CN103236543A - Method for preparing lithium ferrous silicate anode material - Google Patents
Method for preparing lithium ferrous silicate anode material Download PDFInfo
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- CN103236543A CN103236543A CN2013101482543A CN201310148254A CN103236543A CN 103236543 A CN103236543 A CN 103236543A CN 2013101482543 A CN2013101482543 A CN 2013101482543A CN 201310148254 A CN201310148254 A CN 201310148254A CN 103236543 A CN103236543 A CN 103236543A
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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
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
In recent years lithium ion battery with its voltage platform height, energy density height, self discharge is little, cycle performance is good and fail safe is good etc., and advantage has obtained extensive use.Anode material for lithium-ion batteries mainly contains cobalt acid lithium, LiMn2O4, ternary material and LiFePO 4 material, the price comparison height of cobalt acid lithium, and fail safe is relatively poor, and the lithium manganate material cycle performance is relatively poor relatively, the multiplying power discharging ability of ternary material and LiFePO 4 material causes power density little.
Ferrosilicon silicate of lithium is owing to its Stability Analysis of Structures, good cycle, and the gram volume height is widely used as anode material for lithium-ion batteries.Prepare at present the method that ferrous silicate lithium anode material uses always is solid phase method, and the advantage of solid phase method is that cost is low, and technology is simple, and its weak point is that this method easily sneaks into impurity, and the ferrosilicon silicate of lithium material particle size for preparing is inhomogeneous, and crystal grain is bigger.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of ferrous silicate lithium anode material has solved the inhomogeneous problem of ferrous silicate lithium anode material granularity that solid phase method prepares.
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 that adds ferrous sulfate and solvent 1 after oxalic acid mixes again in the emulsion, wash then, filter, drying, obtain iron ion coated Si O
2The shell nuclear material;
Step 2, the iron ion coated Si O that obtains to step 1
2Add Li source compound and carbon-source cpd in the shell nuclear material, finally by cooling off with stove behind the oversintering, grind, namely obtain ferrous silicate lithium anode material.
Characteristics of the present invention also are,
Acid SiO in the step 1
2Emulsion is mixed by solvent 2, surfactant and sodium metasilicate and is obtained, and adds surfactant and sodium metasilicate successively and fully stir in the solvent 2 to be mixed with mixed solution, and again mixed solution being 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.
The adding mode of Li source compound and carbon-source cpd has two kinds in the step 2, a kind ofly is: Li source compound and carbon-source cpd are joined iron ion coated Si O
2In the solution of shell nuclear material, obtain the ferrosilicon silicate of lithium presoma through washing, filtration and drying then; Another kind is: Li source compound and carbon-source cpd are directly joined iron ion coated Si O
2In the shell nuclear material, obtain the ferrosilicon silicate of lithium presoma through ball milling then.
The addition of carbon-source cpd is the 1wt%～20wt% of the ferrous silicate lithium anode material that finally obtains, and the lithium in the Li source compound and the mol ratio of sodium metasilicate are 1.95～2.1:1.
Sintering adopts double sintering or direct sintering in the step 2, double sintering be with the ferrosilicon silicate of lithium presoma under protective atmosphere, temperature is to handle 0.5～6 hour under 250～550 ℃ the environment, mix with organic acid the cooling back then, at rotating speed be on the ball mill of 100rpm～500rpm with the acetone or alcohol be the solvent wet-milling after 2～12 hours 60 ℃～120 ℃ following vacuumizes, at last again under protective atmosphere, temperature is to handle 6～24 hours under 600 ℃～900 ℃ the environment; Direct sintering is that the ferrosilicon silicate of lithium presoma is incubated 0.5～6 hour after being warming up to 250 ℃～550 ℃ under the protective atmosphere, continue to be warming up to 600 ℃～900 ℃ then after the insulation 6 hours～24 hours.
Protective atmosphere is nitrogen, argon gas, CO, CO
2In one or more mist.
