CN201910332U

CN201910332U - Coiled hybrid electrochemical capacitor

Info

Publication number: CN201910332U
Application number: CN2010206333689U
Authority: CN
Inventors: 高建峰; 柳颖; 张娟; 周建国; 郑军伟
Original assignee: Suzhou University
Current assignee: Suzhou University
Priority date: 2010-11-30
Filing date: 2010-11-30
Publication date: 2011-07-27
Anticipated expiration: 2020-11-30

Abstract

The utility model discloses a coiled hybrid electrochemical capacitor which comprises an anode, a cathode, a clapboard and electrolyte which are arranged between the anode and the cathode. The capacitor is characterized in that the anode is a formative thin lead dioxide electrode, the cathode is a thin carbon-powder electrode, and the anode and the cathode are assembled into a hybrid electrochemical capacitor by coiling. The capacitor can be round or rectangular. Due to the thin structure of the anode and the cathode, the internal resistance of the capacitor is very small, and the power density of the capacitor is very high. Due to the formative anode, the cycle lives of the anode and the cathode are matched very well, the service life of the capacitor is long, and the capacitor has good application prospect.

Description

A kind of takeup type hybrid electrochemical capacitor

Technical field

The utility model relates to a kind of electrochemical energy storing device, especially a kind of takeup type hybrid electrochemical capacitor.

Background technology

Along with constant development of economy, the energy, resource and environment etc. becomes the focal issue of society, seeks cleaning, the energy renewable and resource-conserving and be the very urgent and unusual difficult task of human society.

At present, mainly contain three types energy storage device at energy field: battery, physical capacitor and electrochemical capacitor (also claiming ultracapacitor).Electrochemical capacitor is a kind of novel green energy storage device between traditional physical capacitor and battery behavior that grew up in the last few years, has the fast charging and discharging characteristic, power density big (being more than tens times of common batteries), have extended cycle life (cycle-index can reach more than 100,000 times) serviceability temperature wide ranges (between-40 ℃～75 ℃).Based on these special performances, electrochemical capacitor has extraordinary application prospect.

According to the difference of energy storage mechanism, electrochemical capacitor can be divided into double electric layer capacitor and pseudo capacitance device two big classes.Double electric layer capacitor is to utilize the interfacial electric double layer electric capacity that forms between electrode and the electrolyte to come stored energy, and its electrode adopts the porous carbon material with high-specific surface area usually.The pseudo capacitance capacitor is meant on electrode surface or the body two dimension or accurate two-dimensional space in mutually, electrode active material carries out underpotential deposition, make it that quick, reversible chemisorbed/desorption or oxidation/reduction reaction take place, thereby produce the specific capacity higher than double electric layer capacitor, its electrode material mainly is metal oxide and conducting polymer.

In order to obtain high energy density and power density simultaneously, the development in recent years a kind of novel asymmetric electrochemical capacitor (also claiming hybrid electrochemical capacitor) that gets up, promptly a utmost point of capacitor is a double layer electrodes, another is the pseudo capacitance electrode very.Asymmetric electric chemical super capacitor combines the advantage of two class electrochemical capacitors, can satisfy in the practical application load better to the whole requirement of the energy density and the power density of power-supply system.

In the asymmetric electrochemical capacitor of each quasi-metal oxides/carbon, PbO ₂/ C system is because material price is low and PbO ₂Electrode manufacturing technology maturation is fit to make the large capacity version energy storage device very much; Owing to adopt aqueous sulfuric acid, have the highest conductivity, so the capacitor internal resistance is very low simultaneously as electrolyte; The electrochemical window of this system is 2.20 ~ 0.80V in addition, is only second to organic system, is fit to very much make the high power type energy storage device.

Patent 200910212790.9 has been announced colloidal lead carbon supercapacitor, adopts the flat positive pole of brown lead oxide, carbon negative pole, PVC-SiO ₂Dividing plate, the sulfuric acid colloidal electrolyte.Colloidal electrolyte can improve electrolyte stratification, slows down the trend of sulfation.Patent 200910212479.4 has been announced a kind of acid super-capacitor, adopts the flat positive pole of brown lead oxide, carbon negative pole, PE dividing plate, electrolyte sulfuric acid.Although the PE dividing plate has lower resistance and anti-preferably lead dendritic crystal.But above patent, both positive and negative polarity are the powder electrode of plank frame, do not have certain assembling pressure to suppress the expansion of positive and negative pole plate, pole plate softening with come off unavoidably, its cycle life is difficult to be guaranteed.

Patent 200910221793.9 has been announced a kind of hybrid electrochemical capacitor, adopts the flat positive pole of brown lead oxide, carbon negative pole, AGM dividing plate, electrolyte sulfuric acid.The negative plate of sandwich construction has lower equivalent series resistance, the energy density height; But positive and negative pole plate is the compression that relies on the AGM dividing plate, tight assembling suppresses its expansion, and this is effectively for the hundreds of time cycle life only for storage battery, concerning several ten thousand cycle lives of electrochemical capacitor, is far from being enough.The folded carbon negative pole of volume can suppress its expansion, life-saving to a certain extent in the patent.

