CN101269808A - High-density olivine-structure ferrous lithium phosphate and manufacture method thereof - Google Patents
High-density olivine-structure ferrous lithium phosphate and manufacture method thereof Download PDFInfo
- Publication number
- CN101269808A CN101269808A CNA2008100265971A CN200810026597A CN101269808A CN 101269808 A CN101269808 A CN 101269808A CN A2008100265971 A CNA2008100265971 A CN A2008100265971A CN 200810026597 A CN200810026597 A CN 200810026597A CN 101269808 A CN101269808 A CN 101269808A
- Authority
- CN
- China
- Prior art keywords
- density
- source
- preparation
- lifepo
- lithium
- 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
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 high-density olivine structure lithium iron phosphate and a preparation method thereof, and the technical field thereof is a method using a ferric iron source to prepare a battery anode material high-density olivine structure lithium iron phosphate by adopting a mechanical solid phase synthesis process. The preparation method does not need to preliminarily prepare and use ferrous salt easy to be oxidized in the air, and directly adopts the ferric iron source and adopts the mechanical solid phase synthesis process to synthetize lithium iron phosphate materials having small grain diameter, narrow distribution, high purity, high tap and excellent electrochemical properties. A high-density lithium iron phosphate former body is synthetized first by controlling the synthesis process, and then the former body is calcined in specific conditions to obtain the high-density olivine structure lithium iron phosphate. The lithium iron phosphate has an olivine structure; the average grain diameter is 1-8 micron(s); the loose density is not less than 0.5g/cm<3>; the tap density is 1.0-1.4g/cm<3>; the specific surface is not more than 25m<2>/g; the initial discharge specific capacity (1C) is not less than 130mAh/g. The preparation method is simple and easy to do, and can cleanly realize large industrialization production.
Description
Technical field
The present invention relates to a kind of preparation of high-density olivine structural LiFePO 4, particularly a kind of ferric iron source that utilizes adopts mechanical process for solid phase synthesis to prepare the method for cell positive material high-density olivine structural LiFePO 4.
Background technology
From A.K.Padhi reported first in 1997 LiFePO
4Had since the removal lithium embedded function, peridotites shape phosphoric acid salt intercalation materials of li ions receives much concern.Because LiFePO
4Take off the FePO that lithium obtains
4The original volume of volume ratio only lacked 6.81%, volumetric shrinkage in the process of charging can remedy the expansion of carbon negative pole, help to improve the volume utilising efficiency of lithium ion battery, therefore has good cycle performance, Feng Fu iron resources simultaneously, cheap price, (theoretical capacity is 170mAh/g to the specific storage height, energy density is characteristics such as good thermostability of 550W h/Kg and environmental friendliness, is considered to the most promising anode material for lithium-ion batteries.
But following shortcoming has hindered its practical application: the Fe during (1) is synthetic
2+Easily be oxidized to Fe
3+, be difficult to obtain monophasic LiFePO
4(2) lithium ion is at LiFePO
4Middle diffusion difficulty causes the utilization ratio of active material low; (3) LiFePO
4The specific conductivity of itself is also very low, causes its heavy-current discharge performance poor.Existing research mainly improves LiFePO by approach once
4Performance; (1) adopt inert atmosphere to protect Fe
2+(2) LiFePO of synthetic granule warp
4Improve the diffusibility of lithium ion; (3) power up and lead agent and improve specific conductivity.
Directly the method for synthesizing iron lithium phosphate mainly contains high-temperature solid phase reaction method, hydrothermal method at present.
Divide sol-gel method, coprecipitation method, mechanochemistry activation method etc. in addition according to the presoma preparation section.
Summary of the invention
The objective of the invention is weak point, proposed a kind of method for preparing high-density olivine structural LiFePO 4 at the aforesaid method existence.The present invention need not to prepare in advance or use the ferrous salt of easy oxidation in air, and directly adopts tervalent source of iron, adopts the synthetic particle diameter of mechanical process for solid phase synthesis little, narrowly distributing, and the purity height, jolt ramming is big, the ferrousphosphate lithium material that chemical property is good.
The inventive method is simple, can realize the industrialized production of cleaning.
