CN107394124A - Lithium iron phosphate trace-doped ternary positive electrode material positive plate, preparation method thereof and power lithium ion battery - Google Patents

Lithium iron phosphate trace-doped ternary positive electrode material positive plate, preparation method thereof and power lithium ion battery Download PDF

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Publication number
CN107394124A
CN107394124A CN201710422028.8A CN201710422028A CN107394124A CN 107394124 A CN107394124 A CN 107394124A CN 201710422028 A CN201710422028 A CN 201710422028A CN 107394124 A CN107394124 A CN 107394124A
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positive
positive electrode
lifepo4
cathode material
tertiary cathode
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王聪
张家科
张豪
吴正斌
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Tianjin CAS Institute of Advanced Technology
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Tianjin CAS Institute of Advanced Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a lithium iron phosphate micro-mixing ternary positive electrode material positive plate and a preparation method thereof, and a power lithium ion battery, wherein the lithium iron phosphate micro-mixing ternary positive electrode material positive plate comprises a positive electrode material and a current collector, the positive electrode material comprises a positive electrode active material, a positive electrode conductive agent and a positive electrode binder, the ternary positive electrode material and the lithium iron phosphate are uniformly dispersed, stirred and mixed with the positive electrode conductive agent, the positive electrode binder and a positive electrode solvent to form positive electrode slurry, and the mass ratio of the lithium iron phosphate to the whole positive electrode active material is 0.1-15%. The preparation method of the positive plate and the power lithium ion battery adopting the positive plate are also provided. When the battery is subjected to abuse test and is locally short-circuited, the thermal stability is improved, the conductivity of the pole piece is obviously improved after a small amount of lithium iron phosphate is mixed in the positive pole piece, the resistance of the positive pole piece is rapidly reduced, and the heat generation of the pole piece is rapidly reduced in the short-circuiting process, so that the safety performance of the battery is obviously improved.

Description

One kind uses the micro blending tertiary cathode material positive plate of LiFePO4 and its preparation side Method, power lithium-ion battery
Technical field
The invention belongs to technical field of lithium ion, is related to power lithium-ion battery, in particular, is related to one kind and adopts With micro blending tertiary cathode material positive plate of LiFePO4 and preparation method thereof, power lithium-ion battery.
Background technology
Power-performance, the cycle life of power lithium-ion battery are lifted, and it is always product development to improve its security performance Emphasis.Therefore, how on the basis of power of battery performance and cyclical stability is ensured, the peace of electrokinetic cell is further optimized The problem that full performance always faces at present.In the prior art, in order to improve the security performance of battery, on both positive and negative polarity surface, table applies One layer of inert material protective layer increase electrode slice sheet resistance and improve electrode slice heat endurance, so as in battery hot-spot or Safeguard protection and fire-retardant effect are played when short-circuit.But either apply aluminum oxide either metatitanic acid lithium coating in pole piece table Deng the table caused by preparation technology is complicated, table applies the factor such as in uneven thickness being all present and apply ineffective or even influence battery work( The effect of rate performance.
The content of the invention
In view of this, it is an object of the invention to provide one kind to use the micro blending tertiary cathode material positive pole of LiFePO4 Piece and preparation method thereof, power lithium-ion battery.Micro LiFePO4 is dispersed in tertiary cathode material, can be kept away Exempt from inert material top coat the uneven thickness on positive plate and uniformity difference the shortcomings that, and can enough significantly simplifies Sample Cell Preparation flow.Because the structural stability of LiFePO4 in itself is better than ternary material, thus it is micro mixed in tertiary cathode material The structural stability of battery material system will be lifted after LiFePO4 by mixing.The micro LiFePO4 blending ternary of use in the present invention The lithium ion battery of positive electrode positive plate on the basis of battery electrical property is ensured, can further improve the security of battery Energy.
To realize the purpose of the present invention, the invention provides one kind to use the micro blending tertiary cathode material of LiFePO4 just Pole piece, including positive electrode and collector, the positive electrode include positive electrode active materials, positive conductive agent, positive pole bonding Agent, the positive electrode active materials include tertiary cathode material and LiFePO4, the tertiary cathode material and LiFePO4 with just Pole conductive agent, positive electrode binder and the dispersed blending of positive pole solvent form anode sizing agent, and wherein LiFePO4 accounts for positive-active The mass ratio of material is 0.1%-15%.
