CN100511513C

CN100511513C - Mixed super capacitor

Info

Publication number: CN100511513C
Application number: CNB200610148798XA
Authority: CN
Inventors: 许俭红; 王然
Original assignee: Shanghai Aowei Technology Development Co Ltd
Current assignee: Shanghai Aowei Technology Development Co Ltd
Priority date: 2006-12-30
Filing date: 2006-12-30
Publication date: 2009-07-08
Anticipated expiration: 2026-12-30
Also published as: CN101004973A

Abstract

Hybrid material of nickel hydroxide and manganese dioxide is adopted in anode of mixed type super capacitor. Cathode uses hybrid material of active carbon with porous structured material and mesoporous carbon or Nano carbon tubes, or hybrid material of these porous structured materials and other materials of quasi-capacitive character. Strongly basic water solution is adopted in the electrolyte. Features are: very long duty-cycle service life, high power, low cost, safety, and no pollution. The disclosed super capacitor is specifically suitable to condition of high power discharge.

Description

A kind of hybrid super capacitor

Technical field

The present invention relates to a kind of capacitor, particularly disclose a kind of high performance hybrid super capacitor, be particularly suitable for being applied to the occasion of high power discharge.

Background technology

Ultracapacitor is a kind of novel energy-storing device between storage battery and traditional capacitor, and it has the specific capacity height, power is big, the life-span is long, the warm limit for width of working, characteristics such as non-maintaining.In recent years, many applications are more and more higher to the requirement of energy storage device power density and since battery intrinsic operation principle, therefore, being difficult in has bigger breakthrough on the power density, this development and application for ultracapacitor provides boundless space.

According to the difference of energy storage principle, ultracapacitor can be divided three classes: double electric layer capacitor (EDLC), pseudo capacitance ultracapacitor and hybrid super capacitor.1954, Becker at first proposed the patent about double electric layers supercapacitor.Japan NEC electric corporation and PANASONIC the seventies in 20th century successively developed have farad level (F) but double electric layer capacitor " Super Capacitor " and " the Gold Capacitor " of capacity and fast charging and discharging use as small-sized back-up source.At the end of the eighties, Korea S Samsung begins to produce in enormous quantities the double electric layer capacitor of 5V/0.047F, has now formed to produce 3000 ten thousand production capacity per year.At present, the existing industrialization product of the low capacity coin shape unit EDLC of 0.022F～1F and the convoluted EDLC of 0.22F～100F.

Development along with vehicle technology, since nineteen ninety, various countries begin to set up specialized agency exploitation and produce automobile-used ultracapacitor, and unite and set up " international double electric layer capacitor research association " in the U.S. by the nearly various schools of thinkers scientific research institution of tens countries and manufacturing enterprise the same year; " international automobile-used ultracapacitor central laboratory " set up in the Idaho State in the U.S.; Release first international standard-" the automobile-used ultracapacitor test method " of automobile-used ultracapacitor.Thereby the exploitation and the activity in production of automobile-used ultracapacitor in worldwide, have been begun.

Because special advantages that ultracapacitor has makes it in vehicle manufacturing industry, power industry, power supply industry, communications industry, military aerospace industry etc. good application be arranged.

Summary of the invention

The objective of the invention is to disclose a kind of high power, have extended cycle life, cost is low, the hybrid super capacitor of non-environmental-pollution.

The present invention is achieved in that a kind of hybrid super capacitor, form by positive plate, negative plate, the barrier film between positive/negative plate and the alkaline electrolyte with ionic conductivity, it is characterized in that: the described anodal composite material that adopts nickel hydroxide and manganese dioxide, negative pole adopts the composite material with the material activity charcoal of loose structure, mesoporous charcoal or nano carbon tube.The anodal composite material of described ultracapacitor forms and percentage by weight is that nickel hydroxide 40～70%, manganese dioxide 20～50%, conductive agent 5～20%, binding agent are by 1～10%; Described negative pole composite material is formed and percentage by weight is that active carbon 40～70%, mesoporous charcoal or sodium rice charcoal pipe or pseudo-capacitance material 20～50%, conductive agent 5～20%, binding agent are by 1～10%; Binding agent is polytetrafluoroethylene and sodium carboxymethylcellulose in the described anodal composite material; Binding agent is a polytetrafluoroethylene in the described negative pole composite material.Described barrier film is chosen a kind of in the composite membrane of polypropylene non-woven fabric, porous glass fiber, polyethene microporous membrane or PP and PE.Described conductive agent comprises the combination of electrically conductive graphite, conductive black, nickel powder, cobalt powder etc. and their various ratios.

