CN109216654A - A kind of lithium ion battery of multilayer cathode pole piece and its preparation method and application - Google Patents
A kind of lithium ion battery of multilayer cathode pole piece and its preparation method and application Download PDFInfo
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- CN109216654A CN109216654A CN201811215679.0A CN201811215679A CN109216654A CN 109216654 A CN109216654 A CN 109216654A CN 201811215679 A CN201811215679 A CN 201811215679A CN 109216654 A CN109216654 A CN 109216654A
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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
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- 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
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
A kind of multilayer cathode pole piece disclosed by the invention, including metal foil collector, the surface of the metal foil collector are coated with conductive coating；The surface of the conductive coating is coated with main functionality layer；The surface of the main functionality layer is coated with graphite linings.In addition, the invention also discloses a kind of preparation method of multilayer cathode pole piece and its lithium ion batteries of preparation.A kind of lithium ion battery of multilayer cathode pole piece disclosed by the invention and its preparation method and application, the charge efficiency high and low temperature charging and discharging capabilities that the multilayer cathode pole piece has are strong, the high rate charge-discharge performance of lithium ion battery can be significantly improved, extend the high rate charge-discharge inferior pole piece service life, the market application prospect for being conducive to improve cell production companies product, is of great practical significance.
Description
Technical field
The present invention relates to battery technology fields, more particularly to a kind of multilayer cathode pole piece and its preparation method and application
Lithium ion battery.
Background technique
Currently, the negative electrode material in the lithium ion battery being commercialized, mainly graphite carbon material.Graphite is relatively
Lithium iron battery conductivity high for electrode active material, biggish insertion lithium capacity, high chemical stability is met well to want
It asks, while it also has intercalation potential low, abundance is cheap and easy to get, therefore nontoxic and pollution-free advantage eventually becomes
Preferred lithium ion battery negative material.
However, it has been found that some defects as existing for graphite material itself, meeting shadow during research and application
The performance for ringing lithium ion battery plays.First, graphite material and collector bad adhesion easily drop off；Second, the layer of graphite material
In conjunction with relying on Van der Waals force with interlayer, carbon material shows biggish volume change during removal lithium embedded, in circulating battery mistake
This in journey can make to generate larger stress between carbon material particles, cause cathode to lose powder, influence the cycle life of battery；Third, graphite
Interlamellar spacing d002 < 0.34nm of material, since the interlamellar spacing of graphite is small, lithium ion Li+ is smaller in the diffusion rate of graphite layers,
High rate during charging-discharging is lower, is unable to satisfy requirement of the electrical source of power for power characteristic；4th, based on graphite system
Lithium ion battery, the charging ability when low temperature environment uses is not good enough, due to carrying out big multiplying power charging, will lead to cathode and generates lithium
Dendrite generates the deep fades of serious security risk and battery performance.
Therefore, at present there is an urgent need to develop a kind of cathode pole piece out, the charge efficiency high and low temperature charging and discharging capabilities that have
By force, the high rate charge-discharge performance of lithium ion battery can be significantly improved, the high rate charge-discharge inferior pole piece service life is extended.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of lithium ions of multilayer cathode pole piece and its preparation method and application
Battery, the charge efficiency high and low temperature charging and discharging capabilities which has are strong, can significantly improve the big of lithium ion battery
Rate charge-discharge performance extends the high rate charge-discharge inferior pole piece service life, and the market for being conducive to improve cell production companies product is answered
With prospect, it is of great practical significance.
For this purpose, the present invention provides a kind of multilayer cathode pole piece, including metal foil collector, the metal foil collector
Surface is coated with conductive coating；
The surface of the conductive coating is coated with main functionality layer；
The surface of the main functionality layer is coated with graphite linings.
Wherein, it is 25%~75% conductive agent and 25%~75% bonding that the conductive coating, which includes mass percent,
Agent；
Wherein, the conductive agent includes conductive black Super P, electrically conductive graphite KS-6, carbon fiber VGCF and carbon nanotube
At least one of；
Described adhesive includes acrylonitrile multiple copolymer LA133, sodium carboxymethylcellulose, styrene-butadiene latex SBR and gathers inclined
Any one in vinyl fluoride PVDF.
Wherein, the main functionality layer includes the hard carbon, soft carbon that mass percent is 60%~99% or both mixing
Substance, 0%~25% conductive agent, 0%~5% sodium carboxymethylcellulose and 1%~10% adhesive；
Wherein, the conductive agent includes conductive black Super P, electrically conductive graphite KS-6, carbon fiber VGCF and carbon nanotube
At least one of；
Described adhesive includes acrylonitrile multiple copolymer LA133, styrene-butadiene latex SBR or Kynoar PVDF.
Wherein, the graphite linings include mass percent be 60%~99% artificial graphite or natural graphite, 0%~
30% conductive agent, 0%~5% sodium carboxymethylcellulose and 1%~5% adhesive；
Wherein, the conductive agent includes conductive black Super P, electrically conductive graphite KS-6, carbon fiber VGCF and carbon nanotube
At least one of；
Described adhesive includes acrylonitrile multiple copolymer LA133, styrene-butadiene latex SBR or Kynoar PVDF.