Further, the collector is aluminium collector.
Further, described LiFePO4 is primary particle or second particle.
Further, the carbon content of described lithium iron phosphate positive material is 1%-20%, and the D50 particle diameters of material are about 0.5-10μm。
Further, described tertiary cathode material is LiNixMnyCo1-x-yO2(x=y=1/3 or x=0.5, y=0.3 Or x=0.8, y=0.1) and LiNi0.85Mn0.10Al0.05O2One or both of more than.
Further, the compacted density of the negative plate is 2.5-4g/cm3, pole piece resistivity is 0.5-50 Ω cm.
Correspondingly, present invention also offers a kind of preparation using the micro blending tertiary cathode material positive plate of LiFePO4 Method：This method comprises the following steps：By positive-active ternary material and LiFePO4 and positive conductive agent, positive electrode binder and The dispersed blending of positive pole solvent forms anode sizing agent, and then routinely anode pole piece is made in technique.
Correspondingly, present invention also offers a kind of power using the micro blending tertiary cathode material positive plate of LiFePO4 Lithium ion battery, the lithium ion battery include positive plate, negative plate, barrier film, electrolyte；
The positive plate is the micro blending ternary material positive plate of above-mentioned LiFePO4, and composition includes positive electrode and positive pole Metal collector, the positive electrode include positive conductive agent, positive electrode binder and positive electrode active materials, the positive-active material The mass ratio that material accounts for positive electrode is 90%-99%, and the mass ratio that wherein tertiary cathode material accounts for positive electrode active materials is 85%- 99.5%, the mass ratio that LiFePO4 accounts for positive electrode active materials is 0.5%-15%, and the cathode conductive agent is acetylene black, carbon Combination more than one or both of nanotube (CNT), graphene, conductive black, flaky graphite, carbon fiber, it is described Positive electrode binder is polyvinylidene fluoride (PVDF)；
The negative plate includes negative material and negative current collector, and the negative active core-shell material accounts for negative material mass ratio and is 90%-97%, the cathode conductive agent are acetylene black, CNT (CNT), graphene, conductive black, flaky graphite, carbon Combination more than one or both of fiber；
The barrier film is in polyolefin micropore barrier diaphragm, nonwoven cloth diaphragm, PVDF gelatin membranes, ceramic diaphragm, fibre diaphragm One kind；
The electrolyte includes electrolyte lithium salts, electrolyte solvent, film for additive, and the electrolyte lithium salts is LiPF6、 LiBF4、LiClO4、LiN(CF3SO2)2、Li(CF3SO2)3One or both of more than；The electrolyte solvent is ethylene carbonate Ester (EC), propene carbonate (PC), butylene, dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), fluorinated ethylene carbonate (FEC), glutaronitrile (CLN), adiponitrile (ADN), the first and second sulfones (EMS), ethylenedioxy ethane, first Combination more than one or both of epoxide ethyl-methyl sulfone (MEMS)；The film for additive is vinylene carbonate (VC), the combination of one or both of propylene sulfite (PS).
Further, the thickness of the barrier film is 10-40 μm, porosity 20%-50%.
Relative to prior art, beneficial effect possessed by the present invention：
Micro lithium iron phosphate positive material is dispersed in formation blending positive plate, this height in tertiary cathode material Design and application of the security performance positive plate on power lithium-ion battery, it can significantly simplify the preparation flow of Sample Cell, And can enough avoids table from applying application technology inconsistency caused by pole piece.Because the structural stability of LiFePO4 in itself is excellent In ternary material, therefore the structure that battery material system can be lifted in tertiary cathode material after micro blending LiFePO4 is steady It is qualitative, active material risk out of control can be reduced when battery is abused.The micro LiFePO4 of use in the present invention mixes Battery can further be improved on the basis of battery electrical property is ensured by mixing the lithium ion battery of tertiary cathode material positive plate Security performance.
Brief description of the drawings
Fig. 1 is the charged shape of the lithium ion battery prepared respectively according to embodiment 1, comparative example 1, embodiment 2 and embodiment 3 State-power.
Fig. 2 is the charged shape of the lithium ion battery prepared respectively according to embodiment 1, comparative example 1, embodiment 2 and embodiment 3 State-charging DC internal resistance curve map.
