CN111261426A - Super capacitor electrolyte and super capacitor - Google Patents
Super capacitor electrolyte and super capacitor Download PDFInfo
- Publication number
- CN111261426A CN111261426A CN201811465140.0A CN201811465140A CN111261426A CN 111261426 A CN111261426 A CN 111261426A CN 201811465140 A CN201811465140 A CN 201811465140A CN 111261426 A CN111261426 A CN 111261426A
- Authority
- CN
- China
- Prior art keywords
- tetrafluoroborate
- electrolyte
- iminate
- fluorosulfonyl
- supercapacitor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003792 electrolyte Substances 0.000 title claims abstract description 55
- 239000003990 capacitor Substances 0.000 title abstract description 48
- 239000000654 additive Substances 0.000 claims abstract description 21
- 230000000996 additive effect Effects 0.000 claims abstract description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 14
- 239000005486 organic electrolyte Substances 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 239000003880 polar aprotic solvent Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 6
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 4
- -1 alkane nitrile Chemical class 0.000 claims description 103
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 45
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims description 16
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 9
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-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
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-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
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-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
- YBJCDTIWNDBNTM-UHFFFAOYSA-N 1-methylsulfonylethane Chemical compound CCS(C)(=O)=O YBJCDTIWNDBNTM-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
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 2
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims description 2
- 150000002466 imines Chemical class 0.000 claims 1
- 150000002825 nitriles Chemical class 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000012360 testing method Methods 0.000 description 11
- 239000002904 solvent Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000002035 prolonged effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- 239000008151 electrolyte solution Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LELOWRISYMNNSU-UHFFFAOYSA-N Hydrocyanic acid Natural products N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- RDKKQZIFDSEMNU-UHFFFAOYSA-N 2-ethylsulfonylpropane Chemical compound CCS(=O)(=O)C(C)C RDKKQZIFDSEMNU-UHFFFAOYSA-N 0.000 description 1
- 229910019785 NBF4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004134 energy conservation 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
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 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
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000001424 substituent group Chemical group 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
In order to overcome the problems of short cycle life and large gas production rate of the electrolyte under high temperature and high voltage in the prior art, the invention provides a super capacitor electrolyte, which comprises a polar aprotic solvent, an organic electrolyte and an additive, wherein the additive is selected from a compound shown in a structural formula 1: structural formula 1:
wherein R is an alkanenitrile containing 1 to 3 carbon atoms or a compound of formula 2: structural formula 2:
wherein R is1～R3Selected from hydrogen, alkyl containing 1-3 carbon atoms, alkoxy containing 1-3 carbon atoms or aromatic hydrocarbon; r1～R3May be the same or different. Meanwhile, the invention also discloses a super capacitor adopting the electrolyte. The super capacitor containing the super capacitor electrolyte provided by the invention has long cycle life and small gas production rate under high temperature and high voltage.
Description
Technical Field
The invention relates to a super capacitor electrolyte and a super capacitor.
Background
Supercapacitors, also called gold capacitors, electrochemical capacitors, use either ion adsorption (double layer capacitors) or surface fast redox reactions (pseudocapacitors) to store energy. A super capacitor is a new type of energy storage device between a battery and a conventional electrostatic capacitor. The electric charge stored by the super capacitor is hundreds of thousands of times of that of the traditional solid electrolytic capacitor, can be completely charged and discharged within seconds, has higher power input or output than a battery, and can be achieved within shorter time. Meanwhile, the super capacitor has the advantages of short charging and discharging time, long storage life, high stability, wide working temperature range (-40-70 ℃) and the like, so the super capacitor is widely applied to the fields of consumer electronics, new energy power generation systems, distributed energy storage systems, intelligent distributed power grid systems, new energy vehicles and other traffic fields, energy-saving elevator cranes and other load fields, electromagnetic bombs and other military equipment fields, motion control fields and the like, relates to various industries such as new energy power generation, intelligent power grids, new energy vehicles, energy-saving buildings, industrial energy conservation and emission reduction and the like, and belongs to a standard full-series low-carbon economic core product.
As one of the most promising energy storage devices in the new energy field, supercapacitors have become one of the hot spots of research in the cross-discipline fields of materials, electricity, physics, chemistry, etc. in the countries of the united states, japan, korea, and russia. The main research aims to prepare an electrode material with excellent performance and low cost and an electrolytic liquid system material with high conductivity, good chemical and thermal stability and high working voltage (wide electrochemical stability window), and prepare a super capacitor energy storage device which has high energy density, high power density and long service life and can be used for various hybrid power systems of electric and hybrid automobiles, backup power sources of electronic equipment and the like on the basis.
