CN105406083A - Quickly-chargeable/dischargeable lithium ion battery and manufacture method thereof - Google Patents

Quickly-chargeable/dischargeable lithium ion battery and manufacture method thereof Download PDF

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Publication number
CN105406083A
CN105406083A CN201510955980.5A CN201510955980A CN105406083A CN 105406083 A CN105406083 A CN 105406083A CN 201510955980 A CN201510955980 A CN 201510955980A CN 105406083 A CN105406083 A CN 105406083A
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composite
lithium ion
ion battery
discharging
binding agent
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黄灵
唐杰雄
李阳春
马李
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HUNAN GAOYUAN BATTERY Co Ltd
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HUNAN GAOYUAN BATTERY Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Manufacturing & Machinery (AREA)
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Abstract

The invention discloses a quickly-chargeable/dischargeable lithium ion battery and a manufacture method thereof. The method specifically includes the steps of firstly adding aqueous adhesives, conductive agents and additives in a certain proportion into solvent and mixing to be uniformly dispersed to form coating slurry, uniformly coating the coating slurry on a cathode aluminum foil current collector and drying, and thereby obtaining a current collector with a composite cathode; and mixing the adhesives with the conductive agents uniformly and then coating on a membrane to form a composite membrane. The quickly-chargeable/dischargeable lithium ion battery provided by the invention can be manufacture by using the current collector with the composite cathode and the composite membrane through a series of working procedures. According to the quickly-chargeable/dischargeable lithium ion battery and the manufacture method thereof, due to the coating of the current collector with the composite cathode, the bonding strength of the electrode pieces can be obviously enhanced, and the interface state between the cathode active material and the aluminum foil current collector can be improved; the interface contact between the membrane and each of cathode and anode membranes can be improved due to the conductive coatings on two sides of the membrane; and thereby, the internal resistance of the lithium ion battery is greatly reduced, and the quick charging/discharging performance of the lithium ion battery is improved.

Description

A kind of can the lithium ion battery of fast charging and discharging and manufacture method thereof
Technical field
The present invention relates to field of lithium ion battery, especially relating to can the lithium ion battery of fast charging and discharging and manufacture method thereof.
Background technology
Lithium ion battery has the advantages such as operating voltage is high, specific energy is high and have extended cycle life, and obtains in recent years and develops rapidly.Lithium ion battery is used widely now on mobile device, electric tool and electric automobile, along with the continuous lifting of user's request, to can the lithium ion battery demand of fast charging and discharging more and more stronger.Certainly also have different demands for different power consumption equipments to battery charging/discharging characteristic, mobile device and battery for electric automobile needed to be full of electricity fast, for batteries for electric tools then need can heavy-current discharge to improve plant capacity.
Under the prerequisite that other condition is certain, the internal resistance of battery is the bottleneck of restriction battery charging and discharging high rate performance, and the high rate performance of the larger battery of internal resistance is poorer, and the polarization produced in large current density electric process is just large, thus limits the normal use of electrical appliance.Current power of battery performance of improving only uses a kind of coating mostly, and the binding agent in anode pole piece of the prior art generally can only use one, namely can at NMP (N, N-dimethyl pyrrolidone) polyvinylidene fluoride that dissolves under system or the aqueous binders that can dissolve under water-based system, therefore the coating on plus plate current-collecting body be only applicable to active material slurry be with NMP be solvent system or be only applicable to take water as the system of solvent, so in order to improve Technological adaptability, be necessary to develop a kind of plus plate current-collecting body coating being simultaneously applicable to two kinds of systems.Simultaneously in order to improve the interfacial characteristics between barrier film and both positive and negative polarity diaphragm, be also necessary very much to develop a kind of composite coating barrier film improving this interfacial characteristics.
