CN109560249A - A kind of double-layer structure anode pole piece, and its preparation method and application - Google Patents

A kind of double-layer structure anode pole piece, and its preparation method and application Download PDF

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Publication number
CN109560249A
CN109560249A CN201811450509.0A CN201811450509A CN109560249A CN 109560249 A CN109560249 A CN 109560249A CN 201811450509 A CN201811450509 A CN 201811450509A CN 109560249 A CN109560249 A CN 109560249A
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pole piece
coat
anode pole
material layer
electrode material
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巫湘坤
张锁江
宋开放
张兰
陈占
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Hebei Aipuai Technology Development Co ltd
Institute of Process Engineering of CAS
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Hebei Aipuai Technology Development Co ltd
Institute of Process Engineering of CAS
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Priority to CN201811450509.0A priority Critical patent/CN109560249A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • H01M4/0435—Rolling or calendering
    • 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
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The present invention relates to a kind of double-layer structure anode pole piece, the anode pole piece includes collector and the positive-active unit for being set to the collector two sides；The positive-active unit includes the first electrode material layer for being set to the collector two sides and the second electrode material layer for being set to the first electrode material surface；The porosity of the first electrode material layer is 15%~22%；The porosity of the second electrode material layer is 25%~50%.The double-deck pore structure that the present invention is gradually risen using porosity in positive-active unit, that is the porosity of the porosity > first electrode material layer of second electrode material layer, the wellability of electrolyte in positive electrode, the utilization rate of the effective diffusion cofficient of lithium ion and positive active material are improved, and then improves the practical gram volume played of positive electrode.

Description

A kind of double-layer structure anode pole piece, and its preparation method and application
Technical field
The invention belongs to field of batteries, and in particular to a kind of double-layer structure anode pole piece, and its preparation method and application.
Background technique
Lithium ion battery is widely used in the fields such as energy storage and electric car, with the fast development of industrial technology, respectively answers With the development of field, especially electric car, to lithium ion battery, more stringent requirements are proposed, guarantee good safety, In the case where cycle life and high rate performance, lithium ion battery energy density is continuously improved, develops the lithium-ion electric of high-energy-density Pond becomes the inexorable trend of future development.
Currently, countries in the world are all increasing the investment to Study on Li-ion batteries, and the various aspects of battery are carried out Research, purpose are all energy density, power density, safety and the service life etc. for improving lithium ion battery.Want to improve battery Specific energy, first to the more demanding of material, electrolyte and diaphragm, but the design of battery pole piece and manufacture craft are also to mention High essential a part of battery specific energy.
The coating weight for improving pole piece is a kind of method for effectively promoting energy density, can reduce collector, auxiliary material Accounting.In addition, the silicon-carbon composite cathode material of high capacity also starts in industry application, and silicon-carbon cathode capacity is even more than 1000mAh/g, and the thickness of matched anode pole piece is more much larger than cathode.However, with the increasing of anode pole piece thickness Add, compared under high magnification, lithium ion kinetics of diffusion is limited, and electrode active material utilization rate declines therewith, battery energy density It is impaired.
CN101635344 discloses a kind of anode pole piece of secondary lithium battery comprising plus plate current-collecting body and two-sided It is coated on the diaphragm of plus plate current-collecting body, the diaphragm includes at least two layers of membrane layer, the composition material of at least two layers membrane layer Material or proportion are different, have different inter-layer electrical conductivities.The diaphragm of multilayered structure in the secondary lithium battery anode pole piece Compared with being not easy to fall off from plus plate current-collecting body under low range, however compared under high magnification, chemical property and security performance It can be poor.
