CN108428867A - Fast charging type lithium ion battery and preparation method thereof - Google Patents

Fast charging type lithium ion battery and preparation method thereof Download PDF

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Publication number
CN108428867A
CN108428867A CN201810193686.9A CN201810193686A CN108428867A CN 108428867 A CN108428867 A CN 108428867A CN 201810193686 A CN201810193686 A CN 201810193686A CN 108428867 A CN108428867 A CN 108428867A
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positive
carbon
ion battery
lithium ion
fast charging
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CN108428867B (en
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刘新民
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Shenzhen Yijun Science And Technology Co Ltd
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Shenzhen Yijun Science And Technology 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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

Abstract

A kind of fast charging type lithium ion battery of present invention offer and preparation method.The fast charging type based lithium-ion battery positive plate includes plus plate current-collecting body and folded positive carbon-coating, the positive electrode material layer set of stacking；The material of positive electrode material layer includes positive conductive agent, positive electrode binder, the positive active material with clad；Positive conductive agent each component is conductive black in mass ratio：Carbon nanotube：Graphene=1：1：(0.1~0.5), graphene is prepared by chemical vapour deposition technique and the number of plies≤5, and size is 300~700nm；Negative plate includes negative current collector and stacks gradually folded cathode carbon-coating, the negative electrode material layer set；Battery is welded using end face welding manner.The capacity of lithium ion battery 5000mAh or more of the present invention, has good conductive characteristic, while showing good rate charge-discharge performance, rate of charge can be more than 6C, and the cycle life of high rate charge-discharge reaches 1500 weeks capacity retention ratios 85% or more.

Description

Fast charging type lithium ion battery and preparation method thereof
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of fast charging type lithium ion battery and its preparation side Method.
Background technology
Lithium ion battery is widely used due to having many advantages, such as that operating voltage is high, energy density is big, memory-less effect In the various electronic equipments such as digital camera, mobile phone, tablet computer, laptop, and constantly to new-energy automobile field Development.
In recent years, the development of new-energy automobile is like a raging fire, in order to push new-energy automobile industry to develop in a healthy way, and makes it It has the advantage in global competition status, on the one hand the Chinese government puts into effect hair of the relevant policies to domestic new-energy automobile industrial chain Exhibition is helped, and on the other hand also all kinds of capitals is actively being encouraged to enter this field.However it is several compared to conventional fuel oil car Minute fills it up with oil, and new-energy automobile is fully charged, needs several hours, and under the premise of charging pile is not yet universal, fast charge technology is just Becoming influences one of the key factor that electric vehicle is quickly popularized, and quick charging battery also becomes the another of power lithium-ion battery Developing direction.
At present there are also the production method of preferable fast charging type lithium ion battery, such as application No. is 201010174170.3 Chinese patent disclose a kind of Quick-chargeable, including positive and negative collector, battery core, electrolyte, positive and negative anodes Slurry, the anode sizing agent include be by weight ratio respectively 85%~95% positive active material, 0.5%~5% lead Electric agent, 0.2%~2% dispersant and 2%~4% binder are constituted, and the negative electrode slurry includes distinguishing by weight ratio For 90~95% negative electrode active material, 0.1~3% conductive agent, 0.1~1.5% dispersant, 2~4% binder structure At.The battery that the invention obtains can carry out 4C, 6C charging, still, due to its material composition and traditional lithium-ion battery material group At identical, the only difference of material content, big multiplying power charging, which may be implemented, cannot but ensure cycle life, and big multiplying power charging It is a parameter that can not ignore for power lithium-ion battery with good cycle performance.Application No. is 201310160549.2 Chinese patent discloses a kind of preparation method of the high rate lithium iron phosphate cell of quickly-chargeable, fills Electric multiplying power has conventional 1C to be promoted to 5C or more, can charge to battery nominal capacity in 10 minutes 90%, most short charging time Battery can be full of in 15 minutes.But this data is only the data of low capacity (1200mAh) battery, is applied to large-sized power Battery performance is unknown.
Invention content
That there are rate of charge is not high for current lithium ion battery, rate charge-discharge when poor circulation the problems such as, this hair It is bright to provide a kind of fast charging type lithium ion battery and preparation method thereof.
In order to achieve the above-mentioned object of the invention, the technical solution of the embodiment of the present invention is as follows：
A kind of fast charging type lithium ion battery, including positive plate, negative plate, diaphragm and electrolyte；
The positive plate includes plus plate current-collecting body and stacks gradually folded set just outward from the plus plate current-collecting body surface Pole carbon-coating, positive electrode material layer；
The material of the positive electrode material layer includes positive conductive agent, positive electrode binder, the anode work with surface coating layer Property substance；
The positive conductive agent includes conductive black, carbon nanotube, graphene；The positive conductive agent is according to mass ratio Conductive black：Carbon nanotube：Graphene=1：1：(0.1~0.5), the graphene are prepared by chemical vapour deposition technique, And the number of plies≤5, size are 300~700nm；
The negative plate include negative current collector and stacked gradually outward from the negative current collector surface it is folded set it is negative Pole carbon-coating, negative electrode material layer；
The material of the negative electrode material layer includes cathode conductive agent, negative electrode binder, negative electrode active material；
The lug of the fast charging type lithium ion battery is welded using end face welding manner.