Wherein, the conductive coating with a thickness of 2~15 μm；
The surface density of the main functionality layer is 1~3.5 times of the surface density of graphite linings；
The single side surface density of the graphite linings is 15~30g/cm2。
Wherein, the conductive coating with a thickness of 3~9 μm；
The surface density of the main functionality layer is 2~3 times of the surface density of graphite linings；
The single side surface density of the graphite linings is 20~25g/m2。
In addition, the present invention also provides a kind of lithium ion batteries, including multilayer cathode pole piece as elucidated before.
In addition, the present invention also provides a kind of preparation methods of multilayer cathode pole piece, comprising the following steps:
The first step presses conductive black Super P, adhesive acrylonitrile multiple copolymer LA133, sodium carboxymethylcellulose
After the weight ratio mixing of 1:2.5:0.5, as conductive coating materials, be coated on metal foil collector it is two-sided on；
Second step, by default carbon material, conductive black Super P, adhesive acrylonitrile multiple copolymer LA133, carboxylic first
Base sodium cellulosate is mixed and made into slurry, and the mass ratio between each composition is 96:1:2.5:0.5, close according to the first default single side face
Degree is coated on a pole piece two sides, and secondary pole piece is made；
Third step, by artificial graphite, conductive black Super P, adhesive acrylonitrile multiple copolymer LA133, carboxymethyl
Sodium cellulosate is mixed according to the weight ratio of 96:1:2.5:0.5, as graphite layer material, according to the second default single side surface density
It is coated on the two sides of secondary pole piece, is then dried in vacuo 12 hours at 80 degrees Celsius, then rolled, cut multilayer cathode is made
Piece.
Wherein, in the first step, the conductive coating is with a thickness of 4~8 μm；
In second step, the first default single side surface density is 50~55g/m2Single side surface density；
In second step, the default carbon material includes the mixture of hard carbon material, soft carbon material or both；
When the default carbon material includes the mixture of hard carbon material and soft carbon material, the hard carbon material and soft carbon material
Weight ratio between material is 1:1；
In the third step, the second default single side surface density is 15~20g/m2Single side surface density.
Wherein, the metal foil collector is copper foil.
By the above technical solution provided by the invention as it can be seen that compared with prior art, the present invention provides a kind of multilayers
The lithium ion battery of cathode pole piece and its preparation method and application, the charge efficiency high and low temperature which has fill
Discharge capability is strong, can significantly improve the high rate charge-discharge performance of lithium ion battery, extends the high rate charge-discharge inferior pole piece service life,
The market application prospect for being conducive to improve cell production companies product, is of great practical significance.
Detailed description of the invention
Fig. 1 is with a kind of flow chart of the preparation method of multilayer cathode pole piece provided by the invention.
Specific embodiment
In order to enable those skilled in the art to better understand the solution of the present invention, with reference to the accompanying drawing with embodiment to this
Invention is described in further detail.
It the present invention provides a kind of multilayer cathode pole piece, is formed with conductive coating, soft or hard carbon, graphite trilaminate material
Lithium ion battery negative electrode, the multilayer cathode pole piece include metal foil collector (such as copper foil), the metal foil collector
Surface coating (including upper and lower surface full coat cloth) has conductive coating；
The surface coating (including upper and lower surface full coat cloth) of the conductive coating has main functionality layer；
The surface coating (including upper and lower surface full coat cloth) of the main functionality layer has graphite linings.
In the present invention, in specific implementation, the conductive coating includes the conductive agent that mass percent is 25%~75%
With 25%~75% adhesive；
Wherein, the conductive agent includes conductive black Super P (graphite-like), electrically conductive graphite KS-6 (carbon black class), carbon fiber
Tie up at least one of VGCF and carbon nanotube；
Described adhesive includes acrylonitrile multiple copolymer LA133, sodium carboxymethylcellulose, styrene-butadiene latex SBR and gathers inclined
Any one in vinyl fluoride PVDF.Therefore, as its caking property of conductive coating and good conductivity, the removing that pole piece can be improved is strong
Degree, avoids damage of the soft or hard carbon material to collector in the circulating cycle.
In the present invention, in specific implementation, the main functionality layer include mass percent be 60%~99% hard carbon,
Soft carbon or both compounding substances, 0%~25% conductive agent, 0%~5% sodium carboxymethylcellulose and 1%~10%
Adhesive；
Wherein, the conductive agent includes conductive black Super P (graphite-like), electrically conductive graphite KS-6 (carbon black class), carbon fiber
Tie up at least one of VGCF and carbon nanotube；
Described adhesive includes acrylonitrile multiple copolymer LA133, styrene-butadiene latex SBR or Kynoar PVDF.
It should be noted that high rate charge-discharge is its main function as main functionality layer.
In the present invention, in specific implementation, the graphite linings include the artificial graphite that mass percent is 60%~99%
Or natural graphite, 0%~30% conductive agent, 0%~5% sodium carboxymethylcellulose and 1%~5% adhesive；
Wherein, the conductive agent includes conductive black Super P (graphite-like), electrically conductive graphite KS-6 (carbon black class), carbon fiber
Tie up at least one of VGCF and carbon nanotube；
Described adhesive includes acrylonitrile multiple copolymer LA133, styrene-butadiene latex SBR or Kynoar PVDF.
