CN102637870A - Preparation method of anode active material, lithium iron phosphate - Google Patents
Preparation method of anode active material, lithium iron phosphate Download PDFInfo
- Publication number
- CN102637870A CN102637870A CN2012101034294A CN201210103429A CN102637870A CN 102637870 A CN102637870 A CN 102637870A CN 2012101034294 A CN2012101034294 A CN 2012101034294A CN 201210103429 A CN201210103429 A CN 201210103429A CN 102637870 A CN102637870 A CN 102637870A
- Authority
- CN
- China
- Prior art keywords
- aqueous solution
- iron phosphate
- active material
- positive active
- material preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a preparation method of an anode active material, lithium iron phosphate. The preparation method comprises the following steps of: adding mixed solution of FeSO4 aqueous solution and H3PO4 aqueous solution into a preheating reaction kettle, and simultaneously adding LiOH aqueous solution and surfactant aqueous solution into the preheating reaction kettle on line; preheating and mixing all the solution at a temperature of 120 DEG C and then adding all the solution into a reactor at a temperature of 550 DEG C to 700 DEG C for reaction; cooling the obtained reaction solution to a room temperature in a cooling chamber, and then filtering the reaction solution; and washing and drying an obtained filter cake to obtain an aluminum iron phosphate product, wherein the molar ratio of FeSO4, H3PO4 to LiOH equals to 1:1:3. Compared with the prior art, the preparation method can be applied to the large-scale production of the lithium iron phosphate material.
Description
Technical field
The invention belongs to new material and new energy field, especially relate to a kind of iron phosphate serving as positive active material preparation method, its emphasis is a kind of method that adopts continuous hydro thermal method synthesizing iron lithium phosphate positive electrode.
Background technology
Energy crisis and environmental pollution have become two important restraining factors of human kind sustainable development, numerous and confused energy-saving and cost-reducing target, adopt an effective measure the realization energy and the sustainable development of economy formulated in countries in the world.The research and development of new forms of energy are bases that human society is realized sustainable development, and since the nineties in last century, lithium ion battery is as the novel green power supply, in electronic product markets such as mobile phone, notebook computers.Along with continuous advancement in technology, requirements at the higher level have been proposed for the stability and security type of lithium ion battery.Adopt LiFePO4 to have high-energy-density as the lithium ion of positive electrode active materials; Low-cost; And abundant raw material; Characteristics such as environmentally friendly; Lithium ion battery is being used widely aspect Vehicular dynamic battery, valley power storage, wind-force and solar power generation electrical power storage, emergency electric power deposit and the automobile-used accessory power supply equal energy source gradually, and iron phosphate serving as positive active material has crucial strategic importance to the development that promotes ev industry and novel energy-storing industry, and vast market prospect and remarkable social benefit are arranged.
1997, the U.S. J.B Goodenough seminar reported first LiFePO4 of olivine-type (LiFePO4) can be used for anode material for lithium-ion batteries, its electrode potential with respect to lithium is 3.5 volts; Theoretical capacity is 170mAh/g, and LiFePO 4 material has also that also to have security performance fabulous, can adapt to advantages such as extreme condition; About 300 degree, just blast; Environmentally friendly, advantage such as with low cost is considered to the desirable positive electrode of power-type lithium ion battery of new generation.But also exist electronic conductivity low, shortcomings such as big multiplying power discharging property difference have hindered it as the large-scale application of electrokinetic cell on electric automobile.
At present common lithium iron phosphate preparation method has solid phase method, and hydro-thermal is synthetic, template synthetic method, microwave method etc.1) high temperature solid-state method, this method technology is simple, but the product particle is inhomogeneous, and crystalline form is random, and particle size distribution range is wide, and properties of product are not good, influence degradation under the chemical property.2) hydro thermal method, have simple to operate, thing mutually evenly, particle diameter is little, but is difficult to large-scale production.3) template synthetic method, complicated operation, excessive cycle is difficult to suitability for industrialized production.4) microwave method, similar with high temperature solid-state method, simple to operate, process weak point consuming time, but large-scale application is still difficult.
Summary of the invention
The object of the invention is exactly the iron phosphate serving as positive active material preparation method that a kind of suitable suitability for industrialized production is provided for the defective that overcomes above-mentioned prior art existence.
The object of the invention can be realized through following technical scheme: a kind of iron phosphate serving as positive active material preparation method is characterized in that this method specifically may further comprise the steps: with FeSO
4The aqueous solution and H
3PO
4The mixed liquor adding of the aqueous solution preheats in the agitated reactor; Preheat the online aqueous solution that adds the LiOH aqueous solution and surfactant in the agitated reactor at this simultaneously, after 120 ℃ of preheatings mix, add reactor 550-700 ℃ of reaction; The gained reactant liquor is cooled to room temperature in cooling chamber; Filter, the gained filter cake obtains ferric phosphate aluminium finished product, described FeSO through washing, drying
4, H
3PO
4, LiOH mol ratio be 1: 1: 3.
