CN103236543B - Method for preparing lithium ferrous silicate anode material - Google Patents

Method for preparing lithium ferrous silicate anode material Download PDF

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CN103236543B
CN103236543B CN201310148254.3A CN201310148254A CN103236543B CN 103236543 B CN103236543 B CN 103236543B CN 201310148254 A CN201310148254 A CN 201310148254A CN 103236543 B CN103236543 B CN 103236543B
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lithium
acid
anode material
ferrous
silicate
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CN103236543A (en
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任冰
许云华
王娟
强静
李雯
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Xian University of Technology
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Xian University of Technology
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • 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 ferrous silicate anode material. The method comprises the following steps of: 1, adding oxalic acid into an acid SiO2 emulsion, uniformly mixing and then adding a mixed solution of ferrous sulphate and a solvent 1, and then washing, filtering and drying to obtain an iron-ion-coated SiO2 core-shell material; and 2, adding a lithium source compound and a carbon source compound into the iron-ion-coated SiO2 core-shell material, finally carrying out furnace cooling after sintering, and grinding, namely the lithium ferrous silicate anode material is obtained. The preparation method of the lithium ferrous silicate anode material is simple and easy in operation, the prepared lithium ferrous silicate anode material contains no impurities, is fine and uniform in particle size and controllable in morphology, conductivity of the material is improved, and properties at low temperature and heavy load discharge are also improved to some extent.

Description

The preparation method of ferrous silicate lithium anode material
Technical field
The invention belongs to technical field of material, relate to a kind of preparation method of ferrous silicate lithium anode material.
Background technology
Lithium ion battery was high with its voltage platform in recent years, energy density is high, self discharge is little, cycle performance is good and security is good etc., and advantage is widely applied.Anode material for lithium-ion batteries mainly contains cobalt acid lithium, LiMn2O4, ternary material and LiFePO 4 material, the price comparison of cobalt acid lithium is high, and security is poor, and lithium manganate material cycle performance is relatively poor, the multiplying power discharging ability of ternary material and LiFePO 4 material, causes power density little.
Ferrosilicon silicate of lithium is due to its Stability Analysis of Structures, good cycle, and gram volume is high, is widely used as anode material for lithium-ion batteries.The method preparing ferrous silicate lithium anode material at present conventional is solid phase method, and the advantage of solid phase method is that cost is low, and technique is simple, and its weak point is that the method is easily mixed into impurity, and the ferrosilicon silicate of lithium material particle size prepared is uneven, and crystal grain is larger.
Summary of the invention
The object of this invention is to provide a kind of preparation method of ferrous silicate lithium anode material, solve the problem that ferrous silicate lithium anode material granularity that solid phase method prepares is uneven.
The technical solution adopted in the present invention is, the preparation method of ferrous silicate lithium anode material, specifically implements according to following steps:
Step 1, oxytropism SiO 2add the mixed solution adding ferrous sulfate and solvent 1 after oxalic acid mixes again in emulsion, then wash, filter, dry, obtain iron ion coated Si O 2shell nuclear material;
Step 2, to the iron ion coated Si O that step 1 obtains 2add Li source compound and carbon-source cpd in shell nuclear material, cool with stove after eventually passing sintering, grinding, namely obtains ferrous silicate lithium anode material.
Feature of the present invention is also,
Acid SiO in step 1 2emulsion is mixed to get by solvent 2, surfactant and sodium metasilicate, adds surfactant and sodium metasilicate successively and fully stir to be mixed with mixed solution in solvent 2, then mixed solution is adjusted to pH with 3 ~ 10% sulfuric acid solutions is 2 ~ 7, obtains acid SiO 2emulsion.
The mass ratio of surfactant and sodium metasilicate is 0 ~ 3:1, and the mol ratio of sodium metasilicate and solvent 2 is 1:10 ~ 50, and the mol ratio of ferrous sulfate and solvent 1 is 1:30 ~ 100, and the mol ratio of ferrous sulfate, oxalic acid and sodium metasilicate is 1:1:1.
