CN109546109A - A kind of high-temperature stable lithium battery anode - Google Patents

A kind of high-temperature stable lithium battery anode Download PDF

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Publication number
CN109546109A
CN109546109A CN201811340633.1A CN201811340633A CN109546109A CN 109546109 A CN109546109 A CN 109546109A CN 201811340633 A CN201811340633 A CN 201811340633A CN 109546109 A CN109546109 A CN 109546109A
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lithium
anode
lithium battery
temperature stable
lifepo4
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CN109546109B (en
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汪六
汪六一
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ANHUI JINKUNTAI ELECTRONIC TECHNOLOGY Co.,Ltd.
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Hefei Smart Management 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
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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

Abstract

The present invention provides a kind of high-temperature stable lithium battery anode, it is formed by plus plate current-collecting body and coated in the anode sizing agent on plus plate current-collecting body, the anode sizing agent is made of positive active material, conductive agent, binder and solvent, and the positive active material is (0.2~0.8) according to weight ratio by LiMn2O4, nickle cobalt lithium manganate 532, phosphoric acid vanadium lithium, LiFePO4: (1~1.5): (0.5~1): 1 forms.The present invention carries out by using LiMn2O4, nickle cobalt lithium manganate 532, phosphoric acid vanadium lithium, LiFePO4 according to specific ratio compound, pass through the difference using difference and surface energy in different materials structure, structure change of the material in charge and discharge process can be slowed down, reduce dissolution of the bivalent metal ion in charge and discharge process, to improve the stability of material.

Description

A kind of high-temperature stable lithium battery anode
Technical field
The present invention relates to technical field of lithium batteries more particularly to a kind of high-temperature stable lithium battery anodes.
Background technique
Lithium ion battery have open-circuit voltage is high, energy density is big, long service life, memory-less effect, it is pollution-free and from It discharges the advantages that small, is the best battery system of current comprehensive performance and applicable battery system widest in area.By ten Fast development in several years, lithium ion battery industry chain have reached its maturity in China, technical performance, maturity and industrialization Considerable scale is had reached, will be new energy and the matched first choice of ev industry battery within following one period, and have Absolute popularization and application advantage and huge development space.It is well known that the performance of lithium ion battery depend primarily on lithium from The structure and performance of sub- battery material.Lithium ion battery material mainly includes positive electrode, negative electrode material, diaphragm and electrolyte, Wherein positive electrode directly determines the performances such as energy density and the service life of lithium ion battery, is performance of lithium ion battery Key influence factor.
As power type lithium-ion battery anode material, the phosphorus such as the ternary oxide series material of the nickel containing cobalt, LiFePO4 Hydrochlorate series material and lithium manganate having spinel structure material become alternative common used material with its advantage respectively.Wherein spinel-type Lithium manganate material has outstanding advantages of energy density is high, power density is high, operating voltage is high, at low cost, is before most applying The power type lithium-ion battery anode material of scape.But ternary material the problem of there is also itself, wherein high-temperature storage performance is poor And high temperature circulation capacity retention ratio is poor.And lithium battery group even has the control of BMS, mould in electric vehicle actual use Group temperature rise also tends to reach 50 DEG C or more, and ternary material cycle life is unsatisfactory at present, therefore how to promote battery in high temperature In the case of cycle life become extremely important problem.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of high-temperature stable lithium battery anode, it has at high temperature Good cyclical stability can effectively extend the cycle life of battery at high temperature.
In order to solve the above technical problems, the present invention provides a kind of high-temperature stable lithium battery anode, by plus plate current-collecting body and Coated in the anode sizing agent composition on plus plate current-collecting body, the anode sizing agent is by positive active material, conductive agent, binder and molten Agent composition, the positive active material are according to weight ratio by LiMn2O4, nickle cobalt lithium manganate 532, phosphoric acid vanadium lithium, LiFePO4 (0.2~0.8): (1~1.5): (0.5~1): 1 composition.