CN104916869B discloses porous-fine and close bilayer electrolyte pottery based on inorganic solid-state lithium-ion electrolyte material Porcelain sintered body, all solid state secondary lithium battery, all solid state secondary lithium-air battery, and preparation method thereof, it is porous-fine and close double The preparation method of layer electrolyte ceramics sintered body includes the following steps: that (a) provides the powder of the inorganic solid-state lithium-ion electrolyte Body；(b) the part powder is mixed with pore creating material, obtains mixed powder；(c) powder and institute described in rest part are utilized It states mixed powder and forms green body, wherein the green body includes the first green body layer and the second green body layer being layered on top of each other, by its remaining part Divide the powder to form first green body layer, and second green body layer is formed by the mixed powder；(d) by the green body It is sintered, pore creating material described in burning-off, obtains porous-fine and close bilayer electrolyte ceramic sintered bodies, wherein first base Body layer forms compacted zone, and second green body layer forms porous layer.Porous-fine and close double-layer electric that the preparation method is prepared Electrolyte wellability is poor in solution matter ceramic sintered bodies, and chemical property is poor.
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.In the based lithium-ion battery positive plate, electrolyte wellability is poor, and then electric conductivity is poor, can not Meet the requirement of excellent based lithium-ion battery positive plate.
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, described one of the objects of the present invention is to provide a kind of double-layer structure anode pole piece Anode pole piece includes collector and the positive-active unit for being respectively arranged at the collector two sides；
The positive-active unit includes the first electrode material layer set gradually in the collector side and the second electricity Pole material layer.
The present invention using increasing the content of positive active material in such a way that positive-active unit is arranged in collector two sides, And then increase the gram volume and energy density of anode pole piece, electrochemistry of the anode pole piece of the present invention under high current density It can be good.
Preferably, the porosity of the first electrode material layer is less than the porosity of second electrode material layer.
Preferably, the porosity of the first electrode material layer be 15%~22%, such as 16%, 17%, 18%, 18.8%, 19%, 20%, 21% etc..
Preferably, the porosity of the second electrode material layer be 25%~50%, such as 26%, 28%, 30%, 32%, 32.9%, 33%, 35%, 40%, 42%, 45%, 48% etc..
The double-deck pore structure that the present invention is gradually risen using porosity in positive-active unit, i.e. second electrode material layer Porosity > first electrode material layer porosity, the pore structure is sufficient filling with electrolyte inside anode pole piece In hole, the wellability of electrolyte in positive electrode, the benefit of the effective diffusion cofficient of lithium ion and positive active material are improved With rate, and then improve the practical gram volume played of positive electrode.
Pore structure of the present invention may insure that lithium concentration will not fall sharply in the electrolyte on the inside of collector, in turn Anode pole piece of the present invention can also have a good chemical property under higher current density, under 0.5C current density, anode Gram volume >=170mAh/g of activity unit, energy density >=250Wh/kg of battery.
Preferably, the first electrode material layer with a thickness of 40~125 μm, such as 49 μm, 69 μm, 80 μm, 82 μm, 115 μm, 121 μm etc..
Preferably, the second electrode material layer with a thickness of 60~165 μm, such as 60 μm, 83 μm, 100 μm, 133 μm, 140 μm etc..
Preferably, the surface density of the positive-active unit is 50~80mg/cm2, such as 55mg/cm2、60mg/cm2、 65mg/cm2、70mg/cm2、75mg/cm2Deng.
Preferably, the surface density of the first electrode material layer is 15~56mg/cm2, such as 18mg/cm2、25mg/cm2、 30mg/cm2、40mg/cm2、42mg/cm2、45mg/cm2Deng.
Preferably, the surface density of the second electrode material layer is 15~56mg/cm2, such as 18mg/cm2、20mg/cm2、 25mg/cm2、30mg/cm2、40mg/cm2、42mg/cm2Deng.
Preferably, the collector is aluminium foil, and preferred thickness is 7~25 μm, such as 8 μm, 10 μm, 12 μm, 15 μm, 20 μ M, 23 μm etc..
Preferably, the content of first electrode material layer is 30wt%~70wt% in the positive-active unit, such as 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt% etc..
