CN106803593A - A kind of complex function conductive coating and preparation method thereof - Google Patents

A kind of complex function conductive coating and preparation method thereof Download PDF

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Publication number
CN106803593A
CN106803593A CN201710014984.2A CN201710014984A CN106803593A CN 106803593 A CN106803593 A CN 106803593A CN 201710014984 A CN201710014984 A CN 201710014984A CN 106803593 A CN106803593 A CN 106803593A
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conductive
mass ratio
lithium
conductive paste
additive
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CN106803593B (en
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叶和光
黄尚龙
林洪辉
严德荣
颜军
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Zhejiang Ruixin Thin Material Co Ltd
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Zhejiang Ruixin Thin Material Co Ltd
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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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • 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
    • H01M10/058—Construction or manufacture
    • H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
    • 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
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
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Abstract

The invention provides a kind of complex function conductive coating, including collector and functional coating two parts, by being formed after the coated drying of conductive paste, conductive paste is made up of described functional coating conductive agent, bonding agent, additive A, additive B, surfactant and solvent.The complex function conductive coating can cause active material to be drastically reduced with the contact impedance of collector while protecting collector not by the free acid corrosion failure in electrolyte, the electrical property lifting advantage thus brought is clearly.

Description

A kind of complex function conductive coating and preparation method thereof
Technical field
The present invention relates to energy storage material technical field, more particularly to lithium rechargeable battery, capacitor and ultracapacitor Technical field, especially with regard to a kind of complex function conductive coating.
Background technology
Lithium ion battery is mainly made up of positive pole, negative pole, barrier film, the part of electrolyte four, with operating voltage is high, specific energy It is high, have extended cycle life and the advantages of environmental protection, rapid development has been obtained in recent years, especially as the core of new-energy automobile The power lithium-ion battery market of one of heart parts is even more the growth for showing explosion type.Power lithium-ion battery was being used High current, high-power discharge and recharge are needed in journey, so as to the chemical property to battery each side proposes requirement higher.
For battery, the internal resistance of cell is the key factor for restricting battery charging and discharging high rate performance, and internal resistance is bigger, battery times Rate performance is poorer, is polarized during battery high rate charge-discharge also bigger, and battery-heating is serious, and battery performance drastically deteriorates.For The reduction internal resistance of cell, mainly has the method to have：The conductive capability of positive and negative electrode active material is improved, increases conductive agent consumption, increased Conveyance capacity of the conductive components such as collector, lug etc..But, the above method has in various degree to the specific energy of battery Negative effect, it is not notable to the reduction of internal resistance of cell effect.Such as, the excessive addition of conductive agent can not substantially reduce electricity Pond internal resistance, reduces the energy density of battery on the contrary.
Found by studying, the contact internal resistance between positive and negative electrode active material and collector is each to the internal resistance of cell and battery The performance of aspect performance has significant impact.In order to reduce the contact internal resistance between active material and collector, different manufacturers are opened Different conductive coatings are have issued to improve electric conductivity between the two.
China Patent Publication No. CN1427497A is disclosed and a kind of is prepared from conductive agent, bonding agent and organic solvent Organic system conductive coating, it is adaptable to which positive and negative electrode is all the lithium ion battery of organic solvent system.Publication number CN105406083A is public The conductive coating of a kind of compatible organic system being prepared from conductive agent, bonding agent and additive and water system is driven.Publication No. WO2012151880A1 discloses a kind of dilute conductive coating technology of graphite.The patent of Publication No. CN201450056U discloses one Plant the conductive composite coating technology that conductive coating is coated on corrosive aluminum foil.
The conductive coating technology being related in above patent has necessarily to reducing active material with the contact impedance of collector Effect, but the price expensive materials such as CNT, graphite is dilute are employed in its conductive agent mostly, cause production cost high, CNT and the dilute dispersion difficulty of graphite are big, and the easy reunion of characteristic of material high-ratio surface causes slurry free settling, and influence is applied Cloth effect even results in product failure.Conductive coating unitary function and high to the required precision of equipment when preparing conductive coating, if It is standby to be required for dependence on import etc. greatly.Current most domestic conductive coating product market is substantially Japanese, Germany, the ridge such as U.S. Disconnected, the practical domestic conductive coating product of domestic actual real input is less.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of new complex function conductive coating, and the complex function is led Electrocoat can cause that active material is drastically reduced with the contact impedance of collector while protecting collector not by electrolyte Free acid corrosion failure, the electrical property lifting advantage thus brought is clearly.
