WO2011065780A2 - Solution d'électrolyte et supercondensateur l'incluant - Google Patents

Solution d'électrolyte et supercondensateur l'incluant Download PDF

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Publication number
WO2011065780A2
WO2011065780A2 PCT/KR2010/008449 KR2010008449W WO2011065780A2 WO 2011065780 A2 WO2011065780 A2 WO 2011065780A2 KR 2010008449 W KR2010008449 W KR 2010008449W WO 2011065780 A2 WO2011065780 A2 WO 2011065780A2
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WO
WIPO (PCT)
Prior art keywords
electrolyte solution
propionitrile
alkyl
sulfolane
solvent
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.)
Ceased
Application number
PCT/KR2010/008449
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English (en)
Korean (ko)
Other versions
WO2011065780A3 (fr
Inventor
최재훈
박정호
김진호
강주식
장유미
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SK Chemicals Co Ltd
Original Assignee
SK Chemicals Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by SK Chemicals Co Ltd filed Critical SK Chemicals Co Ltd
Publication of WO2011065780A2 publication Critical patent/WO2011065780A2/fr
Publication of WO2011065780A3 publication Critical patent/WO2011065780A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • 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 an electrolyte solution and an ultracapacitor including the same, and more particularly, an electrolyte solution having a low gas generation even at a high temperature used in an ultracapacitor such as an electric double layer capacitor, and having an excellent high temperature reliability. It relates to a high capacity capacitor.
  • the ultracapacitor is an energy storage device with intermediate characteristics between an electrolytic capacitor and a secondary battery. It is capable of rapid charging and discharging, and has characteristics such as high efficiency, a wide operating temperature range, and a semi-permanent lifespan. Electric Double-Layer Capacitor) can be exemplified.
  • Ultracapacitors such as electric double layer capacitors
  • the characteristics are very important as the differentiated characteristics of the capacitor.
  • a solvent is mainly acetonitrile (AN) or propylene carbonate (PC), and the electrolyte salt is tetraethylammonium tetrafluoro.
  • Ammonium salts such as borate (TEABF 4 ) and lithium metal salts (eg LiBF 4 , LiPF 6 ) are often used.
  • acetonitrile (AN) is used as the solvent of the electrolyte solution
  • the boiling point (81 to 82 ° C) of the solvent itself is low, so that a large amount of gas is generated at a relatively high temperature
  • propylene carbonate (PC) is used
  • the high boiling point (240 °C) is advantageous in terms of high temperature reliability, but it is not necessarily advantageous for high voltage operation because it has more side reactions than acetonitrile (AN), and its output characteristics are relatively low due to its high viscosity and low conductivity. There are disadvantages.
  • an object of the present invention is to provide an electrolyte solution having a low amount of gas generation at a high temperature and excellent in high temperature reliability, and an ultracapacitor including the same.
  • At least one solvent selected from the group consisting of propionitrile and gamma butyrolactone, alkyl gamma butyrolactone, propylene carbonate, glutaronitrile, sulfolane and alkyl sulfolane Mixed solvents mixed above; And an electrolyte salt.
  • the electrolyte salt is a cation selected from the group consisting of a spiro structural compound of tetraalkyl ammonium, pyrrolidium, piperidium, pyrrolidium or piperidium and tetrafluoroborate, hexafluorophosphate, perchlorate, hexafluoroarsen It is preferable that an anion selected from the group consisting of nate, bis (trifluoromethylsulfonyl) imide and trifluoromethylsulfonate is bonded, and the weight ratio of the solvent mixed with the propionitrile and the propionitrile ( Propionitrile: solvent mixed with propionitrile) is preferably 1: 9 to 7: 3.
  • the present invention provides an ultracapacitor including the electrolyte solution.
  • the electrolyte solution according to the present invention is a solvent having high dielectric constant and high boiling point such as propionitrile and (alkyl) gamma butyrolactone, propylene carbonate, glutaronitrile, and (alkyl) sulfolane, which have excellent high temperature reliability and voltage characteristics. It is characterized by using a mixed solvent in which at least one solvent is mixed, and the ultra-capacitor using the electrolyte solution is excellent in high temperature reliability, output characteristics and maximum operating voltage characteristics, and the amount of gas generated in the capacitor even at high temperatures.
