CN110071293A - Battery core and battery protect liquid coating and battery pole piece and preparation method thereof - Google Patents
Battery core and battery protect liquid coating and battery pole piece and preparation method thereof Download PDFInfo
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- CN110071293A CN110071293A CN201910410982.4A CN201910410982A CN110071293A CN 110071293 A CN110071293 A CN 110071293A CN 201910410982 A CN201910410982 A CN 201910410982A CN 110071293 A CN110071293 A CN 110071293A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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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- 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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- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
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- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to a kind of battery core and battery, protect liquid coating and battery pole piece and preparation method thereof, wherein, battery core, including the first cathode pole piece of two panels, the anode pole piece between the first cathode pole piece of two panels, and the diaphragm between the first cathode pole piece and anode pole piece；First cathode pole piece includes collector, the active material coating on one surface of collector, and guarantor's liquid coating on another surface of collector；And first guarantor's liquid coating on cathode pole piece is far from anode pole piece；It protects in liquid coating containing solution additive is protected, protecting solution additive is at least one of polyvinylidene fluoride polymer, the blend powders of butyronitrile and polyvinyl chloride, polypropylene micro mist and ultra-high molecular weight polyethylene powder selected from linear crystal type.The present invention contains above-mentioned specific guarantor's solution additive due to protecting, can greatly improve guarantor's liquid measure of battery, and will not influence multiplying power and cycle performance by protecting liquid coating far from the one side setting of anode pole piece in the first cathode pole piece in liquid coating.
Description
Technical field
The present invention relates to battery technology fields, more particularly to a kind of battery core and battery, battery pole piece and preparation method thereof.
Background technique
With scarcity and the whole society's environmental pollution control of non-renewable energy resources, the development of new energy has become irresistible
Gesture.Lithium ion battery is because it is big with specific energy, and light weight, cycle life is good, and self-discharge rate is low, memory-less effect and to ring
The advantages that border is friendly has been widely used for electric car field and energy storage field.As lithium ion battery applications range is continuous
Expand, all trades and professions propose more harsh requirement to the performance of lithium ion battery, promotion, circulating battery such as battery capacity
The increase in service life and the promotion etc. of the anti-deformation nature of battery.Soft bag lithium ionic cell is to be applied to electric car field at present
A kind of major cell type, the electrolysis liquid hold-up in soft bag lithium ionic cell have the cycle performance and high rate performance of battery very big
It influences, the upper of battery can be improved by increasing the guarantor's liquid measure of soft bag lithium ionic cell in the fabrication process to a certain extent
Performance is stated, but in current lithium ion battery other than pole piece and diaphragm have suction-operated to electrolyte, free electrolysis
Liquid can be pulled out out inside battery in battery degasification molding procedure, therefore be electrolysed by increasing in injection soft bag lithium ionic cell
The amount of liquid can not effectively improve guarantor's liquid measure.
In order to improve guarantor's liquid measure of battery, presently mainly by carrying out gluing modification to diaphragm and increasing membrane surface
The modes such as roughness are realized.For example, water system gluing diaphragm is prepared by way of rotary spraying to improve the imbibition energy of diaphragm
Power, although this method can improve battery core to the ownership of electrolyte to a certain extent, diaphragm gluing will increase diaphragm
Ventilative value, so that perineum hinders the transmission of lithium ion to a certain extent, circulation and high rate performance to battery generate negative shadow
It rings；Use polyimides as basement membrane, and the outer surface of polyimides is set as frosting to improve diaphragm to the parent of electrolyte
And power, and then the charge-discharge performance of battery is improved, this method can be improved diaphragm to the physical absorption ability of electrolyte, although energy
Enough guarantor's liquid measures of raising battery, but the limitation improved are also unable to satisfy the high requirement for protecting liquid measure.
Summary of the invention
Based on this, it is necessary to provide a kind of battery core, guarantor's liquid measure of battery can be improved well, and will not influence battery
Cycle performance and high rate performance.
A kind of battery core, including the first cathode pole piece of two panels, the anode pole piece between the first cathode pole piece described in two panels,
And the diaphragm between first cathode pole piece and the anode pole piece；
First cathode pole piece includes collector, the active material coating on one surface of collector, and
Guarantor's liquid coating on another surface of the collector；And guarantor's liquid coating on first cathode pole piece is far from described
Anode pole piece；
Containing solution additive and ceramic microsphere powder is protected in guarantor's liquid coating, guarantor's solution additive is selected from butyronitrile and polychlorostyrene
The Kynoar polymerization of the blend powders, polypropylene micro mist, ultra-high molecular weight polyethylene powder and linear crystal type of ethylene
At least one of object.
