CN101840784A - Electrolyte for super capacitor and super capacitor - Google Patents
Electrolyte for super capacitor and super capacitor Download PDFInfo
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- CN101840784A CN101840784A CN 201010149366 CN201010149366A CN101840784A CN 101840784 A CN101840784 A CN 101840784A CN 201010149366 CN201010149366 CN 201010149366 CN 201010149366 A CN201010149366 A CN 201010149366A CN 101840784 A CN101840784 A CN 101840784A
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- sodium perchlorate
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- 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
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Abstract
The invention provides an electrolyte for a super capacitor. In the electrolyte, a solvent is water, and a solute is 2 to 6M sodium perchlorate. The invention also provides the super capacitor, which comprises an anode, a cathode, a diaphragm between the anode and the cathode, and the electrolyte, wherein the electrolyte is 2 to 6M aqueous solution of sodium perchlorate. The aqueous solution of sodium perchlorate with high concentration has high ionic conductivity, the sodium perchlorate is difficult to separate out at a low temperature, and the aqueous solution of sodium perchlorate has low freezing point and can adapt to a low-temperature work environment; and the aqueous solution of sodium perchlorate has wide electrochemical window and good electrochemical properties at the same time. The super capacitor provided by the invention has high ionic conductivity, the capacity is slowly attenuated during charge and discharge, and the energy density and power density are high; and in addition, the electrolyte and the super capacitor provided by the invention have the advantages of simple preparation process, low cost of raw materials, convenient operation and reduction in production cost and using cost.
Description
Technical field
The present invention relates to technical field of electrochemistry, relate in particular to a kind of electrolyte and ultracapacitor that is used for ultracapacitor.
Background technology
Ultracapacitor is a kind of electrochemical element of realizing energy storage by the polarization electrolyte, have advantages such as high discharge specific power, excellent instantaneous charge-discharge performance and long circulation life, can be used as free of contamination back-up source and be used for multiple electric equipment, also can form composite power source jointly with battery provides power for electric automobile.
Studies show that, the performance of ultracapacitor is main relevant with employed electrolyte, the performances such as electric capacity, energy density and power density of discovering the concentration of electrolyte and capacitor as people such as J.P.Zheng are closely related, concentration of electrolyte is high more, its ionic conductivity is also high more, and the maximum power density and the energy density of corresponding capacitor are also higher; Simultaneously, concentration of electrolyte is high more, the also high more (J.P.Zheng of the maximum working voltage of capacitor, T.R.Jow, The Effect of Salt Concentration in Electrolytes onthe Maximum Energy Storage for Double Layer Capacitors.J Electrochem.Soc.1997,144,2417～2420).Capacitor electrolyte mainly contains with water as the aqueous electrolyte of solvent with the organic system electrolyte two big classes of organic substance as solvent at present, wherein, aqueous electrolyte becomes one of research focus owing to having advantages such as higher conductance, the capacitor internal driving is low, the electrolyte molecule diameter is little, cheap.
Prior art discloses multiple inorganic matter as the electrolyte in the aqueous electrolyte, as neutral salt such as strong alkaline substances such as highly acid material, potassium hydroxide such as high-concentration sulfuric acid and alkali-metal sulfate, nitrate, chlorates, but strong acid, highly basic class electrolyte have corrosivity, and application is restricted; And alkali-metal sulfate, nitrate, the solubility of chlorate in water are all lower, as the solubility of sodium sulphate in 20 ℃ water is 19.5g/100g, the solubility of potassium nitrate in 20 ℃ water is 31.6g/100g, make that the concentration of electrolyte is on the low side, be generally 0.25M～1M, influence the performance of capacitor.
Sodium perchlorate has another name called the sodium perchlorate, and chemical formula is NaClO
4, be the non-toxic, colorless crystal, be commonly used for analytical reagent, oxidant or be used to make explosive.The solubility of sodium perchlorate in water is bigger, and the solubility in the time of 0 ℃ is 167g/100g water, and the solubility in the time of 20 ℃ is 201g/100g water.