Summary of the invention
The object of this invention is to provide a kind of can the lithium ion battery of fast charging and discharging and manufacture method thereof, with improve active material and collector caking property, improve interface between active material and collector, improve interfacial characteristics between barrier film and both positive and negative polarity diaphragm, thus reduce the internal resistance of lithium ion battery.The material system that it be the material system of solvent and water is solvent that coating of the present invention is applicable to NMP.Concrete technical scheme is as follows:
The present invention is a kind of can the lithium ion battery of fast charging and discharging, described battery: positive plate, negative plate, barrier film, electrolyte, described negative plate comprises negative current collector and is distributed in the negative electrode active material on negative current collector, described positive plate comprises anode composite collector and is distributed in positive active material on anode composite collector, and described anode composite collector is made up of plus plate current-collecting body matrix and the composite coating that is coated in matrix surface.
The present invention is a kind of can the lithium ion battery of fast charging and discharging, and the composite coating of described plus plate current-collecting body matrix surface comprises following component and forms by mass percentage:
Binding agent 10-20%,
Conductive agent 70-85%,
Additive 5-10%.
The present invention is a kind of can the lithium ion battery of fast charging and discharging, and in the composite coating of described plus plate current-collecting body matrix surface, binding agent is aqueous polyvinylidene fluoride emulsion;
Conductive agent is selected from least one in superconduction carbon black (Super-P), CNT (carbon nano-tube), carbon fiber, Graphene;
Additive is selected from sodium carboxymethylcellulose (CMC), at least one in polyacrylic acid (PAA) Sodium Polyacrylate, (PAAS);
The present invention is a kind of can the lithium ion battery of fast charging and discharging, and the composite coating one side thickness of described plus plate current-collecting body matrix surface is 1 μm-6 μm.
The present invention is a kind of can the lithium ion battery of fast charging and discharging, and the membrane surface in described battery is coated with composite conductive layers, and the composite conductive layers of described membrane surface is made up of binding agent and conductive agent.
The present invention is a kind of can the lithium ion battery of fast charging and discharging, and the binding agent in the composite conductive layers of described membrane surface and the mass percentage of conductive agent are:
Binding agent accounts for 10-20%, and conductive agent is 80-90%.
The present invention is a kind of can the lithium ion battery of fast charging and discharging, and in the composite conductive layers of described membrane surface, pore size is 0.05-10 micron; Described composite conductive layers one side thickness is 1 μm-4 μm.
The present invention is a kind of can the lithium ion battery of fast charging and discharging, and the composite conductive layers gross thickness of described membrane surface is 2-30 μm.
The present invention is a kind of can the lithium ion battery of fast charging and discharging, and the conductive agent in the composite conductive layers of described membrane surface is selected from least one in superconduction carbon black (Super-P), carbon nano-tube, carbon fiber, Graphene.
The present invention is a kind of can the lithium ion battery of fast charging and discharging, and the binding agent in the composite conductive layers of described membrane surface is Kynoar.
The present invention is a kind of can the lithium ion battery of fast charging and discharging, and described positive active material is selected from least one in the embedding oxidate for lithium of transition metal, phosphate cathode material; Described negative electrode active material is selected from Delanium, native graphite, one or more in Si/C composite material;
The embedding oxidate for lithium of described transition metal is selected from LiCoO 2, LiMn 2o 4, LiCo 1-x-yni xmn yo 2in at least one, wherein LiCo 1-x-yni xmn yo 2in x, y, require x+y < 1;
Described phosphate cathode material is selected from LiFePO 4, Li 3v 2(PO 4) 3, LiVPO 4f, LiVPO 4at least one in O.
The present invention is a kind of can the lithium ion battery of fast charging and discharging, and positive plate and negative plate are full extreme ear structure.
