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CN107768727B - High temperature circulation lithium iron phosphate dynamic battery and its manufacturing method - Google Patents

High temperature circulation lithium iron phosphate dynamic battery and its manufacturing method Download PDF

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Publication number
CN107768727B
CN107768727B CN201710953160.1A CN201710953160A CN107768727B CN 107768727 B CN107768727 B CN 107768727B CN 201710953160 A CN201710953160 A CN 201710953160A CN 107768727 B CN107768727 B CN 107768727B
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cathode
anode
positive electrode
slurry
negative electrode
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CN107768727A (en
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沈晓彦
黄佳俊
顾敏捷
胡丹丹
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Jiangsu haisida power supply Co.,Ltd.
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JIANGSU HIGHSTAR BATTERY MANUFACTURING 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
    • 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
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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)
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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The present invention relates to technical field of lithium batteries, more particularly to high temperature circulation lithium iron phosphate dynamic battery and its manufacturing method, the high temperature circulation lithium iron phosphate dynamic battery, including anode, cathode, diaphragm and electrolyte, the anode is including plus plate current-collecting body and coated in the positive electrode on plus plate current-collecting body, the positive electrode includes carbon coating type LiFePO 4 material, and the particle diameter distribution D50 of the carbon coating type LiFePO 4 material is 1~5 μm；The tap density of the LiFePO4 is 0.9~1.3g/cm3；The specific surface area of the LiFePO4 is 7.5~11.3m2/g；The cathode includes negative current collector and coated in the negative electrode material on negative current collector, and the negative electrode material includes carbonaceous mesophase spherules, and the particle diameter distribution D50 of the carbonaceous mesophase spherules is 3.6~8.5 μm, and tap density is 0.9~1.3g/cm3, specific surface area is 1.2~1.7m2/g.The present invention reduces polarization of electrode by the partial size of adjusting anode and cathode active materials, improves the charge-discharge performance and cycle performance of lithium battery at high temperature.

Description

High temperature circulation lithium iron phosphate dynamic battery and its manufacturing method
Technical field
The present invention relates to technical field of lithium batteries, and in particular to high temperature circulation lithium iron phosphate dynamic battery and its manufacturer Method.
Background technique
The pure electric automobile product sold in country's new-energy automobile market at present is more and more abundant, but most pure electricity It is very fast that electrical automobile has that high temperature day course continuation mileage is decayed.Some researches show that interior when temperature is increased to 40 DEG C from 25 DEG C Actual temperature is much higher than 40 DEG C, and lithium ion battery shows higher initial capacity, but the stable circulation of battery after increasing temperature Property reduce, capacity attenuation rate accelerate.Therefore, high-temperature behavior is shown as an important indicator for considering battery context applicability It obtains particularly important.Common batteries use under high temperature environment, and electrode polarization aggravation is that battery under high temperature is caused to hold in charging process The main reason for amount decays rapidly, and charge transmission resistance increases and since the generation of bulk gas makes electrode under the high temperature conditions Deformation occurs, and discharge capacity is made further to decay.
Summary of the invention
Of the existing technology in order to overcome the problems, such as, an object of the present invention is to provide a kind of high temperature circulation LiFePO4 Power battery, it has good charge-discharge performance and cyclical stability at high temperature.
The second object of the present invention is to provide a kind of preparation method of high temperature circulation lithium iron phosphate dynamic battery.
To achieve the goals above, the present invention provides a kind of high temperature circulation lithium iron phosphate dynamic battery, including positive, negative Pole, diaphragm and electrolyte, the anode is including plus plate current-collecting body and coated in the positive electrode on plus plate current-collecting body, the anode Material includes positive electrode active materials, and the positive electrode active materials include carbon coating type LiFePO 4 material, the carbon coating type phosphorus The particle diameter distribution D50 of sour iron lithium material is 1~5 μm；The tap density of the LiFePO4 is 0.9~1.3g/cm3；The phosphorus The specific surface area of sour iron lithium is 7.5~11.3m2/g；
The cathode includes negative current collector and coated in the negative electrode material on negative current collector, and the negative electrode material includes Negative electrode active material, the negative electrode active material include carbonaceous mesophase spherules, and the particle diameter distribution D50 of the carbonaceous mesophase spherules is 3.6~8.5 μm, tap density is 0.8~1.2g/cm3, specific surface area is 1.1~1.5m2/g。
The present invention also provides a kind of preparation methods of high temperature circulation lithium iron phosphate dynamic battery, comprising the following steps:
1) positive electrode active materials, conductive agent and binder are uniformly mixed in de-airing mixer, obtain positive electrode, it will Organic solvent is added three times in positive electrode, after mixing evenly, obtains the anode sizing agent that viscosity is 6300~7800mPas, Anode sizing agent is crossed into 120~150 meshes, is then coated at least one side in plus plate current-collecting body, dries, roll, slitting, film-making, Obtain lithium battery anode；
2) negative electrode active material, conductive agent and binder are uniformly mixed in de-airing mixer, obtain negative electrode material, it will Water is added three times in negative electrode material, after mixing evenly, the negative electrode slurry that viscosity is 2300~4200mPas is obtained, by cathode Slurry crosses 120 meshes, is then coated at least one side in negative current collector, dries, rolls, slitting, film-making, obtaining lithium battery just Pole；
3) assembly of battery；
4) aging film forming, sealing.
Through the above technical solutions, the present invention has following technical effect that
1, by adjusting the partial size of positive electrode active materials, improving deintercalation efficiency of the lithium ion in charge and discharge process and moving Rate is moved, reduces polarization of electrode, reduces the internal resistance of lithium battery, improves lithium battery charge-discharge performance at high temperature and cyclicity Energy.