Summary of the invention
In view of this, technical problem to be solved by this invention is to provide a kind of electrolyte and ultracapacitor that is used for ultracapacitor, to improve the ionic conductivity of electrolyte, reduce the solidifying point of electrolyte, improve the energy density and the power density of ultracapacitor.
The invention provides a kind of electrolyte that is used for ultracapacitor, solvent is a water, and solute is a sodium perchlorate;
Wherein, the concentration of sodium perchlorate is 2M～6M.
Preferably, the concentration of described sodium perchlorate is 3M～5M.
Preferably, also comprise alcohols.
Preferably, described alcohols is methyl alcohol, ethanol, ethylene glycol or glycerol.
The present invention also provides a kind of ultracapacitor, comprising:
Positive pole, negative pole, the barrier film between positive pole and negative pole and electrolyte;
Described electrolyte is that concentration is the sodium perchlorate aqueous solution of 2M～6M.
Preferably, described electrolyte is that concentration is the sodium perchlorate aqueous solution of 3M～5M.
Preferably, described electrolyte also comprises alcohols.
Preferably, described alcohols is methyl alcohol, ethanol, ethylene glycol or glycerol.
Preferably, described just very material with carbon element electrode.
Preferably, described negative pole is the material with carbon element electrode.
Compared with prior art, the present invention is that electrolyte dissolution is prepared electrolyte in water with the higher sodium perchlorate of solubility, obtains the electrolyte that concentration is 2M～6M.The ionic conductivity of the high concentration sodium perchlorate aqueous solution is higher, and sodium perchlorate is difficult for separating out at low temperatures, and sodium perchlorate aqueous solution solidifying point is lower, can adapt to the operational environment of low temperature.Simultaneously, in the sodium perchlorate aqueous solution, sodium ion is a strong base ion, and resistance to reduction is more intense, and perchlorate is the strong acid ion, and non-oxidizability is more intense, and therefore, the sodium perchlorate aqueous solution has the electrochemical window of broad, and chemical property is better.The present invention is that the sodium perchlorate aqueous solution of 2M～6M has higher ionic conductivity as electrolytical ultracapacitor with concentration, and capacity attenuation is slow when discharging and recharging, and energy density and power density are higher.In addition, electrolyte provided by the invention and ultracapacitor preparation technology is simple, the prices of raw and semifnished materials are cheap, be convenient to the operation, reduced production cost and use cost.
Description of drawings
The electrode of super capacitor that Fig. 1 provides for the embodiment of the invention sweep speed-than capacitance curve figure;
The ragone plot curve chart of the electrode of super capacitor that Fig. 2 provides for the embodiment of the invention;
The concentration of electrolyte that Fig. 3 provides for the embodiment of the invention is the constant current charge-discharge test curve figure of the ultracapacitor of 3M;
The concentration of electrolyte that Fig. 4 provides for the embodiment of the invention is the constant current charge-discharge test curve figure of the ultracapacitor of 5M.
Embodiment
Electrochemical window is one of evaluation index of electrolyte chemical property, and the electrolyte property of current potential window width is better, and the electrochemical window broad of the inorganic salts electrolyte that the cation resistance to reduction is strong more, the anion non-oxidizability is strong more.The cation that resistance to reduction is stronger mainly contains aluminium ion, lithium ion, sodium ion and potassium ion, but aluminium salt facile hydrolysis, instability; Lithium salts costs an arm and a leg, and can increase cost; Sylvite solubility is lower, very easily separate out at low temperatures cause using limited; And sodium salt is generally all comparatively stable, cheap, solubility is high, is suitable for use as electrolyte.The anion that non-oxidizability is stronger mainly contains chloride ion, sulfate ion, but the oxidation easily under certain potentials of the chloride ion in the villaumite is used limited; The solubility of sulfate is lower, separates out to cause concentration of electrolyte lower poor-performing at low temperatures easily.Mainly as oxidant in rocket fuel and the pyrotechnics and the explosive in the air bag, most perchlorate water soluble, especially sodium perchlorates very easily are dissolved in water to perchlorate, and the solubility in 0 ℃ water can reach 167g/100g water.
