CN108461808A - A kind of lithium ion battery of high-energy density and preparation method thereof - Google Patents

A kind of lithium ion battery of high-energy density and preparation method thereof Download PDF

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Publication number
CN108461808A
CN108461808A CN201810234862.9A CN201810234862A CN108461808A CN 108461808 A CN108461808 A CN 108461808A CN 201810234862 A CN201810234862 A CN 201810234862A CN 108461808 A CN108461808 A CN 108461808A
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China
Prior art keywords
plate
lithium
energy density
negative plate
positive
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Pending
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CN201810234862.9A
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Chinese (zh)
Inventor
陈启多
程君
高远鹏
柳听前
朱清
吴方胜
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Shanghai Lixin Energy Science And Technology Co Ltd
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Shanghai Lixin Energy Science And Technology Co Ltd
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Priority to CN201810234862.9A priority Critical patent/CN108461808A/en
Publication of CN108461808A publication Critical patent/CN108461808A/en
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/056Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566Liquid materials
    • H01M10/0567Liquid materials characterised by the additives
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/056Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566Liquid materials
    • H01M10/0568Liquid materials characterised by the solutes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/058Construction or manufacture
    • H01M10/0587Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134Electrodes based on metals, Si or alloys
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses a kind of lithium ion batteries of high-energy density, including positive plate, diaphragm, negative plate, shell, electrolyte, the diaphragm is set between the positive plate and the negative plate, the positive plate, the diaphragm, the negative plate three winding is placed in the shell, the electrolyte is full of the shell, the positive plate includes plus plate current-collecting body and the positive-active layer coated on the plus plate current-collecting body surface, the negative plate uses copper foil current collector, the electrolyte includes lithium salts, solvent, additive, the lithium salts includes LiFSI, LiTFSI one of which, the invention also discloses preparation methods.It is an advantage of the invention that coordinating high-performance lithium salts as negative plate using copper foil current collector, mitigating the quality of negative plate, lithium battery quality is set to reduce, energy density improves, and ensures the cycle life and stability of lithium battery, simplify the process for preparing negative plate, save material, reduces production cost.