The present invention is a kind of can the preparation method of lithium ion battery of fast charging and discharging, comprises the steps:
The first step, the preparation of anode composite collector
By the quality proportioning of binding agent, conductive agent, additive in the composite coating of the plus plate current-collecting body matrix surface of design, take binding agent, conductive agent, additive respectively, with the NMP (N containing mass percent 5 ~ 40%, N-dimethyl pyrrolidone) deionized water be solvent, first by binding agent, conductive agent and solvent add agitator tank and are uniformly dispersed, and then reenter additive and stir, and prepare composite coating slurry; Painting compound coating paste is covered to collector matrix surface post-drying, prepares anode composite collector;
Second step: the preparation of positive/negative plate
Technique routinely, is coated in anode composite collection liquid surface by positive active material, negative electrode active material is coated in negative pole currect collecting surface, obtains positive plate, negative plate;
3rd step, the preparation of membrane surface composite conductive layers
By the quality proportioning of binding agent, conductive agent in the composite conductive layers of the membrane surface of design, take binding agent, conductive agent respectively, first binding agent is dissolved into solvent NMP (N, N-dimethyl pyrrolidone) in, obtain the adhesive solution that mass percentage concentration is 2-6%, then, conductive agent is added in adhesive solution and stirs, obtain mixed liquor, binding agent and conductive agent in mass ratio 1:1-9 mate;
Composite conductive layers slurry is coated to membrane surface and drying, obtains the barrier film that surface-coated has composite conductive layers;
4th step, lithium ion battery is shaping
There is the barrier film of composite conductive layers to prepare core through rolling step both positive and negative polarity pole piece and surface-coated, core is colded pressing through encapsulation, baking, fluid injection, heat, change into, partial volume operation prepares high multiplying power lithium ion battery.
The present invention, by the modifying surface process to anode current collector of lithium ion battery and barrier film, on the one hand, effectively improves the interface impedance between positive electrode active materials and collector, thus reduces the internal resistance of battery; On the other hand, effectively reduce the interface distance between barrier film and both positive and negative polarity diaphragm, be beneficial to the transfer of lithium ion, the conductive agent simultaneously in coating can help lithium ion charge transfer to occur on this interface to carry out electrochemical reaction fast, effectively promotes battery fast charging and discharging performance; The synergy of above-mentioned two aspects, realizes the fast charging and discharging of lithium ion battery.Relative to prior art, the present invention has following good effect:
(1) the composite coating specific area of anode composite collector matrix surface of the present invention is larger, effectively can improve the caking property of positive electrode active materials and collector, prevent battery in use active material depart from from collector, thus reduce the interface impedance between positive electrode active materials and collector.
(2) in the composite coating of anode composite collector matrix surface of the present invention, the Electolyte-absorptive ability of conductive agent is comparatively strong, effectively can improve electronic conductivity and the ionic conductivity of pole piece, thus reduces the internal resistance of battery.
(3) binding agent in the composite coating of anode composite collector matrix surface of the present invention is aqueous polyvinylidene fluoride emulsion, under the effect of additive, the polyvinylidene fluoride of the coating surface that it is prepared can be dissolved in NMP or water on a small quantity, so the interface of active material layer and functional coat can merge, effectively reduce the impedance between two-phase interface.
(4) composite conductive layers of membrane surface of the present invention, can be bonded together with both positive and negative polarity diaphragm in hot pressing process after battery liquid-filling, effectively reduce the interface distance between barrier film and both positive and negative polarity diaphragm, this will more be conducive to the transfer of lithium ion, conductive agent simultaneously in coating can help lithium ion charge transfer to occur on this interface to carry out electrochemical reaction fast, thus improves battery fast charging and discharging performance further.
By the way, utilize the lithium ion battery prepared by the present invention can be filled with the electricity being greater than 80% in 10 minutes, battery is greater than 90% of 1C discharge capacity with the capacity of 20C continuous discharge simultaneously.
Accompanying drawing explanation
Accompanying drawing 1 composite separator structure schematic diagram
Accompanying drawing 2 anode composite chip architecture schematic diagram
In Fig. 1,1 is composite conductive layers, and 2 is diaphragm matrix;
In Fig. 2,3 is current collector aluminum foil, and 4 is composite coating, and 5 is cathode film lamella.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described.
