CN101976734A - Preparation method of high-density lithium iron phosphate as lithium battery anode material - Google Patents
Preparation method of high-density lithium iron phosphate as lithium battery anode material Download PDFInfo
- Publication number
- CN101976734A CN101976734A CN2010105300818A CN201010530081A CN101976734A CN 101976734 A CN101976734 A CN 101976734A CN 2010105300818 A CN2010105300818 A CN 2010105300818A CN 201010530081 A CN201010530081 A CN 201010530081A CN 101976734 A CN101976734 A CN 101976734A
- Authority
- CN
- China
- Prior art keywords
- source
- lithium
- preparation
- precursor
- iron phosphate
- 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
Abstract
The invention discloses a preparation method of high-density lithium iron phosphate as a lithium battery anode material. The preparation method comprises the following steps of: evenly mixing a ferric iron source, a phosphorous source, a lithium source, a doped element compound and a carbon source in a dispersing agent according to proportions; placing the mixture in a ball milling container, and carrying out ball milling for 1-12 hours; placing a ball-milled product in an air atmosphere and baking for 2-20 hours at 250-550 DEG C, naturally cooling and grinding to obtain a lithium iron phosphate precursor; placing the precursor in a high temperature furnace, heating in a heating rate of 15-40 DEG C/min in a hydrogen atmosphere and roasting for 3-15h at the constant temperature of 500-900 DEG C; and cooling to be below 40 DEG C at a cooling speed of 15-40 DEG C/min to obtain doped lithium iron phosphate powder. In the preparation method, the lithium iron phosphate material which has the advantages of small particle diameter, narrow distribution, high purity, large compaction and favorable electrochemical property is mechanically synthesized in a solid phase mode by directly adopting the trivalent iron source, without using ferrite easily-oxidized in air; and the preparation method is simple and easy to implement and realizes the clean industrialized large-scale production.
Description
Technical field
The present invention relates to the preparation method of anode material of lithium battery, be specifically related to a kind of preparation method of high density lithium battery anode material lithium iron phosphate.
Background technology
Directly the method for synthesizing lithium ferrous phosphate mainly contains high-temperature solid phase reaction method, hydro thermal method at present, according to presoma preparation section branch sol-gal process, coprecipitation, mechanochemistry activation method etc. are arranged, existing synthetic method has following shortcoming, has hindered its practical application: the Fe during (1) is synthetic
2+Easily be oxidized to Fe
3+, be difficult to obtain single-phase LiFePO
4(2) lithium ion is at LiFePO
4Middle diffusion difficulty causes the utilance of active material low; (3) LiFePO
4The conductivity of itself is also very low, causes its heavy-current discharge performance poor.
Summary of the invention
The objective of the invention is to: the preparation method that a kind of high density lithium battery anode material lithium iron phosphate is provided, need not to prepare in advance or use the ferrous salt of easy oxidation in air, and directly adopt the source of iron of trivalent, machinery solid phase synthesis grain is through little, narrowly distributing, purity height, jolt ramming is big, chemical property is good ferrousphosphate lithium material, method is simple, and realizes the industrialized production of cleaning.
Technical solution of the present invention is: at first synthetic a kind of high density LiFePO 4 precursor, and this precursor is calcined under given conditions obtained high density olivine structural LiFePO 4 again.
Preparation method of the present invention may further comprise the steps: at first, ferric iron source, phosphorus source, lithium source, doping element compound, carbon source are mixed in dispersant in proportion; Then, said mixture is put into ball mill container, ball milling 1 ~ 12 hour; Secondly, the ball milling product places air atmosphere in 250 ~ 550 ℃ of bakings 2 ~ 20 hours, grinds behind the natural cooling, obtains the LiFePO 4 precursor; Then, this precursor is placed high temperature furnace, in hydrogen atmosphere, heat up with 15 ~ 40 ℃/min rate of heat addition, at 500 ~ 900 ℃ of constant temperature calcining 3 ~ 15h; At last, be cooled to below 40 ℃, get the ferrous phosphate doping lithium powder with 15 ~ 40 ℃/min cooling rate.