It should be noted that forming SEI film (solid electrolyte interface film) in this layer for graphite linings.
In the present invention, in specific implementation, the conductive coating with a thickness of 2~15 μm, preferably 3~9 μm.
In the present invention, in specific implementation, the surface density of the main functionality layer is the 1~3.5 of the surface density of graphite linings
Times, preferably 2~3 times.
In the present invention, in specific implementation, the single side surface density of the graphite linings is 15~30g/cm2, preferably 20~
25g/m2。
In order to solve the above problem existing for lithium ion battery of the graphite material as cathode, the improvement that the present invention carries out
Are as follows: first is that coating one layer of conductive coating on a current collector can be improved the caking property of negative electrode material and conductive agent and collector, subtract
Few contact internal resistance of the negative electrode material with collector；Second is that lithium-ion electric of hard carbon or soft carbon or both the mixing as a new generation
Pond negative electrode material has some battery behaviors for being totally different from graphite material.
The pyrolytic carbon of high molecular polymer it should be noted that hard carbon refers to difficult graphited carbon, this kind of carbon have compared with
High specific capacity.Hard carbon cathode material due to its firm stable macromolecular deck structure, it is preferably under high current charge-discharge
Using and be concerned.The interlamellar spacing of hard carbon may be up to 0.36~0.38nm, and Li+ is very fast in diffusion velocity wherein, can make electricity
Pond quickly charge and discharge.Dohn describes relationship of the graphite layers away from d002 and specific capacity, shows the increase with d002, and discharge ratio
Capacity increases.Takami has studied Mesophase pitch base fiber interlamellar spacing at different temperatures and diffusion coefficient, it is believed that interlayer
Away from the degree of graphitization for depending on carbon, degree of graphitization increase can reduce the activation energy of Li+ diffusion, and be conducive to the diffusion of Li+.
Common hard carbon has resin carbon and carbon black etc..
And soft carbon material refer to material after heat treatment temperature reaches graphitization temperature, degree of graphitization with higher.
It common are coke, graphitized intermediate-phase carbon microballon (MCMB), carbon fiber etc..
The study found that soft carbon negative electrode material has a low and stable charge and discharge potential platform, charge/discharge capacity is greatly and efficiency
The advantages of height, good cycle.Since the charging and discharging curve of hard carbon soft carbon is slightly inclined curve, compare graphite system
Three platforms and relatively very flat discharge curve are more advantageous to the monitoring of the calculating to lithium battery SOC state.
But there is also some defects for hard carbon soft carbon material, comprising: 1, the first charge-discharge efficiency graphite body of two kind of material
It is low；2, the pole piece compaction density of hard carbon soft carbon material is lower, and the processing performance of production process is not so good as graphite system；3, hard carbon is soft
Carbon system is lower as the peel strength of pole piece after unique negative electrode active material, will appear in production process in collector removing
Situation.4, there is presently no very systematic research analyses for the membrane formation mechanism of hard carbon soft carbon.For these problems, the present invention also into
Corresponding processing is gone.
For this purpose, be the negative electrode of lithium ion battery of three-decker for multilayer cathode pole piece provided by the invention, pass through by
Main functionality layer is coated among conductive coating and graphite linings, can use the main functionality layer and conductive coating of hard carbon soft carbon composition
And triple features of graphite system, effectively make up graphite material cycle life, high current charge-discharge, low temperature charging and lithium from
Sub- battery SOC state calculates defect existing for monitoring etc. and soft or hard carbon and graphite and the easily peelable defect of collector bad adhesion.
Specific mechanism of the invention is as follows:
1, in conductive coating, with the higher conductivity of conductive coating materials and the adhesion strength high with collector, increase
Electric conductivity between negative electrode material and conductive agent and collector improves pole piece peel strength, can be effectively improved in cyclic process
Removing between negative electrode material and collector reduces contact internal resistance of the negative electrode material with collector, guarantees the cycle life of battery.
2, the primary active material selection hard carbon of main functionality layer or the mixed system of soft carbon or both, have secured
Stable macromolecular deck structure, battery preferably use under high current charge-discharge, and the interlamellar spacing of the two may be up to 0.36~
0.38nm, Li+ are very fast in diffusion velocity wherein, can make battery quickly charge and discharge, are especially apparent and promote battery under low temperature
Reacting for embedding lithium carbon and electrolyte is effectively reduced in charging performance, and stability is high in the electrolytic solution for hard carbon soft carbon material itself,
Improve cycle performance and the safety of battery.
3, graphite linings mainly with pass through interfacial reaction on electrolyte interface and can generate and stablize close SEI film, be conducive to protect
It demonstrate,proves the cycle performance of battery and improves the efficiency for charge-discharge of cathode system.
Based on the multilayer cathode pole piece that aforementioned present invention provides, the present invention also provides a kind of lithium ion batteries comprising
The all technical features of mentioned-above multilayer cathode pole piece.