Correspondingly, the preparation method of the fast charging type lithium ion battery, at least includes the following steps：
The first slurry is made in positive carbon layer material and the first solvent by step S01., and first slurry is coated on just Pole collection liquid surface, it is dry, for use；Cathode carbon layer material and the second solvent are made the second slurry, and by second slurry It is dry coated on negative current collector surface, for use；
Anode sizing agent is made in the material of positive electrode material layer and third solvent by step S02., and is obtained coated on step S01 Plus plate current-collecting body surface, through drying, roll-in, cut processing, obtain positive plate；By the material of negative electrode material layer and the 4th solvent Negative electrode slurry is made, and is applied to the negative current collector surface that step S01 is obtained, through drying, roll-in, cuts processing, obtains cathode Piece；
Step S03. is according to the structure of positive plate-diaphragm-negative plate, the positive plate that step S02 is prepared, negative plate It is wound with diaphragm, obtains naked battery core；
The naked battery core of acquisition is put into shell at -0.8MPa and vacuum condition below by 80 by step S04.~ 100 DEG C of 25~40h of baking obtain fast charging type lithium ion battery through assembling, noting electrolyte, chemical conversion, two envelopes, partial volume.
Beneficial effects of the present invention：Compared with the existing technology, fast charging type lithium ion battery of the invention, due in positive and negative anodes Collection liquid surface is first folded and sets one layer of carbon-coating respectively, while the materials such as graphene for using the size for being vapor-deposited and obtaining small, in conjunction with The proportioning etc. of positive active material, negative electrode active material, positive conductive agent with clad so that obtained lithium ion battery Good conductive characteristic is shown, the rate charge-discharge performance of lithium ion battery is improved, rate of charge can reach 6C or more, And the cycle life of high rate charge-discharge reaches 1500 weeks or more.
The preparation method of fast charging type lithium ion battery of the present invention, preparation process is simple, and equipment requirement is low, is suitble to scale metaplasia Production, and the lithium ion battery obtained has good big multiplying power charging performance and excellent cycle performance.
Description of the drawings
It to describe the technical solutions in the embodiments of the present invention more clearly, below will be to needed in the embodiment Attached drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for ability For the those of ordinary skill of domain, without creative efforts, it can also be obtained according to these attached drawings other attached Figure.
Fig. 1 is the embodiment of the present invention 1, comparative example 1, the fast charging type lithium ion battery 6C multiplying powers charging property of the preparation of comparative example 2 It can curve graph；
Fig. 2 is the 6C multiplying power charging performance curves of fast charging type lithium ion battery prepared by the embodiment of the present invention 2；
Fig. 3 is that the cycle performance of fast charging type lithium ion battery prepared by the embodiment of the present invention 1~2 and comparative example 1~2 is bent Line.
Specific implementation mode
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments and attached drawing, right The present invention is further elaborated.It should be appreciated that described herein, specific examples are only used to explain the present invention, not For limiting the present invention.
Present example provides a kind of fast charging type lithium ion battery.The fast charging type lithium ion battery include positive plate, Negative plate, diaphragm and electrolyte；
The positive plate includes plus plate current-collecting body and stacks gradually folded set just outward from the plus plate current-collecting body surface Pole carbon-coating, positive electrode material layer；
The material of the positive electrode material layer includes positive conductive agent, positive electrode binder, the anode work with surface coating layer Property substance；
The positive conductive agent includes conductive black, carbon nanotube, graphene；The positive conductive agent is according to mass ratio Conductive black：Carbon nanotube：Graphene=1：1：(0.1~0.5), the graphene are prepared by chemical vapour deposition technique, And the number of plies≤5, size are 300~700nm；
The negative plate include negative current collector and stacked gradually outward from the negative current collector surface it is folded set it is negative Pole carbon-coating, negative electrode material layer；
The material of the negative electrode material layer includes cathode conductive agent, negative electrode binder, negative electrode active material；
The lug of the fast charging type lithium ion battery is welded using end face welding manner.
Technical scheme of the present invention is further explained in detail below.
The fast charging type lithium ion battery of the present invention, by being stacked at the positive carbon-coating on plus plate current-collecting body surface then at institute It states positive carbon-coating surface and coats one layer of positive electrode material layer so that in charge and discharge, electric conductivity obtains effectively lithium ion battery It improves；Similarly, by being stacked at the cathode carbon-coating on negative current collector surface then at cathode carbon-coating surface coating one Layer negative electrode material layer, it is ensured that the electric conductivity of positive and negative anodes, which synchronizes, to be improved.
The plus plate current-collecting body common as technical field of lithium ion, plus plate current-collecting body used in the present invention are aluminium Foil.
Preferably, the material of the positive carbon-coating includes any one of conductive black, carbon nanotube, graphene and first Binder, according to mass percent, the first binder accounts for the 1.5~5.0% of the positive carbon layer material quality.
