WO2017004884A1 - Soluté d'électrolyte, électrolyte et supercondensateur - Google Patents

Soluté d'électrolyte, électrolyte et supercondensateur Download PDF

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Publication number
WO2017004884A1
WO2017004884A1 PCT/CN2015/089163 CN2015089163W WO2017004884A1 WO 2017004884 A1 WO2017004884 A1 WO 2017004884A1 CN 2015089163 W CN2015089163 W CN 2015089163W WO 2017004884 A1 WO2017004884 A1 WO 2017004884A1
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WO
WIPO (PCT)
Prior art keywords
electrolyte
solute
supercapacitor
methyl
capacitor
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PCT/CN2015/089163
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English (en)
Chinese (zh)
Inventor
石桥
向晓霞
钟铃
郑仲天
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深圳新宙邦科技股份有限公司
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Publication of WO2017004884A1 publication Critical patent/WO2017004884A1/fr

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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
    • H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
    • 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
    • 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

Definitions

  • the present invention relates to the field of electrochemistry, and in particular to an electrolyte solute and electrolyte for a supercapacitor and a supercapacitor using the same.
  • Supercapacitors also known as gold capacitors, electrochemical capacitors, use ion adsorption (electric double layer capacitors) or surface rapid redox reactions (tantalum capacitors) to store energy.
  • a supercapacitor is a new type of energy storage device between a battery and a conventional electrostatic capacitor. Supercapacitors store hundreds or thousands of times the charge of conventional electrolytic capacitors. They can be fully charged and discharged in seconds, have higher power input or output than batteries, and can be reached in less time.
  • supercapacitors have the advantages of short charge and discharge time, long storage life, high stability, wide operating temperature range (-40 ° C ⁇ 70 ° C), etc., so they are widely used in the field of consumer electronics, new energy power generation systems, distribution Energy storage systems, smart distributed power grid systems, new energy vehicles and other transportation fields, energy-saving elevator cranes and other load fields, electromagnetic bombs and other military equipment fields and motion control areas, involving new energy generation, smart grid, new energy vehicles
  • Various industries such as energy-saving buildings and industrial energy-saving and emission reduction are standard full-scale low-carbon economic core products.
  • supercapacitor electrolytes are mainly acetonitrile (AN) or propylene carbonate (PC) of tetraethylammonium tetrafluoroborate (Et 4 NBF 4 ) or methyltriethylammonium tetrafluoroborate (Et 3 MeNBF 4 ).
  • AN acetonitrile
  • PC propylene carbonate
  • Et 4 NBF 4 tetraethylammonium tetrafluoroborate
  • Et 3 MeNBF 4 methyltriethylammonium tetrafluoroborate
  • the energy density of a supercapacitor is lower than that of a battery, which limits its practical application; while the operating temperature range is -40 ° C to 70 ° C, which further limits its use as an energy storage device in a special environment (below -40 ° C).
  • the decomposition voltage of the electrolyte determines the operating voltage of the capacitor.
  • the technical problem to be solved by the present invention is to provide an electrolyte solute for an ultracapacitor and an electrolyte thereof and a supercapacitor which have the advantages of high withstand voltage, wide operating temperature range and long life, and are improved in super At the same time as the energy density of the capacitor, the wide operating temperature range and long life characteristics of the supercapacitor are realized.
  • the first technical solution adopted by the present invention is:
  • a - is an anion; and R 1 and R 2 are the same or different and each is an alkyl group having a carbon number of 1-3; n is 0 or 1.
  • the technical solution 2 adopted by the present invention is:
  • An electrolyte for use in a supercapacitor comprising a solute and a solvent, the solute being an electrolyte solute as described in the first aspect of the invention.
  • the third technical solution adopted by the present invention is:
  • a supercapacitor comprising an electrolyte and a battery core immersed in the electrolyte, the battery core is composed of two collector electrodes and a diaphragm disposed between the two collector electrodes, and the two collector electrodes respectively have activated carbon attached thereto, and the electrolyte solution is the above technical solution.
