CN101847515B - Lead-based super capacitor - Google Patents
Lead-based super capacitor Download PDFInfo
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- CN101847515B CN101847515B CN2010101141475A CN201010114147A CN101847515B CN 101847515 B CN101847515 B CN 101847515B CN 2010101141475 A CN2010101141475 A CN 2010101141475A CN 201010114147 A CN201010114147 A CN 201010114147A CN 101847515 B CN101847515 B CN 101847515B
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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Abstract
The invention relates to a lead-based super capacitor, which consists of an anode, a cathode, and a clapboard and an electrolyte between the anode and the cathode. The anode is made of a porous carbon material, the cathode is a lead electrode, and the electrolyte is aqueous solution of sulfuric acid. The capacitor manufactured by the invention has the characteristics of high energy density (6 to 10Wh/Kg), high power density (300 to 2,000W/Kg), long cycle life (more than or equal to 10,000 times) and the like, can be widely applied to the fields of solar energy storage, wind power generation storage, electric automobiles, uninterruptible power supplies and the like.
Description
Technical field
The present invention relates to the capacitor technology field, particularly a kind of lead-based super capacitor.
Background technology
Ultracapacitor is a kind of model electrochemical energy storage device between traditional capacitor and battery, and it compares traditional capacitor higher energy density, and static capacity can reach thousand farads to ten thousand farads levels; Comparing battery has the higher power density and the cycle life of overlength, so it combines the advantage of traditional capacitor and battery, is a kind of chemical power source that has a extensive future.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.
Difference according to energy storage principle, ultracapacitor can be divided three classes: double electric layer capacitor (EDLC), pseudo capacitance ultracapacitor and hybrid super capacitor, wherein double electric layer capacitor mainly is to utilize the formed electric double layer of electrode/electrolyte interface separation of charge to realize the storage of electric charge and energy; The pseudo capacitance ultracapacitor mainly is the storage that realizes electric charge and energy by electrode surface faraday's " pseudo-capacitance " that redox reaction produced fast; And hybrid super capacitor is the unpolarized electrode (as nickel hydroxide) that a utmost point adopts battery, and another utmost point adopts the polarizing electrode (as active carbon) of double electric layer capacitor, and the design of this mixed type can increase substantially the energy density of ultracapacitor.
Because the energy density of hybrid super capacitor is much higher than two class ultracapacitors in addition, so just makes the hybrid super capacitor of different materials, different systems become the focus of research always, and Ni (OH) has successively appearred
2/ KOH/AC, PbO
2/ H
2SO
4/ AC, LiMn
2O
4/ Li
2SO
4Systems such as/AC.PbO wherein
2/ H
2SO
4/ AC hybrid super capacitor becomes the emphasis of commercially produced product exploitation because cost is low, energy density is higher always, but because PbO
2Deficiency such as electrode is perishable, volumetric expansion is big in the charge and discharge process, active material easily comes off causes the cycle life of this capacitor not ideal, so that the appearance of commercially produced product is not arranged always.
Summary of the invention
The cycle life of plumbous negative pole approximately is 2.5～3 times of brown lead oxide positive pole in the lead-acid battery, therefore, uses the cycle life of the ultracapacitor of plumbous negative pole will be better than the ultracapacitor that uses the brown lead oxide positive pole far away.In order to solve the problem of cycle life well, a kind of lead-based super capacitor of the present invention is made up of positive pole, negative pole, marginal dividing plate and electrolyte, wherein, the anodal porous carbon material that adopts, negative pole adopts lead electrode, and electrolyte adopts aqueous sulfuric acid.
Wherein, described porous carbon material comprises active carbon, mesoporous charcoal, charcoal-aero gel, carbon nanotube, charcoal fiber.
Wherein, also add an amount of binding agent in the described positive pole, mainly comprise polytetrafluoroethylene (PTFE), Kynoar (PVDF), polyvinyl alcohol (PVA).
