WO2016101331A1 - Ultra-low temperature chlorine salt aqueous super capacitor electrolyte - Google Patents
Ultra-low temperature chlorine salt aqueous super capacitor electrolyte Download PDFInfo
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- WO2016101331A1 WO2016101331A1 PCT/CN2015/000892 CN2015000892W WO2016101331A1 WO 2016101331 A1 WO2016101331 A1 WO 2016101331A1 CN 2015000892 W CN2015000892 W CN 2015000892W WO 2016101331 A1 WO2016101331 A1 WO 2016101331A1
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 30
- 239000003990 capacitor Substances 0.000 title claims abstract description 23
- 125000001309 chloro group Chemical class Cl* 0.000 title claims abstract 8
- 239000000243 solution Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 125000003277 amino group Chemical group 0.000 claims abstract description 5
- 239000012153 distilled water Substances 0.000 claims abstract description 5
- 239000007772 electrode material Substances 0.000 claims abstract description 4
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 3
- 239000012046 mixed solvent Substances 0.000 claims abstract description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical group NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 4
- 150000003841 chloride salts Chemical class 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 5
- 231100000053 low toxicity Toxicity 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 239000002041 carbon nanotube Substances 0.000 description 8
- 229910021393 carbon nanotube Inorganic materials 0.000 description 8
- 238000012360 testing method Methods 0.000 description 5
- 239000011255 nonaqueous electrolyte Substances 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 150000001804 chlorine Chemical class 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 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
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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Classifications
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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
-
- 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 a low temperature electrolyte, in particular to an ultra-low temperature chlorine brine super capacitor electrolyte which can make a super capacitor battery have excellent electrochemical performance under ultra-low temperature conditions.
- Supercapacitor battery also known as gold capacitor, electric capacitor, electric double layer capacitor (Electrical Double-Layer Capacitor), is a new type of energy storage device, which has short charging time, long service life, good temperature characteristics, energy saving and environmental protection. Features. Since the process of energy storage does not undergo a chemical reaction, this energy storage process is reversible because the supercapacitor can be repeatedly charged and discharged hundreds of thousands of times.
- Supercapacitors are widely used: they are used as power balance power sources for lifting devices, and can provide super-current power: they are used as starting power for vehicles, and their starting efficiency and reliability are higher than those of traditional batteries. They can replace traditional batteries in whole or in part;
- the traction energy of the vehicle can produce electric vehicles, replace traditional internal combustion engines, and retrofit existing trolley buses; it can be used to ensure the smooth start of tanks, armored vehicles and other vehicles (especially in the cold winter).
- the electrolyte is a key component and has a significant influence on the operating voltage, internal resistance, power characteristics and temperature characteristics of the capacitor.
- the liquid electrolyte generally used is an aqueous electrolyte and a nonaqueous electrolyte.
- the nonaqueous electrolytic solution generally uses an organic solvent or an ionic liquid. Compared with the aqueous electrolyte, the non-aqueous electrolyte has a wide operating temperature range, and the minimum operating temperature of the commercially produced non-aqueous supercapacitors has reached -40 °C.
- non-aqueous electrolytes have some fatal shortcomings: low conductivity, high cost, sealing required to insulate moisture in the air, and many high toxicity and environmental pollution, which limits their use.
- the water-based electrolyte is inexpensive, the conductivity is two orders of magnitude higher than that of the organic electrolyte, and it does not need to work under very dry conditions like the non-aqueous electrolyte. Therefore, it is widely used, but its disadvantages are mainly: the freezing point to the boiling point of water. The temperature range makes the capacitor's low temperature performance poor. Therefore, if the research on the water-based electrolyte can improve the low-temperature performance of the supercapacitor battery, it will have extremely important theoretical significance and application value. But so far, relevant research at home and abroad has been reported.
- the chlorine salt-based electrolyte provided by the invention has the advantages of low price, simple operation and low toxicity, and will improve the low-temperature performance of the supercapacitor battery, and has extremely important application value.
- An ultra-low temperature chlorine brine super capacitor electrolyte is prepared by mixing distilled water with an organic solvent containing an amino group in a volume ratio of 1:2 to 2:1, and dissolving the chlorine salt in the mixed solvent.
- a solution having a concentration of 0.5 to 2 mol ⁇ L -1 is formed, that is, an electrolyte solution of a supercapacitor battery using a carbon material as an electrode material.
