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    • 专利摘要:

    公开号:NL2015030A
    申请号:NL2015030
    申请日:2015-06-25
    公开日:2016-03-30
    发明作者:Zheng Zhongtian；Cao Yingjie；Cao Chaowei；Xue Longliang；Xiang Xiaoxia
    申请人:Shenzhen Capchem Technology Co Ltd；
    IPC主号:
    专利说明:

    ELECTROLYTE, AND HIGH-VOLTAGE SUPERCAPACITOR
    BACKGROUND
    Technical Field
    The present invention relates to the electrochemical field, particularly to an electrolyte that is used for a high-voltage supercapacitor, and a high-voltage supercapacitor using the electrolyte.
    Related Art A supercapacitor, also referred to as gold capacitor or electrochemical capacitor, stores energy by means of ion adsorption (electric double layer capacitor) or a rapid surface redox reaction (pseudocapacitor). The supercapacitor is a novel energy storage device in between a cell and a conventional static capacitor. The number of charges stored by the supercapacitor is hundreds or thousands of times of that of a conventional electrolytic capacitor, and the supercapacitor can be completely charged or discharged within a few seconds, which has power input or output higher than that of a cell and can reach such power input or output in a shorter period of time. At the same time, the supercapacitor has the advantages of short charge and discharge time, long storage service life, high stability and wide operating temperature range (-40°C to 70°C), and has been widely applied in the field of consumer electronics products, the field of new energy generation systems, the field of distributed energy storage systems, the field of intelligent distributed grid systems, the transportation field such as new energy vehicles, the load field such as energy-saving elevators and cranes, the field of military equipment such as electromagnetic bombs, the motion control field, and the like, involving various sectors such as new energy generation, smart grid, new energy vehicles, energy-efficient buildings, industrial energy conservation and emissions reduction, and belongs to standard full range of low-carbon economy core products.
    Compared with an electrochemical cell, the supercapacitor has a lower energy density and working voltage, and these disadvantages greatly limit the application of the supercapacitor in hybrid vehicles and electric vehicles. The energy storage formula of the supercapacitor is E=CV2/2, and therefore, the energy density of the supercapacitor can be effectively improved by increasing the working voltage of the supercapacitor. However, when working at a voltage exceeding 2.7 V, an electrolyte of a currently commercialized supercapacitor may be electrochemically decomposed, resulting in a significant increase in the pressure within the capacitor, and a significant decrease in the electrochemical performance, and finally resulting in a failure of the capacitor.
    The working voltage of the capacitor is determined by the decomposition voltage of the electrolyte, and therefore, the bottleneck of the supercapacitor can be effectively broken through by developing an electrolyte used by a high-voltage supercapacitor, especially by finding a high-withstand voltage solute, and moreover, a good balance between a high withstand voltage and a long service life of the supercapacitor can further be achieved. Chinese Patent Publication No. CN100536048C discloses an electrolyte of a supercapacitor containing a mixture of N,N-dihaloalkyl-l,4-cis-l,4-bicyclic octane ammonium tetrafluoroborate and conventional tetraethyl ammonium tetrafluoroborate (EÏ4NBF4). The electrolyte of the supercapacitor has a certain high pressure resistance, but the service life characteristic of the supercapacitor is not described. Chinese Patent Publication No. CN101809693A sets forth that various acid scavengers are added to a conventional Et4NBF4 acetonitrile (AN) solution to alleviate an increasing rate of pressure in a capacitor, so as to achieve the purpose of improving a working voltage of the supercapacitor. This method can have a certain effect in the early period of using the supercapacitor, but with the extension of the service life, the electrochemical performance of the capacitor is significantly degraded, and the service life characteristic of the capacitor needs to be significantly improved.