It is further preferred that the thickness of the anode carbon-coating is 0.1~3.0 μm.Positive carbon-coating is excessively thin, that is, positive carbon When the thickness of layer is less than 0.1 μm, the effect for improving electric conductivity is not had, and if positive carbon layers having thicknesses are more than 3.0 μm, it is coated on The anode active material layer on the anode carbon-coating surface is easy to fall off in high rate charge-discharge, does not have raising lithium ion battery Cycle performance.
Preferably, the first binder is Kynoar.
The positive electrode material layer of the present invention includes positive conductive agent, positive electrode binder, the anode with surface coating layer Active material.
The material of the surface coating layer of the positive active material is carbon, Al2O3、ZrO2、TiO2、AlF3Any one of, By the way that these materials are coated on positive active material surface so that positive active material surface is uniform, while being conducive to shorten Lithium ion deintercalation path improves the electric conductivity of positive electrode, reduces electrode polarization.
Preferably, positive active material is in LiFePO4, nickel-cobalt-manganese ternary material, nickel cobalt aluminium ternary material, LiMn2O4 It is any.
When positive active material is LiFePO4, the surface coating layer of positive active material is carbon-coating, the ferric phosphate D50≤3.0 μm of lithium, specific surface area >=11m2/g。
And when positive active material is nickel-cobalt-manganese ternary material, nickel cobalt aluminium ternary material, LiMn2O4, positive active material Surface coating layer be Al2O3、ZrO2、TiO2、AlF3Any one of, the nickel-cobalt-manganese ternary material, nickel cobalt aluminium ternary material, D50≤5.0 μm of LiMn2O4, specific surface area >=0.8m2/g。
Positive conductive agent include conductive black, carbon nanotube, graphene three mixture, and according to mass ratio be conduction Carbon black, carbon nanotube, graphene=1：1：(0.1~0.5), meanwhile, graphene is prepared using chemical vapour deposition technique, because changing The graphene that vapour deposition process is prepared is learned, thickness is uniform, size uniformity, is conducive to improve electric conductivity, by three at this It is mixed under ratio, positive active material and conductive agent can be made to form the evenly dispersed conductive network of point, line, surface, greatly carried The high electric conductivity of positive plate.
Preferably, negative current collector is copper foil, and copper foil has chemically as conventional negative electrode of lithium ion battery collector Matter is stablized, and feature with good conductivity.
Preferably, the material of the cathode carbon-coating includes any one of conductive black, carbon nanotube, graphene and second Binder, according to mass percent, second binder accounts for the 1.5~5.0% of the cathode carbon layer material quality.By negative Pole carbon-coating is conducive to the cohesive force for improving negative electrode active material and negative current collector, solves negative electrode active material when high magnification charging The problem of matter is easy to fall off.
It is further preferred that the thickness of the cathode carbon-coating is 0.1~3.0 μm.Cathode carbon-coating is excessively thin, that is, cathode carbon When the thickness of layer is less than 0.1 μm, the effect for improving electric conductivity is not had, when cathode carbon layers having thicknesses are less than 3.0 μm, due to cathode Carbon layer material is close with negative electrode active material property, enhances the adhesion of negative electrode active material enough, avoids falling off, But if cathode carbon layers having thicknesses are more than 3.0 μm, the cycle performance of lithium ion battery can't be further increased.
Preferably, second binder is Kynoar.
Preferably, the negative electrode active material is artificial graphite, natural graphite, hard carbon, at least one of soft carbon, described D50≤10 μm of negative electrode active material, specific surface area >=1.5m2/ g, regiospecific I (004)/I (110)≤7.Select this few class grain Diameter is small, large specific surface area, isotropic negative electrode active material, is conducive to shorten lithium ion deintercalation path, reduces electrode polarization, The surface coating layer of positive active material is matched again, to the whole high rate charge-discharge performance for improving lithium ion battery.
Preferably, diaphragm of the present invention is polyethylene-based separators, and the membrane surface has ceramic coating.
For positive and negative electrode of the present invention under the premise of using above-mentioned material, manufactured lithium ion battery is by the way of end face weld It is welded so that the lug of lithium ion battery is end face welding structure, and this structure can not only ensure times of lithium ion battery Rate charging performance can also improve production efficiency, be conducive to large-scale production, while can be fabricated to Soft Roll or hard shell battery.
Preferably, negative electrode binder is any one of butadiene-styrene rubber (SBR), acrylonitrile multiple copolymer.
Preferably, cathode conductive agent is any one of conductive black, carbon nanotube, crystalline flake graphite.
Preferably, in electrolyte, solvent is low viscosity solvent, can be specifically linear carbonate, linear carboxylate, fluorine Two kinds in benzene, hydrofluoroether and the above mixture, solute are lithium hexafluoro phosphate.In addition, functional add can also be contained in electrolyte Add agent, such as vinylene carbonate, fluorinated ethylene carbonate.
It is first folded respectively in positive and negative anodes collection liquid surface due to the lithium ion battery of the present invention and sets one layer of carbon-coating, while using gas The materials such as the small graphene of obtained size are mutually deposited, in conjunction with positive active material, negative electrode active material, just with clad The proportioning etc. of pole conductive agent, on the one hand, the lithium ion battery that capacity is 5000mAh or more can be prepared, on the other hand Obtained lithium ion battery shows good conductive characteristic, while showing good rate charge-discharge performance, rate of charge 6C or more can be reached, and when the cycle life of high rate charge-discharge reaches 1500 weeks or more, capacity retention ratio still reaches 85% or more.
