CN109546080A - A kind of anode pole piece, and its preparation method and application - Google Patents
A kind of anode pole piece, and its preparation method and application Download PDFInfo
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- CN109546080A CN109546080A CN201811446977.0A CN201811446977A CN109546080A CN 109546080 A CN109546080 A CN 109546080A CN 201811446977 A CN201811446977 A CN 201811446977A CN 109546080 A CN109546080 A CN 109546080A
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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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- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of anode pole piece, the anode pole piece includes collector and the first electrode material layer and second electrode material layer that set gradually in the collector side；Conductive agent is the first conductive agent in the first electrode material layer, and conductive agent is the second conductive agent, the conductivity of the second conductive agent of conductivity > of first conductive agent in the second electrode material layer.The present invention uses in the two-layer electrode material layer of anode pole piece, different types of conductive agent is set, and then construct good conductive system, effectively improve the electric conductivity of anode pole piece, the fast transfer for promoting charge, improves the chemical property of battery, the lithium ion battery energy density comprising anode pole piece of the present invention is higher, under 0.2C current density, energy density >=255Wh/kg.
Description
Technical field
The invention belongs to field of batteries, and in particular to a kind of anode pole piece, and its preparation method and application.
Background technique
Lithium ion battery has the advantages such as specific energy is high, operating voltage is high and has extended cycle life, and has obtained since commercialization
Rapid development.As lithium ion battery is in the extensive use of mixed power electric car and new-energy automobile field, to lithium
More stringent requirements are proposed for the energy density of ion battery.Under equal conditions, high energy density can effectively increase vehicle
Course continuation mileage, therefore improve battery energy density, research and develop power type lithium ion battery become the current most important thing.
Start with from process aspect, major battery manufacturer is reached by the ratio of the coating thickness and active material that increase battery
To the raising of energy density, but it is ineffective.On the one hand with the increase of cell thickness, high rate performance is by very big shadow
It rings, under high multiplying power, quickly, cycle performance is poor for capacity attenuation.The increase of another aspect active material ratio, so that conductive
The content of agent is reduced, and battery internal resistance is caused to increase, and influences the transmission of electronics, and then influence the chemical property of battery.
CN107742709A discloses a kind of lithium iron phosphate battery anode active material and its preparation and application, active material
It is two layers, first layer active material, and the second layer active material coated on first layer surface of active material；The first layer
Active material according to parts by weight, by 80~95 parts of lithium iron phosphate positive material, 3~12 parts of conductive agent, the of 3~10 parts
A kind of binder composition；The second layer active material according to parts by weight, by 85~98 parts of lithium iron phosphate positive material, 1
~8 parts of conductive agent, 5~8 parts of the second class binder composition.The double-deck lithium iron phosphate positive material that the method is prepared
Pole piece high rate performance is preferable, but it joined excessive conductive agent and binder, and then positive active material content is lower, lithium from
The energy density of sub- battery is lower.
CN105514349B discloses a kind of based lithium-ion battery positive plate and preparation method thereof, the lithium ion cell positive
Piece includes collector, conductive coating and electrode layer；The conductive coating includes close to the first layer on anode collection side and close
The second layer of electrode layer side；The first layer is formed by the first conductive coating containing binder, conductive agent and water, and described
Two layers are formed by the second conductive coating containing binder, sweller, crosslinking agent, conductive agent and water；Binder is amide-containing
The polyolefin resin of group.Positive active material content is lower in the based lithium-ion battery positive plate that the method is prepared, in turn
The energy density of obtained lithium ion battery is lower.
CN106207092A discloses a kind of combined anode slice of lithium ion battery of conductive agent, including collector and adherency
The component of positive film on a current collector, the anode film includes positive electrode active materials, conductive agent and binder；It is described to lead
Electric agent is CB and CNTs combination, CB and GNPs combination, CNTs and GNPs combination or CB, CNTs and GNPs combination.Preparation process packet
It includes following steps: (1) binder being added in solvent and be uniformly mixed；(2) it is added in CB, CNTs, GNPs into solvent
Two or three of conductive agent group merging is uniformly mixed；(3) positive electrode active materials are added to be uniformly mixed, obtain positive slurry
Material；(4) anode sizing agent is coated on collector, after overbaking and roll-in, anode pole piece used in lithium ion battery is made.Institute
The anode pole piece energy density that the method for stating is prepared is lower, and obtained lithium ion battery energy density is lower.
Therefore, this field needs to develop a kind of new type lithium ion battery anode pole piece, makes it have good electrochemistry
Can, and preparation process is simple, and it can industrialized production.