    SUMMARY
    In view of this, an objective of the present invention is to provide an electrolyte solute and an electrolyte that are used for a high-voltage supercapacitor, and a supercapacitor, so as to improve the energy density of the supercapacitor, and realizing the long-service life characteristic of the supercapacitor. A technical solution used by the present invention is to provide an electrolyte solute, having a chemical structural formula of one or more of a structural formula 1, a structural formula 2, and a structural formula 3 below:
    Structural formula 1 Structural formula 2
    Structural formula 3 where R, Ri, R2, R3 and R4 are respectively a hydrocarbyl group containing 1 to 5 carbon atoms (which may form cyclization in pairs), 'A is an anion, n and m are the number of substituents on the ring, n is an integer of 0 to 6, and m is an integer of 0 to 7.
    Furthermore, a cation of the electrolyte solute is one or more of: N-methyl-1,4-diazabicyclo[2.2.2]octane ammonium, N-ethyl-l,4-diazabicyclo[2.2.2]octane ammonium, N,N-dimethyl-l ,4-diazabicyclo[2.2.2]octane ammonium, N-methyl-N-ethyl-1,4-diazabicyclo[2.2.2]octane ammonium, N,N-diethyl-l ,4-diazabicyclo[2.2.2]octane ammonium, N-methyl-1-azabicyclo[2.2.2]octane ammonium, and N-ethyl-1 -azabicyclo[2.2.2]octane ammonium.
    Furthermore, the cation of the electrolyte solute is one or more of: N-methyl-1,4-diazabicyclo[2.2.2]octane ammonium, N,N-dimethyl-l,4-diazabicyclo[2.2.2]octane ammonium, and N-methyl-1 -azabicyclo[2.2.2]octane ammonium.
    Furthermore, the anion of the electrolyte solute is one or more of: tetrafluoroborate, hexafluorophosphate, bis(fluorosulfonyl) imide, bis(trifluoromethylsulfonyl) imide, tris(trifluoromethylsulfonyl) methyl, and perfluoroalkyl sulfonate.
    Furthermore, the anion of the electrolyte solute is tetrafluoroborate.
    Furthermore, the high-voltage supercapacitor is a supercapacitor having a charge cut-off voltage of 2.7 V to 3.2 V.
    Another technical solution of the present invention is to provide an electrolyte, used for a high-voltage supercapacitor, including a solvent and a solute, and the solute contains the electrolyte solute according to any one of the items above.
    Furthermore, in the electrolyte, the solvent is one of or a mixed solvent of two or more of nitriles, ethers, amides, esters and sulfones solvent.
    Furthermore, the solvent in the electrolyte is one of or a mixed solvent of two or more of acetonitrile, propionitrile, butyronitrile, methoxypropionitrile, ethylene carbonate, dimethyl carbonate, propylene carbonate, γ-butyrolactone, γ-valerolactone, 1,3-propane sultone, 1,4-butane sultone, sulfolane, methyl ethyl sulfone, dimethyl sulfone, diethyl sulfone, dimethyl sulfoxide, diethyl sulfoxide, and tetramethylene sulfoxide.
    Another technical solution of the present invention is to provide a high-voltage supercapacitor, including an electrolyte and an electricity core immersed in the electrolyte, where the electricity core includes two collector electrodes and a membrane disposed in the middle of the two collector electrodes, activated carbon is adhered on the two collector electrodes, the electrolyte solute contains A, and A is one or more of substances having a chemical structural formula of the structural formula 1, the structural formula 2, and the structural formula 3, where R, Ri, R2, R3 and R4 are respectively a hydrocarbyl group containing 1 to 5 carbon atoms, Ά is an anion, n and m are the number of substituents on the ring, n is an integer of 0 to 6, and m is an integer of 0 to 7.
    In the solutions above, the concentration of A in the electrolyte is 0.05 to 2.0 mol/L, and preferably 0.5 to 1.5 mol/L.
    Furthermore, the cation of A in the high-voltage supercapacitor is one or more of: N-methyl-1,4-diazabicyclo[2.2.2]octane ammonium, N,N-dimethyl-l,4-diazabicyclo[2.2.2]octane ammonium, and N-methyl-1 -azabicyclo[2.2.2]octane ammonium.
