CN102623701B - Preparation method for low-temperature nanometer lithium iron phosphate cathode material - Google Patents
Preparation method for low-temperature nanometer lithium iron phosphate cathode material Download PDFInfo
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- CN102623701B CN102623701B CN201210065013.8A CN201210065013A CN102623701B CN 102623701 B CN102623701 B CN 102623701B CN 201210065013 A CN201210065013 A CN 201210065013A CN 102623701 B CN102623701 B CN 102623701B
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Abstract
The invention discloses a preparation method for a low-temperature nanometer lithium iron phosphate cathode material. The preparation method comprises the following steps of: adding a lithium source compound, a ferric source compound, a phosphorous source compound and water according to a proportion for mixing, adding metal ion doped oxide and a primary carbon source for mixing, performing primary high-energy superfine pulverization for 2 to 3 hours, performing spray-drying to obtain powder, and performing sieving; pre-treating the powder in an inert atmosphere at the temperature of 300 to 500 DEG C for 2 to 10 hours, performing cooling, adding a secondary carbon source and water, stirring the mixture, performing secondary high-energy superfine pulverization to obtain spherical powder, and performing sieving; and performing jet milling on the spherical powder, performing treatment in the inert atmosphere at 500 to 600 DEG C for 6 to 30 hours, performing thermal treatment at the high temperature of 600 to 900 DEG C for 10 to 30 hours, and performing cooling to obtain the low-temperature nanometer lithium iron phosphate cathode material with the granularity of 60 to 70 nanometers. When the low-temperature nanometer lithium iron phosphate cathode material is used for manufacturing the anode of a lithium ion battery, the battery has high low-temperature discharge performance.
Description
Technical field
The present invention relates to the technology of preparing of anode material for lithium-ion batteries, particularly a kind of preparation method of low form nano ferric phosphate lithium anode material.
Background technology
There is good security performance, excellent cycle performance and advantages of environment protection as the LiFePO4 of anode material for lithium-ion batteries, and abundant raw materials, specific capacity high (theoretical capacity 170mAh/g, energy density is 550Wg/Kg).But also there are following three problems in lithium iron phosphate positive material: (1) is known according to its lithium ion deintercalation migration models, and the ionic conductance of pure ferric phosphate lithium and electronic conductivity are all on the low side, and wherein electronic conductivity Se is 10
-9the s/cm order of magnitude, and ion transmission efficiency Si is 10
-11the s/cm order of magnitude, the two directly causes electrode transfer rate Sw low (Sw=Se × Si/Se+Si); (2) tap density is low; (3) poor performance at low temperatures.
If the problems referred to above can not effectively solve, LiFePO4 is difficult to be applied to electric automobile.The low problem of solution conductivity can be coated by carbon, the method for ion doping solves.LiFePO4 itself is non-conductor, and conductivity is low directly has influence on the high-power scope of application that has limited high-power lithium ion battery that discharges and recharges, in particular for electric automobile.For address this problem the current way generally adopting be at LiFePO4 coated with carbon to improve its conductivity, research simultaneously shows can also promote by carbon coated the cryogenic property of LiFePO4.The feasible way of another one is to make to occur that thereby free electron or hole promote conductivity in LiFePO4 lattice by ion doping.The method that solves lithium ion transmission performance is, can only shorten ion transfer path and realize by reducing particle diameter, the nanometer that this will realistic existing LiFePO 4 material under the unalterable prerequisite of LiFePO4 olivine one dimension lithium ion channel design.
At present people by the whole bag of tricks, (for example lithium position, iron position, even the doping of phosphoric acid position improves ion and electronic conductivity, by adding extra conductive agent to increase electron conduction etc.) improve the cryogenic property of LiFePO4, but the inherent characteristics of LiFePO 4 material, is difficult to fundamentally solve LiFePO4 cryogenic property.
Summary of the invention
The object of the invention is the poor problem of lithium iron phosphate positive material cryogenic property of preparing for current technology, a kind of preparation method of low form nano ferric phosphate lithium anode material is provided, lithium iron phosphate positive material cryogenic property prepared by the method is superior.
