CN103618065B - LiFePO 4 material and preparation method thereof - Google Patents

LiFePO 4 material and preparation method thereof Download PDF

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Publication number
CN103618065B
CN103618065B CN201310586823.2A CN201310586823A CN103618065B CN 103618065 B CN103618065 B CN 103618065B CN 201310586823 A CN201310586823 A CN 201310586823A CN 103618065 B CN103618065 B CN 103618065B
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lifepo
source
lithium
carbon
tungsten carbide
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CN103618065A (en
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姜应律
张欣瑞
熊辉
钟雅文
王盈来
陈蕾
陈海涛
蔡若愚
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Zhejiang Narada Power Source Co Ltd
Hangzhou Nandu Power Technology Co Ltd
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Zhejiang Narada Power Source Co Ltd
Hangzhou Nandu Power 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
    • H01M4/58—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
    • 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 kind of LiFePO 4 material, containing main body carbon source, tungsten carbide in its carbon encapsulated material.Present invention also offers the preparation method of a kind of LiFePO 4 material.Described preparation method comprises the following steps: it comprises the following steps: by lithium source, phosphorus source, source of iron, main body carbon source and tungsten carbide mixing, ball milling, be dried, pulverize, roasting prepare above-mentioned LiFePO 4 material.The present invention not only optimizes the chemical property of carbon cladding, also reduces carbon content.The most also improve reaction efficiency.The raw material sources used extensively, be easy to get, cheap, the LiFePO 4 material of preparation without environment there being the heavy metal element of bigger pollution, environmental friendliness.This LiFePO 4 material has stable charging/discharging voltage platform, and electric conductivity and high rate during charging-discharging are excellent.And tungsten carbide is as good conductor electrically and thermally, this lithium iron phosphate positive material is made to have the features such as Stability Analysis of Structures, thermal stability is good, cycle performance is excellent.

Description

LiFePO 4 material and preparation method thereof
Technical field
The present invention relates to the preparation method of a kind of anode composite material of lithium ion battery, be coated with the preparation method of LiFePO4 (LiFePO4) positive electrode of activation particularly to a kind of tungsten carbide and carbon altogether.
Background technology
Under energy crisis and environmental protection dual-pressure, countries in the world formulate the target of energy-saving and emission-reduction one after another, adopt an effective measure and realize economic Green Development, finally realize the transition of economic structure, it is achieved the transformation of low-carbon economy.LiFePO 4 material because have that security performance is good, have extended cycle life, aboundresources, advantages of environment protection, being known as by international power supply is lithium ion power and the energy-storage battery positive electrode of most future, development to ev industry and novel energy-storing industry has great significance, wide market, social influence is huge.LiFePO 4 material and battery thereof have become as the strategic industry direction of the focus and emphasis investment that each Main Developed Countries in the world competitively researchs and develops.But, LiFePO4 has electrical conductivity low, poor performance at low temperatures, and tap density is relatively low, preparation technology high in cost of production shortcoming, for these problems, also needs further Improvement.
The shortcoming that electronic conductivity for LiFePO4 is low and lithium ion diffusion rate is slow, researchers have carried out a lot of effort, the method taked includes that element mixes up, Surface coating or modification, changes its charge-discharge mechanism and find solid solution etc. by reducing particle size, additionally, the LiFePO4 of controlledly synthesis crystal plane orientation growth is also an important research direction.
Carbon cladding is to study relatively more in LiFePO4 Surface coating and achieve industrialized method, the good conductivity of material with carbon element and cheap, while improving electrical conductivity, moreover it is possible to improves nucleation rate, suppresses particle growth.Carbon cladding typically has two kinds of approach: one be carbon dust is mixed with raw material in certain proportion after high-temperature roasting；Two is interpolation carbonaceous organic material in the precursor of LiFePO4, carries out pyroreaction afterwards, while forming LiFePO4, forms carbon coating layer on its surface.The chemical property of carbon-coated LiFePO 4 for lithium ion batteries has much relations with the decentralization of carbon source used, the carbon content of composite and carbon.Although LiFePO4 carrying out carbon be coated on and greatly enhance its electrical conductivity, but the introducing of this inert matter, result in the reduction of whole electrode specific capacity, the especially low-density of material with carbon element, reduce the tap density of electrode material, decrease volume and capacity ratio and the energy density of electrode.It addition, utilize the method that material with carbon element carrys out coated LiFePO 4 for lithium ion batteries particle, mainly change the electric conductivity between particle and particle, and the electric conductivity within lithium iron phosphate particles is affected little.Therefore, carbon cladding improves lithium ion ionic conductance in LiFePO4 and electrochemical diffusion coefficient the most in itself.