To realize goal of the invention, the present invention takes following technical scheme：
A kind of complex function conductive coating, including collector and functional coating two parts, described functional coating is by conduction Formed after starching coated drying, conductive paste is by conductive agent, bonding agent, additive A, additive B, surfactant and solvent group Into.
Preferably, described collector includes one or more foils being composited in aluminium foil, Copper Foil, steel foil, 5~20 microns of foil thickness.
Preferably, described collection liquid surface carries out corresponding surface treatment includes but is not limited to pickling, alkali cleaning, infrared Heat treatment, ultraviolet irradiation, plasma impact are shocked by electricity.
Preferably, the mass ratio that conductive agent accounts for conductive paste in described conductive paste is 0.1%~10%, bonding agent is accounted for leads The mass ratio of plasma-based is 0.5%~10%, and the mass ratio that additive A accounts for conductive paste is 0.1%~20%, additive B accounts for conduction The mass ratio of slurry is that the mass ratio that 0.01%~5%, surfactant accounts for conductive paste is 0.001%~5%, and solvent accounts for conductive paste Mass ratio be 50%~99%.
Further, the mass ratio that conductive agent accounts for conductive paste in described conductive paste is 2%~5%, and bonding agent is accounted for leads The mass ratio of plasma-based is 2%~6%, and the mass ratio that additive A accounts for conductive paste is the matter that 5%~10%, additive B accounts for conductive paste Amount is 0.01%~0.1% than accounting for the mass ratio of conductive paste for 0.05%~0.2%, surfactant, and solvent accounts for conductive paste Mass ratio is 60%~90%.
Preferably, the conductive agent is the one kind or several in acetylene black, conductive black, electrically conductive graphite, flaky graphite Plant combination.
Preferably, the bonding agent is Kynoar, polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose, styrene and fourth In diene copolymers, acrylonitrile multiple copolymer, acrylonitrile and butadiene copolymer, vinyl acetate co-polymer, polyurethane One or more combination.
Preferably, the additive A be cobalt acid lithium, LiMn2O4, nickle cobalt lithium manganate, nickel cobalt lithium aluminate, LiFePO 4, Cobalt phosphate lithium, phosphoric acid vanadium lithium, iron manganese phosphate for lithium, nickel manganese/nickel cobalt/cobalt manganese binary material, spinel nickel LiMn2O4, lithium-rich nickel It is LiMn2O4, lithium titanate, lithium metal, lithium sulphur compound, native graphite, Delanium, graphitized intermediate-phase carbosphere (MCMB), soft One or more in carbon, hard carbon, silicon-base alloy, silicon-base oxide, kamash alloy, tin-based oxide, particle size is between 50 Nanometer is to 2 microns.
Preferably, mixture of the additive B for nano-scale lithium carbonate or lithium hydroxide or both.
Preferably, the surfactant is sodium n-alkylbenzenesulfonate (LAS), AEO sulfuric acid Sodium, AESA, sldium lauryl sulfate, Nonyl pheno (10) ether, diglycollic amide (6501) Glycerol stearate monoesters, lignosulfonates, heavy alkylbenzene sulfonate, alkylsulfonate (petroleum sulfonate), alkyl, polyether One or more mixing in (PO-EO copolymers), aliphatic alcohol polyethenoxy (3) ether.
Preferably, the solvent is 1-METHYLPYRROLIDONE or deionized water.
The invention further relates to a kind of preparation method of described conductive composite coating, following technological means is taken：
A kind of preparation method of conductive composite coating, including conductive agent, bonding agent, additive A and additive B are dissolved in molten High speed emulsion dispersion is carried out with emulsification refiner in agent, being subsequently adding surfactant carries out stirring at low speed, vacuumizes except brewed Conductive paste is obtained, gained conductive paste is directly applied on a current collector using coating method.
Preferably, described coating method is selected from dip coated, intaglio printing, nick version printing, spraying coating, curtain coating Coating, transfer coated or extruding one or many coating are formed.
Complex function conductive coating of the invention fills up activity on a current collector by the way that conductive agent and active material are coated Room between material grainses and collector, between active material particle so that by traditional between active material and collector Point contact becomes face contact.This creative surface treatment mode causes lithium-ion electric negative or positive electrode active material and afflux The contact impedance of body is drastically reduced, and the electrical property advantage thus brought is abnormal substantially.