Wherein, described lead electrode mainly is made up of lead powder (Pb) and lead monoxide powder (PbO).
Wherein, also add an amount of conductive agent in described positive pole and the negative pole, mainly comprise conductive black, acetylene black, graphite powder.
Wherein, the ratio of each material is a lead powder in the described negative pole: lead monoxide: conductive agent=(20～40): (50～60): (10～20).
Wherein, described electrolyte is that density is 1.10～1.30g/cm
3Aqueous sulfuric acid.
Wherein, described dividing plate comprises glass fibre separator, microporous rubber separator, polyvinyl chloride (PVC) dividing plate, polyethylene (PE) dividing plate, polypropylene (PP) dividing plate.
Wherein, the collector of described positive pole and negative pole comprises pure stereotype grid or paper tinsel, lead-antimony alloy grid or paper tinsel, lead-calcium alloy slab lattice paper tinsel, terne metal grid or paper tinsel, titanium net or paper tinsel.
The lead-based super capacitor that the present invention makes has have extended cycle life (〉=10000 times), cost is low, power characteristic good (300～2000W/Kg), (6～10Wh/Kg) characteristics are well suited for being applied on ask for something high-energy, low cost, the long-life occasion energy density height.
Embodiment
The present invention will be described in detail below in conjunction with specific embodiment.
A kind of lead-based super capacitor of the present invention is made up of positive pole, negative pole, marginal dividing plate and electrolyte, wherein, the anodal porous carbon material that adopts, negative pole adopts lead electrode, and electrolyte adopts aqueous sulfuric acid.
Porous charcoal described in the present invention mainly is meant the raw material of wood-charcoal material with flourishing pore structure, high-specific surface area, generally comprises active carbon, mesoporous charcoal, charcoal-aero gel, carbon nanotube, charcoal fiber.
Among the present invention, also will add an amount of binding agent when making positive pole, guarantee that porous charcoal contacts with the tight of collector, the general binding agent that uses comprises polytetrafluoroethylene (PTFE), Kynoar (PVDF), polyvinyl alcohol (PVA).
Among the present invention, also add an amount of conductive agent when making anodal and negative pole, general ratio is 10～20%, mainly comprises conductive black, acetylene black, graphite powder.
Among the present invention, the ratio of each material is a lead powder in the described negative pole: lead monoxide: conductive agent=(20～40): (50～60): (10～20).
Among the present invention, electrolyte adopts aqueous sulfuric acid, and according to the height of institute's capacity required, can select density is 1.10～1.30g/cm
3Sulfuric acid.Simultaneously, the dividing plate between both positive and negative polarity can adopt glass fibre separator, microporous rubber separator, polyvinyl chloride (PVC) dividing plate, polyethylene (PE) dividing plate, polypropylene (PP) dividing plate.
Among the present invention, for the cyclical stability that guarantees that capacitor is good, the both positive and negative polarity collector adopts pure stereotype grid or paper tinsel, lead-antimony alloy grid or paper tinsel, lead-calcium alloy slab lattice paper tinsel, terne metal grid or paper tinsel, titanium net or paper tinsel.
Among the present invention, the making step of positive plate is: take by weighing after a certain amount of porous carbon material, binding agent mix, be stirred to be coated on the foil behind the paste or to roll to be pressed into to press behind the film and be attached on the grid, be prepared into positive plate after drying.The making step of negative plate is: take by weighing a certain amount of lead powder, lead monoxide powder, conductive agent, and add an amount of water and sulfuric acid, be stirred to paste then and be coated on grid or the foil, be prepared into negative plate after drying, the curing.
The present invention is according to practical situations, can be made into laminated type (containing bipolarity) square ultracapacitor or convoluted column type ultracapacitor, this capacitor have high-energy-density (6～10Wh/Kg), high power density (300～2000W/Kg), characteristics such as long circulation life, can be widely used in fields such as solar energy storage, wind power generation energy storage, electric automobile, uninterrupted power supply.