Description

A kind of lithium ion battery of high-energy density and preparation method thereof
Technical field
The present invention relates to the lithium ion batteries and its preparation side of field of lithium ion battery more particularly to a kind of high-energy density Method.
Background technology
Lithium ion battery have specific capacity is high, self discharge is small, operating temperature range is wide, voltage platform is high, have extended cycle life, Memory-less effect, it is environmentally friendly the advantages that, be widely used to the fields such as mobile phone, laptop, electric tool, and Gradually promoted and applied in electric vehicle field.With the development of the progress and science and technology in epoch, the energy density of lithium ion battery is not It is disconnected to improve, but cannot still meet lightweight, the market demand of long continuation of the journey.The cruising ability and weight energy of lithium ion battery Metric density is always the direction that lithium ion battery is pursued, especially fast-developing power vehicle field, for high weight energy The pursuit of density is even more extremely urgent.
Invention content
Goal of the invention:In view of the above-mentioned problems, the object of the present invention is to provide a kind of lithium ion battery of high-energy density and Preparation method is improved negative plate and electrolyte, improves energy density.
Technical solution:
A kind of lithium ion battery of high-energy density, including positive plate, diaphragm, negative plate, shell, electrolyte, it is described every Film is set between the positive plate and the negative plate, after the positive plate, the diaphragm, negative plate three winding Be placed in the shell, the electrolyte be full of the shell, the positive plate include plus plate current-collecting body and coated on it is described just The positive-active layer of pole collection liquid surface, the negative plate use copper foil current collector, the electrolyte to include lithium salts, solvent, add It includes LiFSI, LiTFSI one of which to add agent, the lithium salts.Negative plate is not coated with only with copper foil current collector, surface Negative electrode active layer mitigates the weight of negative plate, improves energy density.
Preferably, in order to extend the cycle life of battery, the lithium salts further includes LiBOB, LiODFB one of which.
Preferably, in order to improve the cycle performance of lithium battery, a concentration of 0.9~2.0mol/ of lithium salts in the electrolyte L, the content of LiFSI or LiTFSI is 10~90% in the lithium salts.
Preferably, in order to stablize the cycle characteristics of battery, the additive includes acid anhydrides.
Specifically, the acid anhydrides is succinic anhydride or glutaric anhydride.
Specifically, the plus plate current-collecting body uses aluminum foil current collector, the positive-active layer to include positive active material, lead Electric agent, binder, the positive active material are cobalt acid lithium, nickle cobalt lithium manganate, LiFePO 4 one of which.
Specifically, the solvent includes EC, PC, EMC, the ratio of the solvent is EC/PC/EMC=3:1:6.
The preparation method of the lithium ion battery of the high-energy density, includes the following steps:
The making of step 1, positive plate:Positive active material, conductive agent, binder are stirred evenly, anode collection is coated on On fluid, after rolling and cut;
The making of step 2, negative plate:Negative plate uses copper foil current collector, and is cut;
Positive plate, diaphragm, negative plate are stacked, and are wound by step 3 successively, and winding is completed to be placed on shell In, it is toasted;
Step 4:Prepare electrolyte:Electrolyte includes lithium salts, solvent, additive, lithium salts include LiFSI, LiTFSI its Middle one kind;
Step 5:After the completion of step 3 baking, the prepared electrolyte in injection step 4 into shell, then be melted into, change At vacuum degassing is carried out after the completion, finished battery is obtained.
Wherein, lithium salts further includes LiBOB, LiODFB one of which in step 4.
Wherein, additive includes acid anhydrides in step 4, and acid anhydrides selects succinic anhydride or glutaric anhydride.
Advantageous effect:Compared with prior art, it is an advantage of the invention that using copper foil current collector as negative plate, cooperation is high Performance lithium salts mitigates the quality of negative plate, lithium battery quality is made to reduce, and energy density improves, and ensures the cycle life of lithium battery And stability, simplify the process for preparing negative plate, save material, reduce production cost, improve production efficiency, is suitble to extensive It promotes and applies.
Description of the drawings
Fig. 1 is positive/negative plate section schematic diagram after the completion of winding;
Fig. 2 is the structural schematic diagram of the lithium ion battery of high-energy density;
Fig. 3 is the cycle performance comparison diagram of embodiment 1, embodiment 2, embodiment 3;
Fig. 4 is the cycle performance comparison diagram of embodiment 1 and embodiment 4;
Fig. 5 is the cycle performance comparison diagram of embodiment 1 and embodiment 5;
Fig. 6 is the charge and discharge contrast curve of embodiment 1 and comparative example 1;
Fig. 7 is the cycle performance comparison diagram of embodiment 1 and comparative example 2;
Specific implementation mode
In the following with reference to the drawings and specific embodiments, the present invention is furture elucidated, it should be understood that these embodiments are merely to illustrate It the present invention rather than limits the scope of the invention, after having read the present invention, those skilled in the art are to of the invention each The modification of kind equivalent form falls within the application range as defined in the appended claims.
Embodiment 1
