CN108774459A - A kind of coating and preparation method thereof, battery electrode - Google Patents
A kind of coating and preparation method thereof, battery electrode Download PDFInfo
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- CN108774459A CN108774459A CN201810567412.1A CN201810567412A CN108774459A CN 108774459 A CN108774459 A CN 108774459A CN 201810567412 A CN201810567412 A CN 201810567412A CN 108774459 A CN108774459 A CN 108774459A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/02—Polyamines
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D123/04—Homopolymers or copolymers of ethene
- C09D123/06—Polyethene
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09D127/16—Homopolymers or copolymers of vinylidene fluoride
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
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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
- 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
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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
- 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
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/60—Heating or cooling; Temperature control
- H01M10/65—Means for temperature control structurally associated with the cells
- H01M10/653—Means for temperature control structurally associated with the cells characterised by electrically insulating or thermally conductive materials
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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
- 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
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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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
- Y02E60/10—Energy storage using batteries
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Abstract
The present invention relates to a kind of coatings comprising：The quality of graphene and polymer, graphene accounts for the 20-70% of coating quality, and the quality of polymer accounts for the 30-80% of coating quality；Include conducting polymer and non-conductive polymer in polymer, the mass ratio of conducting polymer and non-conductive polymer is 1~3:1, wherein the non-conductive polymer can be dissolved each other with the conducting polymer with arbitrary ratio.The invention also includes the preparation method of coating and battery electrodes.For electrode under normal working temperature, coating increases the binding force between electrode active material and plus plate current-collecting body by the cohesive force of polymer, reduces internal resistance, and enhance the electric conductivity of electrode active material by graphene.When electrode temperature is excessively high, conducting polymer electric conductivity declines, impedance increases, non-conductive polymer occurs high-temperature expansion and aggravates impedance, cut-out electron channel makes battery be stopped, graphene plays the high efficiency and heat radiation ability that it has at this time, promotes heat dissipation, to improve battery charging and discharging performance and security performance.
Description
Technical field
The invention belongs to technical field of chemical power, more particularly, to a kind of coating applied to battery electrode, preparation side
Method and electrode comprising the coating.
Background technology
Support energetically and guiding with country to new-energy automobile, new-energy automobile is developed rapidly, to make
The demand for obtaining lithium-ion-power cell is increased sharply, and also to the performance of lithium ion battery, more stringent requirements are proposed.Therefore lithium is improved
Ion battery performance includes electrical property and security performance is the developing goal of industry.Electrode is by collector and to be coated in collector
On electrode active material composition, and it is the knot increased between collector and electrode active material one of to put forward high performance approach
Resultant force and electric conductivity to reduce the contact internal resistance between electrode active material and collector (or interface internal resistance), and then improve
Lithium ion battery high rate during charging-discharging.Meanwhile lithium ion battery causes thermal runaway to cause in turn because radiating not in time
Safety problem is also especially prominent.
In the prior art in order to increase the binding force and electric conductivity between collector and electrode active material, select in collector
It is upper first to apply one layer of conducting polymer, then conducting polymer is covered into electrode active material.But conducting polymer only have it is conductive and
Increase the effect of binding force, do not have the additional functions such as heat dissipation, the thermal runaway problem to alleviating lithium battery does not improve.It is at present
The heat dissipation problem of lithium ion battery is solved, easy to use, applicability is wide, do not account for volume, improves radiating for battery energy density
Coating is a kind of relatively good selection.
For this purpose, research and development it is a kind of not only can high efficiency and heat radiation, can also effectively reduce between electrode active material and collector
Contact the coating of internal resistance and the electrode comprising the coating, it will help improve the overall performance of lithium ion battery.
Invention content
In order to solve the above problem of the prior art, the object of the present invention is to provide a kind of coating and include the coating
Electrode realizes the internal resistance reduced between electrode active material and collector by the coating and improves the double of electrode heat dissipation performance simultaneously
Recast is used, and to improve lithium ion battery high rate during charging-discharging, alleviates the thermal runaway of lithium battery, to improve cell safety
The effect of performance.The invention further relates to the preparation methods of the coating.