Correspondingly, the present invention furthermore provides the fast charging type on the basis of providing above-mentioned fast charging type lithium ion battery The preparation method of lithium ion battery.
In one embodiment, the preparation method of the fast charging type lithium ion battery, at least includes the following steps：
The first slurry is made in positive carbon layer material and the first solvent by step S01., and first slurry is coated on just Pole collection liquid surface, it is dry, for use；Cathode carbon layer material and the second solvent are made the second slurry, and by second slurry It is dry coated on negative current collector surface, for use；
Anode sizing agent is made in the material of positive electrode material layer and third solvent by step S02., and is obtained coated on step S01 Plus plate current-collecting body surface, through drying, roll-in, cut processing, obtain positive plate；By the material of negative electrode material layer and the 4th solvent Negative electrode slurry is made, and is applied to the negative current collector surface that step S01 is obtained, through drying, roll-in, cuts processing, obtains cathode Piece；
Step S03. is according to the structure of positive plate-diaphragm-negative plate, the positive plate that step S02 is prepared, negative plate It is wound with diaphragm, obtains battery core；
The battery core of acquisition is put into shell at -0.8MPa and vacuum condition below by 80~100 by step S04. DEG C baking 25~40h, through assemble, note electrolyte, chemical conversion, obtain fast charging type lithium ion battery.
In the following, being further explained explanation to the preparation method.
In step S01, positive carbon layer material is material described above, not reinflated description herein, for dissolving anode First solvent of carbon layer material, primarily to so that positive carbon layer material forms slurry, convenient for being coated in anode collection body surface Face is to form positive carbon-coating.
Preferably, the first solvent is N-Methyl pyrrolidone (NMP).
Cathode carbon layer material is material described above, not reinflated description herein, for dissolving cathode carbon layer material Second solvent, primarily to so that cathode carbon layer material formation slurry, negative to be formed convenient for being coated in negative current collector surface Pole carbon-coating.
Preferably, the second solvent is N-Methyl pyrrolidone (NMP).
In step S02, the material of positive electrode material layer is as described above, herein not reinflated description, and molten with third solvent The material of positive electrode material layer is solved, main purpose is in order to enable the material of positive electrode material layer forms anode sizing agent, to coat In the plus plate current-collecting body surface that step S01 is obtained, and it is to facilitate the material load by positive electrode material layer in step strictly speaking The positive carbon-coating surface that S01 is obtained.
Preferably, third solvent is N-Methyl pyrrolidone (NMP).
The material of negative electrode material layer is as described above, herein not reinflated description, and dissolves quadrupole material with the 4th solvent The material of layer, main purpose are the material formation negative electrode slurries in order to enable negative electrode material layer, are obtained to be coated on step S01 The negative current collector surface obtained, and be to facilitate to bear the material load of negative electrode material layer in what step S01 was obtained strictly speaking Pole carbon-coating surface.
Preferably, the 4th solvent is pure water.
In step S03, the winding-structure of positive plate-diaphragm-negative plate is the winding knot of field of lithium ion battery routine Structure need not use diagram or further literal interpretation explanation herein to save length.
In step S04, in the electrolyte being related to, electrolyte (solute) is lithium hexafluoro phosphate, and solvent is linear carbonate, line At least one of shape carboxylate, fluorobenzene, hydrofluoroether, a concentration of 1.0~1.3mol/L of the lithium hexafluoro phosphate.
Further, electrolyte can also contain functional additive, such as vinylene carbonate, fluorinated ethylene carbonate.Work( There is no particular limitation for the dosage of energy additive.
The preparation method of fast charging type lithium ion battery of the present invention, preparation process is simple, and equipment requirement is low, is suitble to scale metaplasia Production, and the lithium ion battery obtained has good big multiplying power charging performance and excellent cycle performance.
The lithium ion battery being prepared using the method for the present invention, due to high rate charge-discharge performance, and capacity 5000mAh or more can be reached, therefore can be widely applied to the fields such as digital product, electric vehicle, energy storage.
More effectively to illustrate technical scheme of the present invention, the technology of the present invention is illustrated below by multiple specific embodiments Scheme.
Embodiment 1
A kind of fast charging type lithium ion battery and preparation method thereof, wherein the parameter of the fast charging type lithium ion battery is as follows：
Positive active material selects LiNi0.5Co0.2Mn0.3O2, D50 is 5 μm, specific surface area >=0.83m2/ g, surface cladding Account for the Al that positive active material mass percentage is 0.3%2O3, positive conductive agent is conductive black, carbon nanotube, chemical gas The mixture for the graphene three that phase deposition growing obtains, wherein the number of plies≤5 layer of graphene, also, be to lead according to mass ratio Electric carbon black：Carbon nanotube：Graphene=1:1:0.15.Plus plate current-collecting body is aluminium foil, and aluminium foil surface is equipped with by applying overlay The thickness of one layer of conductive black layer, the conductive black layer is 1.0 μm.