The propylene carbonate and the acetonitrile have better electrochemical and chemical stability and better solubility to organic quaternary ammonium salts, so the propylene carbonate and the acetonitrile are widely applied to an electrolyte system of a super capacitor. The currently commercialized supercapacitor electrolyte mainly adopts tetraethylammonium tetrafluoroborate (Et)4NBF4) Or methyltriethylammonium tetrafluoroborate (Et)3MeNBF4) Of Acetonitrile (AN) or Propylene Carbonate (PC). The upper limit of the voltage of the AN system super capacitor is only 2.7V, and the working temperature range is-40-65 ℃; the upper limit of the voltage of the super capacitor of the PC system is only 2.5V, and the working temperature range is-40 ℃ to 70 ℃. With the development of the super-capacity market, the conventional electrolyte at present cannot meet the requirements of high temperature resistance and high pressure resistance of customers on the super capacitor for the sake of safety and increasing market competitivenessThe requirements of (1). The conventional electrolyte can cause electrochemical decomposition of the electrolyte when working at high voltage and high temperature, so that the pressure in the capacitor is remarkably increased, the electrochemical performance is remarkably reduced, and finally the capacitor fails.
Disclosure of Invention
The invention aims to solve the technical problems of short cycle life and large gas production rate of the electrolyte under high temperature and high voltage in the prior art, and provides the electrolyte of the super capacitor.
The technical scheme adopted by the invention for solving the technical problems is as follows:
provided is a supercapacitor electrolyte comprising a polar aprotic solvent, an organic electrolyte and an additive selected from compounds represented by structural formula 1:
structural formula 1:
wherein R is an alkanenitrile containing 1 to 3 carbon atoms or a compound of formula 2:
structural formula 2:
wherein R is1～R3Selected from hydrogen, alkyl containing 1-3 carbon atoms, alkoxy containing 1-3 carbon atoms or aromatic hydrocarbon; r1～R3May be the same or different.
Meanwhile, the invention also provides a super capacitor which comprises a positive electrode, a negative electrode, a diaphragm between the positive electrode and the negative electrode and the super capacitor electrolyte.
The inventor finds that the additive can react with water in a capacitor at high temperature and high voltage in the super capacitor, so that side reactions caused by water are reduced, the stability of electrolyte is improved, the self-discharge and gas generation of the capacitor are reduced, the service life of the super capacitor is prolonged greatly, and the capacitor has good cycle life and high and low temperature performance.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The electrolyte of the super capacitor provided by the invention comprises a polar aprotic solvent, an organic electrolyte and an additive, wherein the additive is selected from a compound shown in a structural formula 1:
structural formula 1:
wherein R is an alkanenitrile containing 1 to 3 carbon atoms or a compound of formula 2:
structural formula 2:
wherein R is1～R3Selected from hydrogen, alkyl containing 1-3 carbon atoms, alkoxy containing 1-3 carbon atoms or aromatic hydrocarbon; r1～R3May be the same or different.
As mentioned above, in formula 1, R may be an alkanenitrile containing 1 to 3 carbon atoms, such as carbonitrile, acetonitrile, propionitrile, preferably carbonitrile. In the above R, if the carbon number of the alkylnitrile exceeds 3, the capacity of the supercapacitor is significantly reduced.
Meanwhile, R in the structural formula 1 can also be a silicon-containing substituent shown in a structural formula 2. Specifically, in the structural formula 2, R1、R2、R3Each independently selected from hydrogen, methyl, methoxy, ethoxy, phenyl.
In the present invention, the additive is preferably at least one selected from the group consisting of benzonitrile, phenylsilane, phenyltrimethoxysilane, phenyltriethoxysilane, methylphenyldimethoxysilane, and diphenyldimethoxysilane.
According to the invention, the content of the above-mentioned additive in the supercapacitor electrolyte may vary within wide limits, preferably in the range of 0.1% to 5%, more preferably in the range of 0.5% to 5%, based on the total weight of the supercapacitor electrolyte.