Fig. 3 is the charged shape of the lithium ion battery prepared respectively according to embodiment 1, comparative example 1, embodiment 2 and embodiment 3 State-electric discharge DC internal resistance curve map.
Fig. 4 is that the 1C multiplying powers of the lithium ion battery prepared according to embodiment 1, comparative example 1, embodiment 2 and embodiment 3 are put Electric percentage-voltage curve.
Embodiment
The present invention is described in further detail below in conjunction with the drawings and specific embodiments.It is it should be appreciated that described herein Specific embodiment only to explain the present invention, be not intended to limit the present invention.
It should be noted that in the case where not conflicting, the feature in embodiment and embodiment in the application can phase Mutually combination.
Embodiment 1：
(1) anode sizing agent is prepared：By the LiNi of 96.33% mass ratio0.5Mn0.3Co0.2O2Positive electrode active materials, 1.92% LiFePO4CNT (CNT) conductive agent, the polyvinylidene fluoride of 1.15% mass ratio of positive electrode, 0.6% mass ratio (PVDF) it is added separately in 1-METHYLPYRROLIDONE (NMP), is stirred under rotating speed 2000r/min and be mixed into positive pole slurry Material.
(2) cathode size is prepared：By the Delanium of 76.6% mass ratio, the native graphite of 19.2% mass ratio, 1% The butadiene-styrene rubber (SBR) of the conductive black of mass ratio, the carboxymethyl cellulose (CMC) of 1.5% mass ratio and 1.80% mass ratio It is added separately in negative pole solvent deionized water, is stirred under rotating speed 2500r/min and be mixed into cathode size.
(3) anode pole piece is prepared：The anode sizing agent being prepared is coated uniformly on cathode metal afflux by coating machine The two sides of body aluminium foil, one side surface density are 16.68mg/cm2, through drying, after roll-in, obtain anode pole piece.
(4) cathode pole piece is prepared：The cathode size being prepared is coated uniformly on negative metal afflux by coating machine The two sides of body copper foil, one side surface density are 9.20mg/cm2, through drying, after roll-in, obtain cathode pole piece.
(5) battery core is prepared：The positive and negative electrode pole piece prepared is stacked or is wound into battery core by the alternate mode of positive and negative electrode, For wherein both positive and negative polarity with porosity 35%, thickness is that 16 μm of barrier film separates, and ensures that attached material area negative pole size is more than positive pole size； Positive and negative electrode lug is by being welded and fixed；Battery core is put into battery container, electrolyte inlet is left on battery container；Battery core 24h, which is toasted, at 80 DEG C removes moisture.
(6) fluid injection is encapsulated：It is LiPF to inject 150g lithium salts into battery container from electrolyte inlet6, electrolyte solvent For (EC), dimethyl carbonate (DMC) and diethyl carbonate (DEC) mixture, additive is the electricity of propylene sulfite (PS) Liquid injection port is sealed after solution liquid.
(7) preliminary filling is melted into：Packaged battery is subjected to preliminary filling chemical conversion in succession using stepped charge and discharge system, first By battery with 0.02C-0.1C electric currents be charged to 4.0V carry out preliminary filling, 45 DEG C ageing 72h after, using cold-hot pressure exclude caused by gas Body；The system then completely discharged using full charge in 2.75V-4.20V voltage range using 0.5C-1C electric currents is entered to battery Row chemical conversion.
Comparative example 1
(1) anode sizing agent is prepared：By the LiNi of 98.25% mass ratio0.5Mn0.3Co0.2O2Positive electrode active materials, 0.75% The graphene conductive agent of mass ratio, the polyvinylidene fluoride (PVDF) of 1% mass ratio are added separately to 1-METHYLPYRROLIDONE (NMP) in, stirred under rotating speed 2200r/min and be mixed into anode sizing agent.
(2) cathode size is prepared：By the Delanium of 76.6% mass ratio, the native graphite of 19.2% mass ratio, 1% The butadiene-styrene rubber (SBR) of the conductive black of mass ratio, the carboxymethyl cellulose (CMC) of 1.5% mass ratio and 1.80% mass ratio It is added separately in negative pole solvent deionized water, is stirred under rotating speed 2500r/min and be mixed into cathode size.