The electrocondution slurry that conductive composite coating of the invention is used, is prepared by adding additive A and surfactant Stability, the superior electrocondution slurry of dispersiveness, be conducive to electrocondution slurry to even application on a current collector, optimize coating Configuration of surface, the problems such as advantageously account for dew paper tinsel in coating process, cut and crawling.
The electrocondution slurry that conductive composite coating of the invention is used, the resistance to of collector is improved by adding additive B Corrosive power, protection collector reduces self-discharge of battery so as to extend battery cycle life, lifts battery performance.
Complex function conductive coating of the invention, with following particularly pertinent advantage：
1st, electrocondution slurry stability is improve, is easy to being smoothed out for coating.
2nd, dew paper tinsel, the cut in coating process and the risk not applied are solved
3rd, the corrosion resistance of collector is improved, the self discharge that battery cycle life reduces battery is extended.
4th, the interracial contact impedance of collector and negative or positive electrode active material is greatly reduced.
The conductive composite coating is used to prepare electrode plates, the composite guide electropaining can be uniformly coated on a current collector Layer, being reached by way of contact of the active material with collector forms face contact by a contact rolling up contact point reduces Contact internal resistance between the two, improves collector corrosion resistance, so as to improve its electric conductivity.
Specific embodiment
Embodiments of the invention are elaborated below, the present embodiment is carried out under premised on technical solution of the present invention Implement, give detailed implementation method and specific operating process, but protection scope of the present invention is not limited to following implementations Example.
Implement 1
Collection liquid surface treatment：It is clear after 15 microns of aluminium foil is surface-treated with 0.1mol/L NaOH aqueous slkalis Wash, drying for standby.
Prepare conductive paste：With flaky graphite (particle size is between 50 nanometers to 2 microns) as additive A, account for and entirely lead The mass ratio of plasma-based material is 5%.With acetylene black as conductive agent, the mass ratio for accounting for whole electrocondution slurry is 2%.To gather inclined difluoro Ethene (PVDF) is bonding agent, and the mass ratio for accounting for whole electrocondution slurry is 2%.With lithium carbonate as additive B, whole conductive paste is accounted for The mass ratio of material is 0.2%.Above-mentioned substance is dissolved in N, (whole electrocondution slurry is accounted in N- dimethyl pyrrolidones (NMP) solution Mass ratio for 90.79%) with emulsification refiner high speed emulsion dispersion 30 minutes.Then 0.01%wt surfaces are added in mass ratio Activating agent dimethicone, stirring at low speed vacuumizes de-bubble and conductive paste is obtained after 30 minutes.By the conduction that solid content is 9.21% The mode of slurry intaglio printing is directly coated in the function that formation thickness after being dried on above-mentioned surface treated aluminium foil is 2 microns and leads Electrocoat.
Prepare positive and negative plate：By the LiFePO 4 that mass ratio is 94%, mass ratio is 4% carbon black, and mass ratio is 4% polyvinylidene fluoride is dissolved in N, is well mixed in N- dimethyl pyrrolidones (NMP) and is made anode sizing agent.By anode sizing agent It is coated uniformly on the aluminium foil containing functional conductive coating, positive plate is made after overbaking, rolling, cutting.The preparation of negative plate Method is：By the native graphite that mass ratio is 93%, mass ratio is 0.5% carbon black, and mass ratio is 2% carboxymethylcellulose calcium Sodium and mass ratio are that 4.5% SBR emulsion (SBR) is dissolved in being well mixed in deionized water and is made cathode size.By negative pole Slurry is coated uniformly on 10 microns of Copper Foils of thickness, and negative plate is made after overbaking, rolling, cutting.
Prepare lithium ion battery：By the above-mentioned positive plate containing functional conductive coating, 15 microns thick three-layer membranes, negative plate according to Battery Pole Core is obtained by winding after secondary superposition.Pole piece is fitted into aluminum hull, injection 1mol/L lithium hexafluoro phosphates are lithium salts, with matter Amount is than being ethylene carbonate (EC)：Methyl ethyl carbonate (EMC)：Dimethyl carbonate (DMC)=1：1：The electrolyte of 1 mixed solvent In, by lithium ion battery is obtained after chemical conversion, partial volume.