Wherein, the mol ratio of the consumption of above-mentioned ferric iron source, phosphorus source, lithium source, doping element compound, carbon source is: ferric iron source: phosphorus source: lithium source: doping element compound: carbon source=(0.7 ~ 1): 1:(0.98 ~ 1.06): (0.02 ~ 0.3): (0.1 ~ 0.5).
Wherein, ferric iron source is selected from a kind of in iron chloride, ferric nitrate, the ferric phosphate; The phosphorus source is selected from phosphoric acid, diammonium hydrogen phosphate, a kind of in the ammonium dihydrogen phosphate; The lithium source is selected from a kind of in lithia, lithium nitrate, the lithium carbonate; Doping element compound is selected from MnCO
3, M
OO
3, Mg (OH)
2In a kind of; Carbon source is selected from a kind of in sucrose, glucose, the starch; Dispersant is selected from a kind of in water, the ethanol.
The present invention has following several characteristics:
(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 adopts mechanical process for solid phase synthesis, and material composition and proportioning are controlled easily, and the jolt ramming of synthetic LiFePO 4 is big, the purity height, and chemical property is good, the LiFePO that the present invention synthesizes
4/ C material and carbon negative pole are assembled into test battery, the big 130mAh/g of specific capacity when the 1C multiplying power discharging, and show outstanding stable circulation performance.
(3) preparation method's technology of the present invention is simple to operation, and employed material is large chemical products, easily realizes the commercial scale cleaner production, three-waste free discharge.
(4) LiFePO 4 that obtains of the present invention is an olivine structural, average grain diameter 1～8 μ m, Song dress Mi Du ≧ 0.5g/cm
3, tap density 1.0～1.4g/cm
3, Bi Biao Mian ≦ 25m
2/ g, room temperature first discharge specific capacity (1C) ≧ 130 mah/g.
Embodiment
Further specify technical solution of the present invention below in conjunction with specific embodiment, these embodiment can not be interpreted as it is restriction to technical scheme.
Embodiment 1:
Take by weighing 1137 the gram iron chloride, 1150 the gram ammonium dihydrogen phosphates, 676 the gram lithium nitrates, 23 the gram manganese carbonates, 342 the gram sucrose in 1L ethanol, mix; Said mixture is put into ball mill container, ball milling 1 hour; The ball milling product places air atmosphere in 250 ℃ of bakings 20 hours, grinds behind the natural cooling, obtains the LiFePO 4 precursor; The LiFePO 4 precursor is placed high temperature furnace, in hydrogen atmosphere, heat up with the 15 ℃/min rate of heat addition, at 500 ℃ of constant temperature calcining 15h; Be cooled to below 40 ℃ with 15 ℃/min cooling rate again, get the ferrous phosphate doping lithium powder.The average grain diameter that records this product is 2～5 μ m, tap density 1.4g/cm
3, specific surface 18m
2/ g, room temperature first discharge specific capacity (1C) ≧ 130 mAh/g.
Embodiment 2:
Take by weighing 1510 the gram ferric phosphates, 980 the gram phosphoric acid, 784 the gram lithium carbonates, 174 the gram magnesium hydroxides, 900 the gram glucose in 2L water, mix; Said mixture is put into ball mill container, ball milling 6.5 hours; The ball milling product places air atmosphere in 400 ℃ of bakings 11 hours, grinds behind the natural cooling, obtains the LiFePO 4 precursor; The LiFePO 4 precursor is placed high temperature furnace, in hydrogen atmosphere, heat up with the 27 ℃/min rate of heat addition, at 700 ℃ of constant temperature calcining 9h; Be cooled to below 40 ℃ with 27 ℃/min cooling rate again, make the ferrous phosphate lithium powder of doping.The average grain diameter that records this product is 1～3 μ m, tap density 1.3g/cm
3, specific surface 22m
2/ g, room temperature records first discharge specific capacity (1C) ≧ 130 mAh/g.