The present inventor has found in long-term R&D process, using LiMn2O4, nickle cobalt lithium manganate 532, vanadium phosphate Lithium, LiFePO4 are compound according to the progress of specific ratio, and the synergistic effect of storeroom can be made to be optimal, improve positive electrode Contact area be conducive to the transmission of lithium ion during the cycle charge-discharge of lithium battery, reduce internal resistance, improve charge and discharge Electrical efficiency；Further, since the difference of difference and surface energy in different materials structure, can slow down material in charge and discharge process Structure change, reduce dissolution of the bivalent metal ion in charge and discharge process, to improve the stability of material.
In order to further increase the cyclical stability of the lithium battery anode at high temperature, manganese in the positive active material Sour lithium, nickle cobalt lithium manganate 532, phosphoric acid vanadium lithium, LiFePO4 weight ratio be preferably (0.35~0.66): (1.15~1.36): (0.58~0.85): 1；Further preferably (0.42~0.6): (1.2~1.32): (0.6~0.75): 1, such as can be 0.35:1.15:0.85:1；0.66:1.36:0.58:1；0.42:1.26:0.68:1；0.6:1.32:0.75:1；0.5:1.2: 0.6:1。
The inventors found that the tap density of each substance follows the high temperature of lithium battery anode in positive electrode active materials Ring performance has significant impact, and the tap density by adjusting each substance in positive electrode active materials can significantly improve lithium battery The cyclical stability of anode at high temperature, it is preferred that the tap density of the LiMn2O4 is 2.8~4.3g/cm3；More preferably 3 ~3.8g/cm3(such as can be 2.8g/cm3；3g/cm3；3.2g/cm3；3.5g/cm3；3.8g/cm3；4g/cm3；4.2g/cm3； 4.3g/cm3)；
The tap density of the nickle cobalt lithium manganate 532 is 2.9~3.5g/cm3；More preferably 3~3.8g/cm3(such as can Think 2.9g/cm3；3g/cm3；3.2g/cm3；3.5g/cm3；)；
The tap density of the phosphoric acid vanadium lithium phosphoric acid vanadium lithium is 2.9~3.8g/cm3；More preferable 3.2~3.6g/cm3(such as It can be 2.9g/cm3；3.2g/cm3；3.5g/cm3；3.6g/cm3；3.8g/cm3)；
The tap density of the LiFePO4 is 2.8~3.6g/cm3；More preferably 3~3.2g/cm3(such as can be 2.8g/cm3；3g/cm3；3.2g/cm3；3.5g/cm3；3.6g/cm3)。
Positive composition in the present invention are as follows: the positive active material of 95 weight %, the conductive agent of 3 weight %, 2 weight % are viscous Tie agent.
The preparation step of the anode is as follows:
(1) LiMn2O4, nickle cobalt lithium manganate 532, LiFePO4 are weighed according to weight ratio, obtains cathode mixture, it will be positive Mixture and conductive agent, above-mentioned binder are added in de-airing mixer, stir 45min under the revolving speed of 20r/min, obtain anode Powder；
(2) above-mentioned positive mix and NMP are stirred evenly in de-airing mixer, obtains anode and close slurry lotion 1, wherein stirs Mixing rate is 1500r/min, mixing time 60min；
(3) anode is closed into slurry lotion 1 and NMP is stirred evenly in de-airing mixer, obtained anode and close slurry lotion 2, wherein Stirring rate is 2000r/min, mixing time 90min；
(4) it is closed in slurry lotion 2 to anode and NMP is added, obtained the slurry that viscosity is 6600mPas, slurry is crossed into 120 mesh Sieve, obtains anode sizing agent；
(5) anode sizing agent after sieving is coated in the tow sides with a thickness of 20 μm of copper foil, then 120 DEG C of drying, Roll-in obtains high-temperature stable lithium battery anode.
Conductive agent in the present invention can be known to the field technical staff, when conductive agent is by electrically conductive graphite and carbon nanometer Pipe according to weight be 1:(1~2) composition when, the cyclical stability of the lithium battery anode at high temperature can be further increased.