Negative electrode active material is artificial graphite, and D50 is 8 μm, specific surface area 1.67m2/ g, regiospecific I (004)/I (110) =5.3, cathode conductive agent is conductive black, and negative current collector is copper foil, and copper foil surface is coated folded equipped with one layer of conduction The thickness of silica aerogel layer, the conductive black layer is 1.0 μm.
Diaphragm is polyethylene surface coated ceramic, mean porosities 47%.
The solvent of electrolyte is ethylene carbonate and ethyl acetate binary mixed solvent, lithium salts LiPF6, additive is carbon Sour vinylene, fluorinated ethylene carbonate.
Battery uses end face welding structure, laminated aluminum film.
The preparation method of the lithium ion battery, includes the following steps：
(1) positive plate makes：
It is according to mass ratio, positive active material：Conductive agent：Kynoar=96.8:2:1.2；
By Kynoar and NMP (N-Methyl pyrrolidone) in mass ratio 6:94 are added in blender, mixing speed For 20rpm, 3h is stirred；Stirring terminates, and conductive black, carbon nanotube conducting slurry, graphene conductive slurry, stirring speed are added thereto Degree is 30rpm, stirs 1h；LiNi is added0.5Co0.2Mn0.3O2, mixing speed 30rpm, stirring 3h；Stirring terminates, and will obtain Slurry cross 150 mesh screens, be coated in carbon-coated aluminum foils on, control single side surface density be 9mg/cm2, and roll-in is to 78 μm.
(2) negative plate makes：
It is according to mass ratio, negative electrode active material：Conductive black：SBR：CMC=96:0.7:1.8:1.5.
By CMC (sodium carboxymethylcellulose) and pure water in mass ratio 1:80 are added in blender, and mixing speed is 20rpm stirs 3h；Conductive black is added, mixing speed 30rpm stirs 2h；Negative electrode active material artificial graphite is added, stirs It is 30rpm to mix speed, stirs 3h；SBR (butadiene-styrene rubber), mixing speed 20rpm is added, stirs 1h；Stirring terminates, and will obtain Slurry cross 120 mesh screens, be coated in apply carbon copper foil on, single side surface density be 4.5mg/cm2, and roll-in is to 80 μm.
(3) assembly, fluid injection, chemical conversion, fixture baking, partial volume：
After positive/negative plate cutting, baking, it is wound into naked battery core with polyethylene ceramic diaphragm, then passes through welding electrode ear, aluminium Plastic film encapsulation, baking, fluid injection, simple encapsulation, high temperature is shelved, is melted into, fixture toasts (face pressure 1MPa, 80 DEG C of 4h), two envelopes, partial volume Process is fabricated to soft pack cell.
Embodiment 2
A kind of fast charging type lithium ion battery and preparation method thereof, wherein the parameter of the fast charging type lithium ion battery is as follows：
It is 1 μm that positive active material, which selects LiFePO4, D50, average specific surface area >=20.3m2/ g, surface cladding account for just The carbon-coating that pole active material mass percentage is 1.5%, positive conductive agent are conductive black, carbon nanotube, chemical vapor deposition The mixture for the graphene three that product growth obtains, wherein the number of plies≤5 layer of graphene, also, be conductive charcoal according to mass ratio It is black：Carbon nanotube：Graphene=1:1:0.3.Plus plate current-collecting body is aluminium foil, and aluminium foil surface is led by applying overlay equipped with one layer The thickness of electric silica aerogel layer, the conductive black layer is 1.5 μm.
Negative electrode active material is the mixture of artificial graphite and hard carbon, and mass ratio is artificial graphite：Hard carbon=1: 0.2, D50 is 9.2 μm, specific surface area 1.8m2/ g, regiospecific I (004)/I (110)=4.6, cathode conductive agent is conductive black, Negative current collector is copper foil, and copper foil surface is coated folded equipped with one layer of conductive black layer, and the thickness of the conductive black layer is 1.0μm。
Diaphragm is polyethylene surface coated ceramic, mean porosities 49%.
The solvent of electrolyte is ethylene carbonate and ethyl acetate binary mixed solvent, lithium salts LiPF6, additive is carbon Sour vinylene, fluorinated ethylene carbonate.
Battery uses end face welding structure, aluminum plastic film packaging.
The preparation method of the lithium ion battery, includes the following steps：
(1) positive plate makes：
It is according to mass ratio, positive active material：Conductive agent：Kynoar=94:3:3；
By Kynoar and NMP (N-Methyl pyrrolidone) in mass ratio 6:94 are added in blender, mixing speed For 30rpm, 1h is stirred；Stirring terminates, and conductive black, carbon nanotube conducting slurry, graphene conductive slurry, stirring speed are added thereto Degree is 35rpm, stirs 3h；LiFePO4 is added, mixing speed 35rpm stirs 3h；Stirring terminates, by the slurry mistake of acquisition 150 mesh screens are coated in carbon-coated aluminum foils, and control single side surface density is 8mg/cm2, and roll-in is to 90 μm.
(2) negative plate makes：
It is according to mass ratio, negative electrode active material：Conductive black：SBR：CMC=94.7:2:1.8:1.5.
