WO2016090979A1 - 一种宽温高电压型超级电容器有机电解液及其制备方法 - Google Patents

一种宽温高电压型超级电容器有机电解液及其制备方法 Download PDF

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WO2016090979A1
WO2016090979A1 PCT/CN2015/089044 CN2015089044W WO2016090979A1 WO 2016090979 A1 WO2016090979 A1 WO 2016090979A1 CN 2015089044 W CN2015089044 W CN 2015089044W WO 2016090979 A1 WO2016090979 A1 WO 2016090979A1
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electrolyte
tetrafluoroborate
ammonium
organic electrolyte
salt
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PCT/CN2015/089044
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English (en)
French (fr)
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阮殿波
左飞龙
傅冠生
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宁波南车新能源科技有限公司
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Publication of WO2016090979A1 publication Critical patent/WO2016090979A1/zh

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    • 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
    • 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
    • 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
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • 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 invention relates to the technical field of supercapacitor electrolytes, in particular to a wide temperature and high voltage type supercapacitor organic electrolyte and a preparation method thereof.
  • Electrochemical electric double layer capacitors also known as super capacitors, extreme capacitors, etc.
  • the secondary battery has a larger power density, and has the advantages of high power density, long cycle life, wide operating temperature range, good cycle stability, maintenance-free, and environmentally friendly, and has been in many fields, such as rail transit, wind power generation, Hybrid electric vehicles and backup power supplies for electronic devices have shown broad application prospects.
  • Current supercapacitor organic system electrolytes are mainly composed of organic solvents and organic salts.
  • the solvent includes, for example, acetonitrile, propylene carbonate and the like
  • the organic salt includes ammonium tetraethylammonium tetrafluoroborate or ammonium triethylmethyltetrafluoroborate.
  • the operating voltage is typically 2.7V and the minimum operating temperature is -50°C. This is because the temperature is lower than -50 ° C, which causes the electrolyte to crystallize, and the capacitor cannot achieve the charge and discharge function.
  • Chinese Patent Application Publication No. CN102254691A, Application Publication Date 2011.11.23 discloses an electrolyte for a supercapacitor, which is made by adding a low melting point solvent to the main solvent of the electrolyte, acetonitrile or propylene carbonate. It has good ion conductivity at low temperatures, enabling supercapacitors to operate at low temperatures.
  • the disadvantage is that the low temperature electrolyte has poor high temperature resistance and high voltage resistance, and the application range is greatly limited.
  • the invention is to solve the problem that the prior art supercapacitor organic electrolyte can not simultaneously have low temperature resistance, high temperature and high voltage performance, so that the application range is greatly restricted, and the invention provides an excellent low temperature resistance at the same time. High temperature and high voltage resistance, wide range of high temperature and high voltage supercapacitor organic electrolytes.
  • the invention also provides a preparation method of a wide temperature high voltage type supercapacitor organic electrolyte, which has simple process steps, strong operability and is suitable for industrial production.
  • Wide-temperature high-voltage supercapacitor organic electrolyte which is composed of electrolyte salt, ionic liquid and mixed organic solvent.
  • concentration of electrolyte salt in organic electrolyte is 0.5-1.5mol/L
  • concentration of ionic liquid is 0.01. ⁇ 0.05 mol/L
  • the mixed organic solvent is prepared by mixing acetonitrile and a low melting point solvent in a volume ratio of 1:0.1 to 2.
  • the invention optimizes and improves the formulation of the supercapacitor organic electrolyte, and increases the high temperature resistance and high voltage resistance of the electrolyte while reducing the freezing point of the electrolyte by adding a low melting point solvent and an ionic liquid to the organic electrolyte, and the temperature range is used. Between -65 and 70 ° C, the temperature range is wide, with good low temperature resistance and high temperature resistance, and the withstand voltage range can reach 2.75V, and the high voltage resistance is good.
  • the electrolyte salt is tetraethylammonium tetrafluoroborate, ammonium tetramethyltetrafluoroborate, ammonium triethylmethyltetrafluoroborate, ammonium N,N-dimethylpyrrolidine tetrafluoroborate, N, N-diethylpyrrolidine ammonium tetrafluoroborate, N-methyl-N-ethylpyrrolidine ammonium tetrafluoroborate, N,N-dimethylpyrrolidine ammonium tetrafluoroborate, 5-aza spiro ring [4 , 4] one or more of decane ammonium tetrafluoroborate.
