CN107046131A - A kind of LiFePO4 system lithium ion battery and preparation method - Google Patents
A kind of LiFePO4 system lithium ion battery and preparation method Download PDFInfo
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- CN107046131A CN107046131A CN201710220018.6A CN201710220018A CN107046131A CN 107046131 A CN107046131 A CN 107046131A CN 201710220018 A CN201710220018 A CN 201710220018A CN 107046131 A CN107046131 A CN 107046131A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A kind of LiFePO4 system lithium ion battery, lithium ion battery includes housing, lamination core body and the electrolyte being filled in housing in the housing, the lamination core body includes positive plate, negative plate and the barrier film being arranged between the positive plate and negative plate, the positive electrode includes positive active material, the negative material includes negative electrode active material, the positive active material is LiFePO 4 material, the negative electrode active material includes native graphite, Delanium, MCMB, at least one of polymer charcoal, electrolyte in the electrolyte includes LiPF6、LiBF4And LiAsF6In one or more.Present invention offer is a kind of to be easy to volume production, circulates excellent high-energy-density LiFePO4 system lithium ion battery.
Description
Technical field
The present invention relates to technical field of lithium ion, specially a kind of LiFePO4 system lithium ion battery and preparation side
Method.
Background technology
Because lithium iron phosphate positive material has high security, long-life, low cost and high voltage platform, make it in new energy
Driving source automobile, including pure electric vehicle (EVs), hybrid-power electric vehicle (HEVs) and plug-in hybrid electric car
(PHEVs) field is used widely.But compared to other power positive electrodes, the matter of LiFePO4 system lithium ion battery
Energy density ratio is relatively low, and electrokinetic cell prepared by industry class only has 130Wh/kg or so.It is limited to the low of LiFePO4 system
Energy density, current iron lithium system battery is mainly used in the larger motor bus of battery bag volume and communication base station and energy storage base
Stand, and small passenger car is mainly monopolized by the ternary system battery of high-energy-density.
LiFePO4 system lithium ion battery is low compared to the mass energy density of ternary system battery, is mainly constrained to
Itself positive pole gram volume is relatively low.Current industry class LiFePO4Actual gram volume play and there was only 110~145mAh/g, and three
The gram volume of member plays 135~165mAh/g.
China Patent Publication No. CN 104810506A, publication date on July 29th, 2015, a kind of entitled high-energy-density
Lithium ion battery patent of invention.This application case discloses negative electrode active material use：Carbon source coats the silicon carbon material of silicon source,
Although having certain inhibitory action to the volumetric expansion of negative pole, realize that industrialized volume production applies also many problems.It is not
Foot part is that negative material processability is difficult, cost is higher and cycle performance is not highly desirable.Want to improve LiFePO4 body
The mass energy density of series lithium ion battery, thus widen LiFePO4 system lithium ion battery application, it is necessary to from design work
Improved in terms of skill, and chemical system two.
In view of this it is special to propose the present invention.
The content of the invention
The technical problem to be solved in the present invention be to overcome the deficiencies in the prior art there is provided a kind of LiFePO4 system lithium from
Sub- battery and preparation method.
The main technical schemes design of the present invention is as follows：
A kind of LiFePO4 system lithium ion battery, including housing, the lamination core body in the housing and filling
Electrolyte in housing, the lamination core body includes positive plate, negative plate and is arranged between the positive plate and negative plate
Barrier film, the positive plate, negative plate are respectively by positive and negative collector and the positive and negative electrode material being coated on the positive and negative collector
Material composition,
The positive electrode includes positive active material, and the negative material includes negative electrode active material, and the positive pole is lived
Property material be LiFePO 4 material, the negative electrode active material include native graphite, Delanium, MCMB, polymerization
Electrolyte at least one of thing charcoal, the electrolyte includes LiPF6、LiBF4And LiAsF6In one or more.
Further, the positive electrode also includes conductive agent and positive electrode binder, and the conductive agent includes conductive black, surpassed
At least one of carbon, electrically conductive graphite, crystalline flake graphite, CNT are led, the positive electrode binder is Kynoar；
Wherein, the positive electrode in mass ratio by 95~97 parts of positive active materials, 1~2 part of conductive agent and 1.5~
2.5 parts of positive electrode binder mixing compositions；
The positive electrode, which is dissolved in N- methyl pyrrole network alkanone organic solvents, is made the anode sizing agent.