Preferably, first electrode material layer is identical with the composition of second electrode material layer in the positive-active unit, institute State the composition of positive-active unit by mass percentage, including following components:
Positive electrode 95%~98%
Conductive agent 1%~2.5%
Binder 1%~2.5%；
The sum of described material layer each component mass percent is calculated as 100%.
Preferably, the mass percent of the positive electrode is 95%~98%, such as 95%, 96%, 97% etc..
Preferably, the mass percent of the conductive agent is 1%~2.5%, such as 1.5%, 2%, 2.5% etc..
Preferably, the mass percent of the binder is 1%~2.5%, such as 1.5%, 2%, 2.5% etc..
The second object of the present invention is to provide a kind of preparation method of double-layer structure anode pole piece, the preparation method includes Following steps:
(1) positive electrode, conductive agent and binder are mixed, mixture is made, the mixture and solvent are mixed To electrode slurry；
(2) according to scheduled porosity, the electrode slurry is successively coated into the first coat and in collector two sides Two coats obtain double-layer structure anode pole piece.
Porosity of the present invention can be calculated according to following formula:
First electrode material layer porosity=1- (the first coat surface density/first electrode layer thickness) × [(first Positive electrode percentage composition/positive electrode real density+conductive agent percentage composition in first electrode material layer/is led in electrode material layer Binder percentage composition/binder real density in electric agent real density+first electrode material layer)]；
Second electrode material layer porosity=1- (the second coat surface density/second electrode layer thickness) × [(second Positive electrode percentage composition/positive electrode real density+conductive agent percentage composition in second electrode material layer/is led in electrode material layer Binder percentage composition/binder real density in electric agent real density+second electrode material layer)]；
In the calculation formula of above-mentioned porosity, the positive electrode real density is 3.6~5.2g/cc, and the binder is true Density is 1.77g/cc, and the conductive agent real density is 2.05~2.26g/cc.
The present invention is coated with the coat of certain surface density and thickness according to porosity formula, in collector two sides, and then obtains To the double-layer structure anode pole piece with predetermined porosity and pore structure.
Preferably, in step (1) the of the present invention mixture positive electrode, conductive agent and binder mass ratio be 95~ 98:1~2.5:1~2.5, such as 98:1:1,97:1:2,96:2:2 etc..
Preferably, the mass ratio of mixture and solvent is 1.5~4:1, such as 2:1,2.5:1,3:1 in the electrode slurry Deng.
Preferably, the positive electrode include cobalt acid lithium, nickle cobalt lithium manganate, LiMn2O4, nickel ion doped, nickel cobalt lithium aluminate, Any one in LiFePO4 or rich lithium manganese, such as cobalt acid lithium, nickel cobalt lithium aluminate, LiMn2O4 etc..
Preferably, the conductive agent include in carbon black, Ketjen black, carbon nanotube and electrically conductive graphite any one or at least Two kinds combination, such as carbon black, Ketjen black, carbon nanotube etc..
Preferably, the binder is Kynoar.
Preferably, the solvent is N-Methyl pyrrolidone.
The present invention uses identical positive electrode, binder and solvent during preparing double-layer structure anode pole piece, into And the compatibility of the first coat and the second coat is good in coating procedure, electrode is not pulverized easily in charge and discharge process, electricity Chemical property is good.
Preferably, the process of step (2) the of the present invention coating includes: by the electrode slurry in collector both side surface The first coat is respectively coated, to the first coat carry out a roll-in, then by the electrode slurry after roll-in first The second coat is coated on coat, finally carries out secondary roll-in, and double-layer structure anode pole piece is made.
Preferably, the coating surface density of first coat is 15~56mg/cm2, such as 18mg/cm2、25mg/cm2、 30mg/cm2、40mg/cm2、42mg/cm2、45mg/cm2Deng.
Preferably, the coating surface density of second coat is 15~56mg/cm2, such as 18mg/cm2、20mg/cm2、 25mg/cm2、30mg/cm2、40mg/cm2、42mg/cm2Deng.
