CN103326022A - Method for preparing lithium ferrous silicate positive pole material from ilmenite - Google Patents
Method for preparing lithium ferrous silicate positive pole material from ilmenite Download PDFInfo
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- CN103326022A CN103326022A CN2013102850932A CN201310285093A CN103326022A CN 103326022 A CN103326022 A CN 103326022A CN 2013102850932 A CN2013102850932 A CN 2013102850932A CN 201310285093 A CN201310285093 A CN 201310285093A CN 103326022 A CN103326022 A CN 103326022A
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- ilmenite
- oxalate
- ferrous
- acid
- anode material
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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
- 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 discloses a method for preparing a lithium ferrous silicate positive pole material from ilmenite. The method is characterized by comprising the following steps of: ball-milling ilmenite, performing reflux leaching on the ilmenite by a volatile acid under a normal pressure, and performing refrigerated centrifugal washing to obtain titanium-enriched slag and iron-enriched leachate; adding a reducer in the iron-enriched leachate and heating, cooling and filtering to remove impurities after the reaction is ended, then adding an oxalate-containing precipitator, controlling the pH of the reaction system to be 5+/-0.5 by ammonia water, and washing, centrifuging and drying the obtained precipitate to obtain a ferrous oxalate precursor after the reaction; and finally, preparing the lithium ferrous silicate positive pole material by taking the ferrous oxalate precursor prepared from the ilmenite as a ferrous source. The method disclosed by the invention has the characteristics that the reserve of the raw material ilmenite is abundant, process flow is simple, energy consumption and cost are low, and environment friendliness is achieved; simultaneously, the titanium-enriched slag is high in TiO2 content and can be used as a production raw material of titanium dioxide, thus realizing comprehensive utilization for the ilmenite.
Description
Technical field
The present invention relates to a kind of preparation method of lithium ferrosilicon silicate of lithium-ion battery cathode material, particularly relate to a kind of method that is prepared ferrous silicate lithium anode material by ilmenite, belong to the energy and material preparing technical field.
Background technology
In recent years, polyanion silicate as positive pole material ferrous lithium (Li
2FeSiO
4) because of its theoretical specific capacity high (333 ~ mAh/g), good, the aboundresources of good cycle, Heat stability is good, fail safe, cheap, advantages of environment protection, be considered to have the anode material for lithium-ion batteries of development potentiality.The analysis pure iron source (such as ferrous oxalate, ferric nitrate, ferrous acetate etc.) of preparation ferrosilicon silicate of lithium is to be made by the purifying technique of iron-stone through complexity mostly at present, and when preparing ferrosilicon silicate of lithium with analysis pure iron source, need again doped metallic elements for improving its chemical property, exist in iron-stone but these doped metallic elements are many.Therefore, utilizing iron-stone to prepare lithium ferrosilicon silicate of lithium-ion battery cathode material is the effective ways that reduce its cost.
Ilmenite (FeTiO
3) large at the reserves of China, be about 3,000 ten thousand tons.At present, people mainly utilize the titanium elements in the ilmenite to produce titanium dioxide, titanium sponge and synthetic rutile etc., and the utilization ratios such as other elements such as iron, manganese, vanadium, aluminium, magnesium are low, and this will cause the wasting of resources and environmental pollution.Therefore, new technology and the new technology of various elements is inexorable trends in the development comprehensive utilization mineral.At present, utilize ilmenite to prepare the report of lithium ion battery electrode material less.Chinese patent 200910310737.2 discloses a kind of method that ilmenite prepares lithium titanate and ferric lithium phosphate precursor that fully utilizes, and the method uses sulfuric acid as the leaching ilmenite medium, with (Fe after the oxidation of rich iron leachate
2+Become Fe
3+), the precipitation reagent that adds phosphorous acid group is prepared the presoma-ferric phosphate of LiFePO4.Chinese patent 200910304079.6 discloses a kind of method of producing battery-grade ferrous oxalate by using ferrous sulfate as titanium pigment byproduct, the method technological process is simple, the rate of recovery of iron is up to 99.9%, but used expensive complexing agent and surfactant, restricted the practical application of the method.Two patents all are based on the sulfate process titanium dioxide production technology, and " three wastes " problem is serious, faces the condition that is eliminated.Up to now, the volatile acid leaching ilmenite that has no based on reusable edible prepares the ferrous oxalate presoma, and it is prepared the report of ferrous silicate lithium anode material as source of iron.