Embodiment 3: take by weighing 3232 gram ferric nitrates, 1320 gram diammonium hydrogen phosphates, 300 gram lithias, 144 gram MoO
3, 1800 the gram starch in 1L ethanol, mix; Said mixture is put into ball mill container, ball milling 12 hours; The ball milling product places air atmosphere in 550 ℃ of bakings 2 hours, grinds behind the natural cooling, obtains the LiFePO 4 precursor; The LiFePO 4 precursor is placed high temperature furnace, in hydrogen atmosphere, heat up with the 40 ℃/min rate of heat addition, at 900 ℃ of constant temperature calcining 3h; Be cooled to below 40 ℃ with 40 ℃/min cooling rate again, get the ferrous phosphate doping lithium powder.The average grain diameter that records this product is 2～5 μ m, tap density 1.4g/cm
3, specific surface 18m
2/ g, room temperature first discharge specific capacity (1C) ≧ 130 mAh/g.
Claims (3)
1. the preparation method of high density lithium battery anode material lithium iron phosphate at first synthesizes a kind of high density LiFePO 4 precursor, this precursor is calcined under given conditions to obtain high density olivine structural LiFePO 4 again; It is characterized in that this preparation method may further comprise the steps: at first, ferric iron source, phosphorus source, lithium source, doping element compound, carbon source are mixed in proportion in dispersant; Then, said mixture is put into ball mill container, ball milling 1 ~ 12 hour; Secondly, the ball milling product places air atmosphere in 250 ~ 550 ℃ of bakings 2 ~ 20 hours, grinds behind the natural cooling, obtains the LiFePO 4 precursor; Then, this precursor is placed high temperature furnace, in hydrogen atmosphere, heat up with 15 ~ 40 ℃/min rate of heat addition, at 500 ~ 900 ℃ of constant temperature calcining 3 ~ 15h; At last, be cooled to below 40 ℃, get the ferrous phosphate doping lithium powder with 15 ~ 40 ℃/min cooling rate.
2. the preparation method of high density lithium battery anode material lithium iron phosphate according to claim 1, it is characterized in that: wherein, the mol ratio of the consumption of above-mentioned ferric iron source, phosphorus source, lithium source, doping element compound, carbon source is: ferric iron source: the phosphorus source: lithium source: doping element compound: carbon source=(0.7 ~ 1): 1:(0.98 ~ 1.06): (0.02 ~ 0.3): (0.1 ~ 0.5).
3. the preparation method of high density lithium battery anode material lithium iron phosphate according to claim 1 is characterized in that: wherein, ferric iron source be selected from iron chloride, ferric nitrate, ferric phosphate, in a kind of; The phosphorus source is selected from a kind of in phosphoric acid, diammonium hydrogen phosphate, the ammonium dihydrogen phosphate; The lithium source is selected from a kind of in lithia, lithium nitrate, the lithium carbonate; Doping element compound is selected from MnCO
3, M
OO
3, Mg (OH)
2In a kind of; Carbon source is selected from a kind of in sucrose, glucose, the starch; Dispersant is selected from a kind of in water, the ethanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105300818A CN101976734A (en) | 2010-11-03 | 2010-11-03 | Preparation method of high-density lithium iron phosphate as lithium battery anode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105300818A CN101976734A (en) | 2010-11-03 | 2010-11-03 | Preparation method of high-density lithium iron phosphate as lithium battery anode material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101976734A true CN101976734A (en) | 2011-02-16 |
Family
ID=43576595
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010105300818A Pending CN101976734A (en) | 2010-11-03 | 2010-11-03 | Preparation method of high-density lithium iron phosphate as lithium battery anode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101976734A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US20150140431A1 (en) * | 2012-04-05 | 2015-05-21 | Hitachi Metals, Ltd. | Method for producing positive electrode active material for nonaqueous secondary batteries, positive electrode for nonaqueous secondary batteries, and nonaqueous secondary battery |
| CN108155361A (en) * | 2017-12-24 | 2018-06-12 | 扬州工业职业技术学院 | A kind of iron lithium phosphate battery |
