CN103745833A - Super capacitor battery and preparation method thereof - Google Patents
Super capacitor battery and preparation method thereof Download PDFInfo
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- CN103745833A CN103745833A CN201310729360.0A CN201310729360A CN103745833A CN 103745833 A CN103745833 A CN 103745833A CN 201310729360 A CN201310729360 A CN 201310729360A CN 103745833 A CN103745833 A CN 103745833A
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- lithium
- super capacitance
- capacitance cell
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Abstract
The invention relates to the technical field of batteries, particularly to a super capacitor battery and a preparation method thereof. The super capacitor battery comprises a shell, a positive electrode, a negative electrode, an electrolyte and a diaphragm between the positive and negative electrodes; positive electrode material includes a vanadium-containing and lithium-containing compound, activated carbon, a conductive additive and a binder; and negative electrode material includes a lithium-containing compound, activated carbon, a conductive additive and a binder. Compared with an existing lithium ion battery, the super capacitor battery in the invention has a higher power density and a longer cycle life, and has a higher energy density compared with an existing capacitor.
Description
Technical field
The present invention relates to battery technology field, particularly relate to a kind of super capacitance cell and preparation method thereof.
Background technology
Along with socioeconomic development, people more and more pay close attention to for green energy resource and biological environment, electric chemical super capacitor and lithium ion battery as energy storage device because of its superiority can not be substituted, more and more in widespread attention.
Electric chemical super capacitor is a kind of novel energy storage device of development in recent years, according to energy storage principle, there are two types of double electric layer capacitor and pseudo capacitance devices, chemical cell is to pass through electrochemical reaction, produce faraday electric charge and shift to store electric charge, its energy density is high, but power density is low, cycle life short (approximately 1000 times); The charge storage of ultracapacitor occurs on the electric double layer of electrode, electrolytical formation and at electrode surface, carries out the migration of the electric charge that underpotential deposition, electrochemistry adsorption and desorption and redox produce, be characterized in that power density is high, have extended cycle life (approximately 100000 times), but energy density is low.
Summary of the invention
In order to address the above problem, the object of the invention is to, a kind of super capacitance cell is provided, and this battery, by the advantages of lithium ion battery and ultracapacitor, has the high-energy-density of lithium ion battery and the high power density of ultracapacitor and long circulation life simultaneously.
Two of object of the present invention is to provide the preparation method of described super capacitance cell.
The present invention is achieved through the following technical solutions:
A kind of super capacitance cell, comprises shell, positive pole, negative pole, electrolyte and the barrier film between both positive and negative polarity; Described positive electrode comprises containing vanadium lithium-containing compound, active carbon, conductive additive and binding agent; Described negative material comprises lithium-containing compound, active carbon, conductive additive and binding agent.
Preferably, described positive electrode comprises the lithium-containing compound 10%～90%, active carbon 0.5%～90%, conductive additive 0.5%～15% and the binding agent 0.5%-15% that calculate by mass percentage.
Preferably, described is phosphoric acid vanadium lithium (Li containing vanadium lithium-containing compound
3v
2(PO
4)
3), fluorophosphoric acid vanadium lithium (LiVPO
4f), lithium vanadate (Li
1+zv
3o
8), the fluorophosphoric acid vanadium lithium of the phosphoric acid vanadium lithium of doped chemical X, doped chemical X or the lithium vanadate of doped chemical X.
Preferably, described doped chemical X is: at least one in Na, K, Mg, Ga, Ba, B, Al, In, S, Se, Si, F, Cl, Ti, Mn, Fe, Co, Ni.
Preferably, described positive electrode comprises lithium-containing compound 10%～90%, active carbon 0.5%～90%, conductive additive 0.5%～15% and the binding agent 0.5%～15% calculated by mass percentage.
Preferably, described lithium-containing compound is zinc titanate lithium (Li
2znTi
3o
8) or the zinc titanate lithium (Li that contains doped chemical Y
2znTi
3o
8).
Preferably, described doped chemical Y is: at least one in Na, K, Mg, Ga, Ba, B, Al, In, S, Se, Si, F, Cl, Ti, Mn, Fe, Co, Ni.
Preferably, described conductive additive is at least one in SP, superconduction carbon black, Ketjen black, electrically conductive graphite, carbon nano-tube, Graphene.