In general, a small amount of moisture is inevitably present in the electrolyte of the supercapacitor, including moisture brought in by the electrolyte, moisture brought in by other parts (such as positive and negative electrodes and separators) of the supercapacitor, and moisture in air brought in during the manufacturing process of the supercapacitor. The inventor finds that the side reaction of the moisture has obvious influence on the performance of the super capacitor, especially under high temperature and high voltage. When the electrolyte contains the additive, the occurrence of side reaction caused by water can be effectively avoided under high temperature and high voltage, so that the service life of the super capacitor under high temperature and high voltage is prolonged, and the gas generation is reduced.
In the present invention, various substances commonly used for the organic electrolyte can be used, for example, the organic electrolyte is selected from tetraethylammonium tetrafluoroborate, tetramethylammonium tetrafluoroborate, tetrapropylammonium tetrafluoroborate, tetrabutylammonium tetrafluoroborate, methyltriethylammonium tetrafluoroborate, diethyldimethylammonium tetrafluoroborate, trimethylethylammonium tetrafluoroborate, N-dimethylpyrrolidinetetrafluoroborate, N-ethyl-N-methylpyrrolidinium tetrafluoroborate, N-propyl-N-methylpyrrolidinium tetrafluoroborate, N-N-tetramethylpyrrolidiniumtetrafluoroborate, spiro- (1, 1') -dipyrrolidinefluoroamine, N-dimethylpiperidine tetrafluoroborate, N-diethylpiperidinefluoroamine, N-dimethylmorpholinefluoroborate, N-dimethylmorpholinefluorobluoroborate, N-dimethylpiperidine tetrafluoroborate, N-diethylpiperidinefluoroborate, N-dimethylpiperidine tetrafluoroborate, 1-Ethyl-3-methylimidazolium tetrafluoroborate, bis (trifluoromethylsulfonyl) imides such as tetraethylammonium tetrafluoroborate, 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-dimethylpyrrolidinedi (trifluoromethylsulfonyl) imide salt, bis (fluorosulfonyl) imides such as tetraethylammonium tetrafluoroborate, 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-dimethylpyrrolidinebis (fluorosulfonyl) imide salt, ammonium hexafluorophosphate species such as tetraethylammonium hexafluorophosphate, tetramethylammonium hexafluorophosphate, tetrapropylammonium hexafluorophosphate, tetrabutylammonium hexafluorophosphate, methyltriethylammonium hexafluorophosphate, triethylmethylammonium hexafluorophosphate or diethyldimethylammonium hexafluorophosphate.
Preferably, the organic electrolyte is selected from the group consisting of N, N-dimethylpyrrolidine tetrafluoroborate, tetraethylammonium tetrafluoroborate, methyltriethylammonium tetrafluoroborate, spiro- (1, 1') -dipyrrolidine tetrafluoroborate, N-dimethylpyrrolidine bis (trifluoromethylsulfonyl) imide salts; n, N-dimethylpyrrolidine bis (fluorosulfonyl) imide salt, N-dimethylpyrrolidine hexafluorophosphate salt.
The content of the organic electrolyte can vary within a wide range, and preferably, the concentration of the organic electrolyte in the electrolyte of the supercapacitor is 0.5 to 3.0mol/L, more preferably 0.8 to 2.0 mol/L.
According to the present invention, the above-mentioned polar aprotic solvent may employ a substance conventional in the art, for example, the polar aprotic solvent is selected from one or more of acetonitrile, propionitrile, methoxypropionitrile, γ -butyrolactone, γ -valerolactone, ethylene carbonate, propylene carbonate, N-dimethylformamide, dimethylacetamide, 1-methyl-2-pyrrolidone, dimethoxyethane, 2-methoxyethyl ether, tetrahydrofuran, dioxolane, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, sulfolane, dimethyl sulfoxide, dimethyl sulfone, methyl ethyl sulfone, methyl isopropyl sulfone, ethyl isobutyl sulfone, isopropyl-s-butyl sulfone, and butyl isobutyl sulfone. Preferably one or two of acetonitrile, propylene carbonate, sulfolane, dimethyl sulfone and ethyl isopropyl sulfone. Especially, when R in the additive is alkane nitrile, the effect is more remarkable.
The invention also discloses a super capacitor, which comprises a positive electrode, a negative electrode, a diaphragm between the positive electrode and the negative electrode and the super capacitor electrolyte.
The positive electrode, the negative electrode and the diaphragm of the super capacitor can be conventional, for example, the positive electrode and the negative electrode are carbon material electrodes, and the diaphragm is a fiber cloth diaphragm.