In step 2, the feed postition of Li source compound and carbon-source cpd has two kinds, Yi Zhongshi: Li source compound and carbon-source cpd are joined iron ion coated Si O 2in the solution of shell nuclear material, then obtain ferrosilicon silicate of lithium presoma through washing, filtration and drying; Another kind is: Li source compound and carbon-source cpd are directly joined iron ion coated Si O 2in shell nuclear material, then obtain ferrosilicon silicate of lithium presoma through ball milling.
The addition of carbon-source cpd is the 1wt% ~ 20wt% of the ferrous silicate lithium anode material finally obtained, and the lithium in Li source compound and the mol ratio of sodium metasilicate are 1.95 ~ 2.1:1.
In step 2, sintering adopts double sintering or direct sintering, double sintering be by ferrosilicon silicate of lithium presoma under protective atmosphere, temperature is process 0.5 ~ 6 hour under the environment of 250 ~ 550 DEG C, then mix with organic acid after cooling, at rotating speed be 100rpm ~ 500rpm ball mill on be solvent wet-milling vacuum drying at 60 DEG C ~ 120 DEG C after 2 ~ 12 hours with acetone or alcohol, last again under protective atmosphere, temperature is process 6 ~ 24 hours under the environment of 600 DEG C ~ 900 DEG C; Direct sintering is incubated 0.5 ~ 6 hour after ferrosilicon silicate of lithium presoma is warming up to 250 DEG C ~ 550 DEG C under protective atmosphere, is incubated 6 hours ~ 24 hours after then continuing to be warming up to 600 DEG C ~ 900 DEG C.
Protective atmosphere is nitrogen, argon gas, CO, CO 2in one or more mist.
Surfactant is any one or more any molar mixture in P123, polyvinyl alcohol, polyethylene glycol, polyethylene glycol oxide, kayexalate, citric acid, malic acid, tartaric acid, gluconic acid sodium salt, salicylic acid, butanedioic acid, glycine, ethylenediamine tetra-acetic acid, Qu Latong S-100, ethylene nonyl phenyl ether, cetyl trimethyl kelene, softex kw, OTAC, Cetyltrimethylammonium bromide; Solvent 1 and solvent 2 are any one or more any molar mixture in deionized water, distilled water, ethanol, acetone.
Li source compound is any one or more any molar mixture in lithium hydroxide, Lithium acetate dihydrate, lithium nitrate, lithium carbonate, lithium chloride, lithium sulfate, lithium iodide, tert-butyl alcohol lithium, lithium benzoate, lithium formate, lithium fluoride, lithium chromate, four water citric acid lithiums, tetrachloro-lithium aluminate, lithium bromide, LiBF4, lithium oxalate, lithium acetate, lithium dihydrogen phosphate, lithium metasilicate, lithium phosphate, lithia, lithium nitrite, lithium molybdate, lithium vanadate, carbon-source cpd is ascorbic acid, furane resins, Lauxite, melamine resin, phenolic resins, epoxy resin, polyvinyl alcohol, polymethyl methacrylate, polytetrafluoroethylene (PTFE), polyacrylonitrile, butadiene-styrene rubber, cellulose, glucose, coal tar pitch, asphalt, polypropylene, polyacrylamide, polyvinyl alcohol, starch, flour, tapioca flour, dehydrated potato powder, corn flour, taro meal, rice meal, carbon dust, bran powder, graphite powder, acetylene black, carbon black, sucrose, citric acid, furfural resin, poly-to benzene, benzene naphthalene dicarboxylic copolymer, benzene anthracene bipolymer, the luxuriant and rich with fragrance bipolymer of benzene, benzene naphthalene terpolymer, benzene naphthalene grace terpolymer, SWCN, any one or more any molar mixture in double-walled carbon nano-tube and multi-walled carbon nano-tubes.
Organic acid is any one or more any molar mixture in citric acid, malic acid, tartaric acid, oxalic acid, salicylic acid, butanedioic acid, glycine, ethylenediamine tetra-acetic acid.
The invention has the beneficial effects as follows,
1. the preparation method of ferrous silicate lithium anode material of the present invention, obtains the presoma of core-shell structure by coprecipitation, and in coprecipitation process, control pattern and the granularity of silica, effectively improves crystal morphology and the covered effect of persursor material; Finally after adding carbon-source cpd and Li source compound, obtain ferrous silicate lithium anode material through oversintering, make its granularity fine uniform, morphology controllable, improve the electrical conductivity of material, the performance under low temperature and heavy-current discharge also makes moderate progress.