  • the ionic liquid is 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium tetrafluoroborate, N-methyl, propylpiperidine double One or more of trifluoromethanesulfonimide salt, N-methyl, propylpyrrolidine bistrifluoromethanesulfonimide salt.
  • the low melting point solvent is diethyl carbonate, ethyl propionate, ethyl butyrate, dimethyl sulfite, diethyl sulfite, isobutyl formate, butyl acetate, hexyl acetate, One or more of butyl valerate.
  • the invention relates to a method for preparing a wide temperature and high voltage type supercapacitor organic electrolyte, characterized in that the specific steps are: after the electrolyte salt, the ionic liquid and the mixed organic solvent are weighed according to the above ratio, the electrolyte salt and the ionic liquid are dissolved and mixed.
  • the organic solvent ultrasonic dispersion under vacuum conditions, that is, wide temperature and high voltage type super electricity Container organic electrolyte.
  • the components are mixed and ultrasonically dispersed under vacuum conditions, and ultrasonic treatment produces certain bubbles, and ultrasonic dispersion under vacuum conditions can effectively eliminate bubbles, and the dispersion uniformity of each component is better.
  • the electrolyte salt is tetraethylammonium tetrafluoroborate, ammonium tetramethyltetrafluoroborate, ammonium triethylmethyltetrafluoroborate, ammonium N,N-dimethylpyrrolidine tetrafluoroborate, N, N-diethylpyrrolidine ammonium tetrafluoroborate, N-methyl-N-ethylpyrrolidine ammonium tetrafluoroborate, N,N-dimethylpyrrolidine ammonium tetrafluoroborate, 5-aza spiro ring [4 , 4] one or more of decane ammonium tetrafluoroborate.
  • the ionic liquid is 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium tetrafluoroborate, N-methyl, propylpiperidine double One or more of trifluoromethanesulfonimide salt, N-methyl, propylpyrrolidine bistrifluoromethanesulfonimide salt.
  • the low melting point solvent is diethyl carbonate, ethyl propionate, ethyl butyrate, dimethyl sulfite, diethyl sulfite, isobutyl formate, butyl acetate, hexyl acetate, One or more of butyl valerate.
  • the temperature during ultrasonic dispersion is controlled at 25 to 35 °C.
  • the dispersion of ultrasonic waves in the liquid mainly depends on the ultrasonic cavitation of the liquid. The cavitation will cause more small bubbles in the electrolyte. These small bubbles will escape slowly in the electrolyte and greatly affect the vacuum removal.
  • the efficiency of the present invention is such that the ultrasonic dispersion temperature is controlled at 25 to 35 ° C to accelerate the escape and rupture of the bubbles, thereby contributing to the improvement of the outgassing efficiency.
  • the glass tube when ultrasonically dispersing, the glass tube is extended into the liquid surface below the liquid surface to be stirred by nitrogen gas, and the nitrogen gas is introduced in such a quantity that the electrolyte does not splash. Since the ultrasonic dispersion causes more small bubbles to be generated inside the electrolyte, these small bubbles escape slowly, and at the same time, the ultrasonic dispersion has a thermal effect, which changes the temperature of the entire electrolyte system, thereby being disadvantageous for the control of the ultrasonic dispersion temperature.
  • the invention solves the above two problems by using a glass tube extending into the bottom of the liquid surface and stirring nitrogen gas, and by bubbling nitrogen gas, the function of stirring and dissipating heat can dissipate the heat generated by the ultrasonic dispersion in time. It is beneficial to keep the dispersion temperature stable; the second is to make the electrolyte roll from bottom to top, which not only accelerates the escape rate of small bubbles in the electrolyte, but also further improves the mixing uniformity of each component in the electrolyte.
  • the present invention has the following beneficial effects:
  • the invention optimizes and improves the formulation of the supercapacitor organic electrolyte, screens the low melting point solvent component added in the organic electrolyte, and adds an ionic liquid to lower the electrolyte
  • the freezing point improves its high temperature resistance and high voltage resistance.
  • the temperature range is between -65 and 70 °C, and the temperature range is wide. It has good low temperature resistance, high temperature resistance and high voltage resistance. Withstand voltage range up to 2.75V;
  • a wide temperature and high voltage type supercapacitor organic electrolyte which is composed of an electrolyte salt, an ionic liquid and a mixed organic solvent.