Ultra-high molecular weight polyethylene (UHMWPE) is the unbranched linear polyethylene of 1,500,000 or more molecular weight.
In one embodiment, the battery core further includes the second cathode pole piece, and second cathode pole piece includes negative pole currect collecting
Body and the negative electrode active material coating being respectively arranged on two surface of negative current collector；
The quantity of the anode pole piece is m, and m is the integer more than or equal to 2；The quantity of second cathode pole piece is m-
1；
Second cathode pole piece described in anode pole piece described in m piece and m-1 piece is arranged alternately, and the adjacent anode pole piece and
The diaphragm is equipped between second cathode pole piece.
Also contain ceramic microsphere powder, the D50 of the ceramic microsphere powder in guarantor's liquid coating in one of the embodiments,
It is 0.1 μm~50 μm, the ceramic microsphere powder is selected from boehmite, silica, aluminum oxide, the hydroxide of globular powder
At least one of magnesium, aluminium oxide, zirconium oxide, magnesia, mullite and cordierite.
D50 is also meso-position radius or median particle diameter, refers to that partial size is greater than its particle and accounts for 50%, less than its particle also point
50%.
Another object of the present invention is to provide a kind of battery, and the battery includes above-mentioned battery core.
Yet another object of that present invention is to provide a kind of guarantor's liquid coating for being used to form above-mentioned guarantor's liquid coating.
A kind of guarantor's liquid coating, by weight, comprising:
58~77 parts of solvents, 5~13 parts of sagging inhibitor, 85~100.8 parts of guarantor's solution additives and 0.3~0.9 part of surface profit
Humectant；
Wherein, guarantor's solution additive is selected from butyronitrile and polyvinyl chloride blend powder, polypropylene micro mist, super high molecular weight
At least one of the polyvinylidene fluoride polymer of polyethylene powders and linear crystal type.
Also contain 65~89 parts of ceramic microsphere powder in guarantor's liquid coating in one of the embodiments,.
Further, the D50 of the ceramic microsphere powder is 0.1 μm~50 μm, and the ceramic microsphere powder is selected from globular powder
Boehmite, silica, aluminum oxide, magnesium hydroxide, aluminium oxide, zirconium oxide, magnesia, in mullite and cordierite
It is at least one.
The solvent is selected from dimethyl carbonate, acetone, dehydrated alcohol and N- crassitude in one of the embodiments,
At least one of ketone；And/or
The sagging inhibitor is selected from sodium carboxymethylcellulose, ammonium polyacrylate salt, polyoxyethylene fatty alcohol sulfate and gathers
At least one of glycol ethers；And/or
The surface active agent is selected from γ-methacryloxypropyl trimethoxy silane, vinyl triethoxyl silicon
Alkane, vinyltrimethoxysilane, vinyl three ('beta '-methoxy ethyoxyl) silane, three second of N- (β-aminoethyl)-γ-aminopropyl
Oxysilane, mercaptopropyl trimethoxysilane, mercaptopropyltriethoxysilane, ethylenediaminepropyltriethoxysilane and ethylenediamine
At least one of hydroxypropyl methyl dimethoxysilane.
The present invention also provides a kind of preparation methods of above-mentioned guarantor's liquid coating, comprising the following steps: by guarantor's liquid coating
Each raw material is by formula mixing
The step of mixing in one of the embodiments, are as follows:
The solvent, the sagging inhibitor and guarantor's solution additive are mixed, stirred evenly, it is mixed to obtain the first mixing；
First mixed liquor, the ceramic microsphere powder and the surface active agent are mixed, stirred under vacuum conditions
Uniformly.
Yet another object of that present invention is to providing a kind of battery pole piece, including collector, it is set on one surface of collector
Active material coating, and guarantor's liquid coating on another surface of the collector；
Wherein, the liquid coating of protecting is applied by above-mentioned guarantor's liquid coating or using guarantor's liquid that above-mentioned preparation method is prepared
Material is made.
Yet another object of that present invention is to provide a kind of preparation method of battery pole piece, comprising the following steps:
Collector is provided；
Active material coating is coated on a surface of the collector, forms active material coating；
Liquid coating is protected in coating on another surface of the collector, is formed and is protected liquid coating, wherein guarantor's liquid coating is
Above-mentioned guarantor's liquid coating or the guarantor's liquid coating being prepared using above-mentioned preparation method.