2. the preparation method of ferrous silicate lithium anode material of the present invention, its preparation method is simple, convenient operation, the ferrous silicate lithium anode material free from admixture prepared, granularity fine uniform, morphology controllable.
Accompanying drawing explanation
Fig. 1 is the x-ray diffraction pattern of the ferrous silicate lithium anode material that the embodiment of the present invention 1 prepares;
Fig. 2 is the electron-microscope scanning figure of the ferrous silicate lithium anode material that the embodiment of the present invention 1 prepares;
Fig. 3 is the first charge-discharge figure of the ferrous silicate lithium anode material that the embodiment of the present invention 1 prepares.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
The preparation method of ferrous silicate lithium anode material of the present invention, specifically implements according to following steps:
Step 1, in solvent 2, add surfactant and sodium metasilicate successively and fully stir and be mixed with mixed solution, the mass ratio of surfactant and sodium metasilicate is 0 ~ 3:1, the mol ratio of sodium metasilicate and solvent 2 be 1:10 ~ 50 again by mixed solution with 3 ~ 10% sulfuric acid solution to be adjusted to pH be 2 ~ 7, obtain acid SiO 2emulsion;
Step 2, to the acid SiO that step 1 obtains 2add the mixed solution adding ferrous sulfate that mol ratio is 1:30 ~ 100 and solvent 1 after oxalic acid mixes again in emulsion, the mol ratio of ferrous sulfate, oxalic acid and sodium metasilicate is 1:1:1, then washs, filters, dry, obtains iron ion coated Si O 2shell nuclear material;
Step 3, to the iron ion coated Si O that step 2 obtains 2add Li source compound and carbon-source cpd in shell nuclear material, cool with stove after eventually passing double sintering or direct sintering, grinding, namely obtains ferrous silicate lithium anode material.
The feed postition of Li source compound and carbon-source cpd has two kinds, Yi Zhongshi: Li source compound and carbon-source cpd are joined iron ion coated Si O 2in the solution of shell nuclear material, then obtain ferrosilicon silicate of lithium presoma through washing, filtration and drying; Another kind is: Li source compound and carbon-source cpd are directly joined iron ion coated Si O 2in shell nuclear material, then obtain ferrosilicon silicate of lithium presoma through ball milling.The addition of carbon-source cpd is the 1wt% ~ 20wt% of the ferrous silicate lithium anode material finally obtained, and the lithium in Li source compound and the mol ratio of sodium metasilicate are 1.95 ~ 2.1:1.
Double sintering be by ferrosilicon silicate of lithium presoma under protective atmosphere, temperature is process 0.5 ~ 6 hour under the environment of 250 ~ 550 DEG C, then mix with organic acid after cooling, at rotating speed be 100rpm ~ 500rpm ball mill on be solvent wet-milling vacuum drying at 60 DEG C ~ 120 DEG C after 2 ~ 12 hours with acetone or alcohol, last again under protective atmosphere, temperature is process 6 ~ 24 hours under the environment of 600 DEG C ~ 900 DEG C; Direct sintering is incubated 0.5 ~ 6 hour after ferrosilicon silicate of lithium presoma is warming up to 250 DEG C ~ 550 DEG C under protective atmosphere, is incubated 6 hours ~ 24 hours after then continuing to be warming up to 600 DEG C ~ 900 DEG C.
Protective atmosphere is nitrogen, argon gas, CO, CO 2in one or more mist.
Surfactant is any one or more any molar mixture in P123, polyvinyl alcohol, polyethylene glycol, polyethylene glycol oxide, kayexalate, citric acid, malic acid, tartaric acid, gluconic acid sodium salt, salicylic acid, butanedioic acid, glycine, ethylenediamine tetra-acetic acid, Qu Latong S-100, ethylene nonyl phenyl ether, cetyl trimethyl kelene, softex kw, OTAC, Cetyltrimethylammonium bromide; Solvent 1 and solvent 2 are any one or more any molar mixture in deionized water, distilled water, ethanol, acetone.