In the present invention, the battery of various shapes that the lithium ion battery can be well known to those skilled in the art,
It such as can be the battery of the shapes such as round, rectangular.
In addition, shown in Figure 1, the present invention also provides a kind of multilayer cathode pole piece preparation method, for producing
State multilayer cathode pole piece provided by the invention, this method specifically includes the following steps:
The first step, by conductive black Super P (graphite-like), adhesive, (acrylonitrile multiple copolymer LA133, be can be
The happy production in Chengdu mattress ground), sodium carboxymethylcellulose (producer: Tao Shi, molecular weight 30000) is according to the weight ratio of 1:2.5:0.5
After mixing, as conductive coating materials, be coated on metal foil collector (copper foil) it is two-sided on；
Second step, by default carbon material (mixture including hard carbon material, soft carbon material or both), conductive black
Super P (graphite-like), adhesive (acrylonitrile multiple copolymer LA133), sodium carboxymethylcellulose (producer: Tao Shi, molecular weight
30000) it is mixed and made into slurry, the mass ratio between each composition is 96:1:2.5:0.5, is applied according to the first default single side surface density
It is distributed in a pole piece two sides, secondary pole piece is made；
Third step, by artificial graphite, conductive black Super P (graphite-like), adhesive (acrylonitrile multiple copolymer
LA133), sodium carboxymethylcellulose (producer: Tao Shi, molecular weight 30000) is mixed according to the weight ratio of 96:1:2.5:0.5, is made
For graphite layer material, the two sides of secondary pole piece is coated on according to the second default single side surface density, it is then dry in 80 degrees Celsius of vacuum
It dry 12 hours, then rolls, cut multilayer negative electrode tab is made.Finally prepare multilayer negative electrode tab of the invention, the negative electrode tab
For conductive coating/hard carbon soft carbon/graphite-structure.
In the first step, in specific implementation, the conductive coating is with a thickness of 4~8 μm.
In second step, in specific implementation, the first default single side surface density can be 50~55g/m2Single side surface density.
In second step, in specific implementation, when the default carbon material includes the mixture of hard carbon material and soft carbon material,
Weight ratio between the hard carbon material and soft carbon material is 1:1.
In the third step, in specific implementation, the second default single side surface density can be 15~20g/m2Single side surface density.
Below with reference to comparative example and the embodiment of the present invention, a specific embodiment of the invention and implementation result are made into one
Walk explanation.
Comparative example 1.
Traditional lithium-ion battery carbon material negative pole.Its making step is by artificial graphite, Super P (graphite-like), bonding
Agent (acrylonitrile multiple copolymer LA133, with can be Chengdu mattress happy production), sodium carboxymethylcellulose (producer: Tao Shi, molecule
30000) amount is mixed according to the weight ratio of 96:1:2.5:0.5 after, in deionized water, cathode slurry is made in uniform stirring for dispersion
Material, then according to single side 75g/m2Surface density be coated on metal foil collector it is two-sided on, 80 degrees Celsius be dried in vacuo 12 hours,
Then it rolls, cut negative electrode tab is made.The negative electrode tab finally prepared is artificial graphene structure.
Comparative example 2.
By soft carbon material, Super P (graphite-like), adhesive, (acrylonitrile multiple copolymer LA133, can be Chengdu mattress
The happy production in ground), sodium carboxymethylcellulose (producer: Tao Shi, molecular weight 30000) mixes according to the weight ratio of 96:1:2.5:0.5
Afterwards, in deionized water, negative electrode slurry is made in uniform stirring, then according to single side 75g/m for dispersion2Surface density be coated on metal
On foil collector is two-sided, 80 degrees Celsius are dried in vacuo 12 hours, are then rolled, are cut negative electrode tab is made.The cathode finally prepared
Piece is soft carbon material monolayer structures.
Comparative example 3.
By hard carbon material, Super P (graphite-like), adhesive (Chengdu LA133 mattress happy), sodium carboxymethylcellulose (factory
Family: Tao Shi, molecular weight 30000) according to 96:1:2.5:0.5 weight ratio mixing after, dispersion in deionized water, uniformly stir
Mixing is at negative electrode slurry, then according to single side 75g/m2Surface density be coated on metal foil collector it is two-sided on, 80 degrees Celsius are true
It sky dry 12 hours, then rolls, cut negative electrode tab is made.The negative electrode tab finally prepared is hard carbon material single layer structure.
Comparative example 4.
By artificial graphite, Super P (graphite-like), adhesive, (acrylonitrile multiple copolymer LA133, can be Chengdu mattress
The happy production in ground), sodium carboxymethylcellulose (producer: Tao Shi, molecular weight 30000) mixes according to the weight ratio of 96:1:2.5:0.5
Afterwards, in deionized water, negative electrode slurry is made in uniform stirring, as first layer graphite layer material, according to single side 20g/m for dispersion2
Surface density be coated on metal foil collector it is two-sided on, drying, a pole piece is made；By hard carbon material, Super P (graphite-like)
The SBR emulsion mixing of KS-6 (carbon black class), sodium carboxymethylcellulose (producer: Tao Shi, molecular weight 30000), mass content 40%
Slurry is made, each composition mass ratio is 96:1:2.5:0.5, according to single side 55g/m2Surface density be coated on a pole piece two sides,
80 degrees Celsius are dried in vacuo 12 hours, then roll, cut negative electrode tab is made.The negative electrode tab finally prepared is that graphite/hard carbon is double
Layer structure.
