CN107394109A - A kind of electrode coating method and the electrode made using the coating method - Google Patents

A kind of electrode coating method and the electrode made using the coating method Download PDF

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Publication number
CN107394109A
CN107394109A CN201710597931.8A CN201710597931A CN107394109A CN 107394109 A CN107394109 A CN 107394109A CN 201710597931 A CN201710597931 A CN 201710597931A CN 107394109 A CN107394109 A CN 107394109A
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active
kinds
electrode
slurry
layers
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CN201710597931.8A
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Inventor
黄苗
侯桃丽
张朋军
许永顺
陈校军
蒋新欣
邓昊昆
徐锋
刘金成
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Eve Energy Co Ltd
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Eve Energy Co Ltd
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Priority to CN201710597931.8A priority Critical patent/CN107394109A/en
Publication of CN107394109A publication Critical patent/CN107394109A/en
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/04Processes of manufacture in general
    • H01M4/0402Methods of deposition of the material
    • H01M4/0404Methods of deposition of the material by coating on electrode collectors
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • H01M4/1391Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • H01M4/1393Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • H01M4/1397Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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

Abstract

The electrode made the invention discloses a kind of electrode coating method and using the coating method, belongs to field of new energy technologies.The method of the present invention includes:At least two kinds of active slurries are prepared respectively, then at least two kinds of active slurries are respectively coated on same collector, are dried, and obtain the electrode with least 2 layers active slurry layer.The new electrode coating method of the present invention, can effectively solve the problem that must use different materials simultaneously when carrying out special battery design in the prior art prepares battery, and different materials blending prepares the problem of difficulty is big, and, the method of the present invention is simple, is adapted to industrialized production.

