CN102751497A - Method for preparing lithium ferrous silicate anode material by rheological phase reaction - Google Patents
Method for preparing lithium ferrous silicate anode material by rheological phase reaction Download PDFInfo
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- CN102751497A CN102751497A CN2012102501320A CN201210250132A CN102751497A CN 102751497 A CN102751497 A CN 102751497A CN 2012102501320 A CN2012102501320 A CN 2012102501320A CN 201210250132 A CN201210250132 A CN 201210250132A CN 102751497 A CN102751497 A CN 102751497A
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- source compound
- lithium
- anode material
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a method for preparing a lithium ferrous silicate anode material by the rheological phase reaction. The method is characterized by including steps of weighing a lithium-source compound, a ferrum-source compound and a silicon-source compound according to a molar ratio of 2:1:1, and weighing a carbon-source compound according to a ratio of 9%-30% by mass of reaction materials; mixing the reaction raw materials, adding a small quantity of solvent to prepare a rheological phase precursor; and calcinating the rheological phase precursor in an inert gas or a reducibility gas to obtain the lithium ferrous silicate coated by an in-situ carbon. The method has both characteristics of a solid-phase reaction method and a liquid-phase reaction method, the prepared anode material is small in particle size, uniform in distribution, good in electrochemistry performance, simple in manufacture process, easy to realize the industrial production, and has an excellent microcosmic structure.
Description
Technical field
The present invention relates to the materials chemistry field, particularly a kind of method of utilizing rheological phase reaction to prepare ferrous silicate lithium anode material.
Background technology
Lithium ion battery is always as the power supply of small-sized portability electrical equipment and used in a large number by people.In recent years, the key component that can effectively store and use intermittence regenerative resource (like solar energy and wind energy) because of it and become emerging pure electric automobile and hybrid-power electric vehicle is by people institute wilderness demand.
Traditional anode material for lithium-ion batteries LiCoO
2And LiCo
1-xNi
xO
2Poisonous because of it, cost an arm and a leg, show when directly contacting with organic electrolyte strong oxidizability, and problems such as fail safe that this strong oxidizing property caused can not become the positive electrode of dynamic lithium battery.Consider based on this safety, people have used and have contained polyanion radicals X O
4 N-The positive electrode of (X=S, P, Si etc.) is used as the carrier that the lithium ion embedding is taken off.Because the covalent bond effect of X-O, this positive electrode that contains the polyanion group is much more stable than traditional transition metal oxide material, therefore also much safe.In this type material, Li
2FeSiO
4Positive electrode has excellent cyclical stability, thermal stability and fail safe, and raw material resources is abundant, and environmentally safe is a kind of new type power anode material for lithium-ion batteries that has development potentiality.
At present, the Li of bibliographical information
2FeSiO
4Typical preparation method high temperature solid phase synthesis, sol-gel process, hydro-thermal assisting sol-gel method, hydro thermal method and the hot method of microwave-assisted solvent are arranged.(1) high temperature solid phase synthesis: people such as Anton Nyten were raw material in 2005 with ferrous oxalate, lithium metasilicate and carbon gel, mixed the back at CO/CO
2The following 750 ℃ of reaction 24h of atmosphere have obtained Li
2FeSiO
4/ C composite material [Electrochemical performance of Li
2FeSiO
4As a new Li-battery cathode material, Electrochemistry Communications, 7 (2005) 156-160].(2) sol-gel process: people such as R. Dominko are raw material at the mixture with ironic citrate, ferric nitrate, lithium acetate and SiO 2 powder in 2006; In the mixture of citric acid and ethylene glycol, process colloidal sol, obtain Li behind reaction 1～96h down through the inert atmosphere in 700 ℃ after drying, the grinding
2FeSiO
4[Structure and electrochemical performance of Li
2MnSiO
4And Li
2FeSiO
4As potential Li-battery cathode materials, Electrochemistry Communications, 8 (2006) 217-222].(3) hydro-thermal assisting sol-gel method: people such as the Yang Yong of Xiamen University placed autoclave to react 20h down for 120 ℃ lithium acetate, ferrous acetate, tetraethyl orthosilicate, ethanol and little acetic acid catalyst in 2008; Mix through the high speed ball milling with sucrose, acetone after the colloid drying that obtains, under nitrogen atmosphere, obtain the Li of nanostructure then in 600 ℃ of roasting 10h
