CN107492664A - Electrodes of lithium-ion batteries coating with heat sinking function - Google Patents

Electrodes of lithium-ion batteries coating with heat sinking function Download PDF

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Publication number
CN107492664A
CN107492664A CN201710572700.1A CN201710572700A CN107492664A CN 107492664 A CN107492664 A CN 107492664A CN 201710572700 A CN201710572700 A CN 201710572700A CN 107492664 A CN107492664 A CN 107492664A
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China
Prior art keywords
coating
graphene
dopamine
solvent
solution
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Pending
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CN201710572700.1A
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Chinese (zh)
Inventor
王丹
赵中令
陈慧明
韩建
张斌
张克金
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FAW Group Corp
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FAW Group Corp
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Priority to CN201710572700.1A priority Critical patent/CN107492664A/en
Publication of CN107492664A publication Critical patent/CN107492664A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/61—Types of temperature control
    • H01M10/613—Cooling or keeping cold
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/65—Means for temperature control structurally associated with the cells
    • H01M10/654—Means for temperature control structurally associated with the cells located inside the innermost case of the cells, e.g. mandrels, electrodes or electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/668—Composites of electroconductive material and synthetic resins
    • 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
    • H01G11/66—Current collectors
    • H01G11/68—Current collectors characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0223—Composites
    • H01M8/0228—Composites in the form of layered or coated products
    • 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
    • Y02E60/10—Energy storage using batteries
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The present invention relates to a kind of electrodes of lithium-ion batteries coating with heat sinking function, it is characterised in that the specific implementation step of coating 1 is as follows：1）DOPA amine monomers are dissolved in certain solvent, it is 50 ~ 100mmol L to be configured to dopamine concentration‑1Alkaline solution；2）By graphene uniform scattered in a solvent 3）By step（1）And step（2）The solution mixing of preparation, battery afflux liquid or pole piece is placed in mixed solution, static placement 48h ~ 72h.After cleaning, dried under 80 DEG C ~ 120 DEG C temperature conditionss, the composite coating of gained poly-dopamine and graphene；It is directed under the conditions of high current charge-discharge, the problem of big calorimetric can not scatter and disappear quickly caused by inside battery, utilize the good thermal conduction characteristic of poly-dopamine and graphene, it is graphene coated with the composite coating of poly-dopamine in collection liquid surface, further improve the bond strength of collector and active material, meanwhile have the function that to reduce internal temperature of battery.