Summary of the invention
In view of the deficiencies of the prior art, one of the objects of the present invention is to provide a kind of anode pole piece, the anode pole pieces
Including collector and the first electrode material layer and second electrode material layer that are set gradually in the collector side；
Conductive agent is the first conductive agent in the first electrode material layer, and conductive agent is the in the second electrode material layer
Two conductive agents, the conductivity of the second conductive agent of conductivity > of first conductive agent.
The present invention uses in the two-layer electrode material layer of anode pole piece, is arranged different types of conductive agent, and then can be with
The contact impedance between positive electrode and collector is significantly improved, good conductive system is constructed, effectively improves anode pole piece
Electric conductivity, promote the fast transfer of charge, improve the chemical property of battery.
The mode of electrode material layer electric conductivity is promoted relative to the content for increasing conductive agent, in anode pole piece of the invention
Positive active material content is higher, and the energy density of anode pole piece is higher, the lithium ion battery energy containing anode pole piece of the present invention
Metric density is higher, under 0.2C current density, energy density >=255Wh/kg.
Preferably, the ratio > 40 of the conductivity of the conductivity and the second conductive agent of first conductive agent, preferably 90~
120, such as 50,60,70,80,90,100,110,120,130,150 etc..
The present invention differs biggish setting (ratio > with the conductivity of the second conductive agent using the conductivity of the first conductive agent
40), so that anode pole piece had not only had good coulombic efficiency for the first time, but also there is excellent cyclical stability, 0.05C current density
Under, for the first time under coulombic efficiency >=82.6%, 0.2C current density, 50 weeks circulation volume conservation rate >=81%.
The electric conductivity of first electrode material layer of the present invention is higher, can significantly improve connecing between positive electrode and collector
Impedance is touched, in the electron-transport to collector for faster carrying out upper layer transport, improves the transmission rate of electronics and lithium ion, into
And anode pole piece has good chemical property.
Second electrode material layer and electrolyte and first electrode material layer contacts, contact impedance is lower, electronics and lithium ion
Transmission rate it is very fast, and then in second electrode material layer conductive agent conductivity without excessively high；At the same time, conductivity is higher
Conductive agent be mostly a peacekeeping two dimension conductive agent, relative to zero dimension conductive agent, specific surface area is larger, and then consumes more electricity
It solves liquid and forms SEI film, reduce the coulombic efficiency for the first time of anode pole piece.
Preferably, the content of first conductive agent and the second conductive agent is each independently selected from 1.5%~5%, excellent
Select 2%~3%, such as 2%, 2.5%, 3%, 3.5%, 4%, 4.5% etc..
Preferably, the second conductive agent in the content Yu second electrode material layer of the first conductive agent in first electrode material layer
Content is identical.
Preferably, first conductive agent and the second conductive agent include Ketjen black, it is any in conductive black SP or CNTs
It is a kind of.
Preferably, positive electrode in the content Yu second electrode material layer of positive electrode in the first electrode material layer
Content is each independently selected from 90%~97%, such as 91%, 92%, 93%, 94%, 95%, 96% etc..
Preferably, the first electrode material layer is identical with the positive electrode of second electrode material layer, preferably nickel cobalt mangaic acid
Lithium or nickel cobalt lithium aluminate.
Preferably, the content of binder is selected each independently in the first electrode material layer and second electrode material layer
From 1.5%~5%, such as 1.8%, 2%, 2.2%, 2.5%, 3%, 3.5%, 4%, 4.5% etc..
Preferably, the first electrode material layer is identical with binder in second electrode material layer, preferably Kynoar.
Preferably, positive electrode in the content and second electrode material layer of positive electrode in the first electrode material layer
Content is identical.
Preferably, in the first electrode material layer in the content and second electrode material layer of binder binder content
It is identical.
First electrode material layer of the present invention and positive electrode, binder in second electrode material layer are identical with solvent, in turn
The compatibility of first electrode material layer and second electrode material layer is good, and the cyclical stability of anode pole piece is high.
Preferably, the collector is aluminium foil, the aluminium foil that preferred thickness is 7~25 μm, such as 8 μm, 10 μm, 12 μm, 15 μ
M, 18 μm, 20 μm, 22 μm etc..
Preferably, the surface density of the first electrode material layer is 10~20mg/cm2, such as 12mg/cm2、14mg/cm2、
15mg/cm2、16mg/cm2、18mg/cm2、19mg/cm2Deng.