Electron conductivity and the ionic conductance of material can also be improved with metallic particles or conductive compound, stop the growth of lithium iron phosphate particles, the particle that prepared particle diameter is less, make Li+Diffusion length reduce, increase FePO4And LiFePO4Contact area so that lithium ion Li+Can be at bigger FePO4/LiFePO4Spread on interface.Croce et al. (DOI:10.1149/1.1449302) is respectively adopted the method for 1% Cu and Ag powder cladding, the sample initial discharge specific capacity of preparation improves 25mAh/g, and speculate that the metal powder of cladding can play the effect of conducting bridge between LiFePO4 particle, thus improve LiFePO4Discharge performance.Y. Lin et al. (DOI:Water heat transfer 10.1016/j.matchemphys.2012.11.062) is utilized to have preferable cycle performance and the LiFePO of relatively high-discharge-rate4/ Si composite, and under high temperature, performance is more prominent.This is mainly due to the introducing of Si, while reducing electric charge transmission resistance, also improves lithium ion Li+Diffusion coefficient.This free bond that can be construed to Si and fluorosilicone compound can suppress Fe2+From the decomposition of olivine phase, and stop sheet resistance and the increase of electric charge transmission resistance.
But, similar to carbon cladding, these claddings the most fundamentally improve LiFePO4Electrical conductivity.
Summary of the invention
The purpose of the present invention is contemplated to overcome the deficiencies in the prior art, it is provided that a kind of LiFePO 4 material, thus optimizes the chemical property of lithium iron phosphate positive material.To this end, the present invention is by the following technical solutions: in its carbon encapsulated material in addition to main body carbon source, possibly together with tungsten carbide.
Another technical problem to be solved of the present invention is to provide the preparation method of a kind of above-mentioned LiFePO 4 material, to this end, the present invention is by the following technical solutions: described preparation method comprises the following steps: it comprises the following steps: by lithium source, phosphorus source, source of iron, main body carbon source and tungsten carbide mixing, ball milling, be dried, pulverize, roasting prepare above-mentioned LiFePO 4 material.
Using on the basis of technique scheme, the present invention also can use technical scheme further below:
Described lithium source, source of iron and phosphorus source mix in proportion, and wherein Li:Fe:P mol ratio is (0.95-1.05): 1:1.
Described lithium source includes one or more in lithium dihydrogen phosphate, lithium carbonate, lithium hydroxide, lithium oxalate, lithium acetate.
Described source of iron includes one or more of ferric phosphate, ferrous oxalate, ferrous acetate, di-iron trioxide, ferric nitrate, ironic citrate etc..
Described phosphorus source includes one or more in ferric phosphate, phosphorus pentoxide, phosphoric acid, ammonium phosphate, pyrophosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate.
Described dominant carbon source material includes one or more in glucose, sucrose, polypropylene, polyacrylamide, polyvinyl alcohol, soluble starch, Graphene, citric acid, CNT, acetylene black, carbon black.
The 25%-60% that dominant carbon source quality is lithium source quality added；After sintering, the phosphorus content mass percent of LiFePO 4 powder material is between 1.2%-1.8%.
The quality adding tungsten carbide is that 0.005-0.5g/mol(is in terms of every mole of phosphoric acid iron lithium).
Described ball grinding method is wet method, and blending agent is deionized water, absolute ethyl alcohol, acetone or industrial alcohol, and the ratio of blending agent is the 75%-150% of solid phase gross mass, is advisable just having mobility；The incorporation time of liquid phase batch mixing is preferably 4-12 hour；To be mixed uniformly and dried, put into carbon and bury in the reducing atmosphere covered and be sintered；Being warming up to 350-450 DEG C and carry out pre-burning, heating rate is preferably 1-5 DEG C/min, constant temperature time 1-3 hour；Being warming up to 650-750 DEG C calcine, heating rate is preferably 1-5 DEG C/min, constant temperature time 6-12 hour.