Li source compound is any one or more any molar mixture in lithium hydroxide, Lithium acetate dihydrate, lithium nitrate, lithium carbonate, lithium chloride, lithium sulfate, lithium iodide, tert-butyl alcohol lithium, lithium benzoate, lithium formate, lithium fluoride, lithium chromate, four water citric acid lithiums, tetrachloro-lithium aluminate, lithium bromide, LiBF4, lithium oxalate, lithium acetate, lithium dihydrogen phosphate, lithium metasilicate, lithium phosphate, lithia, lithium nitrite, lithium molybdate, lithium vanadate, carbon-source cpd is ascorbic acid, furane resins, Lauxite, melamine resin, phenolic resins, epoxy resin, polyvinyl alcohol, polymethyl methacrylate, polytetrafluoroethylene (PTFE), polyacrylonitrile, butadiene-styrene rubber, cellulose, glucose, coal tar pitch, asphalt, polypropylene, polyacrylamide, polyvinyl alcohol, starch, flour, tapioca flour, dehydrated potato powder, corn flour, taro meal, rice meal, carbon dust, bran powder, graphite powder, acetylene black, carbon black, sucrose, citric acid, furfural resin, poly-to benzene, benzene naphthalene dicarboxylic copolymer, benzene anthracene bipolymer, the luxuriant and rich with fragrance bipolymer of benzene, benzene naphthalene terpolymer, benzene naphthalene grace terpolymer, SWCN, any one or more any molar mixture in double-walled carbon nano-tube and multi-walled carbon nano-tubes.
Organic acid is any one or more any molar mixture in citric acid, malic acid, tartaric acid, oxalic acid, salicylic acid, butanedioic acid, glycine, ethylenediamine tetra-acetic acid.
The preparation method of ferrous silicate lithium anode material of the present invention, obtains the presoma of core-shell structure by coprecipitation, and in coprecipitation process, control pattern and the granularity of silica, effectively improves crystal morphology and the covered effect of persursor material; Finally after adding carbon-source cpd and Li source compound, obtain ferrous silicate lithium anode material through oversintering, make its granularity fine uniform, morphology controllable, improve the electrical conductivity of material, the performance under low temperature and heavy-current discharge also makes moderate progress.
The preparation method of ferrous silicate lithium anode material of the present invention, its preparation method is simple, convenient operation, the ferrous silicate lithium anode material free from admixture prepared, granularity fine uniform, morphology controllable.
Embodiment 1
Step 1, adds 2g polyethylene glycol and 0.02mol sodium metasilicate successively and fully stirs and be mixed with mixed solution in 25ml ethanol, then regulates pH value to be 5 with the sulfuric acid solution of 7.5%, obtains the SiO of acidity 2emulsion;
Step 2, to the acid SiO that step 1 obtains 2add the mixed solution Keep agitation 3 hours of the ferrous sulfate of 0.02mol and 25ml deionized water after the oxalic acid adding 0.02mol in emulsion mixes again, then carry out washing, Centrifugal dispersion and drying, obtain iron ion coated Si O 2shell nuclear material;
Step 3, the iron ion coated Si O that step 2 is obtained 2vacuum drying 3 hours at 80 DEG C after carrying out after adding the lithium carbonate of 0.02mol, 5g glucose and 20ml acetone ball grinding stirring in shell nuclear material; obtain ferrosilicon silicate of lithium presoma; again ferrosilicon silicate of lithium presoma is put into tube furnace under argon gas atmosphere protection, to be warming up to 410 DEG C of insulations to take out after 3 hours and add the ascorbic acid of 30ml alcohol and 1.5g; vacuum drying 2 hours at 60 DEG C after vacuum ball milling; under an argon atmosphere finally; cool with stove after processing 6 hours at 850 DEG C; grinding, namely obtains ferrous silicate lithium anode material.
Fig. 1 is the x-ray diffraction pattern of the ferrous silicate lithium anode material that the embodiment of the present invention 1 prepares, and as can be seen from Figure 1, ferrous silicate lithium anode material is pure phase.
Fig. 2 is the electron-microscope scanning figure of the ferrous silicate lithium anode material that the embodiment of the present invention 1 prepares, and as can be seen from Figure 2, the granularity of ferrous silicate lithium anode material is less.
