CN101577180B - Water phase ultra-capacitor used at working voltage of between 2.4 and 3.0V and method for preparing same - Google Patents
Water phase ultra-capacitor used at working voltage of between 2.4 and 3.0V and method for preparing same Download PDFInfo
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- CN101577180B CN101577180B CN2009100120110A CN200910012011A CN101577180B CN 101577180 B CN101577180 B CN 101577180B CN 2009100120110 A CN2009100120110 A CN 2009100120110A CN 200910012011 A CN200910012011 A CN 200910012011A CN 101577180 B CN101577180 B CN 101577180B
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Abstract
The invention belongs to the technical field of ultra-capacitors, and in particular relates to a water phase ultra-capacitor used at a working voltage of between 2.4 and 3.0V and a method for preparing the same. The capacitor consists of a manganese oxide/active carbon composite electrode material, an active carbon cathode, an electrolyte, a diaphragm, an anode lead, a cathode lead and a shell. The invention utilizes dual functions of the active carbon in the positive electrode in different voltage ranges, which are a conductive agent and an anode active material, and simultaneously the capacitor unit shows behaviors of an asymmetrical capacitor as well as a symmetrical capacitor, so that the working voltage of the ultra-capacitor unit is essentially improved; at the same time, the asymmetrical capacitor has better electrochemical behaviors and can more reasonably achieve power density and energy density, so that the high-power quick discharge is made possible, and the range of the working voltage of the capacitor unit is widened; the process of preparing electrode materials is simple; and a neutral water phase electrolyte is used, so that the ultra-capacitor is easy for industrialized application.
Description
Technical field
The invention belongs to the ultracapacitor technical field, particularly a kind ofly can in water electrolyte, stablize use, operating voltage can reach asymmetric ultracapacitor of 2.4～3.0V and preparation method thereof.
Background technology
Ultracapacitor is called electrochemical capacitor again, is a kind of novel energy-storing element between traditional capacitor and battery, has high power density, the life-span is long, operating temperature range is wide in range and characteristics such as environmental friendliness.Ultracapacitor can provide high-energy in the short time, is applicable to the electronic device of fast charging and discharging.But also there is energy density problem on the low side in actual applications in ultracapacitor.Present business-like ultracapacitor adopts organic electrolyte to improve the energy density of its capacitor unit more.But the organic electrolyte existence costs an arm and a leg capacitor preparation condition harshness, shortcomings such as contaminated environment.Therefore obtaining to have than the ultracapacitor of wide operating voltage range in water electrolyte is the focus of Recent study.
Asymmetric ultracapacitor is to have the both positive and negative polarity series connection of different materials, in conjunction with the difference of anodal and negative material overpotential, to have avoided the electrolyte puncture in the particular job voltage range, thereby widened the operating voltage of capacitor unit.According to density energy formula E=1/2CV
2, C be electrode than electric capacity, V is an operating voltage.Along with the raising of operating voltage, energy density produces exponential increase.Result of study shows the asymmetric ultracapacitor of being made up of manganese oxide and charcoal, and operating voltage can reach 2V, and has good electrochemical behavior.This operating voltage range with common water electrolyte 0.6V～0.8V is compared, and asymmetric capacitor arrangement has effectively improved the operating voltage of capacitor unit, thereby has significantly improved energy density.But the electrode series connection has produced adding up of quality simultaneously, and then has caused the operating voltage raising of capacitor unit significantly to reduce than electric capacity simultaneously.The present invention adopts manganese oxide/active carbon combination electrode material to replace manganese oxide, utilizes that active carbon has played conductive agent and positive active material double action in the positive electrode in different voltage ranges, has further widened the operating voltage range of capacitor unit.Compare with the dissymmetrical structure that simple manganese oxide and charcoal are formed, this electrochemical capacitor unit can reach the operating voltage range of 2.4V～3.0V under than the situation of electric capacity small loss, and can keep stability under this operating potential.The present invention selects neutral water electrolyte, is beneficial to environmental protection, and its low-corrosiveness is easy to the selection of encapsulating material, can further reduce cost to have the good prospect of marketing.
Summary of the invention
The objective of the invention is to improve the problem that significantly reduces than electric capacity simultaneously in operating voltage at asymmetric capacitor, utilize manganese oxide/active carbon combination electrode material to replace manganese oxide list material positive pole, be assembled into the asymmetric capacitor working cell of operating voltage range with 2.4V～2.8V.