The present invention compared with prior art, has the advantage that
Tungsten carbide (WC) Electronic Structure is similar with platinum (Pt), has certain catalysis activity, and be good conductor electrically and thermally in chemical reaction；Compared with platinum (Pt), tungsten carbide (WC) belongs to nonmetal, while improving conductivity of lithium iron phosphate material, does not interferes with the crystalline form of LiFePO 4 material, and the dispersive property in material with carbon element is more preferably, improves the conduction uniformity of LiFePO 4 material.Material with carbon element has bigger specific surface area, abundant pore structure and the surface chemical property of uniqueness, can be used as catalyst carrier and battery electrode component etc., when it is as catalyst carrier, and can divided active component and auxiliary agent well.The tungsten carbide of the present invention also serves as the catalyst of conductive agent and solid phase reaction and electrochemical reaction, and plays promotion particle mixing, the effect of micronized particles, and dominant carbon source material is as catalyst carrier and conductive agent.
The present invention addition by tungsten carbide, not only optimizes the chemical property of carbon cladding, also reduces carbon content.Meanwhile, tungsten carbide is as the catalyst of solid phase reaction, and material with carbon element, as catalyst carrier, can improve reaction efficiency.The raw material sources used extensively, be easy to get, cheap, the LiFePO 4 material of preparation without environment there being the heavy metal element of bigger pollution, environmental friendliness.This LiFePO 4 material has stable charging/discharging voltage platform, and electric conductivity and high rate during charging-discharging are excellent.And tungsten carbide is as good conductor electrically and thermally, this lithium iron phosphate positive material is made to have the features such as Stability Analysis of Structures, thermal stability is good, cycle performance is excellent.
Carbon in the present invention buries and covers reducing atmosphere sintering process and make roasting technique simplify, with low costization, while reducing production cost, while optimizing technique, improves production efficiency and uniformity further, it is simple to carry out large-scale production.
Accompanying drawing explanation
Fig. 1 is the lithium iron phosphate positive material (a) X-ray diffracting spectrum (XRD) with the lithium iron phosphate positive material (b) of pure carbon cladding of the carbon cladding altogether of the tungsten carbide prepared by the embodiment of the present invention 1.
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM) of the lithium iron phosphate positive material of carbon cladding altogether of the tungsten carbide prepared by the embodiment of the present invention 1.
Fig. 3 is that the lithium iron phosphate positive material (a) of the carbon cladding altogether of the tungsten carbide prepared by the embodiment of the present invention 1 is assembled into the 0.2C charging and discharging curve after button cell and 2C charging and discharging curve with the lithium iron phosphate positive material (b) of pure carbon cladding, charging/discharging voltage scope is 2.0-4.0V, and electrolyte is the LiPF of 1mol/L6/ ethylene carbonate (EC)+dimethyl carbonate (DMC) (volume ratio 1:1).
Fig. 4 is the cycle performance schematic diagram after the lithium iron phosphate positive material that carbon is coated with altogether of the tungsten carbide prepared by the embodiment of the present invention 1 is assembled into button cell.Charge-discharge magnification is 2C, and charging/discharging voltage scope is 2.0-4.0V, and electrolyte is the LiPF of 1mol/L6/ ethylene carbonate (EC)+dimethyl carbonate (DMC) (volume ratio 1:1).
Detailed description of the invention
The present embodiment is implemented premised on technical solution of the present invention, but protection scope of the present invention is not limited only to following example.
Embodiment 1:
Lithium hydroxide, ferrous oxalate, ammonium dihydrogen phosphate are pressed ion mol ratio Li+:Fe2+:PO4 3-=1.005:1.00:1.00 weighs, and by 26% addition glucose of lithium hydroxide quality, adds tungsten carbide by the amount of 0.01g/mol, press 80% addition absolute ethyl alcohol of reaction mass gross mass again, after ball milling mixes 6 hours, the slurry being uniformly mixed, after 80 DEG C of forced air dryings, it is placed on carbon and buries in the closed container covered, put in Muffle furnace, be warming up to 400 DEG C with the heating rate of 5 DEG C/min, be incubated 1 hour, it is warming up to 700 DEG C with 2 DEG C/min again, is incubated 10 hours.Naturally cool to room temperature with stove, obtain the lithium iron phosphate positive material LiFePO that tungsten carbide is coated with jointly with carbon4/C/WC。
In order to compare needs, under identical preparation condition and composition and ratio, also it is prepared for the lithium iron phosphate positive material of pure carbon cladding respectively.
