KR102495382B1 - Supercapacitor Electrolyte and Supercapacitor - Google Patents
Supercapacitor Electrolyte and Supercapacitor Download PDFInfo
- Publication number
- KR102495382B1 KR102495382B1 KR1020217016491A KR20217016491A KR102495382B1 KR 102495382 B1 KR102495382 B1 KR 102495382B1 KR 1020217016491 A KR1020217016491 A KR 1020217016491A KR 20217016491 A KR20217016491 A KR 20217016491A KR 102495382 B1 KR102495382 B1 KR 102495382B1
- Authority
- KR
- South Korea
- Prior art keywords
- supercapacitor
- electrolyte
- trifluoromethylsulfonyl
- ammonium
- imide
- Prior art date
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 44
- -1 alkyl nitrile Chemical group 0.000 claims abstract description 66
- 239000000654 additive Substances 0.000 claims abstract description 23
- 230000000996 additive effect Effects 0.000 claims abstract description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 13
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 13
- 239000005486 organic electrolyte Substances 0.000 claims abstract description 13
- 239000003880 polar aprotic solvent Substances 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 10
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 9
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 8
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims description 6
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 claims description 6
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 claims description 4
- RDKKQZIFDSEMNU-UHFFFAOYSA-N 2-ethylsulfonylpropane Chemical compound CCS(=O)(=O)C(C)C RDKKQZIFDSEMNU-UHFFFAOYSA-N 0.000 claims description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 3
- LELOWRISYMNNSU-UHFFFAOYSA-N Hydrocyanic acid Natural products N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 2
- DEXXMYGIGZXPML-UHFFFAOYSA-N 1-(2-methylpropylsulfonyl)butane Chemical compound CCCCS(=O)(=O)CC(C)C DEXXMYGIGZXPML-UHFFFAOYSA-N 0.000 claims description 2
- NJAKRNRJVHIIDT-UHFFFAOYSA-N 1-ethylsulfonyl-2-methylpropane Chemical compound CCS(=O)(=O)CC(C)C NJAKRNRJVHIIDT-UHFFFAOYSA-N 0.000 claims description 2
- SFPQDYSOPQHZAQ-UHFFFAOYSA-N 2-methoxypropanenitrile Chemical compound COC(C)C#N SFPQDYSOPQHZAQ-UHFFFAOYSA-N 0.000 claims description 2
- VTWYQAQIXXAXOR-UHFFFAOYSA-N 2-methylsulfonylpropane Chemical compound CC(C)S(C)(=O)=O VTWYQAQIXXAXOR-UHFFFAOYSA-N 0.000 claims description 2
- UMNZUEWMIREWRV-UHFFFAOYSA-N 2-propan-2-ylsulfonylbutane Chemical compound CCC(C)S(=O)(=O)C(C)C UMNZUEWMIREWRV-UHFFFAOYSA-N 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 claims 2
- WXZSOSHKVAZDMU-UHFFFAOYSA-N 2-methyl-1-propan-2-ylsulfonylpropane Chemical compound CC(C)CS(=O)(=O)C(C)C WXZSOSHKVAZDMU-UHFFFAOYSA-N 0.000 claims 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims 1
- 150000003457 sulfones Chemical class 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract description 4
- 125000003545 alkoxy group Chemical group 0.000 abstract description 3
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 3
- 239000003990 capacitor Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzenecarbonitrile Natural products N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JWZZKOKVBUJMES-UHFFFAOYSA-N (+-)-Isoprenaline Chemical compound CC(C)NCC(O)C1=CC=C(O)C(O)=C1 JWZZKOKVBUJMES-UHFFFAOYSA-N 0.000 description 1
- YBJCDTIWNDBNTM-UHFFFAOYSA-N 1-methylsulfonylethane Chemical compound CCS(C)(=O)=O YBJCDTIWNDBNTM-UHFFFAOYSA-N 0.000 description 1
- LMIYMQYNXIALQC-UHFFFAOYSA-N 2-methyl-1-propylsulfonylpropane Chemical compound CCCS(=O)(=O)CC(C)C LMIYMQYNXIALQC-UHFFFAOYSA-N 0.000 description 1
- MRRLMFWFTCYXSE-UHFFFAOYSA-N CC[N+](C)(C)CC.C(F)(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F Chemical compound CC[N+](C)(C)CC.C(F)(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F MRRLMFWFTCYXSE-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- FHKPLLOSJHHKNU-INIZCTEOSA-N [(3S)-3-[8-(1-ethyl-5-methylpyrazol-4-yl)-9-methylpurin-6-yl]oxypyrrolidin-1-yl]-(oxan-4-yl)methanone Chemical compound C(C)N1N=CC(=C1C)C=1N(C2=NC=NC(=C2N=1)O[C@@H]1CN(CC1)C(=O)C1CCOCC1)C FHKPLLOSJHHKNU-INIZCTEOSA-N 0.000 description 1
- JFDZBHWFFUWGJE-KWCOIAHCSA-N benzonitrile Chemical group N#[11C]C1=CC=CC=C1 JFDZBHWFFUWGJE-KWCOIAHCSA-N 0.000 description 1
- BBBSSFZSOUYKLW-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide 1,1-dimethylpyrrolidin-1-ium Chemical compound [N-](S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F.C[N+]1(CCCC1)C BBBSSFZSOUYKLW-UHFFFAOYSA-N 0.000 description 1
- UCFMXKZIBUSKCL-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide ethyl(trimethyl)azanium Chemical compound [N-](S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F.C[N+](CC)(C)C UCFMXKZIBUSKCL-UHFFFAOYSA-N 0.000 description 1
- MTGFSZLZUUOLNB-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide tetrapropylazanium Chemical compound CCC[N+](CCC)(CCC)CCC.C(F)(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F MTGFSZLZUUOLNB-UHFFFAOYSA-N 0.000 description 1
- YWQNGJZYCSFDSO-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide triethyl(methyl)azanium Chemical compound C(C)[N+](C)(CC)CC.[N-](S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F YWQNGJZYCSFDSO-UHFFFAOYSA-N 0.000 description 1
- CFAPFDTWIGBCQK-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;tetrabutylazanium Chemical compound FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F.CCCC[N+](CCCC)(CCCC)CCCC CFAPFDTWIGBCQK-UHFFFAOYSA-N 0.000 description 1
- JTCSZQBQVDPVMT-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;tetramethylazanium Chemical compound C[N+](C)(C)C.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F JTCSZQBQVDPVMT-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QWNFCAFICJVKHE-UHFFFAOYSA-N diethoxy-methyl-phenylsilane;dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1.CCO[Si](C)(OCC)C1=CC=CC=C1 QWNFCAFICJVKHE-UHFFFAOYSA-N 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- NNPPMTNAJDCUHE-UHFFFAOYSA-N trimethylmethane Natural products CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/64—Liquid electrolytes characterised by additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/60—Liquid electrolytes characterised by the solvent
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
-
- 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
- Y02E60/13—Energy storage using capacitors
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
종래 기술 중의 전해액이 고온 고전압 하에서 순환 수명이 짧고 기체 생성량이 큰 문제를 해결하기 위하여, 본 발명에서는 슈퍼커패시터 전해액을 제공하는 바, 극성 비양성자성 용제, 유기 전해질과 첨가제가 포함되고, 상기 첨가제는 구조식1로 표시되는 화합물에서 선택되며,
구조식1:
그 중에서는, R은 1-3개 탄소 원자를 함유하는 알킬 니트릴이거나 또는 구조식2 함유하며,
구조식2:
그 중에서, R1~R3은 수소, 1-3개 탄소 원자를 함유하는 알킬기, 1-3개 탄소 원자를 함유하는 알콕시기 또는 아렌으로부터 선택되며; R1~R3은 같을 수도 있고 다를 수도 있다. 아울러, 본 발명에서는 또한 상기 전해액을 사용하는 슈퍼커패시터를 공개한다. 본 발명에서 제공하는 슈퍼커패시터 전해액을 함유하는 슈퍼커패시터는 고온 고전압 하의 순환 수명이 길고 기체 생성량이 작다.In order to solve the problem of the prior art electrolyte having a short cycle life and a large amount of gas generated under high temperature and high voltage, the present invention provides a supercapacitor electrolyte, which includes a polar aprotic solvent, an organic electrolyte and an additive, the additive comprising: It is selected from compounds represented by structural formula 1,
Structural Formula 1:
Among them, R is an alkyl nitrile containing 1-3 carbon atoms or contains formula 2;
Structural Formula 2:
Among them, R 1 to R 3 are selected from hydrogen, an alkyl group containing 1-3 carbon atoms, an alkoxy group containing 1-3 carbon atoms or an arene; R 1 to R 3 may be the same or different. In addition, the present invention also discloses a supercapacitor using the electrolyte solution. The supercapacitor containing the supercapacitor electrolyte provided in the present invention has a long cycle life under high temperature and high voltage and a small gas generation amount.
