CN101399120A - Novel hybrid supercapacitor - Google Patents
Novel hybrid supercapacitor Download PDFInfo
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- CN101399120A CN101399120A CNA2008102019844A CN200810201984A CN101399120A CN 101399120 A CN101399120 A CN 101399120A CN A2008102019844 A CNA2008102019844 A CN A2008102019844A CN 200810201984 A CN200810201984 A CN 200810201984A CN 101399120 A CN101399120 A CN 101399120A
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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
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Abstract
The invention relates to a novel hybrid super capacitor. It is made of nano MnO 2 The electrode is a positive electrode, the active carbon electrode is a negative electrode, and the alkaline lithium hydroxide aqueous solution is an electrolyte. The positive electrode stores energy mainly by a Faraday oxidation-reduction mechanism, and the negative electrode stores energy by an electric double layer mechanism. With lithium hydroxide electrolyte, nano MnO 2 The reaction mechanism of the electrode is different from that in a potassium hydroxide electrolyte or a neutral aqueous solution electrolyte, and thus has a higher specific capacitance. The super capacitor has excellent high energy density, high power density and high-rate charge-discharge performance, and has long cycle life, low cost and no environmentThe damage advantage is suitable for the high-power charge and discharge occasions.
Description
Technical Field
The invention relates to the field of chemical power supplyIn particular to nano MnO with excellent high-rate charge-discharge performance, high energy and power density, long cycle life, low cost and environmental friendliness and using LiOH aqueous solution as electrolyte 2 An activated carbon hybrid supercapacitor; also relates to a high specific capacity anode material doped with nano MnO 2 The preparation method of (1).
Background
The electrochemical super capacitor is a novel energy storage device with performance between that of a conventional capacitor and that of a secondary battery, has the advantages of high power density of the conventional capacitor and high energy density of the secondary battery, and has wide application prospects in the fields of data memory storage systems, standby power supplies, electronic instruments, electric vehicle hybrid power supply systems and the like. Electrochemical supercapacitors can be divided into two categories according to the energy storage mechanism: the specific capacitance of the redox capacitor is usually much higher than that of the electric double layer capacitor.
Hydrated RuO as an electrode material for redox type supercapacitor 2 Has the advantages of high specific capacitance and good cycle stability in sulfuric acid solution, but is expensive and has limited large-scale commercial application. Thus, other metal oxides such as NiO, co 3 O 4 And MnO 2 Etc. are being emphasized, wherein NiO and Co 3 O 4 The range of the charge and discharge potential of (2) is narrow. Nano MnO 2 The method has the advantages of high specific capacitance, wide charge-discharge potential range, abundant resources, environmental friendliness and the like, and has attracted great attention in the field of super capacitors in recent years. With nano MnO 2 Super capacitor such as nano MnO as anode material 2 Activated carbon hybrid capacitors, usually using non-aqueous organic electrolytes or neutral aqueous electrolytes containing lithium ions, e.g. Na2SO 4 Aqueous solutions, etc., and alkaline KOH electrolytes are also used in a few cases.
Disclosure of Invention
The invention aims to provide a novel hybrid supercapacitor which has the advantages of high energy density, high power density, excellent high-rate charge-discharge performance, low cost and environmental friendliness. The specific capacitance, energy and power density of the material are obviously higher than that of nano MnO using KOH electrolyte 2 Activated carbon capacitor, much higher than nano MnO with neutral aqueous electrolyte 2 Activated carbon capacitor with cycle life far superior to that of nano MnO using KOH electrolyte 2 Activated carbon capacitor. The improvement in capacitor performance results from the improvement in positive performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
the utility model provides a novel mixed ultracapacitor system comprises positive plate, negative pole piece, between the two diaphragm and the alkaline electrolyte that has ionic conductivity, its characterized in that: the positive active material of the capacitor is nano MnO 2 The electrode material, the negative active substance is porous active carbon, the diaphragm is a polypropylene film, and the electrolyte is LiOH aqueous solution with the concentration of 1-3 mol/L.
Nano MnO of positive active material 2 The electrode material is pure nano MnO 2 Materials or doped with nano MnO 2 Materials or nano-metersMnO 2 A carbon nanotube composite material.