In order to reach above-mentioned purpose, solution of the present invention is:
A preparation method for low form nano ferric phosphate lithium anode material, is characterized in that comprising the steps:
The first step, by the stoichiometric ratio wet-mixed that adds water, then adds doped metal ion oxide and a carbon source by Li source compound, ferric iron source compound, P source compound, mixes; The slurry forming carries out a high energy Ultrafine Grinding and processes 2-3 hour, and the slurry D50 obtaining is less than 0.1 μ m, and dry the obtaining of spraying is dried powder, sieves;
Second step, by the powder in the first step in inert atmosphere in 300-500 DEG C of temperature range preliminary treatment 2-10 hour, after cooling, add secondary carbon source and water, stir the slurry forming, after secondary high energy Ultrafine Grinding is processed, the slurry D50 obtaining is less than 0.1 μ m, and spraying is dry obtains spherical powder, sieves;
The 3rd step, spherical powder in second step is carried out to air-flow crushing, powder after pulverizing is processed 6-30 hour through 500-600 DEG C in inert atmosphere, carry out again 600-900 DEG C of high-temperature heat treatment 10-30 hour, after cooling, obtain low form nano ferric phosphate lithium anode material, this material grains is of a size of 60 ~ 70nm.
In the first step, described lithium salts is one or both mixtures in lithium carbonate or lithium hydroxide; Described ferric iron source compound is Fe
2o
3, Fe
3o
4or FePO
4; Described microcosmic salt compound is (NH
4)
3pO
4, (NH
4)
2hPO
4, NH
4h
2pO
4or FePO
4; Described doped metal ion oxide is MnO
2, TiO
2, MgO and Nb
2o
5; Described Li source compound, ferric iron source compound, P source compound and the metering of metal ion oxide chemistry are than in element molal quantity Li:Fe:P: doping metals M=1.01:1:1:(0.01 ~ 0.05) ratio add; A described carbon source is glucose, sucrose and the fructose in soluble sugar compounds.
In second step, described secondary carbon source is sucrose, modified starch and the shitosan in macromolecular organic compound.
In second step and the 3rd step, described inert atmosphere is nitrogen or argon gas.
Adopt after such scheme, the invention has the advantages that: by twice high energy Ultrafine Grinding, effectively reduced once and the granularity of second particle, improved effecting reaction area.Particularly, through high energy Ultrafine Grinding for the first time, the granularity D50 of material is less than 0.1 μ m, has greatly increased the contact area between various raw materials, and the cryogenic property that promotes LiFePO 4 material is played to crucial effect.Through high energy Ultrafine Grinding for the second time, the granularity D50 of material is less than 0.1 μ m, and coordinates wet method to add secondary carbon source, makes carbon source evenly be coated on lithium iron phosphate particles surface, has increased substantially the conductivity of LiFePO 4 material.Through facts have proved, this process of preparing is feasible.Adopting the LiFePO 4 material prepared of the method is nanoscale crystalline material, and crystallite dimension is in 60 ~ 70nm scope, phosphorus content 1.5%～5%.This material is made after battery, and cryogenic property is superior, and when-20 DEG C time, capacity is 80% ,-40 DEG C of normal temperature, capacity is 55% of normal temperature.
Brief description of the drawings
Fig. 1 is the XRD figure of embodiment 1 prepared LiFePO 4 material, and wherein abscissa is angle of diffraction 2 θ (degree), and ordinate is diffracted intensity (a.u);
Fig. 2 is the SEM figure of embodiment 1 prepared LiFePO 4 material;
Fig. 3 is the low temperature discharge curve of embodiment 1 prepared LiFePO 4 material.
Embodiment
Embodiment 1
By 2.55molLi
2cO
3, 2.5molFe
2o
3, 5.0mol NH
4h
2pO
4add in agitator tank, add 2L deionized water, add while stirring 0.01molMnO
2, 0.01molTiO
2with 30g glucose, after stirring, proceed in ball mill, carry out high-energy ball milling 2 ~ 3 hours, the D50 that obtains slurry must be less than 0.1 μ m.Then spraying to be dried forms powder, sieves.By this powder at N
2in atmosphere, use 350 DEG C of sintering of rotary furnace 5 hours.Cooling, sieve, proceed in ball grinder, add 150g shitosan and 900ml deionized water, stir, proceed in ball mill, carry out high-energy ball milling for the second time, until the D50 of slurry is less than 0.1 μ m, the spherical powder of the dry formation of spraying, sieves.This powder is carried out, after air-flow crushing processing, joining in rotary furnace, at N
2650 DEG C of sintering 8 hours in atmosphere, then be warming up to 800 DEG C of sintering after 20 hours, cooling, sieve and obtain product.