Performance test：Take the positive plate resistivity of four probe test pole pieces of 10*10mm.The lithium-ion electric that will be prepared After pond 1C is fully charged, 60 degree of the high temperature test self-discharge performance of storage 30 days is carried out.Carrying out 60 degree of 1C of high temperature accelerates cycle life to survey Examination.
Flaky graphite in embodiment 1 can use cobalt acid lithium, LiMn2O4, nickle cobalt lithium manganate, nickel cobalt lithium aluminate, ferrous phosphate Lithium, cobalt phosphate lithium, phosphoric acid vanadium lithium, iron manganese phosphate for lithium, nickel manganese/nickel cobalt/cobalt manganese binary material, spinel nickel LiMn2O4, rich lithium layer It is shape nickel ion doped, lithium titanate, lithium metal, lithium sulphur compound, Delanium, graphitized intermediate-phase carbosphere (MCMB), soft carbon, hard One or more replacement in carbon, silicon-base alloy, silicon-base oxide, kamash alloy, tin-based oxide, can obtain similar effect Really；Polyvinylidene fluoride can be polynary with polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose, styrene and butadiene copolymer, acrylonitrile One or more replacement in copolymer, acrylonitrile and butadiene copolymer, vinyl acetate co-polymer, polyurethane；Dimethyl Silicone oil can with sodium n-alkylbenzenesulfonate (LAS), sodium sulfate of polyethenoxy ether of fatty alcohol, AESA, Sldium lauryl sulfate, Nonyl pheno (10) ether, diglycollic amide (6501) glycerol stearate monoesters, lignin sulfonic acid Salt, heavy alkylbenzene sulfonate, alkylsulfonate (petroleum sulfonate), alkyl, polyether (PO-EO copolymers), aliphatic alcohol polyethenoxy (3) one or more mixing in ether replace；Acetylene black can with the one kind in conductive black, electrically conductive graphite, flaky graphite or Several combinations replace.
Implement 2
Collection liquid surface treatment：By the infrared heat treatment of the aluminium foil surface of 12 microns of thickness, 200 degree of heat treatment temperature, auxiliary Dry gas remove volatile matter after it is standby.
Prepare conductive paste：With nanoscale LiMn2O4 as additive A, the mass ratio for accounting for whole electrocondution slurry is 10%.With carbon It is black as conductive agent, the mass ratio for accounting for whole electrocondution slurry is 5%.With butadiene-styrene rubber (SBR) as bonding agent, whole conductive paste is accounted for The mass ratio of material is 6%.With lithium hydroxide as additive B, the mass ratio for accounting for whole electrocondution slurry is 0.05%.By above-mentioned substance It is dissolved in the middle emulsification refiner high speed emulsion dispersion 30 of deionized water solution (mass ratio for accounting for whole electrocondution slurry is 78.95%) Minute.Then 0.1%wt surfactant sodium dodecyl base benzene sulfonic acid sodium salts are added in mass ratio, and stirring at low speed is vacuumized after 30 minutes De-bubble is obtained conductive paste.The mode of the conductive paste nick version printing that solid content is 21.05% is above-mentioned by surface against being coated in The functional conductive coating that thickness is 3 microns is formed after being dried on the aluminium foil for the treatment of.
Prepare positive and negative plate：By ternary material nickle cobalt lithium manganate (NCM) that mass ratio is 95.5%, mass ratio is 0.5% CNT and 1% carbon black combined conductive agent, and the polyvinylidene fluoride that mass ratio is 3% is dissolved in N, N- dimethyl pyrrolidines It is well mixed in ketone (NMP) and is made anode sizing agent.Anode sizing agent is coated uniformly on the aluminium foil containing above-mentioned functions conductive coating, Positive plate is made after overbaking, rolling, cutting.The preparation method of negative plate is：By the Delanium that mass ratio is 95%, matter Amount is than the carbon black for 0.5%, the SBR emulsion that mass ratio is 1.5% sodium carboxymethylcellulose and mass ratio is 3% (SBR) it is dissolved in being well mixed in deionized water and is made cathode size.Cathode size is coated uniformly on 10 microns of Copper Foils of thickness, Negative plate is made after overbaking, rolling, cutting.