The invention provides a kind of preparation method with high-density olivine structural LiFePO 4, by the control synthesis technique, at first synthetic a kind of high-density LiFePO 4 precursor, again this precursor is calcined under given conditions, obtain high-density olivine structural LiFePO 4, this method technology is simple, realizes industrialization easily, and has better chemical property.
Realize by following technical proposal during purpose of the present invention:
High-density olivine structural LiFePO 4, this LiFePO 4 are olivine structural, median size 1～8um, loose density 〉=0.5g/cm
3, tap density 1.0～1.4g/cm
3, specific surface≤25m
2/ g, first discharge specific capacity (1C) 〉=130mAh/g.
The preparation method of high-density olivine structural LiFePO 4:
1, ferric iron source, phosphorus source, lithium source, doped element chemicals, carbon source are mixed in proportion in certain amount of dispersant, said mixture is put into ball mill container, ball milling 1～12 hour, the ball milling product places non-oxidizing atmosphere in 250～550 ℃ of bakings 2～20 hours, grind behind the naturally cooling, obtain the LiFePO 4 precursor.This precursor is placed High Temperature Furnaces Heating Apparatus, in reducing atmosphere, heat up with 15～40 ℃/min heating rate, at 500～900 ℃ of constant temperature calcining 3～15h, be cooled to below 40 ℃ the ferrous phosphate lithium powder of system or ferrous phosphate doping lithium powder then with 15～40 ℃/min cooling rate;
2, the molar ratio of the consumption of ferric iron source, phosphorus source, lithium source, doping element compound is: ferric iron source: the phosphorus source: the lithium source: doped element=0.7～1: 1: 0.98～1.06: 0.02～0.3;
3, carbon source is selected from a kind of in sucrose, glucose, dextrin, polypropylene, polyacrylamide, citric acid, the starch;
4, dispersion agent is selected from a kind of in water, the ethanol;
5, source of iron is selected from a kind of in iron(ic) chloride, iron nitrate, tertiary iron phosphate, the ferric ammonium sulfate;
6, the lithium source is selected from a kind of in Lithium Oxide 98min, Lithium Acetate, lithium chloride, lithium nitrate, the Quilonum Retard;
7, the phosphorus source is selected from phosphoric acid, phosphoric acid hydrogen amine, a kind of in tertiary iron phosphate, the phosphoric acid dihydro amine;
8, the doped element chemicals are selected from MnCO
3, Mn (NO
3)
2, Mn
2O
3, MnPO
4, M
0O
3, Mg (OH)
2, Mg (NO
3)
2, NiPO
4In a kind of.
The invention provides a kind of preparation method with high-density olivine structural LiFePO 4, by the control synthesis technique, at first synthetic a kind of high-density LiFePO 4 precursor, again this precursor is calcined under given conditions, obtain high-density olivine structural LiFePO 4, this method technology is simple, realizes industrialization easily, and has better chemical property.
The preparation method of high-density olivine structural LiFePO 4 of the present invention has following several distinguishing feature:
(1) directly uses ferric iron to be source of iron, avoided ferrous salt synthesis step loaded down with trivial details in other synthetic technologys, solved the impure problem of product that often has among the conventional preparation method of the ferrous salt raw material of easy oxidation in air of using.
(2) the present invention's machinery process for solid phase synthesis prepares the method for high-density olivine structural LiFePO 4, and material composition and product prescription are controlled easily, and the jolt ramming of synthetic LiFePO 4 is big, the purity height, and chemical property is good, synthetic LiFePO of the present invention
4/ C material and carbon negative pole are assembled into test battery, the big 130mAh/g of specific storage when the 1C multiplying power discharging, and show outstanding stable circulation performance.
(3) preparation method of high-density olivine structural LiFePO 4 of the present invention, technology is simple to operation, and employed material is large Chemicals, easily realizes the technical scale cleaner production, three-waste free discharge.
Embodiment
Embodiment 1, take by weighing 1074 gram iron(ic) chloride, 801 gram primary ammonium phosphates, 460 gram Lithium Acetates, 40 gram manganous carbonates, 530 gram sucrose mix in 1000ml ethanol, said mixture is put into ball mill container, ball milling 6 hours, the ball milling product places air atmosphere in 450 ℃ of bakings 15 hours, grind behind the naturally cooling, then compound is placed High Temperature Furnaces Heating Apparatus, in the atmosphere of mixing hydrogen+nitrogen, heat up with 35 ℃/min heating rate, at 800 ℃ of constant temperature calcining 15h, be cooled to make the ferrous phosphate doping lithium powder below 40 ℃ with 35 ℃/min cooling rate then.The median size that records this product is 2～5um, tap density 1.4g/cm
3, specific surface 18m
2/ g, under the room temperature, first discharge specific capacity (1C) 〉=130mAh/g.