Products obtained therefrom crystallite dimension is 64nm, and carbon content is that 2.3%, 1C normal temperature discharge capacity is 139.59 mAh/g, and-20 DEG C time, capacity is 111.76mAh/g, and while being 80% ,-40 DEG C of normal temperature, capacity is 76.77mAh/g, is 55% of normal temperature.
Embodiment 2
By 2.55molLi
2cO
3, 5.0molFePO
4add in agitator tank, add 2L deionized water, add while stirring 0.01molMnO
2, 0.01molTiO
2, 0.02mol MgO and 30g glucose, after stirring, proceed in ball mill, carry out high-energy ball milling 2 ~ 3 hours, the D50 that obtains slurry must be less than 0.1 μ m.Then spraying to be dried forms powder, sieves.By this powder at N
2in atmosphere, use 350 DEG C of sintering of rotary furnace 5 hours.Cooling, sieve, proceed in ball grinder, add 150g shitosan and 900ml deionized water, stir, proceed in ball mill, carry out high-energy ball milling for the second time, until the D50 of slurry is less than 0.1 μ m, the spherical powder of the dry formation of spraying, sieves.This powder is carried out, after air-flow crushing processing, joining in rotary furnace, at N
2650 DEG C of sintering 8 hours in atmosphere, then be warming up to 800 DEG C of sintering after 20 hours, cooling, sieve and obtain product.
Products obtained therefrom crystallite dimension is 62nm, and carbon content is that 2.8%, 1C normal temperature discharge capacity is 135.32 mAh/g, and-20 DEG C time, capacity is 107.19mAh/g, and while being 79% ,-40 DEG C of normal temperature, capacity is 73.26mAh/g, is 54% of normal temperature.
Embodiment 3
By 2.55molLi
2cO
3, 2.5molFe
2o
3, 5.0mol NH
4h
2pO
4add in agitator tank, add 2L deionized water, add while stirring 0.01molMnO
2, 0.01molTiO
2with 30g sucrose, after stirring, proceed in ball mill, carry out high-energy ball milling 2 ~ 3 hours, the D50 that obtains slurry must be less than 0.1 μ m.Then spraying to be dried forms powder, sieves.By this powder at N
2in atmosphere, use 350 DEG C of sintering of rotary furnace 5 hours.Cooling, sieve, proceed in ball grinder, add 180g modified starch and 900ml deionized water, stir, proceed in ball mill, carry out high-energy ball milling for the second time, until the D50 of slurry is less than 0.1 μ m, the spherical powder of the dry formation of spraying, sieves.This powder is carried out, after air-flow crushing processing, joining in rotary furnace, at N
2650 DEG C of sintering 8 hours in atmosphere, then be warming up to 800 DEG C of sintering after 20 hours, cooling, sieve and obtain product.
Products obtained therefrom crystallite dimension is 68nm, and carbon content is that 2.1%, 1C normal temperature discharge capacity is 137.91 mAh/g, and-20 DEG C time, capacity is 109.86mAh/g, and while being 79.6% ,-40 DEG C of normal temperature, capacity is 74.62 mAh/g, is 54.1% of normal temperature.
Claims (6)
1. a preparation method for low form nano ferric phosphate lithium anode material, is characterized in that comprising the steps:
The first step, by the stoichiometric ratio wet-mixed that adds water, then adds doped metal ion oxide and a carbon source by Li source compound, ferric iron source compound, P source compound, mixes; Li source compound, ferric iron source compound, P source compound and the metering of metal ion oxide chemistry are than in element molal quantity Li:Fe:P: doping metals M=1.01:1:1:(0.01 ~ 0.05) ratio add; The slurry forming carries out a high energy Ultrafine Grinding and processes 2-3 hour, and the slurry D50 obtaining is less than 0.1 μ m, and dry the obtaining of spraying is dried powder, sieves; A described carbon source is glucose, sucrose and the fructose in soluble sugar compounds;
Second step, by the powder in the first step in inert atmosphere in 300-500 DEG C of temperature range preliminary treatment 2-10 hour, after cooling, add secondary carbon source and water, stir the slurry forming, after secondary high energy Ultrafine Grinding is processed, the slurry D50 obtaining is less than 0.1 μ m, and spraying is dry obtains spherical powder, sieves; Described secondary carbon source is sucrose, modified starch and the shitosan in macromolecular organic compound;
The 3rd step, spherical powder in second step is carried out to air-flow crushing, powder after pulverizing is processed 6-30 hour through 500-600 DEG C in inert atmosphere, carry out again 600-900 DEG C of high-temperature heat treatment 10-30 hour, after cooling, obtain low form nano ferric phosphate lithium anode material, this material grains is of a size of 60 ~ 70nm.