By CMC (sodium carboxymethylcellulose) and pure water in mass ratio 1:80 are added in blender, and mixing speed is 20rpm stirs 3h；Conductive black is added, mixing speed 30rpm stirs 2h；Negative electrode active material artificial graphite and hard is added Carbon, mixing speed 30rpm stir 3h；SBR (butadiene-styrene rubber), mixing speed 20rpm is added, stirs 1h；Stirring terminates, The slurry of acquisition is crossed into 120 mesh screens, is coated on carbon copper foil, single side surface density is 3.8mg/cm2, and roll-in is to 65 μm.
(3) assembly, fluid injection, chemical conversion, fixture baking, partial volume：
After positive/negative plate cutting, baking, it is wound into naked battery core with polyethylene ceramic diaphragm, then passes through welding electrode ear, aluminium Plastic film encapsulation, baking, fluid injection, simple encapsulation, high temperature is shelved, is melted into, fixture toasts (face pressure 1MPa, 80 DEG C of 4h), two envelopes, partial volume Process is fabricated to soft pack cell.
Comparative example 1
A kind of fast charging type lithium ion battery and preparation method thereof, wherein the parameter of the fast charging type lithium ion battery is as follows：
Positive active material selects LiNi0.5Co0.2Mn0.3O2, D50 is 5 μm, specific surface area >=0.83m2/ g, surface cladding Account for the Al that positive active material mass percentage is 0.3%2O3, positive conductive agent be conductive black, carbon nanotube, oxidation also The mixture for the graphene three that former method obtains, wherein 5 layers of the number of plies ＞ of graphene, also, be conductive charcoal according to mass ratio It is black：Carbon nanotube：Graphene=1:1:0.15.Plus plate current-collecting body is aluminium foil, and aluminium foil surface is equipped with one layer by applying overlay The thickness of conductive black layer, the conductive black layer is 1.0 μm.
Negative electrode active material is artificial graphite, and D50 is 8 μm, specific surface area 1.67m2/ g, regiospecific I (004)/I (110) =5.3, cathode conductive agent is conductive black, and negative current collector is copper foil, and copper foil surface is coated folded equipped with one layer of conduction The thickness of silica aerogel layer, the conductive black layer is 1.0 μm.
Diaphragm is polyethylene surface coated ceramic, mean porosities 47%.
The solvent of electrolyte is ethylene carbonate and ethyl acetate binary mixed solvent, lithium salts LiPF6, additive is carbon Sour vinylene, fluorinated ethylene carbonate.
Battery uses end face welding structure, laminated aluminum film.
The preparation method of the lithium ion battery, includes the following steps：
(1) positive plate makes：
It is according to mass ratio, positive active material：Conductive agent：Kynoar=96.8:2:1.2；
By Kynoar and NMP (N-Methyl pyrrolidone) in mass ratio 6:94 are added in blender, mixing speed For 20rpm, 3h is stirred；Stirring terminates, and conductive black, carbon nanotube conducting slurry, graphene conductive slurry, stirring speed are added thereto Degree is 30rpm, stirs 1h；LiNi is added0.5Co0.2Mn0.3O2, mixing speed 30rpm, stirring 3h；Stirring terminates, and will obtain Slurry cross 150 mesh screens, be coated in carbon-coated aluminum foils on, control single side surface density be 9mg/cm2, and roll-in is to 78 μm.
(2) negative plate makes：
It is according to mass ratio, negative electrode active material：Conductive black：SBR：CMC=96:0.7:1.8:1.5.
By CMC (sodium carboxymethylcellulose) and pure water in mass ratio 1:80 are added in blender, and mixing speed is 20rpm stirs 3h；Conductive black is added, mixing speed 30rpm stirs 2h；Negative electrode active material artificial graphite is added, stirs It is 30rpm to mix speed, stirs 3h；SBR (butadiene-styrene rubber), mixing speed 20rpm is added, stirs 1h；Stirring terminates, and will obtain Slurry cross 120 mesh screens, be coated in apply carbon copper foil on, single side surface density be 4.5mg/cm2, and roll-in is to 80 μm.
(3) assembly, fluid injection, chemical conversion, fixture baking, partial volume：
After positive/negative plate cutting, baking, it is wound into naked battery core with polyethylene ceramic diaphragm, then passes through welding electrode ear, aluminium Plastic film encapsulation, baking, fluid injection, simple encapsulation, high temperature is shelved, is melted into, fixture toasts (face pressure 1MPa, 80 DEG C of 4h), two envelopes, partial volume Process is fabricated to soft pack cell.
Comparative example 2
A kind of fast charging type lithium ion battery and preparation method thereof, wherein the parameter of the fast charging type lithium ion battery is as follows：
Positive active material selects LiNi0.5Co0.2Mn0.3O2, D50 is 5 μm, specific surface area >=0.83m2/ g, surface cladding Account for the Al that positive active material mass percentage is 0.3%2O3, positive conductive agent is conductive black, carbon nanotube, chemical gas The mixture for the graphene three that phase deposition growing obtains, wherein the number of plies≤5 layer of graphene, also, be to lead according to mass ratio Electric carbon black：Carbon nanotube：Graphene=1:1:0.05.Plus plate current-collecting body is aluminium foil, and aluminium foil surface is equipped with by applying overlay The thickness of one layer of conductive black layer, the conductive black layer is 1.0 μm.