Embodiment 1
By load weighted aqueous polyvinylidene fluoride emulsion, Super-P and containing 5%NMP (N, N-dimethyl pyrrolidone) deionized water join in agitator tank successively and stir 2h, until conductive agent scatter completely, and then slowly add CMC stir 6h prepare coating paste, in slurry, solid constituent ratio is polyvinylidene fluoride: Super-P:CMC=10%:85%:5%.The two sides using intaglio press coating paste to be coated in collector is also dried and is prepared anode composite collector, one side coating layer thickness 1 μm;
By load weighted polyvinylidene fluoride and NMP (N, N-dimethyl pyrrolidone) be added to vacuum stirring 2h in agitator tank successively until polyvinylidene fluoride is dissolved into clear solution completely, again load weighted CNT (carbon nano-tube) is slowly added in agitator tank, stir 4h and form uniform and stable coating paste, in slurry, solid constituent proportioning is polyvinylidene fluoride: CNT (carbon nano-tube)=10%:90%, the mode of intaglio printing is used by coating paste to be coated in barrier film both sides uniformly and composite diaphragm is prepared in drying, one side coating layer thickness 2 μm.As shown in Figure 1,1 is composite conductive layers, and 2 is diaphragm matrix.
With LiNi 0.5co 0.3mn 0.2o 2as active substance of lithium ion battery anode, be hybridly prepared into LiNi with polyvinylidene fluoride, Super-P, NMP etc. 0.5co 0.3mn 0.2o 2anode sizing agent, is then coated in drying on anode composite collector, rolling, cuts, positive plate that the operation such as soldering polar ear obtains as shown in Figure 2 by anode sizing agent.This Figure illustrates the cross section structure using anode composite collector positive plate, wherein 3 is current collector aluminum foil, and 4 is composite coating, and 5 is cathode film lamella.
Using Delanium as lithium ion battery negative pole active materials, be hybridly prepared into graphite cathode slurry with CMC, SBR (butadiene-styrene rubber), Super-P and deionized water.Then cathode size is coated in drying on Copper Foil, rolling, cuts, soldering polar ear etc. obtains negative plate.
Both positive and negative polarity pole piece and composite diaphragm are prepared core through rolling step; Core through encapsulation, baking, fluid injection, hot pressing, change into, the operation such as partial volume is prepared can the lithium ion battery of fast charging and discharging.
The battery size made is 523450PL (thickness 5.2mm, width 34mm, length 50mm), nominal capacity 1200mAh.Gained battery at room temperature 1C discharge capacity is 1230mAh, with 20C multiplying power discharging capacity for 1113mAh, is 90.5% of 1C discharge capacity.Be filled with electricity 998mAh with 5C current charges 10min under room temperature, being filled with electricity is 81.1%.
The same model lithium ion battery prepared of prior art at room temperature 1C discharge capacity is 1243mAh, with 20C multiplying power discharging capacity for 990mAh, is 79.6% of 1C discharge capacity.Be filled with electricity 202mAh with 5C current charges 10min under room temperature, being filled with electricity is 16.3%.
Embodiment 2
By load weighted aqueous polyvinylidene fluoride emulsion, CNT (carbon nano-tube) and containing 20%NMP (N, N-dimethyl pyrrolidone) deionized water join in agitator tank successively and stir 2h, until conductive agent scatter completely, and then slowly add PAA stir 6h prepare coating paste, in slurry, solid constituent ratio is polyvinylidene fluoride: CNT (carbon nano-tube): PAA=15%:75%:10%.The two sides using intaglio press coating paste to be coated in collector is also dried and is prepared anode composite collector, one side coating layer thickness 4 μm;
By load weighted polyvinylidene fluoride and NMP (N, N-dimethyl pyrrolidone) be added to vacuum stirring 2h in agitator tank successively until polyvinylidene fluoride is dissolved into clear solution completely, again load weighted carbon fiber is slowly added in agitator tank, stir 4h and form uniform and stable coating paste, in slurry, solid constituent proportioning is polyvinylidene fluoride: carbon fiber=20%:80%, the mode of intaglio printing is used by coating paste to be coated in barrier film both sides uniformly and composite diaphragm is prepared in drying, one side coating layer thickness 4 μm.As shown in Figure 1,1 is composite coating, and 2 is diaphragm matrix.
With LiCoO 2as active substance of lithium ion battery anode, be hybridly prepared into LiCoO with polyvinylidene fluoride, Super-P, NMP etc. 2anode sizing agent, is then coated in drying on anode composite collector, rolling, cuts, positive plate that the operation such as soldering polar ear obtains as shown in Figure 2 by anode sizing agent.This Figure illustrates the cross section structure using anode composite collector positive plate, wherein 3 is current collector aluminum foil, and 4 is composite coating, and 5 is cathode film lamella.