    Furthermore, in the high-voltage supercapacitor, the anion is one or more of : tetrafluoroborate, hexafluorophosphate, bis(fluorosulfonyl) imide, bis(trifluoromethylsulfonyl) imide, tris(trifluoromethylsulfonyl) methyl, and perfluoroalkyl sulfonate.
    Furthermore, in the high-voltage supercapacitor, the solvent is one of or a mixed solvent of two or more of acetonitrile, propionitrile, butyronitrile, methoxypropionitrile, ethylene carbonate, dimethyl carbonate, propylene carbonate, γ-butyrolactone, γ-valerolactone, 1,3-propane sultone, 1,4-butane sultone, sulfolane, methyl ethyl sulfone, dimethyl sulfone, diethyl sulfone, dimethyl sulfoxide, diethyl sulfoxide, and tetramethylene sulfoxide.
    Furthermore, the charge cut-off voltage of the high-voltage supercapacitor is 2.7 V to 3.2 V.
    Preferably, the charge cut-off voltage of the high-voltage supercapacitor is 2.7 to 3.0 V, the electrolyte solute is N-methyl-1 -azabicyclo[2.2.2]octane ammonium, and the solvent is propylene carbonate.
    Preferably, the charge cut-off voltage of the high-voltage supercapacitor is 2.8 to 3.2 V, the electrolyte solute is N-methyl-1,4-diazabicyclo[2.2.2]octane ammonium, and the solvent is acetonitrile.
    The present invention has the following beneficial effects: the high-voltage supercapacitor fabricated by using the electrolyte formulated by the electrolyte solute of the present invention can work stably for a long period of time at a voltage of 2.7 V to 3.2 V, the energy density is greatly increased, the property of high power density is maintained, and the working life of the high-voltage supercapacitor is greatly prolonged.
    BRIEF DESCRIPTION OF THE DRAWINGS
    No drawings.
    DETAILED DESCRIPTION
    In order to illustrate the technical contents, structural characteristics, the purpose and effects to be achieved of the present invention in detail, the present invention is described below in detail with embodiments.
    The electrolyte solute in the present invention can be synthesized by using the following method: a corresponding organic amine (such as l,4-diazabicyclo[2.2.2]octane) and dimethyl carbonate (DMC) at a certain molar ratio (DMC/ l,4-diazabicyclo[2.2.2]octane=1.0 to 2.5) are reacted to generate a quaternary ammonium base; the quaternary ammonium base reacts with an acid (such as HBF4) or an ammonium salt (such as NH4PF6) or an organic metal salt (such as L1CF3SO3) containing a corresponding anion to obtain a crude product; and the crude product is purified through recrystallization in a suitable solvent, to obtain a capacitor grade high-purity solute salt. A supercapacitor model is assembled in a glove box: An electricity core including two collector electrodes fabricated by using aluminum foil, two working electrodes fabricated by using activated carbon, and a fiber membrane inserted between the electrodes is wound into a core package, but not limited to this structure. The electricity core is immersed in an electrolyte in the following comparative examples and embodiments, and is assembled and sealed by using an aluminum case and particles. A supercapacitor testing process includes: (1) precycling (10 times): charging at 25°C, a charge cut-off voltage of U, and a constant current of 10 mA/F; and discharging at a lower limit voltage of U/2 and a constant current of 10 mA/F; (2) in a high-temperature test chamber of 65°C, charging at a constant current of 10 mA/F to an upper limit voltage of U, and maintaining at this voltage (U) for a certain period of time; (3) taking out the supercapacitor and cooling to 25°C, then subjecting the supercapacitor to charge-discharge test under the same test condition as that in precycling, and calculating the capacity retention ratio and rate of increase of ESR of the supercapacitor; and (4) taking the capacity retention ratio of less than or equal to 60%, and/or the rate of increase of ESR of greater than or equal to 100% as the judgment standards for the service life of the supercapacitor.