  • the concentration of the electrolyte salt in the organic electrolyte is 0.5 mol/L, and the concentration of the ionic liquid is 0.01 mol/ L
  • the mixed organic solvent is prepared by mixing acetonitrile and a low melting point solvent at a volume ratio of 1:0.1, wherein the electrolyte salt is tetraethylammonium tetrafluoroborate and the ionic liquid is 1-ethyl-3-methylimidazolium tetrafluoroboron.
  • the acid salt and the low melting point solvent are diethyl carbonate.
  • the wide-temperature high-voltage supercapacitor organic electrolyte is obtained by the following method: after the electrolyte salt, the ionic liquid, and the mixed organic solvent are weighed according to the above ratio, the electrolyte salt and the ionic liquid are dissolved in the mixed organic solvent under vacuum conditions. Under ultrasonic dispersion, the wide-temperature high-voltage supercapacitor organic electrolyte is obtained.
  • the temperature is controlled at 25 ° C.
  • the glass tube is extended into the liquid surface below the liquid nitrogen to be stirred, and the nitrogen gas is introduced into the electrolyte. The liquid does not splash.
  • the supercapacitor fabricated by the electrolyte in the present embodiment can achieve 2.75V charge and discharge at a low temperature of -65 ° C; the capacity is maintained at 85% at a normal temperature of 25 ° C at -50 ° C; and the capacity retention rate is -76 at -55 ° C. %, the capacity retention rate at -60 ° C is 61.8%; the capacity retention rate at -65 ° C is 44%; the supercapacitor can achieve 10,000 cycles of charge and discharge at 70 ° C, with a capacity loss of 5%.
  • a wide temperature and high voltage type supercapacitor organic electrolyte which is composed of an electrolyte salt, an ionic liquid and a mixed organic solvent.
  • the concentration of the electrolyte salt in the organic electrolyte is 1.5 mol/L, and the concentration of the ionic liquid is 0.05 mol/ L
  • the mixed organic solvent is prepared by mixing acetonitrile and a low melting point solvent in a volume ratio of 1:2, wherein the electrolyte salts are ammonium tetraethylammonium tetrafluoroborate, ammonium tetramethyltetrafluoroborate and ammonium triethylmethyltetrafluoroborate.
  • the mixture is prepared by mixing 1:1:3 molar ratio, and the ionic liquid is 1-ethyl-3-methylimidazolium tetrafluoroborate and 1-butyl-3-methylimidazolium tetrafluoroborate. : 2 mixed, the low melting point solvent is diethyl carbonate, diethyl sulfite and isobutyl formate mixed in a volume ratio of 1:3:1.
  • the wide-temperature high-voltage supercapacitor organic electrolyte is obtained by the following method: after the electrolyte salt, the ionic liquid, and the mixed organic solvent are weighed according to the above ratio, the electrolyte salt and the ionic liquid are dissolved in the mixed organic solvent under vacuum conditions. Under ultrasonic dispersion, the organic electrolyte with wide temperature and high voltage type supercapacitor is obtained, and the temperature is controlled at 35 ° C during ultrasonic dispersion. When the ultrasonic dispersion is performed, the glass tube is used to extend the nitrogen gas below the liquid surface to stir, and the nitrogen gas is introduced into the electrolyte. The liquid does not splash.
  • the supercapacitor fabricated by the electrolyte in the present embodiment can achieve 2.75V charge and discharge at -65 ° C at a low temperature; the capacity is maintained at -50 ° C when the temperature is 25 ° C at 86 ° C; at -55 ° C when the capacity retention rate is 78 %, -60 ° C capacity retention rate of 65%; -65 ° C capacity retention rate of 49%; super capacitor can achieve 70 ° C charge and discharge cycle 10000 times, capacity loss of 5%.
  • the mixed organic solvent is prepared by mixing acetonitrile and a low melting point solvent at a volume ratio of 1:0.6, wherein the electrolyte salt is N,N-dimethylpyrrolidine ammonium tetrafluoroborate, N-methyl-N-ethylpyrrolidine four Ammonium fluoroborate and N,N-dimethylpyrrolidine tetrafluoroborate are mixed in a molar ratio of 3:1:1.
  • the ionic liquid is N-methyl, propylpyrrolidine bistrifluoromethanesulfonimide salt.
  • the low melting point solvent is a mixture of ethyl butyrate and dimethyl sulfite in a volume ratio of 1:1.
