CN201886905U

CN201886905U - Mixed electrochemical capacitor

Info

Publication number: CN201886905U
Application number: CN2010206354223U
Authority: CN
Inventors: 高建峰; 柳颖; 张娟; 孟波; 郑军伟
Original assignee: Suzhou University
Current assignee: Suzhou University
Priority date: 2010-11-30
Filing date: 2010-11-30
Publication date: 2011-06-29
Anticipated expiration: 2020-11-30

Abstract

The utility model discloses a mixed electrochemical capacitor, which comprises a positive pole, a negative pole, a partition board between the positive pole and the negative pole, and an electrolyte, and is characterized in that the positive pole is an electrode in a tubular structure, and the negative pole is an electrode in a wound structure. Because the negative pole is assembled in a winding mode, capacity attenuation caused by the expansion of the negative pole in the use process can be avoided, and the circulation service life is prolonged; and the negative pole is matched with the capacity of a high-capacity long-life tubular positive pole through adjusting the winding amount of the negative pole so as to increase energy density. The formed small cylindrical capacitor has wide application fields.

Description

A kind of hybrid electrochemical capacitor

Technical field

The utility model relates to a kind of electrochemical energy storing device, especially a kind of 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 ₂ Electrode manufacturing technology maturation is fit to make the high capacity density 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 ₂ Dividing 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 ₂ The asymmetric electrochemical capacitor of/C, the power density height, the energy density height, the cost performance height, but, positive and negative electrode cause active material to come off because of expanding, its cycle life significantly is lower than the electrochemical capacitor of other systems, does not reach the requirement of electric motor car and power battery for hybrid electric vehicle, the requirement that does not reach solar energy and wind energy power plant energy-storage battery, 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 energy density height, the cost performance height, and the hybrid electrochemical capacitor that also significantly improves of cycle life, so that 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.

The technical solution of the utility model is: a kind of hybrid electrochemical capacitor, comprise positive pole, negative pole, the dividing plate between described positive pole and negative pole and electrolyte, and it is characterized in that, described just very tubular structure electrode, described negative pole is volume stack structure electrode.

Preferably, fill the titanium dioxide lead powder in the positive collector that described tubular structure electrode comprises sleeve pipe and is positioned at described cover tube hub, described sleeve pipe, described sleeve pipe can be fiberglass braided tube or polyster fibre woven tube.

Preferably, the negative pole of described volume stack structure comprises two-layer or two-layer above slim carbon powder electrodes and the negative pole dividing plate between the slim carbon powder electrodes of adjacent two layers, and described slim carbon powder electrodes and negative pole dividing plate volume stack.

Preferably, described slim carbon powder electrodes is made of negative current collector and the capacitance electrode material of coating on the described negative current collector.

Preferably, the number of plies of described slim carbon powder electrodes is the 2-12 layer.

Preferably, described negative current collector is flat board or punching flat board.

Preferably, described negative current collector is lead or terne metal.

Preferably, described electrolyte is colloidal electrolyte.

Preferably, described colloidal electrolyte is the dilute sulfuric acid colloidal electrolyte.

Preferably, described plus plate current-collecting body is lead-calcium alloy or lead-antimony alloy, by the casting method manufacturing, also can adopt pressure casting method.

Negative pole described in the utility model is slim carbon powder electrodes, 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, and 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.

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

Directly draw at anodal top in the utility model; And negative pole is the same with prior art, and the top links to each other by negative bus bar, and then draws.

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.

The utility model has the advantages that:

1, this hybrid electrochemical capacitor provided by the 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 tubular pole that adopts described in the utility model, positive active material is fixed in the sleeve pipe with certain packed density, is difficult for softening and shedding, therefore has extremely long cycle life, can realize the life-span coupling with negative pole.

3, the utility model can be realized the capacity coupling of both positive and negative polarity by regulating the capacity that the number of plies of reeling changes negative pole easily because negative pole adopts thin electrode and multilaminate coiled structure, makes the maximization of capacitor energy density; By the connection in series-parallel of monolithic capacitor, can make jumbo electrochemical capacitor, 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 hybrid electrochemical capacitor;

Fig. 2 is the drawing in side sectional elevation of the utility model hybrid electrochemical capacitor;

Fig. 3 is the anodal schematic diagram of tubular type brown lead oxide in the utility model;

Fig. 4 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, positive active material---brown lead oxide; 13, sleeve pipe; 14, plastics back cover; 2, negative pole; 21, negative current collector; 22, carbon dust material 3, AGM dividing plate; 4, negative pole dividing plate; 5, shell.

Embodiment

Embodiment: in conjunction with Fig. 1, shown in Figure 2, this hybrid electrochemical capacitor that present embodiment provides, be packaged with a positive pole 1 and a negative plate 2 in its shell 5, what dividing plate 3 between adjacent positive plate 1 and the negative plate 2 and negative pole dividing plate 4 adopted all is that commercial AGM dividing plate (thickness 0.45mm 10KPa) carries out continuous coating; And the electrolyte of perfusion is dilute sulfuric acid (density 1.28g/cm ³ ).Directly derive at described anodal 1 top, and the top of negative pole 2 then links to each other by negative bus bar 7, and then derives.

As shown in Figure 3, positive pole 1 is tubular type PbO described in the present embodiment ₂ Positive pole is made of plus plate current-collecting body 11, sleeve pipe 13, the positive active material brown lead oxide 12 and the plastics back cover 14 that are filled between plus plate current-collecting body 11 and the sleeve pipe 13.Described plus plate current-collecting body 11: adopt the lead-antimony alloy cast of antimony content 4.5% to form.

Further as shown in Figure 4, negative pole described in the present embodiment 2 is made of negative current collector 21 and the capacitance electrode material of coating negative current collector 21 tow sides water.

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: make latten 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.

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.

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. a hybrid electrochemical capacitor comprises positive pole, negative pole, the dividing plate between described positive pole and negative pole and electrolyte, it is characterized in that, described just very tubular structure electrode, and described negative pole is volume stack structure electrode.

2. hybrid electrochemical capacitor according to claim 1, it is characterized in that, fill the titanium dioxide lead powder in the positive collector that described tubular structure electrode comprises sleeve pipe and is positioned at described cover tube hub, described sleeve pipe, described sleeve pipe can be fiberglass braided tube or polyster fibre woven tube.

3. hybrid electrochemical capacitor according to claim 2, it is characterized in that, the negative pole of described volume stack structure comprises two-layer or two-layer above slim carbon powder electrodes and the negative pole dividing plate between the slim carbon powder electrodes of adjacent two layers, and described slim carbon powder electrodes and negative pole dividing plate volume stack.

4. hybrid electrochemical capacitor according to claim 3 is characterized in that, described slim carbon powder electrodes is made of negative current collector and the capacitance electrode material of coating on the described negative current collector.

5. hybrid electrochemical capacitor according to claim 3 is characterized in that, the number of plies of described slim carbon powder electrodes is the 2-12 layer.

6. hybrid electrochemical capacitor according to claim 4 is characterized in that, described negative current collector is flat board or punching flat board.

7. hybrid electrochemical capacitor according to claim 6 is characterized in that, described negative current collector is lead or terne metal.

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

9. hybrid electrochemical capacitor according to claim 8 is characterized in that, described colloidal electrolyte is the dilute sulfuric acid colloidal electrolyte.

10. hybrid electrochemical capacitor according to claim 2 is characterized in that, described plus plate current-collecting body is lead-calcium alloy or lead-antimony alloy.