Comparative example 5.
By artificial graphite, Super P (graphite-like), adhesive, (acrylonitrile multiple copolymer LA133, can be Chengdu mattress
The happy production in ground), sodium carboxymethylcellulose (producer: Tao Shi, molecular weight 30000) mixes according to the weight ratio of 96:1:2.5:0.5
Afterwards, in deionized water, negative electrode slurry is made in uniform stirring, as first layer graphite layer material, according to single side 20g/m for dispersion2
Surface density be coated on metal foil collector it is two-sided on, drying, a pole piece is made；By soft carbon material, Super P (graphite-like)
The SBR emulsion mixing of KS-6 (carbon black class), sodium carboxymethylcellulose (producer: Tao Shi, molecular weight 30000), mass content 40%
Slurry is made, each composition mass ratio is 96:1:2.5:0.5, according to single side 55g/m2Surface density be coated on a pole piece two sides,
80 degrees Celsius are dried in vacuo 12 hours, then roll, cut negative electrode tab is made.The negative electrode tab finally prepared is that graphite/soft carbon is double
Layer structure.
Comparative example 6.
By artificial graphite, Super P (graphite-like), adhesive (acrylonitrile multiple copolymer LA133, life of finding pleasure in Chengdu mattress
Produce), sodium carboxymethylcellulose (producer: Tao Shi molecular weight 30000) according to 96:1:2.5:0.5 weight ratio mixing after, as
First layer graphite layer material, according to single side 15g/m2Surface density be coated on metal foil collector it is two-sided on, drying is made primary
Pole piece；By hard carbon material, soft carbon material, Super P (graphite-like), adhesive (LA133), sodium carboxymethylcellulose (producer: pottery
Family name, molecular weight 30000) it is mixed and made into slurry, each composition mass ratio is 48.0:48.0:1:2.5:0.5, according to single side 45g/m2
Surface density be coated on a pole piece two sides, secondary pole piece is made；By artificial graphite, Super P (graphite-like), adhesive (third
Alkene nitrile multiple copolymer LA133), sodium carboxymethylcellulose (producer: pottery, molecular weight 30000) is according to the weight of 96:1:2.5:0.5
Amount ratio mixing, as second layer graphite layer material, according to single side 15g/m2Surface density be coated on secondary pole piece two sides, 80 take the photograph
Family name's degree is dried in vacuo 12 hours, is then rolled, is cut negative electrode tab is made.The negative electrode tab finally prepared is graphite/hard carbon soft carbon/stone
Ink structure.
Comparative example 7.
By hard carbon material, soft carbon material, Super P (graphite-like), adhesive, (acrylonitrile multiple copolymer LA133, can be with
The happy production in Chengdu mattress ground), sodium carboxymethylcellulose (producer: Tao Shi, molecular weight 30000) be mixed and made into slurry, each composition matter
Amount is than being 48.0:48.0:1:2.5:0.5, according to single side 60g/m2Surface density coating, drying a pole piece is made；It will be artificial
Graphite, Super P (graphite-like), adhesive (LA133), sodium carboxymethylcellulose (producer: Tao Shi molecular weight 30000) according to
The weight ratio of 96:1:2.5:0.5 mixes, as graphite layer material, according to single side 15g/m2Surface density be coated on secondary pole
Piece two sides, 80 degrees Celsius are dried in vacuo 12 hours, then roll, cut negative electrode tab is made.The negative electrode tab finally prepared is hard soft
Carbon graphite double-layer structure.
Embodiment 1.
Firstly, by Super P (graphite-like), adhesive (acrylonitrile multiple copolymer LA133, it is with can be Chengdu mattress happy
Production), sodium carboxymethylcellulose (producer: Tao Shi, molecular weight 30000) according to 1:2.5:0.5 weight ratio mixing after, as
Conductive coating materials, be coated on metal foil collector it is two-sided on, conductive coating is with a thickness of 4 μm；
Then, by hard carbon material, soft carbon material, Super P (graphite-like), adhesive (acrylonitrile multiple copolymer
LA133), sodium carboxymethylcellulose (producer: Tao Shi, molecular weight 30000) is mixed and made into slurry, and each composition mass ratio is 48.0:
48.0:1:2.5:0.5 according to single side 50g/m2Surface density be coated on a pole piece two sides, secondary pole piece is made；
Then, by artificial graphite, Super P (graphite-like), adhesive (acrylonitrile multiple copolymer LA133), carboxymethyl
Sodium cellulosate (producer: Tao Shi, molecular weight 30000) is mixed according to the weight ratio of 96:1:2.5:0.5, as graphite layer material,
According to single side 20g/m2Surface density be coated on secondary pole piece two sides, then 80 degrees Celsius be dried in vacuo 12 hours, then grind
It presses, cut negative electrode tab is made.The negative electrode tab finally prepared is conductive coating/hard carbon soft carbon/graphite-structure.