The invention has the following advantages:
1) battery core of the invention, by the way that the first cathode pole piece is being arranged, and in the first cathode pole piece far from anode pole piece
Guarantor's liquid coating is equipped on one side (the negative electrode active coating on traditional battery core outermost layer cathode pole piece to be substituted for above-mentioned guarantor's liquid to apply
Layer), guarantor's solution additive in guarantor's liquid coating has long linear structure, and close electrolyte property is good, and its molecular structure easily occurs
It intertwine with each other, after electrolyte injects battery, can be sufficiently submerged in the guarantor's liquid coating formed with above-mentioned guarantor's liquid coating, and be retained
At the intermeshing molecular gap for protecting solution additive, electrolyte is lockked, plays the role of improving battery guarantor's liquid measure, therefore,
In cell operations when electrolyte is constantly consumed, it can be supplemented in time；Due to being located at outermost cathode pole
The negative electrode active material of on piece is not involved in the chemical reaction of inside battery, therefore, is changed into after protecting liquid coating, has reached raising
While battery protects liquid measure, and the performances such as internal resistance, energy density and capacity that will not influence battery, and can significantly be promoted
The cycle performance and high rate performance of battery；
2) also contain ceramic microsphere powder in guarantor's liquid coating of battery core of the present invention, which can be improved the hard of battery core
The problem of degree, elimination inside battery causes battery core to soften because of electrolyte increase, guarantee battery while there is high guarantor's liquid measure
Will not occur the problem of deformation even damages due to by external force.
3) guarantor's liquid coating of the invention with the polymer of long line style be protect solution additive, and with ceramic microsphere powder conduct
Main component, and by proportionally cooperating with other components, obtain the guarantor's liquid coating that can be evenly applied on battery pole piece, shape
Liquid coating is protected at uniform, and good with the binding force of battery pole piece；It is electrophilic since above-mentioned guarantor's solution additive has long linear structure
Solving fluidity can be good, and its molecular structure is easily intertwine with each other, and after electrolyte injects battery, can be sufficiently submerged in above-mentioned guarantor's liquid
It in guarantor's liquid coating that coating is formed, and is retained at the intermeshing molecular gap for protecting solution additive, locks electrolyte, rise
To the effect for improving battery guarantor's liquid measure.
4) preparation method simple process of the invention is easily achieved, and is not required to be transformed existing equipment adjustment substantially, together
When, additionally it is possible to the cost of battery manufacture is reduced, a wide range of promote is suitable for.
Detailed description of the invention
Fig. 1 is the longitudinal section cut-away view of the battery pole piece of one embodiment of the invention；
Fig. 2 is the longitudinal section cut-away view of second cathode pole piece of one embodiment of the invention；
Fig. 3 is the longitudinal section cut-away view of the anode pole piece of one embodiment of the invention；
Fig. 4 is the longitudinal section cut-away view of the battery core of one embodiment of the invention；
Fig. 5 is the longitudinal section cut-away view of the battery core of a comparative example of the invention；
Fig. 6 is the longitudinal section cut-away view of the battery core of another comparative example of the present invention.
Specific embodiment
To facilitate the understanding of the present invention, below will to invention is more fully described, and give it is of the invention compared with
Good embodiment.But the invention can be realized in many different forms, however it is not limited to embodiment described herein.Phase
Instead, purpose of providing these embodiments is makes the disclosure of the present invention more thorough and comprehensive.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term as used herein "and/or" includes one or more phases
Any and all combinations of the listed item of pass.
An embodiment of the present invention provides a kind of guarantor's liquid coating for battery pole piece, by weight, comprising: 58~77
Part solvent, 5~13 parts of sagging inhibitor, 85~100.8 parts of guarantor's solution additives and 0.3~0.9 part of surface active agent；
Wherein, the Kynoar that solution additive is selected from the blend powders of butyronitrile and polyvinyl chloride, linear crystal type is protected
At least one of polymer, polypropylene micro mist and ultra-high molecular weight polyethylene powder.
In one embodiment, protecting liquid coating further includes 65~89 parts of ceramic microsphere powder, and ceramic microsphere powder is selected from globular powder
Boehmite, silica, aluminum oxide, magnesium hydroxide, aluminium oxide, zirconium oxide, magnesia, mullite and cordierite etc. in
At least one, and the D50 of ceramic microsphere powder be 0.1 μm~50 μm.
In one embodiment, solvent in dimethyl carbonate, acetone, dehydrated alcohol and N-Methyl pyrrolidone at least
It is a kind of.
In one embodiment, sagging inhibitor is selected from sodium carboxymethylcellulose, ammonium polyacrylate salt, polyoxyethylene fatty alcohol sulphur
At least one of hydrochlorate and polyglycol ether.
In one embodiment, surface active agent is selected from γ-methacryloxypropyl trimethoxy silane, vinyl three
Ethoxysilane, vinyltrimethoxysilane, vinyl three ('beta '-methoxy ethyoxyl) silane, N- (β-aminoethyl)-γ-ammonia
Propyl-triethoxysilicane, mercaptopropyl trimethoxysilane, mercaptopropyltriethoxysilane, ethylenediaminepropyltriethoxysilane
At least one of with ethylenediamine hydroxypropyl methyl dimethoxysilane.