In the present invention binder can for known to one of ordinary skill in the art, when binder be sodium carboxymethylcellulose and PVDF according to weight ratio be 1:(1.5~2) composition when, it is steady that the circulation of the lithium battery anode at high temperature can be further increased It is qualitative.
Lithium battery anode of the invention is suitble to be combined with existing various cathode of lithium battery, and be made has at high temperature The lithium battery of good circulation stability.When negative electrode active material is artificial graphite, carbonaceous mesophase spherules and porous carbon according to (0.5 ~0.8) when: 1:(0.1~0.3), the cycle performance of lithium battery is best.
Through the above technical solutions, the present invention has following technical effect that
The present invention by using LiMn2O4, nickle cobalt lithium manganate 532, phosphoric acid vanadium lithium, LiFePO4 according to specific ratio into Row is compound, and the synergistic effect of storeroom can be made to be optimal, improve the contact area of positive electrode, filled in the circulation of lithium battery In discharge process, be conducive to the transmission of lithium ion, reduce internal resistance, improve efficiency for charge-discharge；Further, since different materials structure On difference and surface can difference, structure change of the material in charge and discharge process can be slowed down, reduce divalent metal from Dissolution of the son in charge and discharge process, to improve the stability of material.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to Limit the present invention.
Embodiment 1
A kind of high-temperature stable anode material of lithium battery, by plus plate current-collecting body copper foil and coated on plus plate current-collecting body just Pole slurry composition, the anode sizing agent by the positive active material of 95 weight %, 3 weight % conductive agent (by electrically conductive graphite and Carbon nanotube is 1:1.5 composition according to weight ratio), (sodium carboxymethylcellulose and PVDF are 2 weight % binders according to weight ratio 1:1.8) formed with solvent；
The positive active material is according to weight ratio by LiMn2O4, nickle cobalt lithium manganate 532, phosphoric acid vanadium lithium, LiFePO4 0.5:1.2:0.6:1 composition；
The tap density of the LiMn2O4 is 3.5g/cm3；The tap density of the nickle cobalt lithium manganate 532 is 3.2g/cm3； The tap density that the tap density of the phosphoric acid vanadium lithium is is 3.2g/cm3；The tap density of the LiMn2O4 is 3.2g/cm3。
The preparation step of the anode is as follows:
(1) LiMn2O4, nickle cobalt lithium manganate 532, LiFePO4 are weighed according to weight ratio, obtains cathode mixture, it will be positive Mixture and conductive agent, above-mentioned binder are added in de-airing mixer, stir 45min under the revolving speed of 20r/min, obtain anode Powder；
(2) above-mentioned positive mix and NMP are stirred evenly in de-airing mixer, obtains anode and close slurry lotion 1, wherein stirs Mixing rate is 1500r/min, mixing time 60min；
(3) anode is closed into slurry lotion 1 and NMP is stirred evenly in de-airing mixer, obtained anode and close slurry lotion 2, wherein Stirring rate is 2000r/min, mixing time 90min；
(4) it is closed in slurry lotion 2 to anode and NMP is added, obtained the slurry that viscosity is 6600mPas, slurry is crossed into 120 mesh Sieve, obtains anode sizing agent；
(5) anode sizing agent after sieving is coated in the tow sides with a thickness of 20 μm of copper foil, then 120 DEG C of drying, Roll-in obtains high-temperature stable lithium battery anode.
The present embodiment also provides a kind of lithium battery, including anode, diaphragm, cathode and electrolyte, wherein anode is according to above-mentioned Method is prepared.
The composition of cathode are as follows: the cathode is by the carbonaceous mesophase spherules of 95 weight %, the electrically conductive graphite of 1 weight %, 4 weights Measure binder (carboxymethyl cellulose) composition of %；
It according to weight ratio is 0.6:1:0.15 that the negative electrode active material, which is artificial graphite, carbonaceous mesophase spherules and porous carbon, Composition.