Prepare lithium ion battery：By the above-mentioned positive plate containing functional conductive coating, 15 microns thick three-layer membranes, negative plate according to Battery Pole Core is obtained by winding after secondary superposition.Pole piece is fitted into aluminum hull, injection 1mol/L lithium hexafluoro phosphates are lithium salts, with matter Amount is than being ethylene carbonate (EC)：Methyl ethyl carbonate (EMC)：Dimethyl carbonate (DMC)=1：1：The electrolyte of 1 mixed solvent In, by lithium ion battery is obtained after chemical conversion, partial volume.
Performance test：Take the positive plate resistivity of four probe test pole pieces of 10*10mm.The lithium-ion electric that will be prepared After pond 1C is fully charged, 60 degree of the high temperature test self-discharge performance of storage 30 days is carried out.Carrying out 60 degree of 1C of high temperature accelerates cycle life to survey Examination.
Implement 3
Collection liquid surface treatment：Cleaned after 5 microns of aluminium foils of thickness are surface-treated with 0.1mol/L hydrochloric acid solutions, done It is dry standby.
Prepare conductive paste：With nickle cobalt lithium manganate and hard carbon as additive A, the mass ratio for accounting for whole electrocondution slurry is 20%. With conductive black as conductive agent, the mass ratio for accounting for whole electrocondution slurry is 10%.With acrylonitrile multiple copolymer as bonding agent, The mass ratio for accounting for whole electrocondution slurry is 10%.With nanoscale lithium hydroxide as additive B, the mass ratio of whole electrocondution slurry is accounted for It is 5%.Above-mentioned substance is dissolved in deionized water and emulsifies refiner at a high speed with (mass ratio for accounting for whole electrocondution slurry is 50%) Emulsion dispersion 30 minutes.Then 5%wt surfactants aliphatic alcohol polyethenoxy (3) ether, stirring at low speed 30 are added in mass ratio De-bubble is vacuumized after minute conductive paste is obtained.The mode of the conductive paste blade coating that solid content is 50% is coated in above-mentioned by surface The functional conductive coating that thickness is 2 microns is formed after being dried on the aluminium foil for the treatment of.
Prepare positive and negative plate：By the LiFePO 4 that mass ratio is 94%, mass ratio is 4% carbon black, and mass ratio is 4% polyvinylidene fluoride is dissolved in N, is well mixed in N- dimethyl pyrrolidones (NMP) and is made anode sizing agent.By anode sizing agent It is coated uniformly on the aluminium foil containing functional conductive coating, positive plate is made after overbaking, rolling, cutting.The preparation of negative plate Method is：By the native graphite that mass ratio is 93%, mass ratio is 0.5% carbon black, and mass ratio is 2% carboxymethylcellulose calcium Sodium and mass ratio are that 4.5% SBR emulsion (SBR) is dissolved in being well mixed in deionized water and is made cathode size.By negative pole Slurry is coated uniformly on 10 microns of Copper Foils of thickness, and negative plate is made after overbaking, rolling, cutting.
Prepare lithium ion battery：By the above-mentioned positive plate containing functional conductive coating, 5 microns thick three-layer membranes, negative plate according to Battery Pole Core is obtained by winding after secondary superposition.Pole piece is fitted into aluminum hull, injection 1mol/L lithium hexafluoro phosphates are lithium salts, with matter Amount is than being ethylene carbonate (EC)：Methyl ethyl carbonate (EMC)：Dimethyl carbonate (DMC)=1：1：The electrolyte of 1 mixed solvent In, by lithium ion battery is obtained after chemical conversion, partial volume.
Performance test：Take the positive plate resistivity of four probe test pole pieces of 10*10mm.The lithium-ion electric that will be prepared After pond 1C is fully charged, 60 degree of the high temperature test self-discharge performance of storage 30 days is carried out.Carrying out 60 degree of 1C of high temperature accelerates cycle life to survey Examination.
Implement 4
Collection liquid surface treatment：By the infrared heat treatment of the aluminium foil surface of 20 microns of thickness, 200 degree of heat treatment temperature, auxiliary Dry gas remove volatile matter after it is standby.