Embodiment 2.
Firstly, by Super P (graphite-like), adhesive (LA133, with can be Chengdu mattress happy production), carboxymethyl cellulose
After plain sodium (producer: Tao Shi, molecular weight 30000) is according to the weight ratio mixing of 1:2.5:0.5, as conductive coating materials, apply
Be overlying on metal foil collector it is two-sided on, conductive coating is with a thickness of 6 μm；
Then, hard carbon material, soft carbon material, Super P (graphite-like), adhesive (Chengdu LA133 mattress happy), carboxymethyl
Sodium cellulosate (producer: Tao Shi, molecular weight 30000) is mixed and made into slurry, and each composition mass ratio is 48.0:48.0:1:2.5:
0.5, according to single side 55g/m2Surface density be coated on a pole piece two sides, secondary pole piece is made；
Then, by artificial graphite, Super P (graphite-like), adhesive (LA133), sodium carboxymethylcellulose (producer: pottery
Family name, molecular weight 30000) it is mixed according to the weight ratio of 96:1:2.5:0.5, as graphite layer material, according to single side 15g/m2's
Surface density is coated on secondary pole piece two sides, and 80 degrees Celsius are dried in vacuo 12 hours, then rolls, cuts negative electrode tab is made.Finally
The negative electrode tab of preparation is conductive coating/hard carbon soft carbon/graphite-structure.
Embodiment 3.
Firstly, by Super P (graphite-like), adhesive ((acrylonitrile multiple copolymer LA133, it is with can be Chengdu mattress happy
Production), sodium carboxymethylcellulose (producer: Tao Shi, molecular weight 30000) according to 1:2.5:0.5 weight ratio mixing after, as
Conductive coating materials, be coated on metal foil collector it is two-sided on, conductive coating is with a thickness of 4 μm；
Then, hard carbon material, Super P (graphite-like), adhesive (LA133), sodium carboxymethylcellulose (producer: Tao Shi,
Molecular weight 30000) it is mixed and made into slurry, each composition mass ratio is 96:1:2.5:0.5, according to single side 50g/m2Surface density apply
It is distributed in a pole piece two sides, secondary pole piece is made；
Then, by artificial graphite, Super P (graphite-like), adhesive (LA133), sodium carboxymethylcellulose (producer: pottery
Family name, molecular weight 30000) it is mixed according to the weight ratio of 96:1:2.5:0.5, as graphite layer material, according to single side 20g/m2's
Surface density is coated on secondary pole piece two sides, and 80 degrees Celsius are dried in vacuo 12 hours, then rolls, cuts negative electrode tab is made.Finally
The negative electrode tab of preparation is conductive coating/hard carbon/graphite-structure.
Embodiment 4.
Firstly, by Super P (graphite-like), adhesive ((acrylonitrile multiple copolymer LA133, it is with can be Chengdu mattress happy
Production), sodium carboxymethylcellulose (producer: Tao Shi, molecular weight 30000) according to 1:2.5:0.5 weight ratio mixing after, as
Conductive coating materials, be coated on metal foil collector it is two-sided on, conductive coating is with a thickness of 6 μm；
Then, soft carbon material, Super P (graphite-like), adhesive (LA133), sodium carboxymethylcellulose (producer: Tao Shi,
Molecular weight 30000) it is mixed and made into slurry, each composition mass ratio is 96.0:1:2.5:0.5, according to single side 55g/m2Surface density
It is coated on a pole piece two sides, secondary pole piece is made；
Then, by artificial graphite, Super P (graphite-like), adhesive (LA133), sodium carboxymethylcellulose (producer: pottery
Family name, molecular weight 30000) it is mixed according to the weight ratio of 96:1:2.5:0.5, as graphite layer material, according to single side 20g/m2's
Surface density is coated on secondary pole piece two sides, and 80 degrees Celsius are dried in vacuo 12 hours, then rolls, cuts negative electrode tab is made.Finally
The negative electrode tab of preparation is conductive coating/soft carbon/graphite-structure.
Embodiment 5.
Firstly, by Super P (graphite-like), adhesive ((acrylonitrile multiple copolymer LA133, it is with can be Chengdu mattress happy
Production), sodium carboxymethylcellulose (producer: Tao Shi, molecular weight 30000) according to 1:2.5:0.5 weight ratio mixing after, as
Conductive coating materials, be coated on metal foil collector it is two-sided on, conductive coating is with a thickness of 8 μm；
Then, hard carbon material, soft carbon material, Super P (graphite-like), adhesive (LA13), sodium carboxymethylcellulose (factory
Family: Tao Shi, molecular weight 30000) it is mixed and made into slurry, each composition mass ratio is 48.0:48.0:1:2.5:0.5, according to single side
50g/m2Surface density be coated on a pole piece two sides, secondary pole piece is made；
Then, by artificial graphite, Super P (graphite-like), adhesive (LA133), sodium carboxymethylcellulose (producer: pottery
Family name, molecular weight 30000) it is mixed according to the weight ratio of 96:1:2.5:0.5, as graphite layer material, according to single side 20g/m2's
Surface density is coated on secondary pole piece two sides, and 80 degrees Celsius are dried in vacuo 12 hours, then rolls, cuts negative electrode tab is made.Finally
The negative electrode tab of preparation is conductive coating/hard carbon soft carbon/graphite-structure.