Embodiment 2, take by weighing 1620 the gram tertiary iron phosphates, 258 the gram Quilonum Retards, 20 the gram magnesium hydroxides, 550 the gram glucose mix in 2000ml water, said mixture is put into ball mill container, ball milling 8 hours, the ball milling product places air atmosphere in 400 ℃ of bakings 15 hours, grind behind the naturally cooling, then compound is placed High Temperature Furnaces Heating Apparatus, in the atmosphere of mixing hydrogen+nitrogen, heat up with 35 ℃/min heating rate, at 800 ℃ of constant temperature calcining 15h, be cooled to below 40 ℃ with 35 ℃/min cooling rate then, make adulterated ferrous phosphate lithium powder.
The median size that records this product is 1～3um, tap density 1.3g/cm
3, specific surface 22m
2/ g at room temperature, records first discharge specific capacity (1C) 〉=127mAh/g.
Embodiment 3, take by weighing 1734 the gram tertiary iron phosphates, 273 the gram Quilonum Retards, 605 the gram glucose mix in 2000ml water, said mixture is put into ball mill container, ball milling 6 hours, the ball milling product places air atmosphere in 480 ℃ of bakings 15 hours, grind behind the naturally cooling, then compound is placed High Temperature Furnaces Heating Apparatus, in the atmosphere of mixing hydrogen+nitrogen, heat up with 35 ℃/min heating rate, at 850 ℃ of constant temperature calcining 16h, be cooled to below 40 ℃ with 35 ℃/min cooling rate then, make adulterated ferrous phosphate lithium powder.
The median size that records this product is 2～4um, tap density 1.29g/cm
3, specific surface 25.86m
2/ g at room temperature, records first discharge specific capacity (1C) 〉=125mAh/g.
Claims (9)
1, a kind of high-density olivine structural LiFePO 4 is characterized in that this LiFePO 4 is an olivine structural, median size 1～8um, loose density 〉=0.5g/cm
3, tap density 1.0～1.4g/cm
3, specific surface area≤25m
2/ g, first discharge specific capacity (1C) 〉=130mAh/g.
2, a kind of preparation method of high-density olivine structural LiFePO 4, it is characterized in that ferric iron source, the phosphorus source, the lithium source, the doped element chemicals, carbon source mixes in proportion in certain amount of dispersant, said mixture is put into ball mill container, ball milling 1～12 hour, the ball milling product places non-oxidizing atmosphere in 250～550 ℃ of bakings 2～20 hours, grind behind the naturally cooling, obtain the LiFePO 4 precursor, this precursor is placed High Temperature Furnaces Heating Apparatus, in reducing atmosphere, heat up with 15～40 ℃/min heating rate, at 500～900 ℃ of constant temperature calcining 3～15h, be cooled to below 40 ℃ with 15～40 ℃/min cooling rate then, make ferrous phosphate lithium powder or ferrous phosphate doping lithium powder.
3, the preparation method of high-density olivine structural LiFePO 4 according to claim 2 is characterized in that the molar ratio of the consumption of described ferric iron source, phosphorus source, lithium source, doping element compound is: ferric iron source: phosphorus source: lithium source: doped element=0.7～1: 1: 0.98～1.06: 0.02～0.3.
4, the preparation method of high-density olivine structural LiFePO 4 according to claim 2 is characterized in that described carbon source is selected from a kind of in sucrose, glucose, dextrin, polypropylene, polyacrylamide, citric acid, the starch.
5, the preparation method of high-density olivine structural LiFePO 4 according to claim 2 is characterized in that described dispersion agent is selected from a kind of in water, the ethanol.
6, the preparation method of high-density olivine structural LiFePO 4 according to claim 2 is characterized in that described source of iron is selected from a kind of in iron(ic) chloride, iron nitrate, tertiary iron phosphate, the ferric ammonium sulfate.