Existing P bO ₂The asymmetric electrochemical capacitor of/C, the power density height, the energy density height, the cost performance height, but its both positive and negative polarity life-span do not match, promptly after discharging and recharging 300 ~ 400 times, anodal because the capacity attenuation that the active material softening and shedding causes is very obvious with 100%dod; The carbon negative pole behind the thousands of time cycle charge-discharges of experience, because the factor of lead deposit, causes the electrode volumetric expansion and causes coming off of material with carbon element, the electrode capacity decay.Therefore existing technology can not embody PbO fully ₂The long-life characteristic of the asymmetric electrochemical capacitor of/C, this has limited the range of application of this capacitor widely.

Summary of the invention

The utility model purpose is: a kind of not only power density height is provided, the cost performance height, and the takeup type hybrid electrochemical capacitor that has extended cycle life, so that satisfy the requirement of auxiliary energy storage component and the solar energy and the wind energy power plant auxiliary energy storage component of electric motor car and hybrid vehicle.

The technical solution of the utility model is: a kind of takeup type hybrid electrochemical capacitor, comprise tabular positive pole, tabular negative pole, dividing plate and electrolyte between described tabular positive pole and tabular negative pole, it is characterized in that described tabular positive pole, dividing plate and tabular negative pole are formed described takeup type hybrid electrochemical capacitor by the mode of reeling.

Preferably, the described tabular slim lead dioxide electrode of formula that just very forms.

Preferably, described tabular negative pole is slim carbon powder electrodes.

Preferably, the described slim lead dioxide electrode of formula that forms is positioned on the plus plate current-collecting body.

Preferably, described slim carbon powder electrodes is positioned on the negative current collector.

Preferably, described plus plate current-collecting body is stereotype or terne metal plate.

Preferably, described negative current collector is stereotype or terne metal plate.

Preferably, porose on described stereotype or the terne metal plate.

Preferably, described electrolyte is colloidal electrolyte.

Slim carbon powder electrodes described in the utility model is made of negative current collector and the capacitance electrode material of coating on the negative current collector, described capacitance electrode material is made up of material with carbon element, conductive agent and adhesive, their percentage by weights separately are: material with carbon element 30 ~ 90%, conductive agent 3 ~ 50%, adhesive 5 ~ 25%; Wherein said material with carbon element is one or two or more kinds the mixture in active carbon, carbon nano-tube, carbon nano-fiber, carbon/charcoal compound, graphitization active carbon and the carbon aerosol; Described conductive agent is one or two or more kinds the mixture in carbon black, acetylene black, graphite, the expanded graphite carbon fiber; Described adhesive is one or more the mixture in PTFE, PVDF, fluorubber, CMC and the neoprene.

Described plus plate current-collecting body described in the utility model is lead or terne metal flat board, and the surface is through roughened.

Negative current collector described in the utility model is lead or terne metal flat board or punching flat board.

Dividing plate described in the utility model is the AGM dividing plate; And described electrolyte is aqueous or the colloidal dilute sulfuric acid.

The same with prior art in the utility model, described anodal top links to each other by positive bus bar, and the negative pole top links to each other by negative bus bar.

This hybrid electrochemical capacitor described in the utility model is the same with prior art, and its integral body can be designed to common rich solution pattern, perhaps also can be designed to valve-control sealed pattern.

Capacitor described in the utility model can be wound into circle, also can be wound into rectangle.

The utility model has the advantages that:

1, takeup type hybrid electrochemical capacitor of the present utility model because the form that negative pole adopts slim carbon powder electrodes to reel and make up can adopt higher assembling pressure, makes to have extended cycle life the carbon material used as anode difficult drop-off.

2, the anodal employing forms the formula electrode described in the utility model, and internal resistance is very little; The form of the same combination of reeling, positive active material is difficult for softening and shedding; Form the formula electrode, in case positive material comes off, its surface again can be oxidized, forms new active material layer, therefore has extremely long cycle life, can realize the life-span coupling with negative pole.

3, the utility model is because both positive and negative polarity all adopts thin electrode and multilaminate coiled structure, has very large electrode surface area, the aqueous sulfuric acid that adopts high conductivity simultaneously has the high power charge-discharge characteristic as electrolyte, can make the electrochemical capacitor of MW/Kg level.Can satisfy the requirement of electric motor car and power battery for hybrid electric vehicle and the requirement of solar energy and wind energy power plant energy storage device fully.

Description of drawings

Below in conjunction with drawings and Examples the utility model is further described:

Fig. 1 is the principal section figure of the utility model takeup type hybrid electrochemical capacitor;

Fig. 2 is the utility model takeup type hybrid electrochemical capacitor (cylindrical) drawing in side sectional elevation;

Fig. 3 is the utility model takeup type hybrid electrochemical capacitor (square) drawing in side sectional elevation;

Fig. 4 is for forming the anodal schematic diagram of the slim brown lead oxide of formula in the utility model;

Fig. 5 is a double spread capacitance electrode cathode of carbon material schematic diagram in the utility model.