Description
본 발명은 슈퍼커패시터 전해액 및 슈퍼커패시터에 관한 것이다.The present invention relates to a supercapacitor electrolyte and a supercapacitor.
슈퍼커패시터는 또한 골드 커패시터, 전기화학 커패시터라 부르고, 이온 흡착(이중 전기층 커패시터) 또는 표면 쾌속 산화 환원 반응(슈도 커패시터)를 사용하여 에너지를 저장한다. 슈퍼커패시터는 전지와 전통적인 정전기 커패시터 간의 신형 에너지 저장 장치이다. 슈퍼커패시터가 저장하는 전하는 전통적인 고체 전해 커패시터의 수백 수천배에 달하고, 몇 초 내에 완전 충방전이 가능하며, 전지보다 더욱 높은 전력 입력 또는 출력을 갖고, 또한 더욱 짧은 시간 내에 도달할 수 있다. 아울러, 슈퍼커패시터는 충방전 시간이 짧고 저장 수명이 길며 안정성이 높고 작업 온도 범위가 넓은(-40℃~70℃) 등 장점을 갖고있기 때문에, 소비류 전자 제품 분야, 신 에너지 발전 시스템 분야, 배포식 에너지 저장 분야, 스마트 배포식 전력망 시스템 분야, 신 에너지 자동차 등 교통 분야, 에너지 절약 엘리베이터 호이스트 등 부하 분야, 전자기 폭탄 등 군용 장비 분야와 운동 제어 분야 등에 널리 사용되고, 신 에너지 발전, 스마트 전력망, 신 에너지 자동차, 에너지 절약 건축, 산업 에너지 절약 오염물질 배출 감소 등 각 업계와 관련되며, 표준적인 풀 시리즈 저탄소 경제 핵심 제품에 속한다.Supercapacitors, also called gold capacitors, electrochemical capacitors, store energy using ion adsorption (double electric layer capacitors) or surface rapid redox reactions (pseudocapacitors). Supercapacitors are a new type of energy storage device between batteries and traditional electrostatic capacitors. The charge stored by supercapacitors is hundreds of thousands of times that of traditional solid electrolytic capacitors, can be fully charged and discharged in seconds, has higher power input or output than batteries, and can be reached in a shorter time. In addition, since supercapacitors have advantages such as short charge/discharge time, long shelf life, high stability, and wide working temperature range (-40℃~70℃), they are widely used in the field of consumer electronic products, new energy power generation systems, and distribution. It is widely used in the field of food energy storage, smart distributed power grid system, transportation field such as new energy vehicles, load field such as energy saving elevator hoist, field of military equipment such as electromagnetic bomb and motion control field, etc., new energy generation, smart power grid, new energy It is related to various industries such as automobile, energy-saving construction, industrial energy-saving and pollutant emission reduction, and belongs to a standard full series of low-carbon economy core products.
슈퍼커패시터는 신 에너지 분야의 가장 전망성이 있는 에너지 저장 장치 중의 하나로서, 현재 이미 미국, 일본, 한국과 러시아 등 국가의 재료, 전력, 물리, 화학 등 다학제 교차 분야 연구의 중점 중의 하나로 되었다. 주요한 연구 목표는 성능이 우수하고 원가가 낮은 전극 재료와 전기 전도율이 높고 화학 및 열 안정성이 좋으며 작업 전압이 높은(전기 화학 안정 윈도우가 넓은) 전해액 시스템 재료를 제조하고, 또한 이 기초 상에서 고 에너지 밀도, 고 전력 밀도와 사용 수명이 긴 여러 가지 전동 하이브리드 자동차 혼합 동력 시스템과 전자 장치에 사용할 수 있는 예비 전원 등 방면에 사용할 수 있는 슈퍼커패시터 에너지 저장 장치를 제조하는 것이다.Supercapacitors are one of the most promising energy storage devices in the new energy field, and they have already become one of the main points of cross-disciplinary research in materials, power, physics, and chemistry in countries such as the United States, Japan, Korea, and Russia. The main research goal is to produce electrode materials with excellent performance and low cost, electrolyte system materials with high electrical conductivity, chemical and thermal stability, and high working voltage (wide electrochemical stability window), and also high energy density on this basis. , to manufacture supercapacitor energy storage devices that can be used in areas such as high power density and long service life, which can be used in various electric hybrid vehicle mixed power systems and electronic devices, such as standby power supplies.