- the specific capacitance of the supercapacitor battery fabricated by it is more than twice that of a pure water electrolyte supercapacitor battery using the same concentration of chloride salt, and its specific capacitance is about two-thirds of its room temperature specific capacitance.
- the electrolyte is used for a super capacitor battery, and the utility model has the advantages of low price, simple operation, low toxicity, good low temperature performance and high application value.
- the organic solvent containing an amino group is formamide.
- the chloride salt is one of CaCl 2 , KCl, LiCl, and NaCl.
- Figure 1 is a supercapacitor of 2 mol/LCaCl 2 -FA-H 2 O (1:1) solution measured at different temperatures as an electrolyte, circulating at intervals of 10 ° C in a range of -70 ° C to 20 ° C The graph of the voltammetric test.
- Figure 2 is a supercapacitor with 2 mol/LCaCl 2 of H 2 O, DMSO-H 2 O (1:1), and FA-H 2 O (1:1) solution as electrolyte at -60 ° C. The graph of the security test.
- the carbon nanotube solution was prepared to form a carbon nanotube electrode after it was naturally air-dried for 12 hours.
- Distilled water and formamide were mixed at a volume ratio of 1:1, and CaCl 2 was added to FA-H 2 O (1:1) to obtain a CaCl 2 solution having a concentration of 2 mol/L, and this solution was used as an electrolytic solution.
- the three-electrode system is composed of a carbon nanotube working electrode, a graphite electrode counter electrode and an Ag/AgCl reference electrode, and the three-electrode system is fixed on the rubber plug on the beaker (the distance between the working electrode and the counter electrode is close to form a super capacitor).
- the thermometer is inserted; the assembled capacitor is fixed in the cryostat, and the configured electrolyte solution is added. After the indication displayed by the thermometer is stabilized for a period of time, the capacitor is connected with the electrochemical workstation for cyclic voltammetry and Constant current charge and discharge test.
- Cyclic voltammetry was performed at a gradient of 10 ° C in the range of -70 ° C to 20 ° C, and the results are shown in FIG.
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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)
Abstract
An ultra-low temperature chlorine salt aqueous super capacitor electrolyte capable of enabling a super capacitor battery to have excellent electrochemical performance under the condition of an ultra-low temperature. The ultra-low temperature chlorine salt aqueous super capacitor electrolyte is prepared according to the following method that distilled water and an organic solvent containing amino group are mixed at a volume ratio of 1:2-2:1 and a chlorine salt is dissolved in the mixed solvent to form a solution with a concentration of 0.5-2 mol L-1, i.e., the electrolyte solution for the super capacitor battery using a carbon material as an electrode material. At a temperature of -60°C, the specific capacitance of the super capacitor battery made of the above-mentioned electrolyte is more than twice that of a super capacitor battery made of a pure water electrolyte using the chlorine salt with the same concentration and is approximately two thirds that at the room temperature. The electrolyte is used for a super capacitor battery, has a low price, a simple and convenient operation, low toxicity and good low-temperature performance and has a higher application value.
Description
本发明涉及低温电解液，具体是一种在超低温条件下能使超级电容电池具有优良电化学性能的超低温氯盐水系超级电容电解液。The invention relates to a low temperature electrolyte, in particular to an ultra-low temperature chlorine brine super capacitor electrolyte which can make a super capacitor battery have excellent electrochemical performance under ultra-low temperature conditions.
超级电容电池又叫黄金电容、法拉电容、双电层电容器(Electrical Double-Layer Capacitor)，是一种新型储能装置，它具有充电时间短、使用寿命长、温度特性好、节约能源和绿色环保等特点。由于其储能的过程并不发生化学反应，因此这种储能过程是可逆的，正因为此超级电容器可以反复充放电数十万次。超级电容器用途广泛：用作起重装置的电力平衡电源，可提供超大电流的电力：用作车辆启动电源，启动效率和可靠性都比传统的蓄电池高，可以全部或部分替代传统的蓄电池；用作车辆的牵引能源可以生产电动汽车、替代传统的内燃机、改造现有的无轨电车；用在军事上可保证坦克车、装甲车等战车的顺利启动(尤其是在寒冷的冬季)。Supercapacitor battery, also known as gold capacitor, electric capacitor, electric double layer capacitor (Electrical Double-Layer Capacitor), is a new type of energy storage device, which has short charging time, long service life, good temperature characteristics, energy saving and environmental protection. Features. Since the process of energy storage does not undergo a chemical reaction, this energy storage process is reversible because the supercapacitor can be repeatedly charged and discharged hundreds of thousands of times. Supercapacitors are widely used: they are used as power balance power sources for lifting devices, and can provide super-current power: they are used as starting power for vehicles, and their starting efficiency and reliability are higher than those of traditional batteries. They can replace traditional batteries in whole or in part; The traction energy of the vehicle can produce electric vehicles, replace traditional internal combustion engines, and retrofit existing trolley buses; it can be used to ensure the smooth start of tanks, armored vehicles and other vehicles (especially in the cold winter).