Embodiment 1:
The making of positive plate: active carbon, conductive black, polytetrafluoroethylene are pressed 85: 5: 10 mixed of mass ratio, roll the carbon membrane that is pressed into 1.0mm then, two carbon membranes are pressed be attached on lead-calcium grid of 1.2mm, be made into 120*80*2.0mm
3Positive plate.The making of negative plate: lead powder, lead monoxide powder, conductive black are pressed 40: 50: 10 mixed of mass ratio, add an amount of sulfuric acid and water furnishing paste, be coated in then on lead-calcium grid of 0.8mm, after 100 ℃-10min drying, after putting into temperature and be 45 ℃, relative humidity and be 85% environment and solidifying 12h, take out and be made into 120*80*0.8mm
3Negative plate.Selecting glass fibre for use is dividing plate, and 10 positive plates, 10 negative plates are laminated into electric core, and in the polypropylene plastics shell of packing into, injecting 500g density is 1.25g/cm
3Aqueous sulfuric acid, after changing into, capacitor is tested, be that 0.5～1.5V, measuring current are under the situation of 50A in the operating voltage interval, the energy density of capacitor is 7.8Wh/Kg, power density is 800W/Kg, and after 10000 circulations, capability retention is 95%.
Embodiment 2:
The making of positive plate: active carbon, conductive black, polytetrafluoroethylene are pressed 85: 5: 10 mixed of mass ratio, roll the carbon membrane that is pressed into 1.0mm then, two carbon membranes are pressed be attached on lead-calcium grid of 1.2mm, be made into 120*80*2.0mm
3Positive plate.The making of negative plate: lead powder, lead monoxide powder, conductive black are pressed 20: 60: 20 mixed of mass ratio, add an amount of sulfuric acid and water furnishing paste, be coated in then on lead-calcium grid of 0.8mm, after 100 ℃-10min drying, after putting into temperature and be 45 ℃, relative humidity and be 85% environment and solidifying 12h, take out and be made into 120*80*0.8mm
3Negative plate.Selecting glass fibre for use is dividing plate, and 10 positive plates, 10 negative plates are laminated into electric core, and in the polypropylene plastics shell of packing into, injecting 500g density is 1.25g/cm
3Aqueous sulfuric acid, after changing into, capacitor is tested, be that 0.5～1.5V, measuring current are under the situation of 50A in the operating voltage interval, the energy density of capacitor is 6.8Wh/Kg, power density is 900W/Kg, and after 10000 circulations, capability retention is 95.5%.
Embodiment 3:
The making of positive plate: active carbon, conductive black, polytetrafluoroethylene are pressed 85: 5: 10 mixed of mass ratio, roll the carbon membrane that is pressed into 1.0mm then, two carbon membranes are pressed be attached on lead-calcium grid of 1.2mm, be made into 120*80*2.0mm
3Positive plate.The making of negative plate: lead powder, lead monoxide powder, conductive black are pressed 30: 55: 15 mixed of mass ratio, add an amount of sulfuric acid and water furnishing paste, be coated in then on lead-calcium grid of 0.8mm, after 100 ℃-10min drying, after putting into temperature and be 45 ℃, relative humidity and be 85% environment and solidifying 12h, take out and be made into 120*80*0.8mm
3Negative plate.Selecting glass fibre for use is dividing plate, and 10 positive plates, 10 negative plates are laminated into electric core, and in the polypropylene plastics shell of packing into, injecting 500g density is 1.25g/cm
3Aqueous sulfuric acid, after changing into, capacitor is tested, be that 0.5～1.5V, measuring current are under the situation of 50A in the operating voltage interval, the energy density of capacitor is 8.5Wh/Kg, power density is 850W/Kg, and after 10000 circulations, capability retention is 95.2%.