Preferably, described binding agent is at least one in aqueous binders (W811, W812, LA132 etc.) or oiliness binding agent (PVDF, PTFE etc.).Wherein, W811, W812 aqueous assembly glue are TPO compound, are a kind of bonding agents of HMW, and product is white emulsion state, are a kind of nontoxic environment-friendly novel materials; LA132 is a kind of environment-friendly type electrode material adhesive take water as decentralized medium, during use, need not add thickener and organic solvent, can effectively avoid the problem such as solvent type adhesive contaminated environment and poor stability in lithium ion battery production.They can replace NMP and PVDF completely, because water has replaced NMP, have reduced in coating process the NMP pollution that air is caused of volatilizing; Owing to greatly having reduced the cost pressure that uses NMP to cause take water as solvent, reduced battery requirement to humiture in processing procedure simultaneously.Can in normal air environment, prepare burden, be coated with, prick film, cut, operating winding.The pole piece of the slurry coating that adhesive glue is made has good compacted density, can improve cell unit volume capacity.
Prepare the method for described super capacitance cell, comprise and be prepared as follows step:
A. anodal making: first by described amount containing vanadium lithium-containing compound, active carbon, conductive additive and binding agent mixing furnishing slurry, be then coated on and punch in aluminum foil current collector, anode pole piece is made in drying, roll-in, cut-parts, vacuumize successively;
B. the making of negative pole: first by the lithium-containing compound of described amount, active carbon, conductive additive and binding agent mixing furnishing slurry, be then coated on punching Copper Foil collector, cathode pole piece is made in drying, roll-in, cut-parts, vacuumize successively;
C. anode pole piece good cross cutting, barrier film, cathode pole piece are carried out putting into after lamination assembling made aluminum plastic film dry; Then fluid injection, seal, change into and make described super capacitance cell.
The present invention includes shell, positive pole, negative pole, electrolyte and the barrier film between both positive and negative polarity, wherein, positive electrode adopts containing vanadium mutually compound containing capacitance materials such as the lithium ion battery material of lithium and active carbons.Containing the lithium ion battery material of vanadium, have the higher lithium ion diffusion coefficient of other lithium ion battery materials relatively, entirety embodies the superior characteristic of high rate performance, more can take into account high power density and the high-energy-density of body series.
In positive electrode is the high-energy-density that keeps lithium-ion capacitor battery containing the lithium ion battery material effect of lithium containing vanadium; Phosphoric acid vanadium lithium is example, and Stability Analysis of Structures under its hot conditions, so cycle performance is extremely superior; Lithium ion diffusion coefficient under cryogenic conditions is relatively large, so cryogenic property is relatively good.
Wherein, negative material adopts containing capacitance materials such as the lithium ion battery material of lithium and active carbons mutually compound, and zinc titanate lithium surface forms without SEI film substantially, not only there is high security, and adopt containing zinc raw material, reduce its production cost, and there is the advantages such as safety and environmental protection.And can also keep the high-energy-density of lithium-ion capacitor battery.Active carbon in material can keep the high power density of lithium-ion capacitor battery; Conductive additive can keep the high conductivity of lithium-ion capacitor battery electrode; Binding agent can keep the machinability of lithium-ion capacitor battery electrode.Material and collector mutually combine and use the raising and the performance that are more conducive to properties of product.Negative pole adopts zinc titanate lithium can when keeping product high security, reduce the cost of material.And zinc titanate lithium is during as battery material, show higher power density and cycle life preferably.
It adopts punching aluminium foil, Copper Foil as collector, to be conducive to improve power density and the energy density of product.Power density is detected to lithium-ion capacitor battery of the present invention: 4000W/Kg, common lithium ion battery: 1200W/Kg; Energy density is detected to lithium-ion capacitor battery of the present invention: 90Wh/Kg, ordinary capacitor: 10Wh/Kg.
In a word, the super capacitance cell that the present invention proposes has higher power density and longer cycle life than existing lithium ion battery, has higher energy density again than existing capacitor simultaneously.
concrete execution mode
Below in conjunction with embodiment, the present invention is described in further detail, to help those skilled in the art, understands the present invention.
Embodiment 1
A kind of phosphoric acid vanadium lithium (Li
3v
2(PO
4)
3) type super capacitance cell:
The making of positive plate: phosphoric acid vanadium lithium, active carbon, SP and PVDF are mixed according to the ratio of quality 60:30:6:4, and furnishing slurry, is then coated on (surface density 16mg/cm in punching aluminum foil current collector
2).Drying (120 ℃) oven dry, roll-in, cut-parts, 24h vacuumize rear mold cut into pole piece.