7, the preparation method of high-density olivine structural LiFePO 4 according to claim 2 is characterized in that described lithium source is selected from a kind of in Lithium Oxide 98min, Lithium Acetate, lithium chloride, lithium nitrate, the Quilonum Retard.
8, the preparation method of high-density olivine structural LiFePO 4 according to claim 2 is characterized in that described phosphorus source is selected from phosphoric acid, ammonium hydrogen phosphate, a kind of in tertiary iron phosphate, the primary ammonium phosphate.
9, the preparation method of high-density olivine structural LiFePO 4 according to claim 2 is characterized in that described doped element chemicals are selected from MnCO
3, Mn (NO
3)
2, Mn
2O
3, MnPO
4, M
0O
3, Mg (OH)
2, Mg (NO
3)
2, NiPO
4In a kind of.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100265971A CN101269808A (en) | 2008-03-05 | 2008-03-05 | High-density olivine-structure ferrous lithium phosphate and manufacture method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100265971A CN101269808A (en) | 2008-03-05 | 2008-03-05 | High-density olivine-structure ferrous lithium phosphate and manufacture method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101269808A true CN101269808A (en) | 2008-09-24 |
Family
ID=40004073
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008100265971A Pending CN101269808A (en) | 2008-03-05 | 2008-03-05 | High-density olivine-structure ferrous lithium phosphate and manufacture method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101269808A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101901902A (en) * | 2010-04-13 | 2010-12-01 | 新乡市中科科技有限公司 | Preparation method of lithium-iron-phosphate compound |
| CN101941686A (en) * | 2010-09-10 | 2011-01-12 | 绵阳天明新能源科技有限公司 | Preparation method of LiFePO4 |
| CN101976734A (en) * | 2010-11-03 | 2011-02-16 | 江苏方舟新能源股份有限公司 | Preparation method of high-density lithium iron phosphate as lithium battery anode material |
| CN102009971A (en) * | 2010-12-23 | 2011-04-13 | 四川成洪磷化工有限责任公司 | Preparation method for lithium iron phosphate |
| CN102097619A (en) * | 2011-01-12 | 2011-06-15 | 合肥国轩高科动力能源有限公司 | Method for preparing high-performance lithium iron phosphate cathode material by using compound type reducing agent |
| CN102126714A (en) * | 2011-01-12 | 2011-07-20 | 山西泰众新能源有限公司 | Preparation method of lithium iron phosphate with high tap density |
| CN102299331A (en) * | 2011-07-19 | 2011-12-28 | 彩虹集团公司 | Carbon-coated lithium iron phosphate-doped lithium ion battery anode material and preparation method thereof |
| CN102881901A (en) * | 2012-10-10 | 2013-01-16 | 绵阳天明新能源科技有限公司 | Doped modified lithium iron phosphate and preparation method thereof |
| CN103384006A (en) * | 2013-07-29 | 2013-11-06 | 深圳先进技术研究院 | Preparing method of lithium iron phosphate/carbon composite materials |
| CN103682363A (en) * | 2013-12-30 | 2014-03-26 | 云南磷化集团有限公司 | Method for using novel material mixing dispersing agents for preparing lithium iron phosphate battery materials |
| CN103779565A (en) * | 2014-02-12 | 2014-05-07 | 云南磷化集团有限公司 | Preparation method of lithium iron phosphate composite battery material |
-
2008
- 2008-03-05 CN CNA2008100265971A patent/CN101269808A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101901902B (en) * | 2010-04-13 | 2012-07-25 | 新乡市中科科技有限公司 | Preparation method of lithium-iron-phosphate compound |
| CN101901902A (en) * | 2010-04-13 | 2010-12-01 | 新乡市中科科技有限公司 | Preparation method of lithium-iron-phosphate compound |
| CN101941686A (en) * | 2010-09-10 | 2011-01-12 | 绵阳天明新能源科技有限公司 | Preparation method of LiFePO4 |
| CN101976734A (en) * | 2010-11-03 | 2011-02-16 | 江苏方舟新能源股份有限公司 | Preparation method of high-density lithium iron phosphate as lithium battery anode material |
| CN102009971A (en) * | 2010-12-23 | 2011-04-13 | 四川成洪磷化工有限责任公司 | Preparation method for lithium iron phosphate |
| CN102097619A (en) * | 2011-01-12 | 2011-06-15 | 合肥国轩高科动力能源有限公司 | Method for preparing high-performance lithium iron phosphate cathode material by using compound type reducing agent |