The present invention will be further illustrated by the following examples.
Assembling a super capacitor model in a glove box: the cell includes two collecting electrodes made of aluminum foil, two working electrodes made of activated carbon, and a fiber cloth separator interposed therebetween, but is not limited to this structure. Immersing the battery core into the electrolyte in the following comparative examples and examples, and adopting an aluminum shell and colloidal particles to assemble and seal the electrolyte to test the high and low temperature performance; and testing the gas production rate by adopting an aluminum plastic film vacuum seal.
The test process of the super capacitor comprises the following steps:
(1) pre-cycle (10): charging at 25 ℃ with a charging cut-off voltage U and a constant current of 10 mA/F; then, discharging according to the lower limit voltage U/2 and the constant current 10 mA/F;
(2) charging the high-temperature box at 65-70 ℃ with constant current of 10mA/F to an upper limit voltage U, and keeping the voltage U constant for a certain time; taking out the super capacitor, cooling to 25 ℃, performing a charge-discharge test under the same test condition as the pre-circulation, and calculating the capacity retention rate and the ESR increase rate of the super capacitor;
(3) the capacity retention rate is less than or equal to 80 percent, and/or the ESR growth rate is more than or equal to 100 percent, which are used as the judgment standard of the over-capacity service life.
Example 1
Using N, N-dimethylpyrrolidine ammonium tetrafluoroborate as a solute and Acetonitrile (AN) as a solvent, 2.0mol/L of AN electrolyte was prepared, 0.2% by mass of phenylsilane was added based on the total mass of the electrolyte, and the composition of the electrolyte was as shown in table 1, and the conductivity of the electrolyte at 25 ℃ was measured, and the results were as shown in table 1. The electrolyte is used for manufacturing a super capacitor and carrying out electrochemical performance test on the super capacitor, and the service life, the capacity and the ESR test result are respectively listed in Table 1.
Examples 2 to 13
The same as in example 1, except that the solute, solvent, additive and concentration of the electrolyte were different. The solute, solvent, additive and concentration composition of the electrolyte of each example are shown in tables 1 and 2, and the conductivity of the electrolyte at 25 ℃ was measured, and the results are shown in tables 1 and 2, respectively. The electrolytes were used to fabricate supercapacitors and tested for electrochemical performance, with the results of life, capacity and ESR tests shown in tables 1 and 2, respectively.
Comparative example 1
Tetraethylammonium tetrafluoroborate was used as a solute and AN was used as a solvent to prepare 1.0mol/L of AN electrolyte solution, the composition of the electrolyte solution is shown in table 1, and the conductivity of the electrolyte solution at 25 ℃ was measured, and the results are respectively shown in table 1. The electrolyte is used for manufacturing a super capacitor and carrying out electrochemical performance test on the super capacitor, and the service life, the capacity and the ESR test result are respectively listed in Table 1.
Comparative examples 2 to 8
Except that the solute, solvent, additive and concentration of the electrolyte were different from those of comparative example 1. The solute, solvent, additive and concentration composition of each comparative electrolyte are shown in tables 1 and 2, and the conductivity of the electrolyte at 25 ℃ was measured, and the results are shown in tables 1 and 2, respectively. The electrolytes were used to fabricate supercapacitors and tested for electrochemical performance, with the results of life, capacity and ESR tests shown in tables 1 and 2, respectively.
TABLE 1
From the test results in table 1, it can be seen that, after the additive provided by the present invention is added under different solute and acetonitrile solvent systems, the service life of the supercapacitor under high temperature and high voltage conditions is significantly improved, and the gas production is significantly reduced. And with the increase of the content of the additive, the service life is prolonged, and the effect of inhibiting gas generation is more obvious.
TABLE 2
From the test results in table 2, it can be seen that, after the additive provided by the present invention is added under different solutes and propylene carbonate solvent systems, the service life of the supercapacitor under high temperature and high voltage conditions is significantly improved, and the gas production is significantly reduced. And with the increase of the content of the additive, the service life is prolonged, and the effect of inhibiting gas generation is more obvious.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A supercapacitor electrolyte comprising a polar aprotic solvent, an organic electrolyte and an additive selected from compounds represented by structural formula 1:
structural formula 1:
wherein R is an alkanenitrile containing 1 to 3 carbon atoms or a compound of formula 2:
structural formula 2:
wherein R is1～R3Selected from hydrogen, alkyl containing 1-3 carbon atoms, alkoxy containing 1-3 carbon atoms or aromatic hydrocarbon; r1～R3May be the same or different.