A kind of lithium ion battery of high-energy density, including positive plate 1, diaphragm 2, negative plate 3, shell 4, electrolyte, aluminium Lug 5, aluminium pole ears glue 6, nickel lug 7, nickel gel 8.Positive plate 1 is including plus plate current-collecting body and is coated on plus plate current-collecting body surface Positive-active layer, plus plate current-collecting body use aluminum foil current collector, positive-active layer includes positive active material, conductive agent, bonding Agent, positive active material select cobalt acid lithium.Negative plate 3 is using the copper foil current collector after electrolysis, calendering process.Electrolyte packet Include lithium salts, solvent, additive, a concentration of 1.5mol/L of lithium salts, lithium salts are taken using LiFSI and LiBOB bi-components in electrolyte Match, LiFSI:LiBOB=8:2, additive includes 3%PS, 0.5%VEC, 0.5%VC, 0.5% succinic anhydride, and solvent includes The ratio of EC, PC, EMC, solvent are EC/PC/EMC=3:1:6.Aluminium pole ears 5 are fixed by aluminium pole ears glue 6 and positive plate 1, nickel pole Ear 7 is fixed by nickel gel 8 and negative plate 3.Diaphragm 2 is set between positive plate 1 and negative plate 3, positive plate 1, diaphragm 2, Sectional drawing after 3 three of negative plate winding is as shown in Figure 1, be integrally placed in shell 4, and electrolyte is full of shell 4, such as Fig. 2 institutes Show.
The preparation method of the lithium ion battery of the high-energy density includes the following steps:
The making of step 1, positive plate:Plus plate current-collecting body uses aluminum foil current collector, positive active material to select cobalt acid lithium.It will Positive active material, conductive agent, binder put into mixing plant respectively, after stirring, are coated on plus plate current-collecting body, roll It later and is cut, cuts into fixed width;
The making of step 2, negative plate:Negative plate uses copper foil current collector, and is cut, and width is bigger than positive plate by 2~ 4mm;
Step 3 fixes aluminium pole ears and positive plate by aluminium pole ears glue, and nickel lug is solid by nickel gel with negative plate Fixed, positive plate, diaphragm, negative plate stack successively, and diaphragm is arranged between positive plate and negative plate, using volume needle by three Volume together, complete to be placed in shell, is toasted by winding;
Step 4:Prepare electrolyte:Electrolyte includes lithium salts, solvent, additive, a concentration of 1.5mol/ of electrolyte lithium salts L, lithium salts are arranged in pairs or groups using LiFSI and LiBOB bi-components, LiFSI:LiBOB=8:2, additive includes 0.5% VC, 0.5% fourth Dicarboxylic anhydride, solvent include EC, PC, EMC, and the ratio of solvent is EC/PC/EMC=3:1:6.
Step 5:After the completion of step 3 baking, the prepared electrolyte in injection step 4 into shell, then be melted into, change At vacuum degassing is carried out after the completion, finished battery is obtained.
Embodiment 2
The places different from embodiment 1 are that the lithium salts implemented in 1 is become LiFSI arranges in pairs or groups with LiODFB bi-components, LiFSI:LiODFB=8:2, lithium salt is constant, and solvent is not also adjusted with additive.
Embodiment 3
The places different from embodiment 1 are that the lithium salts implemented in 1 is become LiTFSI arranges in pairs or groups with LiBOB bi-components, LiTFSI:LiBOB=8:2, lithium salt is constant, and solvent is not also adjusted with additive.
Lines 1 are the cycle performance of lithium battery in embodiment 1 in Fig. 3, and lines 2 are the cyclicity of lithium battery in embodiment 2 Can, lines 3 are the cycle performance of lithium battery in embodiment 3, and two kinds of differences are used respectively in embodiment 1, embodiment 2, embodiment 3 High-performance lithium salts collocation, effect is almost the same, and using copper foil current collector as negative plate, lithium battery has certain cyclicity Energy.The Mass lost of lithium battery cathode plate made from embodiment 1, embodiment 2, embodiment 3, lithium battery quality are reduced, energy Density >=350Wh/kg.
Embodiment 4
The places different from embodiment 1 are, the lithium salts implemented in 1 is become LiFSI one pack systems, and lithium salt is constant, Solvent is not also adjusted with additive.Fig. 4 is the cycle performance comparison diagram of embodiment 1 and embodiment 4, and lines 1 are embodiment in Fig. 4 The cycle performance of lithium battery in 1, lines 2 are the cycle performance of lithium battery in embodiment 4 in Fig. 4, by figure it is found that using single group High-performance lithium salts, the cycle performance of lithium battery is divided to be not so good as two-component high-performance lithium salts.
Embodiment 5
Difference lies in remove the succinic anhydride in embodiment 1, other parts remain unchanged with embodiment 1.Fig. 5 is The cycle performance comparison diagram of embodiment 1 and embodiment 5, lines 1 are the cycle performance of lithium battery in embodiment 1 in Fig. 5, in Fig. 5 Lines 2 are the cycle performance of lithium battery in embodiment 5, and anhydride additive is beneficial to the cycle performance of lithium battery, in embodiment 5 Anhydride additive is not added, lithium battery cycle deteriorates.
Comparative example 1
Difference lies in the production method of negative plate is with embodiment 1:Cathode graphite, conductive agent, binder are thrown respectively Enter mixing plant, after stirring evenly, is coated on copper foil current collector surface.Fig. 6 is the charge and discharge pair of embodiment 1 and comparative example 1 Than curve graph, lines 1 are the charging curve of lithium battery in embodiment 1 in Fig. 6, and lines 2 are lithium battery in embodiment 1 in Fig. 6 Discharge curve, lines 3 are the charging curve of lithium battery in comparative example 1 in Fig. 6, and lines 4 are lithium battery in comparative example 1 in Fig. 6 Discharge curve, it will be appreciated from fig. 6 that using copper foil current collector as negative material in embodiment 1, charge-discharge performance is preferable, and electric discharge is flat Platform is higher.
Comparative example 2
Difference lies in become LiPF6 one pack systems, lithium salt is constant, molten by the lithium salts in embodiment 1 with embodiment 1 Agent is not also adjusted with additive.Fig. 7 is the cycle performance comparison diagram of embodiment 1 and comparative example 2, and lines 1 are embodiment 1 in Fig. 7 The cycle performance of middle lithium battery, lines 2 are the cycle performance of lithium battery in comparative example 2 in Fig. 7, use other business lithium salts LiPF6, lithium battery cycle performance are deteriorated.
In conclusion the present invention is used using copper foil current collector as negative plate, cooperation two-component high-performance lithium salts combines, And anhydride additive alleviates the quality of negative plate, makes on the basis of ensureing the cycle life and stability of lithium battery Lithium battery quality is reduced, and energy density improves, and is simplified the process for preparing negative plate, is saved material, and production cost is reduced, and is improved Production efficiency is suitble to large-scale promotion application.