Description

Electrodes of lithium-ion batteries coating with heat sinking function
Technical field
The present invention relates to a kind of electrodes of lithium-ion batteries coating with heat sinking function, and there is raising lug, collector to dissipate Hot function, it is mainly used in the new energy energy-storage units such as lithium ion battery, metal-air battery, ultracapacitor field；Belong to Field of new energy technologies.
Background technology
Motor, battery, it is automatically controlled be new-energy automobile development three big core components.Wherein, battery is even more to restrict new energy The core important document of development of automobile.At present, people's pursuit is more energy density, the life-span of battery, to the demand of electric automobile It is more course continuation mileage and low temperature use demand.But current battery is also there is certain safety problem, such as burning or even The problem of blast.Wherein, heat dispersion of the battery in the case of high magnification, and the technical problem of urgent need to resolve how are ensured.
Patent CN103337676B, patent CN103474712B are using cooling water filter unit from flow cooling device, close Water shutoff cold drawing reduces the heat of battery.Patent CN101640286B uses a kind of new-type lug, by increasing current lead-through face Product reduces the purpose of cell heat under the conditions of high-multiplying power discharge to reach.Patent CN102593503B sets up gold by inside battery Category conduit is designed to reduce the purpose of the heat of inside battery.Usually, be all by outside batteries apply water cooling plant and Reach the purpose of radiating by changing the structure design of battery.
Here, we reach reduction battery by way of applying coating by changing the thinking of inside battery design The purpose of heat.A kind of present practical technology is one layer of activity of painting on the copper foil of affluxion body or aluminium foil of lithium ion battery Charcoal material, the bond strength of collector and active material is improved, but in cell fabrication processes, the de- of utter misery material usually occur Fall problem.This patent, by physical-chemical reaction process, it is more with gathering to make graphene from this thinking in collection liquid surface The composite coating of bar amine, the bond strength of collector and active material is further improved, meanwhile, reach reduction internal temperature of battery Effect.
Poly-dopamine is the main active of the stickum of shell biology exocuticle secretion, according to document [Haeshin Lee etc. , NATURE. 2007, 448(19) : 338-342; Haeshin Lee etc. , SCIENCE, 2007, 318:426-430J] to report, dopamine can significantly be modified the surface characteristic of object, and viscous between dopamine modified layer and matrix Knot power is extremely strong, and in recent years, its application in field of surface modification is a lot of [CN 101864670B, CN102061479A], but It is that forming composite coating with graphene is used to improve battery afflux liquid performance, in terms of further improving inside battery heat dispersion Application have not been reported.
On the patent of graphene and poly-dopamine class have focused largely on it is several in terms of.1. changed by poly-dopamine The characteristic of kind graphene, or the method for preparing graphite alkenes material.As CN105153381A disclose it is a kind of poly- more by introducing The method of bar amine substance modification graphene, by it is covalent modified and it is non-covalent it is modified combine, before ensureing that graphene-structured is complete Put the structural stability for improving modified product.CN104229781A and CN104229781B discloses one kind and prepares high itrogen content of getter with nitrogen doped The method of nitrogen-doped graphene.2. for the research of dopamine context of detection, such as a kind of detection dopamines of CN104267085A Modified electrode and its preparation method and application, CN103604849A and CN103604849B be a kind of to detect dopamine, anti-bad simultaneously The electrochemical sensor of hematic acid and uric acid.3. by the active group of dopamine, the grafting of graphene and other materials is realized.Such as A kind of methods of surface of graphene oxide graft modification aramid fiber of CN104047160B, CN104927302A one kind is by graphite Epoxy resin composite material of alkene toughness reinforcing and preparation method thereof, a kind of nanometer composite proton exchange membranes of CN103715438A and its Preparation method and application.
The content of the invention
It is an object of the invention to provide a kind of electrodes of lithium-ion batteries coating with heat sinking function, and it is directed in big electricity It is the problem of big calorimetric can not scatter and disappear quickly caused by inside battery, good using poly-dopamine and graphene under the conditions of flowing discharge and recharge Good thermal conduction characteristic, it is graphene coated with the composite coating of poly-dopamine in collection liquid surface, further improve collector and work Property material bond strength, meanwhile, have the function that reduce internal temperature of battery.
The technical scheme is that be achieved in that：A kind of electrodes of lithium-ion batteries coating with heat sinking function, lithium from Sub- battery pole piece surface includes coating 1 and coating 2, and poly-dopamine and grapheme material are included in coating 1, stone is included in coating 2 Black alkene material；It is characterized in that the specific implementation step of coating 1 is as follows：1）DOPA amine monomers are dissolved in certain solvent, matched somebody with somebody It is 50 ~ 100mmol L that dopamine concentration, which is made,-1Alkaline solution, solution pH value is between 7.5 ~ 11；
2）Graphene uniform is scattered in a solvent, wherein described solvent includes NMP, CMC, PVDF, DMF one or more； Shared volumn concentration ratio is 0.1% ~ 10% to graphene in a solvent；
