CN103811761B - A kind of quick charge lithium battery - Google Patents

A kind of quick charge lithium battery Download PDF

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Publication number
CN103811761B
CN103811761B CN201210439111.3A CN201210439111A CN103811761B CN 103811761 B CN103811761 B CN 103811761B CN 201210439111 A CN201210439111 A CN 201210439111A CN 103811761 B CN103811761 B CN 103811761B
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anode
negative electrode
cathode material
prepared
transition metal
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CN103811761A (en
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李志坚
邓尧平
王小林
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INTELLECT PIONEERING BATTERY TECHNOLOGY Co Ltd
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INTELLECT PIONEERING BATTERY TECHNOLOGY Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

A kind of lithium battery of quickly-chargeable, including battery container and the anode being placed in battery container, negative electrode and electrolyte, the polymeric separator plates of porous is had between anode and negative electrode, battery container has the electrode ear sealing lid and correspondence, it is crucial that the structure of negative electrode is to be provided with cathode material in foil-like support member two sides, the overall interior of this cathode material forms the conductive network being prone to conduction, cathode material is by the transition metal intercalation active substance of lithiumation, nanoscale bentonite, prepared by carbon dust and PVDF, also foil-like support member and anode is had to be prepared by carbonaceous material in the middle of anode, the ratio of anode and the thickness of negative electrode is 1: 1.5～1: 4.The charging interval of the present invention can control within 10 minutes, for compact lithium cell, charging interval is then shorter and can make the further lightweight of miniature portable mobile electronic device, and the present invention breaches the long-standing limitation of prior art, will be widely used.