Summary of the invention
The volatile acid that technical problem to be solved by this invention provides a kind of reusable edible leaches the method that ilmenite prepares the ferrous oxalate presoma, and it is prepared ferrous silicate lithium anode material as source of iron.
The technical solution adopted in the present invention is:
A kind of method that is prepared ferrous silicate lithium anode material by ilmenite is characterized in that step is as follows:
Step 1, with the ilmenite ball milling to d (50)=1 ~ 6 μ m, reflux under normal pressure with volatile acid and to leach ilmenite, the mass ratio of volatile acid and ilmenite is 1.1 ~ 1.9:1, leach 0.5 ~ 24 h under 120 ~ 140 ℃ of temperature, after reaction finishes, adopt refrigerated centrifuge to wash to get rich titanium slag and Fu Tie leachate;
Step 2, in rich iron leachate, add reducing agent, be heated to 40 ~ 80 ℃, reaction 0.5 ~ 5 h, after reaction finished, cold filtration was removed impurity and is got rich Fe
2+Treatment fluid;
Step 3, to rich Fe
2+Add in the treatment fluid and contain oxalate precipitation reagent (saturated solution), simultaneously with the pH=5 of ammoniacal liquor control reaction system ± 0.5, after the reaction with the gained washing of precipitate, centrifugal, dry to get the ferrous oxalate presoma, it is prepared ferrous silicate lithium anode material as source of iron.
Volatile acid described in the step 1 of the present invention is one or more in hydrochloric acid, nitric acid, hydrobromic acid, the hydroiodic acid, the molar concentration 3 ~ 9mol/L of volatile acid.
Reducing agent described in the step 2 of the present invention is one or more in vitamin C, Fe powder, the Mg powder.
The oxalate precipitation reagent (saturated solution) that contains described in the step 3 of the present invention is in the oxalic acid, ammonium oxalate, sodium oxalate, potassium oxalate, potassium binoxalate, lithium oxalate one or more.
Advantage of the present invention embodies in the following areas: 1, the present invention adopts that reserves are abundant, cheap ilmenite is raw material, adopts the volatile acid of reusable edible as the medium that leaches ilmenite, reduces to pollute environmental friendliness; 2, adopt cheap Fe
3+Reducing agent and precipitation reagent are processed the ferrous oxalate presoma that rich iron leachate prepares metal ion mixing, and it is prepared ferrous silicate lithium anode material as source of iron, final doped metallic elements is evenly distributed in the ferrous silicate lithium anode material, solved the problem that doped metallic elements is difficult to be mixed, can improve the conductivity of ferrous silicate lithium anode material, and then improve its chemical property; In a word, the invention provides that a kind of raw material reserves are abundant, technological process is simple, energy consumption is little, cost is low, eco-friendly method, leach ilmenite by the reusable edible volatile acid and prepare the ferrous oxalate presoma, and it is prepared ferrous silicate lithium anode material as source of iron.
Description of drawings
Fig. 1 is the process chart for preparing ferrous silicate lithium anode material from ilmenite.
Fig. 2 is embodiment 1 ferrous oxalate presoma scanning electron microscope (SEM) photograph.
Fig. 3 is the XRD figure of embodiment 1 ferrous oxalate presoma.
Fig. 4 is that embodiment 1 ferrous oxalate presoma is the scanning electron microscope (SEM) photograph of the ferrous silicate lithium anode material of source of iron preparation.
Fig. 5 is the XRD figure of the ferrous silicate lithium anode material of embodiment 1 ferrous oxalate presoma preparation.
Fig. 6 is the charging and discharging curve of ferrous silicate lithium anode material under the 0.1C electric current of embodiment 1 ferrous oxalate presoma preparation.