For the present invention, anode pole piece production: according to LiFePO4 LiFePO490%~95%, adhesive 2%~
5%, anode is made in the mass ratio of conductive agent 3%~5%, and plus plate current-collecting body uses aluminium foil.Wherein, the conductive agent may include
At least one of graphite, agraphitic carbon, acetylene black and conductive black Super P；Described adhesive may include carboxymethyl fibre
It ties up in element CMC, butadiene-styrene rubber, Kynoar, polytetrafluoroethylene (PTFE), epoxy resin, polyvinyl alcohol, polyimides and polyacrylic acid
At least one.
For the present invention, anode pole piece, polypropylene diaphragm and cathode pole piece battery production: are superimposed upon one in sequence
It rises, lamination is fitted into battery case after assembly.Battery cell is put into baking box, vacuum bakeout 60 hours at 90 DEG C, then
Battery cell is transferred between fluid injection, injects electrolyte, lithium ion battery is fabricated to after sealing.Battery testing: it will prepare
Battery cell, with certain technique chemical conversion, voltage range be 2.0~3.65V, test the capacity of battery cell, while testing electricity
The high rate performance and cycle performance of pond monomer, storge quality and security performance, constant-current charge performance.
The above comparative example and embodiment prepare battery according to the manufacturing process of above-mentioned battery, and are tested.
Above-described embodiment and comparative example use following method to test its properties:
1, anode pole piece peel test force.
The aqueous positive-pole slurry that will be prepared carries out pole piece coating with certain technique, the stripping of pole piece is tested after pole piece drying
From power.Test equipment is the skill tech equipment that inclines, and the use of adhesive tape is 3M adhesive tape.Peel strength is bigger to illustrate that pole piece adhesive force is bigger.
2, battery performance test.
The lithium ion battery that will be prepared is tested the capacity of battery cell, is surveyed simultaneously in 2.0~3.65V voltage range
Try the high rate performance and cycle performance of battery cell.
Examples 1 to 5, the peel strength of the cathode pole piece of comparative example 1~4, the test result of flexility such as table 1
It is shown, known by embodiment, with the increase of conductive coating thickness, pole piece peel strength is better.
Table 1:
| Project | Pole piece peel strength N/m |
| Comparative example 1 | 25 |
| Comparative example 2 | 24.4 |
| Comparative example 3 | 23.6 |
| Comparative example 4 | 25.1 |
| Comparative example 5 | 25 |
| Comparative example 6 | 25.7 |
| Comparative example 7 | 23.9 |
| Embodiment 1 | 29.7 |
| Embodiment 2 | 32 |
| Embodiment 3 | 30 |
| Embodiment 4 | 31.8 |
| Embodiment 5 | 34 |
Battery performance test result made from comparative example and embodiment is as shown in table 2 below.Data result is to take test 5
It is averaged after secondary.As can be seen that the present invention has good implementation result.
Table 2:
It is learnt by embodiment and comparative example data, lithium ion battery prepared by prepared by the method multilayer negative electrode tab
High rate performance, cycle performance are more excellent.Known by embodiment 2, after certain thickness conductive coating, lithium prepared by this negative electrode tab
Battery has better electrical property.
It can be seen that the multilayer cathode pole piece prepared within the scope of the present invention from the Comparative result of above-mentioned table 1, table 2, it is made
Standby pole piece peel strength it is higher and preparation lithium ion battery high rate performance, good cycle.In conclusion of the invention
Multilayer cathode pole piece is conducive to the comprehensive performance for improving battery.
Therefore, for multilayer cathode pole piece provided by the invention, conductive coating, graphite material and hard carbon are taken full advantage of
The characteristics of soft carbon material, can effectively improve high current high rate performance, and the lithium ion battery designed with the cathode pole piece has
Good cycle, highly-safe and resistance to high rate charge-discharge and the advantages that meet lithium ion battery charging performance under low temperature, together
When, manufacturing method is simple, and existing lithium ion battery production equipment can be used and produced.
Therefore, based on statement above it is found that compared with prior art, a kind of multilayer cathode pole piece provided by the invention
And its preparation method and application lithium ion battery, the charge efficiency high and low temperature charging and discharging capabilities which has
By force, the high rate charge-discharge performance of lithium ion battery can be significantly improved, extends the high rate charge-discharge inferior pole piece service life, is conducive to mention
The market application prospect of high cell production companies product, is of great practical significance.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of multilayer cathode pole piece, which is characterized in that including metal foil collector, the surface of the metal foil collector is coated with
There is conductive coating；
The surface of the conductive coating is coated with main functionality layer；
The surface of the main functionality layer is coated with graphite linings.