3）By step（1）And step（2）The solution mixing of preparation, battery afflux liquid or pole piece are placed in mixed solution, quiet Only place 48h ~ 72h.After cleaning, dried under 80 DEG C ~ 120 DEG C temperature conditionss, the composite coating of gained poly-dopamine and graphene； Above-mentioned steps（1）And step（2）The preparation of solution, also can step completion.
The implementation steps of coating 2：
1）Charcoal containing graphene is dispersed in a solvent, wherein containing component 1 and component 2 in described solvent, in component 1 Included comprising the one or several kinds in NMP, DMF, ethanol, water, isopropanol, in component 2 one kind in CMC, PVDF, PTFE or Person is several；
2）By on the collector of the material even application of above-mentioned steps to coating 1, one side or two-sided, add under certain temperature Heat abstraction component 1.
Above-mentioned coating implementation steps, which are taken, to be implemented step by step, first upper coating 1, then upper coating 2；Coating 1 and coating 2 may act on The one side or both sides of pole piece.Especially, coating 1 acts on pole piece and lug, and coating 2 is acted on coating 1, the area of coating 2 Less than or equal to the area of coating 1.
The positive effect of the present invention：The graphene and the composite coating of poly-dopamine act on battery afflux liquid, on the one hand, Be advantageous to improve and solve the problems, such as that cell active materials come off from collector；On the other hand, the composite coating is advantageous to change Kind battery is under the conditions of high current charge-discharge, and internal temperature of battery is higher, and inside battery heat does not allow the problem of easy to lose, effectively Reduce by 3 DEG C ~ 10 DEG C of battery surface temperature.
Brief description of the drawings：
The coating structure figure of Fig. 1 embodiments 1.
Pole piece front view in Fig. 2 embodiments 1.
The coating structure figure of Fig. 3 embodiments 2.
Pole piece front view in Fig. 4 embodiments 2.
The coating structure figure of Fig. 5 embodiments 3.
Pole piece front view in Fig. 6 embodiments 3.
Embodiment
Embodiments of the present invention are described below in conjunction with the accompanying drawings, described embodiment is the right to the present invention It is required that specific descriptions, claim includes but is not limited to described embodiment content.
Embodiment 1
50g DOPA amine monomers are dissolved in HCl solvents, it is 50mmol L to be configured to dopamine concentration-1Alkaline solution, solution PH values are 7.5；50g graphene uniforms are dispersed in NMP and CMC in the mixed solvent, wherein NMP and CMC volume ratio are 100:1, shared percent by volume is 0.1% to graphene in a solvent；By above two solution 1:1 mixing, by lithium ion battery Copper foil of affluxion body and aluminium foil be respectively placed in mixed solution, static placement 48h.After cleaning, under 120 DEG C of temperature conditionss, drying The composite coating of poly-dopamine and graphene is obtained at 1h, collector and lug.Then graphene, native graphite and hard charcoal will be contained Component（Wherein the mass percent of graphene, native graphite and hard charcoal is 0.5：83：16.5）It is dispersed in a solvent, on The percent by volume for stating each material in solvent is NMP：DMF：Isopropanol：PVDF=95:2:3:0.05, if using PTFE conducts Component 2, percent by volume 0.1%.By on the finely dispersed substance spray of above-mentioned mixing to collector, dual coating, 120 DEG C Heating removes volatile substances.Pole piece coating structure schematic diagram is as shown in Figure 1 and Figure 2.
Embodiment 2
50g DOPA amine monomers are dissolved in HCl solvents, it is 100mmol L to be configured to dopamine concentration-1Alkaline solution, solution PH values are 11；70g graphene uniforms are dispersed in the in the mixed solvent containing NMP, PVDF and DMF, wherein NMP, DMF and PVDF volume ratio is 70: 30:2, shared percent by volume is 10% to graphene in a solvent；By above two solution 1:2 Mixing, the copper foil of affluxion body of lithium ion battery and aluminium foil is respectively placed in mixed solution, static placement 72h.After cleaning, 80 DEG C Under temperature conditionss, vacuum drying 1h, the composite coating of gained poly-dopamine and graphene.It is visually visible, on copper foil and aluminium foil One layer of black composite coating of even deposition.Then the component containing graphene, native graphite, Delanium and soft charcoal（Wherein graphite Alkene, native graphite, the mass percent of Delanium and soft charcoal are 1.5：55：38.5：5）It is dispersed in a solvent, it is above-mentioned molten The mass percent of each material is water in agent：CMC=99.5:0.5, wherein dodecyl sodium sulfate weight/mass percentage composition is 0.005%, solution temperature is 80 DEG C, and by the finely dispersed substance spray of above-mentioned mixing to lug and part collector, one side applies Cover, 100 DEG C of heating remove volatile substances.Pole piece coating structure schematic diagram is as shown in Figure 3, Figure 4.
Embodiment 3
50g DOPA amine monomers are dissolved in HCl solvents, it is 70mmol L to be configured to dopamine concentration-1Alkaline solution, solution PH values are 10, and the CMC of 1% mass percent is then added in above-mentioned solvent, form homogeneous solution.Will under ul-trasonic irradiation The graphene dispersion that percent by volume is 1.5% is into above-mentioned solution.Electrodes of lithium-ion batteries is immersed in mixed solution, it is quiet Put 60h.After cleaning, vacuum drying 2h under the conditions of 100 DEG C, naked eyes are visible, and one layer of light/dark balance coating is deposited on collector, and quality is equal It is even.By preparation prepares coating 2 the step of embodiment 2.Except that coating 2 takes locally sprayed side on coating 1 Formula, two-sided coatings, to reduce the dosage of graphene, schematic diagram is as shown in Figure 5, Figure 6.

