CN103500666A - Hybrid ternary electrochemistry supercapacitor - Google Patents
Hybrid ternary electrochemistry supercapacitor Download PDFInfo
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- CN103500666A CN103500666A CN201310407969.6A CN201310407969A CN103500666A CN 103500666 A CN103500666 A CN 103500666A CN 201310407969 A CN201310407969 A CN 201310407969A CN 103500666 A CN103500666 A CN 103500666A
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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 provides a hybrid ternary electrochemistry supercapacitor. The hybrid ternary electrochemistry supercapacitor comprises a positive electrode, a negative electrode, a diaphragm, an electrolyte and a shell, wherein the positive electrode is formed by evenly coating foamed nickel with a positive electrode material, and the positive electrode material is composed of a LiCo1/3Nil/3Mn1/3O2 ternary material, carbon aerogel, conductive black and a binder. The negative electrode is formed by evenly coating foamed nickel with a negative electrode material, and the negative electrode material is composed of carbon aerogel, conductive black and a binder. The electrolyte is composed of one or two of a LiOH aqueous solution and a Li2SO4 aqueous solution. According to the hybrid ternary electrochemistry supercapacitor, the advantages of a lithium ion battery and the advantages of the supercapacitor are combined, and the manufactured hybrid ternary electrochemistry supercapacitor has the advantages of being high in energy density, long in cycle life, large in power density, and capable of being used in the fields of electric vehicles, electric bicycles and the like.
Description
Technical field
The present invention relates to a kind of electrochemical energy storing device field, particularly, relate to a kind of mixed type ternary electric chemical super capacitor.
Background technology
In current new energy technology development, the secondary energy storage device has become one of key technology in many major application efficiently.No matter be at portable traffic power, portable type electronic product and various large-scale energy-accumulating power station, all need the secondary energy storage device of high-energy-density, high-specific-power.Common secondary energy storage device has in the market: lithium ion battery, ultracapacitor, Ni-MH battery, nickel-cadmium cell, lead-acid battery etc.Because nickel-cadmium cell and lead-acid battery contain the heavy metals such as lead, cadmium, just progressively by market, eliminated; And Ni-MH battery is due to the memory effect of negative pole hydrogen bearing alloy, it uses cycle-index not reach the requirement of market to the high-performance energy storage device far away.Lithium ion battery has that energy density is high, memory-less effect, but cycle life not oversize (500～1000 times).Electric chemical super capacitor has that power density is large, the characteristics such as have extended cycle life, but its energy density is lower.
The mixed type electric chemical super capacitor is a kind of novel energy-storing device between ultracapacitor and battery, it has energy density and the larger power density of battery that the ratio super capacitance device is higher, in fields such as electric automobile, electric bicycles, has boundless application prospect.
Summary of the invention
For defect of the prior art, the purpose of this invention is to provide a kind of mixed type ternary electric chemical super capacitor, this capacitor has that energy density is high, power density is large, have extended cycle life, safety, eco-friendly characteristics, and the fields such as electric automobile, electric bicycle that are adapted at are used.
For realizing above purpose, the invention provides a kind of mixed type ternary electric chemical super capacitor, comprise positive pole, negative pole, barrier film, electrolyte and shell, barrier film is separated both positive and negative polarity, is infiltrated in electrolyte, with shell, encapsulates.
Wherein: described positive pole is evenly coated in nickel foam by positive electrode and forms, and described positive electrode is by LiCo
1/3ni
1/3mn
1/3o
2ternary material, carbon aerogels, conductive black, binding agent form;
Described negative pole is evenly coated in nickel foam by negative material and forms, and described negative material is comprised of carbon aerogels, conductive black, binding agent;
Described electrolyte is by LiOH, Li
2sO
4in a kind of or aqueous solution of two kinds form.
Preferably, each constituent mass content of described positive electrode is: LiCo
1/3ni
1/3mn
1/3o
2ternary material 50～90%, carbon aerogels 0～40%, conductive black 5～10%, binding agent 5～10%.LiCo wherein
1/3ni
1/3mn
1/3o
2ternary material has tridimensional network, and its specific area is higher than 5m
2/ g; Carbon aerogels is graded porous structure, and pore-size distribution is at 0.6～2nm, 2-4nm and 30～100nm.
Preferably, each constituent mass content of described negative material is: carbon aerogels 70～90%, conductive black 5～20%, binding agent 5～10%.