(3) anode pole piece is prepared：The anode sizing agent being prepared is coated uniformly on cathode metal afflux by coating machine The two sides of body aluminium foil, one side surface density are 16.60mg/cm2, through drying, after roll-in, obtain anode pole piece.
(4) cathode pole piece is prepared：The cathode size being prepared is coated uniformly on negative metal afflux by coating machine The two sides of body copper foil, one side surface density are 9.20mg/cm2, through drying, after roll-in, obtain cathode pole piece.
(5) battery core is prepared：The positive and negative electrode pole piece prepared is stacked or is wound into battery core by the alternate mode of positive and negative electrode, For wherein both positive and negative polarity with porosity 27%, thickness is that 16 μm of barrier film separates, and ensures that attached material area negative pole size is more than positive pole size； Positive and negative electrode lug is by being welded and fixed；Battery core is put into battery container, electrolyte inlet is left on battery container；Battery core 24h, which is toasted, at 80 DEG C removes moisture.
(6) fluid injection is encapsulated：It is LiPF to inject 150g lithium salts into battery container from electrolyte inlet6, electrolyte solvent For (EC), dimethyl carbonate (DMC) and diethyl carbonate (DEC) mixture, additive is the electricity of propylene sulfite (PS) Liquid injection port is sealed after solution liquid.
(7) preliminary filling is melted into：Packaged battery is subjected to preliminary filling chemical conversion in succession using stepped charge and discharge system, first By battery with 0.02C-0.1C electric currents be charged to 4.0V carry out preliminary filling, 45 DEG C ageing 72h after, using cold-hot pressure exclude caused by gas Body；The system then completely discharged using full charge in 2.75V-4.20V voltage range using 0.5C-1C electric currents is entered to battery Row chemical conversion.
Embodiment 2：
(1) anode sizing agent is prepared：By the LiNi of 92.9% mass ratio0.6Mn0.2Co0.2O2Positive electrode active materials, 2.87% LiFePO4CNT (CNT) conductive agent, the polyvinylidene fluoride of 1.15% mass ratio of positive electrode, 0.6% mass ratio (PVDF) it is added separately in 1-METHYLPYRROLIDONE (NMP), is stirred under rotating speed 2000r/min and be mixed into positive pole slurry Material.
(2) cathode size is prepared：By the Delanium of 76.6% mass ratio, the native graphite of 19.2% mass ratio, 1% The butadiene-styrene rubber (SBR) of the conductive black of mass ratio, the carboxymethyl cellulose (CMC) of 1.5% mass ratio and 1.80% mass ratio It is added separately in negative pole solvent deionized water, is stirred under rotating speed 2500r/min and be mixed into cathode size.
(3) anode pole piece is prepared：The anode sizing agent being prepared is coated uniformly on cathode metal afflux by coating machine The two sides of body aluminium foil, one side surface density are 16.72mg/cm2, through drying, after roll-in, obtain anode pole piece.
(4) cathode pole piece is prepared：The cathode size being prepared is coated uniformly on negative metal afflux by coating machine The two sides of body copper foil, one side surface density are 9.20mg/cm2, through drying, after roll-in, obtain cathode pole piece.
(5) battery core is prepared：The positive and negative electrode pole piece prepared is stacked or is wound into battery core by the alternate mode of positive and negative electrode, For wherein both positive and negative polarity with porosity 45%, thickness is that 20 μm of barrier film separates, and ensures that attached material area negative pole size is more than positive pole size； Positive and negative electrode lug is by being welded and fixed；Battery core is put into battery container, electrolyte inlet is left on battery container；Battery core 24h, which is toasted, at 80 DEG C removes moisture.
(6) fluid injection is encapsulated：It is LiPF to inject 150g lithium salts into battery container from electrolyte inlet6, electrolyte solvent For (EC), dimethyl carbonate (DMC) and diethyl carbonate (DEC) mixture, additive is the electricity of propylene sulfite (PS) Liquid injection port is sealed after solution liquid.
(7) preliminary filling is melted into：Packaged battery is subjected to preliminary filling chemical conversion in succession using stepped charge and discharge system, first By battery with 0.02C-0.1C electric currents be charged to 4.0V carry out preliminary filling, 45 DEG C ageing 72h after, using cold-hot pressure exclude caused by gas Body；The system then completely discharged using full charge in 2.75V-4.20V voltage range using 0.5C-1C electric currents is entered to battery Row chemical conversion.