2. The supercapacitor electrolyte according to claim 1, wherein in the structural formula 1, the alkane nitrile containing 1 to 3 carbon atoms is a nitrile; in the formula 2, R1、R2、R3Each independently selected from hydrogen, methyl, methoxy, ethoxy, phenyl.
3. The supercapacitor electrolyte according to claim 1, wherein the additive is selected from at least one of benzonitrile, phenylsilane, phenyltrimethoxysilane, phenyltriethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane.
4. The supercapacitor electrolyte according to any one of claims 1 to 3, wherein the additive is present in the supercapacitor electrolyte in an amount of 0.1% to 5% based on the total weight of the supercapacitor electrolyte.
5. The supercapacitor electrolyte according to claim 4, wherein the concentration of the organic electrolyte in the supercapacitor electrolyte is 0.5 to 3.0 mol/L.
6. The supercapacitor electrolyte according to claim 4, wherein the concentration of the organic electrolyte in the supercapacitor electrolyte is 0.8-2.0 mol/L.
7. The supercapacitor electrolyte according to any one of claims 1 to 3, 5 or 6, wherein the organic electrolyte is selected from tetraethylammonium tetrafluoroborate, tetramethylammonium tetrafluoroborate, tetrapropylammonium tetrafluoroborate, tetrabutylammonium tetrafluoroborate, methyltriethylammonium tetrafluoroborate, diethyldimethylammonium tetrafluoroborate, trimethylethylammonium tetrafluoroborate, N-dimethylpyrrolidine ammonium tetrafluoroborate, N-ethyl-N-methylpyrrolidine ammonium tetrafluoroborate, N-propyl-N-methylpyrrolidine ammonium tetrafluoroborate, N-N-tetramethylenepyrrolidine ammonium tetrafluoroborate, spiro- (1, 1') -dipyrrolidine ammonium tetrafluoroborate, N-dimethylpiperidine ammonium tetrafluoroborate, N-diethylpiperidine ammonium tetrafluoroborate, N, N-dimethylmorpholinium tetrafluoroborate, 1-ethyl-3-methylimidazolium tetrafluoroborate, bis (trifluoromethylsulfonyl) imines such as tetraethylammonium tetrafluoroborate, tetramethylbis (trifluoromethylsulfonyl) iminate, tetrapropylbis (trifluoromethylsulfonyl) iminate, tetrabutylbis (trifluoromethylsulfonyl) iminate, methyltriethylbis (trifluoromethylsulfonyl) iminate, diethyldimethylbis (trifluoromethylsulfonyl) iminate, trimethylethylbis (trifluoromethylsulfonyl) iminate, N-dimethylpyrrolidinebis (trifluoromethylsulfonyl) iminate, bis (fluorosulfonyl) iminates such as tetraethylammonium tetrafluoroborate, tetramethylbis (fluorosulfonyl) iminate, tetrapropylbis (fluorosulfonyl) iminate, tetrabutylbis (fluorosulfonyl) iminate, methyltriethylylbis (fluorosulfonyl) iminate, tetraethylammonium tetrafluoroborate, tetramethylbis (fluorosulfonyl) iminate, tetrapropylbis (fluorosulfonyl) iminate, tetrabutylbis (fluorosulfonyl) iminate, tetramethylbis (fluorosulfonyl) iminate, tetramethylfluorosulfonyl, One or more of diethyldimethylbis (fluorosulfonyl) imide salt, trimethylethylbis (fluorosulfonyl) imide salt, N-dimethylpyrrolidine bis (fluorosulfonyl) imide salt, ammonium hexafluorophosphate such as tetraethylammonium hexafluorophosphate, tetramethylammonium hexafluorophosphate, tetrapropylammonium hexafluorophosphate, tetrabutylammonium hexafluorophosphate, methyltriethylammonium hexafluorophosphate, triethylmethylammonium hexafluorophosphate, or diethyldimethylammonium hexafluorophosphate.
8. The supercapacitor electrolyte according to any one of claims 1 to 3, 5 or 6, wherein the organic electrolyte is selected from the group consisting of N, N-dimethylpyrrolidine tetrafluoroborate, tetraethylammonium tetrafluoroborate, methyltriethylammonium tetrafluoroborate, spiro- (1, 1') -dipyrrolidine tetrafluoroborate, N-dimethylpyrrolidine bis (trifluoromethylsulfonyl) imide salts; n, N-dimethylpyrrolidine bis (fluorosulfonyl) imide salt, N-dimethylpyrrolidine hexafluorophosphate salt.
