CN103956489A - Method for preparing lithium iron phosphate electrode material by using twice carbon adding technology based on liquid phase mixing material - Google Patents

Method for preparing lithium iron phosphate electrode material by using twice carbon adding technology based on liquid phase mixing material Download PDF

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CN103956489A
CN103956489A CN201410162008.8A CN201410162008A CN103956489A CN 103956489 A CN103956489 A CN 103956489A CN 201410162008 A CN201410162008 A CN 201410162008A CN 103956489 A CN103956489 A CN 103956489A
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lithium
source
carbon
iron
liquid phase
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CN103956489B (en
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赵哲
李瑛�
朱明原
夏侯照
张敏
胡业旻
金红明
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University of Shanghai for Science and 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
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • 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 relates to a method for preparing a lithium iron phosphate electrode material by using a twice carbon adding technology based on a liquid phase mixing material. The method comprises the following steps of firstly mixing a lithium source, an iron source, a phosphorus source and a carbon source material to prepare a liquid-state single phase mixture, mixing the obtained solid product with a volatile solvent containing a dissolved solubility organic compound, carrying out mechanical grinding on the obtained mixture so that organic compound and solid particles are mixed fully, so as to reduce the grain diameter of the solid. The carbon source materials in different space positions can respectively and simultaneously reduce ferric iron and coat the surface of lithium iron phosphate with carbon through the twice carbon adding technology, a purpose for preparing carbon coating structure lithium iron phosphate material in a primary high-temperature heating process is reached, and the completeness of a carbothermic reaction and the electric conductivity of the material are good. The method provided by the invention has the advantages that the cost is low, the energy dissipation is low, the cycle is short, and the batch stability is high.

Description

The method that carbon technique is prepared iron phosphate lithium electrode material that adds for twice based on liquid phase batch mixing
Technical field
The present invention relates to a kind of LiFePO 4the method of/C electrode material, particularly a kind of technique that adds carbon for twice based on liquid phase batch mixing are prepared the LiFePO4 with good carbon clad structure and (are write below as LiFePO 4/ C) method of lithium ion power battery cathode material.
Background technology
Lithium rechargeable battery since coming out the beginning of the nineties in last century, due to its compared with high energy density, good cycle performance and charged retentivity and comparatively the feature such as environmental protection be subject to people's extensive concern, developed rapidly in recent years.LiFePO wherein 4there is Stability Analysis of Structures, the advantage such as safe and reliable, cheap, the application potential of the electrokinetic cell using in electric automobile, hybrid vehicle and energy storage etc. is extensively good by people, and relative technical development is considered to there is wide significance to solving the problems such as current energy shortage and air pollution.
LiFePO 4belong to rhombic system, Pnmb space group, structure is orderly olivine-type, and lithium ion moves by one dimension passage, and its lithium ion diffusion coefficient and electronic conductivity are all lower.In order to improve ionic conductivity and the electron conduction of material, generally adopt the method for doping carbon.Good carbon clad structure can improve material conductivity fully, and simultaneously complete carbon is coated can also suppress LiFePO in material preparation process 4crystal growth, reduce material granule particle diameter, thereby further reduce charge transfer impedance, improve chemical property.
The method of preparing LiFePO4 is a lot, current industrial application be mainly solid phase method, the method technique is simple, easily produce in enormous quantities, but its raw material mixes and do not have liquid phase method abundant, solid phase reaction temperature is higher, the reaction time is longer.For the abundant as far as possible mixed material that obtains, usually extend Ball-milling Time, this has also improved energy consumption.In addition, while using ferrous iron as source of iron in solid phase method, its cost of material is comparatively expensive, and ferrous iron is unstable, easily oxidized in the process of storage, transportation and ball milling, thereby the impurity in increase product, and prevent that its oxidized measure meeting from making technique more complicated, therefore use ferrous iron to improve production cost and reduced a batch stability as raw material.
Liquid phase mixing technology can be realized the molecule rank combination of raw material, and technique is simple, is applicable to suitability for industrialized production, can overcome current LiFePO 4in industrial production, consume energy too high, the problem of excessive cycle has also improved performance and the quality of product simultaneously.Carbothermic method is used cheap ferric iron as source of iron, adds excessive carbon source in reactant, utilizes carbon at high temperature by Fe 3+be reduced to Fe 2+, both having solved the problem of oxidation of raw material, the residual carbon of reaction has also improved the conductivity of material.For carbothermic method, desirable carbon dope mode is to make carbon source reduce more fully ferric iron, improves the problem of carbothermic reduction reaction condition harshness, can realize again good carbon coated structure.