Embodiment
The present invention is further described below in conjunction with drawings and Examples, and embodiment further replenishes and explanation of the present invention, rather than limitation of the present invention.
Embodiment 1:
(1) with 10g ilmenite ball milling to d (50)=3.217 μ m, reflux under normal pressure with the hydrochloric acid of molar concentration 7mol/L and to leach ilmenite, the mass ratio 1.5:1 of hydrochloric acid and ilmenite, leach 24 h under 130 ℃ of temperature, after reaction finished, refrigerated centrifuge washed to get rich titanium slag and Fu Tie leachate;
(2) will add vitamin C in the rich iron leachate of gained in the step (1), be heated to 50 ℃ and react 5 h, after reaction finishes, cold filtration is removed impurity, add again saturated oxalic acid hydrogen potassium, and with the pH=5 of ammoniacal liquor control reaction system, after the reaction with the gained washing of precipitate, centrifugal, dry to get the ferrous oxalate presoma.Getting the ferrous oxalate presoma is source of iron, adds silicon source, lithium source by stoichiometric proportion, and adds carbon source, prepares lithium ferrosilicon silicate/carbon composite cathode material by sol-gal process.
Embodiment 2:
(1) with 10g ilmenite ball milling to d (50)=3.217 μ m, reflux under normal pressure with the hydrobromic acid of molar concentration 7mol/L and to leach ilmenite, the mass ratio 1.5:1 of hydrobromic acid and ilmenite, leach 16 h under 130 ℃ of temperature, after reaction finished, refrigerated centrifuge washed to get rich titanium slag and Fu Tie leachate;
(2) will add the Fe powder in the rich iron leachate of gained in the step (1), be heated to 50 ℃ and react 5 h, after reaction finishes, cold filtration is removed impurity, add again the saturated oxalic acid ammonium, and with the pH=5 of ammoniacal liquor control reaction system, after the reaction with the gained washing of precipitate, centrifugal, dry to get the ferrous oxalate presoma.Getting the ferrous oxalate presoma is source of iron, adds silicon source, lithium source by stoichiometric proportion, and adds carbon source, prepares lithium ferrosilicon silicate/carbon composite cathode material by sol-gal process.
Embodiment 3:
(1) with 10g ilmenite ball milling to d (50)=3.217 μ m, reflux under normal pressure with the nitric acid of molar concentration 7mol/L and to leach ilmenite, the mass ratio 1.5:1 of nitric acid and ilmenite, leach 12 h under 130 ℃ of temperature, after reaction finished, refrigerated centrifuge washed to get rich titanium slag and Fu Tie leachate;
(2) will add the Mg powder in the rich iron leachate of gained in the step (1), be heated to 50 ℃ and react 5 h, after reaction finishes, cold filtration is removed impurity, add again saturated oxalic acid, and with the pH=5 of ammoniacal liquor control reaction system, after the reaction with the gained washing of precipitate, centrifugal, dry to get the ferrous oxalate presoma.Getting the ferrous oxalate presoma is source of iron, adds silicon source, lithium source by stoichiometric proportion, and adds carbon source, prepares lithium ferrosilicon silicate/carbon composite cathode material by sol-gal process.
Although the present invention is described in each preferred embodiment, but the technical staff that is familiar with of this area easily understands the present invention and is not limited to above-mentioned example and describes, it can be carried out changes and improvements by multiple alternate manner, and does not break away from the spirit and scope of setting forth in the claim of the present invention.
Claims (4)
1. method that is prepared ferrous silicate lithium anode material by ilmenite, it is characterized in that step is as follows: step 1, with the ilmenite ball milling to d (50)=1 ~ 6 μ m, reflux under normal pressure with volatile acid and to leach ilmenite, the mass ratio of volatile acid and ilmenite is 1.1 ~ 1.9:1, leach 0.5 ~ 24 h under 120 ~ 140 ℃ of temperature, after reaction finished, refrigerated centrifuge washed to get rich titanium slag and Fu Tie leachate;
Step 2, add reducing agent in rich iron leachate, be heated to 40 ~ 80 ℃ and react 0.5 ~ 5 h, after reaction finished, cold filtration was removed impurity and is got rich Fe
2+Treatment fluid;
Step 3, to rich Fe
2+Drip the precipitation reagent (saturated solution) that contains oxalate in the treatment fluid, simultaneously with the pH=5 of ammoniacal liquor control reaction system ± 0.5, after the reaction with the gained washing of precipitate, centrifugal, dry to get the ferrous oxalate presoma, it is prepared ferrous silicate lithium anode material as source of iron.