Another embodiment of the present invention provides a kind of preparation method of above-mentioned guarantor's liquid coating, comprising the following steps:
According to the composition of raw materials of above-mentioned guarantor's liquid coating, each raw material is mixed.
In one embodiment, the step of each raw material mixing of above-mentioned guarantor's liquid coating are as follows:
Solvent, sagging inhibitor and guarantor's solution additive are mixed, stirred evenly, it is mixed to obtain the first mixing；
First mixed liquor, ceramic microsphere powder and surface active agent are mixed, stirred evenly under vacuum conditions.
In one embodiment, the vacuum degree of vacuum condition is -70KPa~-90KPa.
Further, stirring is stirred using blender, and the revolution speed of blender is 10r/min~15r/min, from
Turn 100r/min~300r/min.
Specifically, first solvent, sagging inhibitor and guarantor's solution additive are added in blender, with the 10r/min~15r/ that revolves
Min, rotation 100r/min~300r/min stir 30min~150min, then ceramic microsphere powder powder and table are added into blender
Face wetting agent after being evacuated to -70KPa~-90KPa, is continued to stir 30min~210min with same rotational speed, uniformly be divided
Scattered guarantor's liquid coating.
A further embodiment of this invention provides a kind of battery pole piece 10, as shown in Figure 1, including collector 11 and being set to afflux
Active material coating 12 on 11 1 surface of body, and guarantor's liquid coating 13 on the collection another surface of liquid 11.Wherein, liquid is protected
It include to protect solution additive in coating 13, the solution additive of protecting is selected from the polyvinylidene fluoride polymer of shape crystal type, butyronitrile and gathers
At least one of blend powders, polypropylene micro mist and ultra-high molecular weight polyethylene powder of vinyl chloride.
Specifically, the raw material of liquid coating 13 is protected as above-mentioned guarantor's liquid coating or the guarantor being prepared using above-mentioned preparation method
Liquid coating.
In one embodiment, collector 11 with a thickness of 4 μm~12 μm.
In one embodiment, the thickness for protecting liquid coating 13 is identical as the thickness of active material 12.
In this embodiment, collector 11 is copper foil, and the raw material of active material coating 12 is active material coating, living
Property material coating includes graphite, conductive agent, bonding agent and auxiliary agent.I.e. the battery pole piece 10 is cathode pole piece.
A further embodiment of this invention provides a kind of preparation method of battery pole piece, comprising the following steps:
S1, collector is provided.
Collector refers to the structure or part for collecting electric current, concretely metal foil, such as aluminium foil, copper foil.
In this embodiment, collector is copper foil.It is appreciated that in other embodiments, collector can be it
The collector of his material.
S2, active material coating is coated on a surface of collector, form active material coating.
In this embodiment, active material coating is negative electrode active material coating.
Specifically, graphite, conductive agent, bonding agent and auxiliary agent are mixed, and negative electrode active material is made by homogenate technique
Then negative electrode active material coating is coated on a surface of collector using coating machine, is dried by continuous baking oven by coating
Afterwards, active material coating is formed.
S3, the guarantor's liquid for coating above-mentioned guarantor's liquid coating on another surface of collector or being prepared using the above method
Coating forms and protects liquid coating.
Specifically, it is coated on another surface of collector using coating machine by liquid coating is protected, is dried by continuous baking oven
Afterwards, it is formed and protects liquid coating.
It should be understood that above-mentioned steps S2 and S3 not stringent sequence requirement, step S2 or first can be first carried out
Step S3 is carried out, the operation of step S2 and step S3 can also be carried out simultaneously.
In one embodiment, the preparation method of battery pole piece further include to formed protect liquid coating after coiled material carry out roll-in,
Slitting and crosscutting step.
Another embodiment of the present invention provides a kind of battery core, as shown in Fig. 2, battery core 100 includes the first cathode pole piece of two panels
110, at least a piece of anode pole piece 120 between first cathode pole piece of two panels, and it is located at 110 He of the first cathode pole piece
Diaphragm 130 between anode pole piece 120.
Wherein, the first cathode pole piece 110 includes collector 111, is respectively coated on bearing on respect to two surfaces of collector
Pole active material coating 112 and guarantor's liquid coating 113；Collector 111 is copper foil, protects in liquid coating 113 and adds comprising above-mentioned guarantor's liquid
Add agent, and guarantor's liquid coating 113 on the first cathode pole piece 110 is far from anode pole piece 120.