2FeSiO
4/ C [Nanostructured Li2FeSiO4 electrode material synthesized through hydrothermal-assisted sol-gel process; Electrochemical and Solid State Letters, 11 (5) A60-A63 (2008)].(4) hydro thermal method: people such as R. Dominko were dispersed in lithium hydroxide solution with SiO 2 powder through ultrasonic assisting in 2006; Mix with solution of ferrous chloride then; In airtight autoclave more than 150 ℃ of isothermal reaction 72h; The powder that obtains is the water cyclic washing under argon gas atmosphere, obtains Li after the drying
2FeSiO
4Powder [Structure and electrochemical performance of Li
2MnSiO
4And Li
2FeSiO
4As potential Li-battery cathode materials, Electrochemistry Communications, 8 (2006) 217-222].(5) the hot method of microwave-assisted solvent: people such as T. Muraliganth were dissolved in tetraethyl orthosilicate, lithium hydroxide and ferrous acetate in the tetraethylene glycol in 2010, and (frequency is 2.45GHz, and 600W) heating 25min obtains Li through the microwave radiation system with system then
2FeSiO
4Behind the nanocrystal it is mixed with sucrose, 650 ℃ of roasting 6h obtain Li under argon gas atmosphere
2FeSiO
4/ C composite material [Microwave-solvothermal synthesis of nanostructured Li
2MSiO
4/ C (M=Mn and Fe) cathodes for lithium-ion batteries, Chemistry of Materials, 2010,22,5754-5761].
In the above-mentioned prior synthesizing method, solid-phase synthesis needs higher synthesis temperature, and the material grains and the particle that obtain are big, are unfavorable for the raising of ferrosilicon silicate of lithium chemical property; And the synthetic method of liquid phase (hydro thermal method and solvent-thermal method, sol-gel process and hydro-thermal assisting sol-gel method) is difficult to industrial applications, and the powder body material tap density that obtains is low, is unfavorable for improving the volume of battery energy density.Therefore; A kind of resulting ferrous silicate lithium anode material of synthetic method that has solid-phase synthesis and liquid phase synthesizing method characteristics concurrently will have good electrical chemical property and higher tap density concurrently; For the research and development and the industrialization process that promote ferrous silicate lithium anode material, promote the development of lithium ion battery, electric motor car and related industry that significance is arranged.
Summary of the invention
Problem to the tap density of using the resulting ferrous silicate lithium anode material of prior synthesizing method and chemical property are difficult to take into account the invention provides a kind of rheological phase reaction synthetic method, and specifically summary of the invention is following:
1. a method of utilizing rheological phase reaction to prepare ferrous silicate lithium anode material comprises the steps:
1) according to mol ratio be lithium ion/iron ion/silicon ion=2/1/1 take by weighing Li source compound, Fe source compound and silicon source compound, subsequent use;
2) take by weighing carbon-source cpd by 9%～30% of subsequent use Li source compound, Fe source compound and silicon source compound quality summation, subsequent use;
3) Li source compound, Fe source compound, silicon source compound, carbon-source cpd mixing that weighing is subsequent use, and add solvent and be modulated into sticky shape, rheology attitude presoma obtained;
4) rheology attitude presoma low-temperature bake in inert atmosphere or reducing atmosphere is obtained the ferrosilicon silicate of lithium that original position carbon coats.
As preferred version:
Described Li source compound is one or more the mixture in lithium acetate, lithium nitrate, lithium carbonate, the lithium hydroxide;
Described Fe source compound is the ferric iron source compound, or is the ferrous iron source compound; Specifically comprise one or more the mixture in ferric nitrate, ferric acetate, ferric sulfate, ironic citrate, ferrous nitrate, ferrous acetate, ferrous sulfate, ferrous citrate, the frerrous chloride;
Described silicon source compound is one or more the mixture in silicon dioxide, metasilicic acid, lithium metasilicate, ferric metasilicate, the silane coupler;
Described carbon-source cpd is one or more the mixture in polypropylene, polyethylene glycol, polyvinyl alcohol, phenolic resins, citric acid, glucose, sucrose or the soluble starch;
Described solvent is one or more the mixture in water, ethanol or the acetone;
Described inert atmosphere or reducing atmosphere are one or more gases or the mist of above-mentioned gas and hydrogen or carbon monoxide in nitrogen, argon gas, the carbon dioxide;
The temperature range of described low-temperature bake is 550 ℃～750 ℃, and time range is 3 hours～12 hours.