프로필렌카보네이트(propylene carbonate)와 아세토니트릴(acetonitrile)이 비교적 훌륭한 전기화학과 화학 안정성 및 유기 4차 암모늄계에 대한 비교적 훌륭한 용해성을 갖고 있기 때문에, 널리 슈퍼커패시터의 전해액 시스템에 사용된다. 현재 상용화된 슈퍼커패시터 전해액은 주요하게 (tetraethyl ammonium tetrafluoroborate)테트라에틸테트라플루오로붕산암모늄(Et4NBF4) 또는 메틸트리에틸테트라플루오로붕산암모늄(methyl triethyl ammonium tetrafluoroborate)(Et3MeNBF4)의 아세토니트릴(AN) 또는 프로필렌카보네이트(PC)의 용액을 사용한다. AN 시스템 슈퍼커패시터의 전압 상한은 단지 2.7V이고, 작업 온도 범위는 -40℃~65℃이며; PC 시스템 슈퍼커패시터의 전압 상한은 단지 2.5V이고, 작업 온도 범위는 -40℃~70℃이다. 슈퍼커패시터 시장의 발전에 따라, 안전과 시장 경쟁력을 증가시키기 위하여, 현재의 일반적인 전해액은 이미 고객들의 슈퍼캐패시터의 내고온, 내고압 성능에 대한 요구를 만족시킬 수 없다. 일반적인 전해액은 고전압, 고온 하에서 작동 시 전해액의 전기화학 분해를 일으켜, 커패시터 내 압력이 현저하게 증가하고, 전기화학 성능이 현저하게 낮아지며, 최종적으로 커패시터 효력 상실을 초래한다.Because propylene carbonate and acetonitrile have relatively good electrochemical and chemical stability and relatively good solubility in organic quaternary ammonium systems, they are widely used in the electrolyte system of supercapacitors. Current commercialized supercapacitor electrolytes are mainly composed of acetic acid (tetraethyl ammonium tetrafluoroborate) tetraethyltetrafluoroborate (Et 4 NBF 4 ) or methyl triethyl ammonium tetrafluoroborate (Et 3 MeNBF 4 ). A solution of nitrile (AN) or propylene carbonate (PC) is used. The upper voltage limit of the AN system supercapacitor is only 2.7V, and the working temperature range is -40°C to 65°C; The upper voltage limit of the PC system supercapacitor is only 2.5V, and the working temperature range is -40℃~70℃. With the development of the supercapacitor market, in order to increase safety and market competitiveness, current general electrolytes cannot meet the customers' demand for high-temperature and high-voltage performance of supercapacitors. Common electrolytes cause electrochemical decomposition of the electrolyte when operated under high voltage and high temperature, resulting in a significant increase in pressure in the capacitor, significantly lowered electrochemical performance, and finally loss of capacitor effectiveness.
본 발명에서 해결하고자 하는 기술적 과제로는 종래 기술 중의 전해액이 고온 고전압 하에서 순환 수명이 짧고 기체 생성량이 큰 문제를 해결하고, 슈퍼커패시터 전해액을 제공하는 것이다.The technical problem to be solved by the present invention is to solve the problem of the electrolyte in the prior art having a short cycle life and a large amount of gas generated under high temperature and high voltage, and to provide a supercapacitor electrolyte.
본 발명의 상기 기술문제를 해결하기 위한 기술방안은 하기와 같다.The technical solution to solve the above technical problem of the present invention is as follows.
슈퍼커패시터 전해액을 제공하는 바, 극성 비양성자성 용제, 유기 전해질과 첨가제가 포함되고, 상기 첨가제는 구조식1로 표시되는 화합물에서 선택되며, Provided is a supercapacitor electrolyte solution, which includes a polar aprotic solvent, an organic electrolyte and an additive, wherein the additive is selected from compounds represented by structural formula 1,
구조식1: Structural Formula 1:
그 중에서는, R은 1-3개 탄소 원자를 함유하는 알킬 니트릴(alkyl nitrile)이거나 또는 구조식2 함유하며,Among them, R is an alkyl nitrile containing 1-3 carbon atoms or contains formula 2;
구조식2: Structural Formula 2:
그 중에서, R1~R3은 수소, 1-3개 탄소 원자를 함유하는 알킬기(alkyl), 1-3개 탄소 원자를 함유하는 알콕시기(alkoxy) 또는 아렌(arene)으로부터 선택되며; R1~R3은 같을 수도 있고 다를 수도 있다.Among them, R 1 to R 3 are selected from hydrogen, an alkyl group containing 1-3 carbon atoms, an alkoxy group containing 1-3 carbon atoms, or an arene; R 1 to R 3 may be the same or different.
아울러, 본 발명에서는 또한 슈퍼커패시터를 제공하는 바, 양극, 음극, 양극과 음극 간에 위치하는 분리막과 상기 슈퍼커패시터 전해액이 포함된다.In addition, the present invention also provides a supercapacitor, which includes an anode, a cathode, a separator positioned between the anode and the cathode, and the supercapacitor electrolyte.
발명자는 대량의 실험을 통하여, 슈퍼커패시터에서 상기 첨가제가 고온과 고전압 하에서 커패시터 중의 물과 반응을 진행하여, 물로 인한 부반응이 발생하는 것을 감소시켜, 전해액의 안정성을 향상시키고, 커패시터의 자체 방전 및 기체 생성을 감소시키고, 특히 슈퍼커패시터의 작업 수명을 크게 연장하고, 커패시터가 양호한 순환 수명과 고저온 성능을 갖게 하는 것을 발견하였다.Through a large amount of experiments, the inventors have found that the additive reacts with water in the capacitor under high temperature and high voltage in the supercapacitor, thereby reducing side reactions caused by water, improving the stability of the electrolyte, and improving the self-discharge and gas of the capacitor. It has been found that reducing generation, and in particular greatly prolonging the working life of supercapacitors, makes the capacitors have good cycle life and high-low temperature performance.
본 발명에서 해결하고자 하는 기술적 과제, 기술방안 및 장점을 더욱 명료하게 하기 위하여, 이해 실시예를 참조하여 본 발명에 대하여 진일보로 상세히 설명하도록 한다. 여기에 기재된 구체적인 실시예는 단지 본 발명의 해석에 불과하고 본 발명을 제한하는 것이 아님을 이해하여야 할 것이다.In order to further clarify the technical problems, technical solutions and advantages to be solved by the present invention, the present invention will be further described in detail with reference to the understanding examples. It should be understood that the specific embodiments described herein are merely interpretations of the present invention and are not intended to limit the present invention.
본 발명에서 제공하는 슈퍼커패시터 전해액에는 극성 비양성자성 용제, 유기 전해질과 첨가제가 포함되고, 상기 첨가제는 구조식1로 표시되는 화합물에서 선택되며, The supercapacitor electrolyte provided in the present invention includes a polar aprotic solvent, an organic electrolyte and an additive, wherein the additive is selected from compounds represented by structural formula 1,
구조식1: Structural Formula 1:
그 중에서는, R은 1-3개 탄소 원자를 함유하는 알킬 니트릴이거나 또는 구조식2 함유하며,Among them, R is an alkyl nitrile containing 1-3 carbon atoms or contains formula 2;
구조식2: Structural Formula 2:
그 중에서, R1~R3은 수소, 1-3개 탄소 원자를 함유하는 알킬기, 1-3개 탄소 원자를 함유하는 알콕시기 또는 아렌으로부터 선택되며; R1~R3은 같을 수도 있고 다를 수도 있다.Among them, R 1 to R 3 are selected from hydrogen, an alkyl group containing 1-3 carbon atoms, an alkoxy group containing 1-3 carbon atoms or an arene; R 1 to R 3 may be the same or different.
상술한 바와 같이, 구조식1에서, R은 1-3개 탄소 원자를 함유한 알킬 니트릴, 예를 들면 카르보니트릴(carbonitrile), 아세토니트릴(acetonitrile), 프로피오니트릴(propionitrile)일 수 있고, 바람직하게는 카르보니트릴이다. 상기 R에서, 만일 알킬 니트릴의 탄소 원자수가 3개를 초과하면, 슈퍼커패시터의 용량이 현저하게 낮아진다.As described above, in Structural Formula 1, R may be an alkyl nitrile containing 1 to 3 carbon atoms, for example, carbonitrile, acetonitrile, or propionitrile, preferably is carbonitrile. In the above R, if the number of carbon atoms of the alkyl nitrile exceeds 3, the capacity of the supercapacitor is significantly lowered.