Described FeSO
4The aqueous solution and H
3PO
4The online adding speed ratio of the aqueous solution of the mixed liquor of the aqueous solution and the LiOH aqueous solution, surfactant is 1: 1: (3-6).
Described FeSO
4The concentration of the aqueous solution is 0.01～0.05M.
The concentration of the aqueous solution of described surfactant is (0.1-0.15) g/ml.
Described surfactant is a kind of in lauryl sodium sulfate, polyethylene glycols (PEG), polypropylene glycols (PPG), AEO (AEO), the NPE (TX).
Described filtration is to adopt stainless steel filter.
Deionized water wash is adopted in described washing.
Described drying is dry in 325-560 ℃ vacuum drying oven.
The present invention has adopted continuous hydro thermal method synthesizing iron lithium phosphate positive electrode, and its operation principle is:
FeSO
4+H
3PO
4+3LiOH→LiFePO
4↓+Li2SO
4+3H
2O
Compared with prior art, the present invention has adopted the process route of continuous hydro thermal method synthesizing iron lithium phosphate positive electrode, has realized the large-scale production LiFePO 4 material.Be characterized in adopting water, as reaction medium, continuous fast reaction synthesizing iron lithium phosphate nano anode material in pipeline.
Description of drawings
Fig. 1 is LiFePO4 preparation technology figure;
Fig. 2 is the pipe reaction equipment drawing;
The XRD figure spectrum of Fig. 3 embodiment 1 and 2 gained lithium iron phosphate positive materials;
The SEM collection of illustrative plates of Fig. 4 embodiment 1 and 2 gained lithium iron phosphate positive materials;
The multiplying power discharging curve of Fig. 5 embodiment 1 and 2 gained lithium iron phosphate positive materials.
Embodiment
Elaborate in the face of embodiments of the invention down, present embodiment is implemented under with technical scheme prerequisite of the present invention, has provided detailed execution mode and specific operation process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1:
As shown in Figure 1, utilize balance to take by weighing FeSO
47H
2O (8.34g, 0.03mol), 85%H
3PO
4(3.36g 0.03mol), pours in the 1000ml dissolve measuring bottle, adds deionized water to scale, and concentration 0.03M is subsequent use.Take by weighing LiOH1H
2(3.78g 0.09mol) pours in the 1000ml dissolve measuring bottle O, adds deionized water to scale, and concentration is 0.09M; Take by weighing lauryl sodium sulfate 1g, pour in the 1000ml dissolve measuring bottle, add deionized water to scale; Concentration is that 0.1% above-mentioned solution is put into reaction basin separately, in preheating still, is heated to 120 ℃, gets into the pipeline reactor reaction (as shown in Figure 2) of band heater and thermosistor; Reaction temperature is 650-680 ℃ of reaction, and reactant liquor is cool to room temperature in cooler, reacting liquid filtering; The cakes with deionized water washing, the dry LiFePO4 finished product that gets in 355-360 ℃ of following vacuum drying oven is shown in Fig. 3-5; Can find out that gained LiFePO4 finished product has the perfect crystal structure, obtain particle size at the 1-2 micron, the pure phase lithium iron phosphate positive electrode of consistent appearance; And has good conductive characteristic.Flow velocity ratio: LiOH (1ml/min): FeSO wherein
4-H
3PO
4(1ml/min): deionized water (4ml/min).
Embodiment 2: as shown in Figure 1, and utilize balance to take by weighing FeSO
47H
2O (13.90g, 0.05mol), 85%H
3PO
4(5.60g 0.05mol), pours in the 1000ml dissolve measuring bottle, adds deionized water to scale, and concentration 0.05M is subsequent use.Take by weighing LiOH1H
2(6.32g 0.15mol) pours in the 1000ml dissolve measuring bottle O, adds deionized water to scale; Concentration is 0.09M, takes by weighing lauryl sodium sulfate 1.5g, pours in the 1000ml dissolve measuring bottle; Add deionized water to scale, concentration is that 0.15% above-mentioned solution is put into reaction basin separately, in preheating still, is heated to 120 ℃; The reaction of entering pipeline reactor, reaction temperature is 600-625 ℃ of reaction, reactant liquor is cool to room temperature in cooler; Reacting liquid filtering, cakes with deionized water washing, the dry LiFePO4 finished product that gets in 345-360 ℃ of following vacuum drying oven.Shown in Fig. 3-5, can find out that gained LiFePO4 finished product has the perfect crystal structure, obtain particle size at the 1-2 micron, the pure phase lithium iron phosphate positive electrode of consistent appearance; And has good conductive characteristic.Flow velocity ratio: LiOH (1ml/min): FeSO wherein
4-H
3PO
4(1ml/min): deionized water (5ml/min).