Surfactant is any one or two kinds of above molar mixture arbitrarily 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, polyoxyethylene nonylplenyl ether, cetyl trimethyl kelene, softex kw, OTAC, the octadecyl trimethylammonium bromide; Solvent 1 and solvent 2 are any one or two kinds of above molar mixture arbitrarily in deionized water, distilled water, ethanol, the acetone.
Li source compound is any one or two kinds of above molar mixture arbitrarily in lithium hydroxide, acetate dihydrate lithium, 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, the lithium vanadate; Carbon-source cpd is ascorbic acid, furane resins, Lauxite, melamine resin, phenolic resins, epoxy resin, polyvinyl alcohol, polymethyl methacrylate, polytetrafluoroethylene, polyacrylonitrile; butadiene-styrene rubber; cellulose; glucose; coal tar pitch; petroleum 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; Single Walled Carbon Nanotube; any one or two kinds of above molar mixture arbitrarily in double-walled carbon nano-tube and the multi-walled carbon nano-tubes.
Organic acid is any one or two kinds of above molar mixture arbitrarily in citric acid, malic acid, tartaric acid, oxalic acid, salicylic acid, butanedioic acid, glycine, the 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 controls pattern and the granularity of silicon dioxide in coprecipitation process, has effectively improved crystal morphology and the covered effect of persursor material; Obtain ferrous silicate lithium anode material at adding carbon-source cpd and Li source compound by oversintering at last, make its granularity tiny even, pattern is controlled, has improved conductivity of electrolyte materials, and the performance under low temperature and the 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, is convenient to operation, and ferrous silicate lithium anode material free from admixture, the granularity for preparing is tiny evenly, and pattern is controlled.
Description of drawings
Fig. 1 is the x-ray diffraction pattern of the ferrous silicate lithium anode material for preparing of the embodiment of the invention 1;
Fig. 2 is the electron-microscope scanning figure of the ferrous silicate lithium anode material for preparing of the embodiment of the invention 1;
Fig. 3 is the first charge-discharge figure of the ferrous silicate lithium anode material for preparing of the embodiment of the invention 1.
Embodiment
The present invention is described in detail below in conjunction with the drawings and specific embodiments.
The preparation method of ferrous silicate lithium anode material of the present invention, specifically implement according to following steps:
Step 1, add surfactant and sodium metasilicate in the solvent 2 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 is that again mixed solution to be adjusted to pH with 3～10% sulfuric acid solution be 2～7 in 1:10～50, obtains acid SiO
2Emulsion;
Step 2, the acid SiO that obtains to step 1
2Add in the emulsion and add ferrous sulfate that mol ratio is 1:30～100 and the mixed solution of solvent 1 after oxalic acid mixes again, the mol ratio of ferrous sulfate, oxalic acid and sodium metasilicate is 1:1:1, washs then, filters, drying, obtains iron ion coated Si O
2The shell nuclear material;
Step 3, the iron ion coated Si O that obtains to step 2
2Add Li source compound and carbon-source cpd in the shell nuclear material, after crossing double sintering or direct sintering, cool off with stove, grind, namely obtain ferrous silicate lithium anode material.
The adding mode of Li source compound and carbon-source cpd has two kinds, a kind ofly is: Li source compound and carbon-source cpd are joined iron ion coated Si O
2In the solution of shell nuclear material, obtain the ferrosilicon silicate of lithium presoma through washing, filtration and drying then; Another kind is: Li source compound and carbon-source cpd are directly joined iron ion coated Si O
2In the shell nuclear material, obtain the ferrosilicon silicate of lithium presoma through ball milling then.The addition of carbon-source cpd is the 1wt%～20wt% of the ferrous silicate lithium anode material that finally obtains, and the lithium in the Li source compound and the mol ratio of sodium metasilicate are 1.95～2.1:1.
Double sintering be with the ferrosilicon silicate of lithium presoma under protective atmosphere, temperature is to handle 0.5～6 hour under 250～550 ℃ the environment, mix with organic acid the cooling back then, at rotating speed be on the ball mill of 100rpm～500rpm with the acetone or alcohol be the solvent wet-milling after 2～12 hours 60 ℃～120 ℃ following vacuumizes, at last again under protective atmosphere, temperature is to handle 6～24 hours under 600 ℃～900 ℃ the environment; Direct sintering is that the ferrosilicon silicate of lithium presoma is incubated 0.5～6 hour after being warming up to 250 ℃～550 ℃ under the protective atmosphere, continue to be warming up to 600 ℃～900 ℃ then after the insulation 6 hours～24 hours.