Doped nano MnO 2 The material being nano MnO 2 The medium is doped with Mg and Al elements or co-doped with the Mg and the Al elements.
The conductive agent adopted by the anode and the cathode is acetylene black, the adopted binder is polytetrafluoroethylene, and the adopted current collector is porous foam nickel.
The mass ratio of the anode is nano MnO 2 : acetylene black: and (3) polytetrafluoroethylene = 75-80.
The mass ratio of the negative electrode is activated carbon: acetylene black: polytetrafluoroethylene = 75-80, from 15 to 20; mixing the three components uniformly, stirring into paste, coating into foam nickel current collector, and pressing into sheet.
The novel hybrid supercapacitor provided by the invention is composed of a positive electrode, a negative electrode, a diaphragm between the positive electrode and the negative electrode and a LiOH aqueous solution electrolyte. The main component of the anode is nano MnO 2 The main component of the negative electrode is active carbon having a porous structure, and the separator is a polypropylene film.
The significance of the invention lies in that: by using LiOH electrolyte instead of KOH electrolyte, not only MnO is reduced 2 The specific capacitance, specific energy and specific power of the/active carbon super capacitor are improved, and more importantly, the cycle life is greatly improved. For using the same nano MnO 2 Anode material, nano MnO with 1mol/LLIOH solution as electrolyte under the same test conditions 2 The electrochemical performance of the activated carbon capacitor is better than that of nano MnO taking 1mol/LKOH solution as electrolyte 2 An activated carbon capacitor as shown in fig. 1 and 2. Manganese dioxide is widely used as a positive electrode material in alkaline zinc-manganese batteries using KOH alkaline aqueous solution as electrolyte, and the reaction mechanism is generally considered as a 'proton-electron mechanism', and H is generated during discharge + Embedded in MnO 2 Deep discharges in the electrodes produce electrochemically inactive oxides of manganese, making the reaction irreversible. When LiOH electrolyte is used, li is used + Small radius, H + Low concentration, mnO in the range of 0-0.8V (relative to saturated calomel electrode) for charging 2 The reaction mechanism of the electrode involves Li + In MnO 2 Reversible intercalation/deintercalation reactions in the electrodes, resulting in a large faradaic redox pseudocapacitance with good reversibility.
It is known that when an aqueous electrolyte is used, the voltage of an activated carbon/activated carbon symmetrical capacitor is not high (generally 1 to 1.2V or less), and the specific capacitance of an activated carbon electrode is not large, so that the energy density and power density of the capacitor are not large. In the nano MnO 2 Nano MnO in/active carbon mixed super capacitor 2 Utilization of positive electrodeEnergy is stored by Faraday redox principle, energy is stored by an active carbon cathode by using an electric double layer principle, a capacitor has higher working voltage and nano MnO 2 The specific capacitance of (a) is larger than that of active carbon, so the energy density and power density of the capacitor are much higher than those of the active carbon symmetrical type capacitor. MnO in the present invention 2 The working voltage of the/active carbon mixed super capacitor can reach 1.5-1.8V.
Drawings
FIG. 1 Nano MnO 2 Cyclic voltammograms of the electrodes in 1mol/LLIOH and 1mol/LKOH electrolyte (sweep rate: 1 mV/s).
FIG. 2 shows nano MnO with 1mol/LLIOH and 1mol/LKOH as electrolytes 2 Cycle life of the/AC hybrid capacitor (current density: 100 mA/g).
FIG. 3 shows nano MnO with 1mol/LLIOH as electrolyte 2 The multiplying power discharge performance of the/active carbon mixed super capacitor.
FIG. 4 shows nano MnO with 1mol/LLIOH as electrolyte 2 Cycle life of the/activated carbon hybrid supercapacitor (current density: 500 mA/g).
FIG. 5 Nano MnO 2 Energy-power diagram of the/activated carbon hybrid capacitor (Ragon diagram).
FIG. 6 Nano MnO 2 The charge-discharge curve of the/active carbon mixed capacitor under the current density of 500 mA/g.