Preferably, after a roll-in the first coat with a thickness of 40~125 μm, such as 49 μm, 69 μm, 78 μm, 80 μm, 83 μm, 87 μm, 89 μm, 115 μm, 121 μm etc..
Preferably, after the secondary roll-in the second coat with a thickness of 60~165 μm, such as 60 μm, 61 μm, 83 μm, 88 μm, 91 μm, 100 μm, 102 μm, 119 μm, 133 μm, 139 μm, 140 μm etc..
As optimal technical scheme, the preparation method of double-layer structure anode pole piece of the present invention, the preparation method packet Include following steps:
(1) in mass ratio it is that 95~98:1~2.5:1~2.5 is mixed by nickel cobalt lithium aluminate, carbon black and Kynoar, obtains To mixture, with N-Methyl pyrrolidone in mass ratio it is that 1.5~4:1 is mixed by the mixture, is prepared into electrode slurry Material；
(2) according to scheduled porosity, by the electrode slurry collector both side surface coating surface density be 15~ 56mg/cm2The first coat, to the first coat carry out a roll-in, the first coat is after roll-in with a thickness of 40~125 μ M, it is 15~56mg/cm that surface density is then coated on the first coat by the electrode slurry after roll-in2Second coating Layer, finally carries out secondary roll-in, and double-layer structure anode pole piece is made with a thickness of 60~165 μm in the second coat after roll-in.
The three of the object of the invention are to provide a kind of purposes of double-layer structure anode pole piece as described in the first purpose, the anode Pole piece is applied to field of batteries, is preferred for lithium ion cell positive.
The four of the object of the invention are to provide a kind of lithium ion battery, and the lithium ion battery includes double described in the first purpose Layer structure anode pole piece.
Preferably, one of for the purpose of the lithium ion anode pole piece described in double-layer structure anode pole piece.
Compared with prior art, the invention has the following beneficial effects:
(1) present invention increases containing for positive active material using by the way of collector two sides setting positive-active unit Amount, improves the gram volume and energy density of anode pole piece.
(2) in further preferred technical solution, the present invention is gradually risen using porosity in positive-active unit The double-deck pore structure, the i.e. porosity of the porosity > first electrode material layer of second electrode material layer, and then improve anode The wellability of electrolyte, the utilization rate of the effective diffusion cofficient of lithium ion and positive electrode, improve the electrification of battery in material Learn performance.Pore structure of the present invention may insure that lithium concentration will not fall sharply in the electrolyte on the inside of collector, in turn Anode pole piece of the present invention can carry out electro-chemical test (0.5C) under biggish current density, and chemical property is good, Under 0.5C current density, gram volume >=170mAh/g of positive-active unit, energy density >=250Wh/kg of battery.
Detailed description of the invention
Fig. 1 is the double-layer structure anode pole piece structural schematic diagram that the specific embodiment of the invention 1 is prepared.
Specific embodiment
Of the invention for ease of understanding, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation Example is only to aid in the understanding present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
A kind of preparation method of double-layer structure anode pole piece includes the following steps:
(1) in mass ratio it is that 97:1:2 is mixed by nickel cobalt lithium aluminate, carbon black, Kynoar, mixture is made, then will Mixture is that 3:1 is mixed according to mass ratio with N-Methyl pyrrolidone, is prepared into electrode slurry；
It (2) is 30mg/cm in collector both side surface coating surface density by the electrode slurry2The first coat, it is right First coat carry out a roll-in, the first coat with a thickness of 83 μm, then by the electrode slurry after roll-in first It is 30mg/cm that surface density is coated on coat2The second coat, finally carry out secondary roll-in, the second coating thickness is 102 μ M, the porosity that first electrode material layer is made is 18.0%, the double-layer structure that the porosity of second electrode material layer is 33.0% Anode pole piece.