Patent CN101993054 mixes water-soluble reducing agent, phosphorus source, source of iron and lithium source raw material with distilled water, because its heating-up temperature is than general sol-gal process higher (60 ~ 120 ℃), and save filtering technique directly by moisture evaporate to dryness, simplified technique, but the production cycle is still longer, and raising heating-up temperature is unfavorable for Controlling of particle shape.CN101567439 is by adding liquid combustion adjuvant to make mixed solution or emulsion, and at 150 ~ 300 ℃, heating, makes its spontaneous combustion, and ball milling after acquisition solid mixture carries out afterwards carbothermic reduction reaction and obtains LiFePO 4.This method is simple and the cycle is short, but it has raised cost of material, also may bring environmental problem.Said method is all failed to solve because carbon in carbon thermal reduction process participates in reaction and is difficult to form good carbon coating layer problem on lithium iron phosphate particles surface.
CN102881902 discloses a kind of by adding for twice the so-called two-step method of carbon source machinery batch mixing and secondary high-temperature reaction to prepare LiFePO 4technique, batch mixing, pyroreaction are for completing the synthetic of carbon thermal reduction and LiFePO4 for the first time, and batch mixing pyroreaction technique is to be coated for realizing the carbon of LiFePO4 for the second time, but rerolling and secondary high-temperature reaction make technique more complicated, have also improved energy consumption.
Summary of the invention
The object of this invention is to provide a kind of technique that adds carbon for twice based on liquid phase batch mixing prepares the LiFePO4 with good carbon clad structure and (is write below as LiFePO 4/ C) method of lithium ion power battery cathode material, the method can improve performance and batch stability of material, reduces solid phase synthesis temperature and time, and production cost and energy consumption shorten the production cycle.Thereby meet the requirement that large-scale commercial is produced.
To achieve these goals, the present invention has adopted following technical scheme:
The method that carbon technique is prepared iron phosphate lithium electrode material that adds for twice based on liquid phase batch mixing, is characterized in that the concrete steps of the method are:
A. by ferric iron source, lithium source, phosphorus source by lithium: iron: add after the mixed in molar ratio of phosphorus=0.8 ~ 1.2:0.8 ~ 1.2:0.8 ~ 1.2 can obtain in theory to account for the carbon source that LiFePO4 mass fraction is 1% ~ 5% phosphorus content, gained mixture is dissolved in to the liquid mixture that makes homogeneous phase in deionized water, again this liquid phase mixture is heated to boil, until bone dry obtains solid product;
B. can with ethanol, the miscible chain structure organic substance of acetone or deionized water is dissolved in above-mentioned solvent completely, obtain transparent single-phase liquid mixture, this liquid phase mixture is mixed with the solid product of step a gained, often synthetic 1 mol LiFePO4 need add the above-mentioned solvent of 200ml ~ 600ml, to add organic substance can obtain in theory to account for LiFePO4 mass fraction be 3% ~ 7% phosphorus content, thereby the grain diameter that then reduces solid product through grinding obtains the particle size below 3 microns, the ethanol adding in this process, acetone or deionized water have also played the effect of abrasive media simultaneously, afterwards products therefrom is dried, again under inert atmosphere, at 550 ~ 850 ℃, carry out pyroreaction, reaction time is 4 ~ 12h, the carbon technique that adds for twice making based on liquid phase batch mixing is prepared iron phosphate lithium electrode material.
Above-mentioned carbon source is organic acid, carbohydrate or carbon simple substance.
Above-mentioned organic acid is citric acid, ascorbic acid or acetic acid.
Above-mentioned carbohydrate is sucrose, fructose, maltose or glucose.
Above-mentioned carbon simple substance is carbon black, acetylene black or graphite.
Above-mentioned chain structure organic substance is organic acid, polyalcohols or acylamide polymer.
Above-mentioned organic acid is oleic acid, acetic acid or propionic acid.
Above-mentioned polyalcohols is polyethylene glycol, polyvinyl alcohol or polyglycerol.
Above-mentioned acylamide polymer is polyvinylpyrrolidone, polyacrylamide or poly-N-isopropyl acrylamide.
Above-mentioned phosphorus source is at least one in phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate and diammonium hydrogen phosphate.
Above-mentioned source of iron is at least one in ferric nitrate, iron chloride, di-iron trioxide, ferric phosphate, ferric oxalate and ironic citrate.
Above-mentioned lithium source is at least one in lithium nitrate, lithium chloride, lithium carbonate, lithium phosphate, lithium hydroxide, lithium oxalate and lithium acetate.