The making of negative plate: zinc titanate lithium, active carbon, SP and PVDF are mixed according to the ratio of quality 60:30:6:4, and furnishing slurry, is then coated on punching Copper Foil collector.Drying (120 ℃) oven dry, roll-in, cut-parts, 24h vacuumize rear mold cut into pole piece.
Anode pole piece good cross cutting, barrier film, cathode pole piece are carried out putting into after lamination assembling made aluminum plastic film dry.Then fluid injection, seal, change into and make phosphoric acid vanadium lithium type super capacitance cell.
Embodiment 2
A kind of phosphoric acid vanadium lithium (Li
3v
2(PO
4)
3) type super capacitance cell:
The making of positive plate: phosphoric acid vanadium lithium, active carbon, superconduction carbon black and PTFE are mixed according to the ratio of quality 10:89:0.5:0.5, and furnishing slurry, is then coated on (surface density 16mg/cm in punching aluminum foil current collector
2).Drying (120 ℃) oven dry, roll-in, cut-parts, 24h vacuumize rear mold cut into pole piece.
The making of negative plate: zinc titanate lithium, active carbon, carbon nano-tube and PVDF are mixed according to the ratio of quality 10:89:0.5:0.5, and furnishing slurry, is then coated on punching Copper Foil collector.Drying (120 ℃) oven dry, roll-in, cut-parts, 24h vacuumize rear mold cut into pole piece.
Anode pole piece good cross cutting, barrier film, cathode pole piece are carried out putting into after lamination assembling made aluminum plastic film dry.Then fluid injection, seal, change into and make phosphoric acid vanadium lithium type super capacitance cell.
Embodiment 3
A kind of phosphoric acid vanadium lithium (Li
3v
2(PO
4)
3) type super capacitance cell:
The making of positive plate: the phosphoric acid vanadium lithium of doped chemical B, active carbon, electrically conductive graphite and W811 are mixed according to the ratio of quality 69.5:0.5:15:15, and furnishing slurry, is then coated on (surface density 16mg/cm in punching aluminum foil current collector
2).Drying (120 ℃) oven dry, roll-in, cut-parts, 24h vacuumize rear mold cut into pole piece.
The making of negative plate: zinc titanate lithium, active carbon, Graphene and the PVDF of doped chemical K are mixed according to the ratio of quality 69.5:0.5:15:15, and furnishing slurry, is then coated on punching Copper Foil collector.Drying (120 ℃) oven dry, roll-in, cut-parts, 24h vacuumize rear mold cut into pole piece.
Anode pole piece good cross cutting, barrier film, cathode pole piece are carried out putting into after lamination assembling made aluminum plastic film dry.Then fluid injection, seal, change into and make phosphoric acid vanadium lithium type super capacitance cell.
Embodiment 4
A kind of phosphoric acid vanadium lithium (Li
3v
2(PO
4)
3) type super capacitance cell:
The making of positive plate: the phosphoric acid vanadium lithium of doped chemical Al, active carbon, electrically conductive graphite and W811 are mixed according to the ratio of quality 30:50:10:10, and furnishing slurry, is then coated on (surface density 16mg/cm in punching aluminum foil current collector
2).Drying (120 ℃) oven dry, roll-in, cut-parts, 24h vacuumize rear mold cut into pole piece.
The making of negative plate: zinc titanate lithium, active carbon, SP and PVDF are mixed according to the ratio of quality 30:50:10:10, and furnishing slurry, is then coated on punching Copper Foil collector.Drying (120 ℃) oven dry, roll-in, cut-parts, 24h vacuumize rear mold cut into pole piece.
Anode pole piece good cross cutting, barrier film, cathode pole piece are carried out putting into after lamination assembling made aluminum plastic film dry.Then fluid injection, seal, change into and make phosphoric acid vanadium lithium type super capacitance cell.
Embodiment 5
A kind of fluorophosphoric acid vanadium lithium (LiVPO
4f) type super capacitance cell:
The making of positive plate: fluorophosphoric acid vanadium lithium, active carbon, SP and PVDF are mixed according to the ratio of quality 60:30:6:4, and furnishing slurry, is then coated on (surface density 16mg/cm in punching aluminum foil current collector
2).Drying (120 ℃) oven dry, roll-in, cut-parts, 24h vacuumize rear mold cut into pole piece.
The making of negative plate: zinc titanate lithium, active carbon, SP and PVDF are mixed according to the ratio of quality 60:30:6:4, and furnishing slurry, is then coated on punching Copper Foil collector.Drying (120 ℃) oven dry, roll-in, cut-parts, 24h vacuumize rear mold cut into pole piece.