Embodiment 2
The difference from embodiment 1 is that the surface density of the first coat is 30mg/cm in step (2)2, the first coat With a thickness of 80 μm, the porosity that first electrode material layer in double-layer structure anode pole piece is made is 15%.
Embodiment 3
The difference from embodiment 1 is that the surface density of the first coat is 30mg/cm in step (2)2, the first coat With a thickness of 87 μm, the porosity that first electrode material layer in double-layer structure anode pole piece is made is 22%.
Embodiment 4
The difference from embodiment 1 is that the surface density of the first coat is 30mg/cm in step (2)2, the first coat With a thickness of 78 μm, the porosity that first electrode material layer in double-layer structure anode pole piece is made is 14%.
Embodiment 5
The difference from embodiment 1 is that the surface density of the first coat is 30mg/cm in step (2)2, the first coat With a thickness of 89 μm, the porosity that first electrode material layer in double-layer structure anode pole piece is made is 23%.
Embodiment 6
The difference from embodiment 1 is that the surface density of the second coat is 30mg/cm in step (2)2, the second coat With a thickness of 91 μm, the porosity that second electrode material layer in double-layer structure anode pole piece is made is 25%.
Embodiment 7
The difference from embodiment 1 is that the surface density of the second coat is 30mg/cm in step (2)2, the second coat With a thickness of 136 μm, the porosity that second electrode material layer in double-layer structure anode pole piece is made is 50%.
Embodiment 8
The difference from embodiment 1 is that the surface density of the second coat is 30mg/cm in step (2)2, the second coat With a thickness of 88 μm, the porosity that second electrode material layer in double-layer structure anode pole piece is made is 24%.
Embodiment 9
The difference from embodiment 1 is that the surface density of the second coat is 30mg/cm in step (2)2, the second coat With a thickness of 139 μm, the porosity that second electrode material layer in double-layer structure anode pole piece is made is 51%.
Embodiment 10
A kind of preparation method of double-layer structure anode pole piece includes the following steps:
(1) in mass ratio it is that 95:2.5:2.5 is mixed by nickel cobalt lithium aluminate, Ketjen black and Kynoar, is mixed The mixture with N-Methyl pyrrolidone is that 1.5:1 is mixed, is prepared into electrode slurry by object in mass ratio；
(2) according to scheduled porosity, it is 15mg/ that the electrode slurry, which is coated surface density in collector both side surface, cm2The first coat, to the first coat carry out a roll-in, the first overlay is after roll-in with a thickness of 43 μm, then by institute Stating electrode slurry and coating surface density on the first coat after roll-in is 35mg/cm2The second coat, finally carry out secondary Roll-in, the second overlay is after roll-in with a thickness of 122 μm, and the porosity that first electrode material layer is made is 18.0%, second electrode The double-layer structure anode pole piece that the porosity of material layer is 33.0%.
Embodiment 11
A kind of preparation method of double-layer structure anode pole piece includes the following steps:
(1) in mass ratio it is that 98:1:1 is mixed by nickel cobalt lithium aluminate, electrically conductive graphite and Kynoar, obtains mixture, With N-Methyl pyrrolidone in mass ratio it is that 4:1 is mixed by the mixture, is prepared into electrode slurry；
(2) according to scheduled porosity, it is 42mg/ that the electrode slurry, which is coated surface density in collector both side surface, cm2The first coat, to the first coat carry out a roll-in, the first overlay is after roll-in with a thickness of 115 μm, then by institute Stating electrode slurry and coating surface density on the first coat after roll-in is 18mg/cm2The second coat, finally carry out secondary Roll-in, the second overlay is after roll-in with a thickness of 61 μm, and the porosity that first electrode material layer is made is 18.0%, second electrode material The double-layer structure anode pole piece that the porosity of the bed of material is 33.0%.
Comparative example 1
The difference from embodiment 1 is that being not coated by the second coat in step (2).