In order to achieve the above object, the main technical schemes that the present invention uses include：
A kind of coating comprising：
Graphene and polymer, the quality of the graphene account for the 20-70% of the coating quality, and polymer quality accounts for institute
State the 30-80% of coating quality；Include conducting polymer and non-conductive polymer in the polymer, conducting polymer is led with non-
The mass ratio of electric polymer is 1~3:1；The wherein described non-conductive polymer can be with the conducting polymer with arbitrarily than mutual
It is molten.
Preferably, the conducting polymer is polyaniline (PANI), polypyrrole (PPY), poly- 3,4-ethylene dioxythiophene
(PEDOT) one or more of mixture in.
Preferably, the non-conductive polymer is in PE (polyethylene), PP (polypropylene), PVDF (Kynoar)
One or more of mixtures.
Preferably, the thickness of the coating is 0.2-2 μm；Preferably 0.4 μm~0.6 μm.
The invention further relates to a kind of preparation method of coating, the method includes：
Graphene and mixed with polymers dispersion are stirred evenly to the slurry that a concentration of 0.05-0.2 g/mL are made in a solvent
The slurries are coated on material surface to be coated by liquid, drying, and coating is obtained in the material surface to be coated；The graphite
Alkene quality accounts for the 20-70% of coating quality, and polymer quality accounts for the 30-80% of coating quality；Include conduction in the polymer
The mass ratio of polymer and non-conductive polymer, conducting polymer and non-conductive polymer is 1~3:1；It is wherein described non-conductive
Polymer can be dissolved each other with the conducting polymer with arbitrary ratio.
Preferably, the slurries are to be sprayed on the material surface to be coated by magnetron sputtering method, and coating thickness is 0.5 μm
~4 μm.
Preferably, the coating layer thickness is 0.2-2 μm, preferably 0.4 μm~0.6 μm.
Preferably, the slurries are to be sprayed on electrode current collecting body surface by magnetron sputtering method, and the electrode current collecting body is
Plus plate current-collecting body or negative current collector.Wherein the electrode current collecting body is preferably plus plate current-collecting body, this is because improving leading for anode
It is significantly and more important than improving cathode electrically to the raising of entire battery energy density.
Preferably, the solvent be it is a kind of in absolute ethyl alcohol, n,N-Dimethylformamide, water and N-Methyl pyrrolidone or
It is several.
The present invention also provides a kind of battery electrodes, including electrode current collecting body and the electrode active being attached on the electrode current collecting body
Property substance, wherein including the painting described in any of the above embodiment between the electrode active material and the electrode current collecting body
Layer.
Preferably, the battery electrode is anode, and the electrode current collecting body is aluminium foil or aluminium flake.
The beneficial effects of the invention are as follows：
(1) coating of the invention by with high conductivity and thermal diffusivity graphene and polymer form, the coating application
On electrode current collecting body, for will closely be bonded between electrode active material and electrode current collecting body, increase electrode current collecting body with
Binding force between electrode active material reduces the contact internal resistance between electrode active material and collector.Wherein conducting polymer
Object and non-conductive polymer can be mixed mutually well to dissolve each other, and the two has close chemical property, film forming and bonding force, jointly
The effect for playing bonding and dispersed graphite alkene (graphene viscosity is very difficult direct slurrying greatly), makes the property of conductive layer tend to equal
One.
(2) coating includes graphene (single layer thermal coefficient 5300W/mK, electricity with high-cooling property and high conductivity
Conductance 106S·m-1), therefore the coating is gone back while playing the role of tight bond electrode active material and electrode current collecting body
The coating is set to have very high thermal diffusivity and electric conductivity, high-cooling property helps to alleviate the heat accumulation problem of electrode, improve
The safety of battery, high conductivity provide good electron channel between electrode current collecting body and electrode active material, reduce electrode
Interface resistance between active material and electrode current collecting body.