Technical scheme of the present invention is: the water ultracapacitor that uses under 2.4～3.0V operating voltage is made up of manganese oxide/active carbon combination electrode material, activated carbon cathode, electrolyte, barrier film, anode tap, cathode leg and shell;
Manganese oxide/absorbent charcoal composite material anode is that the ratio of each component is by the mixed uniformly mixture of manganese oxide, active carbon and polytetrafluoroethylene:
Manganese oxide 20～90wt%
Wherein manganese oxide and active carbon are active materials, described manganese oxide be amorphous-, α-, β-, γ-, δ-, ε-MnO
2, its BET specific area excursion is 10m
2/ g～350m
2/ g; Described active carbon is plant base, polymer-matrix or active carbon from coal, and surface energy contains nitrogen base and oxy functional groups; Its BET specific area scope is 700m
2/ g～3000m
2/ g;
The enough multistage holes of active carbon energy charcoal, template charcoal or hollow carbon sphere replace;
Activated carbon cathode is that the ratio of each component is by active carbon and the mixed uniformly mixture of polytetrafluoroethylene:
Active carbon 90～95wt%
Wherein active carbon is an active material, and described active carbon is plant base, polymer-matrix or active carbon from coal, and activated carbon surface can contain nitrogen base and oxy functional groups; Its BET specific area scope is 700m
2/ g～3000m
2/ g;
The enough multistage holes of active carbon energy charcoal, template charcoal or hollow carbon sphere replace;
Electrolyte is for containing K
+, Na
+, Ca
2+And NH
4+The water electrolyte of ion, solution is near neutral, and the change in concentration scope is 0.5mol/L～2mol/L; Membrane thicknesses is 20 μ m～50 μ m.
The method of the water ultracapacitor that preparation is used under 2.4～3.0V operating voltage, step is as follows:
(1) preparation of manganese oxide/absorbent charcoal composite material anode:
The preparation of A, manganese oxide:
Manganese oxide by liquid-phase precipitation or the synthetic even particle size of hydro thermal method;
B, anode preparation:
Manganese oxide, active carbon and teflon mixture are sticked on the stainless (steel) wire, and connect banded stainless steel collector on the stainless (steel) wire matrix, cutting then becomes rectangle or circle;
(2) preparation of activated carbon cathode:
Active carbon, multistage hole charcoal, template charcoal or hollow carbon sphere and teflon mixture are sticked on the stainless (steel) wire, and connect banded stainless steel collector on the stainless (steel) wire matrix, cutting then becomes rectangle or circle;
(3) assembling of capacitor:
Anode, barrier film and negative electrode are superposeed successively, and the composition tight structure injects electrolyte, inserts in the vacuum desiccator to vacuumize, and vacuum degree is 90MPa, and soaked overnight is drawn anode tap and cathode leg then, and the shell package group is dressed up capacitor.
The present invention combines the feature of symmetrical capacitor and asymmetric capacitor, has further widened operating voltage range under than the situation of capacitance small loss.According to density energy formula E=1/2CV
2, C be electrode than electric capacity, V is an operating voltage.Along with the raising of operating voltage, energy density produces exponential increase.Potential window of the present invention is 2.4～3.0V, compares with the operating voltage of the asymmetric capacitor unit of manganese oxide/charcoal 2V in water electrolyte, has largely improved the energy density of capacitor.
Effect benefit of the present invention: utilize active carbon conductive agent and positive active material double action in different voltage ranges in the positive electrode, and capacitor unit shows asymmetric and symmetrical capacitor behavior simultaneously, from having improved the operating voltage of ultracapacitor cell in essence.This asymmetric ultracapacitor has electrochemical behavior and more satisfactory power density and the energy density of obtaining preferably simultaneously, thereby make high-power fast charging and discharging become possibility, widened the capacitor unit operating voltage range, and electrode material preparation technology is simple, adopt neutral water electrolyte, be easy to industrial applications.
Description of drawings
Fig. 1 is the cyclic voltammetry curve of amorphous manganese oxide/absorbent charcoal composite material in the example 1.
Fig. 2 is the cyclic voltammetry curve of active carbon in the example 1.
Fig. 3 is that amorphous manganese oxide in the example 1/absorbent charcoal composite material is made the cyclic voltammetry curve of anodal asymmetric capacitor in the 2.4V operating voltage range.
Fig. 4 is that amorphous manganese oxide in the example 1/absorbent charcoal composite material is made the cyclic voltammetry curve of anodal asymmetric capacitor in the 2.8V operating voltage range.
Fig. 5 is that amorphous manganese oxide in the example 1/absorbent charcoal composite material is made the cyclic voltammetry curve of anodal asymmetric capacitor in the 3.0V operating voltage range.
Fig. 6 is that amorphous manganese oxide/absorbent charcoal composite material is made the crossing current charging and discharging curve of anodal asymmetric capacitor in 2.4V, 2.6V and 2.8V operating voltage range in the example 1.