Beneficial effect of the present invention is:
(1) liquid phase batch mixing makes reactant realize the combination of molecule rank, has shortened the time of pyrocarbon thermal reduction reaction, has reduced reaction temperature.Reduce energy consumption, made reaction more complete simultaneously, reduced impurity generation, improved material property.
(2) make liquid mixture direct evaporate to dryness under micro-state boiling, compare other liquid phase method more simple, to equipment and process control require lower.The process itself that liquid mixture is heated evaporate to dryness at slight boiling condition is also the process of a predecomposition, pre-reaction, thereby has replaced the presintering process in solid phase method.
(3) during by liquid phase batch mixing, add for the first time carbon, the carbon source of adding in a in steps or its thermal decomposition product are blended in granule interior, other contacts to make itself and reactant ferric iron composition form molecular level, reduce follow-up carbothermic reduction reaction activation energy, reduce reaction temperature, Reaction time shorten, be beneficial to the synthetic of carbothermic reduction reaction and LiFePO4, improve batch stability and the product property of material.
(4) (carbon source that step b) adds is after preparing the solid-state reaction mixture of molecule rank mixing to second step, the molecule of the dissolved organic matter adding can evenly must be adsorbed on particle surface, and because the carbon source in a in steps provides the carbon that participates in reduction reaction, what step b provided can form more evenly complete coating layer (as shown in Figure 1) at the residual carbon of particle surface, and the growing up of particle in inhibitory reaction, and make the conductivity of final material better.
(5) carbon source in different spatial is after pyroreaction, played respectively and simultaneously reduction ferric iron and in the effect of LiFePO4 coated with carbon, by secondary, adding carbon technique can make pyroreaction occur in different spaces simultaneously, realized and only needed a high-temperature heating process can prepare the object of carbon-coated LiFePO 4 for lithium ion batteries material, and needn't carry out mechanical batch mixing and pyroreaction repeatedly.
Accompanying drawing explanation
Fig. 1 is the illustraton of model of carbothermic reduction reaction of the present invention
Fig. 2 is the XRD collection of illustrative plates of resulting materials in the embodiment of the present invention 1
Fig. 3 is the XRD collection of illustrative plates of resulting materials in the embodiment of the present invention 2
Fig. 4 is the SEM figure of resulting materials in the embodiment of the present invention 2
Fig. 5 is the charging and discharging curve under resulting materials 0.1C in the embodiment of the present invention 2
Fig. 6 is the cycle performance figure under resulting materials 0.1C in the embodiment of the present invention 2
Fig. 7 is the charging and discharging curve under resulting materials 0.1C in the embodiment of the present invention 3
Fig. 8 is the charging and discharging curve under resulting materials 0.1C in the embodiment of the present invention 4
Fig. 9 is the charging and discharging curve under resulting materials 0.1C in the embodiment of the present invention 5.
Embodiment
The present invention is now described in conjunction with specific embodiments.
Embodiment 1:
With lithium: the molar ratio weighing 1.208gLiClH of iron: phosphorus=1:1:1 2o, 5.406gFeCl 36H 20,2.3006gNH 4h 2pO 4, and the sucrose of 0.35g, be dissolved in 20ml deionized water, be then placed in baking oven and with micro-state boiling, heat at the temperature of 195 ℃.Gained solid residue is mixed to ball milling 5h after it is dried completely with the absolute ethyl alcohol that is dissolved with 0.35gPEG400.Absolute ethyl alcohol in gained ball milling afterproduct is dried, under the protection of the argon gas that flows, carry out pyrocarbon thermal reduction reaction in tube furnace, reaction temperature is 750 ℃, and the reaction time is 8h.As shown in Figure 2, the position of XRD diffraction maximum and LiFePO 4standard card (JCPDS Card No. 83-2092) matches, and shows that products therefrom is LiFePO 4.
Embodiment 2:
Preparation process in the present embodiment is identical with above-described embodiment 1.Difference is: with lithium: the molar ratio weighing 1.379g anhydrous nitric acid lithium of iron: phosphorus=1:1:1,8.08gFe (NO 3) 39H 2o, 2.3006gNH 4h 2pO 4, and the sucrose of 1.25g is as reactant.As shown in Figure 3, the position of XRD diffraction maximum and LiFePO 4standard card (JCPDS Card No. 83-2092) matches, and shows that products therefrom is LiFePO 4.Figure 4 shows that the SEM picture of material, in figure, visible material particle size is hundreds of nanometer.As shown in Figure 5, under the charge-discharge velocity of 0.1C, the discharge capacity first of material is 156mAh/g, the poor 0.15V that is about of platform voltage.In Fig. 6, under 0.1C, the discharge capacity of material can increase along with the abundant infiltration of cell activation and electrolyte gradually several leading circulation, the 14th circulation, reaches 163mAh/g, maintains afterwards 160 mAh/g.