Preferably, the surface density of the second electrode material layer is 20~30mg/cm2, such as 22mg/cm2、24mg/cm2、
25mg/cm2、26mg/cm2、28mg/cm2、29mg/cm2Deng.
Preferably, the first electrode material layer with a thickness of 40~110 μm, such as 50 μm, 60 μm, 70 μm, 90 μm,
100 μm etc..
Preferably, the second electrode material layer with a thickness of 110~160 μm, such as 115 μm, 120 μm, 135 μm, 145
μm, 155 μm etc..
The second object of the present invention is to provide a kind of preparation method of anode pole piece, the preparation method includes following step
It is rapid:
(1) positive electrode, the first conductive agent and binder are mixed, N-Methyl pyrrolidone are then added and adjusts viscosity,
Obtain the first electrode slurry；
(2) positive electrode, the second conductive agent and binder are mixed, N-Methyl pyrrolidone are then added and adjusts viscosity,
Obtain the second electrode slurry；
(3) the first electrode slurry and the second electrode slurry are successively coated in collector side, drying obtains anode pole piece.
Preparation method of the present invention is simple, can industrialized production.
Preferably, the mass ratio of positive electrode, the first conductive agent and binder is in step (1) described the first electrode slurry
90~98:1~5:1~5, such as 92:4:4,94:3:3,95:2.5:2.5,96:2:2,97:2:1 etc..
Preferably, the mass ratio of positive electrode, the second conductive agent and binder is in step (2) described the second electrode slurry
90~98:1~5:1~5, such as 92:4:4,94:3:3,95:2.5:2.5,96:2:2,97:2:1 etc..
Preferably, the viscosity of the first electrode slurry be 4200~4800mPas, such as 4300mPas,
4400mPas, 4500mPas, 4587mPas, 4600mPas, 4700mPas etc..
Preferably, the viscosity of the second electrode slurry be 4200~4800mPas, such as 4300mPas,
4400mPas, 4500mPas, 4587mPas, 4600mPas, 4700mPas etc..
Preferably, the process of step (3) described coating includes: to apply the first electrode slurry in one side surface of collector
It covers, obtains the first coat, the first coat is dry, then the first painting by the second electrode slurry coating after the drying
On coating, the second coat is obtained, finally carries out roll-in, drying obtains anode pole piece.
Preferably, the temperature of the drying is 60~90 DEG C, such as 65 DEG C, 70 DEG C, 80 DEG C, 85 DEG C etc..
Preferably, the time of the drying is 4~8h, such as 5h, 5.5h, 6h, 7h etc..
Preferably, the density of the roll-in is 3.1~3.7mg/cm3, such as 3.2mg/cm3、3.3mg/cm3、3.4mg/
cm3、3.5mg/cm3、3.6mg/cm3Deng.
Preferably, the temperature of the drying is 80~130 DEG C, such as 90 DEG C, 100 DEG C, 110 DEG C, 120 DEG C etc..
Preferably, the time of the drying is 10~20h, such as 12h, 14h, 15h, 16h, 18h etc..
As optimal technical scheme, the preparation method of anode pole piece of the present invention includes the following steps:
(1) nickel cobalt lithium aluminate, CNTs and PVDF are mixed by the mass ratio of 90~98:1~5:1~5, N- methylpyrrole is added
It is 4200~4800mPas that alkanone, which adjusts viscosity, obtains the first electrode slurry；
(2) nickel cobalt lithium aluminate, conductive black SP and PVDF are mixed by the mass ratio of 90~98:1~5:1~5, N- first is added
It is 4200~4800mPas that base pyrrolidones, which adjusts viscosity, obtains the second electrode slurry；
(3) the first electrode slurry is coated on a current collector, obtains the first coat, the first coat is dry at 60~90 DEG C
Then the second electrode slurry is coated on the first coat after the drying, obtains the second coat, finally by dry 4~8h
Roll-in is carried out, the density of roll-in is 3.1~3.7mg/cm3, 80~130 DEG C of 10~20h of drying obtain anode pole piece.
The three of the object of the invention are to provide a kind of purposes of anode pole piece as described in the first purpose, the anode pole piece application
In field of batteries, it is preferred for lithium ion cell positive.
The four of the object of the invention are to provide a kind of lithium ion battery, the lithium ion battery include described in the first purpose just
Pole pole piece.
Preferably, one of for the purpose of the lithium ion anode pole piece described in anode pole piece.
