CN105236494A - Method for synthesizing alpha-LiFeO2 nanoparticles in one-step mode with Qinghai salt lake brine as raw material - Google Patents
Method for synthesizing alpha-LiFeO2 nanoparticles in one-step mode with Qinghai salt lake brine as raw material Download PDFInfo
- Publication number
- CN105236494A CN105236494A CN201510678815.XA CN201510678815A CN105236494A CN 105236494 A CN105236494 A CN 105236494A CN 201510678815 A CN201510678815 A CN 201510678815A CN 105236494 A CN105236494 A CN 105236494A
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- salt lake
- lithium
- organic phase
- raw material
- aqueous solution
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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 synthesizing alpha-LiFeO2 nanoparticles in a one-step mode with Qinghai salt lake brine as a raw material. The method includes the following steps that firstly, the pH of the Qinghai salt lake brine containing lithium is adjusted, FeCl3.6H2O is added, an organic mixture is added, stirring is carried out for extraction, and an organic phase is separated out; secondly, the organic phase and a LiOH aqueous solution are placed in a high-pressure kettle and stirred at room temperature and react in a sealed mode at the temperature of 150-250 DEG C under the stirring reaction; centrifugation is carried out, precipitate is separated out, washed and dried, and the alpha-LiFeO2 nanoparticles are obtained. The method is easy and convenient to operate, high in feasibility and capable of saving time. Meanwhile, the cheap Qinghai salt lake brine serves as the raw material, environmental friendliness is achieved, and production cost is low. After reaction, the organic phase is filtered, washed and then used for extraction again, a lithium salt solution used in synthesis is filtered and then can be used for the high-pressure reaction process again, repeated use can be achieved, and resources are fully used.
Description
Technical field
The invention belongs to electrochemical material preparation field, be specifically related to α-LiFeO
2the preparation method of nanoparticle.
Background technology
Lithium ion battery has plurality of advantages, widespread use in various portable electric appts.In addition, lithium ion battery is also the potential energy source of electric automobiles, space industry.Widespread use in production, life adds the demand to lithium raw material, also promotes constantly bringing forth new ideas of Study on Li-ion batteries.Research and produce that cost is low, reversible capacity is high, the Olivine-type Cathode Material in Li-ion Batteries of green non-pollution, be of great practical significance.
α-LiFeO
2there is the high theoretical specific capacity of 282mAh/g, and iron content is abundant, wide material sources, low price, environmental friendliness, nontoxic pollution-free, is one of study hotspot of current anode material for lithium-ion batteries.α-the LiFeO that the people such as M.M.Rahman adopt molten-salt growth method to synthesize
2nano material, under the electric current of 0.5C, initial discharge specific storage reaches 284mAh/g, and the initial discharge specific storage after coated with carbon reaches 287mAh/g, still up to 230mAh/g after circulation 100 circle.At present, α-LiFeO
2also be applied among lithium ion battery negative material, ultracapacitor.Improvement synthesis α-LiFeO
2method, save production cost, significant.
Salt lake brine is the important sources of elemental lithium.A certain amount of FeCl is added in salt lake brine
3after, with tributyl phosphate (TBP) for lithium is carried in extraction agent extraction, comparatively ripely at present put forward one of lithium method.If the lithium extracted in salt lake brine can be directly used in α-LiFeO
2preparation, then production cost can be made greatly to reduce.
Summary of the invention
The object of this invention is to provide one and salt lake brine is carried lithium technology and α-LiFeO
2synthetic method combine, to be extracted into the Fe in organic phase from salt lake brine
3+and Li
+for raw material, take salt lake brine as raw material one-step synthesis α-LiFeO by what add appropriate necessary raw material
2the method of nanoparticle.