FIG. 7 Nano MnO 2 The cycle life of the/activated carbon hybrid capacitor at a current density of 500 mA/g.
FIG. 8 pure nano MnO 2 Electrode and Al-doped nano MnO 2 The specific capacitance of the electrode under different current densities.
Detailed Description
The preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.
The first embodiment is as follows: this neotype hybrid supercapacitor, by positive plate, negative pole piece, between the two diaphragm and have ion conductivity's alkaline electrolyte and constitute its characterized in that: the positive electrode active material of the capacitor is nano MnO 2 The electrode material, the negative active substance are porous active carbon, the diaphragm is a polypropylene film, and the electrolyte is LiOH aqueous solution with the concentration of 1-3 mol/L.
Manufacturing a positive plate: manganese acetate (MnAc) in a molar ratio of 1: 1 2 ·4H 2 O) and citric acid (C) 6 H 8 O 7 ·H 2 O) as raw material, grinding in mortar, carrying out low-heat solid phase reaction to obtain precursor, calcining the precursor in air atmosphere at 300 ℃ for 10 hours, and then carrying out 2mol/LH 2 SO 4 Acidifying the solution for 2 hours, cleaning and drying to obtain nano MnO 2 A material. Adding nano MnO 2 Acetylene black and PTFE are evenly mixed according to the mass ratio of 80: 15: 5, stirred to be paste, then blade-coated into a foamed nickel current collector, dried for a plurality of hours at the temperature of 80 ℃, rolled into a sheet to obtain the nano MnO 2 And an electrode. And (3) manufacturing a negative plate: uniformly mixing the activated carbon, the acetylene black and the PTFE in a mass ratio of 80: 15: 5, stirring the mixture into paste, then coating the paste into a foamed nickel current collector in a scraping way, drying the paste at 80 ℃ for several hours, and rolling the dried paste into a sheet to obtain the activated carbon electrode. The electrolyte adopts 1mol/LLIOH solution, the diaphragm adopts a polypropylene film to form nano MnO 2 Active carbon super capacitor. The cycle life of the capacitor in charging and discharging in the voltage range of 0.5 to 1.5V is shown in FIG. 2, and the rate discharge performance is shown in FIG. 3. It can be seen that the nano MnO with LiOH solution as electrolyte 2 The activated carbon capacitor has good rate discharge performance and cycle stability far better than that of nano MnO taking KOH solution as electrolyte 2 An active carbon capacitor.
The second embodiment: this example is essentially the same as example 1, except that: manganese chloride (MnCl) in a molar ratio of 1: 2.2 2 ·4H 2 O) and ammonium bicarbonate (NH) 4 HCO 3 ) Grinding in mortar, and grindingReacting raw low-heat solid phase to obtainPrecursor (MnCO) 3 And NH 4 Mixture of Cl), the precursor was calcined at 350 ℃ for 10 hours in an air atmosphere and then subjected to 2mol/L H 2 SO 4 Acidifying the solution for 2 hours, cleaning and drying to obtain nano MnO 2 A material. Nano MnO obtained by adopting the method for the anode 2 The material preparation, negative pole, electrolyte and diaphragm are all the same as example 1, the preparation process of the electrode is also the same as example 1, and the nano MnO is formed 2 Active carbon super capacitor. The charge-discharge cycle life of the capacitor at a voltage of 0.5 to 1.5V and a current density of 500mA/g is shown in FIG. 4. After 5000 times of circulation, the specific capacitance is reduced by only 12 percent.
Example three: this example is essentially the same as example 1, except that: manganese chloride (MnCl) in a molar ratio of 1: 1.2 2 ·4H 2 O) and ammonium oxalate ((NH) 4 ) 2 C 2 O 4 ·H 2 O) is taken as a raw material, and is ground in a mortar, so that low-heat solid phase reaction occurs. Dissolving the solid-phase reaction product in water to remove soluble substances, drying to obtain a manganese oxalate precursor, calcining the precursor in an air atmosphere at 400 ℃ for 10 hours, and then performing 2mol/LH on the calcined precursor 2 SO 4 Acidifying the solution for 2 hours, cleaning and drying to obtain nano MnO 2 And (3) material. The anode adopts the nano MnO obtained by the method 2 The materials are prepared, the negative electrode, the electrolyte and the diaphragm are all the same as the embodiment 1, the electrode preparation process is also the same as the embodiment 1, and the nano MnO is formed 2 Active carbon super capacitor. The energy-power relationship (Ragon graph) of the capacitor in charging and discharging in the voltage range of 0-1.8V is shown in FIG. 5, the charging and discharging curve under the current density of 500mA/g is shown in FIG. 6, and the cycle life is shown in FIG. 7. As can be seen from fig. 5, there is a higher energy density even at a higher power density.