Claims (1)

1. a kind of electrodes of lithium-ion batteries coating with heat sinking function, electrodes of lithium-ion batteries surface includes coating 1 and coating 2, poly-dopamine and grapheme material are included in coating 1, and grapheme material is included in coating 2；It is characterized in that coating 1 is specific Implementation steps are as follows：1）DOPA amine monomers are dissolved in certain solvent, it is 50 ~ 100mmol L to be configured to dopamine concentration-1 Alkaline solution, solution pH value is between 7.5 ~ 11；
2）Graphene uniform is scattered in a solvent, wherein described solvent includes NMP, CMC, PVDF, DMF one or more； Shared volumn concentration ratio is 0.1% ~ 10% to graphene in a solvent；
3）By step（1）And step（2）The solution mixing of preparation, battery afflux liquid or pole piece are placed in mixed solution, quiet Only place 48h ~ 72h；After cleaning, dried under 80 DEG C ~ 120 DEG C temperature conditionss, the composite coating of gained poly-dopamine and graphene； Above-mentioned steps（1）And step（2）The preparation of solution, also can step completion；The implementation steps of coating 2：
1）Charcoal containing graphene is dispersed in a solvent, wherein containing component 1 and component 2 in described solvent, in component 1 Included comprising the one or several kinds in NMP, DMF, ethanol, water, isopropanol, in component 2 one kind in CMC, PVDF, PTFE or Person is several；
2）By on the collector of the material even application of above-mentioned steps to coating 1, one side or two-sided, add under certain temperature Heat abstraction component 1；Above-mentioned coating implementation steps, which are taken, to be implemented step by step, first upper coating 1, then upper coating 2；Coating 1 and coating 2 can be made One side or both sides for pole piece；Especially, coating 1 acts on pole piece and lug, and coating 2 is acted on coating 1, coating 2 Area is less than or equal to the area of coating 1.
CN201710572700.1A 2017-07-14 2017-07-14 Electrodes of lithium-ion batteries coating with heat sinking function Pending CN107492664A (en)

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Cited By (4)

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CN108910863A (en) * 2018-06-26 2018-11-30 中科钢研节能科技有限公司 A kind of intelligence graphene heat conducting film and preparation method thereof
CN110676462A (en) * 2019-10-14 2020-01-10 福建巨电新能源股份有限公司 Carbon-coated aluminum foil for lithium battery and preparation method thereof
CN111224106A (en) * 2018-11-27 2020-06-02 上海其鸿新材料科技有限公司 Lithium ion battery current collector and preparation method thereof
CN111224057A (en) * 2018-11-23 2020-06-02 广州汽车集团股份有限公司 Current collector for silicon-based negative electrode, preparation method of current collector and silicon-based negative electrode piece

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Publication number Priority date Publication date Assignee Title
CN108910863A (en) * 2018-06-26 2018-11-30 中科钢研节能科技有限公司 A kind of intelligence graphene heat conducting film and preparation method thereof
CN108910863B (en) * 2018-06-26 2020-05-15 中科钢研节能科技有限公司 Graphene heat-conducting film and preparation method thereof
CN111224057A (en) * 2018-11-23 2020-06-02 广州汽车集团股份有限公司 Current collector for silicon-based negative electrode, preparation method of current collector and silicon-based negative electrode piece
CN111224106A (en) * 2018-11-27 2020-06-02 上海其鸿新材料科技有限公司 Lithium ion battery current collector and preparation method thereof
CN111224106B (en) * 2018-11-27 2021-05-11 上海其鸿新材料科技有限公司 Lithium ion battery current collector and preparation method thereof
CN110676462A (en) * 2019-10-14 2020-01-10 福建巨电新能源股份有限公司 Carbon-coated aluminum foil for lithium battery and preparation method thereof
CN110676462B (en) * 2019-10-14 2022-06-07 福建巨电新能源股份有限公司 Carbon-coated aluminum foil for lithium battery and preparation method thereof

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Application publication date: 20171219

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