  • the wide-temperature high-voltage supercapacitor organic electrolyte is obtained by the following method: after the electrolyte salt, the ionic liquid, and the mixed organic solvent are weighed according to the above ratio, the electrolyte salt and the ionic liquid are dissolved in the mixed organic solvent under vacuum conditions.
  • ultrasonic dispersion that is, a wide temperature and high voltage type supercapacitor organic electrolyte
  • the temperature is controlled at 30 ° C.
  • the glass tube is used to extend the nitrogen gas below the liquid surface to stir the nitrogen gas. The amount of nitrogen gas is not splashed.
  • the supercapacitor prepared by the electrolyte in the present embodiment can achieve 2.8V charge and discharge at -65 ° C at a low temperature; the capacity maintains 83% at a normal temperature of 25 ° C at -50 ° C; and the capacity retention rate is -75 at -55 ° C %, the capacity retention rate is -60% at -60 °C; the capacity retention rate is -43% at -65 °C; the supercapacitor can achieve 10,000 cycles of charge and discharge at 70 °C, with a capacity loss of 7%.
  • a wide temperature and high voltage type supercapacitor organic electrolyte which is composed of an electrolyte salt, an ionic liquid and a mixed organic solvent.
  • the concentration of the electrolyte salt in the organic electrolyte is 1.5 mol/L, and the concentration of the ionic liquid is 0.02 mol/ L
  • the mixed organic solvent is prepared by mixing acetonitrile and a low melting solvent in a volume ratio of 1:1, wherein the electrolyte salt is ammonium triethylmethyltetrafluoroborate, N,N-diethylpyrrolidine ammonium tetrafluoroborate, N -Methyl-N-ethylpyrrolidine ammonium tetrafluoroborate and N,N-dimethylpyrrolidine tetrafluoroborate ammonium molar ratio 1:2:2:1 mixed, ionic liquid is 1-ethyl- 3-methylimidazolium tetrafluoroborate, 1-butyl-3-