The invention provides a kind of rheological phase reaction synthetic method, rheological phase reaction is the chemical reaction that in reaction system, has rheology to participate in mutually, is a kind of green, softening synthetic method of learning that rheology is combined with synthetic chemistry.In the rheological phase reaction; With reactant through suitably mixing; Add suitable quantity of water or other solvent and be modulated into solids and even, the not stratified thick solid-liquid hybrid system (being the rheology phase system) of Liquid Distribution, reaction obtains required product under proper condition then.The material that is in the rheology attitude had not only demonstrated the character of solid but also had demonstrated the character of liquid on mechanics.Solid particle and liquid substance are uniformly mixed to form the advantage of rheological body: the surface area of solid particle can effectively be utilized, and contacts with fluid closely, and evenly, heat exchange is good, the local overheating phenomenon can not occur, and temperature is easy to regulate.Rheological phase reaction be a kind of energy-conservation, efficient, subtract dirty green chemical synthetic route.
Experimental principle of the present invention is:
1) lithium salts among the present invention, molysite and carbon compound are dissolved in the water; Can reach other even mixing of molecular level; After system furnishing rheology attitude, the reactant abutment surface suction-operated of solubility is evenly distributed on the surface of insoluble silicon-containing compound, and lithium ion and iron ion need not carry out long-distance diffusion during reaction; Therefore roasting process can adopt than lower temperature of traditional solid-phase synthesis or shorter time, and the product that obtains has good uniformity.
2) carbon compound among the present invention is water-soluble with other raw materials mix in the abnormal presoma process of modulated stream, can reach molecular level between the reactant and evenly mix, and in roasting process, carbon compound is carbonized, and realizes that with ferrosilicon silicate of lithium original position carbon coats.If the molysite in the raw material is a ferric iron, then carbon compound also plays a part reducing agent.
3) the abnormal means of the modulated stream among the present invention can be high-energy ball milling or simple the stirring, if use high-energy ball milling, the ferrosilicon silicate of lithium particle that then makes can reach nanoscale size; If using simple stirring and insoluble silicon-containing compound is the silicon dioxide that possesses certain special appearance, the ferrosilicon silicate of lithium that then obtains at last can keep the pattern of reactant silicon dioxide.
Compare with conventional method, the present invention possesses following advantage:
(1) raw material sources are extensive, and cheap, technology is simple, be convenient to suitability for industrialized production.
(2) lower temperature or short period are adopted in roasting, and energy savings is enhanced productivity.
(3) product has realized that original position carbon coats, and has improved the electric conductivity and the chemical property of material effectively.
(4) can effectively control the size and the pattern of product, the positive electrode particle of preparation is tiny, be evenly distributed, have good microstructure.
(5) this synthetic method has the synthetic characteristics with liquid phase synthesizing method of traditional high temperature solid-state concurrently, and therefore synthetic ferrous silicate lithium anode material has higher tap density and good electrochemical concurrently.
Description of drawings
Fig. 1 is the sem photograph of the ferrous silicate lithium anode material press embodiment 1 and synthesize.
Fig. 2 charges and discharge electrograph for the typical case by the synthetic ferrous silicate lithium anode material of embodiment 1.
Fig. 3 is the cycle performance curve of the ferrous silicate lithium anode material press embodiment 1 and synthesize.
Fig. 4 is the sem photograph of the amorphous silicon di-oxide nanosphere press embodiment 4 and synthesize.
Fig. 5 is the sem photograph of the spherical ferrous silicate lithium anode material press embodiment 4 and synthesize.
Embodiment
Through embodiment, further illustrate outstanding feature of the present invention and marked improvement below, only be the present invention is described and certainly do not limit the scope of the invention.