Comparative example 2
It is comparative example with embodiment 1 in CN101635344, preparation method includes the following steps:
(1) by positive active material nickel cobalt lithium aluminate, conductive agent Super-P, binder PVDF according to weight ratio 96.0: 2.0:2.0 is added in a certain amount of solvent NMP, is mixed and stirred for uniformly, adjusting in whipping process by increasing the dosage of NMP Slurry A is coated on the two sides of aluminium foil 13 to obtain positive coating sizing-agent A by the viscosity of mixture, forms thicker diaphragm Layer, and paillon is cold-pressed.
(2) by positive active material LiCoO2, conductive agent Super-P, binder PVDF is according to weight ratio 96.0:2.0: 2.0 are added in a certain amount of solvent NMP, are mixed and stirred for uniformly, adjust mixing by increasing the dosage of NMP in whipping process Slurry B is coated on membrane layer 11 by the viscosity of object to obtain positive coating sizing-agent B, forms relatively thin membrane layer 12, is applied It need to guarantee that membrane layer 12 and membrane layer 11 have different inter-layer electrical conductivities when cloth.
(3) the double-coated aluminium foil 13 of above-mentioned process is cold-pressed, slitting, welding, double-layer structure anode pole piece is made.
Performance test:
The double-layer structure anode pole piece being prepared is performed the following performance tests:
(1) preparation of lithium ion battery: using the double-layer structure anode pole piece being prepared as anode, diaphragm is poly- for micropore Propylene diaphragm, electrolyte are the LiPF of 1.0mol/L6, the preparation process of cathode pole piece include: by silicon carbon material, conductive black, Carboxymethyl cellulose, butadiene-styrene rubber and polyacrylic acid are coated in copper foil current collector according to the ratio of 94.5:1:1.5:1.5:1.5 On, it dries and cathode pole piece is made, lithium ion battery is made in load.
(3) it the energy density of battery and the test of positive electrode gram volume: is tested using new prestige 5V/10A type cell tester The chemical property of battery, charge cutoff voltage 4.2V, discharge cut-off voltage 2.75V, test battery 0.1C, 0.2C, Capacity and energy under 0.5C charging and discharging currents density, positive electrode gram volume=capacity/positive-active unit quality, energy Density=energy/battery quality.
Table 1
It can be seen from Table 1 that being all respectively provided with two-layer electrode material layer using in collector two sides in embodiment 1~11 Anode pole piece, and the anode pole piece has the double-deck pore structure that gradually rises of porosity, i.e. second electrode material layer The porosity of porosity > first electrode material layer, the anode pole piece has good chemical property, close in 0.5C electric current Chemical property under degree, positive electrode gram volume >=170mAh/g, energy density >=250Wh/kg.
It can be seen from Table 1 that embodiment 4, relative to embodiment 1, anode under the conditions of 0.1C, 0.2C and 0.5C is living Property unit gram volume and energy density it is lower, it may be possible to because embodiment 4 in first electrode material layer porosity it is too low, in turn The practical gram volume played of positive electrode and energy are lower in first electrode material layer, thus anode pole piece obtained 0.1C, Positive electrode gram volume and energy density under the conditions of 0.2C and 0.5C is lower.
It can be seen from Table 1 that embodiment 5, relative to embodiment 1, anode under the conditions of 0.1C, 0.2C and 0.5C is living Property unit gram volume and energy density it is lower, it may be possible to because embodiment 5 in first electrode material layer porosity it is excessively high, in turn The thickness of first electrode material layer is larger, causes lithium ion kinetics of diffusion limited, and positive material utilization ratio is lower, so being made Positive-active unit gram volume and energy density of the anode pole piece under the conditions of 0.1C, 0.2C and 0.5C it is lower.
It can be seen from Table 1 that embodiment 8, relative to embodiment 1, anode under the conditions of 0.1C, 0.2C and 0.5C is living Property unit gram volume and energy density it is lower, it may be possible to because embodiment 8 in second electrode material layer porosity it is too low, in turn The practical gram volume played of positive electrode and energy are lower in first electrode material layer and second electrode material layer, so obtained Positive electrode gram volume and energy density of the anode pole piece under the conditions of 0.1C, 0.2C and 0.5C are lower.