More preferably, the carbon aerogels in described negative material is graded porous structure, and pore-size distribution is at 0.6～2nm, 2-4nm and 30～100nm.
Preferably, described binding agent is ptfe emulsion (PTFE).
Preferably, the electrolyte that described electrolyte contains is LiOH, Li
2sO
4in a kind of or two kinds, LiOH, Li
2sO
4molar content in deionized water is respectively 1-2mol/L and 0.5-1mol/L.
Innovative point of the present invention is the advantage in conjunction with lithium ion battery and ultracapacitor, created a kind of assembling mode of brand-new mixed type ternary electric chemical super capacitor, make its characteristics that both there is the high-energy-density of lithium ion battery, have again have extended cycle life, advantage that power density is large.
A kind of mixed type ternary electric chemical super capacitor process of the present invention: a whole set of technological process of coat on nickel foam afflux collection → drying → compressing tablet → cut-parts → lamination → dress shell → fluid injection → sealing of weighing and burden → slurry stirring → slurry obtains.
Compared with prior art, the present invention has following beneficial effect:
A kind of mixed type ternary electric chemical super capacitor proposed by the invention is compared and is had larger power density with existing lithium ion battery: the anodal LiCo with three-dimensional net structure and high-specific surface area that adopts
1/3ni
1/3mn
1/3o
2material, negative pole is used has that conductivity is high, the carbon aerogels material of graded porous structure, the aqueous electrolyte that ionic conductivity is high, the significantly energy density of improving product and power density.With traditional ultracapacitor, compare, the technology of the present invention product has higher energy density, and more wide application.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.Following examples will contribute to those skilled in the art further to understand the present invention, but not limit in any form the present invention.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, can also make some distortion and improvement.These all belong to protection scope of the present invention.
Embodiment 1
By ternary material, be LiCo
1/3ni
1/3mn
1/3o
2, conductive black and binding agent PTFE in mass ratio 90:5:5 take, take the aqueous solution as solvent, after this mixture stirring is formed to uniform slurry in 5 hours, spread upon uniformly on nickel foam, flatten on roll squeezer after drying under the environment of 100 ℃, cut into and be applicable to size and will collect ear being welded on positive plate.
By carbon aerogels, conductive black and binding agent PTFE in mass ratio 90:5:5 take, take the aqueous solution as solvent, after this mixture stirring is formed to uniform slurry in 3 hours, spread upon uniformly on nickel foam, flatten on roll squeezer after drying under the environment of 100 ℃, cut into and be applicable to size and will collect ear being welded on negative plate.
Control positive, negative electrode plate thickness, positive and negative electrode active material mass ratio is controlled as 1:2, then positive and negative plate is separated with barrier film, in the lamination mode, form battery core; Battery core is put into to stainless steel casing, the both positive and negative polarity lug of core bag and the positive and negative terminal of shell are welded together; The cover plate of shell is carried out to seal welding, and reserve the liquid injection hole of a diameter 1mm; Inject electrolyte in the battery core that fills shell, electrolyte consists of the LiOH aqueous solution of 2mol/L; After electrolyte is annotated, with steel ball, will after the liquid injection hole sealing, obtain finished product mixed type electric chemical super capacitor.
With battery charge-discharge test instrument, the mixed type electric chemical super capacitor of making is tested, in the voltage window of 0.4-2.0V, discharged and recharged with 10C, its specific discharge capacity is 296F/g, circulate that capacity is initial capacity after 5000 times 86.7%; The 30C charging, the 15C electric discharge, specific discharge capacity is 183F/g.
Embodiment 2
By ternary material, be LiCo
1/3ni
1/3mn
1/3o
2, carbon aerogels, conductive black and binding agent PTFE in mass ratio 50:40:5:5 take, take the aqueous solution as solvent, after this mixture stirring is formed to uniform slurry in 5 hours, spread upon uniformly on nickel foam, flatten on roll squeezer after drying under the environment of 100 ℃, cut into and be applicable to size and will collect ear being welded on positive plate.
By carbon aerogels, conductive black and binding agent PTFE in mass ratio 70:20:10 take, take the aqueous solution as solvent, after this mixture stirring is formed to uniform slurry in 3 hours, spread upon uniformly on nickel foam, flatten on roll squeezer after drying under the environment of 100 ℃, cut into and be applicable to size and will collect ear being welded on negative plate.