Description

A kind of quick charge lithium battery
Technical field
The invention belongs to a kind of chargeable supply unit, be specifically related to the lithium battery of a kind of quickly-chargeable.
Background technology
Lithium ion battery has obtained increasingly extensive application, it is particularly obtain general application on the mobile apparatus, such as mobile phone, removable computer, field equipment etc., but comparatively speaking, small-sized lithium battery technology comparative maturity, and charging interval shorter (several hours), if any reserve battery, general use all can meet, but the large-scale current technology of lithium battery is also had technical bottleneck, as the charging interval is long.Generally speaking, the basic structure of lithium battery is to have anode and negative electrode, the polymeric barrier films of one porous is set between anode and cathode material, constitute basic module, this assembly turns to cylindricality or flat structure is placed in housing, and during charging, it is to charge from outside to inside, namely relative to the increase of negative electrode or the thickness of anode, although technique can be made relatively easy, but the charging interval increases therewith.For large-scale lithium battery, such as the dynamic lithium battery that automobile or cyclecar use, it is primarily present and has the drawback that battery capacity is less than normal and the charging interval is long.The method solving at present drawbacks described above is that multiple baby battery connection in series-parallel are formed electrokinetic cell, but because the homogeneity between single battery is not well solved, and the too much baby battery combination of quantity can produce new problem, and the charging interval is still without basic solution.Therefore, how to improve lithium battery capacity again, can reduce the charging interval again, be that lithium battery obtains broader applications and the problem that must solve.
Summary of the invention
The goal of the invention of the present invention is open a kind of chargeable lithium cell improving lithium battery capacity and the charging interval being greatly reduced.
The technical solution realizing the present invention is as follows: include battery container and the anode being placed in battery container, negative electrode and electrolyte, the polymeric separator plates of porous is had between anode and negative electrode, battery container has the electrode ear sealing lid and correspondence, it is crucial that the structure of negative electrode is to be provided with cathode material in foil-like support member two sides, the overall interior of this cathode material forms the conductive network being prone to conduction, cathode material is by the transition metal intercalation active substance of lithiumation, nanoscale bentonite, prepared by carbon dust and PVDF, also foil-like support member and anode is had to be prepared by carbonaceous material in the middle of anode, the ratio of anode and the thickness of negative electrode is 1: 1.5～1: 4.
The particle surface of the transition metal intercalation active substance of described lithiumation has a conductive carburization zone, then forms a conductive conductive network in cathode material layer prepared by the transition metal intercalation active substance of the above-mentioned lithiumation with carburization zone and nanoscale bentonite, carbon dust and PVDF.
Described carburization zone is to be prepared through high temperature cabonization by addition carbon dust in phenolic resin.
Described carburization zone is to be prepared through high temperature cabonization by addition carbon dust, graphite powder in phenolic resin.
The described lithiated transition metal intercalation active material in cathode material includes being selected from lithiated transition metal oxides, lithiated metal phosphate, lithiated cobalt oxides, LiCoO2、LiNiCoO2、LiAlNiCoO2、LiMnNiCoO2、LiMnO2、Li2Mn2O4And LiFe(PO4)6One or more compounds.
The described lithiated transition metal intercalation active material in cathode material, nanoscale bentonite and carbon dust by weight respectively 92～94%, 0.5～1.5% and 2～3%, surplus is PVDF.
The bentonitic particle diameter of described nanoscale is 5～50nm, and it is prepared by high speed shear method, and bentonite clay particle processes namely at bentonitic brilliant Intercalation reaction lithium ion through lithiumation；Or described bentonite clay particle processes through graphite material cladding.
The ratio of described anode and the thickness of negative electrode is 1: 1.5 or 1: 2 or 1: 3.5.
The lithium battery of quick charge disclosed by the invention, the macrostructure of its entirety does not do big change, the housing of original lithium battery, electrode ear, interpolar electrical connection and capping etc. all can use prior art, but owing to being mixed with the nanoscale bentonite clay particle of lithiumation in cathode material, and make cathode material is formed the conductive network of entirety, the capacity then making lithium battery improves, the thickness of negative electrode can be reduced simultaneously, particularly improve again the electric conductivity of cathode material, when can be implemented in charging, negative electrode entirety is charged, need not successively be charged.Therefore, present invention is especially suited for preparing large-sized power lithium battery, solve the off-capacity of large-sized power lithium battery and the defect that the charging interval is long, the charging interval of the present invention can control within 10 minutes, for compact lithium cell, charging interval is then shorter and can make the further lightweight of miniature portable mobile electronic device, and the present invention breaches the long-standing limitation of prior art, will be widely used.
Accompanying drawing explanation
Fig. 1 is the local section schematic diagram of the present invention.
Detailed description of the invention
Refer to Fig. 1 partial structurtes provided, embodiments of the invention are as follows: include battery container and the anode being placed in battery container, negative electrode and electrolyte, the polymeric separator plates of porous is had between anode and negative electrode, battery container has the electrode ear (not being shown in detail in the macrostructure of above-mentioned prior art in figure) sealing lid and correspondence, it is crucial that the structure of negative electrode is to be provided with cathode material in foil-like support member two sides, cathode material is by the transition metal intercalation active substance of the lithiumation of coated with conductive material, nanoscale bentonite, prepared by carbon dust and PVDF, the overall interior of this cathode material forms the conductive network being prone to conduction, also foil-like support member and anode is had to be prepared by carbonaceous material in the middle of anode, the ratio of anode and the thickness of negative electrode is 1: 1.5～1: 4.The transition metal intercalation active substance of above-mentioned lithiumation includes being selected from lithiated transition metal oxides, lithiated metal phosphate, lithiated cobalt oxides, LiCoO2、LiNiCoO2、LiAlNiCoO2、LiMnNiCoO2、LiMnO2、Li2Mn2O4And LiFe(PO4)6One or more compounds, certainly also include known or use other oxidate for lithium or lithium salts；During discharging, lithium ion passes through electrolyte from anode, it is inserted into negative electrode, during charging, the flowing of lithium ion is reversible, and lithium ion passes through electrolyte from negative electrode, then return on anode as metallic lithium atoms or ion deposition, being successively depart from negative electrode under lithium ion alive effect outside during charging, therefore the charging interval was longer, up to several hours；And the transition metal intercalation active material surface coated with conductive material layer of the lithiumation in technique scheme, and with nanoscale bentonite, carbon dust and PVDF(polyvinylidene fluoride) collectively form negative electrode after, above-mentioned conductive material layer can make whole cathode internal form a conductive network, carbon dust can further improve electric conductivity simultaneously, existence due to above-mentioned conductive network, when whole negative electrode then can be made to charge, entirety is charged rather than is successively charged, therefore the charging interval is greatly lowered, and the charging interval can be controlled within ten minutes；nullAbove-mentioned conductive material