아울러, 상기 구조식1 중의 R은 구조식2에 표시된 규소 함유 치환기일 수 있다. 구체적으로 말하면, 구조식2에서, R1, R2, R3은 각각 독립적으로 수소, 메틸기(methyl), 메톡시기(methoxy), 에톡시기(ethoxy), 페닐기(phenyl)로부터 선택된다.In addition, R in Structural Formula 1 may be a silicon-containing substituent shown in Structural Formula 2. Specifically, in Structural Formula 2, R 1 , R 2 , and R 3 are each independently selected from hydrogen, a methyl group, a methoxy group, an ethoxy group, and a phenyl group.
본 발명에서, 바람직한 상황에서, 상기 첨가제는 벤조니트릴(benzonitrile), 페닐실란(phenyl silane), 페닐트리메톡시실란(phenyl trimethoxy silane), 페닐트리에톡시실란(phenyl triethoxy silane), 메틸페닐디에톡시실란(methyl phenyl dimethoxy silane), 디페닐디메톡시실란(diphenyl dimethoxy silane) 중의 적어도 한 가지로부터 선택된다.In the present invention, in a preferred situation, the additive is benzonitrile, phenyl silane, phenyl trimethoxy silane, phenyl triethoxy silane, methylphenyl diethoxy silane (methyl phenyl dimethoxy silane) and diphenyl dimethoxy silane.
본 발명에 의하면, 상기 첨가제의 슈퍼커패시터 전해액에서의 함량은 비교적 큰 범위 내에서 변동할 수 있는 바, 바람직한 상황 하에서, 상기 슈퍼커패시터 전해액에서, 슈퍼커패시터 전해액의 총 중량을 기준으로, 상기 첨가제의 함량이 0.1%-5%이고, 더욱 바람직하게는 0.5%-5%이다.According to the present invention, the content of the additive in the supercapacitor electrolyte may vary within a relatively large range. Under preferred circumstances, in the supercapacitor electrolyte, based on the total weight of the supercapacitor electrolyte, the content of the additive is 0.1% - 5%, more preferably 0.5% - 5%.
통상적으로, 슈퍼커패시터의 전해액에는 불가피하게 소량의 수분이 존재하는 바, 전해액이 갖고 가는 수분, 슈퍼커패시터 기타 부품(예를 들면 양/음극, 분리막)이 갖고 가는 수분 및 커패시터를 제작하는 과정에서 갖고 가는 공기 중의 수분이 포함된다. 발명자는 상기 수분이 발생시키는 부반응이 슈퍼커패시터의 성능에 현저한 영향을 미치는 바, 특히 고온 고전압 하에서 영향이 더욱 선명한 것을 발견하였다. 전해액에 상기 첨가제 함유될 때, 고온 고전압 하에서, 효과적으로 물로 인하여 초래되는 부반응의 발생을 피하고, 이로써 슈퍼커패시터의 고온 고전압 하에서의 수명을 연장시키며, 기체의 생성을 낮춘다.Usually, a small amount of moisture is unavoidably present in the electrolyte of a supercapacitor, and the moisture carried by the electrolyte, the moisture carried by other parts of the supercapacitor (e.g., anode/cathode, separator), and the process of manufacturing the capacitor Moisture in the air is included. The inventors have found that the side reaction generated by the moisture has a significant effect on the performance of the supercapacitor, and the effect is more pronounced especially under high temperature and high voltage. When the above additives are contained in the electrolyte, under high temperature and high voltage, the occurrence of side reactions caused by water is effectively avoided, thereby prolonging the lifetime of the supercapacitor under high temperature and high voltage, and reducing the generation of gas.
본 발명에서, 유기 전해질은 일반적인 여러 가지 물질을 사용할 수 있는 바, 예를 들면, 상기 유기 전해질이 테트라플루오로붕산테트라에틸암모늄(tetraethyl ammonium tetrafluoroborate), 테트라메틸테트라플루오로붕산암모늄(tetramethyl ammonium tetrafluoroborate), 테트라프로필테트라플루오로붕산암모늄(tetrapropyl ammonium tetrafluoroborate), 테트라부틸테트라플루오로붕산암모늄(tetrabutyl ammonium tetrafluoroborate), 메틸트리에틸테트라플루오로붕산암모늄(methyl triethoxy ammonium tetrafluoroborate), 디에틸디메틸테트라플루오로붕산암모늄(dimethyl diethyl ammonium tetrafluoroborate), 트리메틸에틸테트라플루오로붕산암모늄(trimethyl ethyl ammonium tetrafluoroborate), N,N-디메틸피롤리딘테트라플루오로붕산아민(N. N-dimethylpyrrolidine tetrafluoroborate amine), N-에틸-N-메틸피롤리딘테트라플루오로붕산아민(N-ethyl-N-methylpyrrolidinium tetrafluoroborate), N-프로필-N-메틸피롤리딘테트라플루오로붕산아민(N-propyl-N-methylpyrrolidinium tetrafluoroborate), N-N-테트라메틸렌피롤리딘테트라플루오로붕산아민(N,N-tetramethylenepyrrolidinium tetrafluoroborate), 스피로-(1,1’)-디피롤리딘테트라플루오로붕산아민(spiro-(1,1')-bipyrrolidinium tetrafluoroborate), N,N-디메틸피페리딘테트라플루오로붕산아민(N,N-dimethylpiperidinium tetrafluoroborate), N,N-디에틸피페리딘테트라플루오로붕산아민(N,N-diethylpiperidinium tetrafluoroborate), N,N-디메틸모르폴린테트라플루오로붕산아민(N,N-dimethylmorphorinium tetrafluoroborate), 1-에틸-3-메틸이미다졸테트라플루오로붕산아민(1-ethyl-3-methylimidazolium tetrafluoroborate), 비스(트리플루오로메틸술포닐)이미드(bis(trifluoromethylsulfonyl)imides)계 예를 들면 테트라플루오로붕산테트라에틸암모늄(tetrafluoroboric acid tetraethyl ammonium), 테트라메틸비스(트리플루오로메틸술포닐)이미드염(tetramethyl ammonium bis(trifluoromethylsulfonyl)imide), 테트라프로필비스(트리플루오로메틸술포닐)이미드염(tetrapropyl ammonium bis(trifluoromethylsulfonyl)imide), 테트라부틸비스(트리플루오로메틸술포닐)이미드염(tetrabutyl ammonium bis(trifluoromethylsulfonyl)imide), 메틸트리에틸비스(트리플루오로메틸술포닐)이미드염(methyl triethyl ammonium bis(trifluoromethylsulfonyl)imide), 디에틸디메틸비스(트리플루오로메틸술포닐)이미드염(diethyl dimethyl ammonium bis(trifluoromethylsulfonyl)imide), 트리메틸에틸비스(트리플루오로메틸술포닐)이미드염(trimethyl ethyl ammonium bis(trifluoromethylsulfonyl)imide), N,N-디메틸피롤리딘비스(트리플루오로메틸술포닐)이미드염(N,N-dimethylpyrrolidinium bis(trifluoromethylsulfonyl)imide), 헥사플루오로인산암모늄(ammonium hexafluorophosphates)계 예를 들면 테트라에틸헥사플루오로인산암모늄(tetraethyl ammonium hexafluorophosphate), 테트라메틸헥사플루오로인산암모늄(tetramethyl ammonium hexafluorophosphate), 테트라프로필헥사플루오로인산암모늄(tetrapropyl ammonium hexafluorophosphate), 테트라부틸헥사플루오로인산암모늄(tetrabutyl ammonium hexafluorophosphate), 메틸트리에틸헥사플루오로인산암모늄(methyl triethyl ammonium hexafluorophosphate), 트리에틸메틸헥사플루오로인산암모늄(triethyl methyl ammonium hexafluorophosphate) 또는 디에틸디메틸헥사플루오로인산암모늄(dimethyl diethyl ammonium hexafluorophosphate) 중의 한 가지 또는 여러 가지로부터 선택된다.In the present invention, the organic electrolyte can use a variety of general materials, for example, the organic electrolyte is tetraethyl ammonium tetrafluoroborate, tetramethyl ammonium tetrafluoroborate , tetrapropyl ammonium tetrafluoroborate, tetrabutyl