Description

A kind of electrode coating method and the electrode made using the coating method
Technical field
The invention belongs to field of new energy technologies, is related to a kind of electrode coating method and the electricity made using the coating method Pole, more particularly to a kind of electrode for being respectively coated the method for electrode using various active slurry and being made using the coating method.
Background technology
Lithium ion battery is mainly had by positive electrode classification at present, cobalt acid lithium (LCO), LiMn2O4 (LMO), ternary nickel cobalt manganese (NCM), the material system such as binary nickel cobalt (NCA) and LiFePO4 (LFP).Different materials system respectively has its advantage and disadvantage, is shown in Table 1.In order to which synthesis obtains the performance and advantage of two kinds and above material, the mode being usually taken at present is that negative or positive electrode material is mixed Mixed mode.Conventional method is in positive pole dispensing stage, from special formulation, by special stirring technique by two kinds or more material systems Into the slurry of blending.Such as traditional blend method:(1) adhesive and partial solvent mix first, (2) and then by negative electrode active Material and conductive agent are well mixed, and obtain mixed slurry, and the mixture of adhesive and solvent is added to step (2) by (3) again In mixed slurry, mediated, mediate to a certain extent after, by residue dissolving adhesive and remaining solvent be added thereto into Row is last to be dispersed with stirring, and obtains the slurry suitable for coating.
However, various problems in actual applications be present, such as blending slurry bad dispersibility, adhesion strength is poor, if moreover, Two kinds of material physical and chemical performance differences are big, are difficult to control using blending technology slurry dispersiveness and stability so as to cause sinking speed It hurry up, good coated face density can not be ensured.Numerous solutions is using property dispersant, bonding agent, Er Qieyou Need gluing technique and the stirring technique of complexity matching.As a result or it is difficult the blending problem for solving the big material of difference.
Table 1
The content of the invention
For that must use different materials simultaneously when carrying out special battery design in the prior art, and different materials are blended Slurry prepares the problem of difficulty is big, is made the invention provides a kind of new electrode coating method and using the coating method Electrode, above mentioned problem is can effectively solve the problem that, preparation method of the invention is simple, without carrying out matching somebody with somebody for material blending and special process Slurry is closed, is adapted to industrialized production.
For the above-mentioned purpose, the present invention uses following technical scheme:
In a first aspect, the present invention provides a kind of electrode coating method, methods described includes:At least two kinds of activity are prepared respectively Slurry, then at least two kinds of active slurries are respectively coated on same collector, dried, obtain that there are at least 2 layers activity to starch The electrode of the bed of material.
In the present invention, the selection to the species and proportioning of at least two kinds of active slurries is not construed as limiting, and those skilled in the art can Selected as needed, and the surface density of various material coatings can be adjusted as needed." at least two kinds of active slurries " The active slurry (such as LiFePO4 and cobalt acid lithium) of at least two kinds of material systems can be referred to, same material system can also be referred to Under at least two kinds of active materials (such as the different trades mark or different model in same material system, such as LiNi0.8Co0.1Mn0.1O2And LiNi0.85Co0.05Mn0.1O2)。
At least two kinds of active slurries, it can be 2 kinds, 3 kinds, 4 kinds, 5 kinds, 6 kinds or 7 kinds etc. in the present invention.
In the present invention, active slurry on a current collector is coated with, by drying, is changed into active slurry layer.
In the present invention, the species of electrode is not construed as limiting, can be positive pole or negative pole.Correspondingly, the afflux Body can be plus plate current-collecting body or negative current collector;The active slurry can be anode sizing agent or negative pole Slurry, those skilled in the art can be selected as needed, such as, for anode sizing agent film, the collector used for Plus plate current-collecting body, the active slurry used obtain the positive pole of active pulp layer for positive-active slurry;For cathode size Film, for the collector used for negative current collector, the active slurry used obtains active pulp layer for negative electrode active slurry Negative pole.
Preferably, the collector is any one in aluminium foil or copper foil.
Preferably, the active material in the positive-active slurry include cobalt acid lithium, LiMn2O4, nickel-cobalt-manganese ternary material, The material system such as nickel cobalt binary material and LiFePO4, but it is not limited to the above-mentioned positive active material enumerated, other this areas Conventional positive active material can also be used for the present invention.
Preferably, the nickel-cobalt-manganese ternary material includes but is not limited to LiNiXCoYMn1-X-YO2, 0<X<1,0<Y<1, preferably For LiNi0.3Co0.3Mn0.3O2、LiNi0.5Co0.3Mn0.2O2、LiNi0.8Co0.1Mn0.1O2Or LiNi0.85Co0.05Mn0.1O2In appoint Anticipate a kind of or at least two combinations.
Preferably, the nickel cobalt binary material includes but is not limited to LiNiXCo1-XO2, 0<X<1, be preferably LiNi0.8Co0.2O2Or LiNi0.7Co0.3O2In any one or two kinds combination.
Preferably, the active material in the negative electrode active slurry includes Delanium, native graphite, silicon-carbon cathode material With lithium titanate etc., but the above-mentioned negative electrode active material enumerated is not limited to, other negative electrode active materials commonly used in the art also may be used For the present invention.
In the present invention, at least two kinds of active slurries can be respectively coated in the both sides of collector, can also be respectively coated and collected The same side of fluid.
The step of also including coating mixed slurry as the optimal technical scheme of the method for the invention, in methods described, " mixed slurry " refers to the species of the active material included in the slurry two or more, can be under two kinds of material systems 2 kinds of materials under 2 kinds of materials or same material system.
As the optimal technical scheme of the method for the invention, the described method comprises the following steps:
2 kinds of active slurries are prepared respectively, 2 kinds of active slurries are respectively coated to the both sides of same collector, are dried, are obtained To the electrode with 2 layers of active slurry layer.