Compared with prior art, the invention has the following beneficial effects:
(1) present invention is arranged different types of conductive agent, makes bilayer using in the two-layer electrode material layer of anode pole piece
Electrode material layer has different electric conductivity, and then can significantly improve the contact impedance between positive electrode and collector, structure
Good conductive system is built, the chemical property of battery is improved, promotes electrode material layer relative to the content for increasing conductive agent
The mode of electric conductivity, positive active material content is higher in anode pole piece of the invention, the lithium containing anode pole piece of the present invention from
Sub- battery energy density is higher, under 0.2C current density, energy density >=255Wh/kg.
(2) in further preferred technical solution, the present invention uses the conductivity and the second conductive agent of the first conductive agent
Conductivity differ biggish setting (ratio > 40), and then positive electrode and collector in first electrode material layer can be improved
Between contact impedance, improve the transmission rate of electronics and lithium ion；Second electrode material layer is led using conductivity is lower
Electric agent, because second electrode material layer contacts impedance is lower, and the higher conductive agent specific surface area of conductivity is larger, can consume more
Electrolyte formed SEI film, reduce the coulombic efficiency for the first time of anode pole piece, anode pole piece of the present invention had both had good library for the first time
Human relations efficiency, and there is excellent cyclical stability, under 0.05C current density, coulombic efficiency >=82.6%, 0.2C electric current is close for the first time
Under degree, 50 weeks circulation volume conservation rate >=81%.
Detailed description of the invention
Fig. 1 is the sample structure schematic diagram that the specific embodiment of the invention 1 is prepared.
Specific embodiment
Of the invention for ease of understanding, the present invention enumerates the conductive black SP that embodiment is as follows, uses in the embodiment of the present invention
For Switzerland Te Migao production, conductivity 10S/cm, the CNTs are the production of Jiangsu Tian Nai Science and Technology Co., Ltd., conductivity
It is 103S/cm, the Ketjen black are the production of Shi Wang LION producer, Japan, conductivity 102S/cm.Those skilled in the art should
It is illustrated, the described embodiments are merely helpful in understanding the present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
A kind of preparation method of anode pole piece includes the following steps:
(1) nickel cobalt lithium aluminate, CNTs and PVDF are mixed by 97:2:1 mass ratio, N-Methyl pyrrolidone is added and adjusts and glues
Degree is 4587mPas, obtains the first electrode slurry；
(2) nickel cobalt lithium aluminate, conductive black SP and PVDF are mixed by 97:2:1 mass ratio, N-Methyl pyrrolidone is added
Adjusting viscosity is 4587mPas, obtains the second electrode slurry；
(3) the first electrode slurry is coated on 10 μm of aluminium foil, obtains the first coat, the first coat is dry at 80 DEG C
Then the second electrode slurry is coated on the first coat after the drying, obtains the second coat, finally carry out by dry 6h
Roll-in, the density of roll-in are 3.5mg/cm3, 120 DEG C of drying 12h, the surface density for obtaining first electrode material layer is 14mg/cm2,
The surface density of second electrode material layer is 28mg/cm2Anode pole piece.
Embodiment 2
The difference from embodiment 1 is that step (2) the conductive black SP replaces with Ketjen black.
Embodiment 3
The difference from embodiment 1 is that step (1) described CNTs replaces with Ketjen black.
Embodiment 4
The difference from embodiment 1 is that the ratio of step (1) the nickel cobalt lithium aluminate, CNTs and PVDF is 96:3:1.
Embodiment 5
The difference from embodiment 1 is that the ratio of step (2) the nickel cobalt lithium aluminate, CNTs and PVDF is 96:3:1.
Embodiment 6
A kind of preparation method of anode pole piece includes the following steps:
(1) nickel cobalt lithium aluminate, CNTs and PVDF are mixed by 97:2:1 mass ratio, N-Methyl pyrrolidone is added and adjusts and glues
Degree is 4200mPas, obtains the first electrode slurry；
(2) nickle cobalt lithium manganate, conductive black SP and PVDF are mixed by 97:2:1 mass ratio, N-Methyl pyrrolidone is added
Adjusting viscosity is 4200mPas, obtains the second electrode slurry；
(3) the first electrode slurry is coated on 7 μm of aluminium foil, obtains the first coat, the first coat is dry at 60 DEG C
Then the second electrode slurry is coated on the first coat after the drying, obtains the second coat, finally carry out by dry 8h
Roll-in, the density of roll-in are 3.1mg/cm3, 130 DEG C of drying 10h, the surface density for obtaining first electrode material layer is 10mg/cm2,
The surface density of second electrode material layer is 20mg/cm2Anode pole piece.