| CN102126714A (en) * | 2011-01-12 | 2011-07-20 | 山西泰众新能源有限公司 | Preparation method of lithium iron phosphate with high tap density |
| CN102299331A (en) * | 2011-07-19 | 2011-12-28 | 彩虹集团公司 | Carbon-coated lithium iron phosphate-doped lithium ion battery anode material and preparation method thereof |
| CN102881901A (en) * | 2012-10-10 | 2013-01-16 | 绵阳天明新能源科技有限公司 | Doped modified lithium iron phosphate and preparation method thereof |
| CN103384006A (en) * | 2013-07-29 | 2013-11-06 | 深圳先进技术研究院 | Preparing method of lithium iron phosphate/carbon composite materials |
| CN103682363A (en) * | 2013-12-30 | 2014-03-26 | 云南磷化集团有限公司 | Method for using novel material mixing dispersing agents for preparing lithium iron phosphate battery materials |
| CN103779565A (en) * | 2014-02-12 | 2014-05-07 | 云南磷化集团有限公司 | Preparation method of lithium iron phosphate composite battery material |
| CN103779565B (en) * | 2014-02-12 | 2016-08-03 | 云南磷化集团有限公司 | A kind of preparation method of LiFePO4 composite battery material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101269808A (en) | High-density olivine-structure ferrous lithium phosphate and manufacture method thereof | |
| CN101330141B (en) | Method for preparing lithium ionic battery anode material spherical LiFePO4 /C | |
| WO2023184960A1 (en) | Preparation method for lithium iron manganese phosphate, anode electrode material and lithium-ion battery | |
| EP1989747B1 (en) | Lithium manganese phosphate positive material for lithium secondary battery | |
| CN100480178C (en) | Particle appearance regulatory lithium iron phosphate preparation method | |
| CN101106194B (en) | Cathode material Li3V2(PO4)3 of lithium ion battery and its making method | |
| CN101693532B (en) | Method for preparing lithium ferrous phosphate | |
| CN100448071C (en) | Lithium battery positive electrode material and preparation method thereof | |
| CN101673819B (en) | Method for preparing manganese lithium phosphate/carbon composite material by manganese phosphate | |
| CN104752718B (en) | A kind of LiMnxFe1‑xPO4Positive electrode active materials and preparation method thereof | |
| CN101630739B (en) | Preparation method of modified doping lithium ferric phosphate | |
| CN101013751A (en) | Ball-shaped lithium-ion battery anode material doped with rare earth and method for making same | |
| EP2207229A1 (en) | Lithium iron phosphate having an oxygen vacancy and doped in the position of Fe and method of quick solid phase sintering for the same | |
| CN102044667A (en) | Method for preparing spherical LFP (lithium iron phosphate)/carbon doped composite powder | |
| CN100486889C (en) | Method for producing active substance ferrous lithium phosphate as lithium-ion battery anode | |
| CN103515601A (en) | Positive pole material LiFePO4 for lithium ion battery and preparation method thereof | |
| CN103985868A (en) | Iron lithium manganese phosphate-carbon composite anode material for lithium ion battery and synthetic method of anode material | |
| Herrera et al. | LiMnPO 4: Review on synthesis and electrochemical properties | |
| CN102420329A (en) | High-tap-density composite modified cathode material of lithium ion battery and preparation method thereof | |
| CN103224226A (en) | Nano-lithium iron phosphate material suitable for high rate power battery and preparation method thereof | |
| CN102208624A (en) | Method for preparing carbon-coated LiFePO4 anode material by using low-temperature solid-phase method | |
| CN101673821B (en) | Method for preparing manganese phosphate lithium/carbon composite material by using manganese hydrogen phosphate | |
| CN105552341A (en) | Electrochemical active positive electrode material and preparation method thereof | |
| CN102942167A (en) | Anhydrous ferric phosphate, lithium iron phosphate prepared from the anhydrous ferric phosphate and use of the lithium iron phosphate | |
| CN100515934C (en) | Method for producing active substance ferrous lithium phosphate as lithium-ion battery anode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20080924 |