  • the wide-temperature high-voltage supercapacitor organic electrolyte is obtained by the following method: after the electrolyte salt, the ionic liquid, and the mixed organic solvent are weighed according to the above ratio, the electrolyte salt and the ionic liquid are dissolved in the mixed organic solvent under vacuum conditions. Under the ultrasonic dispersion, the organic electrolyte with wide temperature and high voltage type supercapacitor is obtained. The temperature is controlled at 28 °C during ultrasonic dispersion. When the ultrasonic dispersion is performed, the glass tube is extended into the liquid surface below the liquid surface to stir the nitrogen gas. The liquid does not splash.
  • the supercapacitor fabricated by the electrolyte in the present embodiment can achieve 2.75V charge and discharge at a low temperature of -70 ° C; the capacity is maintained at -50 ° C and 87% at a normal temperature of 25 ° C; and the capacity retention rate at -55 ° C is 81 %, -60 ° C capacity retention rate of 69%; -65 ° C capacity retention rate of 46%; -70 ° C capacity retention rate of 35%; super capacitor can achieve 70 ° C charge and discharge cycle 10000 times, capacity loss 8%.

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Abstract

一种宽温高电压型超级电容器有机电解液及其制备方法。该有机电解液由电解质盐、离子液体、混合有机溶剂混合而成，有机电解液中电解质盐的浓度为0.5～1.5mol/L，离子液体的浓度为0.01～0.05mol/L，混合有机溶剂由乙腈和低熔点溶剂按体积比1：0.1～2混合而成。该有机电解液的制备方法是对超级电容器有机电解液的配方进行了优化改进，对有机电解液中添加的低熔点溶剂组分进行了筛选设计，添加了离子液体，在降低电解液凝固点的同时提高其耐高温性能和耐高电压性能，使用温度范围在-65～70℃之间，使用温度范围广，耐电压范围可达2.75V左右，兼具良好的耐低温性能、耐高温性能和耐高电压性能，该制备方法工艺步骤简单，可操作性强，适合工业化生产。

Description

一种宽温高电压型超级电容器有机电解液及其制备方法 技术领域
本发明涉及超级电容器电解液技术领域，尤其是涉及一种宽温高电压型超级电容器有机电解液及其制备方法。
背景技术
电化学双电层电容器又称超级电容器(super capacitors)，极端电容器等，是介于二次电池与传统静电电容器之间的新型能量储存器件，比传统静电电容器有更高的能量密度，比二次电池有更大的功率密度，其具有、功率密度高、循环寿命长、工作温度范围宽、循环稳定性好，免维护，环境友好等优点，已经在很多领域，如轨道交通、风力发电、油电混合动力车、电子器件的后备电源等展现出广阔的应用前景。
当前超级电容器有机体系电解液主要由有机溶剂和有机盐。溶剂包括如乙腈、碳酸丙烯酯等，有机盐包括四乙基四氟硼酸铵、三乙基甲基四氟硼酸铵。工作电压一般在2.7V，最低工作温度为-50℃。这是由于温度低于-50℃则会导致电解液结晶，电容器不能实现充放电功能。