The invention provides a kind of electrolyte that is used for ultracapacitor, solvent is a water, and solute is a sodium perchlorate;
Wherein, the concentration of sodium perchlorate is 2M～6M, is preferably 3M～5M.
The present invention does not have specific (special) requirements to described sodium perchlorate, is preferably from the market and buys.
Minimum for the foreign ion in the water is dropped to the influence of electrolyte, the present invention preferably is solvent with the deionized water.
Preferably include alcohols in the electrolyte provided by the invention, the effect of described alcohols is the solidifying point that reduces electrolyte, makes not easy freezing of electrolyte.The present invention does not have particular restriction to described alcohols, is preferably methyl alcohol, ethanol, ethylene glycol or glycerol.
The present invention does not have particular restriction to the compound method of described electrolyte, is preferably Xiang Shuizhong and adds sodium perchlorate, stirs and makes it abundant dissolving, obtains electrolyte.
The present invention also provides a kind of ultracapacitor, comprising:
Positive pole, negative pole, the barrier film between positive pole and negative pole and electrolyte;
Described electrolyte is that concentration is the sodium perchlorate aqueous solution of 2M～6M.
According to the present invention, described positive pole is preferably the material with carbon element electrode, more preferably micro-pore carbon material and meso-porous carbon material electrode; Described negative pole is preferably the material with carbon element electrode, more preferably micro-pore carbon material and meso-porous carbon material electrode; Described barrier film is preferably filter paper.
According to the present invention, described electrolyte is preferably the sodium perchlorate aqueous solution of 3M～5M.
Compared with prior art, the present invention is that electrolyte dissolution is prepared electrolyte in water with the higher sodium perchlorate of solubility, obtains the electrolyte that concentration is 2M～6M.The ionic conductivity of the high concentration sodium perchlorate aqueous solution is higher, and sodium perchlorate is difficult for separating out at low temperatures, and sodium perchlorate aqueous solution solidifying point is lower, can adapt to the operational environment of low temperature.Simultaneously, in the sodium perchlorate aqueous solution, sodium ion is a strong base ion, and resistance to reduction is more intense, and perchlorate is the strong acid ion, and non-oxidizability is more intense, and therefore, the sodium perchlorate aqueous solution has the electrochemical window of broad, and chemical property is better.The present invention is that the sodium perchlorate aqueous solution of 2M～6M has higher ionic conductivity as electrolytical ultracapacitor with concentration, and capacity attenuation is slow when discharging and recharging, and energy density and power density are higher.In addition, electrolyte provided by the invention and ultracapacitor preparation technology is simple, the prices of raw and semifnished materials are cheap, be convenient to the operation, reduced production cost and use cost.
In order further to understand the present invention, electrolyte provided by the invention and ultracapacitor are described in detail below in conjunction with embodiment.
The sodium perchlorate that 280.98g is commercially available is dissolved in the 1L deionized water, obtains the electrolyte that concentration is 2M;
Use DJS～10C type conductivity meter to measure above-mentioned electrolyte conductance at room temperature, be 218mScm
-1
Use the PerkinElmer differential thermal analyzer in 25 ℃～-70 ℃ scope, measure the solidifying point of above-mentioned electrolyte, be-26.23 ℃ with the cooling rate of 1 ℃/min.
The sodium perchlorate that 421.47g is commercially available is dissolved in the 1L deionized water, obtains the electrolyte that concentration is 3M;
Use DJS～10C type conductivity meter to measure above-mentioned electrolyte conductance at room temperature, be 273mScm
-1
Use the PerkinElmer differential thermal analyzer in 25 ℃～-70 ℃ scope, measure the solidifying point of above-mentioned electrolyte, be-30.68 ℃ with the cooling rate of 1 ℃/min.