The lithium iron phosphate positive material of the tungsten carbide prepared by said method carbon cladding altogether and the lithium iron phosphate positive material of pure carbon cladding carry out powder X-ray diffraction, and its collection of illustrative plates is as shown in Figure 1.As seen from Figure 1, the diffraction maximum of the lithium iron phosphate positive material (a) of tungsten carbide carbon cladding altogether and the lithium iron phosphate positive material (b) of pure carbon cladding is essentially identical, what very small amount tungsten carbide was described adds the crystal structure not changing LiFePO4, and does not has impurity to generate mutually.ESEM (SEM) collection of illustrative plates of the tungsten carbide lithium iron phosphate positive material of carbon cladding altogether is as shown in Figure 2, material is made up of lamina block not of uniform size, granular size 0.5-2 μm, less particle and laminar structured lithium ion and electron mobility to improving LiFePO4 bulk material are favourable, thus improve ionic conduction efficiency.
Prepared composite is made as follows electrode:
82:10:8 in mass ratio weighs composite, acetylene black and polytetrafluoroethylene (PTFE) respectively, makes cathode film；Pure metal lithium sheet is as negative pole；Barrier film is import microporous polypropylene membrane (Celgard 2400)；Electrolyte is 1mol/L LiPF6/ ethylene carbonate (EC)+dimethyl carbonate (DMC) (volume ratio 1:1), is assembled into button cell in the glove box of applying argon gas.In order to compare needs, the lithium iron phosphate positive material of the pure carbon cladding of preparation under the same terms is assembled into button cell also according to above-mentioned technique.Above battery carries out 0.2C and 2C charge-discharge test under room temperature, and charging/discharging voltage scope is 2.0-4.0V.From the figure 3, it may be seen that the lithium iron phosphate positive material (a) of tungsten carbide carbon cladding altogether is compared with the lithium iron phosphate positive material (b) that pure carbon is coated with, under 0.2C, there are higher specific capacity, respectively 157 mAh/g and 152 mAh/g；And under high magnification, the lithium iron phosphate positive material of tungsten carbide carbon cladding altogether has higher capability retention (under 2C multiplying power, respectively 145 mAh/g and 134 mAh/g) and more excellent platform voltage.Fig. 4 is lithium iron phosphate positive material (a) and the cycle performance schematic diagram under the 2C multiplying power of the lithium iron phosphate positive material (b) of pure carbon cladding of tungsten carbide carbon cladding altogether, as seen from Figure 4, the lithium iron phosphate positive material of tungsten carbide carbon cladding altogether has more stable cycle performance, in stabilising decay trend under high magnification, and attenuation rate is low.Visible, the lithium iron phosphate positive material of tungsten carbide carbon cladding altogether is applied at power and energy-storage battery has potential using value.
Embodiment 2:
Lithium carbonate, ferric phosphate are pressed ion mol ratio Li+:Fe3+:PO4 3-=1.01:1.00:1.00 weighs, and by 35% addition sucrose of lithium hydroxide quality, adds tungsten carbide by the amount of 0.005g/mol, press 75% addition absolute ethyl alcohol of reaction mass gross mass again, after ball milling mixes 4 hours, the slurry being uniformly mixed, after 85 DEG C of forced air dryings, it is placed on carbon and buries in the closed container covered, put in Muffle furnace, be warming up to 400 DEG C with the heating rate of 2 DEG C/min, be incubated 2 hours, it is warming up to 720 DEG C with 5 DEG C/min again, is incubated 10 hours.Naturally cool to room temperature with stove, obtain the lithium iron phosphate positive material LiFePO that tungsten carbide is coated with jointly with carbon4/C/WC.Preparing cathode film the most as described in Example 1, be assembled into after battery respectively with 0.2C and 2C rate charge-discharge, the reversible capacity recorded is respectively 155mAh/g and 143mAh/g.