Anode pole piece good cross cutting, barrier film, cathode pole piece are carried out putting into after lamination assembling made aluminum plastic film dry.Then fluid injection, seal, change into and make described fluorophosphoric acid vanadium lithium type super capacitance cell.
Embodiment 6
A kind of fluorophosphoric acid vanadium lithium (LiVPO
4f) type super capacitance cell:
The making of positive plate: fluorophosphoric acid vanadium lithium, active carbon, Ketjen black and PTFE are mixed according to the ratio of quality 20:78:1:1, and furnishing slurry, is then coated on (surface density 16mg/cm in punching aluminum foil current collector
2).Drying (120 ℃) oven dry, roll-in, cut-parts, 24h vacuumize rear mold cut into pole piece.
The making of negative plate: zinc titanate lithium, active carbon, Ketjen black and PTFE are mixed according to the ratio of quality 20:78:1:1, and furnishing slurry, is then coated on punching Copper Foil collector.Drying (120 ℃) oven dry, roll-in, cut-parts, 24h vacuumize rear mold cut into pole piece.
Anode pole piece good cross cutting, barrier film, cathode pole piece are carried out putting into after lamination assembling made aluminum plastic film dry.Then fluid injection, seal, change into and make described fluorophosphoric acid vanadium lithium type super capacitance cell.
Embodiment 7
A kind of fluorophosphoric acid vanadium lithium (LiVPO
4f) type super capacitance cell:
The making of positive plate: the fluorophosphoric acid vanadium lithium of doped chemical Co, active carbon, superconduction carbon black and PVDF are mixed according to the ratio of quality 80:10:2:8, and furnishing slurry, is then coated on (surface density 16mg/cm in punching aluminum foil current collector
2).Drying (120 ℃) oven dry, roll-in, cut-parts, 24h vacuumize rear mold cut into pole piece.
The making of negative plate: just zinc titanate lithium, active carbon, Graphene and the PTFE of doped chemical Co mix according to the ratio of quality 80:10:2:8, furnishing slurry, is then coated on punching Copper Foil collector.Drying (120 ℃) oven dry, roll-in, cut-parts, 24h vacuumize rear mold cut into pole piece.
Anode pole piece good cross cutting, barrier film, cathode pole piece are carried out putting into after lamination assembling made aluminum plastic film dry.Then fluid injection, seal, change into and make described fluorophosphoric acid vanadium lithium type super capacitance cell.
Embodiment 8
A kind of lithium vanadate type super capacitance cell:
The making of positive plate: lithium vanadate, active carbon, carbon nano-tube and PVDF are mixed according to the ratio of quality 50:25:12:13, and furnishing slurry, is then coated on (surface density 16mg/cm in punching aluminum foil current collector
2).Drying (120 ℃) oven dry, roll-in, cut-parts, 24h vacuumize rear mold cut into pole piece.
The making of negative plate: just zinc titanate lithium, active carbon, Graphene and the PTFE of doped chemical Ni mix according to the ratio of quality 50:25:12:13, furnishing slurry, is then coated on punching Copper Foil collector.Drying (120 ℃) oven dry, roll-in, cut-parts, 24h vacuumize rear mold cut into pole piece.
Anode pole piece good cross cutting, barrier film, cathode pole piece are carried out putting into after lamination assembling made aluminum plastic film dry.Then fluid injection, seal, change into and make described lithium vanadate type super capacitance cell.
Above-described embodiment, is preferred embodiment of the present invention, is not used for limiting the scope of the present invention, and the equivalence of being done with the feature described in the claims in the present invention and principle therefore all changes or modifies, within all should being included in the claims in the present invention scope.
Claims (10)
1. a super capacitance cell, comprises shell, positive pole, negative pole, electrolyte and the barrier film between both positive and negative polarity; It is characterized in that, described positive electrode comprises containing vanadium lithium-containing compound, active carbon, conductive additive and binding agent; Described negative material comprises lithium-containing compound, active carbon, conductive additive and binding agent.
2. super capacitance cell as claimed in claim 1, is characterized in that, described positive electrode comprises lithium-containing compound 10%～90%, active carbon 0.5%～90%, conductive additive 0.5%～15% and the binding agent 0.5%～15% calculated by mass percentage.
3. super capacitance cell as claimed in claim 2, is characterized in that, described is phosphoric acid vanadium lithium, the fluorophosphoric acid vanadium lithium of doped chemical X or the lithium vanadate of doped chemical X of phosphoric acid vanadium lithium, fluorophosphoric acid vanadium lithium, lithium vanadate, doped chemical X containing vanadium lithium-containing compound.