By ferrous silicate lithium anode material powder, conductive black and polyvinylidene fluoride (PVDF) in mass ratio 80:10:10 ratio mixing, add appropriate 1-METHYLPYRROLIDONE (NMP), fully stirring into is evenly applied on aluminium foil, then dry 8h in vacuum drying chamber under 130 ° of C, the small pieces of 15.5mm diameter are cut to as positive plate after taking-up, with the metal lithium sheet of 15.8mm diameter for negative pole, with diameter 16mm, the Celgard2400 microporous polypropylene membrane of thickness 20um is barrier film, add the ethylene carbonate (EC)/1 that volume ratio is 1:1:1 again, the 1molL-1LiPF6 electrolyte of 2-dimethyl carbonate (DMC)/diethyl carbonate (DEC), CR2032 type button cell is assembled in the glove box being full of argon gas, button cell is placed in U.S. Arbin battery testing and tests its chemical property cashier's office in a shop, charge-discharge magnification is 0.1C, voltage range is 1.5V-4.8V.Fig. 3 is the first charge-discharge figure of the ferrous silicate lithium anode material that the embodiment of the present invention 1 prepares, and as can be seen from Figure 3, the ferrous silicate lithium anode material charging capacity that embodiment 1 obtains reaches 153mAh/g, and reversible capacity is 131mAh/g.
Embodiment 2
Step 1, adds 8g P123 and 0.025mol sodium metasilicate successively and fully stirs and be mixed with mixed solution in 20ml acetone and 20 deionized waters, then is 6 with 9% sulfuric acid solution adjustment pH value, obtains acid SiO 2emulsion;
Step 2, to the acid SiO that step 1 obtains 2add the mixed solution Keep agitation 5 hours of the ferrous sulfate of 0.025mol and the alcohol of 50ml distilled water and 20ml after the oxalic acid adding 0.025mol in emulsion mixes, then carry out washing, Centrifugal dispersion and drying, obtain iron ion coated Si O 2shell nuclear material;
Step 3, the iron ion coated Si O that step 2 is obtained 2vacuum drying 3 hours at 80 DEG C after carrying out after adding the carbon black of the four water citric acid lithiums of 0.04mol, 1g ascorbic acid and 0.7g and 20ml alcohol ball grinding stirring in shell nuclear material; obtain ferrosilicon silicate of lithium presoma; again ferrosilicon silicate of lithium presoma is put into tube furnace under argon gas atmosphere protection, be warming up to 500 DEG C after insulation 1 hour follow-up continuous be warming up to 650 DEG C after insulation 20 hours; finally cool with stove; grinding, namely obtains ferrous silicate lithium anode material.
Embodiment 3
Step 1, adds 0.02mol sodium metasilicate in 15ml acetone and fully stirring is mixed with mixed solution, then 3% sulfuric acid solution regulates pH value to be 2, obtains acid SiO 2emulsion;
Step 2, to the acid SiO that step 1 obtains 2add the mixed solution Keep agitation 3 hours of the ferrous sulfate of 0.02mol and the acetone of 10ml deionized water and 5ml after the oxalic acid adding 0.02mol in emulsion mixes, then carry out washing, Centrifugal dispersion and drying, obtain iron ion coated Si O 2shell nuclear material;
Step 3, the iron ion coated Si O that step 2 is obtained 2the lithium chloride of 0.0195mol is added in shell nuclear material, vacuum drying 3 hours at 80 DEG C after carrying out after 0.483g glucose and 20ml acetone ball grinding stirring, obtain ferrosilicon silicate of lithium presoma, again ferrosilicon silicate of lithium presoma is put into tube furnace under argon gas atmosphere protection, to be warming up to 250 DEG C of insulations to take out after 6 hours and add the malic acid of 20ml acetone and 2.0g, at rotating speed be 100rpm ball mill on wet-milling 12 hours, after vacuum drying at 60 DEG C, under an argon atmosphere finally, cool with stove after processing 24 hours at 600 DEG C, grinding, namely ferrous silicate lithium anode material is obtained.
In embodiment 3, organic acid is malic acid, also can be any one or more any molar mixture in citric acid, malic acid, tartaric acid, oxalic acid, salicylic acid, butanedioic acid, glycine, ethylenediamine tetra-acetic acid.