Embodiment 7
A kind of preparation method of anode pole piece includes the following steps:
(1) nickle cobalt lithium manganate, CNTs and PVDF are mixed by 97:2:1 mass ratio, N-Methyl pyrrolidone is added and adjusts and glues
Degree is 4800mPas, obtains the first electrode slurry；
(2) nickel cobalt lithium aluminate, conductive black SP and PVDF are mixed by 97:2:1 mass ratio, N-Methyl pyrrolidone is added
Adjusting viscosity is 4800mPas, obtains the second electrode slurry；
(3) the first electrode slurry is coated on 25 μm of aluminium foil, obtains the first coat, the first coat is dry at 90 DEG C
Then the second electrode slurry is coated on the first coat after the drying, obtains the second coat, finally carry out by dry 4h
Roll-in, the density of roll-in are 3.7mg/cm3, 80 DEG C of drying 20h, the surface density for obtaining first electrode material layer is 20mg/cm2, the
The surface density of two electrode material layers is 30mg/cm2Anode pole piece.
Comparative example 1
The difference from embodiment 1 is that step (1) described CNTs replaces with conductive black SP.
Comparative example 2
The difference from embodiment 1 is that step (1) described CNTs replaces with conductive black SP, step (2) the conductive charcoal
Black SP replaces with CNTs.
Comparative example 3
The difference from embodiment 1 is that step (1) described CNTs replaces with conductive black SP, step (2) the conductive charcoal
Black SP replaces with Ketjen black.
Comparative example 4
The difference from embodiment 1 is that step (1) described CNTs replaces with Ketjen black, step (2) the conductive black SP
Replace with CNTs.
Comparative example 5
The difference from embodiment 1 is that step (1) described CNTs replaces with Ketjen black, step (2) the conductive black SP
Replace with Ketjen black.
Comparative example 6
The difference from embodiment 1 is that step (2) the conductive black SP replaces with CNTs.
Comparative example 7
A kind of preparation method of anode pole piece includes the following steps:
(1) according to nickel cobalt lithium aluminate: conductive black SP:PVDF is the mass ratio of 82.5:7.5:10, and PVDF is dissolved in
In nmp solution, makes NMP and total weight of solids than preparing the slurry that viscosity is 12000Pa.S for 3:1, be thoroughly mixed molten
Liquid 24 hours, by mixed slurry coating on aluminium foil, coating thickness was 15 μm, moves into baking oven drying, it is living to obtain first layer
Property material coating；
(2) according to nickel cobalt lithium aluminate: conductive black SP:PVDF is the mass ratio of 87.5:2.5:10, so that NMP and solid
Content ratio is 4:1, and the coating paste that viscosity is 8000Pa.S is made, is dried to first coating containing a small amount of NMP and slurry cannot
When voluntarily flowing, by second layer slurry coating in first layer pulp surface, coating thickness is 15 μm, roll-in is carried out after drying, i.e.,
Obtain double coating nickel cobalt lithium aluminate anode pole pieces.
Performance test:
The anode pole piece being prepared is performed the following performance tests:
(1) preparation of lithium ion battery: using the anode pole piece being prepared as anode, diaphragm be capillary polypropylene every
Film, electrolyte are the LiPF of 1.2mol/L6, the preparation process of cathode pole piece includes: by graphite, sodium carboxymethylcellulose CMC, fourth
Benzene rubber SBR and conductive black SP carries out 6~8h of mixing, measurement according to the ratio that mass fraction is 90%, 2%, 3% and 5%
Viscosity is 4587mPas, is then coated on copper foil, and finally drying, roll-in and cross cutting, which are dried, is made cathode pole piece, will be positive
Pole piece, cathode pole piece electrolyte and diaphragm carry out load and lithium ion battery are made.
(2) energy density is tested: using the chemical property of the new prestige 5V/3A type cell tester test battery of blue electricity, being filled
Electric blanking voltage is 4.2V, discharge cut-off voltage 2.75V, tests energy of the battery under 0.2C current density, energy density
=energy/battery quality, energy density of the present invention are lithium ion battery energy density obtained.
(3) coulombic efficiency is tested for the first time: using the electrochemistry of the new prestige 5V/3A type cell tester test battery of blue electricity
Can, charge cutoff voltage 4.2V, discharge cut-off voltage 2.75V test for the first time charge and discharge of the battery under 0.05C current density
Electrical efficiency, for the first time coulombic efficiency=first discharge specific capacity/initial charge specific capacity.