It can be seen from Table 1 that embodiment 9, relative to embodiment 1, anode under the conditions of 0.1C, 0.2C and 0.5C is living Property unit gram volume and energy density it is lower, it may be possible to because embodiment 9 in second electrode material layer porosity it is excessively high, in turn The thickness of second electrode material layer is larger, causes lithium ion kinetics of diffusion limited, and positive material utilization ratio is lower, so being made Positive-active unit gram volume and energy density of the anode pole piece under the conditions of 0.1C, 0.2C and 0.5C it is lower.
It can be seen from Table 1 that comparative example 1, relative to embodiment 1, positive-active unit energy under the conditions of 0.5C is close It spends lower, it may be possible to which, because only coating the first coat in collection liquid surface in comparative example 1, anode pole piece only has first electrode Material layer, so in anode pole piece positive electrode content it is too low, capacity is too low, so anode pole piece obtained is in 0.5C condition Under energy density it is lower.
It can be seen from Table 1 that comparative example 2, relative to embodiment 1, anode under the conditions of 0.1C, 0.2C and 0.5C is living Property unit gram volume and energy density it is lower, it may be possible to because in comparative example 2 in anode pole piece, in two-layer electrode material layer just Pole material is different, and then the compatibility between electrode material layer is poor, while the hole knot that comparative example 2 is arranged without the present invention Structure, and then the wellability of electrolyte is poor, so positive-active of the anode pole piece obtained under the conditions of 0.1C, 0.2C and 0.5C Unit gram volume and energy density 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 double-layer structure anode pole piece, which is characterized in that the anode pole piece includes collector and is respectively arranged at described The positive-active unit of collector two sides；
The positive-active unit includes the first electrode material layer set gradually in the collector side and second electrode material The bed of material.
2. double-layer structure anode pole piece as described in claim 1, which is characterized in that the porosity of the first electrode material layer Less than the porosity of second electrode material layer；
Preferably, the porosity of the first electrode material layer is 15%~22%；
Preferably, the porosity of the second electrode material layer is 25%~50%.
3. double-layer structure anode pole piece as claimed in claim 1 or 2, which is characterized in that the thickness of the first electrode material layer Degree is 40~125 μm；
Preferably, the second electrode material layer with a thickness of 60~165 μm.
4. the double-layer structure anode pole piece as described in one of claim 1-3, which is characterized in that the face of the positive-active unit Density is 50~80mg/cm2；
Preferably, the surface density of the first electrode material layer is 15~56mg/cm2；
Preferably, the surface density of the second electrode material layer is 15~56mg/cm2；
Preferably, the collector is aluminium foil, and preferred thickness is 7~25 μm；
Preferably, the content of first electrode material layer is 30wt%~70wt% in the positive-active unit；
Preferably, first electrode material layer is identical with the composition of second electrode material layer in the positive-active unit, it is described just The composition of pole activity unit by mass percentage, including following components:
Positive electrode 95%~98%
Conductive agent 1%~2.5%
Binder 1%~2.5%；
The sum of described material layer each component mass percent is calculated as 100%.
5. a kind of preparation method of the double-layer structure anode pole piece as described in one of claim 1-4, which is characterized in that the preparation Method includes the following steps:
(1) positive electrode, conductive agent and binder are mixed, mixture is made, the mixture and solvent are mixed to get electricity Pole slurry；
(2) according to scheduled porosity, the electrode slurry is successively coated into the first coat and second in collector two sides and is applied Coating obtains double-layer structure anode pole piece.