在很多领域，如航空航天，军工及极地环境等要求电子储能器件的工作温度在-60℃及以下。美国航空航天局之前报道将甲酸甲酯、1,3-二氧戊环、乙酸甲酯、甲酸乙酯等加入乙腈体系电解液中用于超级电容器，可以实现-60℃的低温环境工作。但是以上溶剂在电解液中存在缺陷，如甲酸甲酯沸点只有39℃，这导致超级电容器高温性能极差，在50℃环境中工作就会使电容器因为溶剂的挥发而鼓胀。另外此电解液体系耐电压性能差，通常只能在2.5V电压下工作。
申请公布号CN102254691A，申请公布日2011.11.23的中国专利公开了一种超级电容器的电解液，通过向电解液的主体溶剂——乙腈或碳酸丙烯酯中添加低熔点溶剂，使得超级电容器的电解液能够在低温下具有较好的离子导通性，从而使超级电容器能够在低温下工作。其不足之处在于，该低温电解液的耐高温性能和耐高电压性能较差，适用范围受大很大限制。
发明内容
本发明是为了解决现有技术的超级电容器有机电解液不能同时兼具耐低温、高温和高电压性能，从而使得适用范围受到较大限制的问题，提供了一种同时兼具优异的耐低温、耐高温和耐高电压性能，适用范围广的宽温高电压型超级电容器有机电解液。
本发明还提供了一种宽温高电压型超级电容器有机电解液的制备方法，该制备方法工艺步骤简单，可操作性强，适合工业化生产。
为了实现上述目的，本发明采用以下技术方案：
一种宽温高电压型超级电容器有机电解液，其由电解质盐、离子液体、混合有机溶剂混合而成，有机电解液中电解质盐的浓度为0.5～1.5mol/L，离子液体的浓度为0.01～0.05mol/L，混合有机溶剂由乙腈和低熔点溶剂按体积比1：0.1～2混合而成。本发明对超级电容器有机电解液的配方进行了优化改进，通过在有机电解液中添加低熔点溶剂和离子液体，在降低电解液凝固点的同时提高其耐高温性能和耐高电压性能，使用温度范围在-65～70℃之间，使用温度范围广，具有良好的耐低温性能和耐高温性能，且耐电压范围可达2.75V左右，耐高电压性能好。
作为优选，所述电解质盐为四乙基四氟硼酸铵、四甲基四氟硼酸铵、三乙基甲基四氟硼酸铵、N,N-二甲基吡咯烷四氟硼酸铵、N,N-二乙基吡咯烷四氟硼酸铵、N-甲基-N-乙基吡咯烷四氟硼酸铵、N,N-二甲基吡咯烷四氟硼酸铵、5-氮杂螺环[4,4]壬烷四氟硼酸铵中的一种或多种。
作为优选，所述离子液体为1-乙基-3-甲基咪唑四氟硼酸盐、1-丁基-3-甲基咪唑四氟硼酸盐、N-甲基,丙基哌啶双三氟甲磺酰亚胺盐、N-甲基,丙基吡咯烷双三氟甲磺酰亚胺盐中的一种或多种。
作为优选，所述低熔点溶剂为碳酸二乙酯、丙酸乙酯、丁酸乙酯、、亚硫酸二甲酯、亚硫酸二乙酯、甲酸异丁酯、乙酸丁酯、乙酸己酯、戊酸丁酯中的一种或多种。
一种宽温高电压型超级电容器有机电解液的制备方法，其特征在于，具体步骤为：按上述配比称取电解质盐、离子液体、混合有机溶剂后，将电解质盐、离子液体溶于混合有机溶剂中，于真空条件下超声分散，即得宽温高电压型超级电 容器有机电解液。本发明将各组分混合后在真空条件下超声分散，超声处理会产生一定的气泡，而在真空条件下进行超声分散可有效消除气泡，各组分的分散均匀性更好。
作为优选，所述电解质盐为四乙基四氟硼酸铵、四甲基四氟硼酸铵、三乙基甲基四氟硼酸铵、N,N-二甲基吡咯烷四氟硼酸铵、N,N-二乙基吡咯烷四氟硼酸铵、N-甲基-N-乙基吡咯烷四氟硼酸铵、N,N-二甲基吡咯烷四氟硼酸铵、5-氮杂螺环[4,4]壬烷四氟硼酸铵中的一种或多种。
作为优选，所述离子液体为1-乙基-3-甲基咪唑四氟硼酸盐、1-丁基-3-甲基咪唑四氟硼酸盐、N-甲基,丙基哌啶双三氟甲磺酰亚胺盐、N-甲基,丙基吡咯烷双三氟甲磺酰亚胺盐中的一种或多种。
作为优选，所述低熔点溶剂为碳酸二乙酯、丙酸乙酯、丁酸乙酯、、亚硫酸二甲酯、亚硫酸二乙酯、甲酸异丁酯、乙酸丁酯、乙酸己酯、戊酸丁酯中的一种或多种。
作为优选，所述超声分散时温度控制在25～35℃。超声波在液体里的分散作用，主要依赖液体的超声空化作用，空化作用会使电解液中产生较多的小气泡，这些小气泡存在于电解液中逸出速度缓慢，大大影响真空脱除的效率，因此本发明将超声分散温度控制在25～35℃，以加速气泡的逸出破裂，从而有利于提高除气效率。
作为优选，超声分散时，用玻璃管伸入液面以下鼓氮气进行搅拌，氮气的通入量以电解液不溅起为准。由于超声分散会使电解液内部产生较多的小气泡，这些小气泡逸出速度缓慢，同时，超声分散又具有热效应，会改变整个电解液体系的温度，从而不利于超声分散温度的控制，因此本发明通过用玻璃管伸入液面以下鼓氮气进行搅拌的方法以解决上述两个问题，通过鼓入氮气，一是起到搅拌散热的作用，可以使超声分散所产生的热量及时散出，有利于保持分散温度的稳定；二是可以使电解液产生从下往上的翻滚，不仅加速了电解液中小气泡的逸出速度，而且能进一步提高电解液中各组分的混合均匀性。