Cathode the preparation method comprises the following steps:
Above-mentioned negative electrode material and deionized water are stirred evenly in de-airing mixer, stirring rate is
1200r/min, mixing time 90min, whipping temp are 40 DEG C, obtain the slurry that viscosity is 3200mPas, Slurry is crossed into 120 meshes, obtains negative electrode slurry；Negative electrode slurry after sieving is coated on to the tow sides of 8 μm of copper foils of thickness again, Then 120 DEG C of drying, roll-ins under the pressure of 1.6MPa, obtaining compacted density is 1.2g/cm3, surface density 68g/cm2It is negative Pole piece.
The assembly of battery
By LiPF6 and methane-disulfonic acid methylene ester, ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC) be configured to solution that LiPF6 concentration is 1mol/L (wherein, the weight ratio of EC, EMC and DMC are 1: 1: 1), wherein methane The content of disulfonic acid methylene ester is the 2% of EC, EMC and DMC total weight, obtains nonaqueous electrolytic solution.
Rectangular aluminum-shell battery successively is wound into up- coiler stacking by above-mentioned anode, with a thickness of 25 μm of PE diaphragms and cathode Obtained electrode group is put into battery case open at one end by IFP2714897-20, is injected above-mentioned nonaqueous electrolytic solution, is then existed After shelving 1 day at 60 DEG C, steel ball sealing is then played in the state of vacuum degree -0.08MPa, chemical property is as shown in table 1.
Embodiment 2
A kind of high-temperature stable anode material of lithium battery, by plus plate current-collecting body copper foil and coated on plus plate current-collecting body just Pole slurry composition, the anode sizing agent by the positive active material of 95 weight %, 3 weight % conductive agent (by electrically conductive graphite and Carbon nanotube is 1:1.5 composition according to weight ratio), (sodium carboxymethylcellulose and PVDF are 2 weight % binders according to weight ratio 1:2) formed with solvent；
The positive active material is according to weight ratio by LiMn2O4, nickle cobalt lithium manganate 532, phosphoric acid vanadium lithium, LiFePO4 0.6:1.32:0.75:1 composition；
The tap density of the LiMn2O4 is 4g/cm3；The tap density of the nickle cobalt lithium manganate 532 is 3.5g/cm3；Institute Stating the tap density that the tap density of phosphoric acid vanadium lithium is is 2.9g/cm3；The tap density of the LiMn2O4 is 2.8g/cm3。
The preparation step of the anode is as follows:
(1) LiMn2O4, nickle cobalt lithium manganate 532, LiFePO4 are weighed according to weight ratio, obtains cathode mixture, it will be positive Mixture and conductive agent, above-mentioned binder are added in de-airing mixer, stir 45min under the revolving speed of 20r/min, obtain anode Powder；
(2) above-mentioned positive mix and NMP are stirred evenly in de-airing mixer, obtains anode and close slurry lotion 1, wherein stirs Mixing rate is 1500r/min, mixing time 60min；
(3) anode is closed into slurry lotion 1 and NMP is stirred evenly in de-airing mixer, obtained anode and close slurry lotion 2, wherein Stirring rate is 2000r/min, mixing time 90min；
(4) it is closed in slurry lotion 2 to anode and NMP is added, obtained the slurry that viscosity is 6600mPas, slurry is crossed into 120 mesh Sieve, obtains anode sizing agent；
(5) anode sizing agent after sieving is coated in the tow sides with a thickness of 20 μm of copper foil, then 120 DEG C of drying, Roll-in obtains high-temperature stable lithium battery anode.
The present embodiment also provides a kind of lithium battery, including anode, diaphragm, cathode and electrolyte, wherein anode is according to above-mentioned Method is prepared；The preparation method of cathode and the assemble method of battery are the same as embodiment 1.