Embodiment 3:
Lithium hydroxide, ferrous acetate, ammonium dihydrogen phosphate are pressed ion mol ratio Li+:Fe2+:PO4 3-=1.02:1.00:1.00 weighs, and by 40% addition citric acid of lithium hydroxide quality, adds tungsten carbide by the amount of 0.02g/mol, press 90% addition absolute ethyl alcohol of reaction mass gross mass again, after ball milling mixing hour, the slurry being uniformly mixed, after 90 DEG C of forced air dryings, it is placed on carbon and buries in the closed container covered, put in Muffle furnace, be warming up to 400 DEG C with the heating rate of 5 DEG C/min, be incubated 3 hours, it is warming up to 750 DEG C with 2 DEG C/min again, is incubated 8 hours.Naturally cool to room temperature with stove, obtain the lithium iron phosphate positive material LiFePO that tungsten carbide is coated with jointly with carbon4/C/WC.Preparing cathode film the most as described in Example 1, be assembled into after battery respectively with 0.2C and 2C rate charge-discharge, the reversible capacity recorded is respectively 158mAh/g and 147mAh/g.
Embodiment 4:
Ferrous oxalate, lithium dihydrogen phosphate are pressed ion mol ratio Li+:Fe2+:PO4 3-=1.00:1.00:1.00 weighs, and by 40% addition polyvinyl alcohol of the lithium hydroxide quality of the amount waiting material, adds tungsten carbide by the amount of 0.05g/mol, press 100% addition absolute ethyl alcohol of reaction mass gross mass again, after ball milling mixes 10 hours, the slurry being uniformly mixed, after 100 DEG C of forced air dryings, it is placed on carbon and buries in the closed container covered, put in Muffle furnace, be warming up to 400 DEG C with the heating rate of 5 DEG C/min, be incubated 3 hours, it is warming up to 680 DEG C with 5 DEG C/min again, is incubated 10 hours.Naturally cool to room temperature with stove, obtain the lithium iron phosphate positive material LiFePO that tungsten carbide is coated with jointly with carbon4/C/WC.Preparing cathode film the most as described in Example 1, be assembled into after battery respectively with 0.2C and 2C rate charge-discharge, the reversible capacity recorded is respectively 151mAh/g and 140mAh/g.
Embodiment 5:
Lithium hydroxide, ferrous oxalate, ammonium dihydrogen phosphate are pressed ion mol ratio Li+:Fe2+:PO4 3-=1.05:1.00:1.00 weighs, and by 30% addition glucose of lithium hydroxide quality, adds tungsten carbide by the amount of 0.04g/mol, press 150% addition absolute ethyl alcohol of reaction mass gross mass again, after ball milling mixes 5 hours, the slurry being uniformly mixed, after 80 DEG C of forced air dryings, it is placed on carbon and buries in the closed container covered, put in Muffle furnace, be warming up to 350 DEG C with the heating rate of 5 DEG C/min, be incubated 3 hours, it is warming up to 750 DEG C with 2 DEG C/min again, is incubated 6 hours.Naturally cool to room temperature with stove, obtain the lithium iron phosphate positive material LiFePO that tungsten carbide is coated with jointly with carbon4/C/WC.Preparing cathode film the most as described in Example 1, be assembled into after battery respectively with 0.2C and 2C rate charge-discharge, the reversible capacity recorded is respectively 159mAh/g and 144mAh/g.
Embodiment 6:
Lithium acetate, di-iron trioxide, ammonium dihydrogen phosphate are pressed ion mol ratio Li+:Fe3+:PO4 3-=1.04:1.00:1.00 weighs, and by 60% addition soluble starch of the lithium hydroxide quality of the amount waiting material, adds tungsten carbide by the amount of 0.015g/mol, press 120% addition absolute ethyl alcohol of reaction mass gross mass again, after ball milling mixes 6 hours, the slurry being uniformly mixed, after 95 DEG C of forced air dryings, it is placed on carbon and buries in the closed container covered, put in Muffle furnace, be warming up to 450 DEG C with the heating rate of 5 DEG C/min, be incubated 2 hours, it is warming up to 650 DEG C with 3 DEG C/min again, is incubated 10 hours.Naturally cool to room temperature with stove, obtain the lithium iron phosphate positive material LiFePO that tungsten carbide is coated with jointly with carbon4/C/WC.Preparing cathode film the most as described in Example 1, be assembled into after battery respectively with 0.2C and 2C rate charge-discharge, the reversible capacity recorded is respectively 153mAh/g and 141mAh/g.
