CN106098409A - A kind of preparation method containing lithium ion conducting polymer coating positive plate - Google Patents
A kind of preparation method containing lithium ion conducting polymer coating positive plate Download PDFInfo
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- CN106098409A CN106098409A CN201610616174.XA CN201610616174A CN106098409A CN 106098409 A CN106098409 A CN 106098409A CN 201610616174 A CN201610616174 A CN 201610616174A CN 106098409 A CN106098409 A CN 106098409A
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- Prior art keywords
- lithium ion
- positive plate
- ion conducting
- lithium
- coated
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
Abstract
The present invention provides a kind of preparation method containing lithium ion conducting polymer coating positive plate.To have lithium ion conducting polymeric material organic alcohols or ketones solvent will dissolve, and form colloidal solution, be then coated with, containing on active material positive plate, obtaining after dry out solvent containing lithium ion conducting polymer coating positive plate.There is advantages that (1) has the positive pole that positive plate is lithium ion super capacitor of lithium ion conducting polymeric material coating and makes negative pole need not add the pre-embedding lithium technique of lithium sheet or complexity, simplify preparation technology, reduce cost.
Description
Technical field
The invention belongs to lithium ion super capacitor technical field, relate to the system of a kind of lithium ion super capacitor positive plate
Preparation Method.
Background technology
In recent years, lithium rechargeable battery has obtained the biggest development, and this battery cathode generally uses the charcoal elements such as graphite
Material, positive pole uses cobalt acid lithium, LiMn2O4 etc. containing lithium metal oxide.After this set of cells is filled with, during charging, negative pole is to positive pole
Lithium ion is provided, and the lithium ion of positive pole returns negative pole when electric discharge, is therefore referred to as " rocking chair type battery ".With use metal
The lithium battery of lithium is compared, and this battery has high security and the feature of high cycle life.
But, owing to positive electrode is susceptible to the deformation of structure, therefore, lithium ion secondary electricity during removal lithium embedded
The cycle life in pond is still restricted.The most in recent years, body lithium rechargeable battery and double layer capacitor combined
System's research becomes new focus.
The carbon materials such as lithium-ion capacitor general anode material selection graphite, hard carbon, positive electrode selects electric double layer special
The absorbent charcoal material of property, is carried out the pre-doping of lithium ion, makes negative pole current potential significantly decline, thus improve by anticathode material
Energy density.Disclosing a kind of lithium-ion capacitor in patent CN200580001498.2, this lithium-ion capacitor uses
Plus plate current-collecting body and negative current collector are respectively provided with the hole running through positive and negative, respectively by positive active material and negative electrode active material shape
Become electrode layer, carry out electrochemical contact by anticathode, in advance lithium ion is carried in negative pole.Patent
CN200780024069.6 discloses the preprocess method of a kind of electrochemical capacitor negative pole, by vapor phase method or liquid phase
Method forms lithium layer on substrate, and then this lithium layer is transferred to the electrode layer of negative pole.The work that the method for these pre-doping relates to
Skill is more complicated, and needs raw material to carry out special handling, brings certain difficulty to manufacture process.
Summary of the invention
The technical problem to be solved in the present invention is to provide the preparation method of a kind of lithium ion super capacitor positive plate, the party
Positive plate prepared by method can provide lithium source in lithium-ion capacitor, at the pre-embedding lithium carrying out complexity without anticathode again
Manage or in lithium-ion capacitor, add lithium sheet, simplifying technical process prepared by lithium-ion capacitor, reduce its technique
Cost.
The preparation method of the lithium ion super capacitor positive plate that the present invention provides is: will have lithium ion conducting polymer
Material organic alcohols or ketones solvent dissolve, and forming mass concentration is 30-70% colloidal solution, are then coated with containing living
On property material positive plate, obtain after dry out solvent containing lithium ion conducting polymer coating positive plate.
Further, described lithium ion conducting polymeric material comprises one or more of polymer: Lithium polyacrylate,
Polymethylacrylic acid lithium, Polyethylene Glycol lithium, number-average molecular weight is 20000-50000.
Further, the mass concentration of described colloidal solution is 30-70%.
Further, described organic alcohols or ketones solvent comprise one or more of: ethanol, propanol, acetone, oneself
Glycol.