ammonium tetrafluoroborate, methyl triethoxy ammonium tetrafluoroborate, diethyldimethyltetrafluoroborate ammonium (dimethyl diethyl ammonium tetrafluoroborate), trimethyl ethyl ammonium tetrafluoroborate, N,N-dimethylpyrrolidine tetrafluoroborate amine, N-ethyl-N- N-ethyl-N-methylpyrrolidinium tetrafluoroborate, N-propyl-N-methylpyrrolidinium tetrafluoroborate, N-N-tetramethylene pyrrolidine tetrafluoroborate amine (N, N-tetramethylenepyrrolidinium tetrafluoroborate), spiro-(1,1')-dipyrrolidine tetrafluoroborate amine (spiro-(1,1')-bipyrrolidinium tetrafluoroborate), N, N-dimethylpiperidine tetrafluoroborate amine (N,N-dimethylpiperidinium tetrafluoroborate), N,N-diethylpiperidinium tetrafluoroborate (N,N-diethylpiperidinium tetrafluoroborate) ate), N,N-dimethylmorphorinium tetrafluoroborate, 1-ethyl-3-methylimidazolium tetrafluoroborate, Bis (trifluoromethylsulfonyl) imide (bis (trifluoromethylsulfonyl) imides) system, for example, tetrafluoroboric acid tetraethyl ammonium, tetramethylbis (trifluoromethylsulfonyl) imide salt ( tetramethyl ammonium bis(trifluoromethylsulfonyl)imide), tetrapropyl bis(trifluoromethylsulfonyl)imide salt (tetrapropyl ammonium bis(trifluoromethylsulfonyl)imide), tetrabutyl bis(trifluoromethylsulfonyl)imide salt (tetrabutyl ammonium bis( trifluoromethylsulfonyl)imide), methyltriethyl bis(trifluoromethylsulfonyl)imide salt (methyl triethyl ammonium bis(trifluoromethylsulfonyl)imide), diethyldimethyl ammonium bis( trifluoromethylsulfonyl)imide), trimethyl ethyl ammonium bis(trifluoromethylsulfonyl)imide), N,N-dimethylpyrrolidine bis(trifluoromethylsulfonyl)imide salt (N ,N-dimethylpyrrolidinium bis(trifluoromethylsulfonyl)imide), ammonium hexafluorophosphates such as tetraethyl ammonium hexafluorophosphate, tetramethylhexafluorophosphate (te tramethyl ammonium hexafluorophosphate, tetrapropyl ammonium hexafluorophosphate, tetrabutyl ammonium hexafluorophosphate, methyl triethyl ammonium hexafluorophosphate, triethylmethyl hexafluorophosphate It is selected from one or more of triethyl methyl ammonium hexafluorophosphate or dimethyl diethyl ammonium hexafluorophosphate.
바람직한 상황 하에서, 상기 유기 전해질이 N,N-디메틸피롤리딘테트라플루오로붕산아민, 테트라플루오로붕산테트라에틸암모늄, 메틸트리에틸테트라플루오로붕산암모늄, 스피로-(1,1’)-디피롤리딘테트라플루오로붕산아민, N,N-디메틸피롤리딘비스(트리플루오로메틸술포닐)이미드염;N,N-디메틸피롤리딘비스(플루오로술포닐)이미드염, N,N-디메틸피롤리딘헥사플루오로인산염(N,N-dimethylpyrrolidinium hexafluorophosphate)으로부터 선택된다.Under preferred circumstances, the organic electrolyte is N,N-dimethylpyrrolidinetetrafluoroborate amine, tetrafluoroborate tetraethylammonium, methyltriethyltetrafluoroborate ammonium, spiro-(1,1′)-dipyrroly Dinetetrafluoroboric acid amine, N,N-dimethylpyrrolidinebis(trifluoromethylsulfonyl)imide salt; N,N-dimethylpyrrolidinebis(fluorosulfonyl)imide salt, N,N-dimethyl It is selected from pyrrolidine hexafluorophosphate (N,N-dimethylpyrrolidinium hexafluorophosphate).
상기 유기 전해질의 함량은 비교적 큰 범위 내에서 변동할 수 있는 바, 바람직한 상황 하에서, 상기 슈퍼커패시터 전해액에서, 유기 전해질의 농도가 0.5-3.0mol/L이고, 더욱 바람직하게는 0.8-2.0mol/L이다.The content of the organic electrolyte can vary within a relatively large range. Under preferred circumstances, in the supercapacitor electrolyte, the concentration of the organic electrolyte is 0.5-3.0 mol/L, more preferably 0.8-2.0 mol/L. am.
본 발명에 의하면, 상기 극성 비양성자성 용제는 당업계의 일반적인 물질을 사용할 수 있는 바, 예를 들면, 상기 극성 비양성자성 용제가 아세토니트릴, 프로피오니트릴, 메톡시프로피오니트릴(methoxy propionitrile), γ-부티롤락톤(γ-butyrolactone), γ-발레로락톤(γ-valerolactone), 에틸렌카보네이트(ethylene carbonate), 프로필렌카보네이트(propylene carbonate), N,N-디메틸메탄아미드(N,N-dimethyl methane amide), 디메틸에탄아미드(dimethyl ethane amide), 1-메틸-2-피롤리디논(1-methyl-2-pyrrolidinone), 디메톡시에탄(dimethoxy ethane), 2-메톡시에테르(2-methoxy ether), 테트라히드로푸란(tetrahydrofuran), 디옥솔란(dioxolane), 디메틸카보네이트(dimethyl carbonate), 디에틸카보네이트(diethyl carbonate), 에틸메틸카보네이트(ethyl methyl carbonate), 술포란(sulfolane), 디메틸술폭시드(dimethyl sulfoxide), 디메틸술폰(dimethyl sulfone), 에틸메틸술폰(ethyl methyl sulfone), 메틸이소프로필술폰(methyl isopropyl sulfone), 에틸이소프로필술폰(ethyl isopropyl sulfone), 에틸이소부틸술폰(ethyl isobutyl sulfone), 이소프로필이소부틸술폰(isopropyl isobutyl sulfone), 이소프로필-s-부틸술폰(isopropyl-s-butyl sulfone), 부틸이소부틸술폰(butyl isobutyl sulfone) 중의 한 가지 또는 여러 가지로부터 선택된다. 바람직하게는, 아세토니트릴, 프로필렌카보네이트, 술포란, 디메틸술폰, 에틸이소프로필술폰 중의 한 가지 또는 두 가지이다. 특히 아세토니트릴은 첨가제 중의 R이 알킬 니트릴일 때, 효과가 더욱 현저하다.According to the present invention, the polar aprotic solvent can use a common material in the art, for example, the polar aprotic solvent is acetonitrile, propionitrile, methoxy propionitrile , γ-butyrolactone, γ-valerolactone, ethylene carbonate, propylene carbonate, N,N-dimethylmethanamide (N,N-dimethyl methane amide, dimethyl ethane amide, 1-methyl-2-pyrrolidinone, dimethoxy ethane, 2-methoxy ether ), tetrahydrofuran, dioxolane, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, sulfolane, dimethyl sulfoxide sulfoxide), dimethyl sulfone, ethyl methyl sulfone, methyl isopropyl sulfone, ethyl isopropyl sulfone, ethyl isobutyl sulfone, iso It is selected from one or more of propyl isobutyl sulfone, isopropyl-s-butyl sulfone, and butyl isobutyl sulfone. Preferably, it is one or two of acetonitrile, propylene carbonate, sulfolane, dimethyl sulfone, and ethyl isopropyl sulfone. In particular, the effect of acetonitrile is more remarkable when R in the additive is an alkyl nitrile.