Fig. 7 is that amorphous manganese oxide/absorbent charcoal composite material is made the cyclic voltammetry curve of anodal asymmetric capacitor in 2.4V and 2.6V operating voltage range in the example 2.
Fig. 8 is that amorphous manganese oxide in the example 3/multistage hole carbon composite is made the cyclic voltammetry curve of anodal asymmetric capacitor in 2.6V and 2.8V operating voltage range.
Fig. 9 is the stability test curve of amorphous manganese oxide/absorbent charcoal composite material in the example 6.
The instantiation mode
The amorphous-MnO that liquid-phase precipitation method is synthetic
2, take by weighing 0.40g potassium permanganate and place flask, adding the 15ml deionized water is solution A.Take by weighing the 0.93g manganese acetate and place flask, adding the 25ml deionized water is solution B.Solution B slowly splashes into solution A, mixed liquor continuous stirring 6h.With the reactant filtration, with ethanol or water washing, collect product at 110 ℃ of dryings, product amorphous-MnO
2The BET specific area be 325m
2/ g; With amorphous-MnO
2, active carbon and polytetrafluoroethylene press amorphous-MnO
2: active carbon: polytetrafluoroethylene=45wt%: 45wt%: 10wt% mixes and forms manganese oxide/active carbon anode composite;
With active carbon and polytetrafluoroethylene by active carbon: polytetrafluoroethylene=90wt%: the 10wt% combined group becomes activated carbon cathode, and the BET specific area that contains active carbon is 1870m
2/ g;
Anode, barrier film and negative electrode are superposeed successively, and the composition tight structure injects electrolyte, inserts in the vacuum desiccator to vacuumize, and vacuum degree is 90MPa, and soaked overnight is drawn anode tap and cathode leg then, and the shell package group is dressed up capacitor.The operating voltage of capacitor is 2.4V or 2.8V in this example, and recording than electric capacity is 24F/g.
Method of operation is identical with embodiment 1, and liquid-phase precipitation method synthesizes amorphous-MnO
2, difference is: amorphous-MnO
2: active carbon: polytetrafluoroethylene=60wt%: 30wt%: 10wt% mixes and forms manganese oxide/active carbon anode composite.The operating voltage of capacitor is 2.8V in this example, and recording than electric capacity is 19F/g.
Method of operation is identical with embodiment 1, and liquid-phase precipitation method synthesizes amorphous-MnO
2, difference is: multistage hole charcoal has replaced active carbon in the positive electrode.Amorphous-MnO
2, multistage hole charcoal and polytetrafluoroethylene press amorphous-MnO
2: multistage hole charcoal: polytetrafluoroethylene=45wt%: 45wt%: 10wt% mixes and forms manganese oxide/multistage hole carbon composite positive pole; The BET specific area of wherein multistage hole charcoal is 2492m
2/ g.The operating voltage of capacitor is 2.8V in this example, and recording than electric capacity is 17F/g.
Take by weighing 1.0g potassium permanganate, the 0.42g manganese sulfate places flask, continues stirring until the solution clarification.Solution is poured in the poly-tetrafluoro reactor of 150ml, stainless steel sealing, 160 ℃ of reaction 12h.With the reactant filtration, with ethanol or water washing, collect product 110 ℃ of dryings, product is α-MnO
2α-MnO that hydro thermal method is synthetic
2Form the composite material positive pole with active carbon.α-MnO wherein
2, multistage hole charcoal and polytetrafluoroethylene press α-MnO
2: multistage hole charcoal: polytetrafluoroethylene=45wt%: 45wt%: 10wt% mixes and forms manganese oxide/multistage hole carbon composite positive pole; α-MnO wherein
2The BET specific area be 51m
2/ g.The operating voltage of capacitor is 2.8V in this example, and recording than electric capacity is 12F/g.
Method of operation is identical with embodiment 1, and liquid-phase precipitation method synthesizes amorphous-MnO
2, difference is: the porous charcoal of template preparation has replaced active carbon in the positive electrode.Amorphous-MnO
2, template charcoal and polytetrafluoroethylene press amorphous-MnO
2: template charcoal: polytetrafluoroethylene=45wt%: 45wt%: 10wt% mixes and forms manganese oxide/template carbon composite positive pole; Choose porous charcoal by template preparation as negative electrode active material.Wherein the porous charcoal BET specific area of template preparation is 1135m
2/ g.The operating voltage of capacitor is 2.8V in this example, and recording than electric capacity is 15F/g.
Embodiment 6
Method of operation is identical with embodiment 1, preparation manganese oxide/active carbon anode composite, and difference is: asymmetric capacitor unit is at 5mA/cm
-2Constant current under the charge-discharge test that flows over, circulation is 600 times, tests its stability, test curve is seen Fig. 9.