2. a kind of method that is prepared ferrous silicate lithium anode material by ilmenite according to claim 1, it is characterized in that the volatile acid described in the step 1 is one or more in hydrochloric acid, nitric acid, hydrobromic acid, the hydroiodic acid, the molar concentration 3 ~ 9mol/L of volatile acid.
3. a kind of method that is prepared ferrous silicate lithium anode material by ilmenite according to claim 1 is characterized in that the reducing agent described in the step 2 is one or more in vitamin C, Fe powder, the Mg powder.
4. a kind of method that is prepared ferrous silicate lithium anode material by ilmenite according to claim 1 is characterized in that the oxalate precipitation reagent that contains described in the step 3 is in oxalic acid, ammonium oxalate, sodium oxalate, potassium oxalate, potassium binoxalate, the lithium oxalate one or more.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112018340A (en) * | 2019-05-31 | 2020-12-01 | 中南大学 | Carbon-coated vanadium titanium sodium fluorophosphate composite material, preparation method thereof and application thereof in sodium-electricity |
| CN112028126A (en) * | 2019-06-03 | 2020-12-04 | 湖南杉杉能源科技股份有限公司 | Small-particle-size lithium supplement additive Li5FeO4Preparation method and application of |
| CN112805851A (en) * | 2018-07-27 | 2021-05-14 | 福恩能源公司 | Negative electrode for electrochemical cell |
| CN113830774A (en) * | 2021-10-18 | 2021-12-24 | 浙江长兴中俄新能源材料技术研究院有限公司 | Method for preparing carbon composite lithium ferrous silicate by ilmenite based on sol-gel method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101709374A (en) * | 2009-11-25 | 2010-05-19 | 中南大学 | Method for preparing precursors of lithium titanate and lithium iron phosphate by comprehensively using ilmenite |
| CN102201574A (en) * | 2011-04-14 | 2011-09-28 | 武汉理工大学 | Oxygen-vacancy-containing lithium ferrous silicate and carbon composite anode material and preparation method |
-
2013
- 2013-07-09 CN CN2013102850932A patent/CN103326022A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101709374A (en) * | 2009-11-25 | 2010-05-19 | 中南大学 | Method for preparing precursors of lithium titanate and lithium iron phosphate by comprehensively using ilmenite |
| CN102201574A (en) * | 2011-04-14 | 2011-09-28 | 武汉理工大学 | Oxygen-vacancy-containing lithium ferrous silicate and carbon composite anode material and preparation method |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112805851A (en) * | 2018-07-27 | 2021-05-14 | 福恩能源公司 | Negative electrode for electrochemical cell |
| CN112018340A (en) * | 2019-05-31 | 2020-12-01 | 中南大学 | Carbon-coated vanadium titanium sodium fluorophosphate composite material, preparation method thereof and application thereof in sodium-electricity |
| CN112028126A (en) * | 2019-06-03 | 2020-12-04 | 湖南杉杉能源科技股份有限公司 | Small-particle-size lithium supplement additive Li5FeO4Preparation method and application of |
| CN113830774A (en) * | 2021-10-18 | 2021-12-24 | 浙江长兴中俄新能源材料技术研究院有限公司 | Method for preparing carbon composite lithium ferrous silicate by ilmenite based on sol-gel method |
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Address after: 264200 Qu Qu Industrial Park, sheep town, Huancui District, Shandong, Weihai Applicant after: Weihai Tosun Energy Technology Co., Ltd. Address before: 264204 Qu Qu Industrial Park, sheep town, Huancui District, Shandong, Weihai Applicant before: Shandong Weigao Dongsheng New Energy Technology Co., Ltd. |
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