因此，本发明具有如下有益效果：
(1)本发明对超级电容器有机电解液的配方进行了优化改进，对有机电解液中添加的低熔点溶剂组分进行了筛选设计，并添加了离子液体，在降低电解液 凝固点的同时提高其耐高温性能和耐高电压性能，使用温度范围在-65～70℃之间，使用温度范围广，兼具良好的耐低温性能、耐高温性能和耐高电压性能好，且耐电压范围可达2.75V左右；
(2)制备方法工艺步骤简单，各组分分散均匀性好，可操作性强，适合工业化生产。
具体实施方式
下面通过具体实施方式对本发明做进一步的描述。
在本发明中，若非特指，所有百分比均为重量单位，所有设备和原料均可从市场购得或是本行业常用的，下述实施例中的方法，如无特别说明，均为本领域常规方法。
实施例1
一种宽温高电压型超级电容器有机电解液，其由电解质盐、离子液体、混合有机溶剂混合而成，有机电解液中电解质盐的浓度为0.5mol/L，离子液体的浓度为0.01mol/L，混合有机溶剂由乙腈和低熔点溶剂按体积比1：0.1混合而成，其中，电解质盐为四乙基四氟硼酸铵，离子液体为1-乙基-3-甲基咪唑四氟硼酸盐，低熔点溶剂为碳酸二乙酯。
该宽温高电压型超级电容器有机电解液通过以下方法制得：按上述配比称取电解质盐、离子液体、混合有机溶剂后，将电解质盐、离子液体溶于混合有机溶剂中，于真空条件下超声分散，即得宽温高电压型超级电容器有机电解液，超声分散时温度控制在25℃，超声分散时，用玻璃管伸入液面以下鼓氮气进行搅拌，氮气的通入量以电解液不溅起为准。
以本实施例中的电解液制作的超级电容器可以实现-65℃低温下2.75V充放电；容量在-50℃时保持了常温25℃时的85％；到-55℃时容量保持率为76％，-60℃时容量保持率为61.8％；-65℃时容量保持率为44％；超级电容器可以实现在70℃充放电循环10000次，容量损失5％。
实施例2
一种宽温高电压型超级电容器有机电解液，其由电解质盐、离子液体、混合有机溶剂混合而成，有机电解液中电解质盐的浓度为1.5mol/L，离子液体的浓度为0.05mol/L，混合有机溶剂由乙腈和低熔点溶剂按体积比1：2混合而成，其中电解质盐为四乙基四氟硼酸铵、四甲基四氟硼酸铵和三乙基甲基四氟硼酸铵按摩尔比1:1:3混合而成，离子液体为1-乙基-3-甲基咪唑四氟硼酸盐与1-丁基-3-甲基咪唑四氟硼酸盐按摩尔比1:2混合而成，低熔点溶剂为碳酸二乙酯、亚硫酸二乙酯和甲酸异丁酯按体积比1:3:1混合而成。
该宽温高电压型超级电容器有机电解液通过以下方法制得：按上述配比称取电解质盐、离子液体、混合有机溶剂后，将电解质盐、离子液体溶于混合有机溶剂中，于真空条件下超声分散，即得宽温高电压型超级电容器有机电解液，超声分散时温度控制在35℃，超声分散时，用玻璃管伸入液面以下鼓氮气进行搅拌，氮气的通入量以电解液不溅起为准。
以本实施例中的电解液制作的超级电容器可以实现-65℃低温下2.75V充放电；容量在-50℃时保持了常温25℃时的86％；到-55℃时容量保持率为78％，-60℃时容量保持率为65％；-65℃时容量保持率为49％；超级电容器可以实现在70℃充放电循环10000次，容量损失5％。
实施例3
一种宽温高电压型超级电容器有机电解液，其由电解质盐、离子液体、混合有机溶剂混合而成，有机电解液中电解质盐的浓度为1mol/L，离子液体的浓度为0.02mol/L，混合有机溶剂由乙腈和低熔点溶剂按体积比1：0.6混合而成，其中电解质盐为N,N-二甲基吡咯烷四氟硼酸铵、N-甲基-N-乙基吡咯烷四氟硼酸铵与N,N-二甲基吡咯烷四氟硼酸铵按摩尔比3:1:1混合而成，离子液体为N-甲基,丙基吡咯烷双三氟甲磺酰亚胺盐，低熔点溶剂为丁酸乙酯和亚硫酸二甲酯按体积比1:1混合而成。
该宽温高电压型超级电容器有机电解液通过以下方法制得：按上述配比称取电解质盐、离子液体、混合有机溶剂后，将电解质盐、离子液体溶于混合有机溶剂中，于真空条件下超声分散，即得宽温高电压型超级电容器有机电解液，超声 分散时温度控制在30℃，超声分散时，用玻璃管伸入液面以下鼓氮气进行搅拌，氮气的通入量以电解液不溅起为准。
以本实施例中的电解液制作的超级电容器可以实现-65℃低温下2.8V充放电；容量在-50℃时保持了常温25℃时的83％；到-55℃时容量保持率为75％，-60℃时容量保持率为60％；-65℃时容量保持率为43％；超级电容器可以实现在70℃充放电循环10000次，容量损失7％。