  • the electrolyte solution according to the present invention is propionitrile and gamma butyrolactone, alkyl gamma butyrolactone, propylene carbonate, glutaronitrile, glutaronitrile, sulfolane and Mixed solvents and electrolyte salts in which at least one solvent selected from the group consisting of alkyl sulfolanes are mixed.
  • the mixed solvent used in the present invention has properties similar to acetonitrile, but has a higher boiling point, excellent high temperature reliability, and good propionitrile with good voltage characteristics. From the group consisting of gamma-butyrolactone, alkyl gamma-butyrolactone, propylene carbonate, glutaronitrile, sulfolane and alkyl sulfolane One or more solvents selected are mixed with the propionitrile.
  • the alkyl gamma butyrolactone is gamma butyrolactone substituted with an alkyl group having 1 to 4 carbon atoms
  • the alkyl sulfolane is a sulfolane substituted with an alkyl group having 1 to 4 carbon atoms.
  • the weight ratio of the propionitrile and the solvent mixed with the propionitrile is 1: 9 to 7: 3, preferably 2: 8 to 5: 5.
  • the weight ratio of the propionitrile and the solvent mixed with the propionitrile is out of the above range and the content of propionitrile having a relatively low electrolyte salt solubility becomes high, it may be difficult to prepare a high concentration electrolyte solution, When the content of propionitrile is too small, there is a fear that the viscosity of the electrolyte solution increases and the conductivity, output characteristics, high temperature reliability, and the like decrease.
  • electrolyte salts used in ultracapacitors such as electric double layer capacitors can be used, and preferably tetraalkyl ammonium (for example, tetraethyl ammonium, tetrapropyl ammonium, tetrabutyl).
  • tetraalkyl ammonium for example, tetraethyl ammonium, tetrapropyl ammonium, tetrabutyl.
  • Spiro structural compounds e.g., spiro-1,1'-bipyrrolidinium, spiro- peperidine-1,1'-pyrrolidinium), pyrrolidinium, peperidinium, pyrrolidium or piperidium etc.
  • borate BF 4 with positive and tetrafluoroethane are selected from the group consisting of -), phosphate (PF 6 hexafluoro -), perchlorate (ClO 4 -), carbonate Arsene hexafluorophosphate (AsF 6 -), bis ( methylsulfonyl trifluoromethanesulfonyl) imide ((CF 3 SO 2) 2 N - can be used for the electrolyte salt anion is coupled is selected from the group consisting of a) -), and trifluoromethyl sulfonate (SO 3 CF 3 .
  • PF 6 hexafluoro - perchlorate
  • the concentration of the electrolyte salt is preferably 0.5 to 2.0 M (molar concentration), more preferably 0.8 to 1.5 M.
  • concentration of the electrolyte salt is less than 0.5M, the conductivity of the electrolyte solution may be lowered to increase the resistance of the capacitor. If the concentration exceeds 2.0M, the electrolyte salt may not be completely dissolved or may be partially precipitated at a low temperature. There is a fear that the conductivity of rather decreases.
  • the ultracapacitor according to the present invention includes the electrolyte solution.
  • the ultracapacitor includes an electrode part consisting of a positive electrode and a negative electrode, a separator for electrically separating the positive electrode and the negative electrode, and the positive electrode and the negative electrode such that an electric double layer is formed on the surfaces of the positive electrode and the negative electrode when a predetermined voltage is applied.
  • a typical electric double layer capacitor including an electrolyte solution filled in a space between them can be exemplified.
  • Propionitrile and propylene carbonate were purified to a high purity solvent of 99.95% (GC) or more using a 50-stage distillation apparatus, respectively, to prepare a mixed solvent of weight ratio 1: 2 (propionitrile: propylene carbonate).
  • a mixed solvent of weight ratio 1: 2 (propionitrile: propylene carbonate).
  • tetraethylammonium tetrafluoroborate (trade name: SkyLyte-TEABF 4 , manufacturer: SK Chemical Co., Ltd., 99.9%) was dissolved in the mixed solvent to prepare a 1M electrolyte solution.
  • the conductivity of the prepared electrolyte solution was measured with a conductivity meter (Thermo, Orion 136S) at 25 ° C., and the results are shown in Table 1 below.
  • Propionitrile and gammabutyrolactone were purified using a 50-stage distillation apparatus to obtain a high purity solvent of 99.95% (GC) or more, respectively, and a mixed solvent of 1: 2 (propionitrile: gammabutyrolactone) by weight ratio.
  • GC 99.95%
  • a mixed solvent 1: 2 (propionitrile: gammabutyrolactone) by weight ratio.
  • tetraethylammonium tetrafluoroborate (trade name: SkyLyte-TEABF 4 , manufacturer: SK Chemical Co., Ltd., 99.9%) was dissolved in the mixed solvent to prepare a 1M electrolyte solution.