Technical scheme of the present invention is summarized as follows:
Take Qinghai Salt Lake Bittern as raw material one-step synthesis α-LiFeO
2the method of nanoparticle, comprises the steps:
1) pH of the Qinghai Salt Lake Bittern regulated containing lithium is 1 ~ 2, adds FeCl
36H
2o makes Li
+/ Fe
3+mol ratio is 0.5 ~ 1, adds the organic mixture of Qinghai Salt Lake Bittern volume 1 ~ 3 times, stirs 0.5 ~ 1h and extracts, isolate organic phase, and described organic mixture is that the tributyl phosphate of 1 ~ 4:1 and thinner form by volume ratio;
2) ratio of 1:1 ~ 5 by volume, be the LiOH aqueous solution of 1 ~ 6mol/L or the mixed aqueous solution of Aqueous Lithium Salts or LiOH and lithium salts by organic phase and lithium concentration, be placed in autoclave, stirred at ambient temperature 5-30min, more under agitation in 150 DEG C ~ 250 DEG C sealed reaction 0.5 ~ 9h; Centrifugal, isolate precipitation, precipitation is ammonium salt aqueous solution or dilute hydrochloric acid, water and the washing with alcohol of 10% successively by ethanol, water, mass concentration, and drying, namely obtains α-LiFeO
2nanoparticle.
Thinner is preferred: methyl iso-butyl ketone (MIBK) or sulfonated kerosene.
In the mixed aqueous solution of LiOH and lithium salts, preferred 1:0.1 ~ 3 of mol ratio of LiOH and lithium salts.
Lithium salts preferred LiCl, CH
3cOOLi, Li
2cO
3, Li
2sO
4or LiNO
3.
The preferred NH of ammonium salt
4cl, (NH
4)
2sO
4, (NH
4)
2cO
3, NH
4hCO
3or NH
4nO
3.
Advantage of the present invention: method of the present invention is easy and simple to handle, and feasibility is strong.Traditionally, need after extraction first Li, Fe to be separated, after producing pure lithium product, then among the preparation being applied to anode material for lithium-ion batteries.Present invention, avoiding above-mentioned series of complex step, operate easier, saved the time.Meanwhile, the present invention is with the Qinghai Salt Lake Bittern of cheapness for raw material, and environmental friendliness, production cost is low, good in economic efficiency.In addition, after reaction terminates, just again can be used for extraction process after organic phase being filtered with distilled water wash, lithium salt solution used in synthesis after filtering also can again for reaction under high pressure process, and all can use by iterative cycles, the utilization of resources is abundant.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the product of preparation in the embodiment of the present invention 1.
Fig. 2 is the SEM figure of the product of preparation in the embodiment of the present invention 1.
Fig. 3 is the TEM figure of the product of preparation in the embodiment of the present invention 1.
Fig. 4 is the SEM figure of the product of preparation in the embodiment of the present invention 2.
Fig. 5 is the TEM figure of the product of preparation in the embodiment of the present invention 2.
Embodiment
Below in conjunction with specific embodiment, content of the present invention is described further.
Embodiment 1
Take Qinghai Salt Lake Bittern as raw material one-step synthesis α-LiFeO
2the method of nanoparticle, comprises the steps:
1) pH of the Qinghai Salt Lake Bittern regulated containing lithium is 1.5, adds FeCl
36H
2o makes Li
+/ Fe
3+mol ratio is 0.78, adds the organic mixture of Qinghai Salt Lake Bittern volume 2 times, stirs 0.5h and extracts, isolate organic phase, and described organic mixture is that the tributyl phosphate of 4:1 and sulfonated kerosene form by volume ratio;
2) ratio of 1:1.9 by volume, is the LiOH aqueous solution of 2.61mol/L by organic phase and lithium concentration, is placed in autoclave, stirred at ambient temperature 30min, more under agitation in 210 DEG C of sealed reaction 1h; Centrifugal, obtain precipitation and liquid phase; Precipitation is the NH of 10% by ethanol, water, mass concentration successively
4the Cl aqueous solution, water and washing with alcohol, dry, namely obtain α-LiFeO
2nanoparticle.The stratified liquid obtained is two-phase, and be separated the upper and lower, upper strata is organic phase, filters and uses distilled water wash, just can again for extraction process; Lower floor is lithium salt solution, can again for reaction under high pressure process after filtration.