layer is actually a kind of carburization zone，The particle surface of the transition metal intercalation active substance of this carburization zone cladding lithiumation，This carburization zone is by adding carbon dust in phenolic resin (or other resin of same or like performance) or adding carbon dust、Graphite powder mixture or add graphite powder or add graphite powder、Carborundum powder mixture is prepared through high temperature cabonization，Specifically by the granule of the transition metal intercalation active substance of lithiumation and the above-mentioned phenolic resin mixing mixing various powder，Then first intermediate temperature setting，Solidification temperature is 160 DEG C～190 DEG C，High temperature cabonization again，Carburizing temperature is 900 DEG C～1050 DEG C，As being mixed with graphite powder in phenolic resin，Then carburizing temperature is 2000 DEG C～2300 DEG C，Then the particle surface of the transition metal intercalation active substance of lithiumation is carbonized layer covering，Can granulating more mechanically，Or solidify for entering temperature chamber in after graininess by being blended with the phenolic resin atomization of above-mentioned various powder，Or solidify after being separated into graininess by centrifugation，The granule solidified carries out high temperature cabonization again，Above-mentioned all kinds of carbonization methods are known technologies，It is not detailed herein.
Except above-mentioned carburization zone structure, cathode material is mixed with nanoscale bentonite clay particle, bentonite has special layer structure, its crystal interlayer is elecrtonegativity, between crystal layer, cation that is adsorbed or that insert can exchange, therefore crystal layer is adsorbable or inserts substantial amounts of lithium ion, at a low price cationic absorption or insert performance more preferably, therefore lithium modification of bentonite can make its crystal layer hold in advance or insert lithium ion；The transition metal intercalation active substance of the lithiumation in above-mentioned cathode material, nanoscale bentonite and carbon dust by weight respectively 92～94%, 0.5～1.5% and 2～3%, surplus is PVDF(polyvinylidene fluoride), by above-mentioned weight ratio, cathode material adds the bentonite of lithiumation, lithium ion in negative electrode or battery increases, and therefore can significantly be reduced by the thickness of negative electrode；The thickness of negative electrode known in the art that is far longer than the thickness of anode, by the present invention, the thickness of negative electrode is the thickness 1.5～4 times of anode, nonaqueous electrolyte can be the solution of one or more lithium salts in organic nonaqueous solvent or solvent mixture simultaneously, for instance lithium salts can include but not limited to LiPF6、LiClO4、LiBF4Deng, solvent can include but not limited to PC(Allyl carbonate), EC(ethylene carbonate), DMC(dimethyl carbonate), DEC(carbonic acid diethyl ester) or suitable various mixed liquors in other this area, and in electrolyte, the concentration of lithium salts can be more than two times of normal concentration；Gap between the crystal layer substantially having due to bentonite, for good porous character, then can make the increase that the bulk density of above-mentioned cathode material is suitable, not only add intensity but also reduce the thickness of negative electrode, such as bulk density can be increased about 10%, difference according to the male or female material to the difference of the requirement of battery performance and selection, the thickness ratio of anode and negative electrode can be 1: 1.8 or 1: 2 or 1: 3 or 1: 3.5, specifically take what thickness proportion, mostly depending on battery capacity requirement, the factors such as the mixed proportion of cathode material, it is substantially that this area would generally be considered；Owing to the thickness of the electrode of battery is relevant with the charging interval, although the aforesaid conductive network being made up of carburization zone can make electrode entirety charge, but the reduction of thickness of electrode still contributes to reduce the charging interval further, save making consumption and reducing the weight of battery of electrode material simultaneously；For above-mentioned nanoscale bentonite, its particle diameter can be between 5～50nm, it is preferably between 20～30nm, it can be prepared (prior art) by high speed shear method, although the excessive preparation of its particle diameter is convenient, but efficiency or the bulk density of holding lithium ion can reduce, particle diameter is too small then because of the character that bentonite is known, and shearing difficulty and granule homogeneity are also impacted；The elecrtonegativity that bentonite has, it can be bear monovalence or negative bivalence or negative trivalent, because of bentonitic electronegative difference, the amount of its cation being inserted into is also different, cation absorption on bentonite is all orientations between crystal layer, so the expansion of crystal layer is minimum, in test, the cathode thickness measured is when charge or discharge complete, its thickness varies less, although this also further illustrates increasing lithium ion content, it is contained between bentonitic crystal layer containing the electropositive lithium ion part inserted in bentonitic cathode material, through test, added with the nanoscale bentonite clay particle being 0.2～0.5% by weight in the carbonaceous material of anode, also advantageously reduce the thickness of anode and reduce the charging interval.
For further appreciating that the present invention, provide specific embodiments of the invention in more detail.
Embodiment 1:
The anode material layer that anode is coated with by Copper Foil and Copper Foil two sides is constituted, described anode material layer is made up of graphite, PVDF or graphite, PVDF and the mixing of nanoscale bentonite, the composition of graphite and PVDF is 92% and 8% by weight, or the bentonitic composition of graphite, PVDF and nanoscale is 90%, 9.7% and 0.3% by weight；Cathode material is by LiNiCoO2Or LiAlNiCoO2、, carbon dust, nanoscale bentonite and PVDF(by weight respectively 92%, 2%, 1% and 5%) mixing, wherein LiNiCoO2Or LiAlNiCoO2、Be coated with by carburization zone, being prepared by of carburization zone after phenolic resin and carbon dust or carbon dust and graphite powder are mixed again with LiNiCoO2Or LiAlNiCoO2、nullMixing，After atomization is for granule, enter temperature chamber in solidify，Solidification temperature is 160 DEG C～190 DEG C，Then carbonization is carried out under high temperature again，As only carbon dust then carburizing temperature is 900 DEG C～1050 DEG C，As containing graphite powder，Then carburizing temperature is 2000 DEG C～2300 DEG C，The two sides that the cathode material of above-mentioned preparation is placed in support member constitute negative electrode，The thickness ratio of anode and negative electrode is 1: 2～2.5，Suitable apertured polymeric film it is provided with as dividing plate between anode and negative electrode，Such as can be selected for the polypropylene screen of porous，Anode、Dividing plate and negative electrode can carry out, by technology known in the art, surround or be arranged in parallel composition column or tabular，Then insert in suitable shell，Pour into electrolyte and connection well known in the art、Sealings etc. constitute required battery，Its specific capacity can reach 400～450mAh/g，Charging interval is within 10 minutes.
Embodiment 2:
Anode material is identical with embodiment 1 with battery structure, and cathode material is by LiMnO2, carbon dust, nanoscale bentonite and PVDF respectively 92%, 2%, 1.5% and 4.5% be mixed with by weight, LiMnO2It is coated with by carburization zone, after phenolic resin and graphite powder or graphite powder and carborundum powder are mixed by being prepared by of carburization zone, method inserts temperature chamber solidification in after preparing particulate by centrifugation, solidification temperature is 160 DEG C～190 DEG C, then carrying out carbonization at 2000 DEG C～2300 DEG C, the thickness of anode and negative electrode are 1: 1.8～2, after measured, the capacity of battery can reach 450～490mAh/g, and the charging interval is within 8 minutes.
Described in present invention book as described above and embodiment, it is possible to decrease production cost, alleviate the weight of battery, be particularly charging interval is greatly reduced and increases the capacity of battery, be more suitable for the preparation of large-sized power battery.