Specifically, the first cathode pole piece 110 is the battery pole piece that above-mentioned collector is copper foil, or use above method system
Standby obtained battery pole piece.
As shown in figure 3, anode pole piece 120 includes plus plate current-collecting body 121 and is respectively arranged on plus plate current-collecting body 121 two relatively
Surface on positive electrode active materials coating 122.
Diaphragm 130 is selected from least one of double-surface ceramics and single side ceramic diaphragm.
Diaphragm 130 includes basement membrane (not shown) and is set to epilamellar ceramic coating (not shown), and wherein basement membrane is PE (poly-
Ethylene) film or PP (polypropylene) film, the porosity of basement membrane is 35%~60%, basement membrane with a thickness of 9 μm~20 μm.
In one embodiment, battery core 100 further includes the second cathode pole piece 140.As shown in figure 4, the second cathode pole piece 140 wraps
The negative electrode active material coating 142 for including negative current collector 141 and being respectively arranged on 141 two opposite surfaces of negative current collector.
Specifically, the quantity of the first cathode pole piece 110 is 2, and the quantity of anode pole piece 120 is m, and m is more than or equal to 2
Integer；The quantity of second cathode pole piece 140 is m-1；M piece anode pole piece 120 and the second cathode pole piece of m-1 piece 140 alternate
Arrangement, and diaphragm 140 is equipped between adjacent anode pole piece 120 and the second cathode pole piece 140.
Specifically, by the first above-mentioned cathode pole piece, anode pole piece, the second cathode pole piece and diaphragm by the way of lamination
It is assembled and is encapsulated, obtain battery core.
Wherein, lamination process is that the first cathode pole piece, anode pole piece, the second cathode pole piece are passed through diaphragm on laminating machine
It is assembled.
Another embodiment of the present invention provides a kind of battery comprising above-mentioned battery core.
Specifically, the battery core that above-mentioned assembled and encapsulation obtains the processes such as fluid injection, infiltration, chemical conversion and partial volume are carried out to be made
Battery.
Wherein, the main component of electrolyte used in fluid injection is PC (polycarbonate), DMC (dimethyl carbonate), EC (carbonic acid
Vinyl acetate), EMC (methyl ethyl carbonate), LiPF6(lithium hexafluoro phosphate) etc..
The following are specific embodiments
Embodiment 1
1, the preparation of negative electrode active material coating
By graphite, conductive black, sodium carboxymethylcellulose, aqueous styrene-butadiene latex SBR and deionized water according to mass ratio
91.5:6:1.2:1.3:102 is added in batches in homogenate blender, and addition sequence is followed successively by deionized water, carboxymethyl cellulose
Sodium, conductive black, graphite and aqueous styrene-butadiene latex SBR are added before graphite with the 15r/min that revolves, rotation 300r/min stirring
300min is added after graphite with the 15r/min that revolves, rotation 800r/min, stirs 150min under the conditions of vacuum degree is -85KPa,
After homogenate, finely dispersed negative electrode active material coating is obtained, coating is placed in transfer tank, and stir with 15r/min low speed
It mixes, it is spare.
2, the preparation of liquid coating is protected
By boehmite microballoon powder, N-Methyl pyrrolidone, sodium carboxymethylcellulose, linear crystal type Kynoar polymerization
Object and γ-methacryloxypropyl trimethoxy silane are in mass ratio are as follows: 7.7:5.8:0.8:9.3:0.03, successively plus
Enter to be homogenized in blender, addition sequence is first that N-Methyl pyrrolidone, sodium carboxymethylcellulose and linear crystal type is poly- inclined
Fluoroethylene polymer is added in blender, and with the 10r/min that revolves, rotation 150r/min stirs 50min, then is added into blender
Boehmite microballoon powder and γ-methacryloxypropyl trimethoxy silane, after being evacuated to -90KPa, with same rotational speed after
Coating is placed in transfer tank, and stir at low speed with 15r/min after obtaining evenly dispersed guarantor's liquid coating by continuous stirring 210min, standby
With.
3, the preparation of battery pole piece
Above-mentioned negative electrode active material coating is first coated on to the side of copper foil of affluxion body with coating machine, is dried by continuous baking oven
After dry, the other side of liquid coating coating and copper foil being protected, the coiled material for completing coating after drying carries out roll-in, slitting and cross cutting,
It is negative electrode active material coating, the battery pole piece that another side is guarantor's liquid coating, the thickness of negative electrode active material coating on one side
It is identical as the thickness of liquid coating is protected, i.e. the first cathode pole piece.
Above-mentioned negative electrode active material coating is respectively coated with coating machine in the two sides of copper foil of affluxion body, by continuous baking oven
After drying, the second cathode pole piece that two surfaces are equipped with negative electrode active material coating is obtained.