Embodiment 3：
(1) anode sizing agent is prepared：By the LiNi of 91.9% mass ratio0.8Mn0.1Co0.1O2Positive electrode active materials, 3.80% LiFePO4The poly- difluoro second partially of positive electrode, the conductive black of 2.5% mass ratio and CNT (CNT), 1.8% mass ratio Alkene (PVDF) is added separately in 1-METHYLPYRROLIDONE (NMP), is stirred under rotating speed 3000r/min and is mixed into positive pole Slurry；
(2) cathode size is prepared：By the Delanium of 9.05% mass ratio, the native graphite of 81.45% mass ratio, 5% The primary particle lithium titanate of mass ratio, the conductive black of 1% mass ratio, 1.5% mass ratio carboxymethyl cellulose (CMC) and The butadiene-styrene rubber (SBR) of 2.0% mass ratio is added separately in negative pole solvent deionized water, is stirred under rotating speed 2500r/min It is uniformly mixed into cathode size；
(3) anode pole piece is prepared：The anode sizing agent being prepared is coated uniformly on to the two sides of aluminium foil by coating machine, it is single Face surface density is 15.99mg/cm2, through drying, after roll-in, obtain anode pole piece.
(4) cathode pole piece is prepared：The cathode size being prepared is coated uniformly on to the two sides of copper foil by coating machine, it is single Face surface density is 9.40mg/cm2, through drying, after roll-in, obtain cathode pole piece.
(5) battery core is prepared：The positive and negative electrode pole piece prepared is stacked or is wound into battery core by the alternate mode of positive and negative electrode, For wherein both positive and negative polarity with porosity 33%, thickness is that 24 μm of barrier film separates, and ensures that attached material area negative pole size is more than positive pole size； Positive and negative electrode lug is by being welded and fixed；Battery core is put into battery container, electrolyte inlet is left on battery container；Battery core 24h, which is toasted, at 80 DEG C removes moisture.
(6) fluid injection is encapsulated：It is LiPF to inject 150g lithium salts into battery container from electrolyte inlet6And LiBF4Group Closing, electrolyte solvent is the mixture of diethyl carbonate (DEC), methyl ethyl carbonate (EMC) and fluorinated ethylene carbonate (FEC), Additive for propylene sulfite (PS) electrolyte after seal liquid injection port.
(7) preliminary filling is melted into：Packaged battery is subjected to preliminary filling chemical conversion in succession using stepped charge and discharge system, first By battery with 0.02C-0.1C electric currents be charged to 4.0V carry out preliminary filling, 45 DEG C ageing 72h after, using cold-hot pressure exclude caused by gas Body；The system then completely discharged using full charge in 2.75V-4.20V voltage range using 0.5C-1C electric currents is entered to battery Row chemical conversion.
Here is the test result of lithium ion battery prepared by embodiment 1, comparative example 1, embodiment 2 and embodiment 3：
The safety of acupuncture test result of the power lithium-ion battery prepared in 1 different embodiments of table
As shown in Figure 1 for according to the charged of the lithium ion battery of embodiment 1, comparative example 1, embodiment 2 and embodiment 3 preparation State-power.Contrast is understood, using the embodiment battery after micro LiFePO4 blending tertiary cathode material negative plate Sample is more excellent than the power-performance of battery sample prepared by blank example, has higher power density, because micro The blending of LiFePO4 can reduce the pole piece resistance of positive plate, reduce the internal resistance of cell, lift the power-performance of battery.Such as Fig. 2 and Fig. 3 show charging process and the electric discharge of the lithium ion battery prepared according to embodiment 1, comparative example 1, embodiment 2 and embodiment 3 Process state-of-charge-D.C. resistance curve map, contrast understand that the D.C. resistance of battery is significantly lower than comparative sample in embodiment In battery, the blending of micro LiFePO4 can significantly improve the power characteristic of electrokinetic cell.It is illustrated in figure 4 according to implementation The discharge curve under 1C current densities of lithium ion battery prepared by example 1, comparative example 1, embodiment 2 and embodiment 3：Contrast Understand occur LiFePO4 on discharge curve using the embodiment battery of micro LiFePO4 blending tertiary cathode material Feature platform, but the capability retention of embodiment battery is similar with blank sample, the blending of micro LiFePO4 is not to electricity The flash-over characteristic in pond causes significantly to influence.