Protective atmosphere is nitrogen, argon gas, CO, CO
2In one or more mist.
Surfactant is any one or two kinds of above molar mixture arbitrarily 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, polyoxyethylene nonylplenyl ether, cetyl trimethyl kelene, softex kw, OTAC, the octadecyl trimethylammonium bromide; Solvent 1 and solvent 2 are any one or two kinds of above molar mixture arbitrarily in deionized water, distilled water, ethanol, the acetone.
Li source compound is any one or two kinds of above molar mixture arbitrarily in lithium hydroxide, acetate dihydrate lithium, 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, the lithium vanadate; Carbon-source cpd is ascorbic acid, furane resins, Lauxite, melamine resin, phenolic resins, epoxy resin, polyvinyl alcohol, polymethyl methacrylate, polytetrafluoroethylene, polyacrylonitrile; butadiene-styrene rubber; cellulose; glucose; coal tar pitch; petroleum 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; Single Walled Carbon Nanotube; any one or two kinds of above molar mixture arbitrarily in double-walled carbon nano-tube and the multi-walled carbon nano-tubes.
Organic acid is any one or two kinds of above molar mixture arbitrarily in citric acid, malic acid, tartaric acid, oxalic acid, salicylic acid, butanedioic acid, glycine, the 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 controls pattern and the granularity of silicon dioxide in coprecipitation process, has effectively improved crystal morphology and the covered effect of persursor material; Obtain ferrous silicate lithium anode material at adding carbon-source cpd and Li source compound by oversintering at last, make its granularity tiny even, pattern is controlled, has improved conductivity of electrolyte materials, and the performance under low temperature and the 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, is convenient to operation, and ferrous silicate lithium anode material free from admixture, the granularity for preparing is tiny evenly, and pattern is controlled.
Embodiment 1
Step 1 adds 2g polyethylene glycol and 0.02mol sodium metasilicate in the 25ml ethanol successively and fully stirs and is mixed with mixed solution, and regulating pH value with 7.5% sulfuric acid solution again is 5, obtains the SiO of acidity
2Emulsion;
Step 2, the acid SiO that obtains to step 1
2The ferrous sulfate that adds 0.02mol after the oxalic acid that adds 0.02mol in the emulsion mixes again continues stirring 3 hours with the mixed solution of 25ml deionized water, washs then, centrifugal dispersion and drying, obtains iron ion coated Si O
2The shell nuclear material;
Step 3, the iron ion coated Si O that step 2 is obtained
2Carry out the back 80 ℃ of following vacuumizes 3 hours after lithium carbonate, 5g glucose and the 20ml acetone ball milling of adding 0.02mol stir in the shell nuclear material; obtain the ferrosilicon silicate of lithium presoma; again the ferrosilicon silicate of lithium presoma is put into tube furnace and under the argon gas atmosphere protection, be warming up to 30ml alcohol and 1.5g were taken out and added in 410 ℃ of insulations after 3 hours ascorbic acid; behind the vacuum ball milling 60 ℃ of following vacuumizes 2 hours; at last under argon gas atmosphere; handle after 6 hours down for 850 ℃ and cool off with stove; grind, namely obtain ferrous silicate lithium anode material.
Fig. 1 is the x-ray diffraction pattern of the ferrous silicate lithium anode material for preparing of the embodiment of the invention 1, 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 for preparing of the embodiment of the invention 1, and as can be seen from Figure 2, the granularity of ferrous silicate lithium anode material is less.