Further, the negative material also includes conductive agent, thickener and negative electrode binder, and the conductive agent includes conduction
At least one of carbon black, superconduction carbon, electrically conductive graphite, crystalline flake graphite, CNT, the thickener are carboxymethyl cellulose
Sodium, the negative electrode binder is butadiene-styrene rubber；
Wherein, the negative material is in mass ratio by 94~96 parts of negative electrode active materials, 1~2 part of conductive agent, 1~2 part of increasing
Thick dose and 2~4 parts of negative electrode binder mixing compositions；
The negative material, which is dissolved in carboxymethyl cellulose gum liquid, is made the cathode size.
Further, the plus plate current-collecting body is made up of utter misery aluminium foil, and the negative current collector is made up of copper foil, the barrier film
It is made up of the one or two kinds of in PP/PE or PP/PE/PP composite diaphragms.
Further, solvent and additive are also included in the electrolyte, the solvent includes ethylene carbonate, methyl ethyl carbonate
At least two in ester, diethyl carbonate, propene carbonate or dimethyl carbonate, the additive include vinylene carbonate,
At least one of sulfuric acid propylene, fourth dicyan or succinic anhydride.
Further, the compacted density of the positive plate is 2.15~2.25g/cm3, thickness is 155~165 μm；It is described negative
The compacted density of pole piece is 1.50~1.60g/cm3, thickness is 102~112 μm.
The thickness of the barrier film is 20um.
A kind of LiFePO4 system lithium ion battery and preparation method, comprise the following steps：
S1：Positive plate is made, and positive electrode is mixed and made into anode sizing agent in N- methyl pyrrole network alkanone organic solvents, will
The anode sizing agent is coated on plus plate current-collecting body, is toasted and is cold-pressed into laminated structure, and the laminated structure is carried out into cross cutting system
Obtain positive plate；
S2：Negative plate makes, and negative material is well mixed in carboxymethyl cellulose gum liquid cathode size is made, by institute
State cathode size to be coated on negative current collector, toast and be cold-pressed into laminated structure, the laminated structure is carried out into cross cutting is made
Negative plate；
S3：Lamination core body makes, and the positive plate, barrier film and negative plate is folded into battery core, and the battery core is entered
Row heat-sealing, then toasts the battery core under vacuum conditions；
S4：Electrolyte quota and fluid injection, are made electrolyte, then the electrolyte is injected after electrolyte is mixed with solvent
In battery core after the completion of baking；
S5：Chemical conversion and encapsulation, the battery core after fluid injection is pre-packaged, infiltration is shelved, then battery core is charged and controlled
Charging voltage causes battery core to be melted into, and vacuumizes battery core after the completion of chemical conversion, encapsulates and partial volume.
Further, the baking temperature of battery core described in S3 steps is 60~80 DEG C, vacuum ranges during baking are-
0.085~-0.095MPa, baking time under vacuum conditions is 20~30 hours.
Further, in the S4 steps, the reservoir quantity in the electrolyte injection battery core is 4.8g~5.8g/Ah.
Further, the charging voltage in the step S5 in battery core formation process is controlled in 3.3~3.5V；Charged during partial volume
Voltage range is 2.0~3.65V.
After adopting the above technical scheme, the present invention has the advantages that compared with prior art：
The LiFePO4 system lithium ion battery energy density of the present invention is high, with good chemical property, electric discharge property
Excellent, the stable circulation of energy, solves the problem of LiFePO4 system battery energy density is relatively low in existing industry.Meanwhile, checking
Go out suitable chemical system, different battery sizes can be fitted in, it is easy to process, being readily mass-produced.
The embodiment to the present invention is described in further detail below in conjunction with the accompanying drawings.