Table 1 show the punctural of the lithium ion battery prepared according to embodiment 1, comparative example 1, embodiment 2 and embodiment 3 Can test result., can using the embodiment battery of the tertiary cathode material positive plate of micro blending LiFePO4 knowable to contrast 8mm lancing test is passed through, the voltage of cell and surface temperature change and unobvious, the safety of battery before and after acupuncture Performance has ensured；The comparative example battery of the tertiary cathode material positive plate of LiFePO4 is not used to fail to survey by 5mm acupunctures Obvious out-of-control phenomenon occurs for examination, battery.
The electrochemistry of the lithium ion battery of the tertiary cathode material positive plate of micro blending LiFePO4 is used in summary Performance is not significantly affected, and the power-performance of battery has obtained relatively obvious improvement after table painting modification.It is in addition, micro The application of the tertiary cathode material positive plate of blending LiFePO4 can significantly improve the security performance of power lithium-ion battery.
Described above is only the preferred embodiment of the present invention, it is noted that for the common skill of the art For art personnel, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications Also it should be regarded as protection scope of the present invention.

Claims (10)

1. one kind uses the micro blending tertiary cathode material positive plate of LiFePO4, it is characterised in that：Including positive electrode and Collector, the positive electrode include positive electrode active materials, positive conductive agent, positive electrode binder, the positive electrode active materials bag Include tertiary cathode material and LiFePO4, the tertiary cathode material and LiFePO4 and positive conductive agent, positive electrode binder and The dispersed blending of positive pole solvent forms anode sizing agent, and the mass ratio that wherein LiFePO4 accounts for positive electrode active materials is 0.1%- 15%.
2. according to claim 1 use the micro blending tertiary cathode material positive plate of LiFePO4, it is characterised in that：Institute It is primary particle or second particle to state LiFePO4.
3. according to claim 1 use the micro blending tertiary cathode material positive plate of LiFePO4, it is characterised in that：Phosphorus The carbon content of sour iron lithium anode material is 1%-20%.
4. according to claim 1 use the micro blending tertiary cathode material positive plate of LiFePO4, it is characterised in that：Phosphorus The D50 of sour iron lithium is 0.5-10 μm.
5. according to claim 1 use the micro blending tertiary cathode material positive plate of LiFePO4, it is characterised in that：Institute It is LiNi to state tertiary cathode materialxMnyCo1-x-yO2(x=y=1/3 or x=0.5, y=0.3 or x=0.8, y=0.1) and LiNi0.85Mn0.10Al0.05O2One or both of more than.
6. use the micro blending tertiary cathode material positive plate of LiFePO4 according to claims 1, it is characterised in that： The compacted density of the positive plate is 2.5-4g/cm3。
7. use the micro blending tertiary cathode material positive plate of LiFePO4 according to claims 1, it is characterised in that： The pole piece resistivity of the positive plate is 0.5-50 Ω cm.
It is 8. a kind of as any one of claim 1-7 using the micro blending tertiary cathode material positive plate of LiFePO4 Preparation method, it is characterised in that：This method comprises the following steps：By positive-active ternary material and LiFePO4 and positive conductive Agent, positive electrode binder and the dispersed blending of positive pole solvent form anode sizing agent, and then routinely anode pole piece is made in technique.
9. a kind of use the micro blending tertiary cathode material positive pole of LiFePO4 using as any one of claim 1-7 The power lithium-ion battery of piece, it is characterised in that：The power lithium-ion battery includes positive plate, negative plate, barrier film, electrolysis Liquid；The positive plate composition includes positive electrode and cathode metal collector, and the positive electrode includes positive conductive agent, positive pole Binding agent and positive electrode active materials.
10. the lithium ion power according to claim 9 using the micro blending tertiary cathode material positive plate of LiFePO4 Battery, it is characterised in that：The thickness of the barrier film be 10-40 μm, barrier film material polyolefin micropore barrier diaphragm, nonwoven cloth diaphragm, One kind in PVDF gelatin membranes, ceramic diaphragm, fibre diaphragm, the porosity of barrier film is 20%-50%.
CN201710422028.8A 2017-06-07 2017-06-07 Lithium iron phosphate trace-doped ternary positive electrode material positive plate, preparation method thereof and power lithium ion battery Pending CN107394124A (en)

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