With the ferrous silicate lithium anode material powder, conductive black and polyvinylidene fluoride (PVDF) mix in the ratio of mass ratio 80:10:10, add an amount of N-methyl pyrrolidone (NMP), be applied on the aluminium foil after fully stirring into evenly, dry 8h in the vacuum drying chamber under 130 ° of C then, be cut to the small pieces of 15.5mm diameter after the taking-up as positive plate, metal lithium sheet with the 15.8mm diameter is negative pole, with diameter 16mm, the Celgard2400 microporous polypropylene membrane of thickness 20um is barrier film, add the ethylene carbonate that volume ratio is 1:1:1 (EC)/1 again, the 1molL-1LiPF6 electrolyte of 2-dimethyl carbonate (DMC)/diethyl carbonate (DEC), in being full of the glove box of argon gas, be assembled into CR2032 type button cell, place U.S. Arbin battery testing to test its chemical property cashier's office in a shop button cell, charge-discharge magnification is 0.1C, and voltage range is 1.5V-4.8V.Fig. 3 is the first charge-discharge figure of the ferrous silicate lithium anode material for preparing of the embodiment of the invention 1, and as can be seen from Figure 3, the ferrous silicate lithium anode material charging capacity that embodiment 1 makes reaches 153mAh/g, and reversible capacity is 131mAh/g.
Embodiment 2
Step 1 adds 8g P123 and 0.025mol sodium metasilicate successively in 20ml acetone and 20 deionized waters and abundant the stirring is mixed with mixed solution, and regulating pH value with 9% sulfuric acid solution again is 6, obtains acid SiO
2Emulsion;
Step 2, the acid SiO that obtains to step 1
2The mixed solution that the oxalic acid that adds 0.025mol in the emulsion mixes ferrous sulfate that the back adds 0.025mol and the alcohol of 50ml distilled water and 20ml continues stirring 5 hours, washs then, centrifugal dispersion and drying, obtains iron ion coated Si O
2The shell nuclear material;
Step 3, the iron ion coated Si O that step 2 is obtained
2Carry out the back 80 ℃ of following vacuumizes 3 hours after the carbon black of four water citric acid lithiums, 1g ascorbic acid and the 0.7g of adding 0.04mol and 20ml alcohol ball milling stir in the shell nuclear material; obtain the ferrosilicon silicate of lithium presoma; after again the ferrosilicon silicate of lithium presoma being put into tube furnace and under argon gas atmosphere protection, being warming up to 500 ℃ insulation 1 hour follow-up continuous be warming up to 650 ℃ after insulation 20 hours; cool off with stove at last; grind, namely obtain ferrous silicate lithium anode material.
Embodiment 3
Step 1 adds the 0.02mol sodium metasilicate in the 15ml acetone and fully stirs and is mixed with mixed solution, and to regulate pH value be 2 to 3% sulfuric acid solution again, obtains acid SiO
2Emulsion;
Step 2, the acid SiO that obtains to step 1
2The oxalic acid that adds 0.02mol in the emulsion mixes the mixed solution that the back adds the acetone of the ferrous sulfate of 0.02mol and 10ml deionized water and 5ml and continues stirring 3 hours, washs then, centrifugal dispersion and drying, obtains iron ion coated Si O
2The shell nuclear material;
Step 3, the iron ion coated Si O that step 2 is obtained
2The lithium chloride that adds 0.0195mol in the shell nuclear material; 0.483g glucose and 20ml acetone ball milling carry out the back 80 ℃ of following vacuumizes 3 hours after stirring; obtain the ferrosilicon silicate of lithium presoma; again the ferrosilicon silicate of lithium presoma is put into tube furnace and under the argon gas atmosphere protection, be warming up to 20ml acetone and 2.0g were taken out and added in 250 ℃ of insulations after 6 hours malic acid; it is wet-milling 12 hours on the ball mill of 100rpm at rotating speed; the back is 60 ℃ of following vacuumizes; at last under argon gas atmosphere; handle after 24 hours down for 600 ℃ and cool off with stove; grind, namely obtain ferrous silicate lithium anode material.
Organic acid is malic acid among the embodiment 3, also can be any one or two kinds of above molar mixture arbitrarily in citric acid, malic acid, tartaric acid, oxalic acid, salicylic acid, butanedioic acid, glycine, the ethylenediamine tetra-acetic acid.