低温条件下，超级电容电池的电化学性能将降低，这就限制了它在航空、航天和军事等特殊领域的应用。由电解液入手来改善超级电容电池的温度性能已经被证明是可行的技术途径，这是因为作为在电池内起传导作用的离子导体，电解液的性能及其与正负极形成的界面状况很大程度上影响电池温度性能，本课题即是针对低温电解液来研究的。Under low temperature conditions, the electrochemical performance of supercapacitor cells will be reduced, which limits its application in special fields such as aerospace, aerospace and military. Starting from the electrolyte to improve the temperature performance of the supercapacitor battery has proven to be a viable technical approach because the performance of the electrolyte and its interface with the positive and negative electrodes are very good as ionic conductors that conduct electricity in the battery. To a large extent affect the battery temperature performance, this topic is to study for low temperature electrolyte.
在超级电容电池的各组成部分中，电解液是关键组分，对电容器的工作电压、内阻、功率特性和温度特性等具有十分重要的影响。Among the components of a supercapacitor battery, the electrolyte is a key component and has a significant influence on the operating voltage, internal resistance, power characteristics and temperature characteristics of the capacitor.
通常使用的液体电解液为水系电解液和非水系电解液。The liquid electrolyte generally used is an aqueous electrolyte and a nonaqueous electrolyte.
非水系电解液一般采用有机溶剂或离子液体。相对于水系电解液而言，非水系电解液工作温度范围宽，目前商业化生产的非水系超级电容器最低操作温度已达到-40℃。但非水系电解液存在一些致命的缺点：电导率较低、成本高、要求密封以隔绝空气中的水分，且很多毒性高、污染环境，从而限制了其使用。The nonaqueous electrolytic solution generally uses an organic solvent or an ionic liquid. Compared with the aqueous electrolyte, the non-aqueous electrolyte has a wide operating temperature range, and the minimum operating temperature of the commercially produced non-aqueous supercapacitors has reached -40 °C. However, non-aqueous electrolytes have some fatal shortcomings: low conductivity, high cost, sealing required to insulate moisture in the air, and many high toxicity and environmental pollution, which limits their use.
水系电解液价格低廉，电导率比有机电解液高二个数量级，无需像非水系电解液那样必须在非常干燥的条件下工作，因此得到广泛应用，但其不足之处主要是：水的凝固点至沸点的温度范围使电容器的低温性能较差。因此，若能对水系电解液开展研究，从而提高超级电容电池的低温性能，将具有极其重要的理论意义和应用价值。但到目前为止，国内外相关研究显有报道。The water-based electrolyte is inexpensive, the conductivity is two orders of magnitude higher than that of the organic electrolyte, and it does not need to work under very dry conditions like the non-aqueous electrolyte. Therefore, it is widely used, but its disadvantages are mainly: the freezing point to the boiling point of water. The temperature range makes the capacitor's low temperature performance poor. Therefore, if the research on the water-based electrolyte can improve the low-temperature performance of the supercapacitor battery, it will have extremely important theoretical significance and application value. But so far, relevant research at home and abroad has been reported.
本发明提供的氯盐水系电解液，价格低廉、操作简便、毒性小，将提高超级电容电池的低温性能，具有极其重要的应用价值。
The chlorine salt-based electrolyte provided by the invention has the advantages of low price, simple operation and low toxicity, and will improve the low-temperature performance of the supercapacitor battery, and has extremely important application value.
发明内容Summary of the invention
本发明的目的在于提供一种用于超级电容电池的价格低廉、操作简便、毒性小且低温电化学性能好的氯盐水系电解液。It is an object of the present invention to provide a chlorine salt-based electrolyte which is inexpensive, easy to operate, has low toxicity, and has low temperature electrochemical performance for use in a supercapacitor battery.