Claims (3)

  1. null1. a quick charge lithium battery，Including battery container and the anode being placed in battery container、Negative electrode and electrolyte，The polymeric separator plates of porous is had between anode and negative electrode，Battery container has the electrode ear sealing lid and correspondence，It is characterized in that the structure of negative electrode is to be provided with cathode material in foil-like support member two sides，Cathode material is by lithiated transition metal intercalation active material、Nanoscale bentonite、Prepared by carbon dust and PVDF，Also foil-like support member and anode is had to be prepared by carbonaceous material in the middle of anode，The ratio of anode and the thickness of negative electrode is 1: 1.5～1: 4，The particle surface of described lithiated transition metal intercalation active material has a conductive carburization zone，There is lithiated transition metal intercalation active material and the nanoscale bentonite of carburization zone、A conductive conductive network is then formed in cathode material layer prepared by carbon dust and PVDF，Carburization zone is to be prepared through high temperature cabonization by addition carbon dust in phenolic resin，In described cathode material，Lithiated transition metal intercalation active material、Nanoscale bentonite and carbon dust by weight respectively 92～94%、0.5～1.5% and 2～3%，Surplus is PVDF，The bentonitic particle diameter of described nanoscale is 20～30nm，It is prepared by high speed shear method，Described bentonite clay particle processes through graphite material cladding.
  2. 2. quick charge lithium battery according to claim 1, it is characterised in that the described lithiated transition metal intercalation active material in cathode material includes being selected from LiCoO2、LiMnO2、Li2Mn2O4One or more compounds.
  3. 3. quick charge lithium battery according to claim 2, it is characterised in that the ratio of described anode and the thickness of negative electrode is 1: 1.5 or 1: 2 or 1: 3.5.
CN201210439111.3A 2012-11-07 2012-11-07 A kind of quick charge lithium battery Active CN103811761B (en)

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CN101388454A (en) * 2008-10-23 2009-03-18 天津斯特兰能源科技有限公司 Method for preparing carbon coated phosphates positive pole material by super critical fluid
CN101540398A (en) * 2008-03-17 2009-09-23 中国科学院物理研究所 Phosphate material having mesoporous structure for lithium secondary batteries and preparation method thereof
CN102544511A (en) * 2012-01-06 2012-07-04 天津大学 Lithium ion battery positive electrode lithium ferrous phosphate material wrapped with strontium cerium doped cobaltate (SCC) and carbon, and preparation method for lithium ion battery positive electrode lithium ferrous phosphate material

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Publication number Priority date Publication date Assignee Title
CN101540398A (en) * 2008-03-17 2009-09-23 中国科学院物理研究所 Phosphate material having mesoporous structure for lithium secondary batteries and preparation method thereof
CN101388454A (en) * 2008-10-23 2009-03-18 天津斯特兰能源科技有限公司 Method for preparing carbon coated phosphates positive pole material by super critical fluid
CN102544511A (en) * 2012-01-06 2012-07-04 天津大学 Lithium ion battery positive electrode lithium ferrous phosphate material wrapped with strontium cerium doped cobaltate (SCC) and carbon, and preparation method for lithium ion battery positive electrode lithium ferrous phosphate material

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