The sodium perchlorate that 561.96g is commercially available is dissolved in the 1L deionized water, obtains the electrolyte that concentration is 4M;
Use DJS～10C type conductivity meter to measure above-mentioned electrolyte conductance at room temperature, be 292mScm
-1
Use the PerkinElmer differential thermal analyzer in 25 ℃～-70 ℃ scope, measure the solidifying point of above-mentioned electrolyte, be-36.33 ℃ with the cooling rate of 1 ℃/min.
Embodiment 4
The sodium perchlorate that 702.45g is commercially available is dissolved in the 1L deionized water, obtains the electrolyte that concentration is 5M;
Use DJS～10C type conductivity meter to measure above-mentioned electrolyte conductance at room temperature, be 296.6mScm
-1
Use the PerkinElmer differential thermal analyzer in 25 ℃～-70 ℃ scope, measure the solidifying point of above-mentioned electrolyte, be-39.32 ℃ with the cooling rate of 1 ℃/min.
Embodiment 5
The sodium perchlorate that 842.94g is commercially available is dissolved in the 1L deionized water, obtains the electrolyte that concentration is 6M;
Use DJS～10C type conductivity meter to measure above-mentioned electrolyte conductance at room temperature, be 286.8mScm
-1
Use the PerkinElmer differential thermal analyzer in 25 ℃～-70 ℃ scope, measure the solidifying point of above-mentioned electrolyte, be-55.2 ℃ with the cooling rate of 1 ℃/min.
Embodiment 6
After 6mgMaxsorb and 3mg electroconductive binder mixed, be coated in 1cm
2* 1cm
2On the stainless (steel) wire current collector, depress to the uniform film of thickness, obtain electrode of super capacitor at the pressure of 3MPa.Described electroconductive binder is that mass ratio is 2: 1 the acetylene black and the mixture of polytetrafluoroethylene.
Electrode with embodiment 6 preparations is that work electrode, platinum electrode are for being reference electrode composition electrode system to electrode, Ag/AgCl (saturated KCl) electrode, place the electrolyte of 20mL embodiment 1, embodiment 2, embodiment 3 and embodiment 4 preparations respectively, adopt the CHI700d electrochemical workstation-0.7V～+ voltage range of 0.5V in, respectively with 1mVs
-1, 5mVs
-1, 10mVs
-1, 20mVs
-1, 50mVs
-1, 100mVs
-1, 150mVs
-1And 200mVs
-1Sweep the cyclic voltammetry curve figure that speed obtains above-mentioned battery system, and sweep speed according to this curve calculation difference and descend the unipolar electric capacity that compares, referring to Fig. 1, the electrode of super capacitor that Fig. 1 provides for the embodiment of the invention sweep speed-than capacitance curve figure, wherein, curve a sweeps speed-than capacitance curve figure for what obtain in the electrolyte of embodiment 1 preparation, curve b sweeps speed-than capacitance curve figure for what obtain in the electrolyte of embodiment 2 preparation, curve c sweeps speed-than capacitance curve figure for what obtain in the electrolyte of embodiment 3 preparation, curve d sweeps speed-than capacitance curve figure for what obtain in the electrolyte of embodiment 4 preparations.
Wherein, than electric capacity SC=i/vm, i represents electric current, and v represents that current potential sweeps speed, and m is the active material quality.
Electrode with embodiment 6 preparations is respectively both positive and negative polarity, with filter paper as the both positive and negative polarity spacer film, the electrolyte of measuring 4mL embodiment 2 and embodiment 4 preparations is respectively put into plastic centrifuge tube, adopt LAND series battery test macro, under the 1.2V operating voltage, respectively at 1mA, 2mA, 3mA, 4mA, 5mA, 6mA, 7mA, 8mA, carry out charge-discharge test under the current density of 9mA and 10mA, obtain the ragone plot curve of electrode, referring to Fig. 2, the ragone plot curve chart of the electrode of super capacitor that Fig. 2 provides for the embodiment of the invention, the ragoneplot curve chart of curve A in the electrolyte of embodiment 2 preparations, obtaining, the ragone plot curve chart of curve B in the electrolyte of embodiment 3 preparations, obtaining.