    Embodiment 1
    An electrolyte of 1.0 mol/L was formulated by using N-methyl-l,4-diazabicyclo[2.2.2]octane ammonium tetrafluoroborate (MDACOBF4) as the solute and AN as the solvent, and the conductivity at 25°C was determined. The solute, the solvent, and the concentration of the electrolyte were adjusted as specifically described in the following embodiments and comparative examples, and the results of conductivity were listed in Table 1. The supercapacitor was fabricated by using the electrolyte of this embodiment and was tested for the electrochemical performance, and the test results of service life were listed in Table 2.
    Embodiments 2 to 12
    The conditions were the same as those in Embodiment 1, the solute, the solvent, and the concentration of the electrolyte were adjusted, and the detailed data was shown in Tables 2 to 5. The chemical structural formulas of the solutes were as follows:
    mdabcobf4
    DMDABCO(BF4)2
    mabcobf4.
    The supercapacitors were fabricated by using the electrolytes of these embodiments, and were tested for the electrochemical performance, and the test results of service life were listed in Tables 2 to 5.
    Comparative example 1
    An electrolyte of 1.0 mol/L was formulated by using tetraethyl ammonium tetrafluoroborate as the solute and AN as the solvent, the conductivity at 25°C was determined, and the results were listed in Table 1. The supercapacitor fabricated by using the electrolyte of this embodiment was tested for the electrochemical performance, and the test results of service life were listed in Table 2.
    Comparative examples 2 to 5
    The conditions were the same as those in Comparative example 1, the solute, the solvent, and the concentration of the electrolyte were adjusted, and the detailed data was shown in Tables 2 to 5. The supercapacitors were fabricated by using the electrolytes of these embodiments, and were tested for the electrochemical performance, and the test results of service life were listed in Tables 2 to 5.
    Table 1 Conductivity of the electrolytes at 25°C
    Table 2 Data of service life of the capacitors
    Table 3 Data of service life of the capacitors
    Table 4 Data of service life of the capacitors
    Table 5 Data of service life of the capacitors
    It can be clearly seen from data in Tables 2 to 5 that, in different solvent systems, at different cut-off voltages, for the supercapacitor fabricated by using the high-voltage solute of the present invention, the service life is significantly prolonged, and the electrochemical performance is significantly improved. It can be seen from the comparative examples that, for the supercapacitor fabricated by using the electrolyte prepared by using the conventional solute, at a high voltage (2.7 V and more), the service life of the capacitor is greatly shortened, and with an increase in the cut-off voltage, the service life of the capacitor attenuates severely.
    The embodiments described above are merely embodiments of the present invention, but the patent scope of the present invention is not limited thereto. Any equivalent structure or equivalent process transformation made by using the specification of the present invention directly or indirectly applied in other relevant technical fields shall fall within the protection scope of the present invention.
    权利要求:
    Claims (11)
    [1]
    An electrolyte used for a high voltage capable capacitor comprising a solvent and a solute, the solute comprising A, wherein A is one or more of substances having a chemical structural formula according to a structural formula 1, a structural formula 2 and a structural formula 3 as below:



    Structural formula 1 Structural formula 2

    Structural formula 3 wherein R, R1, R2, R3, and R4 are respectively a hydrocarbyl group comprising 1-5 carbon atoms, 'A is an anion, n and m is the number of substituents on the ring, n is an integer from 0-6 , and m is an integer from 0-7.
    [2]
    The electrolyte according to claim 1, wherein the solvent is one of, or a mixed solvent of, two or more of a solvent based on nitriles, ethers, amides, esters and sulfones.