The present invention provides the preparation technology flow process of a kind of lithium ion super capacitor as follows:
(1) activated carbon or graphene anode material, conductive agent, binding agent are joined according to the ratio of mass ratio 90:5:5
NMP is mixed into slurry, is then coated with on plus plate current-collecting body aluminium foil, after drying, obtains positive plate.
(2) will have lithium ion conducting polymeric material organic alcohols or ketones solvent will dissolve, form mass concentration
For 30-70% colloidal solution, it is then coated with, containing on active material positive plate, obtaining containing lithium ion conducting after dry out solvent
Polymer coating positive plate.
(3) graphite or carbon cathode material, conductive agent, binding agent firmly are joined according to the ratio of mass ratio 90:5:5
NMP is mixed into slurry, is then coated with on negative current collector Copper Foil paper tinsel, after drying, obtains negative plate.
(4) according to the preparation technology of usual lithium ion battery by negative plate, barrier film and positive plate group by the way of lamination
Becoming battery core, then inject electrolyte in battery case, the electrolyte of injection is 1mol/L LiPF6DOL-DME solution (DOL
It is 1:1 with the volume ratio of DME), sealing, obtain lithium ion super capacitor.
The lithium ion battery that the technique using positive electrode of the present invention to prepare lithium ion super capacitor is general prepares work
Skill, enormously simplify the preparation technology of lithium ion super capacitor.
Prepared by the present invention has the positive plate of lithium ion conducting polymeric material coating as lithium ion super capacitor
During positive plate, having lithium ion conducting polymeric material coating provides lithium source, and when initial charge, lithium ion abjection polymer is inserted
Enter in graphite cathode, thus drag down negative pole current potential, therefore negative pole need not use metal lithium sheet or the pre-embedding lithium of complexity
Technique.
There is advantages that (1) have the positive plate of lithium ion conducting polymeric material coating be lithium from
The positive pole of sub-ultracapacitor makes negative pole need not add the pre-embedding lithium technique of lithium sheet or complexity, simplifies preparation technology,
Reduce cost.
Accompanying drawing explanation
Fig. 1 is lithium ion super capacitor positive plate structural representation of the present invention.
In figure, 1 plus plate current-collecting body, 2 active material positive plates, 3 have lithium ion conducting polymeric material coating.
Detailed description of the invention
Below in conjunction with the accompanying drawings, the preferably embodiment of the present invention is described in further detail:
Embodiment 1
(1) absorbent charcoal material, conductive agent Ketjen black, binding agent PVDF are joined in NMP according to the ratio of mass ratio 90:5:5
It is mixed into slurry, is then coated with on plus plate current-collecting body 1 aluminium foil, after drying, obtains positive plate.
(2) being dissolved by the Lithium polyacrylate ethanol that number-average molecular weight is 20000, forming mass concentration is that 30% glue is molten
Liquid, is then coated with, containing on active material positive plate 2, obtaining containing lithium ion conducting polymer coating positive pole after dry out solvent
Sheet 3.
(3) graphite cathode material, conductive agent Ketjen black, binding agent PVDF are joined according to the ratio of mass ratio 90:5:5
NMP is mixed into slurry, is then coated with on negative current collector Copper Foil paper tinsel, after drying, obtains negative plate.
(4) according to the preparation technology of usual lithium ion battery by negative plate, barrier film and positive plate group by the way of lamination
Becoming battery core, then inject electrolyte in battery case, the electrolyte of injection is 1mol/L LiPF6DOL-DME solution (DOL
It is 1:1 with the volume ratio of DME), sealing, obtain lithium ion super capacitor.
Embodiment 2
(1) absorbent charcoal material, conductive agent Ketjen black, binding agent PVDF are joined in NMP according to the ratio of mass ratio 90:5:5
It is mixed into slurry, is then coated with on plus plate current-collecting body 1 aluminium foil, after drying, obtains positive plate.
(2) being dissolved by the polymethylacrylic acid lithium acetone solvent that number-average molecular weight is 50000, forming mass concentration is
70% colloidal solution, is then coated with, containing on active material positive plate 2, obtaining being polymerized containing lithium ion conducting after dry out solvent
Thing coating positive plate 3.
(3) hard carbon cathode material, conductive agent Ketjen black, binding agent PVDF are joined according to the ratio of mass ratio 90:5:5
NMP is mixed into slurry, is then coated with on negative current collector Copper Foil paper tinsel, after drying, obtains negative plate.