2, the present invention is using the carbonaceous mesophase spherules of small particle as negative electrode active material, times of spherical carbonaceous mesophase spherules Rate performance is better than lamellar graphite, and the small graphite high rate performance of partial size is more preferable, and battery made of the carbonaceous mesophase spherules of small particle exists Circulation can control cathode polarization aggravation effectively to realize the improvement of high temperature circulation under hot conditions, and small particle cathode is filling Volume expansion is unobvious in discharge process, and tap density can embody the pattern and particle diameter distribution of material, and tap density is too small to be led Send a telegraph that pond volume energy density is too low, the small material of specific surface area can make to be formed that SEI membrane area is small, and the lithium ion of consumption is few, Irreversible capacity is few, while it is also few to produce gas.
3, the present invention is by being pre-mixed stirring for material, then mediates, and finally finely dispersed method, can make different materials Expect component mixing more evenly, shorten incorporation time, improves production efficiency.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is charge and discharge cycles of the lithium battery in the case where temperature is 55 DEG C, charge-discharge magnification is 1C in the embodiment of the present invention 1 Curve graph；
Fig. 2 be the embodiment of the present invention 1 lithium battery temperature be -20 DEG C, discharge-rate be 1C under high temperature discharge curve Figure.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more New numberical range, these numberical ranges should be considered as specific open herein.
In order to optimize the charge-discharge performance of lithium battery at high temperature, the present invention provides a kind of lithium battery, which includes Anode, cathode, electrolyte, diaphragm.
According to the present invention, the lithium battery anode includes plus plate current-collecting body and coated in the positive material on plus plate current-collecting body Material, the positive electrode includes positive electrode active materials, conductive agent, binder.Using carbon coating type LiFePO 4 material as When positive electrode active materials preparation anode, carbon coating can enhance the electric conductivity between LiFePO4 particle, have its chemical property bright It is aobvious to improve.Tap density can embody the pattern and particle diameter distribution of material, and tap density is too small to will lead to battery volume energy density Too low, specific surface area will lead to greatly very much material processing difficulties, and material is difficult to disperse easy to reunite, and specific surface area is too small to illustrate material carbon Not enough, the internal resistance of cell and high rate performance cycle performance can be deteriorated cladding, particle diameter distribution D50:1~5 μm of the material, vibration density Degree: 0.9~1.3g/cm3, 7.5~11.3m of specific surface area2/g。
In order to optimize the high temperature cyclic performance of lithium battery, the positive electrode active materials include carbon coating type LiFePO4 material The volume average particle size distribution D50 of material, the carbon coating type LiFePO 4 material is 1~5 μm；The vibration density of the LiFePO4 Degree is 0.9~1.3g/cm3；The specific surface area of the LiFePO4 is 7.5~11.3m2/ g, it is further preferred that the carbon packet The volume average particle size distribution D50 for covering type LiFePO 4 material is 2~4 μm, tap density is 1.0~1.2g/cm3, specific surface Product is 8.2~9.6m2/g。
According to the present invention, the dosage of each substance in positive electrode can be adjusted according to actual needs, for example, at this In a kind of more preferably embodiment of invention, in order to further increase lithium iron phosphate dynamic battery obtained at high temperature Cycle performance, on the basis of the total weight of anode material of lithium battery, the contents of the positive electrode active materials be 93~98 weight %, The content of conductive agent is 1.0~3.5 weight %, the content of binder is 1.0~3.5 weight %.
According to the present invention, the conductive agent can be type commonly used in the art, for example, the conductive agent can select From carbon black, electrically conductive graphite, carbon nanotube, graphene and carbon nano-fiber etc., under preferable case, the conductive agent is selected from carbon nanometer At least two during pipe, acetylene black, conductive black, graphite are dilute.
According to the present invention, the binder can be type commonly used in the art, for example, the binder can select From polyvinyl alcohol, polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose, polyolefins binder and Viton etc., under preferable case, institute Stating binder is the PVDF that molecular weight is 1,300,000.
According to the present invention, in order to advanced optimize the high temperature cyclic performance of lithium battery, under preferable case, the lithium battery is just The compacted density of pole is 1.9~2.6g/cm3, further preferably 2.1~2.4g/cm3。
According to the present invention, in order to advanced optimize the high temperature cyclic performance of lithium battery, under preferable case, the lithium battery is just The surface density of pole is 115~154g/cm2, further preferably 120~140g/cm2。
The present invention also provides a kind of preparation methods of lithium battery anode, comprising the following steps:
1) positive electrode active materials, conductive agent and binder are uniformly mixed in de-airing mixer, obtain positive electrode；
2), positive electrode and first part's organic solvent are uniformly mixed, anode is obtained and closes slurry lotion 1；
3) slurry lotion 1, is closed in anode to be uniformly mixed with second part organic solvent, is obtained anode and is closed slurry lotion 2；
4), remaining organic solvent is added in positive electrode paste 2, adjusting viscosity to 6300~7800mPas, excessively 120~ The sieve of 150 mesh obtains anode sizing agent；
5), the anode sizing agent after sieving is coated on at least one side of plus plate current-collecting body, dry, roll, slitting, film-making, Obtain lithium battery anode.
It in the present invention, by the way that positive electrode is pre-mixed stirring, then mediates, last finely dispersed method can make Different materials component mixes the uniformity for more evenly improving anode, shortens incorporation time, improves production efficiency.
According to the present invention, the dosage of organic solvent and positive electrode can be adjusted according to actual needs, preferable case Under, the weight ratio of the positive electrode and organic solvent is 1:(0.8~1).
According to the present invention, the organic solvent also can choose as type commonly used in the art, for example, can choose For ethylene carbonate, propene carbonate, N-Methyl pyrrolidone etc., under preferable case, the organic solvent is N- methylpyrrole Alkanone.
According to the present invention, in order to optimize the mixture homogeneity of positive electrode, in the preparation method of lithium battery anode, preferably In the case of, on the basis of the total weight of the organic solvent, the content of first part's solvent is 20~30 weight %, described The content of second part solvent is 20~30 weight %.
According to the present invention, in order to optimize the mixture homogeneity of positive electrode, in the preparation method of lithium battery anode, preferably In the case of, in step 1), described be mixed into is stirred, wherein stirring rate be 20~40r/min, mixing time 60~ 90min。
According to the present invention, in order to optimize the mixture homogeneity of positive electrode, in the preparation method of lithium battery anode, preferably In the case of, in step 2), described be mixed into is stirred, wherein whipping temp be 30~50 DEG C, mixing speed be 1200~ 2000r/min, mixing time are 60~90min.