Example four: this example is essentially the same as example 1, except that: respectively weighing certain amount of Mn (Ac) according to molar ratio of n (Mn) to n (Al) = 100: 0, 90: 10, 80: 20 and 70: 30 2 ·4H 2 O and Al 2 (SO 4 ) 3 ·18H 2 O, then n (Mn + Al) to n (C) according to the molar ratio 2 H 2 O 4 ·2H 2 O) = 1: 1.2 addition of oxalic acid (C) 2 H 2 O 4 ·2H 2 O), ground in a mortar, and a low thermal solid phase reaction occurred. Dissolving the solid-phase reaction product in water to remove soluble substances, drying to obtain a precursor, calcining the precursor in an air atmosphere at 400 ℃ for 12 hours, and then performing 2mol/LH on the calcined precursor 2 SO 4 Acidifying the solution for 2 hours, cleaning and drying to obtain nano MnO 2 And (3) materials. Pure nano MnO prepared by the method 2 And Al-doped nano MnO 2 Nano MnO was prepared by the same method as in example 1 2 And an electrode. Testing of Nano MnO 2 Electrochemical performance of electrode in 1mol/LLIOH electrolyte, pure nano MnO 2 Nano MnO with different Al content 2 The specific discharge capacitance of the electrodes at different current densities is shown in fig. 8. As can be seen, in the current density range of 50-1000 mA/g, the specific capacitance of different electrodes has the following relationship under each current density: mnO doped with aluminum 20% 2 >MnO doped with 30% of aluminum 2 >MnO doped with aluminum 10% 2 >Pure MnO 2 . Aluminum-doped 20% nano MnO 2 The specific capacitance of the electrode under the current density of 50mA/g is up to 354.6F/g, and the specific capacitance can also be up to 188.1F/g even under the current density of 1000mA/g, which is far higher than that of pure nano MnO 2 Specific capacitance of the electrode being pure MnO 2 More than 2 times the number of electrodes. Aluminum doping can significantly improve the nano MnO 2 The specific capacitance of (c).
Claims (6)
1. The utility model provides a novel mixed ultracapacitor system, by positive plate, negative pole piece, between the two diaphragm and have ionic conductivity's alkaline electrolyte and constitute which characterized in that: the positive electrode active material of the capacitor is nano MnO 2 The electrode material, the negative active substance is porous active carbon, the diaphragm is a polypropylene film, and the electrolyte is LiOH aqueous solution with the concentration of 1-3 mol/L.
2. The novel hybrid supercapacitor according to claim 1, characterised in that: nano MnO of the positive active material 2 The electrode material is pure nano MnO 2 Materials or doped with nano MnO 2 Materials or nano-MnO 2 A carbon nanotube composite material.
3. The novel hybrid supercapacitor according to claim 2, characterized in that: the doped nano MnO 2 The material being nano MnO 2 And is doped with Mg and Al elements or co-doped with the Mg and the Al elements.
4. The novel hybrid supercapacitor according to claim 1, characterised in that: the conductive agent adopted by the positive electrode and the negative electrode is acetylene black, the binder adopted by the positive electrode and the negative electrode is polytetrafluoroethylene, and the current collector adopted by the positive electrode and the negative electrode is porous foamed nickel.
5. The novel hybrid supercapacitor according to claim 4, characterised in that: the mass ratio of the anode is nano MnO 2 : acetylene black: polytetrafluoroethylene =75 to 80:15 to 20:5, mixing the three components evenly, stirring the mixture into paste, coating the paste into a foamed nickel current collector, and pressing the foamed nickel current collector into a sheet.