(4) according to the preparation technology of usual lithium ion battery by negative plate, barrier film and positive plate group by the way of lamination
Becoming battery core, then inject electrolyte in battery case, the electrolyte of injection is 1mol/L LiPF6DOL-DME solution (DOL
It is 1:1 with the volume ratio of DME), sealing, obtain lithium ion super capacitor.
Embodiment 3
(1) absorbent charcoal material, conductive agent Ketjen black, binding agent PVDF are joined in NMP according to the ratio of mass ratio 90:5:5
It is mixed into slurry, is then coated with on plus plate current-collecting body 1 aluminium foil, after drying, obtains positive plate.
(2) being dissolved by the Polyethylene Glycol lithium propanol solvent that number-average molecular weight is 30000, forming mass concentration is 50% glue
Shape solution, is then coated with, containing on active material positive plate 2, obtaining containing lithium ion conducting polymer coating after dry out solvent
Positive plate 3.
(3) graphite cathode material, conductive agent Ketjen black, binding agent PVDF are joined according to the ratio of mass ratio 90:5:5
NMP is mixed into slurry, is then coated with on negative current collector Copper Foil paper tinsel, after drying, obtains negative plate.
(4) according to the preparation technology of usual lithium ion battery by negative plate, barrier film and positive plate group by the way of lamination
Becoming battery core, then inject electrolyte in battery case, the electrolyte of injection is 1mol/L LiPF6DOL-DME solution (DOL
It is 1:1 with the volume ratio of DME), sealing, obtain lithium ion super capacitor.
Embodiment 4
(1) absorbent charcoal material, conductive agent Ketjen black, binding agent PVDF are joined in NMP according to the ratio of mass ratio 90:5:5
It is mixed into slurry, is then coated with on plus plate current-collecting body 1 aluminium foil, after drying, obtains positive plate.
(2) being dissolved by the Polyethylene Glycol lithium hexanediol solvent that number-average molecular weight is 40000, forming mass concentration is 45%
Colloidal solution, is then coated with, containing on active material positive plate 2, obtaining being coated with containing lithium ion conducting polymer after dry out solvent
Layer positive plate 3.
(3) hard carbon cathode material, conductive agent Ketjen black, binding agent PVDF are joined according to the ratio of mass ratio 90:5:5
NMP is mixed into slurry, is then coated with on negative current collector Copper Foil paper tinsel, after drying, obtains negative plate.
(4) according to the preparation technology of usual lithium ion battery by negative plate, barrier film and positive plate group by the way of lamination
Becoming battery core, then inject electrolyte in battery case, the electrolyte of injection is 1mol/L LiPF6DOL-DME solution (DOL
It is 1:1 with the volume ratio of DME), sealing, obtain lithium ion super capacitor.
Embodiment 5
(1) absorbent charcoal material, conductive agent Ketjen black, binding agent PVDF are joined in NMP according to the ratio of mass ratio 90:5:5
It is mixed into slurry, is then coated with on plus plate current-collecting body 1 aluminium foil, after drying, obtains positive plate.
(2) being dissolved by the Lithium polyacrylate alcohol solvent that molecular weight is 35000, forming mass concentration is that 60% glue is molten
Liquid, is then coated with, containing on active material positive plate 2, obtaining containing lithium ion conducting polymer coating positive pole after dry out solvent
Sheet 3.
(3) graphite cathode material, conductive agent Ketjen black, binding agent PVDF are joined according to the ratio of mass ratio 90:5:5
NMP is mixed into slurry, is then coated with on negative current collector Copper Foil paper tinsel, after drying, obtains negative plate.
(4) according to the preparation technology of usual lithium ion battery by negative plate, barrier film and positive plate group by the way of lamination
Becoming battery core, then inject electrolyte in battery case, the electrolyte of injection is 1mol/L LiPF6DOL-DME solution (DOL
It is 1:1 with the volume ratio of DME), sealing, obtain lithium ion super capacitor.
Its effect is as shown in table 1, as shown in Table 1: lithium ion super capacitor energy density prepared by the present invention reaches
43.1-45.2 wh/kg, has reached the fluence level of conventional lithium ion super capacitor.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Energy density (wh/kg) | 44.3 | 45.2 | 43.1 | 44.1 | 43.5 |
Above content is to combine concrete preferred implementation further description made for the present invention, it is impossible to assert this
Bright being embodied as is confined to these explanations.For general technical staff of the technical field of the invention, do not taking off
On the premise of present inventive concept, it is also possible to make some simple deduction or replace, all should be considered as belonging to the protection of the present invention
Scope.