Control positive, negative electrode plate thickness, positive and negative electrode active material mass ratio is controlled as 1:1.7, then positive and negative plate is separated with barrier film, in the lamination mode, form battery core; Battery core is put into to stainless steel casing, the both positive and negative polarity lug of core bag and the positive and negative terminal of shell are welded together; The cover plate of shell is carried out to seal welding, and reserve the liquid injection hole of a diameter 1mm; Inject electrolyte in the battery core that fills shell, electrolyte consists of the LiOH+Li of 1mol/L
2sO
4the aqueous solution; After electrolyte is annotated, with steel ball, will after the liquid injection hole sealing, obtain finished product mixed type electric chemical super capacitor.
With battery charge-discharge test instrument, the mixed type electric chemical super capacitor of making is tested, in the voltage window of 0.4-2.0V, discharged and recharged with 10C, its specific discharge capacity is 234F/g, circulate that capacity is initial capacity after 5000 times 92.8%; The 30C charging, the 15C electric discharge, specific discharge capacity is 205F/g.
Embodiment 3
By ternary material, be LiCo
1/3ni
1/3mn
1/3o
2, carbon aerogels, conductive black and binding agent PTFE in mass ratio 65:25:5:5 take, take the aqueous solution as solvent, after this mixture stirring is formed to uniform slurry in 5 hours, spread upon uniformly on nickel foam, flatten on roll squeezer after drying under the environment of 100 ℃, cut into and be applicable to size and will collect ear being welded on positive plate.
By carbon aerogels, conductive black and binding agent PTFE in mass ratio 80:10:10 take, take the aqueous solution as solvent, after this mixture stirring is formed to uniform slurry in 3 hours, spread upon uniformly on nickel foam, flatten on roll squeezer after drying under the environment of 100 ℃, cut into and be applicable to size and will collect ear being welded on negative plate.
Control positive, negative electrode plate thickness, positive and negative electrode active material mass ratio is controlled as 1:1.8, then positive and negative plate is separated with barrier film, in the lamination mode, form battery core; Battery core is put into to stainless steel casing, the both positive and negative polarity lug of core bag and the positive and negative terminal of shell are welded together; The cover plate of shell is carried out to seal welding, and reserve the liquid injection hole of a diameter 1mm; Inject electrolyte in the battery core that fills shell, electrolyte consists of the LiOH of 1.5mol/L and the Li of 0.5mol/L
2sO
4the aqueous solution; After electrolyte is annotated, with steel ball, will after the liquid injection hole sealing, obtain finished product mixed type electric chemical super capacitor.
With battery charge-discharge test instrument, the mixed type electric chemical super capacitor of making is tested, in the voltage window of 0.4-2.0V, discharged and recharged with 10C, its specific discharge capacity is 258F/g, circulate that capacity is initial capacity after 5000 times 90.3%; The 30C charging, the 15C electric discharge, specific discharge capacity is 191F/g.
Embodiment 4
By ternary material, be LiCo
1/3ni
1/3mn
1/3o
2, carbon aerogels, conductive black and binding agent PTFE in mass ratio 80:10:5:5 take, take the aqueous solution as solvent, after this mixture stirring is formed to uniform slurry in 5 hours, spread upon uniformly on nickel foam, flatten on roll squeezer after drying under the environment of 100 ℃, cut into and be applicable to size and will collect ear being welded on positive plate.
By carbon aerogels, conductive black and binding agent PTFE in mass ratio 80:10:10 take, take the aqueous solution as solvent, after this mixture stirring is formed to uniform slurry in 3 hours, spread upon uniformly on nickel foam, flatten on roll squeezer after drying under the environment of 100 ℃, cut into and be applicable to size and will collect ear being welded on negative plate.
Control positive, negative electrode plate thickness, positive and negative electrode active material mass ratio is controlled as 1:1.9, then positive and negative plate is separated with barrier film, in the lamination mode, form battery core; Battery core is put into to stainless steel casing, the both positive and negative polarity lug of core bag and the positive and negative terminal of shell are welded together; The cover plate of shell is carried out to seal welding, and reserve the liquid injection hole of a diameter 1mm; Inject electrolyte in the battery core that fills shell, electrolyte consists of the LiOH of 1.5mol/L and the Li of 0.5mol/L
2sO
4the aqueous solution; After electrolyte is annotated, with steel ball, will after the liquid injection hole sealing, obtain finished product mixed type electric chemical super capacitor.