Embodiment 4
Step 1, adds the P123 of 0.02mol sodium metasilicate and 12g in 27ml ethanol and 10ml deionized water and abundant stirring is mixed with mixed solution, then regulates pH value to be 7 with 10% sulfuric acid solution, obtains acid SiO 2emulsion;
Step 2, to the acid SiO that step 1 obtains 2add the mixed solution Keep agitation 4 hours of the ferrous sulfate of 0.02mol and 36ml deionized water after the oxalic acid adding 0.02mol in emulsion mixes, and then carry out washing, Centrifugal dispersion and drying, obtain iron ion coated Si O 2shell nuclear material;
Step 3, the iron ion coated Si O that step 2 is obtained 2the lithium acetate of 0.042mol is added in shell nuclear material, 0.3g acetylene black, vacuum drying 3 hours at 80 DEG C after carrying out after 0.322g carbon black and 20ml acetone ball grinding stirring, obtain ferrosilicon silicate of lithium presoma, again ferrosilicon silicate of lithium presoma is put into tube furnace under argon gas atmosphere protection, to be warming up to 550 DEG C of insulations to take out after 0.5 hour and add citric acid and the 2g malic acid of 20ml acetone and 1g, at rotating speed be 500rpm ball mill on wet-milling 2 hours, after vacuum drying at 120 DEG C, under an argon atmosphere finally, cool with stove after processing 6 hours at 900 DEG C, grinding, namely ferrous silicate lithium anode material is obtained.
Embodiment 5
Step 1, adds 0.02mol sodium metasilicate in 15ml acetone and fully stirring is mixed with mixed solution, then 3% sulfuric acid solution regulates pH value to be 2, obtains acid SiO 2emulsion;
Step 2, to the acid SiO that step 1 obtains 2add the mixed solution Keep agitation 3 hours of the ferrous sulfate of 0.02mol and the acetone of 10ml deionized water and 5ml after the oxalic acid adding 0.02mol in emulsion mixes, and then carry out washing, Centrifugal dispersion and drying, obtain iron ion coated Si O 2shell nuclear material;
Step 3, the iron ion coated Si O that step 2 is obtained 2vacuum drying 3 hours at 80 DEG C after carrying out after adding the lithium chloride of 0.0195mol, 0.483g glucose and 20ml acetone ball grinding stirring in shell nuclear material; obtain ferrosilicon silicate of lithium presoma; again ferrosilicon silicate of lithium presoma is put into tube furnace under argon gas atmosphere protection, be warming up to 250 DEG C after insulation 6 hours follow-up continuous be warming up to 900 DEG C after insulation 6 hours; finally cool with stove; grinding, namely obtains ferrous silicate lithium anode material.
Embodiment 6
Step 1, adds the P123 of 0.02mol sodium metasilicate and 12g in 27ml ethanol and 10ml deionized water and abundant stirring is mixed with mixed solution, then regulates pH value to be 7 with 10% sulfuric acid solution, obtains acid SiO 2emulsion;
Step 2, to the acid SiO that step 1 obtains 2add the mixed solution Keep agitation 4 hours of the ferrous sulfate of 0.02mol and 36ml deionized water after the oxalic acid adding 0.02mol in emulsion mixes, and then carry out washing, Centrifugal dispersion and drying, obtain iron ion coated Si O 2shell nuclear material;
Step 3, the iron ion coated Si O that step 2 is obtained 2vacuum drying 3 hours at 80 DEG C after carrying out after adding the lithium acetate of 0.042mol, 0.3g acetylene black, 0.322g carbon black and 20ml acetone ball grinding stirring in shell nuclear material; obtain ferrosilicon silicate of lithium presoma; again ferrosilicon silicate of lithium presoma to be put into after being warming up to 550 DEG C in tube furnace under argon gas atmosphere protection insulation 0.5 hour follow-up continuous be warming up to 600 DEG C after insulation 24 hours; finally cool with stove; grinding, namely obtains ferrous silicate lithium anode material.
Being P123 in embodiment 6, also can be any one or more any molar mixture in P123, polyvinyl alcohol, polyethylene glycol, polyethylene glycol oxide, kayexalate, citric acid, malic acid, tartaric acid, gluconic acid sodium salt, salicylic acid, butanedioic acid, glycine, ethylenediamine tetra-acetic acid, Qu Latong S-100, ethylene nonyl phenyl ether, cetyl trimethyl kelene, softex kw, OTAC, Cetyltrimethylammonium bromide.