Brief description of the drawings
Accompanying drawing is as the part of the application, and for providing further understanding of the invention, of the invention is schematic
Embodiment and its illustrate to be used to explain the present invention, but do not constitute inappropriate limitation of the present invention.Clearly limit or do not rush no
In the case of prominent, the technical characteristic in embodiments herein and embodiment can be mutually combined.Below with reference to the accompanying drawings and tie
Embodiment is closed to illustrate the present invention in further detail.Obviously, described embodiment is only the part of the application
Embodiment, rather than whole embodiments.Based on embodiments herein, those of ordinary skill in the art are not making creation
Property work on the premise of the every other embodiment that is obtained, should all belong to the protection domain of the application.In the accompanying drawings：
Fig. 1 is the LiFePO4 high energy density cells discharge curve first of embodiment one, two, three；
Fig. 2 is the LiFePO4 high energy density cells cyclic curve figure of embodiment one, two, three.
It should be noted that these accompanying drawings and word description are not intended as the design model for limiting the present invention in any way
Enclose, but be that those skilled in the art illustrate idea of the invention by reference to specific embodiment.
Embodiment
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below in conjunction with the embodiment of the present invention
In accompanying drawing, the technical scheme in embodiment is clearly and completely described, following examples be used for illustrate the present invention, but
It is not limited to the scope of the present invention.
The present invention provides a kind of LiFePO4 system lithium ion battery, including housing, the lamination in the housing
Core body and the electrolyte being filled in housing, the lamination core body include positive plate, negative plate and be arranged on the positive plate and
Barrier film between negative plate, the positive plate, negative plate by positive and negative collector and are coated on the positive and negative collector respectively
Positive and negative electrode material composition.
The positive electrode is powder body material, including positive active material, conductive agent and positive electrode binder.Specifically, institute
Positive active material is stated for LiFePO 4 material, the positive electrode binder can be using viscous known to Kynoar or other
Tie agent.The conductive agent is the one or several kinds in conductive black, superconduction carbon, electrically conductive graphite, crystalline flake graphite, CNT.
Wherein, the positive electrode is in mass ratio by 95~97 parts of positive active materials, 1~2 part of conductive agent and 1.5~2.5 parts of positive poles
Binding agent mixing composition；
The positive pole powder material is well mixed in N- methyl pyrrole network alkanone (NMP) organic solvent, is made with good
Good viscosity, contain admittedly and fineness anode sizing agent, the anode sizing agent is coated uniformly on plus plate current-collecting body, specifically, institute
Stating plus plate current-collecting body can be made of carbon-coated aluminum foils, and the thickness of the utter misery aluminium foil is 12~15 μm；.Then it is coated with positive pole
The plus plate current-collecting body of material is toasted and is die cut after cold pressing, and the positive plate is made.The compacted density of the positive plate is
2.15~2.25g/cm3, thickness is 155~165 μm.
The negative material is powder body material, including negative electrode active material, conductive agent, thickener and negative electrode binder.Tool
Body, the negative electrode active material includes at least one of native graphite, Delanium, MCMB, polymer charcoal.
The conductive agent is similar to the conductive agent in positive electrode, by conductive black, superconduction carbon, electrically conductive graphite, crystalline flake graphite, carbon nanometer
At least one of pipe is constituted.The thickener can use sodium carboxymethylcellulose, and the negative electrode binder can use butylbenzene
Rubber.Wherein, the negative material is in mass ratio by 94~96 parts of negative electrode active materials, 1~2 part of conductive agent, 1~2 part of thickening
Agent and 2~4 parts of negative electrode binder mixing compositions.
The negative material is dissolved in and is prepared into cathode size in carboxymethyl cellulose gum liquid and is uniformly dispersed, the negative pole
Slurry has good viscosity, contained admittedly and fineness, is then coated onto on negative current collector, and the negative current collector can be used
Copper foil is made, and the thickness of the copper foil is 5~8 μm.Then the negative current collector for being coated with negative material toasted
And be die cut after cold pressing, negative plate is made.The compacted density of the negative plate is 1.50~1.60g/cm3, thickness be 102~
112μm。
The electrolyte includes electrolyte, solvent and additive, and the electrolyte is LiPF6、LiBF4And LiAsF6In
At least one, the solvent includes ethylene carbonate (EC), methyl ethyl carbonate (EMC), diethyl carbonate (DEC), propylene carbonate
At least two in ester (PC) or dimethyl carbonate (DMC), the additive includes vinylene carbonate (VC), sulfuric acid propylene
(PS), at least one of fourth dicyan (SN) and succinic anhydride (SA).Electrolyte uses different adaptation systems, different to match
Both positive and negative polarity system, optimizes corresponding chemical system.