Embodiment 4:
The making of positive plate: mesoporous charcoal, conductive black, polytetrafluoroethylene are pressed 85: 5: 10 mixed of mass ratio, roll the carbon membrane that is pressed into 1.0mm then, two carbon membranes are pressed be attached on lead-calcium grid of 1.2mm, be made into 120*80*2.0mm
3Positive plate.The making of negative plate: lead powder, lead monoxide powder, conductive black are pressed 40: 50: 10 mixed of mass ratio, add an amount of sulfuric acid and water furnishing paste, be coated in then on lead-calcium grid of 0.8mm, after 100 ℃-10min drying, after putting into temperature and be 45 ℃, relative humidity and be 85% environment and solidifying 12h, take out and be made into 120*80*0.8mm
3Negative plate.Selecting glass fibre for use is dividing plate, and 10 positive plates, 10 negative plates are laminated into electric core, and in the polypropylene plastics shell of packing into, injecting 500g density is 1.25g/cm
3Aqueous sulfuric acid, after changing into, capacitor is tested, be that 0.5～1.5V, measuring current are under the situation of 50A in the operating voltage interval, the energy density of capacitor is 7.6Wh/Kg, power density is 1000W/Kg, and after 10000 circulations, capability retention is 96%.
Embodiment 5:
The making of positive plate: charcoal fiber, conductive black, polytetrafluoroethylene are pressed 85: 5: 10 mixed of mass ratio, roll the carbon membrane that is pressed into 1.0mm then, two carbon membranes are pressed be attached on lead-calcium grid of 1.2mm, be made into 120*80*2.0mm
3Positive plate.The making of negative plate: lead powder, lead monoxide powder, conductive black are pressed 40: 50: 10 mixed of mass ratio, add an amount of sulfuric acid and water furnishing paste, be coated in then on lead-calcium grid of 0.8mm, after 100 ℃-10min drying, after putting into temperature and be 45 ℃, relative humidity and be 85% environment and solidifying 12h, take out and be made into 120*80*0.8mm
3Negative plate.Selecting glass fibre for use is dividing plate, and 10 positive plates, 10 negative plates are laminated into electric core, and in the polypropylene plastics shell of packing into, injecting 500g density is 1.25g/cm
3Aqueous sulfuric acid, after changing into, capacitor is tested, be that 0.5～1.5V, measuring current are under the situation of 50A in the operating voltage interval, the energy density of capacitor is 7.7Wh/Kg, power density is 1200W/Kg, and after 10000 circulations, capability retention is 94%.
According to the embodiment of front, can be summarized as follows:
| Anodal | Negative pole | Energy density (Wh/Kg) | Power density (W/Kg) | 5000 circulation back capability retentions (%) |
| Active carbon: conductive black: PTFE=85: 5: 10 | Pb: PbO: conductive black=40: 50: 10 | 7.8 | 800 | 95 |
| Active carbon: conductive black: PTFE=85: 5: 10 | Pb: PbO: conductive black=20: 60: 20 | 6.8 | 900 | 95.5 |
| Active carbon: conductive black: PTFE=85: 5: 10 | Pb: PbO: conductive black=30: 55: 15 | 8.5 | 850 | 95.2 |
| Mesoporous charcoal: conductive black: PTFE=85: 5: 10 | Pb: PbO: conductive black=40: 50: 10 | 7.6 | 1000 | 96 |
| Charcoal fiber: conductive black: PTFE=85: 5: 11 | Pb: PbO: conductive black=40: 50: 10 | 7.7 | 1200 | 94 |
From as can be seen above, the negative pole different proportion is bigger to capacitor energy density influence, and anodal different raw material of wood-charcoal material to capacitor the power characteristic influence bigger.
Described in this specification is several preferred embodiment of the present invention, and above embodiment is only in order to illustrate technical scheme of the present invention but not limitation of the present invention.All those skilled in the art all should be within the scope of the present invention under this invention's idea by the available technical scheme of logical analysis, reasoning, or a limited experiment.