Embodiment 3:
A kind of iron phosphate serving as positive active material preparation method, this method specifically may further comprise the steps: with FeSO
4The aqueous solution (concentration is 0.01M), H
3PO
4Aqueous solution preheats in the agitated reactor with the speed adding of 1ml/min; Preheat simultaneously that the speed with 1ml/min adds the LiOH aqueous solution in the agitated reactor at this; Add the aqueous solution (concentration is 0.1g/ml) of polyethylene glycols (PEG) with the speed of 3ml/min, after 120 ℃ of preheatings mix, add reactor 550-600 ℃ of reaction; The gained reactant liquor is cooled to room temperature in cooling chamber; The employing stainless steel filter filters, and the gained filter cake is through deionised water, drying obtains ferric phosphate aluminium finished product, described FeSO in 325-350 ℃ vacuum drying oven
4, H
3PO
4, LiOH mol ratio be 1: 1: 3.
Embodiment 4:
A kind of iron phosphate serving as positive active material preparation method, this method specifically may further comprise the steps: with FeSO
4The aqueous solution (concentration is 0.05M), H
3PO
4Aqueous solution preheats in the agitated reactor with the speed adding of 1ml/min; Preheat simultaneously that the speed with 1ml/min adds the LiOH aqueous solution in the agitated reactor at this; Add the aqueous solution (concentration is 0.15g/ml) of AEO (AEO) with the speed of 6ml/min, after 120 ℃ of preheatings mix, add reactor 650-700 ℃ of reaction; The gained reactant liquor is cooled to room temperature in cooling chamber; The employing stainless steel filter filters, and the gained filter cake is through deionised water, drying obtains ferric phosphate aluminium finished product, described FeSO in 535-560 ℃ vacuum drying oven
4, H
3PO
4, LiOH mol ratio be 1: 1: 3.
Claims (8)
1. an iron phosphate serving as positive active material preparation method is characterized in that, this method specifically may further comprise the steps: with FeSO
4The aqueous solution and H
3PO
4The mixed liquor adding of the aqueous solution preheats in the agitated reactor; Preheat the online aqueous solution that adds the LiOH aqueous solution and surfactant in the agitated reactor at this simultaneously, after 120 ℃ of preheatings mix, add reactor 550-700 ℃ of reaction; The gained reactant liquor is cooled to room temperature in cooling chamber; Filter, the gained filter cake obtains ferric phosphate aluminium finished product, described FeSO through washing, drying
4, H
3PO
4, LiOH mol ratio be 1: 1: 3.
2. a kind of iron phosphate serving as positive active material preparation method according to claim 1 is characterized in that described FeSO
4The aqueous solution and H
3PO
4The online adding speed ratio of the aqueous solution of the mixed liquor of the aqueous solution and the LiOH aqueous solution, surfactant is 1: 1: (3-6).
3. a kind of iron phosphate serving as positive active material preparation method according to claim 1 is characterized in that described FeSO
4The concentration of the aqueous solution is 0.01～0.05M.
4. a kind of iron phosphate serving as positive active material preparation method according to claim 1 is characterized in that, the concentration of the aqueous solution of described surfactant is (0.1-0.15) g/ml.
5. according to claim 1 or 4 described a kind of iron phosphate serving as positive active material preparation methods; It is characterized in that described surfactant is a kind of in lauryl sodium sulfate, polyethylene glycols (PEG), polypropylene glycols (PPG), AEO (AEO), the NPE (TX).
6. a kind of iron phosphate serving as positive active material preparation method according to claim 1 is characterized in that, described filtration is to adopt stainless steel filter.
7. a kind of iron phosphate serving as positive active material preparation method according to claim 1 is characterized in that, deionized water wash is adopted in described washing.