In addition, the barrier film is the one or two kinds of in PP/PE or PP/PE/PP composite diaphragms.
The energy density for the LiFePO4 system lithium ion battery being prepared into using above-mentioned material is higher, can reach
More than 165Wh/kg, meets LiFePO4 discharge curve performance requirement, with good cycle performance.
The preparation method of LiFePO4 system lithium ion battery of the present invention, comprises the following steps：
S1：Positive plate is made, and by positive electrode, routinely technique is mixed in N- methyl pyrrole network alkanone organic solvent solvents
Uniformly, anode sizing agent is made, the anode sizing agent is coated on the plus plate current-collecting body, toasts and is cold-pressed into laminated structure,
Again to the laminated structure is die cut, finished product positive plate is obtained；
S2：Negative plate is made, and by negative material, routinely technique is well mixed in carboxymethyl cellulose gum liquid, is added viscous
Cathode size is made in knot agent, and the cathode size is coated on the negative current collector, toasts and is cold-pressed into laminated structure, then
To the laminated structure is die cut, obtains finished product and negative plate is made；
S3：Lamination core body is made, and the positive plate, barrier film and negative plate are folded into electricity according to conventional lamination process
Core, and the battery core is sealed, then the battery core is toasted under vacuum conditions；
S4：Electrolyte quota and fluid injection, are made electrolyte after lithium salts electrolyte is mixed by a certain percentage with solvent, then will
In battery core after the completion of the electrolyte injection baking；
S5：Chemical conversion and encapsulation, the battery core after fluid injection is pre-packaged, infiltration is shelved, then battery core charges and controls to charge
Voltage causes battery core to be melted into, and vacuumizes battery core after the completion of chemical conversion, encapsulates and partial volume.
Preparation method shown in the present invention eliminates unnecessary process, optimizes the flow of preparation, improves production effect
Rate reduces production cost simultaneously.
Specifically, the baking temperature of battery core described in the S3 steps is 60~80 DEG C, vacuum ranges are -0.085~-
0.095MPa, baking time under vacuum conditions is 20~30 hours.Battery core is being toasted under the conditions of condition of high vacuum degree, can be with
The N- methyl pyrrole network alkanones for removing the moisture content between battery core positive plate, negative plate and barrier film well and remaining in positive plate are molten
Agent, baking efficiency is not only high but also safe.
In S4 steps, the battery core is shelved to room temperature after baking carries out fluid injection operation, and the reservoir quantity of electrolyte is
The no suitable film formation reaction for both having had influence on battery and cell discharge voltage platform, have influence on the final service life of battery, enter again
And it is shown in the overall chemical property of battery.And fluid injection is excessive and can cause to waste, and increases battery cost.Consider,
Reservoir quantity under different systems in the electrolyte injection battery core is 4.8g~5.8g/Ah, under this reservoir quantity, institute of the present invention
Obtained LiFePO4 system lithium ion battery has excellent charge-discharge performance, while the cycle life of battery is permanent.
Refer to carry out first time charging to the battery of preparation in battery core formation process described in the step S5 so that battery
Interior active material enters line activating, while generating the charging voltage in solid electrolyte interface film (SEI films), battery core formation process
Control is in 3.3~3.5V, the problem of brownout can influence generation and the aerogenesis of SEI films when this is mainly consideration chemical conversion.Point
Charging voltage control is in 2.0~3.65V during appearance, primarily to preventing the excessive caused both positive and negative polarity of lithium ion deintercalation in charge and discharge
Material structure irreversible breaking, is equally also prevented from electrolyte decomposition caused by overtension, influences the overall performance of battery.
Above-mentioned LiFePO4 system battery and preparation method thereof is illustrated below by way of multiple embodiments.