Wherein: 1, positive pole; 11, plus plate current-collecting body; 12, coarse plumbous surface; 2, negative pole; 21, negative current collector; 22, carbon dust material 3, AGM dividing plate; 5, shell; 6, positive bus bar; 7, negative bus bar.

Embodiment

Embodiment: 1: in conjunction with Fig. 1, shown in Figure 2, this hybrid electrochemical capacitor (cylindrical) that present embodiment provides, be packaged with a positive plate 1 and negative plate 2 in its shell 5 and be wound into cylindricly, that the dividing plate 3 between adjacent positive plate 1 and the negative plate 2 adopts is commercial AGM dividing plate (thickness 0.45mm 10KPa); And the electrolyte of perfusion is dilute sulfuric acid (density 1.275g/cm ³).Described anodal 1 top links to each other by positive bus bar 6, and the top of negative pole 2 then links to each other by negative bus bar 7.

As shown in Figure 4, described plus plate current-collecting body 11: laminate after the terne metal of employing tin content 1.0% rolls, thickness is about 0.5mm, is cut into the strip of band lug then.Tow sides all pass through roughened, and processing method can be the direct annular knurl in surface in the process of rolling, and laminates after also can rolling with the polishing of copper wire roller.

Described positive pole forms formula brown lead oxide film and forms on coarse plumbous surface 12 with the anode electrochemical mode of oxidizing in hybrid electrochemical capacitor initial charge process.

Further as shown in Figure 5, negative pole described in the present embodiment 2 is made of negative current collector 21 and the capacitance electrode material of coating on negative current collector 21 tow sides.

Described capacitance electrode material components by weight is as follows: active carbon 70%, graphite powder 15%, acetylene black 5%, PVDF10%, wherein active carbon adopts specific area 1500m ²/ g, middle porosity greater than 40%, the commercialization active carbon of granularity 5-10 μ m.Earlier active carbon, graphite powder and acetylene black are done and mixed 5 minutes, add the solution of the N-methyl pyrrolidone (NMP) of PVDF, use an amount of N-methyl pyrrolidone furnishing thin pulp shape then, stirred 1-2 hour, fully mixing.

Described negative current collector 21: laminate after the terne metal of employing tin content 0.6% rolls, thickness is about 0.5mm, is cut into strip then.At the above-mentioned capacitance electrode material of the double spread of every monolithic pole plate, after roll extrusion, partial desiccation, promptly make slim carbon powder electrodes 2.Every lateral capacitance electrode material THICKNESS CONTROL is about 1mm.

A slice positive pole 1, a slice negative pole 2 and dividing plate 3 are wound into by Fig. 2 mode cylindric, 100 ℃ of dryings 4 hours.

Embodiment 2:

As shown in Figure 3, the difference of present embodiment and embodiment 1 is: be wound into square with dividing plate 3 by Fig. 2 mode a slice positive pole 1, a slice negative pole 2.

Present embodiment all the other with embodiment 1.

The above only is the utility model preferred embodiment, and the various variations that those skilled in the art carries out in not breaking away from claim limited range of the present utility model all should be in protection range of the present utility model.

Claims

1. takeup type hybrid electrochemical capacitor, comprise tabular positive pole, tabular negative pole, dividing plate and electrolyte between described tabular positive pole and tabular negative pole, it is characterized in that described tabular positive pole, dividing plate and tabular negative pole are formed described takeup type hybrid electrochemical capacitor by the mode of reeling.

2. takeup type hybrid electrochemical capacitor according to claim 1 is characterized in that, the described tabular slim lead dioxide electrode of formula that just very forms.

3. takeup type hybrid electrochemical capacitor according to claim 1 is characterized in that, described tabular negative pole is slim carbon powder electrodes.

4. takeup type hybrid electrochemical capacitor according to claim 2 is characterized in that, the described slim lead dioxide electrode of formula that forms is positioned on the plus plate current-collecting body.

5. takeup type hybrid electrochemical capacitor according to claim 3 is characterized in that, described slim carbon powder electrodes is positioned on the negative current collector.

6. takeup type hybrid electrochemical capacitor according to claim 4 is characterized in that, described plus plate current-collecting body is stereotype or terne metal plate.

7. takeup type hybrid electrochemical capacitor according to claim 5 is characterized in that, described negative current collector is stereotype or terne metal plate.

8. according to claim 6 or 7 described takeup type hybrid electrochemical capacitors, it is characterized in that, porose on described stereotype or the terne metal plate.

9. takeup type hybrid electrochemical capacitor according to claim 1 is characterized in that, described electrolyte is colloidal electrolyte.

10. takeup type hybrid electrochemical capacitor according to claim 1 is characterized in that, the mode of described coiling can for circular roll around or rectangle reel.