According to the present invention, in order to optimize the mixture homogeneity of positive electrode, in the preparation method of lithium battery anode, preferably In the case of, in step 3), described be mixed into is stirred, whipping temp be 30~50 DEG C, mixing speed be 1800~ 2500r/min, mixing time are 60~90min.
In the case of, according to the invention it is preferred to, the plus plate current-collecting body is 15~20 μm of carbon-coated aluminum foils of thickness.
Using carbonaceous mesophase spherules prepare cathode as negative electrode active material when, spherical carbonaceous mesophase spherules it is forthright again It can be better than lamellar graphite, the small graphite high rate performance of partial size is more preferable, and battery made of the carbonaceous mesophase spherules of small particle is in high temperature Under the conditions of circulation can control cathode polarization aggravation effectively to realize the improvement of high temperature circulation, small particle cathode is in charge and discharge Volume expansion is unobvious in the process, and tap density can embody the pattern and particle diameter distribution of material, and tap density is too small to will lead to electricity Pond volume energy density is too low, and the small material of specific surface area can make to be formed that SEI membrane area is small, and the lithium ion of consumption is few, can not Inverse capacity is few, while it is also few to produce gas.According to the present invention, the cathode of lithium battery include negative current collector and be coated in negative pole currect collecting Negative electrode material on body, the negative electrode material include negative electrode active material, conductive agent, binder, the negative electrode active material packet Carbonaceous mesophase spherules are included, the volume average particle size distribution D50 of the carbonaceous mesophase spherules is 3.6~8.5 μm, further preferably 4~8 μm.
According to the present invention, the high rate performance of carbonaceous mesophase spherules is better than lamellar graphite, and the small graphite high rate performance of partial size is more It is good, battery made of the carbonaceous mesophase spherules of small particle recycle under the high temperature conditions can effectively control cathode polarization aggravate from And realize the improvement of high temperature circulation, the volume expansion in charge and discharge process of small particle cathode is unobvious, and tap density can embody material The pattern and particle diameter distribution of material, tap density is too small to will lead to that battery volume energy density is too low, and the small material of specific surface area can So as to be formed, SEI membrane area is small, and the lithium ion of consumption is few, and irreversible capacity is few, while it is also few to produce gas.But if its vibration density Height is spent, then the brittleness that will lead to cathode becomes larger, and pole piece is broken when winding battery pole piece, cannot not only improve electricity The high temperature cyclic performance in pond, even more so that the preparation of battery is unable to complete.Under preferable case, the jolt ramming of the carbonaceous mesophase spherules Density is 0.9~1.3g/cm3, further preferably 1.0~1.2g/cm3
According to the present invention, the specific surface area of the carbonaceous mesophase spherules is 1.2~1.7m2/g；Preferably 1.3~1.6m2/ g。
According to the present invention, the dosage of each substance in negative electrode material can be adjusted according to actual needs, for example, at this In a kind of more preferably embodiment of invention, in order to further increase lithium iron phosphate dynamic battery obtained at high temperature Cycle performance, on the basis of the total weight of lithium cell cathode material, the content of the negative electrode active material be 92~97 weight %, The content of conductive agent is 1~3 weight %, the content of binder is 2~5 weight %.
According to the present invention, the conductive agent can be type commonly used in the art, for example, the conductive agent can select From acetylene black, conductive black, electrically conductive graphite, carbon nanotube, graphene and carbon nano-fiber etc., under preferable case, the conduction Agent is acetylene black and/or conductive black.
According to the present invention, the binder can be type commonly used in the art, for example, the binder can select From polyvinyl alcohol, polytetrafluoroethylene (PTFE), carboxymethyl cellulose, polyolefins binder, butadiene-styrene rubber and Viton etc., preferably feelings Under condition, the binder is butadiene-styrene rubber and/or carboxymethyl cellulose.
According to the present invention, in order to advanced optimize the high temperature cyclic performance of lithium battery, under preferable case, the lithium battery is negative The compacted density of pole is 1.3~1.8g/cm3, further preferably 1.4~1.7g/cm3。
According to the present invention, in order to advanced optimize the high temperature cyclic performance of lithium battery, under preferable case, the lithium battery is negative The surface density of pole is 62~70g/cm2, further preferably 63~66g/cm2。
The present invention also provides the preparation methods of the cathode of lithium battery, comprising the following steps:
1) negative electrode active material, conductive agent and binder are uniformly mixed in de-airing mixer, obtain negative electrode material；
2) negative electrode material and first part's water are uniformly mixed, obtain cathode and closes slurry lotion 1；
3) cathode is closed into slurry lotion 1 and second part water is uniformly mixed, obtained cathode and close slurry lotion 2；
4) cathode is added in remaining water to close in slurry lotion 2, adjusts viscosity to 2300~4200mPas, crosses 120 meshes Obtain negative electrode slurry；
5) negative electrode slurry after sieving is coated on at least one side of negative current collector, dries, roll, slitting, film-making, obtaining To cathode of lithium battery.
It in the present invention, by the way that negative electrode material is pre-mixed stirring, then mediates, last finely dispersed method can make Different materials component mixes more evenly, improves the uniformity of cathode, shortens incorporation time, improves production efficiency.
According to the present invention, negative electrode material and the dosage of water can be adjusted according to actual needs, described under preferable case Negative electrode material and the weight ratio of water are 1:(1~1.2).
According to the present invention, in the preparation process of cathode of lithium battery, under preferable case, using the total weight of the water as base Standard, the content of first part's water are 20~30 weight %, and the content of the second part water is 20~30 weight %.
According to the present invention, described to be mixed into step 1) under preferable case in the preparation process of cathode of lithium battery It is stirred, wherein stirring rate is 20~40r/min, and mixing time is 60~90min.