4. super capacitance cell as claimed in claim 3, is characterized in that, described doped chemical X is: at least one in Na, K, Mg, Ga, Ba, B, Al, In, S, Se, Si, F, Cl, Ti, Mn, Fe, Co, Ni.
5. super capacitance cell as claimed in claim 1, is characterized in that, described negative material comprises lithium-containing compound 10%～90%, active carbon 0.5%～90%, conductive additive 0.5%～15% and the binding agent 0.5%～15% calculated by mass percentage.
6. super capacitance cell as claimed in claim 5, is characterized in that, described lithium-containing compound is zinc titanate lithium or the zinc titanate lithium that contains doped chemical Y.
7. super capacitance cell as claimed in claim 6, is characterized in that, described doped chemical Y is: at least one in Na, K, Mg, Ga, Ba, B, Al, In, S, Se, Si, F, Cl, Ti, Mn, Fe, Co, Ni.
8. super capacitance cell as claimed in claim 1, is characterized in that, described conductive additive is at least one in SP, superconduction carbon black, Ketjen black, electrically conductive graphite, carbon nano-tube, Graphene.
9. super capacitance cell as claimed in claim 1, is characterized in that, described binding agent is aqueous binders or oiliness binding agent.
10. the method for preparation super capacitance cell as described in any one in claim 1～9, is characterized in that, comprises and is prepared as follows step:
A. anodal making: first by described amount containing vanadium lithium-containing compound, active carbon, conductive additive and binding agent mixing furnishing slurry, be then coated on and punch in aluminum foil current collector, anode pole piece is made in drying, roll-in, cut-parts, vacuumize successively;
B. the making of negative pole: first by the lithium-containing compound of described amount, active carbon, conductive additive and binding agent mixing furnishing slurry, be then coated on punching Copper Foil collector, cathode pole piece is made in drying, roll-in, cut-parts, vacuumize successively;
C. anode pole piece good cross cutting, barrier film, cathode pole piece are carried out putting into after lamination assembling made aluminum plastic film dry; Then fluid injection, seal, change into and make described super capacitance cell.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104658757A (en) * | 2014-12-17 | 2015-05-27 | 宁波南车新能源科技有限公司 | Method for dispersing complex conducting agent in electrode slurry for lithium ion capacitor |
| WO2016090958A1 (en) * | 2014-12-12 | 2016-06-16 | 宁波南车新能源科技有限公司 | Preparation method for mixed capacitor negative electrode slurry |
| CN105789580A (en) * | 2016-03-21 | 2016-07-20 | 福建师范大学 | Preparation method for copper-doped lithium zinc titanate nano particles and application thereof |
| CN105977039A (en) * | 2016-06-29 | 2016-09-28 | 陈小刚 | Graphene activity composite electrode super-capacitor cell |
| CN105990603A (en) * | 2016-07-04 | 2016-10-05 | 吴杨 | High-power super-capacitor lithium battery and preparation method thereof |
| CN106549145A (en) * | 2015-09-16 | 2017-03-29 | 中国科学院大连化学物理研究所 | A kind of application of vanadium phosphate cathode material of doping sulphur in lithium ion battery |
| CN107369567A (en) * | 2017-07-17 | 2017-11-21 | 深圳中科瑞能实业有限公司 | Zinc ion hybrid super capacitor electrolyte, zinc ion hybrid super capacitor and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2016090958A1 (en) * | 2014-12-12 | 2016-06-16 | 宁波南车新能源科技有限公司 | Preparation method for mixed capacitor negative electrode slurry |
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| CN106549145A (en) * | 2015-09-16 | 2017-03-29 | 中国科学院大连化学物理研究所 | A kind of application of vanadium phosphate cathode material of doping sulphur in lithium ion battery |
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| CN105789580B (en) * | 2016-03-21 | 2018-07-20 | 福建师范大学 | A kind of preparation method and applications of Copper-cladding Aluminum Bar zinc titanate lithium nano-particle |
| CN105977039A (en) * | 2016-06-29 | 2016-09-28 | 陈小刚 | Graphene activity composite electrode super-capacitor cell |
| CN105990603A (en) * | 2016-07-04 | 2016-10-05 | 吴杨 | High-power super-capacitor lithium battery and preparation method thereof |
| CN107369567A (en) * | 2017-07-17 | 2017-11-21 | 深圳中科瑞能实业有限公司 | Zinc ion hybrid super capacitor electrolyte, zinc ion hybrid super capacitor and preparation method thereof |
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Application publication date: 20140423 |
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