  • the invention has the beneficial effects that the supercapacitor prepared by using the electrolyte solute of the invention to prepare the electrolyte, the AN system can work stably for a long time under the voltage of 2.85V-3.2V and the working temperature range of -50°C-65°C, PC
  • the system can work stably for a long time under the voltage range of 2.7V-3.0V and operating temperature range of -40°C-70°C, greatly improving the energy density and maintaining its high power density characteristics, which can meet the requirements in the energy field.
  • the wider operating temperature range has broadened the application range of supercapacitors, especially extending the working life of supercapacitors, and improving the capacity and ESR performance at low temperatures.
  • the most critical idea of the present invention is to use an alkyl disubstituted pyrrolidine or piperidine having a carbon number of 1-3 as a cation of an electrolyte solution, and the obtained electrolyte solute can effectively improve the work of the supercapacitor. Voltage and gives the supercapacitor the ability to work stably over a wide operating temperature range for extended periods of time.
  • the electrolyte solute of the embodiment of the present invention is used for a supercapacitor, and its chemical structural formula is as follows:
  • a - is an anion; and R 1 and R 2 are the same or different and each is an alkyl group having a carbon number of 1-3; n is 0 or 1.
  • the A - anion may be selected from any of the anions of the known electrolyte solute, including but not limited to one of the following:
  • Tetrafluoroborate (- BF 4), hexafluorophosphate (- PF 6), bis (fluorosulfonyl) imide root (- N (FSO 2) 2 ), bis (trifluoromethanesulfonyl) imide root (- N (CF 3 SO 2 ) 2), bis (trifluoromethanesulfonyl) methyl root (- C (CF 3 SO 2 ) 2), perfluoroalkyl sulfonate (- n F 2n C + 1 SO 3 ).
  • the A - anion used in the present invention is tetrafluoroborate or hexafluorophosphate.
  • N,N-dimethylpyrrolidine (R 1 and R 2 are both methyl), and N,N-diethylpyrrolidine (R 1 , R) 2 is the same as ethyl), N,N-dipropylpyrrolidine (R 1 and R 2 are both propyl) and N-methyl-N-ethylpyrrolidine (R 1 and R 2 are different, respectively Or ethyl), N-methyl-N-propylpyrrolidine (R 1 , R 2 different, respectively methyl or propyl), N-ethyl-N-propylpyrrolidine (R 1 , R 2 different, respectively, ethyl or propyl);
  • n is 0 or 1
  • R 1 and R 2 are each a methyl group or an ethyl group, and at least one of R 1 and R 2 is a methyl group, and the cation is N,N-dimethylpyrrolidine, N-methyl-N-ethylpyrrolidine, N,N-dimethylpiperidine or N-methyl-N-ethylpiperidine.
  • n is 0, R 1 and R 2 are both methyl and the cation is N,N-dimethylpyrrolidine.
  • the electrolyte of the embodiment of the present invention is used for a supercapacitor including a solute and a solvent, and the solute contains an electrolyte solute represented by the following chemical structural formula:
  • a - is an anion; and R 1 and R 2 are the same or different and each is an alkyl group having a carbon number of 1-3; n is 0 or 1.
  • the A - anion may be selected from any of the anions of the known electrolyte solute, including but not limited to one of the following:
  • Tetrafluoroborate (- BF 4), hexafluorophosphate (- PF 6), bis (fluorosulfonyl) imide root (- N (FSO 2) 2 ), bis (trifluoromethanesulfonyl) imide root (- N (CF 3 SO 2 ) 2), bis (trifluoromethanesulfonyl) methyl root (- C (CF 3 SO 2 ) 2), perfluoroalkyl sulfonate (- n F 2n C + 1 SO 3 ).
  • the A - anion used in the present invention is tetrafluoroborate or hexafluorophosphate.
  • N,N-dimethylpyrrolidine (R 1 and R 2 are both methyl), and N,N-diethylpyrrolidine (R 1 , R) 2 is the same as ethyl), N,N-dipropylpyrrolidine (R 1 and R 2 are both propyl) and N-methyl-N-ethylpyrrolidine (R 1 and R 2 are different, respectively Or ethyl), N-methyl-N-propylpyrrolidine (R 1 , R 2 different, respectively methyl or propyl), N-ethyl-N-propylpyrrolidine (R 1 , R 2 different, respectively, ethyl or propyl);
  • n is 0 or 1
  • R 1 and R 2 are each a methyl group or an ethyl group, and at least one of R 1 and R 2 is a methyl group, and the cation is N,N-dimethylpyrrolidine, N-methyl-N-ethylpyrrolidine, N,N-dimethylpiperidine or N-methyl-N-ethylpiperidine.
  • n is 0, R 1 and R 2 are both methyl and the cation is N,N-dimethylpyrrolidine.
  • the solvent may be any one or a mixture of solvents of the known electrolyte solvents, including but not limited to the following:
  • the solvent used in the present invention is acetonitrile, propylene carbonate or a mixed solvent of the two.
  • the supercapacitor (AN system) prepared by using the electrolyte can work stably for a long time under the charging cut-off voltage of 2.85V-3.2V and the working temperature range of -50°C-65°C;
  • the supercapacitor (PC system) obtained by using the electrolyte can be stably operated for a long time at a charge cut-off voltage of 2.7V-3.0V and an operating temperature range of -40°C to 70°C.