本发明的目的是通过以下技术方案实现的：The object of the invention is achieved by the following technical solutions:
一种超低温氯盐水系超级电容电解液，按下述方法制备：将蒸馏水与一种含有氨基的有机溶剂按体积比为1∶2～2∶1混合，将氯盐溶解在该混合溶剂中，形成浓度为0.5～2mol·L-1的溶液，即为以碳材料作为电极材料的超级电容电池的电解质溶液。An ultra-low temperature chlorine brine super capacitor electrolyte is prepared by mixing distilled water with an organic solvent containing an amino group in a volume ratio of 1:2 to 2:1, and dissolving the chlorine salt in the mixed solvent. A solution having a concentration of 0.5 to 2 mol·L -1 is formed, that is, an electrolyte solution of a supercapacitor battery using a carbon material as an electrode material.
采用上述技术方案的本发明，其特别之处是：The invention adopting the above technical solution is particularly:
-60℃时，用其制作的超级电容电池的比电容为使用同浓度氯盐的纯水电解液超级电容电池的两倍多，其比电容约为其室温比电容的三分之二。将该电解液用于超级电容电池，价格低廉、操作简便、毒性小、低温性能好，具有较高的应用价值。At -60 ° C, the specific capacitance of the supercapacitor battery fabricated by it is more than twice that of a pure water electrolyte supercapacitor battery using the same concentration of chloride salt, and its specific capacitance is about two-thirds of its room temperature specific capacitance. The electrolyte is used for a super capacitor battery, and the utility model has the advantages of low price, simple operation, low toxicity, good low temperature performance and high application value.
本发明更进一步的技术方案是：A further technical solution of the present invention is:
所述含有氨基的有机溶剂为甲酰胺。The organic solvent containing an amino group is formamide.
所述氯盐为CaCl2、KCl、LiCl、NaCl其中之一。The chloride salt is one of CaCl 2 , KCl, LiCl, and NaCl.
图1是不同温度下测定的2mol/LCaCl2的-FA-H2O(1∶1)溶液为电解质的超级电容，在-70℃至20℃范围内，每隔10℃为一个梯度进行循环伏安测试的曲线图。Figure 1 is a supercapacitor of 2 mol/LCaCl 2 -FA-H 2 O (1:1) solution measured at different temperatures as an electrolyte, circulating at intervals of 10 ° C in a range of -70 ° C to 20 ° C The graph of the voltammetric test.
图2是-60℃时，分别以2mol/LCaCl2的H2O、DMSO-H2O(1∶1)、FA-H2O(1∶1)溶液为电解质的超级电容，进行循环伏安测试的曲线图。Figure 2 is a supercapacitor with 2 mol/LCaCl 2 of H 2 O, DMSO-H 2 O (1:1), and FA-H 2 O (1:1) solution as electrolyte at -60 ° C. The graph of the security test.
以下结合实施例详述本发明，目的仅在于更好的理解本发明内容，所举之例并非限制本发明内容。The invention is described in detail below with reference to the embodiments, which are intended to provide a better understanding of the invention.
制备碳纳米管电极：Preparation of carbon nanotube electrodes:
(1)配好合适浓度的分散剂溶液，将电极材料碳纳米管粉体和分散剂溶液按适当比例混合，在超声波中超声30分钟，制备成分散性良好的碳纳米管溶液；(1) Preparing a proper concentration of the dispersant solution, mixing the electrode material carbon nanotube powder and the dispersant solution in an appropriate ratio, and ultrasonicating for 30 minutes in the ultrasonic wave to prepare a carbon nanotube solution having good dispersibility;
(2)碳纳米管溶液中加入适量的聚四氟乙烯黏结剂，超声10分钟，得到混合液；(2) adding an appropriate amount of polytetrafluoroethylene binder to the carbon nanotube solution, and ultrasonicizing for 10 minutes to obtain a mixed solution;
(3)石墨棒(d＝6mm)每次使用前需打磨以将其上残存的杂质磨掉，用蒸馏水冲洗干净，在烘箱中常温30分钟，然后再在相同面积的石墨棒上滴加适量的的碳纳米管溶液，待其自然风干12小时，则制备成碳纳米管电极。(3) Graphite rod (d=6mm) should be ground before each use to grind off the remaining impurities, rinse with distilled water, and keep it at room temperature for 30 minutes in the oven, then add the appropriate amount to the graphite rod of the same area. The carbon nanotube solution was prepared to form a carbon nanotube electrode after it was naturally air-dried for 12 hours.