Claims (10)
1. the preparation method of a lithium ion super capacitor positive plate, it is characterised in that will have lithium ion conducting polymer
Material organic alcohols or ketones solvent dissolve, and form colloidal solution, are then coated with, containing on active material positive plate, drying
Obtain after dry solvent containing lithium ion conducting polymer coating positive plate.
2. the method for claim 1, it is characterised in that described lithium ion conducting polymeric material comprise following one or
Multiple polymers: Lithium polyacrylate, polymethylacrylic acid lithium, Polyethylene Glycol lithium.
3. the method for claim 1, it is characterised in that described its number-average molecular weight of lithium ion conducting polymeric material is
20000-50000。
4. the method for claim 1, it is characterised in that the mass concentration of described colloidal solution is 30-70%.
5. the method for claim 1, it is characterised in that described organic alcohols or ketones solvent comprise following one or
Multiple: ethanol, propanol, acetone T hexanediol.
6. the preparation technology of a lithium ion super capacitor, it is characterised in that include following several step:
Step A: activated carbon or graphene anode material, conductive agent, binding agent are joined and be mixed into slurry in NMP, then
It is coated on plus plate current-collecting body aluminium foil, after drying, obtains positive plate；
Step B: will have lithium ion conducting polymeric material organic alcohols or ketones solvent dissolves, and form quality glue molten
Liquid, is then coated with, containing on active material positive plate, obtaining containing lithium ion conducting polymer coating positive pole after dry out solvent
Sheet；
Step C: graphite or hard carbon cathode material, conductive agent, binding agent are mixed into slurry, then according to joining in NMP
It is coated on negative current collector Copper Foil paper tinsel, after drying, obtains negative plate；
Step D: negative plate, barrier film and positive plate are formed by the way of lamination battery core, then injects electrolysis in battery case
Liquid, sealing, obtain lithium ion super capacitor.
7. preparation technology as claimed in claim 6, it is characterised in that in described step A, activated carbon or Graphene positive pole material
Material, conductive agent, the mass ratio of binding agent are 90:5:5.
8. preparation technology as claimed in claim 6, it is characterised in that in described step B, mass concentration is that 30-70% glue is molten
Liquid.
9. preparation technology as claimed in claim 6, it is characterised in that in described step C, graphite or firmly carbon cathode material,
Conductive agent, binding agent mass ratio are 90:5:5.
10. preparation technology as claimed in claim 6, it is characterised in that in described step D, electrolyte is 1mol/L LiPF6's
DOL-DME solution, the volume ratio of DOL and DME is 1:1.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018023321A1 (en) * | 2016-07-31 | 2018-02-08 | 肖丽芳 | Preparation method for positive electrode sheet containing lithium-ion conductive polymer coating |
| CN109698076A (en) * | 2017-10-20 | 2019-04-30 | 中能中科（天津）新能源科技有限公司 | Lithium ion super capacitor and preparation method thereof |
| CN117334918A (en) * | 2023-12-01 | 2024-01-02 | 宁德时代新能源科技股份有限公司 | Pole piece, secondary battery and electricity utilization device |
| CN117334916A (en) * | 2023-12-01 | 2024-01-02 | 宁德时代新能源科技股份有限公司 | Negative electrode plate, preparation method thereof, battery and electric equipment |
| CN117543007A (en) * | 2024-01-09 | 2024-02-09 | 华北电力大学 | High-nickel ternary nickel-cobalt-aluminum positive electrode material and preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2018023321A1 (en) * | 2016-07-31 | 2018-02-08 | 肖丽芳 | Preparation method for positive electrode sheet containing lithium-ion conductive polymer coating |
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| CN117543007A (en) * | 2024-01-09 | 2024-02-09 | 华北电力大学 | High-nickel ternary nickel-cobalt-aluminum positive electrode material and preparation method and application thereof |
| CN117543007B (en) * | 2024-01-09 | 2024-03-29 | 华北电力大学 | High-nickel ternary nickel-cobalt-aluminum positive electrode material and preparation method and application thereof |
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Application publication date: 20161109 |