Embodiment 4
Step 1 adds the 0.02mol sodium metasilicate in 27ml ethanol and the 10ml deionized water with the P123 of 12g and fully stirs and is mixed with mixed solution, is 7 with 10% sulfuric acid solution adjusting pH value again, obtains the SiO of acidity
2Emulsion;
Step 2, the acid SiO that obtains to step 1
2The oxalic acid that adds 0.02mol in the emulsion mixes that the back adds the ferrous sulfate of 0.02mol and the mixed solution of 36ml deionized water continues to stir 4 hours, and then wash, centrifugal dispersion and drying, obtain iron ion coated Si O
2The shell nuclear material;
Step 3, the iron ion coated Si O that step 2 is obtained
2The lithium acetate that adds 0.042mol in the shell nuclear material; 0.3g acetylene black; 0.322g carbon black and 20ml acetone ball milling carry out the back 80 ℃ of following vacuumizes 3 hours after stirring; obtain the ferrosilicon silicate of lithium presoma; again the ferrosilicon silicate of lithium presoma is put into tube furnace and under the argon gas atmosphere protection, be warming up to 20ml acetone and 1g were taken out and added in 550 ℃ of insulations after 0.5 hour citric acid and 2g malic acid; it is wet-milling 2 hours on the ball mill of 500rpm at rotating speed; the back is 120 ℃ of following vacuumizes; at last under argon gas atmosphere; handle after 6 hours down for 900 ℃ and cool off with stove; grind, namely obtain ferrous silicate lithium anode material.
Embodiment 5
Step 1 adds the 0.02mol sodium metasilicate in the 15ml acetone and fully stirs and is mixed with mixed solution, and to regulate pH value be 2 to 3% sulfuric acid solution again, obtains acid SiO
2Emulsion;
Step 2, the acid SiO that obtains to step 1
2The oxalic acid that adds 0.02mol in the emulsion mixes the mixed solution that the back adds the acetone of the ferrous sulfate of 0.02mol and 10ml deionized water and 5ml and continues stirring 3 hours, and then wash, centrifugal dispersion and drying, obtain iron ion coated Si O
2The shell nuclear material;
Step 3, the iron ion coated Si O that step 2 is obtained
2Carry out the back 80 ℃ of following vacuumizes 3 hours after lithium chloride, 0.483g glucose and the 20ml acetone ball milling of adding 0.0195mol stir in the shell nuclear material; obtain the ferrosilicon silicate of lithium presoma; after again the ferrosilicon silicate of lithium presoma being put into tube furnace and under argon gas atmosphere protection, being warming up to 250 ℃ insulation 6 hours follow-up continuous be warming up to 900 ℃ after insulation 6 hours; cool off with stove at last; grind, namely obtain ferrous silicate lithium anode material.
Embodiment 6
Step 1 adds the 0.02mol sodium metasilicate in 27ml ethanol and the 10ml deionized water with the P123 of 12g and fully stirs and is mixed with mixed solution, is 7 with 10% sulfuric acid solution adjusting pH value again, obtains the SiO of acidity
2Emulsion;
Step 2, the acid SiO that obtains to step 1
2The oxalic acid that adds 0.02mol in the emulsion mixes that the back adds the ferrous sulfate of 0.02mol and the mixed solution of 36ml deionized water continues to stir 4 hours, and then wash, centrifugal dispersion and drying, obtain iron ion coated Si O
2The shell nuclear material;
Step 3, the iron ion coated Si O that step 2 is obtained
2Carry out the back 80 ℃ of following vacuumizes 3 hours after lithium acetate, 0.3g acetylene black, 0.322g carbon black and the 20ml acetone ball milling of adding 0.042mol stir in the shell nuclear material; obtain the ferrosilicon silicate of lithium presoma; again the ferrosilicon silicate of lithium presoma is put in the tube furnace after being warming up to 550 ℃ under the argon gas atmosphere protection insulation 0.5 hour follow-up continuous be warming up to 600 ℃ after insulation 24 hours; cool off with stove at last; grind, namely obtain ferrous silicate lithium anode material.