制备超低温氯盐水系超级电容电解液：Preparation of ultra-low temperature chlorine brine super capacitor electrolyte:
蒸馏水与甲酰胺按1∶1体积比混合，将CaCl2加入FA-H2O(1∶1)中，得到浓度为2mol/L的CaCl2溶液，将该溶液作为电解液。
Distilled water and formamide were mixed at a volume ratio of 1:1, and CaCl 2 was added to FA-H 2 O (1:1) to obtain a CaCl 2 solution having a concentration of 2 mol/L, and this solution was used as an electrolytic solution.
循环伏安测试和恒电流充放电测试：Cyclic voltammetry test and constant current charge and discharge test:
以碳纳米管工作电极和石墨电极对电极以及Ag/AgCl参比电极组成三电极体系，将三电极体系固定在烧杯上的胶塞上(工作电极和对电极距离要近组合成超级电容)，同时插入温度计；将组装好的电容器固定在低温恒温槽中，加入配置好的电解质溶液，待温度计显示的示数稳定一段时间后，将电容器与电化学工作站连接在一起，进行循环伏安测试和恒电流充放电测试。The three-electrode system is composed of a carbon nanotube working electrode, a graphite electrode counter electrode and an Ag/AgCl reference electrode, and the three-electrode system is fixed on the rubber plug on the beaker (the distance between the working electrode and the counter electrode is close to form a super capacitor). At the same time, the thermometer is inserted; the assembled capacitor is fixed in the cryostat, and the configured electrolyte solution is added. After the indication displayed by the thermometer is stabilized for a period of time, the capacitor is connected with the electrochemical workstation for cyclic voltammetry and Constant current charge and discharge test.
在-70℃至20℃范围内，每隔10℃为一个梯度进行循环伏安测试，结果如图1所示。Cyclic voltammetry was performed at a gradient of 10 ° C in the range of -70 ° C to 20 ° C, and the results are shown in FIG.
同样方法测定同浓度CaCl2不同溶剂的电解液性能，如图2所示。The same method was used to determine the electrolyte performance of different solvents of the same concentration of CaCl 2 , as shown in FIG. 2 .
结果表明，当碳纳米管超级电容的电解液为CaCl2-FA-H2O(其中FA与H2O为1∶1，CaCl2浓度为2mol/L)时，在低温条件下具有相对较高的比容量，为同浓度CaCl2水溶液作为电解液时的两倍多。The results show that when the electrolyte of the carbon nanotube supercapacitor is CaCl 2 -FA-H 2 O (wherein FA and H 2 O are 1:1 and CaCl 2 concentration is 2 mol/L), it is relatively low under low temperature conditions. The high specific capacity is more than twice that of the same concentration of CaCl 2 aqueous solution as the electrolyte.
本领域技术人员不脱离本发明的实质和精神，可以有多种变形方案实现本发明，以上所述仅为本发明较佳可行的实施例而已，并非因此局限本发明的权利范围，凡运用本发明说明书内容所作的等效变化，均包含于本发明的权利范围之内。
A person skilled in the art can implement the present invention in various modifications without departing from the spirit and scope of the invention. The foregoing is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Equivalent changes made in the contents of the specification of the invention are included in the scope of the invention.
Claims (3)
- 一种超低温氯盐水系超级电容电解液，其特征在于，按下述方法制备：将蒸馏水与一种含有氨基的有机溶剂按体积比为1∶2～2∶1混合，将氯盐溶解在该混合溶剂中，形成浓度为0.5～2mol·L-1的溶液，即为以碳材料作为电极材料的超级电容电池的电解质溶液。An ultra-low temperature chlorine salt-based super capacitor electrolyte prepared by mixing distilled water and an organic solvent containing an amino group in a volume ratio of 1:2 to 2:1 to dissolve a chlorine salt therein. In the mixed solvent, a solution having a concentration of 0.5 to 2 mol·L -1 is formed, that is, an electrolyte solution of a supercapacitor battery using a carbon material as an electrode material.
- 根据权利要求1所述的超低温氯盐水系超级电容电解液，其特征在于，所述含有氨基的有机溶剂为甲酰胺。The ultra-low temperature chlorine salt-based supercapacitor electrolyte according to claim 1, wherein the amino group-containing organic solvent is formamide.
- 根据权利要求1所述的超底温氯盐水系超级电容电解液，其特征在于，所述氯盐为CaCl2、KCl、LiCl、NaCl其中之一。 The ultra-low temperature chlorinated brine-based supercapacitor electrolyte according to claim 1, wherein the chloride salt is one of CaCl 2 , KCl, LiCl, and NaCl.
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