Using Delanium as lithium ion battery negative pole active materials, be hybridly prepared into graphite cathode slurry with CMC, SBR (butadiene-styrene rubber), Super-P and deionized water.Then cathode size is coated in drying on Copper Foil, rolling, cuts, soldering polar ear etc. obtains negative plate.
Both positive and negative polarity pole piece and composite diaphragm are prepared core through rolling step; Core through encapsulation, baking, fluid injection, hot pressing, change into, the operation such as partial volume is prepared can the lithium ion battery of fast charging and discharging.
The battery size made is 345573PL (thickness 3.4mm, width 55mm, length 73mm), nominal capacity 1900mAh.Gained battery at room temperature 1C discharge capacity is 1950mAh, with 20C multiplying power discharging capacity for 1769mAh, is 87.1% of 1C discharge capacity.Be filled with electricity 1667mAh with 5C current charges 10min under room temperature, being filled with electricity is 85.5%.
The same model lithium ion battery prepared of prior art at room temperature 1C discharge capacity is 1974mAh, with 20C multiplying power discharging capacity for 1575mAh, is 79.8% of 1C discharge capacity.Under room temperature, 10min is filled with electricity 412mAh, and being filled with electricity is 20.9%.
Embodiment 3
By load weighted aqueous polyvinylidene fluoride emulsion, carbon fiber and containing 40%NMP (N, N-dimethyl pyrrolidone) deionized water join in agitator tank successively and stir 2h, until conductive agent scatter completely, and then slowly add PAAS stir 6h prepare coating paste, in slurry, solid constituent ratio is polyvinylidene fluoride: carbon fiber: PAAS=20%:70%:10%.The two sides using intaglio press coating paste to be coated in collector is also dried and is prepared anode composite collector, one side coating layer thickness 6 μm;
By load weighted polyvinylidene fluoride and NMP (N, N-dimethyl pyrrolidone) be added to vacuum stirring 2h in agitator tank successively until polyvinylidene fluoride is dissolved into clear solution completely, again load weighted carbon fiber is slowly added in agitator tank, stir 4h and form uniform and stable coating paste, in slurry, solid constituent proportioning is polyvinylidene fluoride: carbon fiber=15%:85%, the mode of intaglio printing is used by coating paste to be coated in barrier film both sides uniformly and composite diaphragm is prepared in drying, one side coating layer thickness 2 μm.As shown in Figure 1,1 is composite coating, and 2 is diaphragm matrix.
With LiMn 2o 4as active substance of lithium ion battery anode, be hybridly prepared into LiMn with polyvinylidene fluoride, Super-P, NMP etc. 2o 4anode sizing agent, is then coated in drying on anode composite collector, rolling, cuts, positive plate that the operation such as soldering polar ear obtains as shown in Figure 2 by anode sizing agent.This Figure illustrates the cross section structure using anode composite collector positive plate, wherein 3 is current collector aluminum foil, and 4 is composite coating, and 5 is cathode film lamella.
Using Delanium as lithium ion battery negative pole active materials, be hybridly prepared into graphite cathode slurry with CMC, SBR (butadiene-styrene rubber), Super-P and deionized water.Then cathode size is coated in drying on Copper Foil, rolling, cuts, soldering polar ear etc. obtains negative plate.
Both positive and negative polarity pole piece and composite diaphragm are prepared core through rolling step; Core through encapsulation, baking, fluid injection, hot pressing, change into, the operation such as partial volume is prepared can the lithium ion battery of fast charging and discharging.
The battery size made is 436495PL (thickness 4.3mm, width 64mm, length 95mm), nominal capacity 2500mAh.Gained battery at room temperature 1C discharge capacity is 2592mAh, with 20C multiplying power discharging capacity for 2375mAh, is 91.6% of 1C discharge capacity.Be filled with electricity 2120mAh with 5C current charges 10min under room temperature, being filled with electricity is 81.8%.