(3) coating includes graphene, conducting polymer and non-conductive polymer simultaneously, and wherein graphene and conduction is poly-
Closing object all has high conductivity, therefore electrode, under normal working temperature, both graphene and conducting polymer can be jointly
Increase the conductivity between electrode current collecting body and electrode active material, reduces internal resistance；When electrode temperature is high, conducting polymer due to
Chanza, electric conductivity is gone to decline, impedance increases, and graphene mainly plays its high cooling effect in the coating at this time.In this hair
In bright, which substantially constitutes a kind of ptc material with graphene, which is about 110-200
DEG C, preferably 110-150 DEG C.Therefore, when the temperature of electrode is excessively high reaches transition temperature, the non-conductive polymer is at high temperature
High-temperature expansion effect occurs, makes the conductive components such as graphene and conducting polymer by excess dilution, leads to the internal resistance of electrode drastically
Increase, cuts off electron channel, so that battery is stopped, graphene plays its high heat dispersion at this time, to ensure the safety of battery.
Therefore, non-conductive polymer has the function of " discharge cock " of similar battery in the coating.
(4) due to containing non-conductive polymer in the coating, and the conductivity of non-conductive polymer is relatively low, and the present invention passes through
Its additive amount is controlled, and under conducting polymer and graphene existence condition, (is especially using the graphene and conducting polymer
Graphene) ultra-high conductivity that has, weaken the problem of coating resistance caused by due to the incorporation of non-conductive polymer increases,
Make final coating obtained that can still play good electric conductivity, to ensure the high rate during charging-discharging of lithium ion battery.
(5) present invention between electrode active material and electrode current collecting body by magnetron sputtering method on electrode current collecting body surface
The coating is formed, makes that there is very strong binding force between the coating and electrode current collecting body surface and coating is very fine and close and uniform,
Then on the coating layer by the coating of the slurry of electrode active material, relative to directly by electrode active material coated on aluminium flake or copper
For the electrode current collecting bodies such as piece, between coating and electrode active material because property close to thus associativity is more preferable, thus increase indirectly
Being firmly combined with property of the electrode active material on electrode current collecting body.
Description of the drawings
Fig. 1 is a kind of electrode structure schematic diagram comprising coating of the present invention.
Fig. 2 is that the resistivity of 1 floating coat of the embodiment of the present invention varies with temperature trend curve figure.
Specific implementation mode
In order to preferably explain the present invention, in order to understand, below in conjunction with the accompanying drawings, by specific implementation mode, to this hair
It is bright to be described in detail.
Technical scheme of the present invention includes mainly a kind of coating, including graphene and polymer, the wherein quality of graphene
The 20-70% of the coating quality is accounted for, polymer quality accounts for the 30-80% of the coating quality；Include to lead in the polymer
The mass ratio of electric polymer and non-conductive polymer, conducting polymer and non-conductive polymer is 1~3:1；It is wherein described non-to lead
Electric polymer can be dissolved each other with the conducting polymer with arbitrary ratio.
Preferably, the conducting polymer is polyaniline (PANI), polypyrrole (PPY), poly- 3,4-ethylene dioxythiophene
(PEDOT) one or more of mixture in.Preferably, the non-conductive polymer be PE (polyethylene), PP (polypropylene),
The mixture of one or more of PVDF (Kynoar).Wherein, the incorporation of non-conductive polymer cannot be excessive, otherwise
The resistance of final coating can be caused larger, be unfavorable for reducing the interface resistance between electrode active material and electrode current collecting body.
The thickness of coating is too low, cannot play effect good enough, and coating is too thick, and can influence the energy density of battery.
Therefore, the thickness of the coating is 0.2-2 μm；Preferably 0.4 μm~0.6 μm, be more preferably 0.5 μm.
The invention also includes the preparation method of above-mentioned coating, the method includes：
S1:Graphene and mixed with polymers dispersion are stirred evenly be made a concentration of 0.05-0.2g/mL's in a solvent
Slurries.The solvent is one or more of in absolute ethyl alcohol, n,N-Dimethylformamide, water and N-Methyl pyrrolidone.
S2:The slurries are coated on to material surface to be coated, are then dried, are applied in the material surface to be coated
Layer.
When wherein preparing the slurries in step sl, it is ensured that graphene in coating after drying, non-is led at conducting polymer
The content of electric polymer.In general, graphene quality accounts for the 20-70% of coating quality, and polymer quality accounts for coating quality
30-80%；The mass ratio of conducting polymer and non-conductive polymer is 1~3 in polymer:1；The wherein described non-conductive polymer
It can be dissolved each other with arbitrary ratio with the conducting polymer.