Prepare conductive paste：With lithium-rich nickel ion doped as additive A, the mass ratio for accounting for whole electrocondution slurry is 0.1%. With carbon black as conductive agent, the mass ratio for accounting for whole electrocondution slurry is 0.3%.With butadiene-styrene rubber (SBR) as bonding agent, account for whole The mass ratio of electrocondution slurry is 0.5%.With lithium hydroxide as additive B, the mass ratio for accounting for whole electrocondution slurry is 0.1%.Will Above-mentioned substance uses emulsification refiner at a high speed in being dissolved in deionized water solution (mass ratio for accounting for whole electrocondution slurry is 98.999%) Emulsion dispersion 30 minutes.Then 0.001%wt surfactant sldium lauryl sulfates, stirring at low speed 30 minutes are added in mass ratio After vacuumize de-bubble be obtained conductive paste.The mode of the conductive paste nick version printing that solid content is 1.001% is above-mentioned against being coated in The functional conductive coating that thickness is 3 microns is formed after being dried on surface treated aluminium foil.
Prepare positive and negative plate：By ternary material nickle cobalt lithium manganate (NCM) that mass ratio is 95.5%, mass ratio is 0.5% CNT and 1% carbon black combined conductive agent, and the polyvinylidene fluoride that mass ratio is 3% is dissolved in N, N- dimethyl pyrrolidines It is well mixed in ketone (NMP) and is made anode sizing agent.Anode sizing agent is coated uniformly on the aluminium foil containing above-mentioned functions conductive coating, Positive plate is made after overbaking, rolling, cutting.The preparation method of negative plate is：By the Delanium that mass ratio is 95%, matter Amount is than the carbon black for 0.5%, the SBR emulsion that mass ratio is 1.5% sodium carboxymethylcellulose and mass ratio is 3% (SBR) it is dissolved in being well mixed in deionized water and is made cathode size.Cathode size is coated uniformly on 10 microns of Copper Foils of thickness, Negative plate is made after overbaking, rolling, cutting.
Prepare lithium ion battery：By the above-mentioned positive plate containing functional conductive coating, 15 microns thick three-layer membranes, negative plate according to Battery Pole Core is obtained by winding after secondary superposition.Pole piece is fitted into aluminum hull, injection 1mol/L lithium hexafluoro phosphates are lithium salts, with matter Amount is than being ethylene carbonate (EC)：Methyl ethyl carbonate (EMC)：Dimethyl carbonate (DMC)=1：1：The electrolyte of 1 mixed solvent In, by lithium ion battery is obtained after chemical conversion, partial volume.
Performance test：Take the positive plate resistivity of four probe test pole pieces of 10*10mm.The lithium-ion electric that will be prepared After pond 1C is fully charged, 60 degree of the high temperature test self-discharge performance of storage 30 days is carried out.Carrying out 60 degree of 1C of high temperature accelerates cycle life to survey Examination.
Comparative example 1
Collection liquid surface treatment：Aluminium foil is not processed.
Prepare conductive paste：Without conductive paste.
Prepare positive and negative plate：Without functional conductive coating.
Prepare lithium ion battery：With embodiment 1.
Performance test：With embodiment 1.
Comparative example 2
Collection liquid surface treatment：With embodiment 1.
Prepare conductive paste：Additive-free A.
Prepare positive and negative plate：With embodiment 1.
Prepare lithium ion battery：With embodiment 1.
Performance test：With embodiment 1.
Comparative example 3
Collection liquid surface treatment：With embodiment 1.
Prepare conductive paste：Additive-free B.
Prepare positive and negative plate：With embodiment 1.
Prepare lithium ion battery：With embodiment 1.
Performance test：With embodiment 1.
Comparative example 4
Collection liquid surface treatment：Aluminium foil is not processed.
Prepare conductive paste：Without conductive paste.
Prepare positive and negative plate：Without functional conductive coating.
Prepare lithium ion battery：With embodiment 2.
Performance test：With embodiment 2.
Comparative example 5
Collection liquid surface treatment：With embodiment 2.
Prepare conductive paste：Additive-free A.
Prepare positive and negative plate：With embodiment 2.
Prepare lithium ion battery：With embodiment 2.
Performance test：With embodiment 2.
Comparative example 6
Collection liquid surface treatment：With embodiment 2.
Prepare conductive paste：Additive-free B.
Prepare positive and negative plate：With embodiment 2.
Prepare lithium ion battery：With embodiment 2.
Performance test：With embodiment 2.
Table 1 is embodiment 1 and embodiment 3 and its comparative example performance test data.
Table 2 is the box embodiment 4 of embodiment 2 and its comparative example performance test data.
Table 1
Table 2

Claims (10)

1. a kind of conductive composite coating, it is characterised in that including collector and functional coating two parts, described functional coating by Formed after the coated drying of conductive paste, conductive paste is by conductive agent, bonding agent, additive A, additive B, surfactant and solvent Composition.