With battery charge-discharge test instrument, the mixed type electric chemical super capacitor of making is tested, in the voltage window of 0.4-2.0V, discharged and recharged with 10C, its specific discharge capacity is 277F/g, circulate that capacity is initial capacity after 5000 times 89.2%; The 30C charging, the 15C electric discharge, specific discharge capacity is 197F/g.
Embodiment 5
By ternary material, be LiCo
1/3ni
1/3mn
1/3o
2, carbon aerogels, conductive black and binding agent PTFE in mass ratio 70:10:10:10 take, take the aqueous solution as solvent, after this mixture stirring is formed to uniform slurry in 5 hours, spread upon uniformly on nickel foam, flatten on roll squeezer after drying under the environment of 100 ℃, cut into and be applicable to size and will collect ear being welded on positive plate.
By carbon aerogels, conductive black and binding agent PTFE in mass ratio 85:7:8 take, take the aqueous solution as solvent, after this mixture stirring is formed to uniform slurry in 4 hours, spread upon uniformly on nickel foam, flatten on roll squeezer after drying under the environment of 100 ℃, cut into and be applicable to size and will collect ear being welded on negative plate.
Control positive, negative electrode plate thickness, positive and negative electrode active material mass ratio is controlled as 1:1.6, then positive and negative plate is separated with barrier film, in the lamination mode, form battery core; Battery core is put into to stainless steel casing, the both positive and negative polarity lug of core bag and the positive and negative terminal of shell are welded together; The cover plate of shell is carried out to seal welding, and reserve the liquid injection hole of a diameter 1mm; Inject electrolyte in the battery core that fills shell, electrolyte consists of the Li of 1mol/L
2sO
4the aqueous solution; After electrolyte is annotated, with steel ball, will after the liquid injection hole sealing, obtain finished product mixed type electric chemical super capacitor.
With battery charge-discharge test instrument, the mixed type electric chemical super capacitor of making is tested, in the voltage window of 0.4-2.0V, discharged and recharged with 10C, its specific discharge capacity is 263F/g, circulate that capacity is initial capacity after 5000 times 90.3%; The 30C charging, the 15C electric discharge, specific discharge capacity is 190F/g.
Embodiment 6
By ternary material, be LiCo
1/3ni
1/3mn
1/3o
2, carbon aerogels, conductive black and binding agent PTFE in mass ratio 70:15:7:8 take, take the aqueous solution as solvent, after this mixture stirring is formed to uniform slurry in 3 hours, spread upon uniformly on nickel foam, flatten on roll squeezer after drying under the environment of 100 ℃, cut into and be applicable to size and will collect ear being welded on positive plate.
By carbon aerogels, conductive black and binding agent PTFE in mass ratio 80:13:7 take, take the aqueous solution as solvent, after this mixture stirring is formed to uniform slurry in 4 hours, spread upon uniformly on nickel foam, flatten on roll squeezer after drying under the environment of 100 ℃, cut into and be applicable to size and will collect ear being welded on negative plate.
Control positive, negative electrode plate thickness, positive and negative electrode active material mass ratio is controlled as 1:1.8, then positive and negative plate is separated with barrier film, in the lamination mode, form battery core; Battery core is put into to stainless steel casing, the both positive and negative polarity lug of core bag and the positive and negative terminal of shell are welded together; The cover plate of shell is carried out to seal welding, and reserve the liquid injection hole of a diameter 1mm; Inject electrolyte in the battery core that fills shell, electrolyte consists of the LiOH of 1.5mol/L and the Li of 0.7mol/L
2sO
4the aqueous solution; After electrolyte is annotated, with steel ball, will after the liquid injection hole sealing, obtain finished product mixed type electric chemical super capacitor.
With battery charge-discharge test instrument, the mixed type electric chemical super capacitor of making is tested, in the voltage window of 0.4-2.0V, discharged and recharged with 10C, its specific discharge capacity is 281F/g, circulate that capacity is initial capacity after 5000 times 91.2%; The 30C charging, the 15C electric discharge, specific discharge capacity is 195F/g.
The present invention combines the advantage of lithium ion battery and ultracapacitor, the mixed type electric chemical super capacitor produced have energy density high, have extended cycle life and the advantage such as power density is large, can use in fields such as electric automobile, electric bicycles.
