; nitrile group; hydroxy group; Alkyl thioxy group; boron group; amino group; hydrazine; amide group; nitro group; thiol; phosphonates; silyl group; aldehyde group; ester group; carboxyl groups or salts thereof; sulfonyl group; Sulfamoyl group; sulfonic acid groups or salts thereof; and phosphoric acid or a salt thereof.
상기 화학식 1 내지 3에서 Rn1, Rn2, Rn3, Rn4, Rn5 및 Rn6은 서로 동일하거나 상이하며, 각각 독립적으로,
치환 또는 비치환된 탄소수 30 이하의 알킬기, 알케닐기, 알카이닐기, 아릴기, 헤테로아릴기, 아릴알킬기, 헤테로아릴알킬기, 탄소고리기, 탄소고리알킬기, 헤테로고리기 및 헤테로고리알킬기 중에서 선택되는,
이차전지용 전해질.
According to claim 1,
In Chemical Formulas 1 to 3, Rn 1 , Rn 2 , Rn 3 , Rn 4 , Rn 5 and Rn 6 are the same as or different from each other, and each independently,
A substituted or unsubstituted alkyl group having 30 or less carbon atoms, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an arylalkyl group, a heteroarylalkyl group, a carbocyclic group, a carbocyclic alkyl group, a heterocyclic group, and a heterocyclic alkyl group,
Electrolyte for secondary batteries.
상기 화학식 1 내지 3에서 Rn1, Rn2, Rn3, Rn4, Rn5 및 Rn6은 서로 동일하거나 상이하며, 각각 독립적으로,
치환 또는 비치환된 아릴기, 헤테로아릴기, 아릴알킬기 및 헤테로아릴알킬기 중에서 선택되는,
이차전지용 전해질.
According to claim 1,
In Chemical Formulas 1 to 3, Rn 1 , Rn 2 , Rn 3 , Rn 4 , Rn 5 and Rn 6 are the same as or different from each other, and each independently,
A substituted or unsubstituted aryl group, a heteroaryl group, selected from an arylalkyl group and a heteroarylalkyl group,
Electrolyte for secondary batteries.
상기 화학식 1 내지 3에서 Rp1 및 Rp2 중 어느 하나, 또는 Rp1 및 Rp2 은 할로겐인,
이차전지용 전해질.
According to claim 1,
Any one of Rp 1 and Rp 2 in Formulas 1 to 3, or Rp 1 and Rp 2 halogen,
Electrolyte for secondary batteries.
상기 아미노포스핀(aminophosphine) 화합물은 하기 화학식 1-1로 표시되는 화합물인,
이차전지용 전해질:
[화학식 1-1]
According to claim 1,
The aminophosphine compound is a compound represented by Formula 1-1 below,
Electrolyte for secondary battery:
[Formula 1-1]
상기 화학식 1로 표시되는 아미노포스핀(aminophosphine) 화합물은 이차전지용 전해질 전체 대비 0.05 내지 20중량%로 첨가되는,
이차전지용 전해질.
According to claim 1,
The aminophosphine compound represented by Formula 1 is added in an amount of 0.05 to 20% by weight relative to the total electrolyte for a secondary battery,
Electrolyte for secondary batteries.
첨가제로서 비닐렌카보네이트(vinylidene carbonate, VC), 프로판설톤(propanesultone, PS) 및 에틸렌설페이트(ethylene sulfate, ESA) 중에서 선택되는 어느 하나 이상의 화합물을 더 포함하는,
이차전지용 전해질.
According to claim 1,
Further comprising any one or more compounds selected from vinylene carbonate (VC), propanesultone (PS) and ethylene sulfate (ESA) as an additive,
Electrolyte for secondary batteries.
비수계 용매; 및
리튬염;을 더 포함하는,
이차전지용 전해질.
According to claim 1,
non-aqueous solvent; and
Lithium salt; further comprising,
Electrolyte for secondary batteries.
음극; 및
상기 제 1 항에 의한 이차전지용 전해질;을 포함하는,
이차전지.
anode;
cathode; and
Including; the electrolyte for a secondary battery according to claim 1;
secondary battery.
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