Circulation volume conservation rate test in (4) 50 weeks: using the electrification of the new prestige 5V/3A type cell tester test battery of blue electricity
Learn performance, charge cutoff voltage 4.2V, discharge cut-off voltage 2.75V, test battery under 0.2C current density for the first time
Efficiency for charge-discharge and 50 weeks circulation volume conservation rates, 50 weeks circulation volume conservation rates=the 50th specific discharge capacity/discharge for the first time
Specific capacity.
Table 1
It can be seen from Table 1 that anode pole piece all uses the conductivity > second of the first conductive agent to lead in Examples 1 to 7
The setting of the conductivity of electric agent, the anode pole piece have good chemical property, under 0.2C current density, positive electrode
Energy density >=255Wh/kg, for the first time coulombic efficiency >=82.6%, 50 week circulation volume conservation rate >=81%, especially embodiment
In 1, in 90~120 ranges, chemical property is outstanding for the ratio of CNTs conductivity and the ratio of conductive black SP conductivity.
It can be seen from Table 1 that embodiment 2, relative to embodiment 1, under 0.2C current density, positive electrode energy is close
Degree, coulombic efficiency and 50 weeks circulation volume conservation rates are lower for the first time, it may be possible to because replacing with conductive black SP in embodiment 2
Ketjen black, the conductivity of CNTs and the conductivity ratio < 40 of Ketjen black, so embodiment 2 is relative to embodiment 1, it is electric in 0.2C
Under current density, positive electrode energy density, for the first time coulombic efficiency and 50 weeks circulation volume conservation rates are lower.
It can be seen from Table 1 that embodiment 3, relative to embodiment 1, under 0.2C current density, positive electrode energy is close
Degree, coulombic efficiency and 50 weeks circulation volume conservation rates are lower for the first time, it may be possible to because CNTs is replaced with section's qin in embodiment 3
It is black, although the conductivity of the conductivity > conductive black SP of Ketjen black, the conductivity of Ketjen black and the conduction of conductive black SP
Rate ratio < 40, so embodiment 3 is relative to embodiment 1, under 0.2C current density, positive electrode energy density, for the first time library
Human relations efficiency and 50 weeks circulation volume conservation rates are lower.
It can be seen from Table 1 that embodiment 6 and embodiment 7 relative to embodiment 1, under 0.2C current density, are followed for 50 weeks
Ring capacity retention ratio is lower, it may be possible to because embodiment 6 is different with the type of positive electrode in embodiment 7, and then two-layer electrode
Compatibility is poor between material layer, so embodiment 6 and embodiment 7 were relative to embodiment 1, under 0.2C current density, 50 weeks
Circulation volume conservation rate is lower.
It can be seen from Table 1 that comparative example 1, relative to embodiment 1, under 0.2C current density, positive electrode energy is close
Degree, coulombic efficiency and 50 weeks circulation volume conservation rates are lower for the first time, it may be possible to because first conductive agent is led with second in comparative example 1
Electric agent all uses conductive black SP, and the conductivity of conductive black SP is smaller, and then between first electrode material layer and collector
Contact impedance is larger, and the transmission rate of electronics and lithium ion is slower, and the practical energy density played of positive electrode is lower, so right
Ratio 1 is relative to embodiment 1, and under 0.2C current density, positive electrode energy density, for the first time coulombic efficiency and 50 weeks circulations are held
It is lower to measure conservation rate.
It can be seen from Table 1 that comparative example 2, relative to embodiment 1, under 0.2C current density, positive electrode energy is close
Degree, coulombic efficiency and 50 weeks circulation volume conservation rates are lower for the first time, it may be possible to because 2 first conductive agent of comparative example is conductive black
The conductivity of SP, conductive black SP are smaller, and then the contact impedance between first electrode material layer and collector is larger, electronics with
The transmission rate of lithium ion is slower, and the practical energy density played of positive electrode is lower, and chemical property is poor；Second conductive agent
Conductivity for CNTs, CNTs is larger, but its specific surface area is larger, and then consumes more electrolyte and form SEI film, further
The coulombic efficiency for the first time for reducing anode pole piece, so comparative example 2 is relative to embodiment 1, under 0.2C current density, positive electrode
Energy density, for the first time coulombic efficiency and 50 weeks circulation volume conservation rates are lower.