Above specific embodiments of the invention are described.It will be appreciated that, the present invention is not limited to above-mentioned specific implementations, and those skilled in the art can make various distortion or modification within the scope of the claims, and this does not affect flesh and blood of the present invention.
Claims (8)
1. a mixed type ternary electric chemical super capacitor, is characterized in that, described ultracapacitor comprises positive pole, negative pole, barrier film, electrolyte and shell, wherein:
Described positive pole is evenly coated in nickel foam by positive electrode and forms, and described positive electrode is by LiCo
1/3ni
1/3mn
1/3o
2ternary material, carbon aerogels, conductive black, binding agent form;
Described negative pole is evenly coated in nickel foam by negative material and forms, and described negative material is comprised of carbon aerogels, conductive black, binding agent;
Described electrolyte is by LiOH, Li
2sO
4in a kind of or aqueous solution of two kinds form.
2. a kind of mixed type ternary electric chemical super capacitor according to claim 1, is characterized in that, the mass content of described each component of positive electrode is: LiCo
1/3ni
1/3mn
1/3o
2ternary material 50～90%, carbon aerogels 0～40%, conductive black 5～10%, binding agent 5～10%.
3. a kind of mixed type ternary electric chemical super capacitor according to claim 2, is characterized in that described LiCo
1/3ni
1/3mn
1/3o
2ternary material has tridimensional network, and its specific area is higher than 5m
2/ g.
4. according to the described a kind of mixed type ternary electric chemical super capacitor of claim 1-3 any one, it is characterized in that, described carbon aerogels is graded porous structure, and pore-size distribution is at 0.6～2nm, 2-4nm and 30～100nm.
5. a kind of mixed type ternary electric chemical super capacitor according to claim 1, is characterized in that, the mass content of described each component of negative material is: carbon aerogels 70～90%, conductive black 5～20%, binding agent 5～10%.
6. a kind of mixed type ternary electric chemical super capacitor according to claim 5, is characterized in that, described carbon aerogels is graded porous structure, and pore-size distribution is at 0.6～2nm, 2-4nm and 30～100nm.
7. according to claim 1 or 2 or 3 or 5 described a kind of mixed type ternary electric chemical super capacitors, it is characterized in that, described binding agent is ptfe emulsion.
8. according to claim 1 or 2 or 3 or 5 described a kind of mixed type ternary electric chemical super capacitors, it is characterized in that, in described electrolyte, electrolyte LiOH, Li
2sO
4molar content in deionized water is respectively 1-2mol/L and 0.5-1mol/L.
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|---|---|---|---|
| CN201310407969.6A CN103500666A (en) | 2013-09-09 | 2013-09-09 | Hybrid ternary electrochemistry supercapacitor |
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|---|---|---|---|
| CN201310407969.6A CN103500666A (en) | 2013-09-09 | 2013-09-09 | Hybrid ternary electrochemistry supercapacitor |
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|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106159232A (en) * | 2016-08-19 | 2016-11-23 | 宁波中车新能源科技有限公司 | A kind of battery capacitor |
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| JP2008177346A (en) * | 2007-01-18 | 2008-07-31 | Sanyo Electric Co Ltd | Energy storage device |
| CN101847516A (en) * | 2010-02-26 | 2010-09-29 | 上海奥威科技开发有限公司 | Capacitor battery of high-specific-energy organic system |
| CN101847513A (en) * | 2010-02-26 | 2010-09-29 | 上海奥威科技开发有限公司 | Preparation process of long-lived negative pole piece and capacitor battery using negative pole piece |
-
2013
- 2013-09-09 CN CN201310407969.6A patent/CN103500666A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008177346A (en) * | 2007-01-18 | 2008-07-31 | Sanyo Electric Co Ltd | Energy storage device |
| CN101847516A (en) * | 2010-02-26 | 2010-09-29 | 上海奥威科技开发有限公司 | Capacitor battery of high-specific-energy organic system |
| CN101847513A (en) * | 2010-02-26 | 2010-09-29 | 上海奥威科技开发有限公司 | Preparation process of long-lived negative pole piece and capacitor battery using negative pole piece |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106159232A (en) * | 2016-08-19 | 2016-11-23 | 宁波中车新能源科技有限公司 | A kind of battery capacitor |
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Application publication date: 20140108 |