The XRD figure of products obtained therefrom as shown in Figure 1, all diffraction peaks all with standard α-LiFeO
2spectrum peak-to-peak position is identical, inclusion-free peak.As shown in Figure 2, TEM figure as shown in Figure 3 for the SEM figure of product.
With (NH
4)
2cO
3, NH
4hCO
3or NH
4nO
3substitute the NH of the present embodiment
4cl, other same the present embodiment, can obtain α-LiFeO
2nanoparticle.
Embodiment 2
Take Qinghai Salt Lake Bittern as raw material one-step synthesis α-LiFeO
2the method of nanoparticle, comprises the steps:
1) pH of the Qinghai Salt Lake Bittern regulated containing lithium is 1, adds FeCl
36H
2o makes Li
+/ Fe
3+mol ratio is 0.5, adds the organic mixture of Qinghai Salt Lake Bittern volume 1 times, stirs 0.5h and extracts, isolate organic phase, and described organic mixture is that the tributyl phosphate of 2:1 and methyl iso-butyl ketone (MIBK) form by volume ratio;
2) ratio of 1:1 by volume, is the LiCl aqueous solution of 6mol/L by organic phase and lithium concentration, is placed in autoclave, stirred at ambient temperature 20min, more under agitation in 250 DEG C of sealed reaction 0.5h; Centrifugal, isolate precipitation, precipitation uses ethanol, water, dilute hydrochloric acid, water and washing with alcohol successively, dry, namely obtains α-LiFeO
2nanoparticle.
The XRD figure of products obtained therefrom is similar to the result of embodiment 1, and as shown in Figure 4, TEM figure as shown in Figure 5 for SEM figure.Embodiment 3
Take Qinghai Salt Lake Bittern as raw material one-step synthesis α-LiFeO
2the method of nanoparticle, comprises the steps:
1) pH of the Qinghai Salt Lake Bittern regulated containing lithium is 2, adds FeCl
36H
2o makes Li
+/ Fe
3+mol ratio is 1, adds the organic mixture of Qinghai Salt Lake Bittern volume 3 times, stirs 1h and extracts, isolate organic phase, and described organic mixture is that the tributyl phosphate of 1:1 and methyl iso-butyl ketone (MIBK) form by volume ratio;
2) ratio of 1:5 by volume, is LiOH and the CH of 1mol/L by organic phase and lithium concentration
3the mixed aqueous solution of COOLi, is placed in autoclave, stirred at ambient temperature 5min, more under agitation in 150 DEG C of sealed reaction 9h; Centrifugal, isolate precipitation, precipitation is the (NH of 10% by ethanol, water, mass concentration successively
4)
2sO
4, water and washing with alcohol, dry, namely obtain α-LiFeO
2nanoparticle.Wherein: LiOH and CH
3the mol ratio of COOLi is 1:0.1.XRD figure, SEM figure is similar with the result of embodiment 1 with TEM figure.
Experiment proves: LiOH and CH
3the mol ratio of COOLi can be the Arbitrary Digit of 1:0.1 ~ 3, can also use Li
2cO
3, Li
2sO
4or LiNO
3substitute CH
3cOOLi, other same the present embodiment, prepares the α-LiFeO similar to the present embodiment
2nanoparticle.
Claims (5)
1. be raw material one-step synthesis α-LiFeO with Qinghai Salt Lake Bittern
2the method of nanoparticle, is characterized in that comprising the steps:
1) pH of the Qinghai Salt Lake Bittern regulated containing lithium is 1 ~ 2, adds FeCl
36H
2o makes Li
+/ Fe
3+mol ratio is 0.5 ~ 1, adds the organic mixture of Qinghai Salt Lake Bittern volume 1 ~ 3 times, stirs 0.5 ~ 1h and extracts, isolate organic phase, and described organic mixture is that the tributyl phosphate of 1 ~ 4:1 and thinner form by volume ratio;
2) ratio of 1:1 ~ 5 by volume, be the LiOH aqueous solution of 1 ~ 6mol/L or the mixed aqueous solution of Aqueous Lithium Salts or LiOH and lithium salts by organic phase and lithium concentration, be placed in autoclave, stirred at ambient temperature 5-30min, more under agitation in 150 DEG C ~ 250 DEG C sealed reaction 0.5 ~ 9h; Centrifugal, isolate precipitation, precipitation is ammonium salt aqueous solution or dilute hydrochloric acid, water and the washing with alcohol of 10% successively by ethanol, water, mass concentration, and drying, namely obtains α-LiFeO
2nanoparticle.