  • the conductivity of the prepared electrolyte solution was measured with a conductivity meter (Thermo, Orion 136S) at 25 ° C., and the results are shown in Table 1 below.
  • Propionitrile and ⁇ -methyl-gammabutyrolactone were purified to have a high purity solvent of 99.95% (GC) or more using a 50-stage distillation unit each, and a weight ratio of 1: 2 (propionitrile: ⁇ -methyl- A mixed solvent of gamma butyrolactone) was prepared.
  • tetraethylammonium tetrafluoroborate (trade name: SkyLyte-TEABF 4 , manufacturer: SK Chemical Co., Ltd., 99.9%) was dissolved in the mixed solvent to prepare a 1M electrolyte solution.
  • the conductivity of the prepared electrolyte solution was measured with a conductivity meter (Thermo, Orion 136S) at 25 ° C., and the results are shown in Table 1 below.
  • Acetonitrile (AN) was purified to a high purity solvent of 99.95% (GC) or higher using a theoretical 50-stage distillation apparatus, and tetraethylammonium tetrafluoroborate (product name: SkyLyte-TEABF) was purified on purified acetonitrile (AN). 4 , Manufacturer: SK Chemical Co., Ltd., 99.9%) was dissolved to prepare a 1M electrolyte solution. The conductivity of the prepared electrolyte solution was measured with a conductivity meter (Thermo, Orion 136S) at 25 ° C., and the results are shown in Table 1 below.
  • a conductivity meter Thermo, Orion 136S
  • the propylene carbonate (PC) was purified to a high purity solvent of 99.95% (GC) or more using a 50-stage distillation unit, and tetraethylammonium tetrafluoroborate (product name: SkyLyte-TEABF) was purified on the purified propylene carbonate (PC). 4 , Manufacturer: SK Chemical Co., Ltd., 99.9%) was dissolved to prepare a 1M electrolyte solution. The conductivity of the prepared electrolyte solution was measured with a conductivity meter (Thermo, Orion 136S) at 25 ° C., and the results are shown in Table 1 below.
  • a conductivity meter Thermo, Orion 136S
  • GBL Gamma-butyrolactone
  • GC cyclopentadiene
  • GBL tetraethylammonium tetrafluoroborate
  • GL gamma-butyrolactone
  • SkyLyte-TEABF 4 manufacturer: SK Chemical Co., Ltd., 99.9%
  • the conductivity of the prepared electrolyte solution was measured with a conductivity meter (Thermo, Orion 136S) at 25 ° C., and the results are shown in Table 1 below.
  • the slurry solution was coated on aluminum foil (Al Foil) and roll pressed to prepare activated carbon electrodes used as a positive electrode and a negative electrode. Next, the prepared electrode was cut into a size of 5 cm ⁇ 5 cm, and the anode, a separator (PP: polypropylene, manufacturer: Celgard), and the cathode were placed in this order, and then inserted into a pouch.
  • Example 1 to 3 and Comparative Examples 1 to 3 The prepared electrolyte solution was injected into the pouch to prepare a pouch type capacitor.
  • the basic characteristics (capacitance) of capacitors manufactured using an electrochemical analyzer (Electrochemical Analyzer, manufacturer: CH Instrument, product name: 608B) were evaluated, and a high temperature acceleration test was carried out at 75 ° C. for 1000 hours, before and after high temperature load.
  • the change of the characteristics (% reduction in capacitance) was compared, and the change in pouch thickness according to the gas generated inside the pouch type capacitor was compared. The results are shown in Table 1 below.
  • the capacitor (Comparative Example 4) to which the electrolyte solution (Comparative Example 1) using acetonitrile (AN) as a solvent is high in conductivity, but the pouch is inflated due to the large amount of gas generated at high temperature (75 ° C). It can be seen that it is not suitable to use at high temperature, and the capacitor (Comparative Example 5) and the gamma butyrolactone (GBL) to which the electrolyte solution (Comparative Example 2) using propylene carbonate (PC) as the solvent are used as the solvent. It can be seen that the capacitor (Comparative Example 6) to which the solution (Comparative Example 3) is applied has a relatively higher rate of decrease in capacitance after the high temperature acceleration test.
  • the capacitors (Examples 4 to 6) to which the electrolyte solutions (Examples 1 to 3) according to the present invention are applied have a very low capacitance reduction rate and a small amount of gas generated according to the high temperature acceleration test. It can be seen that the conductivity of can be greatly improved.
  • the electrolyte solution of the present invention is useful for ultracapacitors such as electric double layer capacitors, and the supercapacitors using the electrolyte solution have excellent high temperature reliability, output characteristics and maximum operating voltage characteristics, It can be seen that the generation amount is small.
  • the electrolyte solution according to the present invention is useful for ultracapacitors such as electric double layer capacitors.