Embodiment 9
Electrode with embodiment 6 preparations is respectively both positive and negative polarity, with filter paper as the both positive and negative polarity spacer film, the electrolyte of measuring 4mL embodiment 2 preparations is put into plastic centrifuge tube, adopt LAND series battery test macro, under the 1.2V operating voltage, under the current density of 1mA, 2mA, 3mA, 4mA, 5mA, 6mA, 7mA, 8mA, 9mA and 10mA, carry out charge-discharge test 10000 times respectively, referring to Fig. 3, the concentration of electrolyte that Fig. 3 provides for the embodiment of the invention is the constant current charge-discharge test curve figure of the ultracapacitor of 3M.
Embodiment 10
Electrode with embodiment 6 preparations is respectively both positive and negative polarity, with filter paper as the both positive and negative polarity spacer film, the electrolyte of measuring 4mL embodiment 4 preparations is put into plastic centrifuge tube, adopt LAND series battery test macro, under the 1.2V operating voltage, under the current density of 1mA, 2mA, 3mA, 4mA, 5mA, 6mA, 7mA, 8mA, 9mA and 10mA, carry out charge-discharge test 10000 times respectively, referring to Fig. 4, the concentration of electrolyte that Fig. 4 provides for the embodiment of the invention is the constant current charge-discharge test curve figure of the ultracapacitor of 5M.
Embodiment 11
The sodium perchlorate that 702.45g is commercially available is dissolved in the 1L deionized water, obtains the electrolyte that concentration is 5M;
In above-mentioned electrolyte, add 0.25g methyl alcohol, obtain containing the electrolyte of methyl alcohol.
Use DJS～10C type conductivity meter to measure the above-mentioned electrolyte conductance at room temperature that contains methyl alcohol, be 235.2mScm
-1
Use the PerkinElmer differential thermal analyzer in 25 ℃～-70 ℃ scope, measure the above-mentioned solidifying point that contains the electrolyte of methyl alcohol, be-66.8 ℃ with the cooling rate of 1 ℃/min.
Comparative Examples 1
The sodium sulphate that 142.04g is commercially available is dissolved in the 1L deionized water, obtains the electrolyte that concentration is 1M;
Use DJS～10C type conductivity meter to measure above-mentioned electrolyte conductance at room temperature, be 142.6mScm
-1
Use the PerkinElmer differential thermal analyzer in 25 ℃～-70 ℃ scope, measure the solidifying point of above-mentioned electrolyte, be-14.8 ℃ with the cooling rate of 1 ℃/min.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection range of claim of the present invention.
Claims (10)
1. an electrolyte that is used for ultracapacitor is characterized in that, solvent is a water, and solute is a sodium perchlorate;
Wherein, the concentration of sodium perchlorate is 2M～6M.
2. electrolyte according to claim 1 is characterized in that, the concentration of described sodium perchlorate is 3M～5M.
3. electrolyte according to claim 1 is characterized in that, also comprises alcohols.
4. electrolyte according to claim 3 is characterized in that, described alcohols is methyl alcohol, ethanol, ethylene glycol or glycerol.
5. a ultracapacitor is characterized in that, comprising:
Positive pole, negative pole, the barrier film between positive pole and negative pole and electrolyte;
Described electrolyte is that concentration is the sodium perchlorate aqueous solution of 2M～6M.
6. ultracapacitor according to claim 5 is characterized in that, described electrolyte is that concentration is the sodium perchlorate aqueous solution of 3M～5M.
7. ultracapacitor according to claim 5 is characterized in that described electrolyte also comprises alcohols.
8. ultracapacitor according to claim 7 is characterized in that, described alcohols is methyl alcohol, ethanol, ethylene glycol or glycerol.