Embodiment one
A kind of LiFePO4 system lithium ion battery, including core body in battery container, housing and be filled in housing
Electrolyte, the core body is made up of positive plate, negative plate and the barrier film being attached between positive plate and negative plate.The positive pole
Piece and negative plate are made up of positive and negative electrode collector and the positive and negative electrode material being coated on the positive and negative collector respectively.
The positive active material that the positive electrode is used is LiFePO 4 material, and conductive agent is conductive black, just very viscous
Knot agent is Kynoar.Wherein, the mass percent of LiFePO 4 material is 96.5%, conductive black in the positive electrode
Mass percent be 1.5%, the mass percent of Kynoar is 2.0%.
The negative electrode active material that the negative material is used is Delanium, and conductive agent is conductive black, and thickener is carboxylic
Sodium carboxymethylcellulose pyce, negative electrode binder is butadiene-styrene rubber.Wherein, the mass percent of Delanium is in the negative material
95.5%, the mass percent of conductive black is 1.2%, and the mass percent of sodium carboxymethylcellulose is 1.3%, butadiene-styrene rubber
Mass percent be 2.0%.The barrier film uses 20um PP composite diaphragms.
Wherein, the preparation method of above-mentioned LiFePO4 system lithium ion battery includes following several steps：
Positive plate makes：Positive electrode is well mixed in N- methyl pyrrole network alkanone organic solvents, anode sizing agent is made,
The anode sizing agent is coated uniformly on thickness that utter misery aluminium foil is made on 12um plus plate current-collecting body, through supercooling after baking
Pressure, compacted density is 2.20g/cm3, and the positive plate thickness of preparation is 160 μm.Then positive plate is die cut, obtains size
For 192mm × 233.5mm finished product positive plate.
Negative plate makes：Negative material is well mixed in carboxymethyl cellulose gum liquid cathode size is made, by negative pole
Slurry is coated uniformly on thickness that copper foil is made on 6um negative current collector, by cold pressing after baking, compacted density is
1.55g/cm3, the negative plate thickness of preparation is 107 μm.Then negative plate is cut out, acquisition size be 195mm ×
237.5mm finished product negative plate.
Folded core makes：Finished product positive plate, thickness are folded into battery core for 20um PP composite diaphragms, finished product negative plate, institute
State battery core to weld with aluminium pole ears and copper polar ear respectively, and sealed with aluminum plastic film, then by battery core 80 DEG C, vacuum for-
Toasted 24 hours under conditions of 0.095Mpa, uninterrupted displacement nitrogen is vacuumized in baking process.
Electrolyte quota and fluid injection：Lithium hexafluoro phosphate (LiPF6) of the electrolyte using concentration as 1.0mol/L is electrolyte；With
Ethylene carbonate (EC), methyl ethyl carbonate (EMC), the mixture of diethyl carbonate (DEC) and propene carbonate (PC) are solvent,
Wherein, EC, EMC, DEC and PC weight ratio are EC：EMC：DEC：PC=40：25：30：5.After the completion of battery core baking, by 5.2g/
Ah injects electrolyte into battery.
Chemical conversion and encapsulation：Battery core after fluid injection is pre-packaged, infiltration 24h is shelved, then battery core is charged and controls to fill
Piezoelectric voltage causes battery core chemical conversion in the range of 3.3~3.5V, and battery core is vacuumized again after the completion of chemical conversion, battery existed after encapsulation
0.5C partial volumes are carried out under the conditions of 2.0~3.65V, the LiFePO4 system lithium ion battery of the embodiment 1 is obtained.
Embodiment two
In the present embodiment in ferric phosphate lithium ion battery, positive plate makes, folds the chemical conversion after core making and fluid injection and this
Inventive embodiments one are completely the same.Difference part is：In example 2, negative plate makes：Routinely technique exists negative material
It is well mixed in carboxymethyl cellulose gum liquid, cathode size is made, cathode size is coated uniformly on into the thickness that copper foil is made is
On 6um negative current collector, by cold pressing, compacted density 1.60g/cm after baking3, the negative plate thickness of preparation is 104 μm.So
Negative plate is die cut afterwards, the finished product negative plate that size is 195mm × 237.5mm is obtained.