In order to obtain, thickness is appropriate and uniform Painting effect, the present invention are preferentially prepared step S1 using magnetron sputtering method
Slurries be sprayed on the material surface to be coated, coating thickness is 0.5 μm~4 μm, after drying, because of the volatilization of solvent, applies thickness
Degree becomes 0.2-2 μm.
Magnetron sputtering method is to be filled with suitable argon gas in high vacuum, in cathode (Style Columu Talget or flat target) and anode (plated film
Locular wall) between apply hundreds of K DC voltages, magnet controlled abnormal glow discharge is generated in coating chamber, argon gas is made to ionize.Argon
Ion accelerates simultaneously bombarding cathode target surface by cathode, and target material surface atom sputtering is out deposited on the substrate surface of coating chamber
Form film.By the target of the replacement unlike material sputtering time different with control, unlike material and different thickness can be obtained
The film of degree.Magnetron sputtering method has that the binding force of film plating layer and base material is strong, film plating layer is fine and close, thickness controllable precise, uniformly etc.
Advantage.When spraying the slurries using magnetron sputtering method, which is placed in the substrate of coating chamber.
Since the coating of the present invention is mainly applied on electrode, it is set on electrode current collecting body, and electrode active material is then
It is attached on the coating.Therefore, the operation of step S2 is preferably：One electrode current collecting body is placed in the substrate of coating chamber,
Then slurries step S1 prepared inject the storage bin of magnetron sputtering method, start magnetic control sputtering device, when being sputtered by controlling
Between, the film that thickness is 0.5 μm~4 μm is formed on the electrode current collecting body surface, drying forms thickness on the electrode current collecting body surface
The coating that degree is 0.2-2 μm.The electrode current collecting body is plus plate current-collecting body or negative current collector, preferably plus plate current-collecting body, example
Such as aluminium flake or aluminium foil.
In conjunction with shown in Fig. 1, the present invention also provides a kind of battery electrode 10, including electrode current collecting body 11 and being attached to the electricity
Electrode active material 13 on pole collector 11, and coating 12 is equipped between electrode active material 13 and electrode current collecting body 11.
When preparing the battery electrode 10, first coating 12 is formed on the electrode current collecting body 11, then again by prepared electrode active
Property substance 13 slurry (include electrode active material, conductive agent and binder) be coated on the coating 12, then baking and curing
Complete the making of the battery electrode 10.Preferably, if the coating 12 is using graphene, conducting polymer and non-conductive poly-
It closes object PVDF (Kynoar) to be made, then the also selection PVDF of the binder in the slurry of the electrode active material 13, due to
The presence of same polymer contributes to the slurry for increasing electrode active material 13 and 12 bonding force of coating, is conducive to reduce boundary
Face internal resistance.
In order to illustrate more clearly of the present invention, illustrated below in conjunction with specific embodiment：
Embodiment 1
At room temperature, by polymer (polyaniline PANI and the poly- second of the graphene of quality accounting 70% and quality accounting 30%
Alkene PE mass ratioes 1:1) it is dispersed in N-Methyl pyrrolidone, after stirring, the slurries of a concentration of 0.1g/mL is made.
By the slurries by magnetron sputtering method even application in one piece of aluminum flake surface, 2 μm of coating thickness；The slurries of coating are dried；Again
Positive plate further is made after the slurry of surface coating electrode active material, drying.Again by made positive plate and negative plate,
Lithium ion battery is made in diaphragm, electrolyte and outer packing group.
Embodiment 2
At room temperature, by the graphene of quality accounting 30% and polymer (polypyrrole PPY and the polyethylene of quality accounting 70%
PE mass ratioes 1:1) it is dispersed in N-Methyl pyrrolidone, after stirring, the slurries of a concentration of 0.2g/mL is made.It will
The slurries are by magnetron sputtering method even application in one piece of aluminum flake surface, 0.5 μm of coating thickness；The slurries of coating are dried；Again
Positive plate further is made after the slurry of surface coating electrode active material, drying.Again by made positive plate and negative plate,
Lithium ion battery is made in diaphragm, electrolyte and outer packing group.