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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)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

La présente invention concerne une solution d'électrolyte, qui est utilisée pour un supercondensateur tel qu'un condensateur double couche électrique ou similaires, a une faible vitesse de génération de gaz même à haute température, et présente une excellente fiabilité à haute température. L'invention concerne en outre le supercondensateur la comprenant. La solution d'électrolyte comprend : un solvant mixte qui est un mélange comprenant au moins un type de solvants choisis dans un groupe qui comprend le propionitrile et la gamma-butyrolactone, une alkyl gamma-butyrolactone, du carbonate de propylène, du glutaronitrile, et du sulfolane et un alkyl sulfolane ; et un sel d'électrolyte.
PCT/KR2010/008449 2009-11-30 2010-11-26 Solution d'électrolyte et supercondensateur l'incluant Ceased WO2011065780A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020090116787A KR20110060253A (ko) 2009-11-30 2009-11-30 전해질 용액 및 이를 포함하는 초고용량 커패시터
KR10-2009-0116787 2009-11-30

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WO2011065780A2 true WO2011065780A2 (fr) 2011-06-03
WO2011065780A3 WO2011065780A3 (fr) 2011-11-03

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019149812A1 (fr) * 2018-02-01 2019-08-08 Robert Bosch Gmbh Composition électrolytique pour cellule électrochimique pour des applications à haute température

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107527750A (zh) * 2017-08-23 2017-12-29 吴江佳亿电子科技有限公司 一种低温型的超级电容器电解液、其制备方法及超级电容器

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TW521451B (en) * 2000-03-13 2003-02-21 Canon Kk Process for producing an electrode material for a rechargeable lithium battery, an electrode structural body for a rechargeable lithium battery, process for producing said electrode structural body, a rechargeable lithium battery in which said electrode
DE10143172A1 (de) * 2001-09-04 2003-03-20 Solvay Fluor & Derivate Sulfonylsalze in der Elektrotechnik
EP1673830A2 (fr) * 2003-09-30 2006-06-28 Honeywell International Inc. Electrolyte avec temoin

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019149812A1 (fr) * 2018-02-01 2019-08-08 Robert Bosch Gmbh Composition électrolytique pour cellule électrochimique pour des applications à haute température

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WO2011065780A3 (fr) 2011-11-03
KR20110060253A (ko) 2011-06-08

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