Be P123 among the embodiment 6, also can be any one or two kinds of above molar mixture arbitrarily 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, polyoxyethylene nonylplenyl ether, cetyl trimethyl kelene, softex kw, OTAC, the octadecyl trimethylammonium bromide.
Solvent 2 is 27ml ethanol and 10ml deionized water among the embodiment 6, also can be any one or two kinds of above molar mixture arbitrarily in deionized water, distilled water, ethanol, the acetone.
Solvent 1 is deionized water among the embodiment 6, also can be any one or two kinds of above molar mixture arbitrarily in deionized water, distilled water, ethanol, the acetone.
Li source compound is lithium acetate among the embodiment 6, also can be any one or two kinds of above molar mixture arbitrarily in lithium hydroxide, acetate dihydrate lithium, 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, the lithium vanadate.
Carbon-source cpd is the mixture of 0.3g acetylene black and 0.322g carbon black among the embodiment 6, also can be ascorbic acid, furane resins, Lauxite, melamine resin, phenolic resins, epoxy resin, polyvinyl alcohol, polymethyl methacrylate, polytetrafluoroethylene, polyacrylonitrile; butadiene-styrene rubber; cellulose; glucose; coal tar pitch; petroleum 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; Single Walled Carbon Nanotube; any one or two kinds of above molar mixture arbitrarily in double-walled carbon nano-tube and the multi-walled carbon nano-tubes.
Protective atmosphere is argon gas atmosphere among the embodiment 6, also can be nitrogen, argon gas, CO, CO
2In one or more mist.
Claims (10)
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 that adds ferrous sulfate and solvent 1 after oxalic acid mixes again in the emulsion, wash then, filter, drying, obtain iron ion coated Si O
2The shell nuclear material;
Step 2, the iron ion coated Si O that obtains to step 1
2Add Li source compound and carbon-source cpd in the shell nuclear material, finally by cooling off with stove behind the oversintering, grind, namely obtain ferrous silicate lithium anode material.
2. the preparation method of ferrous silicate lithium anode material according to claim 1 is characterized in that, acid SiO in the described step 1
2Emulsion is mixed by solvent 2, surfactant and sodium metasilicate and is obtained, and adds surfactant and sodium metasilicate successively and fully stir in the solvent 2 to be mixed with mixed solution, and again mixed solution being adjusted to pH with 3～10% sulfuric acid solutions is 2～7, obtains acid SiO
2Emulsion.
3. the preparation method of ferrous silicate lithium anode material according to claim 2, 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.
4. the preparation method of ferrous silicate lithium anode material according to claim 3, it is characterized in that, the adding mode of Li source compound and carbon-source cpd has two kinds in the described step 2, a kind ofly is: Li source compound and carbon-source cpd are joined iron ion coated Si O
2In the solution of shell nuclear material, obtain the ferrosilicon silicate of lithium presoma through washing, filtration and drying then; Another kind is: Li source compound and carbon-source cpd are directly joined iron ion coated Si O
2In the shell nuclear material, obtain the ferrosilicon silicate of lithium presoma through ball milling then.
5. the preparation method of ferrous silicate lithium anode material according to claim 4, it is characterized in that, the addition of described carbon-source cpd is the 1wt%～20wt% of the ferrous silicate lithium anode material that finally obtains, and the lithium in the Li source compound and the mol ratio of sodium metasilicate are 1.95～2.1:1.
6. the preparation method of ferrous silicate lithium anode material according to claim 5, it is characterized in that, sintering adopts double sintering or direct sintering in the described step 2, double sintering be with the ferrosilicon silicate of lithium presoma under protective atmosphere, temperature is to handle 0.5～6 hour under 250～550 ℃ the environment, mix with organic acid the cooling back then, at rotating speed be on the ball mill of 100rpm～500rpm with the acetone or alcohol be the solvent wet-milling after 2～12 hours 60 ℃～120 ℃ following vacuumizes, at last again under protective atmosphere, temperature is to handle 6～24 hours under 600 ℃～900 ℃ the environment; Direct sintering is that the ferrosilicon silicate of lithium presoma is incubated 0.5～6 hour after being warming up to 250 ℃～550 ℃ under the protective atmosphere, continue to be warming up to 600 ℃～900 ℃ then after the insulation 6 hours～24 hours.