6. preparation method as claimed in claim 5, which is characterized in that positive electrode, conductive agent in step (1) described mixture Mass ratio with binder is 95~98:1~2.5:1~2.5；
Preferably, the mass ratio of mixture and solvent is 1.5~4:1 in the electrode slurry；
Preferably, the positive electrode includes cobalt acid lithium, nickle cobalt lithium manganate, LiMn2O4, nickel ion doped, nickel cobalt lithium aluminate, phosphoric acid Any one in iron lithium or rich lithium manganese；
Preferably, the conductive agent includes any one in carbon black, Ketjen black, carbon nanotube and electrically conductive graphite or at least two Combination；
Preferably, the binder is Kynoar；
Preferably, the solvent is N-Methyl pyrrolidone.
7. such as preparation method described in claim 5 or 6, which is characterized in that the process of step (2) described coating includes: by institute It states electrode slurry and the first coat is respectively coated in collector both side surface, a roll-in is carried out to the first coat, then will The electrode slurry coats the second coat on the first coat after roll-in, finally carries out secondary roll-in, and the double-deck knot is made Structure anode pole piece；
Preferably, the coating surface density of first coat is 15~56mg/cm2；
Preferably, the coating surface density of second coat is 15~56mg/cm2；
Preferably, after a roll-in the first coat with a thickness of 40~125 μm；
Preferably, after the secondary roll-in the second coat with a thickness of 60~165 μm.
8. the preparation method of double-layer structure anode pole piece as described in one of claim 5-7, which is characterized in that the preparation method Include the following steps:
(1) in mass ratio it is that 95~98:1~2.5:1~2.5 is mixed by nickel cobalt lithium aluminate, carbon black and Kynoar, is mixed Object is closed, with N-Methyl pyrrolidone is in mass ratio that 1.5~4:1 is mixed by the mixture, is prepared into electrode slurry；
(2) according to scheduled porosity, it is 15~56mg/cm that the electrode slurry, which is coated surface density in collector both side surface,2 The first coat, to the first coat carry out a roll-in, after roll-in the first coat with a thickness of 40~125 μm, then will The electrode slurry coats surface density on the first coat after roll-in be 15~56mg/cm2The second coat, it is most laggard The secondary roll-in of row, double-layer structure anode pole piece is made with a thickness of 60~165 μm in the second coat after roll-in.
9. a kind of purposes of the double-layer structure anode pole piece as described in one of claim 1-4, which is characterized in that the anode pole piece Applied to field of batteries, it is preferred for lithium ion cell positive.
10. a kind of lithium ion battery, which is characterized in that the lithium ion battery includes bilayer described in one of claim 1-4 Structure anode pole piece；
Preferably, the lithium ion anode pole piece is double-layer structure anode pole piece described in one of claim 1-4.
CN201811450509.0A 2018-11-30 2018-11-30 A kind of double-layer structure anode pole piece, and its preparation method and application Pending CN109560249A (en)

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CN110492102A (en) * 2019-08-19 2019-11-22 珠海冠宇电池有限公司 A kind of electrodes of lithium-ion batteries and preparation method thereof and lithium ion battery
CN112542571A (en) * 2019-09-23 2021-03-23 珠海冠宇电池股份有限公司 Novel lithium ion battery positive pole piece and preparation method and application thereof
CN112652734A (en) * 2019-10-11 2021-04-13 广州汽车集团股份有限公司 Thick negative pole piece and preparation method thereof, lithium ion battery cell, lithium ion battery pack and application thereof
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CN111682162A (en) * 2020-05-25 2020-09-18 惠州亿纬创能电池有限公司 Battery pole piece and preparation method thereof
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CN112687887A (en) * 2020-12-29 2021-04-20 长沙迅洋新材料科技有限公司 Magnesium metal air battery anode catalyst and continuous coating preparation method thereof
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WO2023133881A1 (en) * 2022-01-17 2023-07-20 宁德时代新能源科技股份有限公司 Positive electrode sheet, secondary battery, battery module, battery pack, and electrical device
CN115394954A (en) * 2022-10-08 2022-11-25 厦门海辰储能科技股份有限公司 Electrode sheet and electrochemical device
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