2. multilayer cathode pole piece as described in claim 1, which is characterized in that the conductive coating is comprising mass percent
25%~75% conductive agent and 25%~75% adhesive；
Wherein, the conductive agent includes in conductive black Super P, electrically conductive graphite KS-6, carbon fiber VGCF and carbon nanotube
It is at least one；
Described adhesive includes acrylonitrile multiple copolymer LA133, sodium carboxymethylcellulose, styrene-butadiene latex SBR and polyvinylidene fluoride
Any one in alkene PVDF.
3. multilayer cathode pole piece as described in claim 1, which is characterized in that the main functionality layer is including mass percent
60%~99% hard carbon, soft carbon or both compounding substances, 0%~25% conductive agent, 0%~5% carboxymethyl cellulose
Plain sodium and 1%~10% adhesive；
Wherein, the conductive agent includes in conductive black Super P, electrically conductive graphite KS-6, carbon fiber VGCF and carbon nanotube
It is at least one；
Described adhesive includes acrylonitrile multiple copolymer LA133, styrene-butadiene latex SBR or Kynoar PVDF.
4. multilayer cathode pole piece as described in claim 1, which is characterized in that the graphite linings include that mass percent is 60%
~99% artificial graphite or natural graphite, 0%~30% conductive agent, 0%~5% sodium carboxymethylcellulose, and
1%~5% adhesive；
Wherein, the conductive agent includes in conductive black Super P, electrically conductive graphite KS-6, carbon fiber VGCF and carbon nanotube
It is at least one；
Described adhesive includes acrylonitrile multiple copolymer LA133, styrene-butadiene latex SBR or Kynoar PVDF.
5. multilayer cathode pole piece according to any one of claims 1 to 4, which is characterized in that the thickness of the conductive coating
It is 2~15 μm；
The surface density of the main functionality layer is 1~3.5 times of the surface density of graphite linings；
The single side surface density of the graphite linings is 15~30g/cm2。
6. multilayer cathode pole piece as claimed in claim 5, which is characterized in that the conductive coating with a thickness of 3~9 μm；
The surface density of the main functionality layer is 2~3 times of the surface density of graphite linings；
The single side surface density of the graphite linings is 20~25g/m2。
7. a kind of lithium ion battery, which is characterized in that including multilayer cathode pole piece such as described in any one of claims 1 to 6.
8. a kind of preparation method of multilayer cathode pole piece, which comprises the following steps:
The first step, by conductive black Super P, adhesive acrylonitrile multiple copolymer LA133, sodium carboxymethylcellulose according to 1:
After the weight ratio mixing of 2.5:0.5, as conductive coating materials, be coated on metal foil collector it is two-sided on；
It is second step, default carbon material, conductive black Super P, adhesive acrylonitrile multiple copolymer LA133, carboxymethyl is fine
It ties up plain sodium and is mixed and made into slurry, the mass ratio between each composition is 96:1:2.5:0.5, is applied according to the first default single side surface density
It is distributed in a pole piece two sides, secondary pole piece is made；
Third step, by artificial graphite, conductive black Super P, adhesive acrylonitrile multiple copolymer LA133, carboxymethyl cellulose
Plain sodium is mixed according to the weight ratio of 96:1:2.5:0.5, as graphite layer material, is coated with according to the second default single side surface density
It in the two sides of secondary pole piece, is then dried in vacuo 12 hours at 80 degrees Celsius, then rolls, cuts multilayer negative electrode tab is made.
9. preparation method as claimed in claim 8, which is characterized in that in the first step, the conductive coating is with a thickness of 4~8 μ
m；
In second step, the first default single side surface density is 50~55g/m2Single side surface density；
In second step, the default carbon material includes the mixture of hard carbon material, soft carbon material or both；
When the default carbon material includes the mixture of hard carbon material and soft carbon material, the hard carbon material and soft carbon material it
Between weight ratio be 1:1；
In the third step, the second default single side surface density is 15~20g/m2Single side surface density.
10. preparation method as claimed in claim 8, which is characterized in that the metal foil collector is copper foil.
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| CN110364733A (en) * | 2019-06-05 | 2019-10-22 | 江西力能新能源科技有限公司 | A kind of anode plate for lithium ionic cell containing conductive coating |
| CN110474052A (en) * | 2019-07-29 | 2019-11-19 | 湖南文理学院 | A kind of lithium ion battery electrode material and preparation method |
| CN111935858A (en) * | 2020-08-18 | 2020-11-13 | 领航博创新能源电池技术研究院(北京)有限公司 | Flexible carbon fiber electrothermal film and preparation method thereof |
| CN112271283A (en) * | 2020-10-26 | 2021-01-26 | 四川虹微技术有限公司 | Negative pole piece and lithium ion battery |
| CN112331814A (en) * | 2020-09-29 | 2021-02-05 | 广东维都利新能源有限公司 | Lithium ion battery negative plate and preparation method thereof |
| CN114156439A (en) * | 2021-10-21 | 2022-03-08 | 浙江南都电源动力股份有限公司 | Negative pole piece and lithium iron phosphate battery |
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