7. the preparation method of ferrous silicate lithium anode material according to claim 6 is characterized in that, described protective atmosphere is nitrogen, argon gas, CO, CO
2In one or more mist.
8. the preparation method of ferrous silicate lithium anode material according to claim 7, 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, the polyoxyethylene nonylplenyl ether, the cetyl trimethyl kelene, softex kw, OTAC, any one or two kinds of above molar mixture arbitrarily in the octadecyl trimethylammonium bromide; Described solvent 1 and solvent 2 are any one or two kinds of above molar mixture arbitrarily in deionized water, distilled water, ethanol, the acetone.
9. the preparation method of ferrous silicate lithium anode material according to claim 8, it is characterized in that described Li source compound is any one or two kinds of above molar mixture arbitrarily in lithium hydroxide, acetate dihydrate lithium, 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, the lithium vanadate; Described carbon-source cpd is ascorbic acid, furane resins, Lauxite, melamine resin, phenolic resins, epoxy resin, polyvinyl alcohol, polymethyl methacrylate, polytetrafluoroethylene, polyacrylonitrile; butadiene-styrene rubber; cellulose; glucose; coal tar pitch; petroleum 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; Single Walled Carbon Nanotube; any one or two kinds of above molar mixture arbitrarily in double-walled carbon nano-tube and the multi-walled carbon nano-tubes.
10. the preparation method of ferrous silicate lithium anode material according to claim 9, it is characterized in that described organic acid is any one or two kinds of above molar mixture arbitrarily in citric acid, malic acid, tartaric acid, oxalic acid, salicylic acid, butanedioic acid, glycine, the ethylenediamine tetra-acetic acid.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107634221A (en) * | 2017-08-18 | 2018-01-26 | 华北理工大学 | A kind of synthetic method for the ferrous silicate lithium anode material that bismuth doping is prepared using iron tailings as raw material |
| CN107665985A (en) * | 2017-10-17 | 2018-02-06 | 黄冈林立新能源科技有限公司 | The preparation method of lithium ferrosilicon silicate of lithium-ion battery cathode material |
| CN113594434A (en) * | 2021-07-21 | 2021-11-02 | 昆明理工大学 | Preparation method of dandelion-shaped core-shell structure silicon-ferrous oxalate lithium ion battery material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5277899A (en) * | 1975-12-23 | 1977-06-30 | Agency Of Ind Science & Technol | Production of lithium ferrosilicate single crystal |
| CN101499527A (en) * | 2009-03-11 | 2009-08-05 | 中南大学 | Production method of lithium ferric metasilicate anode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5277899A (en) * | 1975-12-23 | 1977-06-30 | Agency Of Ind Science & Technol | Production of lithium ferrosilicate single crystal |
| CN101499527A (en) * | 2009-03-11 | 2009-08-05 | 中南大学 | Production method of lithium ferric metasilicate anode material |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107634221A (en) * | 2017-08-18 | 2018-01-26 | 华北理工大学 | A kind of synthetic method for the ferrous silicate lithium anode material that bismuth doping is prepared using iron tailings as raw material |
| CN107634221B (en) * | 2017-08-18 | 2020-04-21 | 华北理工大学 | Synthetic method for preparing bismuth-doped lithium ferrous silicate cathode material by taking iron tailings as raw materials |
| CN107665985A (en) * | 2017-10-17 | 2018-02-06 | 黄冈林立新能源科技有限公司 | The preparation method of lithium ferrosilicon silicate of lithium-ion battery cathode material |
| CN113594434A (en) * | 2021-07-21 | 2021-11-02 | 昆明理工大学 | Preparation method of dandelion-shaped core-shell structure silicon-ferrous oxalate lithium ion battery material |
| CN113594434B (en) * | 2021-07-21 | 2022-12-02 | 昆明理工大学 | Preparation method of dandelion-shaped core-shell structure silicon-ferrous oxalate lithium ion battery material |
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