본 발명에서는 또한 슈퍼커패시터를 공개하는 바, 양극, 음극, 양극과 음극 간에 위치하는 분리막과 상기 슈퍼커패시터 전해액이 포함된다.The present invention also discloses a supercapacitor, which includes an anode, a cathode, a separator positioned between the anode and the cathode, and the supercapacitor electrolyte.
상기 슈퍼커패시터의 양극, 음극과 분리막은 일반적인 것을 사용할 수 있는 바, 예를 들면 상기 양극과 음극은 탄소 재료 전극이고, 상기 분리막은 섬유포 분리막이다.As the anode, cathode, and separator of the supercapacitor, general ones can be used. For example, the anode and cathode are carbon material electrodes, and the separator is a fiber cloth separator.
아래 실시예를 통하여 본 발명에 대하여 진일보의 설명을 진행하도록 한다.The following examples will be used to further explain the present invention.
글로브 박스에 슈퍼커패시터 모델을 구성하는 바, 셀에는 알루미늄 포일로 제작된 두 개의 집전극, 활성탄으로 제작된 두 작업 전극과 그 사이에 삽입된 섬유포 분리막이 포함되나, 이러한 구조에 제한되는 것이 아니다. 셀을 하기 비교예와 실시예 중의 전해액에 침지시키고, 알루미늄 케이스와 미셀로 실을 구성하며, 고저온 성능을 테스트하며; 알루미늄 플라스틱 필름 진공 실링으로 기체 생성량을 테스트한다.A supercapacitor model is configured in a glove box, and the cell includes two collecting electrodes made of aluminum foil, two working electrodes made of activated carbon, and a fiber cloth separator inserted therebetween, but is not limited to this structure. The cell was immersed in the electrolyte solution in the following Comparative Examples and Examples, the cell was constructed with an aluminum case and micelles, and the high-low temperature performance was tested; Gas production is tested with aluminum plastic film vacuum sealing.
슈퍼커패시터 테스트 과정은 하기와 같다.The supercapacitor test process is as follows.
(1) 프리사이클링(10회): 25℃, 충전 마감 전압 U, 정전류 10mA/F로 충전을 진행하며; 그 후 하한 전압 U/2, 정전류 10mA/F로 방전을 진행하며;(1) pre-cycling (10 times): charging at 25° C., charging end voltage U, constant current 10 mA/F; After that, discharge is performed at a lower limit voltage U/2 and a constant current of 10 mA/F;
(2) 65℃~70℃ 고온 챔버에서, 정전류 10mA/F로 상한 전압 U까지 충전하고, 정전압 (U)로 일정 시간 유지하며; 슈퍼커패시터를 취출하고 25℃까지 냉각시키고, 다시 충반전 테스트를 진행하는 바, 테스트 조건은 프리사이클링과 같고, 또한 슈퍼커패시터의 용량 유지율, ESR 증가율을 계산하며;(2) in a high-temperature chamber at 65° C. to 70° C., charging with a constant current of 10 mA/F to the upper limit voltage U, and maintaining the constant voltage (U) for a certain period of time; The supercapacitor is taken out and cooled to 25° C., and the charge/discharge test is performed again, the test conditions are the same as those of precycling, and the capacity retention rate and ESR increase rate of the supercapacitor are calculated;
(3) 용량 유지율≤80% 및/또는 ESR 증가율≥100%일 때를 슈퍼커패시터 수명의 판단 표준으로 한다.(3) The case where the capacity retention rate ≤ 80% and/or the ESR increase rate ≥ 100% is the criterion for determining the lifetime of the supercapacitor.
실시예1Example 1
N,N-디메틸피롤리딘테트라플루오로붕산아민 을 용질로 하고, 아세토니트릴(AN)를 용제로 하여, 2.0mol/L 전해액을 제조하고, 다시 전해액 총 질량 대비 0.2%의 페닐실란을 첨가하며, 전해액 조성은 표1에 표시되어 있고, 또한 전해액의 25℃ 시의 전도율을 측정하여, 결과를 표1에 표시한다. 해당 전해액으로 슈퍼커패시터를 제작하고 또한 이에 대하여 전기화학 성능 테스트를 진행하며, 수명, 용량과 ESR 테스트 결과를 각각 표1에 표시한다.Using N,N-dimethylpyrrolidinetetrafluoroboric acid amine as a solute and acetonitrile (AN) as a solvent, a 2.0 mol/L electrolyte was prepared, and 0.2% of the total mass of the electrolyte was added with phenylsilane. , The composition of the electrolyte is shown in Table 1, and the conductivity of the electrolyte at 25 ° C was measured, and the results are shown in Table 1. Supercapacitors were fabricated with the corresponding electrolyte, and electrochemical performance tests were conducted on them, and the lifespan, capacity, and ESR test results are shown in Table 1, respectively.
실시예2-13Examples 2-13
전해액의 용질, 용제, 첨가제 및 농도가 실시예1과 다른 외, 기타는 모두 같다. 각 실시예의 전해액의 용질, 용제, 첨가제 및 농도 조성이 표1과 표2에 표시되고, 또한 전해액의 25℃ 시의 전도율을 측정하여, 표1과 표2에 표시한다. 이러한 전해액으로 슈퍼커패시터를 제작하고 또한 이에 대하여 전기화학 성능 테스트를 진행하며, 수명, 용량과 ESR 테스트 결과를 각각 표1과 표2에 표시한다.Except for the solute, solvent, additive and concentration of the electrolyte solution different from Example 1, everything else is the same. The solutes, solvents, additives, and concentration compositions of the electrolytes of each Example are shown in Tables 1 and 2, and the conductivity of the electrolytes at 25°C is measured and shown in Tables 1 and 2. Supercapacitors were fabricated with these electrolytes, and electrochemical performance tests were conducted on them, and the lifespan, capacity, and ESR test results are shown in Table 1 and Table 2, respectively.