9. ultracapacitor according to claim 5 is characterized in that, described just very material with carbon element electrode.
10. ultracapacitor according to claim 5 is characterized in that, described negative pole is the material with carbon element electrode.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102683039A (en) * | 2012-05-15 | 2012-09-19 | 中国科学院长春应用化学研究所 | Electrochemical capacitor |
| CN103811196A (en) * | 2014-01-22 | 2014-05-21 | 东风商用车有限公司 | Water-based electrolyte of super capacitor |
| CN104518233A (en) * | 2013-09-29 | 2015-04-15 | 中国科学院大连化学物理研究所 | Chlorine-containing all-vanadium redox flow battery anode electrolyte |
| CN105280397A (en) * | 2014-05-26 | 2016-01-27 | 中国科学院长春应用化学研究所 | Aqueous electrolyte and super-capacitor |
| CN107204243A (en) * | 2017-05-03 | 2017-09-26 | 中国第汽车股份有限公司 | A kind of zinc ion electrolytic solution for super capacitor |
| CN108428950A (en) * | 2018-05-15 | 2018-08-21 | 华中科技大学 | A kind of aqueous electrolyte of width decomposition voltage |
| US10102982B2 (en) | 2015-03-03 | 2018-10-16 | Ut-Battelle Llc | Electrolytes for supercapacitors |
| CN111244540A (en) * | 2020-01-17 | 2020-06-05 | 中国科学院兰州化学物理研究所 | Aqueous high-voltage window anti-freezing electrolyte and application thereof |
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| CN1183562C (en) * | 1998-10-13 | 2005-01-05 | 松下电器产业株式会社 | Aluminium electrolyte capacitor |
| TW201001784A (en) * | 2008-04-07 | 2010-01-01 | Univ Carnegie Mellon | Sodium ion based aqueous electrolyte electrochemical secondary energy storage device |
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2010
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| CN1183562C (en) * | 1998-10-13 | 2005-01-05 | 松下电器产业株式会社 | Aluminium electrolyte capacitor |
| TW201001784A (en) * | 2008-04-07 | 2010-01-01 | Univ Carnegie Mellon | Sodium ion based aqueous electrolyte electrochemical secondary energy storage device |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102683039A (en) * | 2012-05-15 | 2012-09-19 | 中国科学院长春应用化学研究所 | Electrochemical capacitor |
| CN104518233A (en) * | 2013-09-29 | 2015-04-15 | 中国科学院大连化学物理研究所 | Chlorine-containing all-vanadium redox flow battery anode electrolyte |
| CN103811196A (en) * | 2014-01-22 | 2014-05-21 | 东风商用车有限公司 | Water-based electrolyte of super capacitor |
| CN103811196B (en) * | 2014-01-22 | 2016-08-17 | 东风商用车有限公司 | A kind of ultracapacitor aqueous electrolyte |
| CN105280397A (en) * | 2014-05-26 | 2016-01-27 | 中国科学院长春应用化学研究所 | Aqueous electrolyte and super-capacitor |
| CN105280397B (en) * | 2014-05-26 | 2018-07-03 | 中国科学院长春应用化学研究所 | A kind of aqueous electrolyte and ultracapacitor |
| US10102982B2 (en) | 2015-03-03 | 2018-10-16 | Ut-Battelle Llc | Electrolytes for supercapacitors |
| CN107204243A (en) * | 2017-05-03 | 2017-09-26 | 中国第汽车股份有限公司 | A kind of zinc ion electrolytic solution for super capacitor |
| CN108428950A (en) * | 2018-05-15 | 2018-08-21 | 华中科技大学 | A kind of aqueous electrolyte of width decomposition voltage |
| CN111244540A (en) * | 2020-01-17 | 2020-06-05 | 中国科学院兰州化学物理研究所 | Aqueous high-voltage window anti-freezing electrolyte and application thereof |
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Application publication date: 20100922 |