Claims (2)
1. the water ultracapacitor that uses under 2.4～3.0V operating voltage is characterized in that, this capacitor is made up of manganese oxide/active carbon combination electrode material, activated carbon cathode, electrolyte, barrier film, anode tap, cathode leg and shell;
Manganese oxide/absorbent charcoal composite material anode is that the ratio of each component is by the mixed uniformly mixture of manganese oxide, active carbon and polytetrafluoroethylene:
Manganese oxide 20～90wt%
Active carbon 5～70wt%
Polytetrafluoroethylene 5～10wt%
Wherein manganese oxide and active carbon are active materials, and described manganese oxide is amorphous-MnO
2, α-MnO
2, β-MnO
2, γ-MnO
2, δ-MnO
2Or ε-MnO
2, its BET specific area excursion is 10m
2/ g～350m
2/ g; Described active carbon is plant base, polymer-matrix or active carbon from coal, and nitrogen base and oxy functional groups are contained in the surface; Its BET specific area scope is 700m
2/ g～3000m
2/ g;
Activated carbon cathode is that the ratio of each component is by active carbon and the mixed uniformly mixture of polytetrafluoroethylene:
Active carbon 90～95wt%
Polytetrafluoroethylene 5～10wt%
Wherein active carbon is an active material, and described active carbon is plant base, polymer-matrix or active carbon from coal, and activated carbon surface contains nitrogen base and oxy functional groups; Its BET specific area scope is 700m
2/ g～3000m
2/ g;
Described active carbon is multistage hole charcoal, template charcoal or hollow carbon sphere;
Electrolyte is for containing K
+, Na
+, Ca
2+And NH
4 +The water electrolyte of ion, solution is near neutral, and the change in concentration scope is 0.5mol/L～2mol/L; Membrane thicknesses is 20 μ m～50 μ m.
2. prepare the method for the described water ultracapacitor that under 2.4～3.0V operating voltage, uses of claim 1, it is characterized in that step is as follows:
(1) preparation of manganese oxide/absorbent charcoal composite material anode:
The preparation of A, manganese oxide:
Manganese oxide by liquid-phase precipitation or the synthetic even particle size of hydro thermal method;
B, anode preparation:
Manganese oxide, active carbon and teflon mixture are sticked on the stainless (steel) wire, and connect banded stainless steel collector on the stainless (steel) wire matrix, cutting then becomes rectangle or circle;
(2) preparation of activated carbon cathode:
Active carbon, multistage hole charcoal, template charcoal or hollow carbon sphere and teflon mixture are sticked on the stainless (steel) wire, and connect banded stainless steel collector on the stainless (steel) wire matrix, cutting then becomes rectangle or circle;
(3) assembling of capacitor:
Anode, barrier film and negative electrode are superposeed successively, and the composition tight structure injects electrolyte, inserts in the vacuum desiccator to vacuumize, and vacuum degree is 90MPa, and soaked overnight is drawn anode tap and cathode leg then, and the shell package group is dressed up capacitor.
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| CN101916666B (en) * | 2010-08-18 | 2012-05-23 | 湖南金福达电子有限公司 | Method for impregnating elements of aluminum electrolytic capacitor |
| CN102142318B (en) * | 2011-03-17 | 2012-12-19 | 上海工程技术大学 | Ordered mesoporous carbon/MnO2 nano composite electrode material and preparation method thereof |
| CN103401030B (en) * | 2013-07-09 | 2016-05-04 | 哈尔滨工程大学 | A kind of water system can be filled magnesium or zinc ion capacitor batteries |
| CN105858828A (en) * | 2016-06-03 | 2016-08-17 | 华东师范大学 | Asymmetric-flow electrode desalting plant |
| CN106024409B (en) * | 2016-08-12 | 2019-01-22 | 深圳博磊达新能源科技有限公司 | A kind of supercapacitor composite positive pole and preparation method thereof, supercapacitor |
| CN109192540B (en) * | 2018-09-18 | 2021-07-27 | 中联西北工程设计研究院有限公司 | Biomass carbonized product and manganese dioxide composite electrode material and preparation method thereof |
| 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 |
| CN113921294B (en) * | 2021-09-17 | 2022-05-27 | 西南交通大学 | Asymmetric super capacitor and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1545114A (en) * | 2003-11-18 | 2004-11-10 | 哈尔滨工程大学三金高新技术有限责任 | Method for making metal oxide/carbon electrochemical capacitor and electrode |
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| CN1545114A (en) * | 2003-11-18 | 2004-11-10 | 哈尔滨工程大学三金高新技术有限责任 | Method for making metal oxide/carbon electrochemical capacitor and electrode |
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