2. a kind of conductive composite coating according to claim 1, it is characterised in that the collector includes aluminium foil, Copper Foil, steel One or more foils being composited in paper tinsel, 5~20 microns of foil thickness.
3. a kind of conductive composite coating according to claim 2, it is characterised in that the collection liquid surface carries out corresponding table Face treatment includes but is not limited to pickling, alkali cleaning, infrared heat treatment, ultraviolet irradiation, plasma impact or shocks by electricity.
4. a kind of conductive composite coating according to claim 1, it is characterised in that conductive agent accounts for conduction in described conductive paste The mass ratio of slurry is 0.1%~10%, and the mass ratio that bonding agent accounts for conductive paste is 0.5%~10%, and additive A accounts for conductive paste Mass ratio is that the mass ratio that 0.1%~20%, additive B accounts for conductive paste is that 0.01%~5%, surfactant accounts for conductive paste Mass ratio is 0.001%~5%, and the mass ratio that solvent accounts for conductive paste is 50%~99%.
5. a kind of conductive composite coating according to claim 4, it is characterised in that conductive agent accounts for conduction in described conductive paste The mass ratio of slurry is 2%~5%, and the mass ratio that bonding agent accounts for conductive paste is 2%~6%, and additive A accounts for the mass ratio of conductive paste For the mass ratio that 5%~10%, additive B accounts for conductive paste is that 0.05%~0.2%, surfactant accounts for the mass ratio of conductive paste It is 0.01%~0.1%, the mass ratio that solvent accounts for conductive paste is 60%~90%.
6. a kind of conductive composite coating according to claim 1, it is characterised in that the additive A be cobalt acid lithium, LiMn2O4, Nickle cobalt lithium manganate, nickel cobalt lithium aluminate, LiFePO 4, cobalt phosphate lithium, phosphoric acid vanadium lithium, iron manganese phosphate for lithium, nickel manganese/nickel cobalt/cobalt manganese Binary material, spinel nickel LiMn2O4, lithium-rich nickel ion doped, lithium titanate, lithium metal, lithium sulphur compound, native graphite, people In making graphite, graphitized intermediate-phase carbosphere, soft carbon, hard carbon, silicon-base alloy, silicon-base oxide, kamash alloy, tin-based oxide One or more, its particle size is between 50 nanometers to 2 microns；The additive B is nano-scale lithium carbonate or lithium hydroxide In one or two mixing.
7. a kind of conductive composite coating according to claim 1, it is characterised in that the surfactant is linear alkylbenzene (LAB) Sodium sulfonate, sodium sulfate of polyethenoxy ether of fatty alcohol, AESA, sldium lauryl sulfate, polyoxyethylene nonyl phenyl Ethene (10) ether, diglycollic amide glycerol stearate monoesters, lignosulfonates, heavy alkylbenzene sulfonate, alkylsulfonate (stone Oily sulfonate), alkyl, polyether, aliphatic alcohol polyethenoxy (3) ether, one or more mixing in dimethicone.
8. a kind of conductive composite coating according to claim 1, it is characterised in that described bonding agent be polyvinylidene fluoride, Polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose, styrene and butadiene copolymer, acrylonitrile multiple copolymer, acrylonitrile and fourth two One or more combination in alkene copolymer, vinyl acetate co-polymer, polyurethane；Conductive agent is acetylene black, conductive black, leads One or more combination in electro-graphitic, flaky graphite.
9. a kind of conductive composite coating according to claim 1, it is characterised in that described solvent is N- methyl pyrroles Pyrrolidone or deionized water.
10. a kind of preparation method of conductive composite coating, it is characterised in that including by conductive agent, bonding agent, additive A and addition Agent B carries out high speed emulsion dispersion in being dissolved in solvent with emulsification refiner, and being subsequently adding surfactant carries out stirring at low speed, takes out true Empty de-bubble is obtained conductive paste, and gained conductive paste is directly applied on a current collector using coating method.
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CN114361464A (en) * 2021-12-31 2022-04-15 东江环保股份有限公司 Self-repairing conductive coating modified bipolar current collector and preparation method and application thereof
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CN114361464A (en) * 2021-12-31 2022-04-15 东江环保股份有限公司 Self-repairing conductive coating modified bipolar current collector and preparation method and application thereof

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