The making step of positive plate of the present invention is as follows:

Take by weighing after nickel hydroxide, manganese dioxide, graphite, poly-tetrafluoro emulsion, sodium carboxymethylcellulose, isopropyl alcohol mix according to the certain mass ratio, be stirred to paste, be coated in then on the collector, drying (120～130 ℃), roll after, be cut into certain size.Being made as of negative plate: take by weighing after active carbon, mesoporous charcoal or sodium rice charcoal pipe or pseudo-capacitance material, carbon black, poly-tetrafluoro emulsion, deionized water mix according to the certain mass ratio, be stirred to paste, be coated in then on the collector, drying (120～130 ℃), roll after, be cut into the size that needs.

Electrolyte adopts the water system alkaline solution among the present invention, as KOH, NaOH, LiOH or their mixed solution.

The current collector material of positive/negative plate can be used holey metal materials such as nickel foam, burr steel belt, Punching steel strip, punching stainless steel band, copper mesh among the present invention.

The present invention uses the mixed type material by both positive and negative polarity, reduces the cost of positive plate on the one hand, keeps the superperformance of positive plate; Give full play to the excellent properties of each raw material of wood-charcoal material, pseudo-capacitance material on the other hand, optimize negative plate, finally improve the overall performance of hybrid super capacitor.

The invention has the beneficial effects as follows: owing to use manganese dioxide to replace nickel hydroxide, significantly reduced the cost of capacitor, but still can keep anodal good performance, negative pole adopts the composite material of multiple raw material of wood-charcoal material or the composite material of raw material of wood-charcoal material and pseudo-capacitance material simultaneously, fully optimize the advantage of each material, significantly improve negative plate capacity, reduced the internal resistance of negative plate, thereby improve the various aspects of performance of ultracapacitor.The raising of trafficability characteristic price ratio will make this novel ultracapacitor have the stronger market competitiveness.

Description of drawings

Fig. 1 is a hybrid super capacitor structural representation of the present invention;

Fig. 2 is the charging and discharging curve of novel ultracapacitor.

In the drawings: 1, positive plate; 2, negative plate; 3, barrier film; 4, pole; 5, housing; 6, cap; 7, safety valve.

Embodiment

The present invention is further illustrated below in conjunction with embodiment.

Embodiment 1:

The making of positive plate: the anodal composite material of ultracapacitor is formed nickel hydroxide 45%, manganese dioxide 35%, electrically conductive graphite 10%, polytetrafluoroethylene 5%, sodium carboxymethylcellulose 5% mixing by weight percentage, furnishing slurry then, be coated on the nickel foam, drying, roll, cut-parts, make positive plate.The making of negative plate: the negative pole composite material forms by weight percentage that active carbon 50%, mesoporous charcoal 30%, conductive black 10%, polytetrafluoroethylene 10% mix furnishing slurry then, be coated on the nickel foam, drying, roll, cut-parts, make positive plate.With reference to the accompanying drawings 1, selecting polyethene microporous membrane for use is barrier film, and positive plate, barrier film, negative plate are laminated into electric core, is assembled into the square capacitor, injects the potassium hydroxide solution of 3mol/l, then the performance of test capacitors.Capacitor charging/discharging curve such as accompanying drawing 2, under the measuring current of 80mA/cm2, the specific capacity of capacitor is 260F/g, after 10000 circulations, capability retention is 90%.