Embodiment 3
At room temperature, by the graphene of quality accounting 20% and polymer (polypyrrole PPY and the PVDF matter of quality accounting 80%
Measure ratio 6:4) it is dispersed in absolute ethyl alcohol, after stirring, the slurries of a concentration of 0.05g/mL is made.The slurries are passed through
Magnetron sputtering method even application is in one piece of aluminum flake surface, 4 μm of coating thickness；The slurries of coating are dried；Further on surface
Positive plate is made after drying in the slurry of coating electrode active material.Again by made positive plate and negative plate, diaphragm, electrolyte
And lithium ion battery is made in outer packing group.
Embodiment 4
At room temperature, by the graphene of quality accounting 50% and polymer (PEDOT and the PVDF mass of quality accounting 50%
Than 1:1) it is dispersed in absolute ethyl alcohol, after stirring, the slurries of a concentration of 0.1g/mL is made.The slurries are passed through into magnetic
Sputtering method even application is controlled in one piece of aluminum flake surface, 3 μm of coating thickness；The slurries of coating are dried；Further applied on surface
Slurry (Ningbo gold and acetylene black=95 new material S800 (NC82) lithium nickel cobalt dioxide+PVDF+ of cloth electrode active material:5:5) it, dries
Positive plate is made after dry.Lithium-ion electric is made in obtained positive plate and negative plate, diaphragm, electrolyte and outer packing group again
Pond.
Embodiment 5
At room temperature, by the graphene of quality accounting 50% and polymer (polypyrrole PPY and the PE mass of quality accounting 50%
Than 1:1) it is dispersed in absolute ethyl alcohol, after stirring, the slurries of a concentration of 0.1g/mL is made.The slurries are passed through into magnetic
Sputtering method even application is controlled in one piece of aluminum flake surface, 3 μm of coating thickness；The slurries of coating are dried；Further applied on surface
Slurry (Ningbo gold and acetylene black=95 new material S800 (NC82) lithium nickel cobalt dioxide+PVDF+ of cloth electrode active material:5:5) it, dries
Positive plate is made after dry.Lithium ion battery is made in made positive plate and negative plate, diaphragm, electrolyte and outer packing group again.
Comparative example 1
At room temperature, polypyrrole PPY is dispersed in absolute ethyl alcohol, after stirring, is made a concentration of 0.1g/mL's
Slurries.By the slurries even application in one piece of surface of aluminum plate, 3 μm of coating thickness, drying, for contrast experiment.
The heat dissipation of coating is tested
In surface of aluminum plate, the slurries prepared by embodiment 1-5 are respectively coated, dry.Then each aluminium sheet is added with alcolhol burner
Hot 20s places 3s after removing alcolhol burner, and with thermometer measure metallic surface temperature, the aluminium sheet of wherein comparative example 1, which is only coated with, leads
Electric polymer PPY surveys each surface of aluminum plate temperature, as a result as follows：
1 each embodiment and comparative example test result of table
Note：Aluminium sheet specification is identical, and only the coating on surface is different.
As seen from the above table, surface is only coated with the aluminium sheet of the comparative example 1 of conducting polymer PPY coatings, adds identical
Under hot radiating condition, surface temperature reaches 97 DEG C, is substantially higher out compared to the aluminium sheet for being coated with slurries prepared by embodiment 1-5
Very much.Thus illustrate, coating of the invention has good thermal diffusivity, when being used for electrode, can help to the hot polymerization for alleviating electrode
Collection problem improves the safety of battery.
The resistivity of coating is tested：
The slurry of the preparation of embodiment 1 is filled in the hollow plastic cylinder of (r=4mm, L=20cm) known to section and length
Liquid, drying, solidification.Then the measuring resistance under variation of ambient temperature.