Embodiment 3
A kind of high-temperature stable anode material of lithium battery, by plus plate current-collecting body copper foil and coated on plus plate current-collecting body just Pole slurry composition, the anode sizing agent by the positive active material of 95 weight %, 3 weight % conductive agent (by electrically conductive graphite and Carbon nanotube according to weight ratio be 1:1.5 form), (sodium carboxymethylcellulose and butadiene-styrene latex are according to weight for 2 weight % binders Than being formed for 1:1.5) and solvent；
The positive active material is according to weight ratio by LiMn2O4, nickle cobalt lithium manganate 532, phosphoric acid vanadium lithium, LiFePO4 0.42:1.26:0.68:1 composition；
The tap density of the LiMn2O4 is 3.8g/cm3；The tap density of the nickle cobalt lithium manganate 532 is 2.9g/cm3； The tap density that the tap density of the phosphoric acid vanadium lithium is is 2.9g/cm3；The tap density of the LiMn2O4 is 3.8g/cm3。
The preparation step of the anode is as follows:
(1) LiMn2O4, nickle cobalt lithium manganate 532, LiFePO4 are weighed according to weight ratio, obtains cathode mixture, it will be positive Mixture and conductive agent, above-mentioned binder are added in de-airing mixer, stir 45min under the revolving speed of 20r/min, obtain anode Powder；
(2) above-mentioned positive mix and NMP are stirred evenly in de-airing mixer, obtains anode and close slurry lotion 1, wherein stirs Mixing rate is 1500r/min, mixing time 60min；
(3) anode is closed into slurry lotion 1 and NMP is stirred evenly in de-airing mixer, obtained anode and close slurry lotion 2, wherein Stirring rate is 2000r/min, mixing time 90min；
(4) it is closed in slurry lotion 2 to anode and NMP is added, obtained the slurry that viscosity is 6600mPas, slurry is crossed into 120 mesh Sieve, obtains anode sizing agent；
(5) anode sizing agent after sieving is coated in the tow sides with a thickness of 20 μm of copper foil, then 120 DEG C of drying, Roll-in obtains high-temperature stable lithium battery anode.
The present embodiment also provides a kind of lithium battery, including anode, diaphragm, cathode and electrolyte, wherein anode is according to above-mentioned Method is prepared；The preparation method of cathode and the assemble method of battery are the same as embodiment 1.
Embodiment 4
A kind of high-temperature stable anode material of lithium battery, by plus plate current-collecting body copper foil and coated on plus plate current-collecting body just Pole slurry composition, the anode sizing agent by the positive active material of 95 weight %, 3 weight % conductive agent (by electrically conductive graphite and Carbon nanotube according to weight ratio be 1:1 form), (sodium carboxymethylcellulose and butadiene-styrene latex are according to weight ratio for 2 weight % binders It is formed for 1:1.8) and solvent；
The positive active material is according to weight ratio by LiMn2O4, nickle cobalt lithium manganate 532, phosphoric acid vanadium lithium, LiFePO4 0.66:1.36:0.58:1 composition；
The tap density of the LiMn2O4 is 2.8g/cm3；The tap density of the nickle cobalt lithium manganate 532 is 3.5g/cm3； The tap density that the tap density of the phosphoric acid vanadium lithium is is 3.0g/cm3；The tap density of the LiMn2O4 is 3.5g/cm3。
The preparation step of the anode is as follows:
(1) LiMn2O4, nickle cobalt lithium manganate 532, LiFePO4 are weighed according to weight ratio, obtains cathode mixture, it will be positive Mixture and conductive agent, above-mentioned binder are added in de-airing mixer, stir 45min under the revolving speed of 20r/min, obtain anode Powder；
(2) above-mentioned positive mix and NMP are stirred evenly in de-airing mixer, obtains anode and close slurry lotion 1, wherein stirs Mixing rate is 1500r/min, mixing time 60min；
(3) anode is closed into slurry lotion 1 and NMP is stirred evenly in de-airing mixer, obtained anode and close slurry lotion 2, wherein Stirring rate is 2000r/min, mixing time 90min；
(4) it is closed in slurry lotion 2 to anode and NMP is added, obtained the slurry that viscosity is 6600mPas, slurry is crossed into 120 mesh Sieve, obtains anode sizing agent；
(5) anode sizing agent after sieving is coated in the tow sides with a thickness of 20 μm of copper foil, then 120 DEG C of drying, Roll-in obtains high-temperature stable lithium battery anode.