As another optimal technical scheme of the method for the invention, the described method comprises the following steps:
2 kinds of active slurries are prepared respectively, a kind of active slurry is first respectively coated to the both sides of same collector, are dried, Then another a kind of active slurry is coated with the both sides of the collector with 2 layers of active slurry layer again, dries, obtain that there are 4 layers of activity The electrode of pulp layer.
As the another optimal technical scheme of the method for the invention, the described method comprises the following steps:
3 kinds of active slurries are prepared respectively, a kind of active slurry is first applied to the both sides of same collector, are dried, then Another a kind of active slurry is coated with the both sides of the collector with 2 layers of active slurry layer, is dried, finally with 4 layers of active slurry The both sides of the collector of layer are coated with last a kind of active slurry, dry, and obtain with obtaining the electrode with 6 layers of active slurry layer.
In the present invention, the species and the number of plies of the material of coating are not construed as limiting, those skilled in the art can be as needed Carry out selection coating.
The electrode of the active pulp layer of the present invention is used to prepare the method for lithium ion battery as prior art, this area Technical staff refers to prior art and carries out film-making, winding, assembling, baking, fluid injection, chemical conversion and shaping, and uses normal capacity Method of testing is tested.
Second aspect, the present invention provide the electrode made using the method described in first aspect.
Compared with the prior art, the present invention has the advantages that:
(1) present invention proposes the mode that different materials are separately coated with, without carrying out complicated and big difficulty multiple material body The slurry technique of system.By the adjustment to different materials ratio, the multiple material system electrode that performance is taken into account can be obtained.
(2) present invention proposes the thinking of continuation film on the basis of film, obtains different material coating films, so as to comprehensive Play various material properties.
(3) mode of the two-sided each coating different materials of foil is proposed, equally realizes multiple material system pole piece, it is comprehensive Play the characteristic of various materials.
(4) preparation method of the invention is simple, without carrying out the cooperation slurry of material blending and special process, is adapted to industry Metaplasia is produced.
Brief description of the drawings
Fig. 1 is the structural representation for the product that the step of embodiment 1 (1) obtains.
Fig. 2 is the structural representation for the product that the step of embodiment 1 (2) obtains.
Fig. 3 is the structural representation for the product that the step of embodiment 2 (1) obtains.
Fig. 4 is the structural representation for the product that the step of embodiment 2 (2) obtains.
Fig. 5 is the structural representation for the product that the step of embodiment 3 (3) obtains.
Embodiment
Further illustrate technical scheme below in conjunction with the accompanying drawings and by embodiment.
Embodiment 1
(1) A slurry is coated with the both sides of aluminum foil current collector, is dried, obtains the pole piece with 2 layers of A films (referring to figure 1);
(2) there is the pole piece of 2 layers of A films as carrying object using what step (1) obtained, continues to be coated with B slurries in both sides, do It is dry, obtain the pole piece with 2 layers of A films and 2 layers of B films (referring to Fig. 2).
The product that the present embodiment obtains has 2 kinds of materials (i.e. the feature of A materials and B material), wherein, A is cobalt acid lithium (LCO), B is LiFePO4 (LFP).
Embodiment 2
(1) in the side of aluminum foil current collector (alternatively referred to as one side) coating A slurry, dry, obtain that there is 1 layer of A film Pole piece (referring to Fig. 3);
(2) B slurry is coated with the opposite side (alternatively referred to as another side) of aluminum foil current collector again, obtains that there is 1 layer of A film With the pole piece of 1 layer of B film (referring to Fig. 4).
The product that the present embodiment obtains has 2 kinds of materials (i.e. the feature of A materials and B material), wherein, A is cobalt acid lithium (LCO), B is LiFePO4 (LFP).
Embodiment 3
(1) A slurry is coated with the both sides of aluminum foil current collector, is dried, obtains the pole piece with 2 layers of A films;
(2) there is the pole piece of 2 layers of A films as carrying object using what step (1) obtained, continues to be coated with B slurries in both sides, do It is dry, obtain the pole piece with 2 layers of A films and 2 layers of B films;
(3) there is the pole piece of 2 layers of A films and 2 layers of B films as carrying object using what step (2) obtained, continues to apply in both sides Cloth C slurries, dry, obtain the pole piece with 2 layers of A films, 2 layers of B films and 2 layers of C films (referring to Fig. 5).
The product that the present embodiment obtains has 3 kinds of materials (i.e. the feature of A materials, B material and C-material), wherein, A is cobalt Sour lithium (LCO), B are LiFePO4 (LFP), and C is ternary nickel cobalt manganese (NCM).
Embodiment 4
Except aluminium foil is replaced with into copper foil, and A and B are replaced with outside Delanium and native graphite respectively, other preparation sides Method and condition are same as Example 1.
Embodiment 5
In addition to the A films side for the pole piece that step (2) obtains B slurry coated in step (1), other preparation methods and Condition is same as Example 2.
The A films and B films that the present embodiment obtains are in the same side of collector.
Embodiment 6
Except continuation is using the pole piece with 2 layers of A films, 2 layers of B films and 2 layers of C films that step (3) obtains as carrying object, Outside its both sides coating D slurry, other preparation methods and condition are same as Example 3.
The present embodiment obtains the pole piece with 2 layers of A films, 2 layers of B films, 2 layers of C films and 2 layers of D films, wherein, D is manganese Sour lithium (LMO).
Embodiment 7
In addition to step (3) is only coated with C slurries in side, other preparation methods and condition are same as Example 3.
The present embodiment obtains the pole piece with 2 layers of A films, 2 layers of B films and 1 layer of C film.
Applicant states that the present invention illustrates the method detailed of the present invention, but not office of the invention by above-described embodiment It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implemented.Art Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosing.