    [3]
    The electrolyte of claim 2, wherein the solvent is one of, or a mixed solvent of, two of, acetonitrile, propionitrile, butyronitrile, methoxypropionitrile, ethylene carbonate, dimethyl carbonate, propylene carbonate, γ-butyrolactone, γ-valerolactone, 1,3-propane sultone , 1,4-butane sultone, sulfolane, methyl ethyl sulfone, dimethyl sulfone, diethyl sulfone, dimethyl sulfoxide, diethyl sulfoxide, and tetramethylene sulfoxide
    [4]
    4. A high voltage capable super capacitor, comprising an electrolyte and an electrical core immersed in the electrolyte, the electrical core comprising two collector electrodes and a membrane located in the center of the two collector electrodes, activated carbon bonded to the two collector electrodes, the solute of the electrolyte comprises A, wherein A is one or more of substances having a chemical structural formula according to the structural formula 1, the structural formula 2 and the structural formula 3, wherein R, R1, R2, R3 and R4 are respectively a hydrocarbyl group 1-5 contains carbon atoms, 'A is an anion, letter n and m are the number of substituents on the ring, n is an integer from 0-6, and m is an integer from 0-7.
    [5]
    The high voltage suitable super capacitor according to claim 4, wherein the cation of A is one or more of: N-methyl-1,4-diazabicyclo [2.2.2] octane ammonium, Ν, Ν-dimethyl-1,4-diazabicyclo [ 2.2.2] octane ammonium, and N-methyl-1-azabicyclo [2.2.2] octane ammonium.
    [6]
    The high voltage suitable super capacitor according to claim 4, wherein the anion is one or more of: tetrafluoroborate, hexafluorophosphate, bis (fluorosulfonyl) imide, bis (trifluoromethylsulfonyl) imide, tris (trifluoromethylsulfonyl) methyl, and perfluoroalkyl sulfonate.
    [7]
    The high-voltage suitable super capacitor according to claim 4, wherein the solvent is one of, or a mixed solvent of, two of, acetonitrile, propionitrile, butyronitrile, methoxypropionitrile, ethylene carbonate, dimethyl carbonate, propylene carbonate, γ-butyrolactone, γ-valerolactone, 1 3-propane sultone, 1,4-butane sultone, sulfolane, methyl ethyl sulfone, dimethyl sulfone, diethyl sulfone, dimethyl sulfoxide, diethyl sulfoxide, and tetramethylene sulfoxide.
    [8]
    The high voltage suitable super capacitor according to claim 4, wherein the charge cut-off voltage is 2.7-3.2 volts.
    [9]
    The high voltage suitable super capacitor according to claim 4, wherein the charge cut off voltage is 2.7-3.0 volts, the electrolyte solute is N-methyl-1-azabicyclo [2.2.2] octane ammonium, and the solvent is propylene carbonate.
    [10]
    The high voltage suitable super capacitor according to claim 4, wherein the charge cut-off voltage is 2.8-3.2 volts, the solute of the electrolyte is N-methyl-1,4-diazabicyclo [2.2.2] octane ammonium, and the solvent is acetonitrile.
    [11]
    A high voltage suitable super capacitor according to any of claims 4-10, wherein the concentration of A in the electrolyte is 0.5-1.5 mol / L.
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    引用文献:
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    CN101261899A|2008-04-24|2008-09-10|李青海|A high working voltage super capacitor and its making method|
    JP2011159895A|2010-02-03|2011-08-18|Japan Carlit Co Ltd:The|Electrolyte for electric double layer capacitor, and electric double layer capacitor|
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    CN103730263A|2013-12-27|2014-04-16|深圳新宙邦科技股份有限公司|Organic electrolytic solution for super capacitor and super capacitor|CN106920702B|2015-12-28|2018-09-21|江苏国泰超威新材料有限公司|A kind of electrolyte for double-layer capacitor and double layer capacitor|
    CN107910196A|2017-11-06|2018-04-13|肇庆绿宝石电子科技股份有限公司|A kind of high tension super capacitor|
    CN110379645B|2019-07-18|2020-10-09|中国科学院长春应用化学研究所|Mixed salt electrolyte for high-voltage super capacitor and application thereof|
    法律状态:
    优先权:
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