2. method according to claim 1, is characterized in that described thinner is methyl iso-butyl ketone (MIBK) or sulfonated kerosene.
3. method according to claim 1, is characterized in that in the mixed aqueous solution of described LiOH and lithium salts, and the mol ratio of LiOH and lithium salts is 1:0.1 ~ 3.
4. the method according to claim 1 or 3, is characterized in that described lithium salts is LiCl, CH
3cOOLi, Li
2cO
3, Li
2sO
4or LiNO
3.
5. method according to claim 1, is characterized in that described ammonium salt is NH
4cl, (NH
4)
2sO
4, (NH
4)
2cO
3, NH
4hCO
3or NH
4nO
3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510678815.XA CN105236494A (en) | 2015-10-19 | 2015-10-19 | Method for synthesizing alpha-LiFeO2 nanoparticles in one-step mode with Qinghai salt lake brine as raw material |
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|---|---|---|---|
| CN201510678815.XA CN105236494A (en) | 2015-10-19 | 2015-10-19 | Method for synthesizing alpha-LiFeO2 nanoparticles in one-step mode with Qinghai salt lake brine as raw material |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106611846A (en) * | 2017-01-17 | 2017-05-03 | 扬州大学 | Synthesis method of alpha-LiFeO2/porous carbon composite material of lithium-ion battery anode |
| CN107445210A (en) * | 2017-07-03 | 2017-12-08 | 电子科技大学 | A kind of high power capacity iron-based anode material for lithium-ion batteries α LiFeO2Preparation method |
Citations (4)
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|---|---|---|---|---|
| JPH01119520A (en) * | 1987-10-31 | 1989-05-11 | Toda Kogyo Corp | Lithium ferrite fine particulate powder and its production |
| JPH08217453A (en) * | 1995-02-17 | 1996-08-27 | Agency Of Ind Science & Technol | Production of lithium ferrite powder and heat-resistant yellow pigment and magnetic material therefrom |
| CN102992358A (en) * | 2012-02-24 | 2013-03-27 | 中国科学院青海盐湖研究所 | Method for extracting lithium salt from lithium brine |
| CN104692465A (en) * | 2015-02-04 | 2015-06-10 | 天津大学 | Preparation method of alpha-LiFeO2 nano powder for positive pole material of lithium-ion battery |
-
2015
- 2015-10-19 CN CN201510678815.XA patent/CN105236494A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01119520A (en) * | 1987-10-31 | 1989-05-11 | Toda Kogyo Corp | Lithium ferrite fine particulate powder and its production |
| JPH08217453A (en) * | 1995-02-17 | 1996-08-27 | Agency Of Ind Science & Technol | Production of lithium ferrite powder and heat-resistant yellow pigment and magnetic material therefrom |
| CN102992358A (en) * | 2012-02-24 | 2013-03-27 | 中国科学院青海盐湖研究所 | Method for extracting lithium salt from lithium brine |
| CN104692465A (en) * | 2015-02-04 | 2015-06-10 | 天津大学 | Preparation method of alpha-LiFeO2 nano powder for positive pole material of lithium-ion battery |
Non-Patent Citations (1)
| Title |
|---|
| 贾旭宏等: "磷酸三丁酯萃取体系从盐湖卤水提取锂", 《无机盐工业》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106611846A (en) * | 2017-01-17 | 2017-05-03 | 扬州大学 | Synthesis method of alpha-LiFeO2/porous carbon composite material of lithium-ion battery anode |
| CN107445210A (en) * | 2017-07-03 | 2017-12-08 | 电子科技大学 | A kind of high power capacity iron-based anode material for lithium-ion batteries α LiFeO2Preparation method |
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Application publication date: 20160113 |
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