The present embodiment also provides a kind of lithium battery, including anode, diaphragm, cathode and electrolyte, wherein anode is according to above-mentioned Method is prepared；The preparation method of cathode and the assemble method of battery are the same as embodiment 1.
Embodiment 5
A kind of high-temperature stable anode material of lithium battery, by plus plate current-collecting body copper foil and coated on plus plate current-collecting body just Pole slurry composition, the anode sizing agent by the positive active material of 95 weight %, 3 weight % conductive agent (by electrically conductive graphite and Carbon nanotube according to weight ratio be 1:2 form), (sodium carboxymethylcellulose and butadiene-styrene latex are according to weight ratio for 2 weight % binders It is formed for 1:1.8) and solvent；
The positive active material is according to weight ratio by LiMn2O4, nickle cobalt lithium manganate 532, phosphoric acid vanadium lithium, LiFePO4 0.35:1.15:0.85:1 composition；
The tap density of the LiMn2O4 is 3.2g/cm3；The tap density of the nickle cobalt lithium manganate 532 is 3.2g/cm3； The tap density that the tap density of the phosphoric acid vanadium lithium is is 3.8g/cm3；The tap density of the LiMn2O4 is 3.5g/cm3。
The preparation step of the anode is as follows:
(1) LiMn2O4, nickle cobalt lithium manganate 532, LiFePO4 are weighed according to weight ratio, obtains cathode mixture, it will be positive Mixture and conductive agent, above-mentioned binder are added in de-airing mixer, stir 45min under the revolving speed of 20r/min, obtain anode Powder；
(2) above-mentioned positive mix and NMP are stirred evenly in de-airing mixer, obtains anode and close slurry lotion 1, wherein stirs Mixing rate is 1500r/min, mixing time 60min；
(3) anode is closed into slurry lotion 1 and NMP is stirred evenly in de-airing mixer, obtained anode and close slurry lotion 2, wherein Stirring rate is 2000r/min, mixing time 90min；
(4) it is closed in slurry lotion 2 to anode and NMP is added, obtained the slurry that viscosity is 6600mPas, slurry is crossed into 120 mesh Sieve, obtains anode sizing agent；
(5) anode sizing agent after sieving is coated in the tow sides with a thickness of 20 μm of copper foil, then 120 DEG C of drying, Roll-in obtains high-temperature stable lithium battery anode.
The present embodiment also provides a kind of lithium battery, including anode, diaphragm, cathode and electrolyte, wherein anode is according to above-mentioned Method is prepared；The preparation method of cathode and the assemble method of battery are the same as embodiment 1.
Comparative example 1
According to the method for embodiment 1, unlike: the positive active material is by LiMn2O4, nickle cobalt lithium manganate 532, phosphorus Sour vanadium lithium, LiFePO4 are 0.1:1.8:1.5:1 composition according to weight ratio.
Comparative example 2
According to the method for embodiment 1, unlike: the positive active material is by LiMn2O4, nickle cobalt lithium manganate 532, phosphorus Sour vanadium lithium, LiFePO4 are 1:0.5:0.2:1 composition according to weight ratio.
Comparative example 3
According to the method for embodiment 1, unlike, the tap density of the LiMn2O4 is 2.5g/cm3；The nickel cobalt manganese The tap density of sour lithium 532 is 4g/cm3；The tap density of the phosphoric acid vanadium lithium is 2.5g/cm3；The jolt ramming of the LiFePO4 Density is 4.2g/cm3。
Comparative example 4
According to the method for embodiment 1, unlike, the tap density of the LiMn2O4 is 4.5g/cm3；The nickel cobalt manganese The tap density of sour lithium 532 is 2.1g/cm3；The tap density of the phosphoric acid vanadium lithium is 4g/cm3；The jolt ramming of the LiFePO4 Density is 2.5g/cm3。
Comparative example 5
According to the method for embodiment 1, unlike: the positive active material is by LiMn2O4, nickle cobalt lithium manganate 532, phosphorus Sour iron lithium is 0.5:1.8:1 composition according to weight ratio.