Above-described embodiment is the present invention preferably embodiment; but embodiment of the present invention are also not restricted to the described embodiments; the change of other any Spirit Essences without departing from the present invention and principle, modify, substitute, combine, simplify; all should be the substitute mode of equivalence, within being included in protection scope of the present invention.

Claims (9)

1. LiFePO 4 material, it is characterised in that in its carbon encapsulated material in addition to main body carbon source, possibly together with tungsten carbide；The preparation method of described LiFePO 4 material comprises the following steps:
By lithium source, phosphorus source, source of iron, main body carbon source and tungsten carbide mixing, ball milling, be dried, pulverize, roasting prepares described LiFePO 4 material.
2. LiFePO 4 material as claimed in claim 1, it is characterised in that in described preparation method, lithium source, source of iron and phosphorus source mix in proportion, and wherein Li:Fe:P mol ratio is (0.95-1.05): 1:1.
3. LiFePO 4 material as claimed in claim 1, it is characterised in that in described preparation method, described lithium source includes one or more in lithium dihydrogen phosphate, lithium carbonate, lithium hydroxide, lithium oxalate, lithium acetate.
4. LiFePO 4 material as claimed in claim 1, it is characterised in that in described preparation method, described source of iron includes one or more of ferric phosphate, ferrous oxalate, ferrous acetate, di-iron trioxide, ferric nitrate, ironic citrate etc..
5. LiFePO 4 material as claimed in claim 1, it is characterised in that in described preparation method, described phosphorus source includes one or more in ferric phosphate, phosphorus pentoxide, phosphoric acid, ammonium phosphate, pyrophosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate.
6. LiFePO 4 material as claimed in claim 1, it is characterized in that in described preparation method, described dominant carbon source material includes one or more in glucose, sucrose, polypropylene, polyacrylamide, polyvinyl alcohol, soluble starch, Graphene, citric acid, CNT, acetylene black, carbon black.
7. the LiFePO 4 material as described in claim 1 or 6, it is characterised in that in described preparation method, the 25%-60% that dominant carbon source quality is lithium source quality of addition；After sintering, the phosphorus content mass percent of LiFePO 4 powder material is between 1.2%-1.8%.
8. LiFePO 4 material as claimed in claim 1, it is characterised in that in described preparation method, the addition of tungsten carbide is: every mole of phosphoric acid iron lithium, the quality adding tungsten carbide is 0.005-0.5g.
9. LiFePO 4 material as claimed in claim 1, it is characterized in that in described preparation method, described ball grinding method is wet ball grinding, blending agent is deionized water, absolute ethyl alcohol, acetone or industrial alcohol, the ratio of blending agent is the 75%-150% of solid phase gross mass, is advisable just having mobility；The incorporation time of liquid phase batch mixing is preferably 4-12 hour；To be mixed uniformly and dried, put into carbon and bury in the reducing atmosphere covered and be sintered；Being warming up to 350-450 DEG C and carry out pre-burning, heating rate is preferably 1-5 DEG C/min, constant temperature time 1-3 hour；Being warming up to 650-750 DEG C calcine, heating rate is preferably 1-5 DEG C/min, constant temperature time 6-12 hour.
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CN105633362A (en) * 2015-12-25 2016-06-01 四会市达博文实业有限公司 Tungsten carbide shell layer coated lithium iron phosphate positive electrode material and preparation method therefor
CN105742592B (en) * 2016-03-02 2018-05-11 合肥国轩高科动力能源有限公司 A kind of carbon-coated method for preparing anode material of lithium-ion battery of W/W2C/ activity
CN106935840A (en) * 2017-05-23 2017-07-07 苏州思创源博电子科技有限公司 A kind of preparation method of tungsten coated LiFePO 4 for lithium ion batteries positive electrode
CN109888277B (en) * 2019-01-29 2020-06-23 无锡凯帕德瑞科技有限公司 Preparation method of positive electrode material
CN112670485B (en) * 2020-12-25 2022-08-23 格林美(湖北)新能源材料有限公司 Lithium ion battery anode material and preparation method thereof
CN114551880B (en) * 2021-12-21 2023-07-14 杭州华宏通信设备有限公司 Carbon-coated porous Cr-Cu alloy/lithium iron phosphate anode and preparation method thereof

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