Embodiment 3:
Preparation process in the present embodiment is identical with above-described embodiment 2.Difference is: (1) to add the mol ratio of raw material be lithium: iron: phosphorus=1.05:1:1.(2) PEG400 adding while adding chain organic substance is 0.45g.As shown in Figure 7, the discharge capacity of the material in example 3 under 0.1C is 158 mAh/g.
Embodiment 4:
Preparation process in the present embodiment is identical with above-described embodiment 2.Difference is: (1) ball-milling technology time used is 3h.(2) temperature of carbon thermal response is 650 ℃.As shown in Figure 8, the discharge capacity of the material in example 4 under 0.1C is 148 mAh/g.
Embodiment 5:
Preparation process in the present embodiment is identical with above-described embodiment 2.Difference is: the PEG400 that (1) adds while adding chain organic substance is 0.45g.(2) reaction time of carbothermic reduction reaction is 4h.As shown in Figure 9, the discharge capacity of the material in example 5 under 0.1C is 152mAh/g.
Embodiment 6:
Preparation process in the present embodiment is identical with above-described embodiment 2.Difference is: (1) weighs the glucose of 1.25g as the carbon source adding in step a, and mix in phosphorus source, source of iron, lithium source.(2) weigh 0.29g polyvinylpyrrolidone as the chain organic substance adding in step b.
Embodiment 7:
Preparation process in the present embodiment is identical with above-described embodiment 2.Difference is: (1) weighs the fructose of 1.30g as the carbon source adding in step a, and mix in phosphorus source, source of iron, lithium source.(2) weigh 0.31g polyacrylamide as the chain organic substance adding in step b.
Embodiment 8:
Preparation process in the present embodiment is identical with above-described embodiment 2.Difference is: (1) weighs 1.31g maltose as the carbon source adding in step a, and mix in phosphorus source, source of iron, lithium source.(2) weigh 0.30g poly-N-isopropyl acrylamide as the chain organic substance adding in step b.
Embodiment 9:
Preparation process in the present embodiment is identical with above-described embodiment 2.Difference is: (1) weighs 1.33g sucrose as the carbon source adding in step a, and mix in phosphorus source, source of iron, lithium source.(2) weigh 0.25g oleic acid as the chain organic substance adding in step b.
Embodiment 10:
Preparation process in the present embodiment is identical with above-described embodiment 2.Difference is: (1) weighs 0.53g carbon black as the carbon source adding in step a, and mix in phosphorus source, source of iron, lithium source.(2) weigh 0.28g acetic acid as the chain organic substance adding in step b.
Embodiment 11:
Preparation process in the present embodiment is identical with above-described embodiment 2.Difference is: (1) weighs 0.53g acetylene black as the carbon source adding in step a, and mix in phosphorus source, source of iron, lithium source.(2) weigh 0.29g propionic acid as the chain organic substance adding in step b.
Embodiment 12:
Preparation process in the present embodiment is identical with above-described embodiment 2.Difference is: (1) weighs 0.53g graphite as the carbon source adding in step a, and mix in phosphorus source, source of iron, lithium source.(2) weigh 0.37g polyvinyl alcohol as the chain organic substance adding in step b.
Embodiment 13:
Preparation process in the present embodiment is identical with above-described embodiment 2.Difference is: (1) weighs 1.87g citric acid as the carbon source adding in step a, and mix in phosphorus source, source of iron, lithium source.(2) weigh 0.40g polyglycerol as the chain organic substance adding in step b.
Embodiment 14:
Preparation process in the present embodiment is identical with above-described embodiment 2.Difference is: (1) weighs 2.10g acetic acid as the carbon source adding in step a, and mix in phosphorus source, source of iron, lithium source.(2) weigh 0.40g polyglycerol as the chain organic substance adding in step b.
Embodiment 15:
Preparation process in the present embodiment is identical with above-described embodiment 2.Difference is: (1) weighs 1.90g ascorbic acid as the carbon source adding in step a, and mix in phosphorus source, source of iron, lithium source.(2) weigh 0.40g polyglycerol as the chain organic substance adding in step b.
Embodiment 14:
Preparation process in the present embodiment is identical with above-described embodiment 2.Difference is: (1) to add the mol ratio of raw material be lithium: iron: phosphorus=1.05:1:1.(2) PEG400 adding while adding chain organic substance is 0.45g.(3) reaction temperature of carbothermic reduction reaction is 650 ℃.