  • the solubility of the electrolytic solution is usually 0.2 to 2.0 mol/L, and in the present invention, preferably 0.5 to 1.5 mol/L.
  • the supercapacitor of the embodiment of the present invention includes an electrolyte and a battery core immersed in the electrolyte, the battery core is composed of two collectors and a separator disposed between the two collectors, the electrolyte including a solute and a solvent.
  • the solute contains an electrolyte solute as shown by the following chemical structural formula:
  • a - is an anion; and R 1 and R 2 are the same or different and each is an alkyl group having a carbon number of 1-3; n is 0 or 1.
  • the A - anion may be selected from any of the anions of the known electrolyte solute, including but not limited to one of the following:
  • Tetrafluoroborate (- BF 4), hexafluorophosphate (- PF 6), bis (fluorosulfonyl) imide root (- N (FSO 2) 2 ), bis (trifluoromethanesulfonyl) imide root (- N (CF 3 SO 2 ) 2), bis (trifluoromethanesulfonyl) methyl root (- C (CF 3 SO 2 ) 2), perfluoroalkyl sulfonate (- n F 2n C + 1 SO 3 ).
  • the A - anion used in the present invention is tetrafluoroborate or hexafluorophosphate.
  • N,N-dimethylpyrrolidine (R 1 and R 2 are both methyl), and N,N-diethylpyrrolidine (R 1 , R) 2 is the same as ethyl), N,N-dipropylpyrrolidine (R 1 and R 2 are both propyl) and N-methyl-N-ethylpyrrolidine (R 1 and R 2 are different, respectively Or ethyl), N-methyl-N-propylpyrrolidine (R 1 , R 2 different, respectively methyl or propyl), N-ethyl-N-propylpyrrolidine (R 1 , R 2 different, respectively, ethyl or propyl);
  • n is 0 or 1
  • R 1 and R 2 are each a methyl group or an ethyl group, and at least one of R 1 and R 2 is a methyl group, and the cation is N,N-dimethylpyrrolidine, N-methyl-N-ethylpyrrolidine, N,N-dimethylpiperidine or N-methyl-N-ethylpiperidine.
  • n is 0, R 1 and R 2 are both methyl and the cation is N,N-dimethylpyrrolidine.
  • the solvent may be any one or a mixture of solvents of the known electrolyte solvents, including but not limited to the following:
  • the solvent used in the present invention is acetonitrile, propylene carbonate or a mixed solvent of the two.
  • the agent is acetonitrile
  • the obtained supercapacitor (AN system) can work stably for a long time at a charge cut-off voltage of 2.85V-3.2V and an operating temperature range of -50 ° C to 65 ° C;
  • the solvent is propylene carbonate
  • the supercapacitor (PC system) can work stably for a long time with a charge cut-off voltage of 2.7V-3.0V and an operating temperature range of -40°C to 70°C.
  • the solubility of the electrolytic solution is usually 0.2 to 2.0 mol/L, and in the present invention, preferably 0.5 to 1.5 mol/L.
  • the material of the two collectors may be selected from the conventionally known collector materials, and the present invention preferably has activated carbon attached to the two collectors, respectively.
  • the supercapacitor model is assembled in a glove box: the battery core includes two collector 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.
  • the cells were immersed in the following comparative examples and the electrolytes in the examples, and sealed with aluminum shells and colloidal particles.
  • the supercapacitor testing process is:
  • the constant current 10mA/F is charged to the upper limit voltage U, and the constant voltage (U) is fixed for a certain period of time; the supercapacitor is taken out and cooled to 25°C, and then the charge and discharge test is performed. Cycle and calculate the capacity retention and ESR growth rate of the supercapacitor.
  • test conditions are the same as pre-cycle, and calculate the capacity and ESR of the supercapacitor.
  • Example 2 The same was true except that the solute, solvent and concentration of the electrolytic solution were different from those in Example 1.
  • the solute, solvent and concentration compositions of the electrolytic solutions of the respective examples are shown in Table 1, and the electrical conductivity at 25 ° C was measured.
  • the results are shown in Table 2-5.
  • the supercapacitors were fabricated using these electrolytes and tested for electrochemical performance. The life, capacity and ESR test results are listed in Table 2-5, respectively.
  • Example 9 N,N-dimethylpyrrolidine ammonium hexafluorophosphate Acetonitrile 1mol/L
  • Example 10 N-methyl-N-ethylpyrrolidine bis(trifluoromethylsulfonyl)imide ammonium Acetonitrile 1mol/L
  • Example 11 N,N-dimethylpiperidine bis(fluorosulfonyl)imide ammonium Acetonitrile 1mol/L
  • Example 11 N,N-dimethylpiperidine bis(fluorosulfonyl)imide ammonium Acetonitrile 1mol/L
  • the supercapacitor made by using the conventional solute to prepare the electrolyte at high voltage (2.7V and above), the life of the capacitor is greatly shortened, and the life of the capacitor is attenuated as the cutoff voltage increases. More severe; poor capacity and ESR performance at -40 ° C (or -50 ° C).