It can be seen from Table 1 that comparative example 3, relative to embodiment 1, under 0.2C current density, positive electrode energy is close
Degree, coulombic efficiency and 50 weeks circulation volume conservation rates are lower for the first time, it may be possible to because 3 first conductive agent of comparative example is conductive black
The conductivity of SP, conductive black SP are smaller, and then the contact impedance between first electrode material layer and collector is larger, electronics with
The transmission rate of lithium ion is slower, and the practical energy density played of positive electrode is lower, so comparative example 3 is relative to embodiment 1,
Under 0.2C current density, positive electrode energy density, for the first time coulombic efficiency and 50 weeks circulation volume conservation rates are lower.
It can be seen from Table 1 that comparative example 4, relative to embodiment 1, under 0.2C current density, positive electrode energy is close
Degree, coulombic efficiency and 50 weeks circulation volume conservation rates are lower for the first time, it may be possible to because 4 first conductive agent of comparative example is Ketjen black,
The conductivity of Ketjen black is smaller, and then the contact impedance between first electrode material layer and collector is larger, electronics and lithium ion
Transmission rate it is slower, the practical energy density played of positive electrode is lower, and chemical property is poor；Second conductive agent is
The conductivity of CNTs, CNTs are larger, but its specific surface area is larger, and then consume more electrolyte and form SEI film, further drop
The coulombic efficiency for the first time of low anode pole piece, so comparative example 4 is relative to embodiment 1, under 0.2C current density, positive electrode energy
Metric density, for the first time coulombic efficiency and 50 weeks circulation volume conservation rates are lower.
It can be seen from Table 1 that comparative example 5, relative to embodiment 1, under 0.2C current density, positive electrode energy is close
Degree, coulombic efficiency and 50 weeks circulation volume conservation rates are lower for the first time, it may be possible to because first conductive agent is led with second in comparative example 5
Electric agent all uses Ketjen black, and the conductivity of Ketjen black is smaller, and then the contact impedance between first electrode material layer and collector
Larger, the transmission rate of electronics and lithium ion is slower, and the practical energy density played of positive electrode is lower, so 5 phase of comparative example
For embodiment 1, under 0.2C current density, positive electrode energy density, for the first time coulombic efficiency and 50 weeks circulation volumes are kept
Rate is lower.
It can be seen from Table 1 that comparative example 6 is relative to embodiment 1, under 0.2C current density, for the first time coulombic efficiency and
Circulation volume conservation rate is lower within 50 weeks, it may be possible to double because first conductive agent and the second conductive agent all use CNTs in comparative example 6
Layer is all CNTs, and the consumption of electrolyte is excessive, forms excessive SEI film, reduces the coulombic efficiency for the first time and circulation of anode pole piece
Stability, so comparative example 6, relative to embodiment 1, under 0.2C current density, coulombic efficiency and 50 weeks circulation volumes are protected for the first time
Holdup is lower.
It can be seen from Table 1 that comparative example 7, relative to embodiment 1, under 0.2C current density, positive electrode energy is close
Degree, coulombic efficiency and 50 weeks circulation volume conservation rates are lower for the first time, it may be possible to because using increase first electrode material in comparative example 7
The amount of conductive black SP increases the electric conductivity of first electrode material layer in the bed of material, and then occurs electrification in first electrode material layer
The active material for learning reaction is less, so the energy density of anode pole piece is lower, at the same time, by increasing conductive black SP's
Measure that increased electric conductivity is smaller, the conductivity of conductive agent is led with conductive agent in second electrode material layer in first electrode material layer
Electric rate ratio is not in 90~120 ranges, so comparative example 7 is relative to embodiment 1, under 0.2C current density, positive electrode
Energy density, for the first time coulombic efficiency and 50 weeks circulation volume conservation rates are lower.
The Applicant declares that the present invention is explained by the above embodiments detailed process equipment and process flow of the invention,
But the present invention is not limited to the above detailed process equipment and process flow, that is, it is above-mentioned detailed not mean that the present invention must rely on
Process equipment and process flow could be implemented.It should be clear to those skilled in the art, any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within of the invention
Within protection scope and the open scope.
Claims (10)
1. a kind of anode pole piece, which is characterized in that the anode pole piece includes collector and successively sets in the collector side
The first electrode material layer and second electrode material layer set；
Conductive agent is the first conductive agent in the first electrode material layer, and conductive agent is led in the second electrode material layer for second
Electric agent, the conductivity of the second conductive agent of conductivity > of first conductive agent.
2. anode pole piece as described in claim 1, which is characterized in that the conductivity and the second conductive agent of first conductive agent
Conductivity ratio > 40, preferably 90~120；
Preferably, the content of first conductive agent and the second conductive agent is each independently selected from 1.5%~5%, preferably 2%
~3%；
Preferably, in first electrode material layer in the content Yu second electrode material layer of the first conductive agent the second conductive agent content
It is identical；
Preferably, first conductive agent and the second conductive agent include Ketjen black, any one in conductive black SP or CNTs.