Negative electrode active material is artificial graphite, and D50 is 8 μm, specific surface area 1.67m2/ g, regiospecific I (004)/I (110) =5.3, cathode conductive agent is conductive black, and negative current collector is copper foil, and copper foil surface is coated folded equipped with one layer of conduction The thickness of silica aerogel layer, the conductive black layer is 1.0 μm.
Diaphragm is polyethylene surface coated ceramic, mean porosities 47%.
The solvent of electrolyte is ethylene carbonate and ethyl acetate binary mixed solvent, lithium salts LiPF6, additive is carbon Sour vinylene, fluorinated ethylene carbonate.
Battery uses end face welding structure, laminated aluminum film.
The preparation method of the lithium ion battery, includes the following steps：
(1) positive plate makes：
It is according to mass ratio, positive active material：Conductive agent：Kynoar=96.8:2:1.2；
By Kynoar and NMP (N-Methyl pyrrolidone) in mass ratio 6:94 are added in blender, mixing speed For 20rpm, 3h is stirred；Stirring terminates, and conductive black, carbon nanotube conducting slurry, graphene conductive slurry, stirring speed are added thereto Degree is 30rpm, stirs 1h；LiNi is added0.5Co0.2Mn0.3O2, mixing speed 30rpm, stirring 3h；Stirring terminates, and will obtain Slurry cross 150 mesh screens, be coated in carbon-coated aluminum foils on, control single side surface density be 9mg/cm2, and roll-in is to 78 μm.
(2) negative plate makes：
It is according to mass ratio, negative electrode active material：Conductive black：SBR：CMC=96:0.7:1.8:1.5.
By CMC (sodium carboxymethylcellulose) and pure water in mass ratio 1:80 are added in blender, and mixing speed is 20rpm stirs 3h；Conductive black is added, mixing speed 30rpm stirs 2h；Negative electrode active material artificial graphite is added, stirs It is 30rpm to mix speed, stirs 3h；SBR (butadiene-styrene rubber), mixing speed 20rpm is added, stirs 1h；Stirring terminates, and will obtain Slurry cross 120 mesh screens, be coated in apply carbon copper foil on, single side surface density be 4.5mg/cm2, and roll-in is to 80 μm.
(3) assembly, fluid injection, chemical conversion, fixture baking, partial volume：
After positive/negative plate cutting, baking, it is wound into naked battery core with polyethylene ceramic diaphragm, then passes through welding electrode ear, aluminium Plastic film encapsulation, baking, fluid injection, simple encapsulation, high temperature is shelved, is melted into, fixture toasts (face pressure 1MPa, 80 DEG C of 4h), two envelopes, partial volume Process is fabricated to soft pack cell.
Further, the lithium ion battery that the present invention also obtains above-described embodiment 1~2 and comparative example 1~2 carries out corresponding Performance test：
(1) chemical property
Big multiplying power charging performance test：
Specific testing procedure is as follows：
1) by battery 1C constant-current discharges to blanking voltage；
2) 5min is shelved
3) by battery 6C constant-current constant-voltage chargings to blanking voltage, by electric current be 0.05C；
4) 10min is shelved；
5) by battery 1C constant-current discharges to blanking voltage；
The charging/discharging voltage section of wherein Fig. 1 is 3.0-4.2V, and the charging/discharging voltage section of Fig. 2 is 2.5-3.65V
Cycle performance is tested：
Specific testing procedure is as follows：
By battery 6C constant-current constant-voltage chargings to blanking voltage, cut-off current 0.05C；
Shelve 10min；
By battery 1C constant-current discharges to blanking voltage；
Step 1~3 are repeated, are recycled with this.
From fig. 1, it can be seen that other parameters are constant, only change the preparation method of graphene in positive conductive agent, it is chemical with using Graphene prepared by vapour deposition process is compared, and battery can be substantially reduced by doing conductive agent using graphene made from oxidation-reduction method Multiplying power charging performance, 6C charging constant current ratios are down to 86.4% from 96.2%.Other parameters are constant, reduce graphene in positive conductive Adding proportion in agent can reduce the rapid charging performance of battery to a certain extent, when graphene accounting is down to 0.05,6C chargings Constant current ratio is down to 92.5%.
As can be seen from Figure 2, battery 6C made from embodiment 2 charges constant current ratio up to 97.1%.
As can be seen from Figure 3, compared with using graphene made from oxidation-reduction method, using stone made from chemical vapour deposition technique Black alkene has better cycle performance, meanwhile, the adding proportion of graphene also has an impact the cycle performance of battery, lower stone Black alkene additive amount can reduce the cycle performance of battery.The lithium ion battery that namely embodiment of the present invention 1~2 obtains passes through After 1500 cycles, capacity retention ratio still has 85% or more, and comparative example 1~2 is unable to reach corresponding cycle-index, and Not to 1400 cycles, capacity retention ratio is already below 85%.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention All any modification, equivalent and improvement etc. made by within refreshing and principle should all include within protection scope of the present invention.