Embodiment 2:

The making of positive plate: the anodal composite material of ultracapacitor is formed nickel hydroxide 55%, manganese dioxide 25%, electrically conductive graphite 10%, polytetrafluoroethylene 5%, sodium carboxymethylcellulose 5% mixing by weight percentage, furnishing slurry then, be coated on the nickel foam, drying, roll, cut-parts, make positive plate.The making of negative plate: the negative pole composite material is formed by weight percentage active carbon 60%, nano carbon tube 20%, conductive black 10%, polytetrafluoroethylene 10% and is mixed, and the furnishing slurry is coated on the nickel foam then, drying, roll, cut-parts, make positive plate.With reference to the accompanying drawings 1, selecting polyethene microporous membrane for use is barrier film, and positive plate, barrier film, negative plate are laminated into electric core, is assembled into the square capacitor, injects the potassium hydroxide solution of 3mol/l, then the performance of test capacitors.Under the measuring current of 80mA/cm2, the specific capacity of capacitor is 290F/g, and after 10000 circulations, capability retention is 89%.

Embodiment 3:

The anodal composite material of ultracapacitor is formed by weight percentage, and nickel hydroxide 45%, manganese dioxide 35%, electrically conductive graphite 10%, polytetrafluoroethylene 5%, sodium carboxymethylcellulose 5% mix, furnishing slurry then, be coated on the nickel foam, drying, roll, cut-parts, make positive plate.The making of negative plate: the negative pole composite material is formed by weight percentage active carbon 50%, RuO2 30%, conductive black 10%, polytetrafluoroethylene 10% and is mixed, and the furnishing slurry is coated on the nickel foam then, drying, roll, cut-parts, make positive plate.With reference to the accompanying drawings 1, selecting polyethene microporous membrane for use is barrier film, and positive plate, barrier film, negative plate are laminated into electric core, is assembled into the square capacitor, injects the potassium hydroxide solution of 3mol/l, then the performance of test capacitors.Under the measuring current of 80mA/cm2, the specific capacity of capacitor is 350F/g, and after 10000 circulations, capability retention is 88%.

Claims

1. hybrid super capacitor, be made up of positive plate, negative plate, the barrier film between positive/negative plate and the alkaline electrolyte with ionic conductivity, it is characterized in that: the anodal composite material of described ultracapacitor forms and percentage by weight is that nickel hydroxide 40～70%, manganese dioxide 20～50%, conductive agent 5～20%, binding agent are by 1～10%; Described negative pole composite material is formed and percentage by weight is that active carbon 40～70%, mesoporous charcoal or sodium rice charcoal pipe or pseudo-capacitance material 20～50%, conductive agent 5～20%, binding agent are by 1～10%; Binding agent is polytetrafluoroethylene and sodium carboxymethylcellulose in the described anodal composite material; Binding agent is a polytetrafluoroethylene in the described negative pole composite material.

2. a kind of hybrid super capacitor according to claim 1 is characterized in that: the anodal composite material of described ultracapacitor forms and percentage by weight is that nickel hydroxide 45%, manganese dioxide 35%, conductive agent 10%, binding agent are by 10%; Described negative pole composite material is formed and percentage by weight is that active carbon 50%, mesoporous charcoal or sodium rice charcoal pipe or pseudo-capacitance material 30%, conductive agent 10%, binding agent are by 10%.

3. a kind of hybrid super capacitor according to claim 1 is characterized in that: the anodal composite material of described ultracapacitor forms and percentage by weight is that nickel hydroxide 60%, manganese dioxide 20%, conductive agent 10%, binding agent are by 10%; Described negative pole composite material is formed and percentage by weight is that active carbon 40%, mesoporous charcoal or sodium rice charcoal pipe or pseudo-capacitance material 40%, conductive agent 10%, binding agent are by 10%.

4. a kind of hybrid super capacitor according to claim 1 is characterized in that: described conductive agent is chosen one or more in electrically conductive graphite, conductive black, nickel powder and cobalt powder.

5. a kind of hybrid super capacitor according to claim 1 is characterized in that: described barrier film is chosen a kind of in the composite membrane of polypropylene non-woven fabric, porous glass fiber, polyethene microporous membrane or PP and PE.