비교예1Comparative Example 1
테트라에틸테트라플루오로붕산암모늄을 용질로 하고, AN를 용제로 하여, 1.0mol/L 전해액을 제조하고, 전해액 조성은 표1에 표시되어 있고, 또한 전해액의 25℃ 시의 전도율을 측정하여, 결과를 각각 표1에 표시한다. 해당 전해액으로 슈퍼커패시터를 제작하고 또한 이에 대하여 전기화학 성능 테스트를 진행하며, 수명, 용량과 ESR 테스트 결과를 각각 표1에 표시한다.Using ammonium tetraethyltetrafluoroborate as a solute and AN as a solvent, a 1.0 mol/L electrolyte solution was prepared, the composition of the electrolyte solution is shown in Table 1, and the conductivity of the electrolyte solution at 25° C. was measured, and the results are shown in Table 1, respectively. Supercapacitors were fabricated with the corresponding electrolyte, and electrochemical performance tests were conducted on them, and the lifespan, capacity, and ESR test results are shown in Table 1, respectively.
비교예2-8Comparative Example 2-8
전해액의 용질, 용제, 첨가제 및 농도가 비계예1과 다른 외, 기타는 모두 같다. 각 비교예의 전해액의 용질, 용제, 첨가제 및 농도 조성이 표1과 표2에 표시되고, 또한 전해액의 25℃ 시의 전도율을 측정하여, 표1과 표2에 표시한다. 이러한 전해액으로 슈퍼커패시터를 제작하고 또한 이에 대하여 전기화학 성능 테스트를 진행하며, 수명, 용량과 ESR 테스트 결과를 각각 표1과 표2에 표시한다.Except for the solute, solvent, additive and concentration of the electrolyte solution being different from Scaffolding Example 1, everything else is the same. The solutes, solvents, additives, and concentration compositions of the electrolytes of each comparative example are shown in Tables 1 and 2, and the conductivity of the electrolytes at 25°C was measured and displayed in Tables 1 and 2. Supercapacitors were fabricated with these electrolytes, and electrochemical performance tests were conducted on them, and the lifespan, capacity, and ESR test results are shown in Table 1 and Table 2, respectively.
표1Table 1
표1의 테스트 결과로부터 알 수 있는 바와 같이, 서로 다른 용질과 아세토니트릴 용제 시스템 하에서, 본 발명에서 제공하는 첨가제를 첨가한 후, 슈퍼커패시터의 고온과 고전압 하에서의 수명이 현저하게 증가하고, 기체 생성량이 현저하게 낮아진다. 또한 첨가제 함량이 증가함에 따라, 수명이 증가되고 기체 생성을 억제하는 효과가 더욱 현저하다.As can be seen from the test results in Table 1, under different solutes and acetonitrile solvent systems, after adding the additives provided in the present invention, the lifetime of the supercapacitor under high temperature and high voltage was significantly increased, and the amount of gas produced was significantly increased. significantly lowered In addition, as the additive content increases, the lifespan is increased and the effect of suppressing gas generation is more remarkable.
표2Table 2
표2의 테스트 결과로부터 알 수 있는 바와 같이, 서로 다른 용질과 프로필렌카보네이트 용제 시스템 하에서, 본 발명에서 제공하는 첨가제를 첨가한 후, 슈퍼커패시터의 고온과 고전압 하에서의 수명이 현저하게 증가하고, 기체 생성량이 현저하게 낮아진다. 또한 첨가제 함량이 증가함에 따라, 수명이 증가되고 기체 생성을 억제하는 효과가 더욱 현저하다.이상에서는 본 발명을 특정의 실시예에 대해서 도시하고 설명하였지만, 본 발명은 상술한 실시예에만 한정되는 것은 아니며, 본 발명이 속하는 기술분야에서 속하는 기술분야에서 통상의 지식을 가진 자라면 이하의 청구범위에 기재된 본 발명의 기술적 사상의 요지를 벗어나지 않는 범위에서 얼마든지 다양하게 변경하여 실시할 수 있을 것이다.As can be seen from the test results in Table 2, under different solutes and propylene carbonate solvent systems, after adding the additives provided in the present invention, the lifespan of the supercapacitor under high temperature and high voltage was significantly increased, and the amount of gas produced significantly lowered In addition, as the content of additives increases, the lifespan increases and the effect of suppressing gas generation becomes more remarkable. Although the present invention has been shown and described with respect to specific embodiments above, the present invention is not limited to the above-described embodiments. No, those skilled in the art in the technical field to which the present invention belongs will be able to make various changes and practice without departing from the gist of the technical idea of the present invention described in the claims below.
Claims (11)
극성 비양성자성 용제, 유기 전해질과 첨가제가 포함되고, 상기 첨가제는 구조식 1로 표시되는 화합물에서 선택되며,
구조식 1:
여기에서, R은 1-3개 탄소 원자를 함유하는 알킬 니트릴인 것을 특징으로 하는 슈퍼커패시터 전해액.In the supercapacitor electrolyte,
A polar aprotic solvent, an organic electrolyte and an additive are included, wherein the additive is selected from compounds represented by Structural Formula 1,
Structural Formula 1:
wherein R is an alkyl nitrile containing 1-3 carbon atoms.
상기 구조식 1에서, 상기 1-3개 탄소 원자를 함유하는 알킬 니트릴이 카르보니트릴인 것을 특징으로 하는 슈퍼커패시터 전해액.According to claim 1,
In the structural formula 1, the supercapacitor electrolyte, characterized in that the alkyl nitrile containing 1 to 3 carbon atoms is carbonitrile.
상기 슈퍼커패시터 전해액에서, 슈퍼커패시터 전해액의 총 중량을 기준으로, 상기 첨가제의 함량이 0.1%-5%인 것을 특징으로 하는 슈퍼커패시터 전해액.According to claim 1,
In the supercapacitor electrolyte, the content of the additive is 0.1%-5% based on the total weight of the supercapacitor electrolyte.
상기 슈퍼커패시터 전해액에서, 유기 전해질의 농도가 0.5-3.0mol/L인 것을 특징으로 하는 슈퍼커패시터 전해액.According to claim 4,
In the supercapacitor electrolyte, the concentration of the organic electrolyte is 0.5-3.0 mol / L, characterized in that the supercapacitor electrolyte solution.
상기 슈퍼커패시터 전해액에서, 유기 전해질의 농도가 0.8-2.0mol/L인 것을 특징으로 하는 슈퍼커패시터 전해액.According to claim 4,
In the supercapacitor electrolyte, the concentration of the organic electrolyte is 0.8-2.0 mol / L, characterized in that the supercapacitor electrolyte solution.
상기 유기 전해질이 비스(트리플루오로메틸술포닐)이미드, 비스(플루오로술포닐)이미드, 및 헥사플루오로인산암모늄 중의 한 가지 또는 여러 가지로부터 선택되는 것을 특징으로 하는 슈퍼커패시터 전해액.According to claim 1,
The supercapacitor electrolyte solution, characterized in that the organic electrolyte is selected from one or more of bis (trifluoromethylsulfonyl) imide, bis (fluorosulfonyl) imide, and ammonium hexafluorophosphate.