In addition, lithium hexafluoro phosphate (LiPF6) of the electrolyte of the present embodiment using concentration as 1.3mol/L is electrolyte；With carbon
The mixture of vinyl acetate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC) is solvent, EC, EMC and DMC weight
Than for EC：EMC：DMC=35：40：25.In addition the vinylene carbonate that weight percentage is 15% is added in the electrolytic solution
(VC) and 5% sulfuric acid propylene (PS).Obtain the LiFePO4 system lithium ion battery of the embodiment 2.
Embodiment three
In the LiFePO4 system lithium ion battery of embodiment three, positive plate makes, folded core makes, the configuration of electrolyte and
Forming and capacity dividing and the embodiment of the present invention two after fluid injection is completely the same.Difference part is：In embodiment three, by cathode size
Thickness that copper foil is made is coated uniformly on on 6um negative current collectors, by cold pressing, compacted density 1.60g/cm after baking3, system
Standby negative plate thickness is 104 μm.Then negative plate is die cut, obtains the finished product negative pole that size is 195mm × 237.5mm
Piece.The battery being prepared into using above-mentioned material and technique is designated as the battery of embodiment three.
Each 1 of the sample of the LiFePO4 system lithium ion battery of the embodiment of the present invention one, two, three is taken, electricity is tested respectively
Tankage, weight and calculating energy density, test result are as shown in table 1.
The ferric phosphate lithium ion battery of 1. embodiment of table 1,2,3
The embodiment of the present invention one, two, each 1 of the sample of triphosphoric acid iron lithium ion battery are taken, discharge capacity is drawn with electricity
Change curve is pressed, as shown in Figure 1.
The embodiment of the present invention one, two, each 1 of the sample of triphosphoric acid iron lithium ion battery are taken, under the conditions of drawing 1C
2.0~3.65V normal temperature 100%DOD circulation figures, as shown in Figure 2.
It can be seen that from the comparing result of table 1：The appearance of lithium ion battery each sample of the embodiment of the present invention one, two, three
Amount, weight are basically identical, and resulting mass energy density is all higher than 165Wh/kg.The present invention is can be seen that from Fig. 1 and Fig. 2
The discharge curve platform of each sample of the lithium ion battery of embodiment one, two, three is basically identical, meets LiFePO4 discharge curve
Performance requirement.The cycle performance of lithium ion battery each sample of the embodiment of the present invention 1,2,3 is excellent, in normal temperature 1C, 100%DOD
Under the conditions of circulate 500 weeks capability retention >=95%, lithium ion battery of the embodiment of the present invention has good cycle performance.
Described above is only presently preferred embodiments of the present invention, not makees any formal limitation to the present invention, though
So the present invention is disclosed above with preferred embodiment, but is not limited to the present invention, any technology people for being familiar with this patent
Member without departing from the scope of the present invention, when the technology contents using above-mentioned prompting make it is a little change or be modified to
The equivalent embodiment of equivalent variations, as long as being the content without departing from technical solution of the present invention, the technical spirit pair according to the present invention
Any simple modification, equivalent variations and modification that above example is made, in the range of still falling within the present invention program.
Claims (10)
1. a kind of LiFePO4 system lithium ion battery, it is characterised in that the lamination core including housing, in the housing
Body and the electrolyte being filled in housing, the lamination core body include positive plate, negative plate and are arranged on the positive plate and negative
Barrier film between pole piece, the positive plate, negative plate by positive and negative collector and are coated on the positive and negative collector respectively
Positive and negative electrode material is constituted,
The positive electrode includes positive active material, and the negative material includes negative electrode active material, the positive electrode active material
Matter is LiFePO 4 material, and the negative electrode active material includes native graphite, Delanium, MCMB, polymer charcoal
At least one of, the electrolyte in the electrolyte includes LiPF6、LiBF4And LiAsF6In one or more.
2. a kind of LiFePO4 system lithium ion battery according to claim 1, it is characterised in that：
The positive electrode also includes conductive agent and positive electrode binder, and the conductive agent includes conductive black, superconduction carbon, conductive stone
At least one of ink, crystalline flake graphite, CNT, the positive electrode binder are Kynoar；
Wherein, the positive electrode is in mass ratio by 95~97 parts of positive active materials, 1~2 part of conductive agent and 1.5~2.5 parts
Positive electrode binder mixing composition；
The positive electrode, which is dissolved in N- methyl pyrrole network alkanone organic solvents, is made the anode sizing agent.