According to the present invention, described to be mixed into step 2) under preferable case in the preparation process of cathode of lithium battery It is stirred, wherein mixing speed is 1200~1500r/min, and mixing time is 60~90min, and whipping temp is 20~50 ℃。
According to the present invention, described to be mixed into step 3) under preferable case in the preparation process of cathode of lithium battery It is stirred, wherein mixing speed is 1600~2200r/min, and mixing time is 60~90min, and whipping temp is 20~50 ℃。
In the case of, according to the invention it is preferred to, the negative current collector is 8~12 μm of copper foils of thickness.
According to the present invention, the electrolyte is the mixed solution of electrolyte lithium salt and nonaqueous solvents, and this field can be used Conventional nonaqueous electrolytic solution.For example electrolyte lithium salt is selected from lithium hexafluoro phosphate (LiPF6), lithium perchlorate, LiBF4, hexafluoro One or more of arsenic acid lithium, lithium halide, chlorine lithium aluminate and fluorohydrocarbon base Sulfonic Lithium.The electrolyte can be conventional for this field The type used, such as can be dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), carbonic acid first third Ester (MPC), dipropyl carbonate (DPC), ethylene carbonate (EC), propene carbonate (PC), vinylene carbonate (VC), γ-fourth At least one of lactone (γ-BL) and dimethyl carbonate (DMC) etc..In order to advanced optimize the high temperature circulation of lithium battery Can, under preferable case, the electrolyte includes ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate.The migration rate of ion is An important factor for influencing battery high-temperature discharge performance, and electrolyte is an important factor for influencing ion mobility, in order to optimize The high temperature discharge performance of lithium battery, it is further preferred that the mass ratio of ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate is 1:(0.8~1.2): (0.8~1.2), further preferably 1:1:1.The concentration of electrolyte is generally 1~1.3mol/L.
In order to advanced optimize the high temperature cyclic performance of lithium battery, under preferable case, the electrolyte also includes dioxalic acid Lithium borate, it is further preferred that on the basis of the total weight of the electrolyte, the content of the dioxalic acid lithium borate is 0.5~ 1.5 weight %.
In the case of, according to the invention it is preferred to, the diaphragm is the PP diaphragm with a thickness of 20~25 μm.
The present invention also provides a kind of preparation methods of lithium battery, comprising the following steps:
1) positive preparation, the preparation method of the anode are same as above；
2) preparation method of the preparation of cathode, the cathode is same as above；
3) electrolyte and encapsulated moulding will be injected after the positive electrode, the negative electrode and the separator coiling and molding；
4) aging, sealing.
According to the present invention, in the preparation process of lithium battery, under preferable case, in step 4), the aging film forming Technique can be the conventional application method of this field, such as may is that and shelve at 45 DEG C 2 days.
According to the present invention, in the preparation process of lithium battery, under preferable case, in step 4), steel ball is beaten using vacuum Mode be sealed, under preferable case, when the sealing, the vacuum degree of lithium battery interior is -0.05MPa~-0.09MPa.
According to the preparation method of lithium battery provided by the invention, the coiling and molding technique, electrolyte injection technology and envelope Filling moulding process can be known to those skilled in the art, and details are not described herein by the present invention.
The present invention will be described in detail by way of examples below.Carbon coating type LiFePO4 material in following embodiment Material reaches new energy Co., Ltd, model HSD-1 purchased from Hai Si；Carbonaceous mesophase spherules are purchased from Bei Terui new energy materials, model For S360-MB；Conductive black, the electrically conductive graphite of Te Migao is purchased from Te Migao graphite Co., Ltd；Carbon nanotubes is purchased from Wuxi Dong Heng New Energy Technology Co., Ltd.；N-Methyl pyrrolidone is purchased from Nanjing Jin Long Chemical Co., Ltd.；Graphite is dilute to be purchased from Qingdao Hao Xin New Energy Technology Co., Ltd.；PVDF is purchased from Su Wei (SOLVAY) group, model 5130；Butadiene-styrene rubber is purchased from Japan A& L Co., Ltd.；Carboxymethyl cellulose is purchased from good gram force scholar；LiPF6Purchased from Duo-fluoride Chemicals Co., Ltd.；Dioxalic acid boric acid Lithium is purchased from Quzhou Ming Feng Chemical Co., Ltd.；Ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC) purchase From Shandong, stone wins magnificent Chemical Group completely.
Embodiment 1
1, positive preparation
By 95.5kg carbon coating type LiFePO 4 material, (D50 is 3 μm, tap density 1.1g/cm3, specific surface area be 9.2m2/ g), 0.5kg conductive black, 1kg carbon nanotubes, 2.5kg PVDF 5130 vacuum degree≤- 0.08MPa vacuum dry In case, 300min is dried at 120 DEG C；
Above-mentioned carbon coating type LiFePO 4 material, conductive black, carbon nanotubes are added in de-airing mixer, in 25r/ 60min is stirred under the revolving speed of min, obtains positive electrode；
Above-mentioned positive electrode and 30kgN- methyl pyrrolidone (NMP) are stirred evenly in de-airing mixer, obtained just Slurry lotion 1 is closed in pole, and wherein stirring rate is 1800r/min, and mixing time 90min, whipping temp is 40 DEG C；
Anode is closed slurry lotion 1 and 30kg NMP to stir evenly in de-airing mixer, anode is obtained and closes slurry lotion 2, Middle stirring rate is 2200r/min, and mixing time 90min, whipping temp is 40 DEG C；
It is closed in slurry lotion 2 to anode and 40kg NMP is added, obtained the slurry that viscosity is 7200mPas, slurry is crossed 150 Mesh obtains anode sizing agent；
Anode sizing agent after sieving is coated in the tow sides of the carbon aluminium foil with a thickness of 15 μm, then 120 DEG C of drying, In Cutting obtains the anode having a size of 2720mm × 155mm × 20 μm on cutting machine after roll-in under the pressure of 1.6MPa, described The compacted density of anode is 2.2g/cm3, surface density 133g/cm2Positive plate.