Claims (9)

1. a kind of fast charging type lithium ion battery, including positive plate, negative plate, diaphragm and electrolyte, it is characterised in that：The anode Piece includes plus plate current-collecting body and stacks gradually folded positive carbon-coating, the positive electrode set outward from the plus plate current-collecting body surface Layer；
The material of the positive electrode material layer includes positive conductive agent, positive electrode binder, the positive electrode active material with surface coating layer Matter；
The positive conductive agent includes conductive black, carbon nanotube, graphene；The positive conductive agent is conduction according to mass ratio Carbon black：Carbon nanotube：Graphene=1：1：(0.1~0.5), the graphene is prepared by chemical vapour deposition technique, and layer Number≤5, size are 300~700nm；
The negative plate includes negative current collector and stacks gradually the folded cathode carbon set outward from the negative current collector surface Layer, negative electrode material layer；
The material of the negative electrode material layer includes cathode conductive agent, negative electrode binder, negative electrode active material；
The lug of the fast charging type lithium ion battery is welded using end face welding manner.
2. fast charging type lithium ion battery as described in claim 1, it is characterised in that：The clad of the positive active material Material is carbon, Al2O3、ZrO2、TiO2、AlF3Any one of；The clad accounts for the mass fraction of the positive active material It is 0.2~1.0%.
3. such as claims 1 or 2 any one of them fast charging type lithium ion battery, it is characterised in that：The positive active material For any one of LiFePO4, nickel-cobalt-manganese ternary material, nickel cobalt aluminium ternary material, LiMn2O4；
The clad of the LiFePO4 is carbon-coating, D50≤3.0 μm of the LiFePO4, specific surface area >=11m2/g；
The nickel-cobalt-manganese ternary material, nickel cobalt aluminium ternary material, LiMn2O4 clad be Al2O3、ZrO2、TiO2、AlF3In It is any, the nickel-cobalt-manganese ternary material, nickel cobalt aluminium ternary material, LiMn2O4 D50≤5.0 μm, specific surface area >=0.8m2/ g。
4. such as claims 1 or 2 any one of them fast charging type lithium ion battery, it is characterised in that：The negative electrode active material For at least one of artificial graphite, natural graphite, hard carbon, soft carbon, D50≤10 μm of the negative electrode active material, specific surface Product >=1.5m2/ g, regiospecific I (004)/I (110)≤7.
5. fast charging type lithium ion battery as described in claim 1, it is characterised in that：The material of the anode carbon-coating includes conduction Any one of carbon black, carbon nanotube, graphene and first binder, according to mass percent, the first binder accounts for institute State the 1.5~5.0% of carbon layer material quality；The material of the cathode carbon-coating includes in conductive black, carbon nanotube, graphene Any and the second binder, according to mass percent, second binder account for the carbon layer material quality 1.5~ 5.0%；
And/or the thickness of the positive carbon-coating, cathode carbon-coating is 0.1~3.0 μm；And/or it is the first binder, second viscous It is Kynoar to tie agent.
6. such as claims 1 or 2 any one of them fast charging type lithium ion battery, it is characterised in that：The diaphragm is polyethylene Base diaphragm, and the membrane surface has ceramic coating.
7. a kind of preparation method of such as claim 1~6 any one of them fast charging type lithium ion battery, includes at least following step Suddenly：
The first slurry is made in positive carbon layer material and the first solvent by step S01., and first slurry is coated on anode and is collected Flow surface, it is dry, for use；The second slurry is made in cathode carbon layer material and the second solvent, and second slurry is coated It is dry in negative current collector surface, for use；
Anode sizing agent is made in the material of positive electrode material layer and third solvent by step S02., and is obtained just coated on step S01 Pole collection liquid surface through drying, roll-in, cuts processing, obtains positive plate；The material of negative electrode material layer and the 4th solvent are made Negative electrode slurry, and it is applied to the negative current collector surface that step S01 is obtained, through drying, roll-in, processing is cut, obtains negative plate；
Step S03. according to positive plate-diaphragm-negative plate structure, the positive plate that step S02 is prepared, negative plate and every Film is wound, and obtains naked battery core；
The naked battery core of acquisition is put into shell at -0.8MPa and vacuum condition below by 80~100 DEG C by step S04. 25~40h of baking obtains fast charging type lithium ion battery through assembling, noting electrolyte, chemical conversion, two envelopes, partial volume.
8. the preparation method of fast charging type lithium ion battery as claimed in claim 7, which is characterized in that the electrolysis of the electrolyte Matter is lithium hexafluoro phosphate, and solvent is at least one of linear carbonate, linear carboxylate, fluorobenzene, hydrofluoroether, the hexafluoro phosphorus A concentration of 1.0~1.3mol/L of sour lithium.
9. the preparation method of fast charging type lithium ion battery as claimed in claim 7, which is characterized in that first solvent is N- Methyl pyrrolidone；Second solvent is N-Methyl pyrrolidone；The third solvent is N-Methyl pyrrolidone；Described Four solvents are pure water.
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