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  • 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)
  • Secondary Cells (AREA)

Abstract

La présente invention concerne un soluté d'électrolyte, un électrolyte et un supercondensateur. De la pyrrolidine disubstituée d'alkyle ou de la pipéridine ayant de un à trois atomes de carbone sert de cation d'un soluté d'électrolyte et un supercondensateur est fabriqué à partir d'un électrolyte préparé avec le soluté d'électrolyte obtenu. Un système AN ​​peut fonctionner de manière stable pendant une longue période à la tension de 2,85 V à 3,2 V et dans la plage de températures de fonctionnement de -50 °C à 65 °C, et un système PC peut fonctionner de façon stable pendant une longue période à la tension de 2,7 V à 3,0 V et dans la plage de températures de fonctionnement de -40 °C à 70 °C. La densité d'énergie est grandement améliorée, et la propriété de haute densité de puissance est maintenue. L'exigence d'une plage de températures de fonctionnement plus étendue dans le domaine de l'énergie peut être satisfaite, et une plage d'application du supercondensateur est augmentée. En particulier, la durée de vie du supercondensateur est considérablement prolongée, et la capacité et la performance ESR à basse température sont sensiblement améliorées.
PCT/CN2015/089163 2015-07-08 2015-09-08 Soluté d'électrolyte, électrolyte et supercondensateur WO2017004884A1 (fr)

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CN201510399883.2A CN104979102A (zh) 2015-07-08 2015-07-08 一种电解液溶质、电解液及超级电容器
CN201510399883.2 2015-07-08

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CN107424848B (zh) * 2016-05-24 2020-01-07 深圳新宙邦科技股份有限公司 一种用于超级电容器的电解液、超级电容器
CN108573816B (zh) * 2017-03-14 2020-07-10 深圳新宙邦科技股份有限公司 用于超级电容器的有机电解液及超级电容器
CN107910196A (zh) * 2017-11-06 2018-04-13 肇庆绿宝石电子科技股份有限公司 一种高电压超级电容器

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CN1641922A (zh) * 2004-01-15 2005-07-20 松下电器产业株式会社 电化学元件用非水电解液
CN101615515A (zh) * 2008-06-25 2009-12-30 Tdk株式会社 光电转换元件
CN102217015A (zh) * 2008-11-14 2011-10-12 大金工业株式会社 双电层电容器
CN103201806A (zh) * 2010-11-10 2013-07-10 大金工业株式会社 双电层电容器用电解液

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EP1394824A4 (fr) * 2001-05-11 2008-01-23 Mitsubishi Chem Corp Solution electrolytique pour condensateur electrolytique et condensateur electrolytique utilisant cette solution
JP2008205485A (ja) * 2003-12-05 2008-09-04 Masayuki Yoshio 黒鉛を用いた電気二重層キャパシタ用正電極及び電気二重層キャパシタ
CN102306549A (zh) * 2011-06-30 2012-01-04 深圳市惠程电气股份有限公司 一种聚酰亚胺超级电容器及其制备方法
CN102432474B (zh) * 2011-09-19 2014-03-19 渤海大学 超级电容器用高纯度四氟硼酸季铵盐的制备方法
CN103730263A (zh) * 2013-12-27 2014-04-16 深圳新宙邦科技股份有限公司 一种用于超级电容器的有机电解液及超级电容器

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CN1641922A (zh) * 2004-01-15 2005-07-20 松下电器产业株式会社 电化学元件用非水电解液
CN101615515A (zh) * 2008-06-25 2009-12-30 Tdk株式会社 光电转换元件
CN102217015A (zh) * 2008-11-14 2011-10-12 大金工业株式会社 双电层电容器
CN103201806A (zh) * 2010-11-10 2013-07-10 大金工业株式会社 双电层电容器用电解液

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