2, the preparation of cathode
By 95kg carbonaceous mesophase spherules, (D50 is 5 μm, tap density 1.1g/cm3, specific surface area 1.5m2/g)、1kg Electrically conductive graphite (SP), 1.5kg carboxymethyl cellulose (CMC) and 2.5kg butadiene-styrene rubber (SBR) stir under the revolving speed of 30r/min 60min obtains negative electrode material；
It by above-mentioned positive electrode and 36kg deionized water, is stirred evenly in de-airing mixer, obtains cathode and close slurry lotion 1, wherein stirring rate is 1200r/min, and mixing time 90min, whipping temp is 40 DEG C；
Cathode is closed slurry lotion 1 and 36kg deionized water to stir evenly in de-airing mixer, cathode is obtained and closes slurry lotion 2, wherein stirring rate is 2000r/min, and mixing time 90min, whipping temp is 40 DEG C；
It is closed in slurry lotion 2 to cathode and 48kg deionized water is added, the slurry that viscosity is 3200mPas is obtained, by slurry mistake 120 meshes, obtain 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, In Cutting obtains the cathode having a size of 2890mm × 160mm × 8 μm on cutting machine after roll-in under the pressure of 1.6MPa, is pressed Real density is 1.5g/cm3, surface density 66g/cm2Negative electrode tab.
3, the assembly of battery
By LiPF6With dioxalic acid lithium borate, ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC) It is configured to LiPF6The solution (wherein, the weight ratio of EC, EMC and DMC are 1:1:1) that concentration is 1mol/L, wherein dioxalic acid boric acid The content of lithium is the 1% of EC, EMC and DMC total weight, obtains nonaqueous electrolytic solution.
It successively is wound into electrode group with up- coiler stacking by above-mentioned anode, with a thickness of 25 μm of PP diaphragms and cathode, will To electrode group be put into battery case open at one end, inject above-mentioned nonaqueous electrolytic solution, after then shelving 2 days at 45 DEG C, so Steel ball sealing is played in the state of vacuum degree -0.08MPa afterwards, obtains lithium battery A1, chemical property is as shown in table 1.
Embodiment 2
According to the method for embodiment 1, unlike, it is described anode the preparation method is as follows:
By 96kg carbon coating type LiFePO 4 material, (D50 is 2 μm, tap density 1.0g/cm3, specific surface area be 9.6m2/ g), 1kg conductive black, 1.5kg graphite is dilute, 1.5kg PVDF 5130 is in vacuum degree≤- 0.08MPa vacuum drying oven In, 300min is dried at 120 DEG C；
By above-mentioned carbon coating type LiFePO 4 material, conductive black, graphite is dilute, PVDF 5130 is added to de-airing mixer In, 75min is stirred under the revolving speed of 30r/min, obtains positive electrode；
Above-mentioned positive electrode and 24kg N-Methyl pyrrolidone (NMP) are stirred evenly in de-airing mixer, obtained just Slurry lotion 1 is closed in pole, and wherein stirring rate is 1600r/min, and mixing time 60min, whipping temp is 30 DEG C；
Anode is closed slurry lotion 1 and 24kg NMP to stir evenly in de-airing mixer, anode is obtained and closes slurry lotion 2, Middle stirring rate is 2200r/min, and mixing time 60min, whipping temp is 30 DEG C；
It is closed in slurry lotion 2 to anode and 72kg NMP is added, obtained the slurry that viscosity is 6500mPas, slurry is crossed 120 Mesh obtains anode sizing agent.
Anode sizing agent after sieving is coated in the tow sides of the carbon aluminium foil with a thickness of 15 μm, then 120 DEG C of drying, In Cutting obtains the anode having a size of 2720mm × 155mm × 20 μm on cutting machine after roll-in under the pressure of 1.6MPa, described The compacted density of anode is 2.1g/cm3, surface density 120g/cm2Positive plate, obtain lithium battery A2, chemical property is such as Shown in table 1.
Embodiment 3
According to the method for embodiment 1, unlike, it is described anode the preparation method is as follows:
By 95kg carbon coating type LiFePO 4 material, (D50 is 4 μm, tap density 1.2g/cm3, specific surface area be 8.2m2/ g), 1kg acetylene black, 1kg graphite is dilute, 3kg PVDF 5130 is in vacuum degree≤- 0.08MPa vacuum drying oven, In 300min is dried at 120 DEG C；
By above-mentioned carbon coating type LiFePO 4 material, acetylene black, graphite is dilute, PVDF 5130 is added in de-airing mixer, 90min is stirred under the revolving speed of 35r/min, obtains positive electrode；
Above-mentioned positive electrode and 20kg N-Methyl pyrrolidone (NMP) are stirred evenly in de-airing mixer, obtained just Slurry lotion 1 is closed in pole, and wherein stirring rate is 1500r/min, and mixing time 90min, whipping temp is 50 DEG C；
Anode is closed slurry lotion 1 and 25kg NMP to stir evenly in de-airing mixer, anode is obtained and closes slurry lotion 2, Middle stirring rate is 2000r/min, and mixing time 90min, whipping temp is 50 DEG C；
It is closed in slurry lotion 2 to anode and 55kg NMP is added, obtained the slurry that viscosity is 7200mPas, slurry is crossed 100 Mesh obtains anode sizing agent.
Anode sizing agent after sieving is coated in the tow sides of the carbon aluminium foil with a thickness of 15 μm, then 120 DEG C of drying, In Cutting obtains the anode having a size of 2720mm × 155mm × 20 μm on cutting machine after roll-in under the pressure of 1.6MPa, described The compacted density of anode is 2.4g/cm3, surface density 140g/cm2Positive plate, obtain lithium battery A3, chemical property is such as Shown in table 1.