6. The novel hybrid supercapacitor according to claim 5, characterised in that: the mass ratio of the negative electrode is activated carbon: acetylene black: polytetrafluoroethylene =75 to 80: 15-20: and 5, uniformly mixing the three components, stirring the mixture into paste, coating the paste into a foamed nickel current collector, and pressing the foamed nickel current collector into sheets.
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| CNA2008102019844A CN101399120A (en) | 2008-10-30 | 2008-10-30 | Novel hybrid supercapacitor |
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| CNA2008102019844A CN101399120A (en) | 2008-10-30 | 2008-10-30 | Novel hybrid supercapacitor |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102376452A (en) * | 2011-12-07 | 2012-03-14 | 北京科技大学 | Super capacitor assembled by manganese series oxide electrodes with meshed nano-structures |
| CN102543470A (en) * | 2012-01-16 | 2012-07-04 | 中国电力科学研究院 | Low inner resistance manganese dioxide electrode for water system supercapacitor and preparation method thereof |
| CN102568833A (en) * | 2010-12-24 | 2012-07-11 | 同济大学 | Hybrid electrochemical capacitor with mesoporous cobaltosic oxide as positive pole |
| CN102683037A (en) * | 2012-05-10 | 2012-09-19 | 中国第一汽车股份有限公司 | Manganese dioxide asymmetric super capacitor and manufacturing method thereof |
| CN107317063A (en) * | 2017-05-18 | 2017-11-03 | 宁波中车新能源科技有限公司 | A kind of recovery and treatment method of ternary system battery capacitor positive pole |
| CN110188452A (en) * | 2019-05-27 | 2019-08-30 | 清华大学 | The dynamic-simulation method of composite super capacitor |
| US11923140B2 (en) * | 2020-04-08 | 2024-03-05 | The Board Of Trustees Of The University Of Illinois | Carbon-metal oxide composite electrode for a supercapacitor and method of making a carbon-metal oxide composite electrode |
-
2008
- 2008-10-30 CN CNA2008102019844A patent/CN101399120A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102568833A (en) * | 2010-12-24 | 2012-07-11 | 同济大学 | Hybrid electrochemical capacitor with mesoporous cobaltosic oxide as positive pole |
| CN102568833B (en) * | 2010-12-24 | 2014-03-05 | 同济大学 | Hybrid electrochemical capacitor with mesoporous cobaltosic oxide as positive pole |
| CN102376452A (en) * | 2011-12-07 | 2012-03-14 | 北京科技大学 | Super capacitor assembled by manganese series oxide electrodes with meshed nano-structures |
| CN102376452B (en) * | 2011-12-07 | 2013-07-24 | 北京科技大学 | Super capacitor assembled by manganese series oxide electrodes with meshed nano-structures |
| CN102543470A (en) * | 2012-01-16 | 2012-07-04 | 中国电力科学研究院 | Low inner resistance manganese dioxide electrode for water system supercapacitor and preparation method thereof |
| CN102543470B (en) * | 2012-01-16 | 2014-12-03 | 中国电力科学研究院 | Low inner resistance manganese dioxide electrode for water system supercapacitor and preparation method thereof |
| CN102683037A (en) * | 2012-05-10 | 2012-09-19 | 中国第一汽车股份有限公司 | Manganese dioxide asymmetric super capacitor and manufacturing method thereof |
| CN102683037B (en) * | 2012-05-10 | 2016-06-01 | 中国第一汽车股份有限公司 | Manganese dioxide asymmetric super-capacitor and preparation method thereof |
| CN107317063A (en) * | 2017-05-18 | 2017-11-03 | 宁波中车新能源科技有限公司 | A kind of recovery and treatment method of ternary system battery capacitor positive pole |
| CN110188452A (en) * | 2019-05-27 | 2019-08-30 | 清华大学 | The dynamic-simulation method of composite super capacitor |
| US11923140B2 (en) * | 2020-04-08 | 2024-03-05 | The Board Of Trustees Of The University Of Illinois | Carbon-metal oxide composite electrode for a supercapacitor and method of making a carbon-metal oxide composite electrode |
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