8. a kind of iron phosphate serving as positive active material preparation method according to claim 1 is characterized in that, described drying is dry in 325-560 ℃ vacuum drying oven.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101034294A CN102637870A (en) | 2012-04-10 | 2012-04-10 | Preparation method of anode active material, lithium iron phosphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101034294A CN102637870A (en) | 2012-04-10 | 2012-04-10 | Preparation method of anode active material, lithium iron phosphate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102637870A true CN102637870A (en) | 2012-08-15 |
Family
ID=46622177
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012101034294A Pending CN102637870A (en) | 2012-04-10 | 2012-04-10 | Preparation method of anode active material, lithium iron phosphate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102637870A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105439207A (en) * | 2015-11-20 | 2016-03-30 | 王立卓 | Method for preparing lithium nickel cobalt manganese oxide battery cathode material by using quick pipe reactor |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101327922A (en) * | 2008-07-07 | 2008-12-24 | 杭州赛诺索欧电池有限公司 | Preparation of LiFePO4 |
| CN101764215A (en) * | 2009-10-14 | 2010-06-30 | 孙琦 | Hydrothermal synthesis method for preparing iron phosphate lithium as anode material of lithium ion battery |
| CN101759173A (en) * | 2009-12-25 | 2010-06-30 | 北京工业大学 | Device for continuously producing LiFeP04 by utilizing hydro-thermal reaction in industry |
| KR20120023270A (en) * | 2010-09-01 | 2012-03-13 | 고려대학교 산학협력단 | Method of manufacturing lifepo4 for lithium secondary battery cathode material by using hydrothermal synthesis |
-
2012
- 2012-04-10 CN CN2012101034294A patent/CN102637870A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101327922A (en) * | 2008-07-07 | 2008-12-24 | 杭州赛诺索欧电池有限公司 | Preparation of LiFePO4 |
| CN101764215A (en) * | 2009-10-14 | 2010-06-30 | 孙琦 | Hydrothermal synthesis method for preparing iron phosphate lithium as anode material of lithium ion battery |
| CN101759173A (en) * | 2009-12-25 | 2010-06-30 | 北京工业大学 | Device for continuously producing LiFeP04 by utilizing hydro-thermal reaction in industry |
| KR20120023270A (en) * | 2010-09-01 | 2012-03-13 | 고려대학교 산학협력단 | Method of manufacturing lifepo4 for lithium secondary battery cathode material by using hydrothermal synthesis |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105439207A (en) * | 2015-11-20 | 2016-03-30 | 王立卓 | Method for preparing lithium nickel cobalt manganese oxide battery cathode material by using quick pipe reactor |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2020019311A1 (en) | Polyanionic sodium ion battery anode material and preparation method thereof | |
| CN105742622A (en) | Olivine-structured LiMPO<4> surface modification layered lithium-rich manganese-based positive electrode material and preparation method therefor | |
| CN102311109B (en) | Method for preparing LiFePO4/C composite cathode material by continuous reaction | |
| CN102867954B (en) | Method for synthesizing lithium iron phosphate anode material by adopting emulsion liquid phase | |
| CN101630733B (en) | LiFePO4/C preparation method | |
| CN103435104B (en) | A kind of preparation method of lithium ion battery negative electrode material-nano zinc ferrite | |
| CN102464309B (en) | Novel method for preparing lithium iron phosphate complex salt positive electrode materials from scrap iron, phosphoric acid and lithium hydroxide | |
| CN103594707A (en) | High-temperature solid-phase synthesis method of one-dimensional nano-sodion cell anode material NaxMnO2 | |
| CN103346323B (en) | A kind of with the preparation method of polystyrene microsphere and the polyethylene glycol carbon-coated LiFePO 4 for lithium ion batteries material that is carbon source | |
| CN103887499A (en) | Iron phosphate, lithium iron phosphate as well as preparation methods of iron phosphate and lithium iron phosphate | |
| CN103996836B (en) | A kind of preparation method of alloying silicon based anode material and application | |
| CN109742340A (en) | A kind of iron manganese phosphate for lithium composite material and preparation method, application | |
| CN102275890A (en) | Microwave-assisted synthesis method of nanometer lithium iron phosphate | |
| CN102903918B (en) | Preparation method for manganese phosphate lithium nanosheet | |
| CN104466110A (en) | Preparation method of high-performance lithium ion battery negative electrode material | |
| CN104269529B (en) | A kind of preparation method of lithium ion battery negative material boric acid vanadium | |
| CN105406071A (en) | High-rate lithium vanadium phosphate positive electrode material, and preparation method and application thereof | |
| CN101764217A (en) | Method for preparing nano-scale lithium iron phosphate | |
| CN104876203B (en) | Method for liquid-phase synthesis of nano spherical lithium battery anode material lithium iron phosphate | |
| CN108321390B (en) | Three-dimensional flower-shaped single crystal lithium iron phosphate and preparation method thereof | |
| CN107445210B (en) | High-capacity iron-based lithium ion battery anode material α -LiFeO2Preparation method of (1) | |
| CN102447099B (en) | New method for preparing lithium ferrous phosphate double-salt anode material by using iron chippings, phosphoric acid and lithium hydroxide | |
| CN102130328A (en) | Preparation method of vanadium lithium phosphate/carbon superfine powder positive pole material | |
| CN103367722A (en) | Preparation method of carbon-coated lithium iron phosphate nanometer composite material | |
| CN102437335B (en) | Method for coating lithium ion battery anode material LiFePO4 by self-segregation of aluminum |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20120815 |