Claims (10)

1. a kind of lithium ion battery of high-energy density, it is characterised in that:Including positive plate (1), diaphragm (2), negative plate (3), Shell (4), electrolyte, the diaphragm (2) are set between the positive plate (1) and the negative plate (3), the positive plate (1), the diaphragm (2), the negative plate (3) three's winding are placed in the shell (4), and the electrolyte is full of described Shell (4), the positive plate (1) include plus plate current-collecting body and the positive-active layer coated on the plus plate current-collecting body surface, institute It includes lithium salts, solvent, additive to state negative plate (3) and use copper foil current collector, the electrolyte, the lithium salts include LiFSI, LiTFSI one of which.
2. a kind of lithium ion battery of high-energy density according to claim 1, it is characterised in that:The lithium salts further includes LiBOB, LiODFB one of which.
3. a kind of lithium ion battery of high-energy density according to claim 2, it is characterised in that:Lithium in the electrolyte A concentration of 0.9~2.0mol/L of salt, the content of LiFSI or LiTFSI is 10~90% in the lithium salts.
4. a kind of lithium ion battery of high-energy density according to any one of claim 1-2, it is characterised in that:Institute It includes acid anhydrides to state additive.
5. a kind of lithium ion battery of high-energy density according to claim 4, it is characterised in that:The acid anhydrides is fourth two Acid anhydrides or glutaric anhydride.
6. a kind of lithium ion battery of high-energy density according to claim 1, it is characterised in that:The plus plate current-collecting body Using aluminum foil current collector, the positive-active layer includes positive active material, conductive agent, binder, the positive active material For cobalt acid lithium, nickle cobalt lithium manganate, LiFePO 4 one of which.
7. a kind of lithium ion battery of high-energy density according to claim 1, it is characterised in that:The solvent includes The ratio of EC, PC, EMC, the solvent are EC/PC/EMC=3:1:6.
8. a kind of preparation method of the lithium ion battery of high-energy density described in claim 1, it is characterised in that including following Step:
The making of step 1, positive plate:Positive active material, conductive agent, binder are stirred evenly, plus plate current-collecting body is coated on On, after rolling and cut;
The making of step 2, negative plate:Negative plate uses copper foil current collector, and is cut;
Positive plate, diaphragm, negative plate are stacked, and are wound by step 3 successively, and winding is completed to be placed in shell, into Row baking;
Step 4:Prepare electrolyte:Electrolyte includes lithium salts, solvent, additive, and lithium salts includes LiFSI, LiTFSI wherein one Kind;
Step 5:After the completion of step 3 baking, the prepared electrolyte in injection step 4 into shell, then be melted into, it has been melted into At rear carry out vacuum degassing, finished battery is obtained.
9. a kind of preparation method of the lithium ion battery of high-energy density according to claim 8, it is characterised in that:Step In 4, lithium salts further includes LiBOB, LiODFB one of which.
10. a kind of preparation method of the lithium ion battery of high-energy density according to claim 8, it is characterised in that:Step In rapid 4, additive includes acid anhydrides, and acid anhydrides selects succinic anhydride or glutaric anhydride.
CN201810234862.9A 2018-03-21 2018-03-21 A kind of lithium ion battery of high-energy density and preparation method thereof Pending CN108461808A (en)

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CN111793824A (en) * 2020-07-21 2020-10-20 苏州华赢新能源材料科技有限公司 Surface-modified high-nickel cathode material and preparation method and application thereof
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