3. a kind of LiFePO4 system lithium ion battery according to claim 1, it is characterised in that：
The negative material also includes conductive agent, thickener and negative electrode binder, and the conductive agent includes conductive black, superconduction
At least one of carbon, electrically conductive graphite, crystalline flake graphite, CNT, the thickener are sodium carboxymethylcellulose, the negative pole
Binding agent is butadiene-styrene rubber；
Wherein, the negative material is in mass ratio by 94~96 parts of negative electrode active materials, 1~2 part of conductive agent, 1~2 part of thickener
And 2~4 parts of negative electrode binder mixing compositions；
The negative material, which is dissolved in carboxymethyl cellulose gum liquid, is made the cathode size.
4. a kind of LiFePO4 system lithium ion battery according to claim 1, it is characterised in that：
The plus plate current-collecting body is made up of utter misery aluminium foil, and the negative current collector is made up of copper foil, the barrier film by PP/PE or
One or two kinds of in PP/PE/PP composite diaphragms is made.
5. a kind of LiFePO4 system lithium ion battery according to claim 1, it is characterised in that：In the electrolyte also
Including solvent and additive, the solvent includes ethylene carbonate, methyl ethyl carbonate, diethyl carbonate, propene carbonate or carbon
At least two in dimethyl phthalate, the additive is included in vinylene carbonate, sulfuric acid propylene, fourth dicyan or succinic anhydride
At least one.
6. a kind of LiFePO4 system lithium ion battery according to claim 1, it is characterised in that：
The compacted density of the positive plate is 2.15~2.25g/cm3, and thickness is 155~165 μm；The compacting of the negative plate is close
Spend for 1.50~1.60g/cm3, thickness is 102~112 μm.
The thickness of the barrier film is 20um.
7. a kind of preparation method of LiFePO4 system lithium ion battery, it is characterised in that：Comprise the following steps：
S1：Positive plate is made, and positive electrode is mixed into anode sizing agent in N- methyl pyrrole network alkanone organic solvents, will be described
Anode sizing agent is coated on plus plate current-collecting body, is toasted and is cold-pressed into laminated structure, and the laminated structure is carried out into cross cutting is made just
Pole piece；
S2：Negative plate makes, and negative material is well mixed in carboxymethyl cellulose gum liquid cathode size is made, will be described negative
Pole slurry coating toasts on negative current collector and is cold-pressed into laminated structure, and the laminated structure is carried out into cross cutting is made negative pole
Piece；
S3：Lamination core body makes, and the positive plate, barrier film and negative plate is folded into battery core, and the battery core is carried out into heat
Envelope, then toasts the battery core under vacuum conditions；
S4：Electrolyte quota and fluid injection, are made electrolyte, then the electrolyte is injected into baking after electrolyte is mixed with solvent
After the completion of battery core in；
S5：Chemical conversion and encapsulation, the battery core after fluid injection is pre-packaged, infiltration is shelved, then battery core is charged and controls to charge
Voltage causes battery core to be melted into, and vacuumizes battery core after the completion of chemical conversion, encapsulates and partial volume.
8. the preparation method of LiFePO4 system lithium ion battery according to claim 7, it is characterised in that：
The baking temperature of battery core described in S3 steps is 60~80 DEG C, vacuum ranges during baking are -0.085~-
0.095MPa, baking time under vacuum conditions is 20~30 hours.
9. a kind of preparation method of LiFePO4 system lithium ion battery according to claim 7, it is characterised in that：
In the S4 steps, the reservoir quantity in the electrolyte injection battery core is 4.8g~5.8g/Ah.
10. a kind of preparation method of LiFePO4 system lithium ion battery according to claim 7, it is characterised in that：
Charging voltage in the step S5 in battery core formation process is controlled in 3.3~3.5V；Charge voltage range is during partial volume
2.0~3.65V.
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Application publication date: 20170815 |