Embodiment 1
One, preparation anode material for lithium-ion batteries
1) gets 2.04g CH
3COOLi2H
2O, 4.04g Fe (NO
3)
39H
2O, 0.60g SiO
2With the 2.00g polyethylene glycol, 5 ml ethanol, subsequent use;
2) place high speed ball mill with 500rpm ball milling 3h above-mentioned subsequent use raw material, the mixture behind the ball milling is dry, add a small amount of distilled water, be modulated into sticky shape, obtain rheology attitude presoma;
3) be transferred to presoma in the porcelain boat and place in the tube furnace, be warming up to 350 ℃,, be warming up to 600 ℃ with 2 ℃/min speed then,, obtain the ferrous silicate lithium anode material that original position carbon coats at 600 ℃ of constant temperature 10h at 350 ℃ of constant temperature 3h with 1 ℃/min speed.
Two, preparation battery and performance test
1) ferrosilicon silicate of lithium, conductive agent carbon black, binding agent PVDF are mixed by a certain percentage, be coated on the aluminum foil current collector, oven dry, compressing tablet makes positive plate, and is assembled into button cell with metal lithium sheet;
2) discharge and recharge with 16 mA/g current densities, record the reversible capacity of this material between 1.5-4.8V and can reach 160 mAh/g, and cycle performance is good.Fig. 1 is the sem photograph of ferrous silicate lithium anode material; Fig. 2 is the voltage-specific capacity curve chart of ferrous silicate lithium anode material first to the tenth charge and discharge cycles under 16 mA/g current densities, and Fig. 3 is the cycle performance figure of ferrous silicate lithium anode material the first five ten charge and discharge cycles under 16 mA/g current densities.
Embodiment 2
The preparation anode material for lithium-ion batteries
1) gets 0.84g LiOHH
2O, 4.04g Fe (NO
3)
39H
2O, 0.60g SiO
2With 0.55g glucose, 5 ml distilled water, subsequent use:
2) place high speed ball mill with 500rpm ball milling 3h above-mentioned subsequent use raw material.Mixture behind the ball milling is dried to remaining low amounts of water, grinds, be modulated into sticky shape, obtain rheology attitude presoma;
3) be transferred to presoma in the porcelain boat and place in the tube furnace, be warming up to 350 ℃,, be warming up to 550 ℃ with 2 ℃/min speed then,, obtain the ferrous silicate lithium anode material that original position carbon coats at 550 ℃ of constant temperature 3h at 350 ℃ of constant temperature 3h with 1 ℃/min speed.
Embodiment 3
The preparation anode material for lithium-ion batteries
1) gets 2.04g CH
3COOLi2H
2O, 4.04g Fe (NO
3)
39H
2O, 0.60g SiO
2With the 2.00g polyethylene glycol, 5 ml ethanol, subsequent use;
2) place high speed ball mill with 500rpm ball milling 3h above-mentioned subsequent use raw material, the mixture behind the ball milling is dry, add a small amount of distilled water, be modulated into sticky shape, obtain rheology attitude presoma;
3) be transferred to presoma in the porcelain boat and place in the tube furnace, be warming up to 350 ℃,, be warming up to 750 ℃ with 2 ℃/min speed then,, obtain the ferrous silicate lithium anode material that original position carbon coats at 750 ℃ of constant temperature 12h at 350 ℃ of constant temperature 3h with 1 ℃/min speed.
Embodiment 4
One, preparation amorphous state SiO
2Nanosphere
Measure 40ml absolute ethyl alcohol, 10ml distilled water and 10ml concentrated ammonia liquor respectively in there-necked flask, flask is placed in 40 ℃ of thermostat water baths magnetic agitation; Dropwise be added drop-wise to the 10ml tetraethyl orthosilicate in the mixed solution simultaneously; Isothermal reaction 4h is transferred to baking oven with the milky white solution that obtains at last, at 80 ℃ with solvent evaporation; Grind, the white powder that obtains is amorphous state SiO
2Nanosphere.
Two, preparation anode material for lithium-ion batteries
1) gets 2.04g CH
3COOLi2H
2O, 4.04g Fe (NO
3)
39H
2O, the synthetic amorphous state SiO of 0.60g
2Nanosphere and 2.00g polyethylene glycol mix, and adding distil water stirs 3h;
Grind when 2) being dried in the mixture only surplus low amounts of water, be modulated into rheology attitude presoma;
3) be transferred to presoma in the porcelain boat and place in the tube furnace, be warming up to 350 ℃,, be warming up to 650 ℃ with 2 ℃/min speed then,, obtain the ferrous silicate lithium anode material that original position carbon coats at 650 ℃ of constant temperature 10h at 350 ℃ of constant temperature 3h with 1 ℃/min speed.