2. a kind of preparation method of low form nano ferric phosphate lithium anode material according to claim 1, is characterized in that in the first step, described Li source compound is one or both mixtures in lithium carbonate or lithium hydroxide.
3. a kind of preparation method of low form nano ferric phosphate lithium anode material according to claim 1, is characterized in that in the first step, described ferric iron source compound is Fe
2o
3, Fe
3o
4or FePO
4.
4. a kind of preparation method of low form nano ferric phosphate lithium anode material according to claim 1, is characterized in that in the first step, described P source compound is (NH
4)
3pO
4, (NH
4)
2hPO
4, NH
4h
2pO
4or FePO
4.
5. a kind of preparation method of low form nano ferric phosphate lithium anode material according to claim 1, is characterized in that in the first step, described doped metal ion oxide is MnO
2, TiO
2, MgO and Nb
2o
5.
6. a kind of preparation method of low form nano ferric phosphate lithium anode material according to claim 1, is characterized in that described inert atmosphere is nitrogen or argon gas in second step and the 3rd step.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102969502B (en) * | 2012-11-26 | 2015-04-08 | 厦门钨业股份有限公司 | Preparation method of high-vibration-compaction low-specific-surface-area lithium iron phosphate made by positive pole material |
| CN104269553A (en) * | 2014-09-23 | 2015-01-07 | 上海宝钢磁业有限公司 | Method for preparing lithium iron phosphate material by adopting cold-rolled byproduct iron oxide |
| CN105428648B (en) * | 2015-11-27 | 2018-06-05 | 中信大锰矿业有限责任公司大新锰矿分公司 | A kind of preparation method of battery anode material of lithium iron phosphate |
| CN108063250A (en) * | 2016-08-15 | 2018-05-22 | 海宁永欣科技咨询有限公司 | The production technology of the nanometer lithium iron phosphate cathode material of improvement |
| CN107240696A (en) * | 2017-07-12 | 2017-10-10 | 北方奥钛纳米技术有限公司 | The preparation method and carbon-coated LiFePO 4 for lithium ion batteries and lithium ion battery of carbon-coated LiFePO 4 for lithium ion batteries |
| CN114772572A (en) * | 2022-02-28 | 2022-07-22 | 山东精工电子科技有限公司 | Nano metal ion coated lithium iron phosphate cathode material and preparation method thereof |
| CN115548293B (en) * | 2022-09-23 | 2024-01-30 | 长沙学院 | Spherical LiMnFeVPO 4 Composite positive electrode material/C, and preparation method and application thereof |
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| CN101081696A (en) * | 2007-05-15 | 2007-12-05 | 深圳市贝特瑞电子材料有限公司 | Ferric phosphate lithium material for lithium ion powder cell and preparation method thereof |
| CN101428781A (en) * | 2008-12-08 | 2009-05-13 | 广州丰江电池新技术有限公司 | Conglobation type nanostructured lithium iron phosphate anode material and method for producing the same |
| CN102275887A (en) * | 2011-01-17 | 2011-12-14 | 横店集团东磁股份有限公司 | Preparation method of high capacity high compacted density lithium iron phosphate material and product thereof |
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2012
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101081696A (en) * | 2007-05-15 | 2007-12-05 | 深圳市贝特瑞电子材料有限公司 | Ferric phosphate lithium material for lithium ion powder cell and preparation method thereof |
| CN101428781A (en) * | 2008-12-08 | 2009-05-13 | 广州丰江电池新技术有限公司 | Conglobation type nanostructured lithium iron phosphate anode material and method for producing the same |
| CN102275887A (en) * | 2011-01-17 | 2011-12-14 | 横店集团东磁股份有限公司 | Preparation method of high capacity high compacted density lithium iron phosphate material and product thereof |
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