9. The supercapacitor electrolyte according to any one of claims 1 to 3, 5 or 6, wherein the polar aprotic solvent is selected from one or more of acetonitrile, propionitrile, methoxypropionitrile, γ -butyrolactone, γ -valerolactone, ethylene carbonate, propylene carbonate, N-dimethylformamide, dimethylacetamide, 1-methyl-2-pyrrolidone, dimethoxyethane, 2-methoxyethyl ether, tetrahydrofuran, dioxolane, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, sulfolane, dimethyl sulfoxide, dimethyl sulfone, methyl ethyl sulfone, methyl isopropyl sulfone, ethyl isobutyl sulfone, isopropyl s-butyl sulfone, butyl isobutyl sulfone.
10. A supercapacitor comprising a positive electrode, a negative electrode, a separator between the positive and negative electrodes and a supercapacitor electrolyte according to any one of claims 1 to 9.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811465140.0A CN111261426B (en) | 2018-12-03 | 2018-12-03 | Super capacitor electrolyte and super capacitor |
| PCT/CN2019/122300 WO2020114338A1 (en) | 2018-12-03 | 2019-12-02 | Supercapacitor electrolyte and supercapacitor |
| KR1020217016491A KR102495382B1 (en) | 2018-12-03 | 2019-12-02 | Supercapacitor Electrolyte and Supercapacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811465140.0A CN111261426B (en) | 2018-12-03 | 2018-12-03 | Super capacitor electrolyte and super capacitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111261426A true CN111261426A (en) | 2020-06-09 |
| CN111261426B CN111261426B (en) | 2022-08-09 |
Family
ID=70951995
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811465140.0A Active CN111261426B (en) | 2018-12-03 | 2018-12-03 | Super capacitor electrolyte and super capacitor |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR102495382B1 (en) |
| CN (1) | CN111261426B (en) |
| WO (1) | WO2020114338A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113206283A (en) * | 2021-05-01 | 2021-08-03 | 南开大学 | Aqueous zinc ion battery electrolyte based on eutectic salt electrolyte |
| CN115959645A (en) * | 2022-12-30 | 2023-04-14 | 深圳新宙邦科技股份有限公司 | Preparation method of hexafluorophosphate alkali metal salt, electrolyte and lithium ion battery |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101184691A (en) * | 2005-05-27 | 2008-05-21 | 住友化学株式会社 | Electric double layer capacitor |
| CN103620714A (en) * | 2011-05-10 | 2014-03-05 | Cap-Xx有限公司 | Electrolyte |
| CN105359238A (en) * | 2013-07-12 | 2016-02-24 | Ioxus公司 | Stability enhancing additive for electrochemical devices |
| JP2017142940A (en) * | 2016-02-09 | 2017-08-17 | 三菱ケミカル株式会社 | Nonaqueous electrolytic solution and nonaqueous electrolyte secondary battery |
| CN107078352A (en) * | 2014-09-30 | 2017-08-18 | 三菱化学株式会社 | Nonaqueous electrolytic solution and the rechargeable nonaqueous electrolytic battery for having used the nonaqueous electrolytic solution |
| CN107210144A (en) * | 2015-01-26 | 2017-09-26 | Ioxus公司 | Additive for reducing the ESR gains in electrochemical double layer capacitor |
| CN108475821A (en) * | 2015-12-17 | 2018-08-31 | 巴斯夫欧洲公司 | Cyanoalkyl sulfuryl fluoride for high-performance lithium ion battery group electrolyte composition |
| CN108899212A (en) * | 2018-07-17 | 2018-11-27 | 中国科学院过程工程研究所 | A kind of preparation method and application of ternary poly ion liquid base solid electrolyte |
-
2018
- 2018-12-03 CN CN201811465140.0A patent/CN111261426B/en active Active
-
2019
- 2019-12-02 KR KR1020217016491A patent/KR102495382B1/en active IP Right Grant
- 2019-12-02 WO PCT/CN2019/122300 patent/WO2020114338A1/en active Application Filing
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101184691A (en) * | 2005-05-27 | 2008-05-21 | 住友化学株式会社 | Electric double layer capacitor |
| CN103620714A (en) * | 2011-05-10 | 2014-03-05 | Cap-Xx有限公司 | Electrolyte |
| CN105359238A (en) * | 2013-07-12 | 2016-02-24 | Ioxus公司 | Stability enhancing additive for electrochemical devices |