Fig. 4 is the amorphous state SiO of preparation
2The sem photograph of nanosphere.
Fig. 5 shows that for taking the nanosphere as the sem photograph of the synthetic ferrous silicate lithium anode material in silicon source synthetic ferrosilicon silicate of lithium has kept the pattern of silica material.
Claims (8)
1. a method of utilizing rheological phase reaction to prepare ferrous silicate lithium anode material is characterized in that: comprise the steps:
1) be that lithium ion/iron ion/silicon ion=2/1/1 takes by weighing Li source compound, Fe source compound and silicon source compound according to mol ratio, subsequent use;
2) take by weighing carbon-source cpd by 9%～30% of subsequent use Li source compound, Fe source compound and silicon source compound quality summation, subsequent use;
3) Li source compound, Fe source compound, silicon source compound, carbon-source cpd mixing that weighing is subsequent use, and add solvent and be modulated into sticky shape, rheology attitude presoma obtained;
4) rheology attitude presoma low-temperature bake in inert atmosphere or reducing atmosphere is obtained the ferrosilicon silicate of lithium that original position carbon coats.
2. a kind of method of utilizing rheological phase reaction to prepare ferrous silicate lithium anode material according to claim 1 is characterized in that: described Li source compound is one or more the mixture in lithium acetate, lithium nitrate, lithium carbonate, the lithium hydroxide.
3. a kind of method of utilizing rheological phase reaction to prepare ferrous silicate lithium anode material according to claim 1 is characterized in that: described Fe source compound is the ferric iron source compound, or is the ferrous iron source compound; Specifically comprise one or more the mixture in ferric nitrate, ferric acetate, ferric sulfate, ironic citrate, ferrous nitrate, ferrous acetate, ferrous sulfate, the ferrous citrate.
4. a kind of method of utilizing rheological phase reaction to prepare ferrous silicate lithium anode material according to claim 1 is characterized in that: described silicon source compound is one or more the mixture in silicon dioxide, metasilicic acid, lithium metasilicate, ferric metasilicate, the silane coupler.
5. a kind of method of utilizing rheological phase reaction to prepare ferrous silicate lithium anode material according to claim 1 is characterized in that: described carbon-source cpd is one or more the mixture in polypropylene, polyethylene glycol, polyvinyl alcohol, phenolic resins, citric acid, glucose, sucrose, the soluble starch.
6. according to each described a kind of method of utilizing rheological phase reaction to prepare ferrous silicate lithium anode material of claim 1-5, it is characterized in that: described solvent is one or more the mixture in water, ethanol or the acetone.
7. according to each described a kind of method of utilizing rheological phase reaction to prepare ferrous silicate lithium anode material of claim 1-5, it is characterized in that: described inert atmosphere or reducing atmosphere are one or more gases or the mist of above-mentioned gas and hydrogen or carbon monoxide in nitrogen, argon gas, the carbon dioxide.
8. according to each described a kind of method of utilizing rheological phase reaction to prepare ferrous silicate lithium anode material of claim 1-5, it is characterized in that: described low-temperature bake process temperature is 550 ℃～750 ℃, and the time is 3 hours～12 hours.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104362318A (en) * | 2014-11-10 | 2015-02-18 | 湖南文理学院 | Method for preparing ferrous silicate lithium/carbon composite positive pole material with micropore spherical structure |
| CN106887572A (en) * | 2017-03-08 | 2017-06-23 | 东华大学 | A kind of antimony carbon composite and its preparation method and application |
| 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 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104362318A (en) * | 2014-11-10 | 2015-02-18 | 湖南文理学院 | Method for preparing ferrous silicate lithium/carbon composite positive pole material with micropore spherical structure |
| CN106887572A (en) * | 2017-03-08 | 2017-06-23 | 东华大学 | A kind of antimony carbon composite and its preparation method and application |
| 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 |
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