| CN108172788A (en) * | 2017-12-24 | 2018-06-15 | 扬州工业职业技术学院 | The LiFePO of nickel doping vario-property4/ C composite and its application as anode material of lithium battery |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101269808A (en) * | 2008-03-05 | 2008-09-24 | 广州融捷材料科技有限公司 | High-density olivine-structure ferrous lithium phosphate and manufacture method thereof |
-
2010
- 2010-11-03 CN CN2010105300818A patent/CN101976734A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101269808A (en) * | 2008-03-05 | 2008-09-24 | 广州融捷材料科技有限公司 | High-density olivine-structure ferrous lithium phosphate and manufacture method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150140431A1 (en) * | 2012-04-05 | 2015-05-21 | Hitachi Metals, Ltd. | Method for producing positive electrode active material for nonaqueous secondary batteries, positive electrode for nonaqueous secondary batteries, and nonaqueous secondary battery |
| 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 |
| CN108155361A (en) * | 2017-12-24 | 2018-06-12 | 扬州工业职业技术学院 | A kind of iron lithium phosphate battery |
| CN108172788A (en) * | 2017-12-24 | 2018-06-15 | 扬州工业职业技术学院 | The LiFePO of nickel doping vario-property4/ C composite and its application as anode material of lithium battery |
| CN108155361B (en) * | 2017-12-24 | 2020-06-26 | 扬州工业职业技术学院 | Lithium iron phosphate battery |
| CN108172788B (en) * | 2017-12-24 | 2020-06-30 | 扬州工业职业技术学院 | Nickel-doped modified LiFePO4/C composite material and application thereof as lithium battery anode material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100448071C (en) | Lithium cell positive electrode materials and preparing method thereof | |
| JP5113081B2 (en) | Lithium manganese phosphate cathode material for lithium secondary battery | |
| CN101269808A (en) | High-density olivine-structure ferrous lithium phosphate and manufacture method thereof | |
| CN101355158B (en) | Lithium ion battery anode material LiFePO4Preparation method of (1) | |
| CN100369302C (en) | Method for preparing positive electrode material for lithium cell, and lithium cell | |
| CN109326781A (en) | A kind of preparation method of high voltage lithium cobalt oxide anode | |
| CN102738465B (en) | Preparation method of lithium iron manganese phosphate cathode composite material | |
| CN101638227B (en) | Preparation method of lithium iron phosphate oxide of cathode material of lithium ion battery | |
| TW201221469A (en) | Manufacturing method for lithium iron phosphate material and lithium iron phosphate powder produced thereby | |
| CN101152959A (en) | Method of producing lithium iron phosphate series composite oxides | |
| CN103985868A (en) | Iron lithium manganese phosphate-carbon composite anode material for lithium ion battery and synthetic method of anode material | |
| CN105185993B (en) | A kind of synthetic method of high-purity phosphoric acid iron and its doped metallic elements | |
| CN102881901A (en) | Doped modified lithium iron phosphate and preparation method thereof | |
| CN102332565A (en) | Synthesis method for lithium iron phosphate/carbon composite material | |
| CN101262060B (en) | A method for making anode material Li3V2(PO4)3 of lithium ion battery | |
| CN101976734A (en) | Preparation method of high-density lithium iron phosphate as lithium battery anode material | |
| CN102420329A (en) | High-tap-density composite modified cathode material of lithium ion battery and preparation method thereof | |
| CN102208624A (en) | Method for preparing carbon-coated LiFePO4 anode material by using low-temperature solid-phase method | |
| CN102610816A (en) | Fiber-ball-shaped lithium manganese phosphate anode material of lithium ion battery and preparation method of fiber-ball-shaped lithium manganese phosphate anode material | |
| CN103515601A (en) | Positive pole material LiFePO4 for lithium ion battery and preparation method thereof | |
| CN115403023A (en) | Method for preparing lithium iron manganese phosphate by supercritical hydrothermal method assisted spray drying | |
| CN101673821B (en) | Method for preparing manganese phosphate lithium/carbon composite material by using manganese hydrogen phosphate | |
| CN106684382A (en) | Preparation method of lithium iron phosphate/graphene composite material | |
| CN101445229B (en) | A colloidal sols- jelly glue method for preparing lithium vanadium phosphate lithium ion battery positive pole material adulterating titanium | |
| CN101941686A (en) | Preparation method of LiFePO4 |
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 |
Application publication date: 20110216 |