In embodiment 6, solvent 2 is 27ml ethanol and 10ml deionized water, also can be any one or more any molar mixture in deionized water, distilled water, ethanol, acetone.
In embodiment 6, solvent 1 is deionized water, also can be any one or more any molar mixture in deionized water, distilled water, ethanol, acetone.
In embodiment 6, Li source compound is lithium acetate, also can be any one or more any molar mixture in lithium hydroxide, Lithium acetate dihydrate, lithium nitrate, lithium carbonate, lithium chloride, lithium sulfate, lithium iodide, tert-butyl alcohol lithium, lithium benzoate, lithium formate, lithium fluoride, lithium chromate, four water citric acid lithiums, tetrachloro-lithium aluminate, lithium bromide, LiBF4, lithium oxalate, lithium acetate, lithium dihydrogen phosphate, lithium metasilicate, lithium phosphate, lithia, lithium nitrite, lithium molybdate, lithium vanadate.
In embodiment 6, carbon-source cpd is the mixture of 0.3g acetylene black and 0.322g carbon black, also can be ascorbic acid, furane resins, Lauxite, melamine resin, phenolic resins, epoxy resin, polyvinyl alcohol, polymethyl methacrylate, polytetrafluoroethylene (PTFE), polyacrylonitrile, butadiene-styrene rubber, cellulose, glucose, coal tar pitch, asphalt, polypropylene, polyacrylamide, polyvinyl alcohol, starch, flour, tapioca flour, dehydrated potato powder, corn flour, taro meal, rice meal, carbon dust, bran powder, graphite powder, acetylene black, carbon black, sucrose, citric acid, furfural resin, poly-to benzene, benzene naphthalene dicarboxylic copolymer, benzene anthracene bipolymer, the luxuriant and rich with fragrance bipolymer of benzene, benzene naphthalene terpolymer, benzene naphthalene grace terpolymer, SWCN, any one or more any molar mixture in double-walled carbon nano-tube and multi-walled carbon nano-tubes.
In embodiment 6, protective atmosphere is argon gas atmosphere, also can be nitrogen, argon gas, CO, CO 2in one or more mist.

Claims (9)

1. the preparation method of ferrous silicate lithium anode material, is characterized in that, specifically implements according to following steps:
Step 1, oxytropism SiO 2add the mixed solution adding ferrous sulfate and solvent 1 after oxalic acid mixes again in emulsion, then wash, filter, dry, obtain iron ion coated Si O 2shell nuclear material;
Step 2, to the iron ion coated Si O that step 1 obtains 2add Li source compound and carbon-source cpd in shell nuclear material, cool with stove after eventually passing sintering, grinding, namely obtains ferrous silicate lithium anode material;
Acid SiO in described step 1 2emulsion is mixed to get by solvent 2, surfactant and sodium metasilicate, adds surfactant and sodium metasilicate successively and fully stir to be mixed with mixed solution in solvent 2, then mixed solution is adjusted to pH with 3 ~ 10% sulfuric acid solutions is 2 ~ 7, obtains acid SiO 2emulsion;
Described solvent 1 and solvent 2 are any one or more any molar mixture in deionized water, distilled water, ethanol, acetone.
2. the preparation method of ferrous silicate lithium anode material according to claim 1, it is characterized in that, the mass ratio of described surfactant and sodium metasilicate is 0 ~ 3:1, the mol ratio of sodium metasilicate and solvent 2 is 1:10 ~ 50, the mol ratio of ferrous sulfate and solvent 1 is 1:30 ~ 100, and the mol ratio of ferrous sulfate, oxalic acid and sodium metasilicate is 1:1:1.
3. the preparation method of ferrous silicate lithium anode material according to claim 2, it is characterized in that, in described step 2, the feed postition of Li source compound and carbon-source cpd has two kinds, Yi Zhongshi: Li source compound and carbon-source cpd are joined iron ion coated Si O 2in the solution of shell nuclear material, then obtain ferrosilicon silicate of lithium presoma through washing, filtration and drying; Another kind is: Li source compound and carbon-source cpd are directly joined iron ion coated Si O 2in shell nuclear material, then obtain ferrosilicon silicate of lithium presoma through ball milling.