Lithium battery anode reactive coating is respectively coated with coating machine in the two sides of current collector aluminum foil, is dried by continuous baking oven
After dry, the positive plate that two surfaces are equipped with positive electrode active materials coating is obtained.
4, the preparation of battery core and battery
First negative electrode tab, the second negative electrode tab and anode pole piece are assembled on automatic laminating machine by diaphragm, it is used
Diaphragm be double-surface ceramics diaphragm, basement membrane PE, porosity 45%, with a thickness of 9 μm, be made battery core.The quantity of anode pole piece is
15, the quantity of the first cathode pole piece is 2, and the quantity of the second negative electrode tab is 15, and it is the first cathode pole that the sequence of lamination, which is the 1st layer,
Piece, the 2nd~30th layer is alternately stacked for anode pole piece and the second cathode pole piece, and the 31st layer is the first negative electrode tab, wherein the 1st layer and
The one side that 31st the first negative electrode tab is equipped with negative electrode active material coating is opposite with the anode pole piece of the 2nd layer and the 30th layer respectively,
And it is spaced apart by diaphragm between adjacent pole piece.
After the completion of battery core preparation, the high lithium ion battery for protecting liquid is made using processes such as encapsulation, fluid injection, chemical conversion, partial volumes.
Embodiment 2
Embodiment 2 is substantially the same manner as Example 1, the difference is that embodiment 2 protects boehmite microballoon ceramics in liquid coating
Powder, N-Methyl pyrrolidone, sodium carboxymethylcellulose, linear crystal type polyvinylidene fluoride polymer and γ-methacryl
The mass ratio of oxygroup propyl trimethoxy silicane are as follows: 8.9:7.7:1.3:8.5:0.05.
Embodiment 3
Embodiment 3 is substantially the same manner as Example 1, the difference is that when liquid coating is protected in the preparation of embodiment 3, each component is same
When be added in blender, then with the 10r/min that revolves, rotation 150r/min stirs 260min, and when being up to 50min in stirring
Vacuum is opened, and vacuum degree is same as Example 1.
Comparative example 1
Comparative example 1 is substantially the same manner as Example 1, the difference is that, the first cathode pole piece in the battery core of documents 1
Quantity is 1, and in addition a piece of first cathode pole piece is substituted with the second cathode pole piece.Specifically, in comparative example 1 lamination sequence are as follows:
1st layer is the first cathode pole piece, and the 2nd~31st layer is alternately stacked for anode pole piece with the second cathode pole piece, wherein the of the 1st layer
The one side that one cathode pole piece is coated with negative electrode active material coating is opposite with the 2nd layer of anode pole piece, remaining process and 1 phase of embodiment
Together, battery core 200 as shown in Figure 5 is obtained, battery core 200 only contains 1 first cathode pole piece 110.Comparative example 2
Comparative example 2 is substantially the same manner as Example 1, the difference is that, there is no the first cathode pole in the battery core of documents 2
Piece, i.e., using two the first negative electrode tabs in the second negative electrode tab alternate embodiment 1, as shown in fig. 6, battery core 300 is by the second cathode
Pole piece 140 is alternately stacked with anode pole piece 120, and the second adjacent cathode pole piece 140 and anode pole piece 120 are equipped with diaphragm
130。
Comparative example 3
Comparative example 3 is substantially the same manner as Example 1, the difference is that, comparative example 3 will protect two of liquid coating coated in PE film
Side, PE film are 9 μm, and double spread diaphragm is made in porosity 45%, by gluing diaphragm obtained and 15 anode pole pieces and 16
The second cathode pole piece of piece is assembled by laminating machine, and battery core is made, and anode pole piece is successively handed over the second cathode pole piece in battery core
For stacking；The processes such as subsequent fluid injection, infiltration, chemical conversion, partial volume are carried out again, and battery is made.
Wherein, the dosage for protecting liquid coating is same as Example 1, that is, takes guarantor's liquid coating of weight same as Example 1, uniformly
The PE film surface for being coated on comparative example 3, then assembled with anode pole piece and the second cathode pole piece by laminating machine.
Comparative example 4
Comparative example 4 is substantially the same manner as Example 1, the difference is that, boehmite is not added in guarantor's liquid coating of comparative example 4
Ceramic microsphere powder.
Comparative example 5
Comparative example 5 is substantially the same manner as Example 1, the difference is that, comparative example 5 is with the ptfe micropowder generation of equivalent
For the linear crystal type polyvinylidene fluoride polymer in embodiment 1.