实施例4
一种宽温高电压型超级电容器有机电解液，其由电解质盐、离子液体、混合有机溶剂混合而成，有机电解液中电解质盐的浓度为1.5mol/L，离子液体的浓度为0.02mol/L，混合有机溶剂由乙腈和低熔点溶剂按体积比1：1混合而成，其中电解质盐为三乙基甲基四氟硼酸铵、N,N-二乙基吡咯烷四氟硼酸铵、N-甲基-N-乙基吡咯烷四氟硼酸铵和N,N-二甲基吡咯烷四氟硼酸铵按摩尔比1:2:2:1混合而成，离子液体为1-乙基-3-甲基咪唑四氟硼酸盐、1-丁基-3-甲基咪唑四氟硼酸盐、N-甲基,丙基哌啶双三氟甲磺酰亚胺盐和N-甲基,丙基吡咯烷双三氟甲磺酰亚胺盐按摩尔比1:3:1:3混合而成，低熔点溶剂为碳酸二乙酯和丙酸乙酯按体积比1:1混合而成。
该宽温高电压型超级电容器有机电解液通过以下方法制得：按上述配比称取电解质盐、离子液体、混合有机溶剂后，将电解质盐、离子液体溶于混合有机溶剂中，于真空条件下超声分散，即得宽温高电压型超级电容器有机电解液，超声分散时温度控制在28℃，超声分散时，用玻璃管伸入液面以下鼓氮气进行搅拌，氮气的通入量以电解液不溅起为准。
以本实施例中的电解液制作的超级电容器可以实现-70℃低温下2.75V充放电；容量在-50℃时保持了常温25℃时的87％；到-55℃时容量保持率为81％，-60℃时容量保持率为69％；-65℃时容量保持率为46％；-70℃时容量保持率为35％；超级电容器可以实现在70℃充放电循环10000次，容量损失8％。
以上所述的实施例只是本发明的一种较佳的方案，并非对本发明作任何形式上的限制，在不超出权利要求所记载的技术方案的前提下还有其它的变体及改 型。

Claims (10)

  1. 一种宽温高电压型超级电容器有机电解液，其特征在于，其由电解质盐、离子液体、混合有机溶剂混合而成，有机电解液中电解质盐的浓度为0.5～1.5mol/L，离子液体的浓度为0.01～0.05mol/L，混合有机溶剂由乙腈和低熔点溶剂按体积比1：0.1～2混合而成。
  2. 根据权利要求1所述的一种宽温高电压型超级电容器有机电解液，其特征在于，所述电解质盐为四乙基四氟硼酸铵、四甲基四氟硼酸铵、三乙基甲基四氟硼酸铵、N,N-二甲基吡咯烷四氟硼酸铵、N,N-二乙基吡咯烷四氟硼酸铵、N-甲基-N-乙基吡咯烷四氟硼酸铵、N,N-二甲基吡咯烷四氟硼酸铵、5-氮杂螺环[4,4]壬烷四氟硼酸铵中的一种或多种。
  3. 根据权利要求1所述的一种宽温高电压型超级电容器有机电解液，其特征在于，所述离子液体为1-乙基-3-甲基咪唑四氟硼酸盐、1-丁基-3-甲基咪唑四氟硼酸盐、N-甲基,丙基哌啶双三氟甲磺酰亚胺盐、N-甲基,丙基吡咯烷双三氟甲磺酰亚胺盐中的一种或多种。
  4. 根据权利要求1所述的一种宽温高电压型超级电容器有机电解液，其特征在于，所述低熔点溶剂为碳酸二乙酯、丙酸乙酯、丁酸乙酯、亚硫酸二甲酯、亚硫酸二乙酯、甲酸异丁酯、乙酸丁酯、乙酸己酯、戊酸丁酯中的一种或多种。
  5. 一种如权利要求1所述的宽温高电压型超级电容器有机电解液的制备方法，其特征在于，具体步骤为：按上述配比称取电解质盐、离子液体、混合有机溶剂后，将电解质盐、离子液体溶于混合有机溶剂中，于真空条件下超声分散，即得宽温高电压型超级电容器有机电解液。
  6. 根据权利要求5所述的制备方法，其特征在于，所述电解质盐为四乙基四氟硼酸铵、四甲基四氟硼酸铵、三乙基甲基四氟硼酸铵、N,N-二甲基吡咯烷四氟硼酸铵、N,N-二乙基吡咯烷四氟硼酸铵、N-甲基-N-乙基吡咯烷四氟硼酸铵、N,N-二甲基吡咯烷四氟硼酸铵、5-氮杂螺环[4,4]壬烷四氟硼酸铵中的一种或多种。
  7. 根据权利要求5所述的制备方法，其特征在于，所述离子液体为1-乙基-3-甲基咪唑四氟硼酸盐、1-丁基-3-甲基咪唑四氟硼酸盐、N-甲基,丙基哌啶双三氟甲磺酰亚胺盐、N-甲基,丙基吡咯烷双三氟甲磺酰亚胺盐中的一种或多种。
  8. 根据权利要求5所述的制备方法，其特征在于，所述低熔点溶剂为碳酸二乙酯、丙酸乙酯、丁酸乙酯、亚硫酸二甲酯、亚硫酸二乙酯、甲酸异丁酯、乙酸丁 酯、乙酸己酯、戊酸丁酯中的一种或多种。
  9. 根据权利要求5所述的制备方法，其特征在于，所述超声分散时温度控制在25～35℃。
  10. 根据权利要求5或9所述的制备方法，其特征在于，超声分散时，用玻璃管伸入液面以下鼓氮气进行搅拌，氮气的通入量以电解液不溅起为准。
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