4. the preparation method of ferrous silicate lithium anode material according to claim 3, it is characterized in that, the addition of described carbon-source cpd is the 1wt% ~ 20wt% of the ferrous silicate lithium anode material finally obtained, and the lithium in Li source compound and the mol ratio of sodium metasilicate are 1.95 ~ 2.1:1.
5. the preparation method of ferrous silicate lithium anode material according to claim 4, it is characterized in that, in described step 2, sintering adopts double sintering or direct sintering, double sintering be by ferrosilicon silicate of lithium presoma under protective atmosphere, temperature is process 0.5 ~ 6 hour under the environment of 250 ~ 550 DEG C, then mix with organic acid after cooling, at rotating speed be 100rpm ~ 500rpm ball mill on be solvent wet-milling vacuum drying at 60 DEG C ~ 120 DEG C after 2 ~ 12 hours with acetone or alcohol, last again under protective atmosphere, temperature is process 6 ~ 24 hours under the environment of 600 DEG C ~ 900 DEG C, direct sintering is incubated 0.5 ~ 6 hour after ferrosilicon silicate of lithium presoma is warming up to 250 DEG C ~ 550 DEG C under protective atmosphere, is incubated 6 hours ~ 24 hours after then continuing to be warming up to 600 DEG C ~ 900 DEG C.
6. the preparation method of ferrous silicate lithium anode material according to claim 5, is characterized in that, described protective atmosphere is nitrogen, argon gas, CO, CO 2in one or more mist.
7. the preparation method of ferrous silicate lithium anode material according to claim 6, it is characterized in that, described surfactant is P123, polyvinyl alcohol, polyethylene glycol, polyethylene glycol oxide, kayexalate, citric acid, malic acid, tartaric acid, gluconic acid sodium salt, salicylic acid, butanedioic acid, glycine, ethylenediamine tetra-acetic acid, Qu Latong S-100, ethylene nonyl phenyl ether, cetyl trimethyl kelene, softex kw, OTAC, any one or more any molar mixture in Cetyltrimethylammonium bromide, described solvent 1 and solvent 2 are any one or more any molar mixture in deionized water, distilled water, ethanol, acetone.
8. the preparation method of ferrous silicate lithium anode material according to claim 7, it is characterized in that, described Li source compound is any one or more any molar mixture in lithium hydroxide, Lithium acetate dihydrate, lithium nitrate, lithium carbonate, lithium chloride, lithium sulfate, lithium iodide, tert-butyl alcohol lithium, lithium benzoate, lithium formate, lithium fluoride, lithium chromate, four water citric acid lithiums, tetrachloro-lithium aluminate, lithium bromide, LiBF4, lithium oxalate, lithium acetate, lithium dihydrogen phosphate, lithium metasilicate, lithium phosphate, lithia, lithium nitrite, lithium molybdate, lithium vanadate, described carbon-source cpd is ascorbic acid, furane resins, Lauxite, melamine resin, phenolic resins, epoxy resin, polyvinyl alcohol, polymethyl methacrylate, polytetrafluoroethylene (PTFE), polyacrylonitrile, butadiene-styrene rubber, cellulose, glucose, coal tar pitch, asphalt, polypropylene, polyacrylamide, polyvinyl alcohol, starch, flour, tapioca flour, dehydrated potato powder, corn flour, taro meal, rice meal, carbon dust, bran powder, graphite powder, acetylene black, carbon black, sucrose, citric acid, furfural resin, poly-to benzene, benzene naphthalene dicarboxylic copolymer, benzene anthracene bipolymer, the luxuriant and rich with fragrance bipolymer of benzene, benzene naphthalene anthracene terpolymer, SWCN, any one or more any molar mixture in double-walled carbon nano-tube and multi-walled carbon nano-tubes.
9. the preparation method of ferrous silicate lithium anode material according to claim 8, it is characterized in that, described organic acid is any one or more any molar mixture in citric acid, malic acid, tartaric acid, oxalic acid, salicylic acid, butanedioic acid, glycine, ethylenediamine tetra-acetic acid.
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