Comparative example 6
According to the method for embodiment 1, unlike: the positive active material by nickle cobalt lithium manganate 532, phosphoric acid vanadium lithium, LiFePO4 is 1.2:1.1:1 composition according to weight ratio.
Comparative example 7
According to the method for embodiment 1, unlike: the positive active material is pressed by nickle cobalt lithium manganate 532, LiFePO4 It is 2.3:1 composition according to weight ratio.
Comparative example 8
According to the method for embodiment 1, unlike: the positive active material is LiFePO4.
Experimental example
It at 65 DEG C, is charged with constant voltage charging method, limitation electric current is 0.5C, final voltage 3.5V, with constant current Discharge mode discharges, discharge current 0.5C, and the blanking voltage of electric discharge is 2.5 volts, is recycled 600 times, calculates circulation 600 times Capacity retention ratio R afterwards, experimental result are as shown in table 1.
Table 1:
Capacity retention ratio R/%
Embodiment 1 84.3
Embodiment 2 83.2
Embodiment 3 81.9
Embodiment 4 79.6
Embodiment 5 80.6
Comparative example 1 65.2
Comparative example 2 68.4
Comparative example 3 72.3
Comparative example 4 73.1
Comparative example 5 62.8
Comparative example 6 63.2
Comparative example 7 61.9
Comparative example 8 58.3
Foregoing description is only the description to section Example of the present invention, not to any restriction of the scope of the invention, current row The those of ordinary skill of industry can according to the present invention make above-described embodiment and improve or modify, but belong to present invention protection model It encloses.

Claims (9)

1. a kind of high-temperature stable lithium battery anode, by plus plate current-collecting body and coated in the anode sizing agent group on plus plate current-collecting body At the anode sizing agent is made of positive active material, conductive agent, binder and solvent, which is characterized in that the positive-active Substance is (0.2~0.8): (1~1.5) according to weight ratio by LiMn2O4, nickle cobalt lithium manganate 532, phosphoric acid vanadium lithium, LiFePO4: (0.5~1): 1 composition.
2. high-temperature stable lithium battery anode according to claim 1, which is characterized in that the positive active material is by manganese Sour lithium, nickle cobalt lithium manganate 532, phosphoric acid vanadium lithium, LiFePO4 are (0.35~0.66): (1.15~1.36) according to weight ratio: (0.58~0.85): 1 composition.
3. high-temperature stable lithium battery anode according to claim 2, which is characterized in that the positive active material is by manganese Sour lithium, nickle cobalt lithium manganate 532, phosphoric acid vanadium lithium, LiFePO4 are (0.42~0.6): (1.2~1.32): (0.6 according to weight ratio ~0.75): 1 composition.
4. high-temperature stable lithium battery anode according to any one of claims 1 to 3, which is characterized in that the manganese The tap density of sour lithium is 2.8~4.3g/cm3；
Preferably, the tap density of the LiMn2O4 is 3~3.8g/cm3。
5. high-temperature stable lithium battery anode according to claim 4, which is characterized in that the nickle cobalt lithium manganate 532 Tap density is 2.9~3.5g/cm3；
Preferably, the tap density of nickle cobalt lithium manganate 532 is 3~3.8g/cm3。
6. high-temperature stable lithium battery anode according to claim 5, which is characterized in that the vibration density of the phosphoric acid vanadium lithium Degree is 2.9~3.8g/cm3；
Preferably, the tap density of the phosphoric acid vanadium lithium is 3.2~3.6g/cm3。
7. high-temperature stable lithium battery anode according to claim 6, which is characterized in that the vibration density of the LiFePO4 Degree is 2.8~3.6g/cm3；
Preferably, the tap density of the LiFePO4 is 3~3.2g/cm3。
8. high-temperature stable lithium battery anode according to claim 7, which is characterized in that the conductive agent is by electrically conductive graphite With carbon nanotube according to weight be 1:(1~2) composition.
9. high-temperature stable lithium battery anode according to claim 8, which is characterized in that the binder is that carboxymethyl is fine It is 1:(1.5~2 that plain sodium and PVDF, which are tieed up, according to weight ratio) composition.
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