3. anode pole piece as claimed in claim 1 or 2, which is characterized in that positive electrode in the first electrode material layer
The content of positive electrode is each independently selected from 90%~97% in content and second electrode material layer；
Preferably, the first electrode material layer is identical with the positive electrode of second electrode material layer, preferably nickle cobalt lithium manganate or
Nickel cobalt lithium aluminate；
Preferably, the content of binder is each independently selected from the first electrode material layer and second electrode material layer
1.5%~5%；
Preferably, the first electrode material layer is identical with binder in second electrode material layer, preferably Kynoar；
Preferably, in the first electrode material layer in the content and second electrode material layer of positive electrode positive electrode content
It is identical；
Preferably, in the first electrode material layer in the content and second electrode material layer of binder binder content phase
Together.
4. the anode pole piece as described in one of claim 1-3, which is characterized in that the collector is aluminium foil, preferred thickness 7
~25 μm of aluminium foil；
Preferably, the surface density of the first electrode material layer is 10~20mg/cm2；
Preferably, the surface density of the second electrode material layer is 20~30mg/cm2；
Preferably, the first electrode material layer with a thickness of 40~110 μm；
Preferably, the second electrode material layer with a thickness of 110~160 μm.
5. a kind of preparation method of the anode pole piece as described in one of claim 1-4, which is characterized in that the preparation method includes
Following steps:
(1) positive electrode, the first conductive agent and binder are mixed, N-Methyl pyrrolidone is then added and adjusts viscosity, obtains
The first electrode slurry；
(2) positive electrode, the second conductive agent and binder are mixed, N-Methyl pyrrolidone is then added and adjusts viscosity, obtains
The second electrode slurry；
(3) the first electrode slurry and the second electrode slurry are successively coated in collector side, drying obtains anode pole piece.
6. preparation method as claimed in claim 5, which is characterized in that positive electrode in step (1) described the first electrode slurry,
The mass ratio of first conductive agent and binder is 90~98:1~5:1~5；
Preferably, in step (2) described the second electrode slurry positive electrode, the second conductive agent and binder mass ratio be 90~
98:1~5:1~5；
Preferably, the viscosity of the first electrode slurry is 4200~4800mPas；
Preferably, the viscosity of the second electrode slurry is 4200~4800mPas.
7. such as preparation method described in claim 5 or 6, which is characterized in that the process of step (3) described coating includes:
The first electrode slurry is coated in one side surface of collector, obtains the first coat, the first coat is dry, so
The second electrode slurry is coated afterwards on the first coat after the drying, obtain the second coat, finally carry out roll-in, dried
It is dry to obtain anode pole piece；
Preferably, the temperature of the drying is 60~90 DEG C；
Preferably, the time of the drying is 4~8h；
Preferably, the density of the roll-in is 3.1~3.7mg/cm3；
Preferably, the temperature of the drying is 80~130 DEG C；
Preferably, the time of the drying is 10~20h.
8. the preparation method as described in one of claim 5-7, which is characterized in that the preparation method includes the following steps:
(1) nickel cobalt lithium aluminate, CNTs and PVDF are mixed by the mass ratio of 90~98:1~5:1~5, N-Methyl pyrrolidone is added
Adjusting viscosity is 4200~4800mPas, obtains the first electrode slurry；
(2) nickel cobalt lithium aluminate, conductive black SP and PVDF are mixed by the mass ratio of 90~98:1~5:1~5, N- methyl pyrrole is added
It is 4200~4800mPas that pyrrolidone, which adjusts viscosity, obtains the second electrode slurry；
(3) the first electrode slurry is coated on a current collector, obtains the first coat, by the first coat at 60~90 DEG C dry 4
Then the second electrode slurry is coated on the first coat after the drying, obtains the second coat, finally carry out by~8h
Roll-in, the density of roll-in are 3.1~3.7mg/cm3, 80~130 DEG C of 10~20h of drying obtain anode pole piece.
9. a kind of purposes of the anode pole piece as described in one of claim 1-4, which is characterized in that the anode pole piece is applied to electricity
Pond field, is preferred for lithium ion cell positive.
10. a kind of lithium ion battery, which is characterized in that the lithium ion battery includes anode described in one of claim 1-4
Pole piece；
Preferably, the lithium ion anode pole piece is anode pole piece described in one of claim 1-4.
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