Embodiment 4
According to the method for embodiment 1, unlike, it is described anode the preparation method is as follows:
By 98kg carbon coating type LiFePO 4 material, (D50 is 1 μm, tap density 0.9g/cm3, specific surface area be 11.6m2/ g), 0.5kg acetylene black, 0.5kg graphite is dilute, 1kg PVDF 5130 is in vacuum degree≤- 0.08MPa vacuum drying oven In, 300min is dried at 120 DEG C；
By above-mentioned carbon coating type LiFePO 4 material, acetylene black, graphite is dilute, PVDF 5130 is added in de-airing mixer, 75min is stirred under the revolving speed of 40r/min, obtains positive electrode；
Above-mentioned positive electrode and 30kg N-Methyl pyrrolidone (NMP) are stirred evenly in de-airing mixer, obtained just Slurry lotion 1 is closed in pole, and wherein stirring rate is 2000r/min, and mixing time 60min, whipping temp is 40 DEG C；
Anode is closed slurry lotion 1 and 30kg NMP to stir evenly in de-airing mixer, anode is obtained and closes slurry lotion 2, Middle stirring rate is 2500r/min, and mixing time 90min, whipping temp is 40 DEG C；
It is closed in slurry lotion 2 to anode and 60kg NMP is added, obtained the slurry that viscosity is 6300mPas, slurry is crossed 150 Mesh obtains anode sizing agent.
Anode sizing agent after sieving is coated in the tow sides of the carbon aluminium foil with a thickness of 15 μm, then 120 DEG C of drying, In Cutting obtains the anode having a size of 2720mm × 155mm × 20 μm on cutting machine after roll-in under the pressure of 1.6MPa, described The compacted density of anode is 1.9g/cm3, surface density 115g/cm2Positive plate, obtain lithium battery A4, chemical property is such as Shown in table 1.
Embodiment 5
According to the method for embodiment 1, unlike, it is described anode the preparation method is as follows:
By 93kg carbon coating type LiFePO 4 material, (D50 is 5 μm, tap density 1.3g/cm3, specific surface area be 7.5m2/ g), 1.5kg carbon nanotube, 2kg graphite is dilute, 3.5kg PVDF 5130 is in vacuum degree≤- 0.08MPa vacuum drying oven In, 300min is dried at 120 DEG C；
By above-mentioned carbon coating type LiFePO 4 material, carbon nanotube, graphite is dilute, PVDF 5130 is added to de-airing mixer In, 75min is stirred under the revolving speed of 20r/min, obtains positive electrode；
Above-mentioned positive electrode and 24kg N-Methyl pyrrolidone (NMP) are stirred evenly in de-airing mixer, obtained just Slurry lotion 1 is closed in pole, and wherein stirring rate is 1200r/min, and mixing time 75min, whipping temp is 40 DEG C；
Anode is closed slurry lotion 1 and 24kg NMP to stir evenly in de-airing mixer, anode is obtained and closes slurry lotion 2, Middle stirring rate is 1800r/min, and mixing time 75min, whipping temp is 40 DEG C；
It is closed in slurry lotion 2 to anode and 48kg NMP is added, obtained the slurry that viscosity is 7800mPas, slurry is crossed 120 Mesh obtains anode sizing agent.
Anode sizing agent after sieving is coated in the tow sides of the carbon aluminium foil with a thickness of 20 μm, then 120 DEG C of drying, In Cutting obtains the anode having a size of 2720mm × 155mm × 20 μm on cutting machine after roll-in under the pressure of 1.6MPa, described The compacted density of anode is 2.6g/cm3, surface density 154g/cm2Positive plate, obtain lithium battery A5, chemical property is such as Shown in table 1.
Embodiment 6
According to the method for embodiment 1, unlike, the cathode the preparation method is as follows:
By 94.5kg carbonaceous mesophase spherules, (D50 is 3.6 μm, tap density 1.0g/cm3, specific surface area is 1.3m2/ g), 2kg electrically conductive graphite (SP), 3.5kg carboxymethyl cellulose (CMC) stir 60min under the revolving speed of 25r/min, obtain To negative electrode material；
It by above-mentioned negative electrode material and 20kg deionized water, is stirred evenly in de-airing mixer, obtains cathode and close slurry lotion 1, wherein stirring rate is 1350r/min, and mixing time 75min, whipping temp is 40 DEG C；
Cathode is closed slurry lotion 1 and 25kg deionized water to stir evenly in de-airing mixer, cathode is obtained and closes slurry lotion 2, wherein stirring rate is 2000r/min, and mixing time 90min, whipping temp is 40 DEG C；
It is closed in slurry lotion 2 to cathode and 55kg deionized water is added, the slurry that viscosity is 2800mPas is obtained, by slurry mistake 120 meshes, obtain 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, In Cutting obtains the cathode having a size of 2900mm × 160mm × 8 μm on cutting machine after roll-in under the pressure of 1.6MPa, is pressed Real density is 1.7g/cm3, surface density 63g/cm2Negative electrode tab, obtain lithium battery A6, chemical property is as shown in table 1.
Embodiment 7
According to the method for embodiment 1, unlike, the cathode the preparation method is as follows:
By 96kg carbonaceous mesophase spherules, (D50 is 8.5 μm, tap density 1.2g/cm3, specific surface area 1.6m2/g)、 1kg electrically conductive graphite (SP), 1kg conductive black, 2kg butadiene-styrene rubber stir 60min under the revolving speed of 30r/min, obtain cathode material Material；
It by above-mentioned negative electrode material and 24kg deionized water, is stirred evenly in de-airing mixer, obtains cathode and close slurry lotion 1, wherein stirring rate is 1400r/min, and mixing time 75min, whipping temp is 40 DEG C；
Cathode is closed slurry lotion 1 and 24kg deionized water to stir evenly in de-airing mixer, cathode is obtained and closes slurry lotion 2, wherein stirring rate is 1800r/min, and mixing time 75min, whipping temp is 40 DEG C；
It is closed in slurry lotion 2 to cathode and 72kg deionized water is added, the slurry that viscosity is 3600mPas is obtained, by slurry mistake 120 meshes, obtain negative electrode slurry；
Negative electrode slurry after sieving is coated on to the tow sides of 12 μm of copper foils of thickness again, then 120 DEG C of drying, In Cutting obtains the cathode having a size of 2900mm × 160mm × 8 μm on cutting machine after roll-in under the pressure of 1.6MPa, is pressed Real density is 1.4g/cm3, surface density 66g/cm2Negative electrode tab, obtain lithium battery A7, chemical property is as shown in table 1.
Embodiment 8
According to the method for embodiment 1, unlike, the cathode the preparation method is as follows:
By 92kg carbonaceous mesophase spherules, (D50 is 4 μm, tap density 0.9g/cm3, specific surface area 1.7m2/g)、 3kg carboxymethyl cellulose (CMC) and 5kg butadiene-styrene rubber (SBR) stir 60min under the revolving speed of 20r/min, obtain cathode material Material；
It by above-mentioned negative electrode material and 25kg deionized water, is stirred evenly in de-airing mixer, obtains cathode and close slurry lotion 1, wherein stirring rate is 1200r/min, and mixing time 90min, whipping temp is 30 DEG C；
Cathode is closed slurry lotion 1 and 20kg deionized water to stir evenly in de-airing mixer, cathode is obtained and closes slurry lotion 2, wherein stirring rate is 1600r/min, and mixing time 90min, whipping temp is 30 DEG C；
It is closed in slurry lotion 2 to cathode and 55kg deionized water is added, the slurry that viscosity is 2300mPas is obtained, by slurry mistake 120 meshes, obtain negative electrode slurry；
Negative electrode slurry after sieving is coated on to the tow sides of 10 μm of copper foils of thickness again, then 120 DEG C of drying, In Cutting obtains the cathode having a size of 2900mm × 160mm × 8 μm on cutting machine after roll-in under the pressure of 1.6MPa, is pressed Real density is 1.3g/cm3, surface density 62g/cm2Negative electrode tab, obtain lithium battery A8, chemical property is as shown in table 1.
Embodiment 9
According to the method for embodiment 1, unlike, the cathode the preparation method is as follows:
By 97kg carbonaceous mesophase spherules, (D50 is 8 μm, tap density 1.3g/cm3, specific surface area 1.2m2/g)、 1kg acetylene black, 2kg carboxymethyl cellulose (CMC) stir 90min under the revolving speed of 40r/min, obtain negative electrode material；
Above-mentioned negative electrode material and 30kg deionized water are stirred evenly in de-airing mixer, cathode is obtained and closes slurry lotion 1, Wherein stirring rate is 1500r/min, and mixing time 60min, whipping temp is 50 DEG C；
Cathode is closed slurry lotion 1 and 30kg deionized water to stir evenly in de-airing mixer, cathode is obtained and closes slurry lotion 2, wherein stirring rate is 2200r/min, and mixing time 60min, whipping temp is 50 DEG C；
It is closed in slurry lotion 2 to cathode and 60kg deionized water is added, the slurry that viscosity is 4200mPas is obtained, by slurry mistake 120 meshes, obtain 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, In Cutting obtains the cathode having a size of 2900mm × 160mm × 8 μm on cutting machine after roll-in under the pressure of 1.6MPa, is pressed Real density is 1.8g/cm3, surface density 70g/cm2Negative electrode tab, obtain lithium battery A9, chemical property is as shown in table 1.
Embodiment 10
According to the method for embodiment 1, unlike, the configuration method of the electrolyte is as follows:
By LiPF6With dioxalic acid lithium borate, ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC) It is configured to LiPF6The solution (wherein, the weight ratio of EC, EMC and DMC are 1:0.8:0.8) that concentration is 1.1mol/L, wherein two grass The content of sour lithium borate is the 0.5% of EC, EMC and DMC total weight, obtains nonaqueous electrolytic solution, obtains lithium battery A10, electrification It is as shown in table 1 to learn performance.
Embodiment 11
According to the method for embodiment 1, unlike, the configuration method of the electrolyte is as follows:
By LiPF6With dioxalic acid lithium borate, ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC) It is configured to LiPF6The solution (wherein, the weight ratio of EC, EMC and DMC are 1:1.2:1.2) that concentration is 1.3mol/L, wherein two grass The content of sour lithium borate is the 1.5% of EC, EMC and DMC total weight, obtains nonaqueous electrolytic solution, obtains lithium battery A11, electrification It is as shown in table 1 to learn performance.
Comparative example 1
According to the method for embodiment 1, unlike, the positive electrode active materials LiFePO4Partial size D50 be 0.5 μm, vibration Real density is 1.5g/cm3, specific surface area 6.3m2/ g, obtains lithium battery B1, and chemical property is as shown in table 1.
Comparative example 2
According to the method for embodiment 1, unlike, the positive electrode active materials LiFePO4Partial size D50 be 6 μm, jolt ramming Density is 0.7g/cm3, specific surface area 15m2/ g, obtains lithium battery B2, and chemical property is as shown in table 1.
Comparative example 3
According to the method for embodiment 1, unlike, the partial size D50 of the negative electrode active material carbonaceous mesophase spherules is 3 μ M, tap density is 0.6g/cm3, specific surface area 0.9m2/ g, obtains lithium battery B3, and chemical property is as shown in table 1.
Comparative example 4
According to the method for embodiment 1, unlike, the partial size D50 of the negative electrode active material carbonaceous mesophase spherules is 9 μ M, tap density is 1.5g/cm3, specific surface area 1.8m2/ g, obtains lithium battery B4, and chemical property is as shown in table 1.
Comparative example 5
According to the method for embodiment 1, unlike, dioxalic acid lithium borate is not contained in the electrolyte, obtains lithium battery B5, chemical property are as shown in table 1.
Comparative example 6
According to the method for embodiment 1, unlike, anode sizing agent is different with the preparation method of negative electrode slurry, specific as follows:
1, positive preparation
(D50 is 3 μm to 95.5kg carbon coating type LiFePO 4 material, tap density 1.1g/cm3, specific surface area be 9.2m2/ g), 0.5kg conductive black, 1kg carbon nanotubes, 2.5kg PVDF 5130 vacuum degree≤- 0.08MPa vacuum dry In case, 300min is dried at 120 DEG C；
By above-mentioned LiFePO4, conductive black, graphite are dilute and 100kg NMP is uniformly mixed in de-airing mixer, cross 120 Mesh obtains anode sizing agent；
The coating method of anode sizing agent is the same as embodiment 1.
2, the preparation of cathode
By 95kg carbonaceous mesophase spherules, (D50 is 5 μm, tap density 1.5g/cm3, specific surface area 1.3m2/g)、1kg Electrically conductive graphite (SP), 1.5kg carboxymethyl cellulose (CMC) and 2.5kg butadiene-styrene rubber (SBR) and 120kg water are in de-airing mixer In stir evenly, slurry is crossed into 120 meshes, obtains negative electrode slurry；
The coating method of negative electrode slurry is the same as embodiment 1.
3, the assembly method of battery obtains lithium battery B6 with embodiment 1, and chemical property is as shown in table 1.
Test method:
1, high temperature cyclic performance: at 55 DEG C, being charged in a manner of constant-current constant-voltage charging, and limitation electric current is 0.5C, eventually Only voltage is 3.65V, and termination electric current is 3.5A, is discharged in a manner of constant-current discharge, discharge current 1C, the cut-off electricity of electric discharge Pressure is 2.5 volts, is recycled 2000 times, after calculating separately 2000 initial discharge capacity C1, circulation discharge capacity C2, recycling 2000 times Capacity retention ratio R.
2, low temperature performance: at 25 DEG C, being charged with constant voltage charging method, and limitation electric current is 0.5C, terminates electricity Pressure is 3.65V, and termination electric current is 3.5A, is discharged in a manner of constant-current discharge, discharge current 1C, then with constant voltage charging method It charges, limitation electric current is 0.5C, and final voltage 3.65V, termination electric current is that 3.5A is put under the conditions of -20 DEG C with constant current Electric mode is discharged, discharge current 1C, and the blanking voltage of electric discharge is 2.0V, calculates separately 25 DEG C of discharge capacity C3, -20 DEG C Discharge capacity C4.
The chemical property of each lithium battery in 1 embodiment 1~11 of table and comparative example 1~6
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should also be regarded as the disclosure of the present invention.

Claims (1)

1. a kind of preparation method of high temperature circulation lithium iron phosphate dynamic battery, which is characterized in that
The high temperature circulation lithium iron phosphate dynamic battery include anode, cathode, diaphragm and electrolyte, which is characterized in that it is described just Pole includes plus plate current-collecting body and coated in the positive electrode on plus plate current-collecting body, and the positive electrode includes positive electrode active materials, The positive electrode active materials include carbon coating type LiFePO 4 material, the particle diameter distribution of the carbon coating type LiFePO 4 material D50 is 2 ~ 4 μm；The tap density of the LiFePO4 is 1.0 ~ 1.2g/cm3；The specific surface area of the LiFePO4 be 8.2 ~ 9.6 m2/g；
The cathode includes negative current collector and coated in the negative electrode material on negative current collector, and the negative electrode material includes cathode Active material, the negative electrode active material include carbonaceous mesophase spherules, and the particle diameter distribution D50 of the carbonaceous mesophase spherules is 3.6 ~ 5 μm, tap density is 0.9 ~ 1.1g/cm3, specific surface area is 1.3 ~ 1.7m2/g；
The compacted density of the anode is 1.9 ~ 2.6 g/cm3, surface density is 115 ~ 154 g/cm2；
The compacted density of the cathode is 1.3 ~ 1.8g/cm3, surface density is 62 ~ 70g/cm2；
The electrolyte includes ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate；Wherein, ethylene carbonate, methyl ethyl carbonate Ester, dimethyl carbonate mass ratio be 1:(1 ~ 1.2): (1 ~ 1.2)；
The electrolyte also includes dioxalic acid lithium borate, on the basis of the total weight of the electrolyte, the dioxalic acid lithium borate Content be 0.5 ~ 1.5 weight %；
It the described method comprises the following steps:
1) positive electrode active materials, conductive agent and binder are uniformly mixed in de-airing mixer, obtain positive electrode, mixing Condition is 20-40 revs/min of stirring rate, mixing time 60-90 minutes；Positive electrode and first part's organic solvent are mixed Uniformly, obtain anode close slurry lotion 1, mixed condition be 30-50 DEG C of whipping temp, 1200-2000 revs/min of mixing speed, Mixing time 60-90 minutes；Slurry lotion 1 is closed in anode to be uniformly mixed with second part organic solvent, is obtained anode and is closed slurry lotion 2, mixed condition is 30-50 DEG C of whipping temp, 1800-2500 revs/min of mixing speed, mixing time 60-90 minutes；It will remain Remaining organic solvent is added in positive electrode paste 2, adjusts viscosity to 6300 ~ 7800 mPas, the sieve for crossing 120 ~ 150 mesh obtains Anode sizing agent；
Wherein, the weight ratio of the positive electrode and organic solvent is 1:(0.8 ~ 1)；Using the total weight of the organic solvent as base Standard, the content of first part's organic solvent are 20 ~ 30 weight %, and the content of the second part organic solvent is 20 ~ 30 weights Measure %；
2) negative electrode active material, conductive agent and binder are uniformly mixed in de-airing mixer, obtain cathode powder body material, mixed The condition of conjunction is 20-40 revs/min of stirring rate, mixing time 60-90 minutes；Powder body material and first part's water are mixed equal It is even, it obtains cathode and closes slurry lotion 1, mixed condition is 20-50 DEG C of whipping temp, 1200-1500 revs/min of mixing speed, stirs Mix time 60-90 minute；Cathode is closed into slurry lotion 1 and second part water is uniformly mixed, cathode is obtained and closes slurry lotion 2, mixing Condition is 20-50 DEG C of whipping temp, 1600-2200 revs/min of mixing speed, mixing time 60-90 minutes；Remaining water is added Enter cathode to close in slurry lotion 2, adjusts viscosity to 2300 ~ 4200mPas, cross 120 meshes and obtain negative electrode slurry；
Wherein, the weight ratio of the cathode powder body material and water is 1:(1 ~ 1.2), it is described on the basis of the total weight of the water The content of first part's water is 20 ~ 30 weight %, and the content of the second part water is 20 ~ 30 weight %；
3) assembly of battery；
4) aging film forming, sealing.
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