비스(트리플루오로메틸술포닐)이미드가 테트라메틸비스(트리플루오로메틸술포닐)이미드염, 테트라프로필비스(트리플루오로메틸술포닐)이미드염, 테트라부틸비스(트리플루오로메틸술포닐)이미드염, 메틸트리에틸비스(트리플루오로메틸술포닐)이미드염, 디에틸디메틸비스(트리플루오로메틸술포닐)이미드염, 트리메틸에틸비스(트리플루오로메틸술포닐)이미드염, N,N-디메틸피롤리딘비스(트리플루오로메틸술포닐)이미드염 중의 한 가지 또는 여러 가지로부터 선택되고;
비스(플루오로술포닐)이미드가 테트라메틸비스(플루오로술포닐)이미드염, 테트라프로필비스(플루오로술포닐)이미드염, 테트라부틸비스(플루오로술포닐)이미드염, 메틸트리에틸비스(플루오로술포닐)이미드염, 디에틸디메틸비스(플루오로술포닐)이미드염, 트리메틸에틸비스(플루오로술포닐)이미드염, N,N-디메틸피롤리딘비스(플루오로술포닐)이미드염 중의 한 가지 또는 여러 가지로부터 선택되고;
헥사플루오로인산암모늄이 테트라에틸헥사플루오로인산암모늄, 테트라메틸헥사플루오로인산암모늄, 테트라프로필헥사플루오로인산암모늄, 테트라부틸헥사플루오로인산암모늄, 메틸트리에틸헥사플루오로인산암모늄, 트리에틸메틸헥사플루오로인산암모늄, 디에틸디메틸헥사플루오로인산암모늄, N,N-디메틸피롤리딘헥사플루오로인산염 중의 한 가지 또는 여러 가지로부터 선택되는 것을 특징으로 하는 슈퍼커패시터 전해액.According to claim 7,
Bis(trifluoromethylsulfonyl)imide is tetramethylbis(trifluoromethylsulfonyl)imide salt, tetrapropylbis(trifluoromethylsulfonyl)imide salt, tetrabutylbis(trifluoromethylsulfonyl) Imide salt, methyltriethylbis(trifluoromethylsulfonyl)imide salt, diethyldimethylbis(trifluoromethylsulfonyl)imide salt, trimethylethylbis(trifluoromethylsulfonyl)imide salt, N,N - is selected from one or more of dimethylpyrrolidinebis(trifluoromethylsulfonyl)imide salts;
Bis (fluorosulfonyl) imide is tetramethylbis (fluorosulfonyl) imide salt, tetrapropylbis (fluorosulfonyl) imide salt, tetrabutylbis (fluorosulfonyl) imide salt, methyltriethylbis ( Fluorosulfonyl) imide salt, diethyldimethylbis(fluorosulfonyl)imide salt, trimethylethylbis(fluorosulfonyl)imide salt, N,N-dimethylpyrrolidine bis(fluorosulfonyl)imide salt selected from one or more of;
Ammonium hexafluorophosphate is tetraethylhexafluoroammonium, tetramethylhexafluoroammonium, tetrapropylhexafluoroammonium, tetrabutylhexafluoroammonium, methyltriethylhexafluoroammonium, triethylmethyl A supercapacitor electrolyte solution characterized in that it is selected from one or more of ammonium hexafluorophosphate, diethyldimethylhexafluorophosphate, and N,N-dimethylpyrrolidine hexafluorophosphate.
상기 극성 비양성자성 용제가 아세토니트릴, 프로피오니트릴, 메톡시프로피오니트릴, γ-부티롤락톤, γ-발레로락톤, 에틸렌카보네이트, 프로필렌카보네이트, N,N-디메틸메탄아미드, 디메틸에탄아미드, 1-메틸-2-피롤리디논, 디메톡시에탄, 2-메톡시에테르, 테트라히드로푸란, 디옥솔란, 디메틸카보네이트, 디에틸카보네이트, 에틸메틸카보네이트, 술포란, 디메틸술폭시드, 디메틸술폰, 에틸메틸술폰, 메틸이소프로필술폰, 에틸이소프로필술폰, 에틸이소부틸술폰, 이소프로필이소부틸술폰, 이소프로필-s-부틸술폰, 부틸이소부틸술폰 중의 한 가지 또는 여러 가지로부터 선택되는 것을 특징으로 하는 슈퍼커패시터 전해액.According to claim 1,
The polar aprotic solvent is acetonitrile, propionitrile, methoxypropionitrile, γ-butyrolactone, γ-valerolactone, ethylene carbonate, propylene carbonate, N,N-dimethylmethanamide, dimethylethaneamide, 1-methyl-2-pyrrolidinone, dimethoxyethane, 2-methoxyether, tetrahydrofuran, dioxolane, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, sulfolane, dimethyl sulfoxide, dimethyl sulfone, ethyl methyl A supercapacitor characterized by being selected from one or more of sulfone, methyl isopropyl sulfone, ethyl isopropyl sulfone, ethyl isobutyl sulfone, isopropyl isobutyl sulfone, isopropyl-s-butyl sulfone, and butyl isobutyl sulfone electrolyte.
양극, 음극, 양극과 음극 간에 위치하는 분리막과 제1항에 따른 슈퍼커패시터 전해액을 포함하는 것을 특징으로 하는 슈퍼커패시터.In the supercapacitor,
A supercapacitor comprising an anode, a cathode, a separator positioned between the anode and the cathode, and the supercapacitor electrolyte according to claim 1.
상기 유기 전해질이 테트라플루오로붕산테트라에틸암모늄, 테트라메틸테트라플루오로붕산암모늄, 테트라프로필테트라플루오로붕산암모늄, 테트라부틸테트라플루오로붕산암모늄, 메틸트리에틸테트라플루오로붕산암모늄, 디에틸디메틸테트라플루오로붕산암모늄, 트리메틸에틸테트라플루오로붕산암모늄, N,N-디메틸피롤리딘테트라플루오로붕산아민, N-에틸-N-메틸피롤리딘테트라플루오로붕산아민, N-프로필-N-메틸피롤리딘테트라플루오로붕산아민, N-N-테트라메틸렌피롤리딘테트라플루오로붕산아민, 스피로-(1,1')-디피롤리딘테트라플루오로붕산아민, N,N-디메틸피페리딘테트라플루오로붕산아민, N,N-디에틸피페리딘테트라플루오로붕산아민, N,N-디메틸모르폴린테트라플루오로붕산아민, 1-에틸-3-메틸이미다졸테트라플루오로붕산아민 중 한 가지 또는 여러 가지로부터 선택되는 것을 특징으로 하는 슈퍼커패시터 전해액.According to claim 1,
The organic electrolyte is tetraethylammonium tetrafluoroborate, tetramethyltetrafluoroborate ammonium, tetrapropyltetrafluoroborate ammonium, tetrabutyltetrafluoroborate ammonium, methyltriethyltetrafluoroborate ammonium, diethyldimethyltetrafluoro Ammonium roborate, trimethylethyltetrafluoroborate ammonium, N,N-dimethylpyrrolidinetetrafluoroboric acid amine, N-ethyl-N-methylpyrrolidinetetrafluoroboric acid amine, N-propyl-N-methylphy Rolidinetetrafluoroboric acid amine, NN-tetramethylenepyrrolidinetetrafluoroboric acid amine, spiro-(1,1')-dipyrrolidinetetrafluoroboric acid amine, N,N-dimethylpiperidinetetrafluoro One of amine borates, N,N-diethylpiperidine tetrafluoroboric acid amines, N,N-dimethylmorpholine tetrafluoroboric acid amines, 1-ethyl-3-methylimidazole tetrafluoroboric acid amines, or A supercapacitor electrolyte solution characterized in that it is selected from various types.
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