Comparative example 6
Comparative example 6 is substantially the same manner as Example 1, the difference is that, comparative example 6 protect liquid coating in boehmite microballoon powder,
N-Methyl pyrrolidone, sodium carboxymethylcellulose, linear crystal type polyvinylidene fluoride polymer and γ-methacryloxy
The mass ratio of propyl trimethoxy silicane are as follows: 5.0:5.8:0.8:9.3:0.03.
Performance test
1, liquid measure and inner walkway are protected
By battery core made of above-described embodiment 1~3 and comparative example 1~6, the imbibition rate of each group battery core is counted respectively, loses liquid
Rate, and internal resistance is tested, as a result as shown in table 1 below.
Imbibition rate=liquid absorption amount/reservoir quantity * 100%；Lose liquid rate=liquid loss amount/reservoir quantity * 100%.
Table 1
As known from Table 1, Examples 1 to 3 compares comparative example 1~6, can guarantee high guarantor's liquid rate and low mistake liquid rate.Implement
With the presence of the relatively large difference of guarantor's liquid rate of guarantor the liquid rate and other battery cores of another battery core in example 3, analysis reason may be system
All raw materials are added in blender simultaneously in the standby homogenate technique for protecting liquid coating, cause slurry mixing uneven, to cause
There are difference for guarantor's liquid rate of battery core.Guarantor's liquid measure of Examples 1 to 3 is obviously increased compared with comparative example 2 (conventional battery core), and its internal resistance
It is not much different with conventional battery core, i.e., the battery of Examples 1 to 3 protects liquid measure and is improved significantly, and it is low to lose liquid rate, and will not influence
Its internal resistance.
2, electrochemical property test
Battery core prepared by Examples 1 to 3, comparative example 1~6 is subjected to low temperature, room temperature discharge-rate performance and normal temperature circulation
Performance test and recording capacity conservation rate, the results are shown in Table 2.
Table 2
As shown in Table 2, the battery of Examples 1 to 3 compares the battery (i.e. conventional batteries) of comparative example 2, and room temperature is forthright again
It can be significantly improved with cycle performance；Meanwhile the battery of comparative example 1 only has 1 first cathode pole piece, high rate performance and cyclicity
Although can be improved, it improves limitation.
The first cathode pole piece of two panels is set it is found that the embodiment of the present invention passes through in conjunction with the data of Tables 1 and 2, it can be significant
The electrolyte ownership for improving battery, greatly improves the high rate performance and cycle performance of battery, and will not influence the internal resistance of battery.
3, anti-deformation nature test
Battery core prepared by Examples 1 to 3, the method for comparative example 1~4 is each 1000 (ea), full with 0.7C at normal temperature
3 hours are stood after filling, then extruding and drop test is carried out according to GB/T 31485-2015, counts the deformation journey of every group of battery core
(deformation extent judgment criteria is as shown in table 3) and experiment percent of pass are spent, test result is as shown in table 4.
3 battery core deformation extent of table defines standard
Table 4
The initial K value of 1~4 each group battery core of Examples 1 to 3 and comparative example is tested and recorded, and is squeezed passing through
The tracking and testing of K value is carried out with the battery core of drop test, each test interval three days, test result is averaged, test result
As shown in table 5.
Table 5
Note: K value unit is mV/day；K0It is tested after completing for battery core, i.e. the initial K value of battery core；K1To fall or squeezing
Rear third day test is tested in compacting；K2For K1Third day is tested after the completion of test；K3For K2Third day is tested after the completion of test, above
Every group of data are the corresponding other testing mean of group.
By the test result table 4 and table 5 of Examples 1 to 3 and comparative example 2~4 it is found that the embodiment of the present invention is protecting liquid coating
In joined the ceramic microsphere powder of hard, significantly improve the non-deformability of battery, after falling and squeezing test, battery
Deformation extent is significantly less than comparative example 2~4, in subsequent K value tracking and testing, it was also found that since deformation extent is small, embodiment 1
~3 battery through extruding and drop test after the variation of K value it is smaller, illustrate battery after falling and squeezing test, it is interior
The micro-short circuit region in portion is less, and the battery of comparative example 2~4, after falling and squeezing test, K value dramatically increases, and illustrates pair
The ability that 2~4 battery of ratio resists plastic deformation is poor.