Claims (10)

1. a kind of electrode coating method, it is characterised in that methods described includes:At least two kinds of active slurries are prepared respectively, then will At least two kinds of active slurries are respectively coated on same collector, are dried, and obtain the electrode with least 2 layers active slurry layer.
2. according to the method for claim 1, it is characterised in that the electrode is any one in negative or positive electrode.
3. method according to claim 1 or 2, it is characterised in that the collector is plus plate current-collecting body or negative pole currect collecting Any one in body;
Preferably, the collector is any one in aluminium foil or copper foil.
4. according to the method described in claim any one of 1-3, it is characterised in that the active slurry be positive-active slurry or Any one in negative electrode active slurry;
Preferably, the active material in the positive-active slurry includes cobalt acid lithium, LiMn2O4, nickel-cobalt-manganese ternary material, nickel cobalt Any one in binary material or LiFePO4;
Preferably, the nickel-cobalt-manganese ternary material includes LiNiXCoYMn1-X-YO2, 0<X<1,0<Y<1, be preferably LiNi0.3Co0.3Mn0.3O2、LiNi0.5Co0.3Mn0.2O2、LiNi0.8Co0.1Mn0.1O2Or LiNi0.85Co0.05Mn0.1O2In it is any It is a kind of or at least two combination;
Preferably, the nickel cobalt binary material includes LiNiXCo1-XO2, 0<X<1, preferably LiNi0.8Co0.2O2Or LiNi0.7Co0.3O2In any one or two kinds combination.
5. according to the method for claim 4, it is characterised in that the active material in the negative electrode active slurry includes artificial Any one in graphite, native graphite, silicon-carbon cathode material or lithium titanate.
6. according to the method described in claim any one of 1-5, it is characterised in that at least two kinds of active slurries, which are respectively coated, to be collected The both sides of fluid;
Preferably, at least two kinds of active slurries are coated on the same side of collector.
7. according to the method described in claim any one of 1-6, it is characterised in that also include coating mixed slurry in methods described The step of.
8. according to the method described in claim any one of 1-7, it is characterised in that the described method comprises the following steps:
2 kinds of active slurries are prepared respectively, 2 kinds of active slurries are respectively coated to the both sides of same collector, dry, are had There is the electrode of 2 layers of active slurry layer.
9. according to the method described in claim any one of 1-7, it is characterised in that the described method comprises the following steps:
2 kinds of active slurries are prepared respectively, a kind of active slurry is first respectively coated to the both sides of same collector, are dried, then Another a kind of active slurry is coated with the both sides of the collector with 2 layers of active slurry layer again, dries, obtains that there are 4 layers of active slurry The electrode of layer.
10. the method according to right wants any one of 1-7, it is characterised in that the described method comprises the following steps:
3 kinds of active slurries are prepared respectively, a kind of active slurry is first applied to the both sides of same collector, dry, are then having The both sides for having the collector of 2 layers of active slurry layer are coated with another a kind of active slurry, dry, finally with 4 layers of active slurry layer The both sides of collector are coated with last a kind of active slurry, dry, and obtain the electrode with 6 layers of active slurry layer.
CN201710597931.8A 2017-07-20 2017-07-20 A kind of electrode coating method and the electrode made using the coating method Pending CN107394109A (en)

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CN108470636A (en) * 2018-02-07 2018-08-31 宁波中车新能源科技有限公司 A kind of Graphene electrodes piece and preparation method thereof and the method for preparing ultracapacitor with it
CN109301251A (en) * 2018-09-17 2019-02-01 曾文飞 A kind of graphene lithium battery material and preparation method thereof
CN109360938A (en) * 2018-09-11 2019-02-19 天津市捷威动力工业有限公司 A kind of high safety structure lithium battery
CN109411751A (en) * 2018-12-05 2019-03-01 珠海光宇电池有限公司 A kind of lithium ion cell positive and preparation method thereof and the lithium ion battery cell containing the anode

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CN104538584A (en) * 2014-12-03 2015-04-22 惠州市恒泰科技有限公司 Multilayer cathode sheet, method for producing cathode sheet and lithium ion battery
CN104600244A (en) * 2014-12-29 2015-05-06 惠州市恒泰科技有限公司 Multilayer positive plate, production method of positive plate and lithium ion battery

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CN101159324A (en) * 2007-09-17 2008-04-09 东莞新能源电子科技有限公司 Secondary lithium ionic cell and preparation method of cathode pole piece thereof
CN101635344A (en) * 2008-07-24 2010-01-27 东莞新能源科技有限公司 Anode pole piece of secondary lithium ion battery and preparation method thereof
CN102386379A (en) * 2011-10-19 2012-03-21 广州市云通磁电有限公司 Manufacturing method of lithium iron phosphate-cobalt acid lithium composite anode plate of lithium ion battery
CN202996958U (en) * 2012-12-20 2013-06-12 中国东方电气集团有限公司 Asymmetric negative pole piece of lithium ion secondary battery
CN104538584A (en) * 2014-12-03 2015-04-22 惠州市恒泰科技有限公司 Multilayer cathode sheet, method for producing cathode sheet and lithium ion battery
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108470636A (en) * 2018-02-07 2018-08-31 宁波中车新能源科技有限公司 A kind of Graphene electrodes piece and preparation method thereof and the method for preparing ultracapacitor with it
CN109360938A (en) * 2018-09-11 2019-02-19 天津市捷威动力工业有限公司 A kind of high safety structure lithium battery
CN109301251A (en) * 2018-09-17 2019-02-01 曾文飞 A kind of graphene lithium battery material and preparation method thereof
CN109411751A (en) * 2018-12-05 2019-03-01 珠海光宇电池有限公司 A kind of lithium ion cell positive and preparation method thereof and the lithium ion battery cell containing the anode

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Application publication date: 20171124