As shown in Fig. 2, for the change curve of the resistivity at 25 DEG C~140 DEG C, resistance when between about 120~130 DEG C
There is jumping characteristic to increase, illustrates that non-conductive polymer is expanded in the temperature range in slurries prepared by embodiment 1, is caused
Its resistance value increased dramatically.To illustrate, when electrode temperature is excessively high (such as 120~130 DEG C), go to mix due to conducting polymer
The electric conductivity of miscellaneous effect, conducting polymer declines, and impedance increases, and the high-temperature expansion effect that non-conductive polymer occurs is further
Aggravate impedance, cut off electron channel, battery is made to be stopped, graphene plays its efficient heat dissipation performance at this time, helps electrode
Heat dissipation, to improve the security performance of battery high rate during charging-discharging and battery.
In above example 1~5, by applying one layer by graphene, conducting polymer on plus plate current-collecting body surface and non-leading
The coating of electric polymer composition, under the normal operating temperature of electrode, the coating is by conducting polymer and non-conductive polymer
Cohesive force, increase the binding force between electrode active material and plus plate current-collecting body, reduce contact internal resistance；Had by graphene
High conductivity, ensure the electric conductivity of the coating, good electron channel between electrode current collecting body and electrode active material be provided, increase
The electric conductivity of strong electrode active material and electrode current collecting body.When electrode temperature is excessively high, conducting polymer removes chanza, leads
The electric conductivity of electric polymer declines, and impedance increases, and the high-temperature expansion effect that non-conductive polymer occurs is further exacerbated by impedance,
Electron channel is cut off, battery is made to be stopped, graphene plays its efficient heat dissipation performance at this time, helps electrode heat dissipation, to
Improve the security performance of battery high rate during charging-discharging and battery.
Claims (10)
1. a kind of coating, which is characterized in that including：
Graphene and polymer, the quality of the graphene account for the 20-70% of the coating quality, and the quality of the polymer accounts for
The 30-80% of the coating quality；Include conducting polymer and non-conductive polymer, the conducting polymer in the polymer
Mass ratio with the non-conductive polymer is 1~3:1；The wherein described non-conductive polymer can with the conducting polymer with
Arbitrary ratio dissolves each other.
2. coating according to claim 1, which is characterized in that the conducting polymer is polyaniline, polypyrrole, poly- 3,4-
One or more of mixture in ethylenedioxy thiophene.
3. coating according to claim 2, which is characterized in that the non-conductive polymer is polyethylene, polypropylene, gathers partially
The mixture of one or more of vinyl fluoride.
4. coating according to claim 1, which is characterized in that the thickness of the coating is 0.2-2 μm.
5. a kind of preparation method of coating, which is characterized in that the method includes：
Graphene and mixed with polymers dispersion are stirred evenly to the slurries that a concentration of 0.05-0.2g/mL is made in a solvent, by institute
It states slurries and is coated on material surface to be coated, dry, coating is obtained in the material surface to be coated；
The quality of the graphene accounts for the 20-70% of coating quality, and the quality of the polymer accounts for the 30-80% of coating quality；
Include conducting polymer and non-conductive polymer in the polymer, the mass ratio of conducting polymer and non-conductive polymer is 1
~3:1；The wherein described non-conductive polymer can be dissolved each other with the conducting polymer with arbitrary ratio.
6. preparation method according to claim 5, which is characterized in that the slurries are to be sprayed on this by magnetron sputtering method
Material surface to be coated, coating thickness are 0.5 μm~4 μm.
7. preparation method according to claim 5, which is characterized in that the coating layer thickness is 0.2-2 μm.
8. preparation method according to claim 5, which is characterized in that the slurries are to be sprayed on electricity by magnetron sputtering method
Pole collection liquid surface, the electrode current collecting body are plus plate current-collecting body or negative current collector.
9. a kind of battery electrode, including electrode current collecting body and the electrode active material being attached on the electrode current collecting body, feature
It is, any coatings of claim 1-4 or right is equipped between the electrode active material and the electrode current collecting body
It is required that the coating prepared by any preparation methods of 5-8.
10. battery electrode according to claim 9, which is characterized in that the battery electrode is anode, the electrode current collecting
Body is aluminium foil or aluminium flake.
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| CN113462235A (en) * | 2021-09-06 | 2021-10-01 | 北京石墨烯技术研究院有限公司 | Coating for preventing thermal runaway of lithium ion battery and preparation method and application thereof |
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