Embodiment 15:
Preparation process in the present embodiment is identical with above-described embodiment 2.Difference is: the PEG400 that (1) adds while adding chain organic substance is 0.45g.(2) reaction temperature of carbothermic reduction reaction is 650 ℃.(3) reaction time of carbothermic reduction reaction is 4h.
Embodiment 16:
Preparation process in the present embodiment is identical with above-described embodiment 2.Difference is: the PEG400 that (1) adds while adding chain organic substance is 0.45g.(2) reaction temperature of carbothermic reduction reaction is 550 ℃.(3) reaction time of carbothermic reduction reaction is 4h.
Embodiment 17:
Preparation process in the present embodiment is identical with above-described embodiment 2.Difference is: (1) to add the mol ratio of raw material be lithium: iron: phosphorus=1.05:1:1.(2) the ball-milling technology time used is 3h.(3) reaction time of carbothermic reduction reaction is 4h.

Claims (12)

1. the method that carbon technique is prepared iron phosphate lithium electrode material that adds for twice based on liquid phase batch mixing, is characterized in that the concrete steps of the method are:
A. by ferric iron source, lithium source, phosphorus source by lithium: iron: add after the mixed in molar ratio of phosphorus=0.8 ~ 1.2:0.8 ~ 1.2:0.8 ~ 1.2 can obtain in theory to account for the carbon source that LiFePO4 mass fraction is 1% ~ 5% phosphorus content, gained mixture is dissolved in to the liquid mixture that makes homogeneous phase in deionized water, again this liquid phase mixture is heated to boil, until bone dry obtains solid product;
B. can with ethanol, the miscible chain structure organic substance of acetone or deionized water is dissolved in above-mentioned solvent completely, obtain transparent single-phase liquid mixture, this liquid phase mixture is mixed with the solid product of step a gained, often synthetic 1 mol LiFePO4 need add the above-mentioned solvent of 200ml ~ 600ml, to add organic substance can obtain in theory to account for LiFePO4 mass fraction be 3% ~ 7% phosphorus content, thereby the grain diameter that then reduces solid product through grinding obtains the particle size below 3 microns, the ethanol adding in this process, acetone or deionized water have also played the effect of abrasive media simultaneously, afterwards products therefrom is dried, again under inert atmosphere, at 550 ~ 850 ℃, carry out pyroreaction, reaction time is 4 ~ 12h, the carbon technique that adds for twice making based on liquid phase batch mixing is prepared iron phosphate lithium electrode material.
2. method according to claim 1, is characterized in that described carbon source is organic acid, carbohydrate or carbon simple substance.
3. method according to claim 2, is characterized in that described organic acid is citric acid, ascorbic acid or acetic acid.
4. method according to claim 2, is characterized in that described carbohydrate is sucrose, fructose, maltose or glucose.
5. method according to claim 2, is characterized in that described carbon simple substance is carbon black, acetylene black or graphite.
6. preparation method according to claim 1, is characterized in that described chain structure organic substance is organic acid, polyalcohols or acylamide polymer.
7. preparation method according to claim 6, is characterized in that described organic acid is oleic acid, acetic acid or propionic acid.
8. preparation method according to claim 6, is characterized in that described polyalcohols is polyethylene glycol, polyvinyl alcohol or polyglycerol.
9. preparation method according to claim 6, is characterized in that described acylamide polymer is polyvinylpyrrolidone, polyacrylamide or poly-N-isopropyl acrylamide.
10. method according to claim 1: it is characterized in that described phosphorus source is at least one in phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate and diammonium hydrogen phosphate.
11. methods according to claim 1: it is characterized in that described source of iron is at least one in ferric nitrate, iron chloride, di-iron trioxide, ferric phosphate, ferric oxalate and ironic citrate.
12. methods according to claim 1: it is characterized in that described lithium source is at least one in lithium nitrate, lithium chloride, lithium carbonate, lithium phosphate, lithium hydroxide, lithium oxalate and lithium acetate.
CN201410162008.8A 2014-04-22 2014-04-22 Method for preparing lithium iron phosphate electrode material by using twice carbon adding technology based on liquid phase mixing material Expired - Fee Related CN103956489B (en)

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CN107240696A (en) * 2017-07-12 2017-10-10 北方奥钛纳米技术有限公司 The preparation method and carbon-coated LiFePO 4 for lithium ion batteries and lithium ion battery of carbon-coated LiFePO 4 for lithium ion batteries
CN107452949A (en) * 2017-08-06 2017-12-08 长沙小新新能源科技有限公司 A kind of LiFe1‑XNiXPO4The preparation method of/C Anode of lithium cell materials

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