The same model lithium ion battery prepared of prior art at room temperature 1C discharge capacity is 2606mAh, with 20C multiplying power discharging capacity for 2125mAh, is 81.5% of 1C discharge capacity.Be filled with electricity 454mAh with 5C current charges 10min under room temperature, being filled with electricity is 17.4%.
Embodiment 4
By load weighted aqueous polyvinylidene fluoride emulsion, Graphene and containing 30%NMP (N, N-dimethyl pyrrolidone) deionized water join in agitator tank successively and stir 2h, until conductive agent scatter completely, and then slowly add PAA stir 6h prepare coating paste, in slurry, solid constituent ratio is polyvinylidene fluoride: Graphene: PAA=15%:77%:8%.The two sides using intaglio press coating paste to be coated in collector is also dried and is prepared anode composite collector, one side coating layer thickness 3 μm;
By load weighted polyvinylidene fluoride and NMP (N, N-dimethyl pyrrolidone) be added to vacuum stirring 2h in agitator tank successively until polyvinylidene fluoride is dissolved into clear solution completely, again load weighted Graphene is slowly added in agitator tank, stir 4h and form uniform and stable coating paste, in slurry, solid constituent proportioning is polyvinylidene fluoride: Graphene=15%:85%, the mode of intaglio printing is used by coating paste to be coated in barrier film both sides uniformly and composite diaphragm is prepared in drying, one side coating layer thickness 1.5 μm.
With LiNi 1/3co 1/3mn 1/3o 2and LiFePO 4as active substance of lithium ion battery anode, be hybridly prepared into anode sizing agent with polyvinylidene fluoride, Super-P, NMP etc., then anode sizing agent be coated in drying on anode composite collector, rolling, cut, positive plate that the operation such as soldering polar ear obtains as shown in Figure 2.
Using Delanium as lithium ion battery negative pole active materials, be hybridly prepared into graphite cathode slurry with CMC, SBR (butadiene-styrene rubber), Super-P and deionized water.Then cathode size is coated in drying on Copper Foil, rolling, cuts, soldering polar ear etc. obtains negative plate.
Both positive and negative polarity pole piece and composite diaphragm are prepared core through rolling step; Core through encapsulation, baking, fluid injection, hot pressing, change into, the operation such as partial volume is prepared can the lithium ion battery of fast charging and discharging.
The battery size made is 855085PL (thickness 8.5mm, width 50mm, length 85mm), nominal capacity 2600mAh.Gained battery at room temperature 1C discharge capacity is 2706mAh, with 20C multiplying power discharging capacity for 2543mAh, is 94.0% of 1C discharge capacity.Be filled with electricity 2334mAh with 5C current charges 10min under room temperature, being filled with electricity is 86.3%.
The same model lithium ion battery prepared of prior art at room temperature 1C discharge capacity is 2723mAh, with 20C multiplying power discharging capacity for 2217mAh, is 81.4% of 1C discharge capacity.Be filled with electricity 468mAh with 5C current charges 10min under room temperature, being filled with electricity is 17.2%.
According to the data of above embodiment and comparative example, can find out: prepared by the present invention can the lithium ion battery of fast charging and discharging at room temperature 1C discharge capacity is suitable with prior art, with the comparatively prior art lifting more than 10% of 20C multiplying power discharging capacity, under room temperature, 10min is filled with electricity comparatively prior art lifting more than 60%.

Claims (10)

1. one kind can the lithium ion battery of fast charging and discharging, described battery: positive plate, negative plate, barrier film, electrolyte, described negative plate comprises negative current collector and is distributed in the negative electrode active material on negative current collector, described positive plate comprises anode composite collector and is distributed in positive active material on anode composite collector, and described anode composite collector is made up of plus plate current-collecting body matrix and the composite coating that is coated in matrix surface; The composite coating of described plus plate current-collecting body matrix surface comprises following component and forms by mass percentage:
Binding agent 10-20%,
Conductive agent 70-85%,
Additive 5-10%.
2. according to claim 1 a kind of can the lithium ion battery of fast charging and discharging, it is characterized in that: in the composite coating of described plus plate current-collecting body matrix surface,
Binding agent is aqueous polyvinylidene fluoride emulsion;
Conductive agent is selected from least one in superconduction carbon black, CNT (carbon nano-tube), carbon fiber, Graphene;
Additive is selected from sodium carboxymethylcellulose, at least one in polyacrylic acid, Sodium Polyacrylate.