| CN107078352A (en) * | 2014-09-30 | 2017-08-18 | 三菱化学株式会社 | Nonaqueous electrolytic solution and the rechargeable nonaqueous electrolytic battery for having used the nonaqueous electrolytic solution |
| CN107210144A (en) * | 2015-01-26 | 2017-09-26 | Ioxus公司 | Additive for reducing the ESR gains in electrochemical double layer capacitor |
| CN108475821A (en) * | 2015-12-17 | 2018-08-31 | 巴斯夫欧洲公司 | Cyanoalkyl sulfuryl fluoride for high-performance lithium ion battery group electrolyte composition |
| JP2017142940A (en) * | 2016-02-09 | 2017-08-17 | 三菱ケミカル株式会社 | Nonaqueous electrolytic solution and nonaqueous electrolyte secondary battery |
| CN108899212A (en) * | 2018-07-17 | 2018-11-27 | 中国科学院过程工程研究所 | A kind of preparation method and application of ternary poly ion liquid base solid electrolyte |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113206283A (en) * | 2021-05-01 | 2021-08-03 | 南开大学 | Aqueous zinc ion battery electrolyte based on eutectic salt electrolyte |
| CN115959645A (en) * | 2022-12-30 | 2023-04-14 | 深圳新宙邦科技股份有限公司 | Preparation method of hexafluorophosphate alkali metal salt, electrolyte and lithium ion battery |
| CN115959645B (en) * | 2022-12-30 | 2023-09-08 | 深圳新宙邦科技股份有限公司 | Preparation method of hexafluorophosphate alkali metal salt, electrolyte and lithium ion battery |
Also Published As
| Publication number | Publication date |
|---|---|
| KR102495382B1 (en) | 2023-02-06 |
| WO2020114338A1 (en) | 2020-06-11 |
| KR20210094553A (en) | 2021-07-29 |
| CN111261426B (en) | 2022-08-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sharma et al. | Current technology of supercapacitors: a review | |
| JP2014517507A (en) | Polyimide capacitor battery and manufacturing method thereof | |
| CA2454305A1 (en) | Ionic liquid and method of dehydration thereof, electrical double-layer capacitor, and secondary cell | |
| CN103730263A (en) | Organic electrolytic solution for super capacitor and super capacitor | |
| US20130283580A1 (en) | Electrical double layer capacitor with enhanced working voltage | |
| US9870874B2 (en) | Electrolyte solute, electrolyte, and high-voltage supercapacitor | |
| CN104715934A (en) | Hybrid super capacitor and manufacturing method thereof | |
| CN109741967A (en) | A kind of hybrid super capacitor based on graphite anode and zinc load | |
| CN111261426B (en) | Super capacitor electrolyte and super capacitor | |
| Jadhav et al. | Electrochemical supercapacitors: history, types, designing processes, operation mechanisms, and advantages and disadvantages | |
| Sun et al. | Determination strategy of stable electrochemical operating voltage window for practical lithium-ion capacitors | |
| CN111312526A (en) | Battery-super capacitor hybrid energy storage device and preparation method thereof | |
| CN107887176B (en) | Organic electrolyte for super capacitor and super capacitor | |
| NL2015030B1 (en) | Electrolyte, and high-voltage supercapacitor. | |
| WO2017004884A1 (en) | Electrolyte solute, electrolyte, and super-capacitor | |
| CN103943376A (en) | Electrolyte of mixed type super capacitor | |
| CN110349759B (en) | Super capacitor electrolyte and super capacitor | |
| CN102496469A (en) | High-power double electric layer capacitor | |
| CN108573816B (en) | Organic electrolyte for super capacitor and super capacitor | |
| CN107845506B (en) | Enhanced graphene-based supercapacitor and preparation method thereof | |
| CN104779075A (en) | High-voltage nonaqueous electrolyte for supercapacitor | |
| CN102254691A (en) | Electrolyte of low-temperature super capacitor | |
| CN112490015A (en) | Asymmetric high-voltage super capacitor | |
| CN114121500A (en) | Electrolyte for super capacitor and super capacitor | |
| CN107424848B (en) | Electrolyte for super capacitor and super capacitor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |