CN107768727A - High temperature circulation lithium iron phosphate dynamic battery and its manufacture method - Google Patents

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

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Publication number
CN107768727A
CN107768727A CN201710953160.1A CN201710953160A CN107768727A CN 107768727 A CN107768727 A CN 107768727A CN 201710953160 A CN201710953160 A CN 201710953160A CN 107768727 A CN107768727 A CN 107768727A
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negative
high temperature
positive electrode
pole
iron phosphate
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CN107768727B (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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Abstract

The present invention relates to technical field of lithium batteries, more particularly to high temperature circulation lithium iron phosphate dynamic battery and its manufacture method, the high temperature circulation lithium iron phosphate dynamic battery, including positive pole, negative pole, barrier film and electrolyte, the positive pole includes 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 negative pole includes negative current collector and coated in the negative material on negative current collector, and the negative material includes carbonaceous mesophase spherules, and the particle diameter distribution D50 of the carbonaceous mesophase spherules is 3.6~8.5 μm, and its tap density is 0.9~1.3g/cm3, its specific surface area is 1.2~1.7m2/g.Particle diameter of the invention by adjusting anode and cathode active materials, reduce polarization of electrode, improve the charge-discharge performance and cycle performance of lithium battery at high temperature.

Description

High temperature circulation lithium iron phosphate dynamic battery and its manufacture 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 technology
The pure electric automobile product sold in current domestic new-energy automobile market is increasingly abundanter, but most pure electricity The problem of course continuation mileage decay of high temperature day is very fast be present in electrical automobile.There are some researches show in-car when temperature is increased to 40 DEG C from 25 DEG C Actual temperature is far above 40 DEG C, and lithium ion battery shows higher initial capacity, but the stable circulation of battery after raising temperature Property reduce, capacity attenuation speed accelerate.Therefore, high-temperature behavior shows as an important indicator for considering battery context applicability Obtain particularly important.Common batteries use in high temperature environments, and electrode polarization aggravation is to cause battery under high temperature to hold in charging process The main reason for amount decays rapidly, and electric charge transmission resistance increases and because the generation of a large amount of gases makes electrode under the high temperature conditions Deform upon, discharge capacity is further decayed.
The content of the invention
The problem of in order to overcome prior art to exist, an object of the present invention are to provide a kind of high temperature circulation LiFePO4 Electrokinetic cell, 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 these goals, the present invention provides a kind of high temperature circulation lithium iron phosphate dynamic battery, including positive pole, negative Pole, barrier film and electrolyte, the positive pole include plus plate current-collecting body and coated in the positive electrode on plus plate current-collecting body, the positive poles 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 negative pole includes negative current collector and included coated in the negative material on negative current collector, the negative material Negative active core-shell material, the negative active core-shell material include carbonaceous mesophase spherules, and the particle diameter distribution D50 of the carbonaceous mesophase spherules is 3.6~8.5 μm, its tap density is 0.8~1.2g/cm3, its specific surface area is 1.1~1.5m2/g。
The present invention also provides a kind of preparation method of high temperature circulation lithium iron phosphate dynamic battery, comprises the following steps：
1) positive electrode active materials, conductive agent and binding agent are well mixed in de-airing mixer, obtain positive electrode, will In 3 addition positive electrodes of organic solvent point, after stirring, the anode sizing agent that viscosity is 6300~7800mPas is obtained, Anode sizing agent is crossed into 120~150 mesh sieves, is then coated with least one side in plus plate current-collecting body, dry, roll, slitting, film-making, Obtain lithium battery anode；
2) negative active core-shell material, conductive agent and binding agent are well mixed in de-airing mixer, obtain negative material, will In 3 addition negative materials of moisture, after stirring, the cathode size that viscosity is 2300~4200mPas is obtained, by negative pole Slurry crosses 120 mesh sieves, is then coated with least one side in negative current collector, dry, roll, slitting, film-making, obtaining lithium battery just Pole；
3) assembling of battery；
4) aging film forming, sealing.
Pass through above-mentioned technical proposal, the present invention have following technique effect：
1st, by adjusting the particle diameter of positive electrode active materials, improve deintercalation efficiency of the lithium ion in charge and discharge process and move Speed 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.
2nd, the present invention uses the carbonaceous mesophase spherules of small particle as negative active core-shell material, times of spherical carbonaceous mesophase spherules Rate performance is better than lamellar graphite, and the small graphite high rate performance of particle diameter is more preferable, and battery made of the carbonaceous mesophase spherules of small particle exists Circulation can effectively control negative pole polarization to aggravate so as to realize the improvement of high temperature circulation under hot conditions, and small particle negative pole is filling Volumetric expansion unobvious in discharge process, 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 areas are small, and the lithium ion of consumption is few, Irreversible capacity is few, while aerogenesis is also few.
3rd, the present invention by material by being pre-mixed stirring, then mediates, and finally finely dispersed method, can make different materials Expect component mixing evenly, shorten incorporation time, improve production efficiency.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Accompanying drawing is for providing a further understanding of the present invention, and a part for constitution instruction, 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 map；
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.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more New number range, these number 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, and the lithium battery includes Positive pole, negative pole, electrolyte, barrier film.
According to the present invention, the lithium battery anode includes plus plate current-collecting body and coated in the positive pole material on plus plate current-collecting body Material, the positive electrode include positive electrode active materials, conductive agent, binding agent.Using carbon coating type LiFePO 4 material as When positive electrode active materials prepare positive pole, carbon coating can strengthen the electric conductivity between LiFePO4 particles, 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 cause battery volume energy density Too low, specific surface area too conference causes material processing difficulties, and material is difficult to scattered easily reunion, the too small explanation material carbon of specific surface area Cladding is inadequate, and the internal resistance of cell and high rate performance cycle performance can be deteriorated, the particle diameter distribution D50 of the material:1~5 μm, 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 Material, the volume average particle size distribution D50 of the carbon coating type LiFePO 4 material is 1~5 μm；The vibration density of the LiFePO4 Spend for 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 bag 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, compare surface Product is 8.2~9.6m2/g。
According to the present invention, the dosage of each material in positive electrode can be adjusted according to being actually needed, for example, at this In a kind of embodiment being more highly preferred to of invention, in order to further improve obtained lithium iron phosphate dynamic battery at high temperature Cycle performance, on the basis of the gross weight of anode material of lithium battery, the contents of the positive electrode active materials is 93~98 weight %, The content of conductive agent is 1.0~3.5 weight %, the content of binding agent 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, CNT, 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 binding agent can be type commonly used in the art, for example, the binding agent can select From polyvinyl alcohol, polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose, TPO binding agent and Viton etc., under preferable case, institute It is the PVDF that molecular weight is 1,300,000 to state binding agent.
According to the present invention, in order to further 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, more preferably 2.1~2.4g/cm3。
According to the present invention, in order to further 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, more preferably 120~140g/cm2。
The present invention also provides a kind of preparation method of lithium battery anode, comprises the following steps：
1), positive electrode active materials, conductive agent and binding agent are well mixed in de-airing mixer, obtain positive electrode；
2), positive electrode and Part I organic solvent are well mixed, positive pole is obtained and closes slurry lotion 1；
3), close slurry lotion 1 in positive pole to be well mixed with Part II organic solvent, obtain positive pole and close slurry lotion 2；
4), remaining organic solvent is added in positive electrode paste 2, regulation viscosity to 6300~7800mPas, excessively 120~ The sieve of 150 mesh obtains anode sizing agent；
5), by the anode sizing agent after sieving be coated on plus plate current-collecting body at least one side, dry, roll, slitting, film-making, Obtain lithium battery anode.
In the present invention, by the way that positive electrode is pre-mixed into stirring, then mediate, last finely dispersed method, can make Different materials component mixes evenly, improves the uniformity of positive pole, shortens incorporation time, improves production efficiency.
According to the present invention, the dosage of organic solvent and positive electrode can be adjusted according to being actually needed, 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 can also be selected as type commonly used in the art, for example, can select For ethylene carbonate, propene carbonate, 1-METHYLPYRROLIDONE etc., under preferable case, the organic solvent is N- methylpyrroles 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 gross weight of the organic solvent, the content of the Part I solvent is 20~30 weight %, described The content of Part II 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, and wherein stir speed (S.S.) is 20~40r/min, and 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 negative pole as negative active core-shell material when, spherical carbonaceous mesophase spherules it is forthright again Lamellar graphite can be better than, the small graphite high rate performance of particle diameter is more preferable, and battery is in high temperature made of the carbonaceous mesophase spherules of small particle Under the conditions of circulation can effectively control negative pole polarization aggravation so as to realize the improvement of high temperature circulation, small particle negative pole is in discharge and recharge During volumetric expansion unobvious, tap density can embody the pattern and particle diameter distribution of material, and tap density is too small to cause electricity Pond volume energy density is too low, and the small material of specific surface area can make to be formed that SEI membrane areas are small, and the lithium ion of consumption is few, can not Inverse capacity is few, while aerogenesis is also few.According to the present invention, the cathode of lithium battery includes negative current collector and coated in negative pole currect collecting Negative material on body, the negative material include negative active core-shell material, conductive agent, binding agent, the negative active core-shell material bag Carbonaceous mesophase spherules are included, the volume average particle size distribution D50 of the carbonaceous mesophase spherules is 3.6~8.5 μm, more 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 particle diameter is more It is good, battery made of the carbonaceous mesophase spherules of small particle circulate under the high temperature conditions can effectively control negative pole polarization aggravation from And the improvement of high temperature circulation is realized, small particle negative pole volumetric expansion unobvious in charge and discharge process, tap density can embody material The pattern and particle diameter distribution of material, tap density is too small to cause battery volume energy density too low, and the small material of specific surface area can So as to be formed, SEI membrane areas are small, and the lithium ion of consumption is few, and irreversible capacity is few, while aerogenesis is also few.But if its vibration density Height is spent, then the fragility of negative pole can be caused to become big, pole piece is broken when winding battery pole piece, can not only improve electricity The high temperature cyclic performance in pond, even more so that the preparation of battery can not be completed.Under preferable case, the jolt ramming of the carbonaceous mesophase spherules Density is 0.9~1.3g/cm3, more 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 material in negative material can be adjusted according to being actually needed, for example, at this In a kind of embodiment being more highly preferred to of invention, in order to further improve obtained lithium iron phosphate dynamic battery at high temperature Cycle performance, on the basis of the gross weight of lithium cell cathode material, the content of the negative active core-shell material is 92~97 weight %, The content of conductive agent is 1~3 weight %, the content of binding agent 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, CNT, 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 binding agent can be type commonly used in the art, for example, the binding agent can select From polyvinyl alcohol, polytetrafluoroethylene (PTFE), carboxymethyl cellulose, TPO binding agent, butadiene-styrene rubber and Viton etc., preferably feelings Under condition, the binding agent is butadiene-styrene rubber and/or carboxymethyl cellulose.
According to the present invention, in order to further optimize the high temperature cyclic performance of lithium battery, under preferable case, the lithium battery is born The compacted density of pole is 1.3~1.8g/cm3, more preferably 1.4~1.7g/cm3。
According to the present invention, in order to further optimize the high temperature cyclic performance of lithium battery, under preferable case, the lithium battery is born The surface density of pole is 62~70g/cm2, more preferably 63~66g/cm2。
The present invention also provides the preparation method of described cathode of lithium battery, comprises the following steps：
1) negative active core-shell material, conductive agent and binding agent are well mixed in de-airing mixer, obtain negative material；
2) negative material and Part I water are well mixed, obtain negative pole and close slurry lotion 1；
3) negative pole is closed into slurry lotion 1 and Part II water is well mixed, obtained negative pole and close slurry lotion 2；
4) remaining water is added into negative pole to close in slurry lotion 2, regulation viscosity to 2300~4200mPas, crosses 120 mesh sieves Obtain cathode size；
5) by the cathode size after sieving be coated on negative current collector at least one side, dry, roll, slitting, film-making, obtain To cathode of lithium battery.
In the present invention, by the way that negative material is pre-mixed into stirring, then mediate, last finely dispersed method, can make Different materials component mixes evenly, improves the uniformity of negative pole, shortens incorporation time, improves production efficiency.
According to the present invention, the dosage of negative material and water can be adjusted according to being actually needed, described under preferable case The weight of negative material and water ratio is 1：(1~1.2).
According to the present invention, in the preparation process of cathode of lithium battery, under preferable case, using the gross weight of the water as base Standard, the content of the Part I water is 20~30 weight %, and the content of the Part II water is 20~30 weight %.
It is described to be mixed into step 1) under preferable case in the preparation process of cathode of lithium battery according to the present invention It is stirred, wherein, stir speed (S.S.) is 20~40r/min, and mixing time is 60~90min.
It is described to be mixed into step 2) under preferable case in the preparation process of cathode of lithium battery according to the present invention It is stirred, wherein, mixing speed is 1200~1500r/min, and mixing time is 60~90min, and whipping temp is 20~50 ℃。
It is described to be mixed into step 3) under preferable case in the preparation process of cathode of lithium battery according to the present invention 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, can use this area Conventional nonaqueous electrolytic solution.For example electrolyte lithium salt is selected from lithium hexafluoro phosphate (LiPF6), lithium perchlorate, LiBF4, hexafluoro One or more in arsenic acid lithium, lithium halide, chlorine lithium aluminate and fluorohydrocarbon base Sulfonic Lithium.The electrolyte can be that this area is conventional 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 further 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 influenceing battery high-temperature discharge performance, and electrolyte is an important factor for influenceing 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), more preferably 1:1:1.The concentration of electrolyte is generally 1~1.3mol/L.
In order to further 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 gross weight of the electrolyte, the content of the dioxalic acid lithium borate for 0.5~ 1.5 weight %.
In the case of, according to the invention it is preferred to, the barrier film is the PP barrier films that thickness is 20~25 μm.
The present invention also provides a kind of preparation method of lithium battery, comprises the following steps：
1) preparation of positive pole, the preparation method of the positive pole are same as above；
2) preparation of negative pole, the preparation method of the negative pole are same as above；
3) electrolyte and encapsulated moulding are injected after being molded positive pole, negative pole and membrane winding；
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 area, such as can be：Shelved 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 sealed, under preferable case, during the sealing, the vacuum 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 with known to those skilled in the art, and the present invention will not be repeated here.
The present invention will be described in detail by way of examples below.Carbon coating type LiFePO4 material in following examples Material reaches new energy Co., Ltd, model HSD-1 purchased from Hai Si；Carbonaceous mesophase spherules are purchased from Bei Terui new energy materialses, model For S360-MB；Te Migao conductive black, electrically conductive graphite is purchased from Te Migao graphite Co., Ltd；CNT is purchased from Wuxi Dong Heng New Energy Technology Co., Ltd.s；1-METHYLPYRROLIDONE is purchased from Nanjing Jin Long Chemical Co., Ltd.s；Graphite is dilute to be purchased from Qingdao Hao Xin New Energy Technology Co., Ltd.s；PVDF is purchased from Su Wei (SOLVAY) group, model 5130；Butadiene-styrene rubber is purchased from Japanese 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.s；Ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC) purchase From Shandong, stone wins magnificent Chemical Group completely.
Embodiment 1
1st, the preparation of positive pole
By 95.5kg carbon coating types LiFePO 4 material, (D50 is 3 μm, tap density 1.1g/cm3, specific surface area be 9.2m2/ g), 0.5kg conductive blacks, 1kg CNTs, 2.5kg PVDF 5130 vacuum≤- 0.08MPa vacuum dry In case, 300min is dried at 120 DEG C；
Above-mentioned carbon coating type LiFePO 4 material, conductive black, CNT are added in de-airing mixer, in 25r/ 60min is stirred under min rotating speed, obtains positive electrode；
Above-mentioned positive electrode and 30kgN- methyl pyrrolidones (NMP) are stirred in de-airing mixer, obtained just Slurry lotion 1 is closed in pole, and wherein stir speed (S.S.) is 1800r/min, and mixing time 90min, whipping temp is 40 DEG C；
Positive pole is closed into slurry lotion 1 and 30kg NMP to stir in de-airing mixer, positive pole is obtained and closes slurry lotion 2, its Middle stir speed (S.S.) is 2200r/min, and mixing time 90min, whipping temp is 40 DEG C；
Closed to positive pole in slurry lotion 2 and add 40kg NMP, obtained the slurry that viscosity is 7200mPas, slurry is crossed 150 Mesh sieve, obtain anode sizing agent；
By the anode sizing agent after sieving coated in thickness be 15 μm carbon aluminium foil tow sides, then 120 DEG C drying, Cutting obtains the positive pole that size is 2720mm × 155mm × 20 μm on cutting machine after roll-in under 1.6MPa pressure, described The compacted density of positive pole is 2.2g/cm3, surface density 133g/cm2Positive plate.
2nd, the preparation of negative pole
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 celluloses (CMC) and 2.5kg butadiene-styrene rubber (SBR) stir under 30r/min rotating speed 60min, obtain negative material；
By above-mentioned positive electrode and 36kg deionized waters, stirred in de-airing mixer, obtain negative pole and close slurry lotion 1, wherein stir speed (S.S.) is 1200r/min, and mixing time 90min, whipping temp is 40 DEG C；
Negative pole is closed into slurry lotion 1 and 36kg deionized waters to stir in de-airing mixer, negative pole is obtained and closes slurry lotion 2, wherein stir speed (S.S.) is 2000r/min, and mixing time 90min, whipping temp is 40 DEG C；
Closed to negative pole in slurry lotion 2 and add 48kg deionized waters, the slurry that viscosity is 3200mPas is obtained, by slurry mistake 120 mesh sieves, obtain cathode size；
Again by the cathode size after sieving be coated on 8 μm of copper foils of thickness tow sides, then 120 DEG C drying, Cutting obtains the negative pole that size is 2890mm × 160mm × 8 μm on cutting machine after roll-in under 1.6MPa pressure, is pressed Real density is 1.5g/cm3, surface density 66g/cm2Negative plate.
3rd, the assembling of battery
By LiPF6With dioxalic acid lithium borate, ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC) It is configured to LiPF6(wherein, EC, EMC and DMC weight ratio are 1 to the solution that concentration is 1mol/L：1：1), wherein dioxalic acid boric acid The content of lithium is the 1% of EC, EMC and DMC gross weight, obtains nonaqueous electrolytic solution.
Above-mentioned positive pole, the PP barrier films that thickness is 25 μm and negative pole are wound into electrode group with up- coiler stacking successively, will To electrode group be put into the battery case of one end open, inject above-mentioned nonaqueous electrolytic solution, after 2 days are then shelved at 45 DEG C, so Steel ball sealing is played in the state of vacuum -0.08MPa afterwards, obtains lithium battery A1, its chemical property is as shown in table 1.
Embodiment 2
According to the method for embodiment 1, the difference is that, the preparation method of the positive pole is as follows：
By 96kg carbon coating types LiFePO 4 material, (D50 is 2 μm, tap density 1.0g/cm3, specific surface area be 9.6m2/ g), 1kg conductive blacks, 1.5kg graphite is dilute, 1.5kg PVDF 5130 vacuum≤- 0.08MPa vacuum drying oven In, dry 300min 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 30r/min rotating speed, obtains positive electrode；
Above-mentioned positive electrode and 24kg 1-METHYLPYRROLIDONEs (NMP) are stirred in de-airing mixer, obtained just Slurry lotion 1 is closed in pole, and wherein stir speed (S.S.) is 1600r/min, and mixing time 60min, whipping temp is 30 DEG C；
Positive pole is closed into slurry lotion 1 and 24kg NMP to stir in de-airing mixer, positive pole is obtained and closes slurry lotion 2, its Middle stir speed (S.S.) is 2200r/min, and mixing time 60min, whipping temp is 30 DEG C；
Closed to positive pole in slurry lotion 2 and add 72kg NMP, obtained the slurry that viscosity is 6500mPas, slurry is crossed 120 Mesh sieve, obtain anode sizing agent.
By the anode sizing agent after sieving coated in thickness be 15 μm carbon aluminium foil tow sides, then 120 DEG C drying, Cutting obtains the positive pole that size is 2720mm × 155mm × 20 μm on cutting machine after roll-in under 1.6MPa pressure, described The compacted density of positive pole is 2.1g/cm3, surface density 120g/cm2Positive plate, obtain lithium battery A2, its chemical property is such as Shown in table 1.
Embodiment 3
According to the method for embodiment 1, the difference is that, the preparation method of the positive pole is as follows：
By 95kg carbon coating types LiFePO 4 material, (D50 is 4 μm, tap density 1.2g/cm3, specific surface area be 8.2m2/ g), 1kg acetylene blacks, 1kg graphite is dilute, 3kg PVDF 5130 in vacuum≤- 0.08MPa vacuum drying oven, 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 35r/min rotating speed, obtains positive electrode；
Above-mentioned positive electrode and 20kg 1-METHYLPYRROLIDONEs (NMP) are stirred in de-airing mixer, obtained just Slurry lotion 1 is closed in pole, and wherein stir speed (S.S.) is 1500r/min, and mixing time 90min, whipping temp is 50 DEG C；
Positive pole is closed into slurry lotion 1 and 25kg NMP to stir in de-airing mixer, positive pole is obtained and closes slurry lotion 2, its Middle stir speed (S.S.) is 2000r/min, and mixing time 90min, whipping temp is 50 DEG C；
Closed to positive pole in slurry lotion 2 and add 55kg NMP, obtained the slurry that viscosity is 7200mPas, slurry is crossed 100 Mesh sieve, obtain anode sizing agent.
By the anode sizing agent after sieving coated in thickness be 15 μm carbon aluminium foil tow sides, then 120 DEG C drying, Cutting obtains the positive pole that size is 2720mm × 155mm × 20 μm on cutting machine after roll-in under 1.6MPa pressure, described The compacted density of positive pole is 2.4g/cm3, surface density 140g/cm2Positive plate, obtain lithium battery A3, its chemical property is such as Shown in table 1.
Embodiment 4
According to the method for embodiment 1, the difference is that, the preparation method of the positive pole is as follows：
By 98kg carbon coating types LiFePO 4 material, (D50 is 1 μm, tap density 0.9g/cm3, specific surface area be 11.6m2/ g), 0.5kg acetylene blacks, 0.5kg graphite is dilute, 1kg PVDF 5130 vacuum≤- 0.08MPa vacuum drying oven In, dry 300min 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 40r/min rotating speed, obtains positive electrode；
Above-mentioned positive electrode and 30kg 1-METHYLPYRROLIDONEs (NMP) are stirred in de-airing mixer, obtained just Slurry lotion 1 is closed in pole, and wherein stir speed (S.S.) is 2000r/min, and mixing time 60min, whipping temp is 40 DEG C；
Positive pole is closed into slurry lotion 1 and 30kg NMP to stir in de-airing mixer, positive pole is obtained and closes slurry lotion 2, its Middle stir speed (S.S.) is 2500r/min, and mixing time 90min, whipping temp is 40 DEG C；
Closed to positive pole in slurry lotion 2 and add 60kg NMP, obtained the slurry that viscosity is 6300mPas, slurry is crossed 150 Mesh sieve, obtain anode sizing agent.
By the anode sizing agent after sieving coated in thickness be 15 μm carbon aluminium foil tow sides, then 120 DEG C drying, Cutting obtains the positive pole that size is 2720mm × 155mm × 20 μm on cutting machine after roll-in under 1.6MPa pressure, described The compacted density of positive pole is 1.9g/cm3, surface density 115g/cm2Positive plate, obtain lithium battery A4, its chemical property is such as Shown in table 1.
Embodiment 5
According to the method for embodiment 1, the difference is that, the preparation method of the positive pole is as follows：
By 93kg carbon coating types LiFePO 4 material, (D50 is 5 μm, tap density 1.3g/cm3, specific surface area be 7.5m2/ g), 1.5kg CNTs, 2kg graphite is dilute, 3.5kg PVDF 5130 vacuum≤- 0.08MPa vacuum drying oven In, dry 300min at 120 DEG C；
By above-mentioned carbon coating type LiFePO 4 material, CNT, graphite is dilute, PVDF 5130 is added to de-airing mixer In, 75min is stirred under 20r/min rotating speed, obtains positive electrode；
Above-mentioned positive electrode and 24kg 1-METHYLPYRROLIDONEs (NMP) are stirred in de-airing mixer, obtained just Slurry lotion 1 is closed in pole, and wherein stir speed (S.S.) is 1200r/min, and mixing time 75min, whipping temp is 40 DEG C；
Positive pole is closed into slurry lotion 1 and 24kg NMP to stir in de-airing mixer, positive pole is obtained and closes slurry lotion 2, its Middle stir speed (S.S.) is 1800r/min, and mixing time 75min, whipping temp is 40 DEG C；
Closed to positive pole in slurry lotion 2 and add 48kg NMP, obtained the slurry that viscosity is 7800mPas, slurry is crossed 120 Mesh sieve, obtain anode sizing agent.
By the anode sizing agent after sieving coated in thickness be 20 μm carbon aluminium foil tow sides, then 120 DEG C drying, Cutting obtains the positive pole that size is 2720mm × 155mm × 20 μm on cutting machine after roll-in under 1.6MPa pressure, described The compacted density of positive pole is 2.6g/cm3, surface density 154g/cm2Positive plate, obtain lithium battery A5, its chemical property is such as Shown in table 1.
Embodiment 6
According to the method for embodiment 1, the difference is that, the preparation method of the negative pole is as follows：
By 94.5kg carbonaceous mesophase spherules, (D50 is 3.6 μm, and its tap density is 1.0g/cm3, its specific surface area is 1.3m2/ g), 2kg electrically conductive graphites (SP), 3.5kg carboxymethyl celluloses (CMC) stir 60min under 25r/min rotating speed, obtain To negative material；
By above-mentioned negative material and 20kg deionized waters, stirred in de-airing mixer, obtain negative pole and close slurry lotion 1, wherein stir speed (S.S.) is 1350r/min, and mixing time 75min, whipping temp is 40 DEG C；
Negative pole is closed into slurry lotion 1 and 25kg deionized waters to stir in de-airing mixer, negative pole is obtained and closes slurry lotion 2, wherein stir speed (S.S.) is 2000r/min, and mixing time 90min, whipping temp is 40 DEG C；
Closed to negative pole in slurry lotion 2 and add 55kg deionized waters, the slurry that viscosity is 2800mPas is obtained, by slurry mistake 120 mesh sieves, obtain cathode size；
Again by the cathode size after sieving be coated on 8 μm of copper foils of thickness tow sides, then 120 DEG C drying, Cutting obtains the negative pole that size is 2900mm × 160mm × 8 μm on cutting machine after roll-in under 1.6MPa pressure, is pressed Real density is 1.7g/cm3, surface density 63g/cm2Negative plate, obtain lithium battery A6, its chemical property is as shown in table 1.
Embodiment 7
According to the method for embodiment 1, the difference is that, the preparation method of the negative pole is as follows：
By 96kg carbonaceous mesophase spherules, (D50 is 8.5 μm, tap density 1.2g/cm3, its specific surface area is 1.6m2/g)、 1kg electrically conductive graphites (SP), 1kg conductive blacks, 2kg butadiene-styrene rubber stir 60min under 30r/min rotating speed, obtain negative pole material Material；
By above-mentioned negative material and 24kg deionized waters, stirred in de-airing mixer, obtain negative pole and close slurry lotion 1, wherein stir speed (S.S.) is 1400r/min, and mixing time 75min, whipping temp is 40 DEG C；
Negative pole is closed into slurry lotion 1 and 24kg deionized waters to stir in de-airing mixer, negative pole is obtained and closes slurry lotion 2, wherein stir speed (S.S.) is 1800r/min, and mixing time 75min, whipping temp is 40 DEG C；
Closed to negative pole in slurry lotion 2 and add 72kg deionized waters, the slurry that viscosity is 3600mPas is obtained, by slurry mistake 120 mesh sieves, obtain cathode size；
Again by the cathode size after sieving be coated on 12 μm of copper foils of thickness tow sides, then 120 DEG C drying, Cutting obtains the negative pole that size is 2900mm × 160mm × 8 μm on cutting machine after roll-in under 1.6MPa pressure, is pressed Real density is 1.4g/cm3, surface density 66g/cm2Negative plate, obtain lithium battery A7, its chemical property is as shown in table 1.
Embodiment 8
According to the method for embodiment 1, the difference is that, the preparation method of the negative pole is as follows：
By 92kg carbonaceous mesophase spherules, (D50 is 4 μm, and its tap density is 0.9g/cm3, its specific surface area is 1.7m2/g)、 3kg carboxymethyl celluloses (CMC) and 5kg butadiene-styrene rubber (SBR) stir 60min under 20r/min rotating speed, obtain negative pole material Material；
By above-mentioned negative material and 25kg deionized waters, stirred in de-airing mixer, obtain negative pole and close slurry lotion 1, wherein stir speed (S.S.) is 1200r/min, and mixing time 90min, whipping temp is 30 DEG C；
Negative pole is closed into slurry lotion 1 and 20kg deionized waters to stir in de-airing mixer, negative pole is obtained and closes slurry lotion 2, wherein stir speed (S.S.) is 1600r/min, and mixing time 90min, whipping temp is 30 DEG C；
Closed to negative pole in slurry lotion 2 and add 55kg deionized waters, the slurry that viscosity is 2300mPas is obtained, by slurry mistake 120 mesh sieves, obtain cathode size；
Again by the cathode size after sieving be coated on 10 μm of copper foils of thickness tow sides, then 120 DEG C drying, Cutting obtains the negative pole that size is 2900mm × 160mm × 8 μm on cutting machine after roll-in under 1.6MPa pressure, is pressed Real density is 1.3g/cm3, surface density 62g/cm2Negative plate, obtain lithium battery A8, its chemical property is as shown in table 1.
Embodiment 9
According to the method for embodiment 1, the difference is that, the preparation method of the negative pole is as follows：
By 97kg carbonaceous mesophase spherules, (D50 is 8 μm, and its tap density is 1.3g/cm3, its specific surface area is 1.2m2/g)、 1kg acetylene blacks, 2kg carboxymethyl celluloses (CMC) stir 90min under 40r/min rotating speed, obtain negative material；
Above-mentioned negative material and 30kg deionized waters are stirred in de-airing mixer, negative pole is obtained and closes slurry lotion 1, Wherein stir speed (S.S.) is 1500r/min, and mixing time 60min, whipping temp is 50 DEG C；
Negative pole is closed into slurry lotion 1 and 30kg deionized waters to stir in de-airing mixer, negative pole is obtained and closes slurry lotion 2, wherein stir speed (S.S.) is 2200r/min, and mixing time 60min, whipping temp is 50 DEG C；
Closed to negative pole in slurry lotion 2 and add 60kg deionized waters, the slurry that viscosity is 4200mPas is obtained, by slurry mistake 120 mesh sieves, obtain cathode size；
Again by the cathode size after sieving be coated on 8 μm of copper foils of thickness tow sides, then 120 DEG C drying, Cutting obtains the negative pole that size is 2900mm × 160mm × 8 μm on cutting machine after roll-in under 1.6MPa pressure, is pressed Real density is 1.8g/cm3, surface density 70g/cm2Negative plate, obtain lithium battery A9, its chemical property is as shown in table 1.
Embodiment 10
According to the method for embodiment 1, the difference is that, the collocation 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 LiPF6(wherein, EC, EMC and DMC weight ratio are 1 to the solution that concentration is 1.1mol/L：0.8：0.8), wherein two grass The content of sour lithium borate is the 0.5% of EC, EMC and DMC gross weight, obtains nonaqueous electrolytic solution, obtains lithium battery A10, its electrification It is as shown in table 1 to learn performance.
Embodiment 11
According to the method for embodiment 1, the difference is that, the collocation 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 LiPF6(wherein, EC, EMC and DMC weight ratio are 1 to the solution that concentration is 1.3mol/L：1.2：1.2), wherein two grass The content of sour lithium borate is the 1.5% of EC, EMC and DMC gross weight, obtains nonaqueous electrolytic solution, obtains lithium battery A11, its electrification It is as shown in table 1 to learn performance.
Comparative example 1
According to the method for embodiment 1, the difference is that, the positive electrode active materials LiFePO4Particle diameter D50 for 0.5 μm, shake Real density is 1.5g/cm3, specific surface area 6.3m2/ g, lithium battery B1 is obtained, its chemical property is as shown in table 1.
Comparative example 2
According to the method for embodiment 1, the difference is that, the positive electrode active materials LiFePO4Particle diameter D50 be 6 μm, jolt ramming Density is 0.7g/cm3, specific surface area 15m2/ g, lithium battery B2 is obtained, its chemical property is as shown in table 1.
Comparative example 3
According to the method for embodiment 1, the difference is that, the particle diameter D50 of the negative active core-shell material carbonaceous mesophase spherules is 3 μ M, tap density is 0.6g/cm3, specific surface area 0.9m2/ g, lithium battery B3 is obtained, its chemical property is as shown in table 1.
Comparative example 4
According to the method for embodiment 1, the difference is that, the particle diameter D50 of the negative active core-shell material carbonaceous mesophase spherules is 9 μ M, tap density is 1.5g/cm3, specific surface area 1.8m2/ g, lithium battery B4 is obtained, its chemical property is as shown in table 1.
Comparative example 5
According to the method for embodiment 1, the difference is that, dioxalic acid lithium borate is not contained in the electrolyte, obtains lithium battery B5, its chemical property are as shown in table 1.
Comparative example 6
According to the method for embodiment 1, the difference is that, the preparation method of anode sizing agent and cathode size is different, specific as follows：
1st, the preparation of positive pole
(D50 is 3 μm to 95.5kg carbon coating types LiFePO 4 material, tap density 1.1g/cm3, specific surface area be 9.2m2/ g), 0.5kg conductive blacks, 1kg CNTs, 2.5kg PVDF 5130 vacuum≤- 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 are well mixed in de-airing mixer, cross 120 Mesh sieve, obtain anode sizing agent；
The painting method of anode sizing agent is the same as embodiment 1.
2nd, the preparation of negative pole
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 celluloses (CMC) and 2.5kg butadiene-styrene rubber (SBR) and 120kg water are in de-airing mixer In stir, slurry is crossed into 120 mesh sieves, obtains cathode size；
The painting method of cathode size is the same as embodiment 1.
3rd, the assembly method of battery obtains lithium battery B6, its chemical property is as shown in table 1 with embodiment 1.
Method of testing：
1st, high temperature cyclic performance：At 55 DEG C, charged in a manner of constant-current constant-voltage charging, 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 Press as 2.5 volts, circulate 2000 times, after calculating initial discharge capacity C1,2000 discharge capacity C2 of circulation, circulation 2000 times respectively Capability retention R.
2nd, low temperature performance：At 25 DEG C, charged with constant voltage charging method, limitation electric current is 0.5C, terminates electricity It is 3.5A to press as 3.65V, termination electric current, is discharged in a manner of constant-current discharge, discharge current 1C, then with constant voltage charging method Charged, limitation electric current is 0.5C, and final voltage 3.65V, termination electric current is 3.5A, under the conditions of -20 DEG C, is put with constant current Electrically discharged, discharge current 1C, the blanking voltage of electric discharge is 2.0V, respectively calculate 25 DEG C of discharge capacity C3, -20 DEG C Discharge capacity C4.
The chemical property of each lithium battery in the embodiment 1~11 of table 1 and comparative example 1~6
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can The combination of energy no longer separately illustrates.
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 equally be considered as content disclosed in this invention.

Claims (10)

1. a kind of high temperature circulation lithium iron phosphate dynamic battery, including positive pole, negative pole, barrier film and electrolyte, it is characterised in that described Positive pole includes plus plate current-collecting body and includes positive-active material coated in the positive electrode on plus plate current-collecting body, the positive electrode Material, the positive electrode active materials include carbon coating type LiFePO 4 material, the particle diameter point of the carbon coating type LiFePO 4 material Cloth D50 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 negative pole includes negative current collector and includes negative pole coated in the negative material on negative current collector, the negative material Active material, the negative active core-shell material include carbonaceous mesophase spherules, and the particle diameter distribution D50 of the carbonaceous mesophase spherules is 3.6 ~8.5 μm, its tap density is 0.9~1.3g/cm3, its specific surface area is 1.2~1.7m2/g。
2. high temperature circulation lithium iron phosphate dynamic battery according to claim 1, wherein, the carbon coating type LiFePO4 material The particle diameter distribution D50 of material is 2~4 μm；And/or
The tap density of the carbon coating type LiFePO 4 material is 1.0~1.2g/cm3；And/or
The specific surface area of the carbon coating type LiFePO 4 material is 8.2~9.6m2/g。
3. high temperature circulation lithium iron phosphate dynamic battery according to claim 1 or 2, wherein, the carbonaceous mesophase spherules Particle diameter distribution D50 is 4~8 μm；And/or
The tap density of the carbonaceous mesophase spherules is 1.0~1.2g/cm3；And/or
The specific surface area of the carbonaceous mesophase spherules is 1.3~1.6m2/g。
4. high temperature circulation lithium iron phosphate dynamic battery according to claim 1, wherein, the compacting of the lithium battery anode is close Spend for 1.9~2.6g/cm3, surface density is 115~154g/cm2。
5. the high temperature circulation lithium iron phosphate dynamic battery according to claim 1 or 4, wherein, the pressure of the cathode of lithium battery Real density is 1.3~1.8g/cm3, surface density is 62~70g/cm2。
6. high temperature circulation lithium iron phosphate dynamic battery according to claim 1, wherein, the electrolyte includes ethylene carbonate Ester, methyl ethyl carbonate, dimethyl carbonate；
Wherein, ethylene carbonate, methyl ethyl carbonate, the mass ratio of dimethyl carbonate are 1:(0.8~1.2):(0.8~1.2).
7. high temperature circulation lithium iron phosphate dynamic battery according to claim 6, wherein, the electrolyte also includes dioxalic acid Lithium borate, on the basis of the gross weight of the electrolyte, the content of the dioxalic acid lithium borate is 0.5~1.5 weight %.
8. a kind of preparation method of high temperature circulation lithium iron phosphate dynamic battery as claimed in any of claims 1 to 7, It is characterised in that it includes following steps：
1) positive electrode active materials, conductive agent and binding agent are well mixed in de-airing mixer, obtain positive electrode, will be organic In 3 addition positive electrodes of solvent point, after stirring, the anode sizing agent that viscosity is 6300~7800mPas is obtained, will just Pole slurry crosses 120~150 mesh sieves, is then coated with least one side in plus plate current-collecting body, dry, roll, slitting, film-making, obtain Lithium battery anode；
2) negative active core-shell material, conductive agent and binding agent are well mixed in de-airing mixer, negative material are obtained, by moisture In 3 addition negative materials, after stirring, the cathode size that viscosity is 2300~4200mPas is obtained, by cathode size Cross 120 mesh sieves, be then coated with least one side in negative current collector, dry, roll, slitting, film-making, obtain lithium battery anode；
3) assembling of battery；
4) aging film forming, sealing.
9. the preparation method of high temperature circulation lithium iron phosphate dynamic battery according to claim 8, wherein, in step 1), The preparation method of the anode sizing agent is：
A, positive electrode active materials, conductive agent and binding agent are well mixed in de-airing mixer, obtain positive electrode；
B, positive electrode and Part I organic solvent are well mixed, obtain positive pole and close slurry lotion 1；
C, close slurry lotion 1 in positive pole to be well mixed with Part II organic solvent, obtain positive pole and close slurry lotion 2；
D, remaining organic solvent is added in positive electrode paste 2, regulation viscosity to 6300~7800mPas, crosses 120~150 mesh Sieve obtain anode sizing agent；
Wherein, the weight ratio of the positive electrode and organic solvent is 1：(0.8~1)；And/or
On the basis of the gross weight of the organic solvent, the content of the Part I organic solvent is 20~30 weight %, institute The content for stating Part II organic solvent is 20~30 weight %.
10. the preparation method of high temperature circulation lithium iron phosphate dynamic battery according to claim 9, wherein, in step 1), The preparation method of the cathode size is：
A, negative active core-shell material, conductive agent and binding agent are well mixed in de-airing mixer, obtain negative pole powder body material；
B, powder body material and Part I water are well mixed, obtain negative pole and close slurry lotion 1；
C, negative pole is closed into slurry lotion 1 and Part II water is well mixed, obtained negative pole and close slurry lotion 2；
D, remaining water is added into negative pole to close in slurry lotion 2, regulation viscosity to 2300~4200mPas, crosses 120 mesh sieves and obtain Cathode size；
Wherein, the weight ratio of the negative pole powder body material and water is 1：(1~1.2), it is described on the basis of the gross weight of the water The content of Part I water is 20~30 weight %, and the content of the Part II water is 20~30 weight %.
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108511788A (en) * 2018-03-29 2018-09-07 东莞市智盈新能源有限公司 A kind of high magnification ternary system start and stop lithium ion battery and preparation method thereof
CN109088033A (en) * 2018-08-07 2018-12-25 江西省汇亿新能源有限公司 Macrocyclic 18650 lithium battery of ferric phosphate lithium type of high safety high-energy and preparation method thereof
CN109742322A (en) * 2018-12-05 2019-05-10 江苏海四达电源股份有限公司 A kind of high power lithium iron phosphate cell and preparation method thereof
EP3547418A1 (en) * 2018-03-30 2019-10-02 Sumitomo Osaka Cement Co., Ltd. Electrode material for lithium-ion battery and lithium-ion battery comprising the same
CN112331833A (en) * 2020-11-10 2021-02-05 江西省汇亿新能源有限公司 Lithium iron phosphate starting battery and manufacturing method thereof
CN115148983A (en) * 2022-09-01 2022-10-04 蜂巢能源科技股份有限公司 Lithium ion battery
CN115498247A (en) * 2022-10-27 2022-12-20 欣旺达电动汽车电池有限公司 Secondary battery and electric equipment

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101162776A (en) * 2007-10-26 2008-04-16 深圳市贝特瑞新能源材料股份有限公司 Lithium iron phosphate suitable for high multiplying power electrokinetic cell and method for producing the same
CN103531794A (en) * 2013-10-28 2014-01-22 金瑞新材料科技股份有限公司 Lithium ion battery positive material lithium ferrous phosphate and preparation method
US20140023937A1 (en) * 2012-07-17 2014-01-23 Zhengcheng Zhang Electrolytes including an organosilicon solvent and propylene carbonate for lithium ion batteries
CN103682413A (en) * 2013-12-27 2014-03-26 山东精工电子科技有限公司 High-rate long-cycle-life lithium iron phosphate battery and preparation method thereof
CN105591110A (en) * 2015-12-18 2016-05-18 山东精工电子科技有限公司 Preparation method of low-temperature lithium iron phosphate battery
CN106299485A (en) * 2016-10-19 2017-01-04 江苏海四达电源股份有限公司 High specific energy lithium-ion-power cell and preparation method thereof
CN106374096A (en) * 2016-11-03 2017-02-01 江西安驰新能源科技有限公司 Lithium iron phosphate battery with high energy density
CN106450429A (en) * 2016-10-19 2017-02-22 江苏海四达电源股份有限公司 High-cycle high-specific energy lithium ion power battery and preparation method thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101162776A (en) * 2007-10-26 2008-04-16 深圳市贝特瑞新能源材料股份有限公司 Lithium iron phosphate suitable for high multiplying power electrokinetic cell and method for producing the same
US20140023937A1 (en) * 2012-07-17 2014-01-23 Zhengcheng Zhang Electrolytes including an organosilicon solvent and propylene carbonate for lithium ion batteries
CN103531794A (en) * 2013-10-28 2014-01-22 金瑞新材料科技股份有限公司 Lithium ion battery positive material lithium ferrous phosphate and preparation method
CN103682413A (en) * 2013-12-27 2014-03-26 山东精工电子科技有限公司 High-rate long-cycle-life lithium iron phosphate battery and preparation method thereof
CN105591110A (en) * 2015-12-18 2016-05-18 山东精工电子科技有限公司 Preparation method of low-temperature lithium iron phosphate battery
CN106299485A (en) * 2016-10-19 2017-01-04 江苏海四达电源股份有限公司 High specific energy lithium-ion-power cell and preparation method thereof
CN106450429A (en) * 2016-10-19 2017-02-22 江苏海四达电源股份有限公司 High-cycle high-specific energy lithium ion power battery and preparation method thereof
CN106374096A (en) * 2016-11-03 2017-02-01 江西安驰新能源科技有限公司 Lithium iron phosphate battery with high energy density

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108511788A (en) * 2018-03-29 2018-09-07 东莞市智盈新能源有限公司 A kind of high magnification ternary system start and stop lithium ion battery and preparation method thereof
EP3547418A1 (en) * 2018-03-30 2019-10-02 Sumitomo Osaka Cement Co., Ltd. Electrode material for lithium-ion battery and lithium-ion battery comprising the same
US10680240B2 (en) 2018-03-30 2020-06-09 Sumitomo Osaka Cement Co., Ltd. Electrode material for lithium ion battery and lithium ion battery
CN109088033A (en) * 2018-08-07 2018-12-25 江西省汇亿新能源有限公司 Macrocyclic 18650 lithium battery of ferric phosphate lithium type of high safety high-energy and preparation method thereof
CN109742322A (en) * 2018-12-05 2019-05-10 江苏海四达电源股份有限公司 A kind of high power lithium iron phosphate cell and preparation method thereof
CN112331833A (en) * 2020-11-10 2021-02-05 江西省汇亿新能源有限公司 Lithium iron phosphate starting battery and manufacturing method thereof
CN115148983A (en) * 2022-09-01 2022-10-04 蜂巢能源科技股份有限公司 Lithium ion battery
CN115498247A (en) * 2022-10-27 2022-12-20 欣旺达电动汽车电池有限公司 Secondary battery and electric equipment
CN115498247B (en) * 2022-10-27 2023-08-15 欣旺达电动汽车电池有限公司 Secondary battery and electric equipment
WO2024087389A1 (en) * 2022-10-27 2024-05-02 欣旺达动力科技股份有限公司 Secondary battery and electrical device

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