3. according to claim 2 a kind of can the lithium ion battery of fast charging and discharging, it is characterized in that: the composite coating one side thickness of described plus plate current-collecting body matrix surface is 1 μm-6 μm.
4. a kind of according to claim 1-3 any one can the lithium ion battery of fast charging and discharging, and it is characterized in that: the membrane surface in described battery is coated with composite conductive layers, the composite conductive layers of described membrane surface is made up of binding agent and conductive agent.
5. according to claim 4 a kind of can the lithium ion battery of fast charging and discharging, it is characterized in that: the binding agent in the composite conductive layers of described membrane surface and the mass percentage of conductive agent are:
Binding agent accounts for 10-20%, and conductive agent is 80-90%.
6. according to claim 5 a kind of can the lithium ion battery of fast charging and discharging, it is characterized in that: the composite conductive layers one side thickness of described membrane surface is 1 μm-4 μm.
7. according to claim 6 a kind of can the lithium ion battery of fast charging and discharging, it is characterized in that: the conductive agent in the composite conductive layers of described membrane surface is selected from least one in superconduction carbon black, carbon nano-tube, carbon fiber, Graphene; Binding agent in the composite conductive layers of described membrane surface is Kynoar.
8. according to claim 7 a kind of can the lithium ion battery of fast charging and discharging, it is characterized in that: described positive active material is selected from least one in the embedding oxidate for lithium of transition metal, phosphate cathode material;
The embedding oxidate for lithium of described transition metal is selected from LiCoO 2, LiMn 2o 4, LiCo 1-x-yni xmn yo 2in at least one, wherein LiCo 1-x-yni xmn yo 2in x, y, require x+y < 1;
Described phosphate cathode material is selected from LiFePO 4, Li 3v 2(PO 4) 3, LiVPO 4f, LiVPO 4at least one in O;
Described negative electrode active material is selected from Delanium, native graphite, one or more in Si/C composite material.
9. according to claim 8 a kind of can the lithium ion battery of fast charging and discharging, it is characterized in that: positive plate and negative plate are full extreme ear structure.
10. can the preparation method of lithium ion battery of fast charging and discharging, comprise the steps:
The first step, the preparation of anode composite collector
By the quality proportioning of binding agent, conductive agent, additive in the composite coating of the plus plate current-collecting body matrix surface of design, take binding agent, conductive agent, additive respectively, with the deionized water of the NMP containing mass percent 5 ~ 40% for solvent, first by binding agent, conductive agent and solvent add agitator tank and are uniformly dispersed, then reenter additive to stir, prepare composite coating slurry; Composite coating slurry is coated to collector matrix surface post-drying, prepares anode composite collector;
Second step: the preparation of positive/negative plate
Technique routinely, is coated in anode composite collection liquid surface by positive active material, negative electrode active material is coated in negative pole currect collecting surface, obtains positive plate, negative plate;
3rd step, the preparation of membrane surface composite conductive layers
By the quality proportioning of binding agent, conductive agent in the composite conductive layers of the membrane surface of design, take binding agent, conductive agent respectively, first binding agent is dissolved in solvent NMP, obtain the adhesive solution that mass percentage concentration is 2-6%, then, added in adhesive solution by conductive agent and stir, obtain mixed liquor, binding agent and conductive agent in mass ratio 1:1-9 mate;
Composite conductive layers slurry is coated to membrane surface and drying, obtains the barrier film that surface-coated has composite conductive layers;
4th step, lithium ion battery is shaping
There is the barrier film of composite conductive layers to prepare core through rolling step both positive and negative polarity pole piece and surface-coated, core is colded pressing through encapsulation, baking, fluid injection, heat, change into, partial volume operation prepares high multiplying power lithium ion battery.
CN201510955980.5A 2015-12-17 2015-12-17 Quickly-chargeable/dischargeable lithium ion battery and manufacture method thereof Pending CN105406083A (en)

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