To sum up, the embodiment of the present invention 1~3 has the first cathode pole piece for protecting liquid coating by setting, due to protecting liquid coating
In containing specific protect solution additive and ceramic microsphere powder, guarantor's liquid measure of battery can be greatly improved, improve multiplying power and circulation
Performance, and will not influence the internal resistance of battery；The non-deformability of battery can also be improved simultaneously.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of battery core, which is characterized in that including the first cathode pole piece of two panels, between the first cathode pole piece described in two panels
Anode pole piece, and the diaphragm between first cathode pole piece and the anode pole piece；
First cathode pole piece includes collector, the active material coating on one surface of collector, and is set to
Guarantor's liquid coating on another surface of collector；And guarantor's liquid coating on first cathode pole piece is far from the anode
Pole piece；
Containing solution additive is protected in guarantor's liquid coating, guarantor's solution additive is selected from the blend powder of butyronitrile and polyvinyl chloride
At least one of end, polypropylene micro mist, ultra-high molecular weight polyethylene powder and the polyvinylidene fluoride polymer of linear crystal type.
2. battery core according to claim 1, which is characterized in that the battery core further includes the second cathode pole piece, and described second
Cathode pole piece includes negative current collector and the negative electrode active material coating that is respectively arranged on two surface of negative current collector；
The quantity of the anode pole piece is m, and m is the integer more than or equal to 2；The quantity of second cathode pole piece is m-1；
Second cathode pole piece described in anode pole piece described in m piece and m-1 piece is arranged alternately, and the adjacent anode pole piece and described
The diaphragm is equipped between second cathode pole piece.
3. battery core according to claim 1 or 2, which is characterized in that also contain ceramic microsphere powder, institute in guarantor's liquid coating
The D50 for stating ceramic microsphere powder is 0.1 μm~50 μm, and the ceramic microsphere powder is selected from boehmite, the silica, three of globular powder
At least one of Al 2 O, magnesium hydroxide, aluminium oxide, zirconium oxide, magnesia, mullite and cordierite.
4. a kind of battery, which is characterized in that the battery pack described in any item battery cores containing claims 1 to 33.
5. a kind of guarantor's liquid coating, which is characterized in that by weight, comprising:
58~77 parts of solvents, 5~13 parts of sagging inhibitor, 85~100.8 parts of guarantor's solution additives and 0.3~0.9 part of surface active agent；
Wherein, the blend powders for protecting solution additive selected from butyronitrile and polyvinyl chloride, polypropylene micro mist, super high molecular weight are poly-
At least one of the polyvinylidene fluoride polymer of ethylene powder and linear crystal type.
6. guarantor's liquid coating according to claim 5, which is characterized in that also contain 65~89 parts of ceramics in guarantor's liquid coating
Microballoon powder, the D50 of the ceramic microsphere powder are 0.1 μm~50 μm, and the ceramic microsphere powder is selected from the boehmite of globular powder, two
At least one of silica, aluminum oxide, magnesium hydroxide, aluminium oxide, zirconium oxide, magnesia, mullite and cordierite；
And/or
The solvent is selected from least one of dimethyl carbonate, acetone, dehydrated alcohol and N-Methyl pyrrolidone；And/or
The sagging inhibitor is selected from sodium carboxymethylcellulose, ammonium polyacrylate salt, polyoxyethylene fatty alcohol sulfate and polyglycols
At least one of ether；And/or
The surface active agent is selected from γ-methacryloxypropyl trimethoxy silane, vinyltriethoxysilane, second
Alkenyl trimethoxy silane, vinyl three ('beta '-methoxy ethyoxyl) silane, N- (β-aminoethyl)-gamma-aminopropyl-triethoxy
Silane, mercaptopropyl trimethoxysilane, mercaptopropyltriethoxysilane, ethylenediaminepropyltriethoxysilane and ethylenediamine propyl
At least one of methyl dimethoxysilane.
7. the preparation method described in claim 5 or 6 for protecting liquid coating, which comprises the following steps: by guarantor's liquid
Each raw material of coating is by formula mixing.
8. preparation method according to claim 7, which is characterized in that the step of mixing includes:
The solvent, the sagging inhibitor and guarantor's solution additive are mixed, stirred evenly, it is mixed to obtain the first mixing；
First mixed liquor, the ceramic microsphere powder and the surface active agent are mixed, stirred evenly under vacuum conditions.
9. a kind of battery pole piece, which is characterized in that the active material including collector, on one surface of collector applies
Layer, and guarantor's liquid coating on another surface of the collector；
Wherein, guarantor's liquid coating wants guarantor's liquid coating described in 5 or 6 as right or uses preparation side described in claim 7 or 8
Guarantor's liquid coating that method is prepared is made.
10. a kind of preparation method of battery pole piece, which comprises the following steps:
Collector is provided；
Active material coating is coated on a surface of the collector, forms active material coating；
Liquid coating is protected in coating on another surface of the collector, is formed and is protected liquid coating, wherein guarantor's liquid coating is as weighed
Benefit protects guarantor's liquid coating that preparation method described in liquid coating or use claim 7 or 8 is prepared described in requiring 5 or 6.
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