Claims (6)
1. a lead-based super capacitor is made up of positive pole, negative pole, marginal dividing plate and electrolyte, it is characterized in that the anodal porous carbon material that adopts; The lead electrode that negative pole adopts mainly is made up of lead powder (Pb) and lead monoxide powder (PbO), and the ratio of each material is a lead powder in the negative pole: lead monoxide: conductive agent=(20～40): (50～60): (10～20); Electrolyte is that density is 1.10～1.30g/cm
3Aqueous sulfuric acid.
2. lead-based super capacitor according to claim 1 is characterized in that described porous carbon material comprises active carbon, mesoporous charcoal, charcoal-aero gel, carbon nanotube, charcoal fiber.
3. lead-based super capacitor according to claim 1 is characterized in that also adding in the described positive pole an amount of binding agent, and described binding agent comprises polytetrafluoroethylene (PTFE), Kynoar (PVDF), polyvinyl alcohol (PVA).
4. lead-based super capacitor according to claim 1 is characterized in that also adding an amount of conductive agent in described positive pole and the negative pole, and described conductive agent comprises conductive black, acetylene black, graphite powder.
5. lead-based super capacitor according to claim 1 is characterized in that described dividing plate comprises glass fibre separator, microporous rubber separator, polyvinyl chloride (PVC) dividing plate, polyethylene (PE) dividing plate, polypropylene (PP) dividing plate.
6. lead-based super capacitor according to claim 1 is characterized in that the collector of described positive pole and negative pole comprises pure stereotype grid or paper tinsel, lead-antimony alloy grid or paper tinsel, lead-calcium alloy slab lattice paper tinsel, terne metal grid or paper tinsel, titanium net or paper tinsel.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101141475A CN101847515B (en) | 2010-02-26 | 2010-02-26 | Lead-based super capacitor |
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| CN2010101141475A CN101847515B (en) | 2010-02-26 | 2010-02-26 | Lead-based super capacitor |
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| CN101847515B true CN101847515B (en) | 2011-12-21 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD252925A1 (en) * | 1986-09-25 | 1987-12-30 | Univ Dresden Tech | PROCESS FOR TIREING AND FORMING THE ACTIVE MASS |
| CN1249062A (en) * | 1997-11-11 | 2000-03-29 | 科学生产企业(埃克信) | Capacitor with dual electricity layer |
| US6452784B2 (en) * | 2000-05-31 | 2002-09-17 | Matsushita Electric Industrial Co., Ltd. | Aluminum electrolytic capacitor and method for producing the same |
| CN1838352A (en) * | 2005-03-22 | 2006-09-27 | 中国电子科技集团公司第十八研究所 | Electrochemical capacitor and preparation method thereof |
-
2010
- 2010-02-26 CN CN2010101141475A patent/CN101847515B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD252925A1 (en) * | 1986-09-25 | 1987-12-30 | Univ Dresden Tech | PROCESS FOR TIREING AND FORMING THE ACTIVE MASS |
| CN1249062A (en) * | 1997-11-11 | 2000-03-29 | 科学生产企业(埃克信) | Capacitor with dual electricity layer |
| US6452784B2 (en) * | 2000-05-31 | 2002-09-17 | Matsushita Electric Industrial Co., Ltd. | Aluminum electrolytic capacitor and method for producing the same |
| CN1838352A (en) * | 2005-03-22 | 2006-09-27 | 中国电子科技集团公司第十八研究所 | Electrochemical capacitor and preparation method thereof |
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| CN101847515A (en) | 2010-09-29 |
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Denomination of invention: Lead-based super capacitor Effective date of registration: 20131120 Granted publication date: 20111221 Pledgee: Pudong New Area Shanghai Zhangjiang microfinance Limited by Share Ltd Pledgor: Shanghai Aowei Technology Development Co., Ltd. Registration number: 2013310000067 |
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