CN101640268A - Preparation method of precursor iron phosphate of cathode material lithium iron phosphate of lithium ion battery - Google Patents
Preparation method of precursor iron phosphate of cathode material lithium iron phosphate of lithium ion battery Download PDFInfo
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- CN101640268A CN101640268A CN200910306742A CN200910306742A CN101640268A CN 101640268 A CN101640268 A CN 101640268A CN 200910306742 A CN200910306742 A CN 200910306742A CN 200910306742 A CN200910306742 A CN 200910306742A CN 101640268 A CN101640268 A CN 101640268A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a preparation method of precursor iron phosphate of cathode material lithium iron phosphate of a lithium ion battery, which comprises the following steps: simultaneously addingferrous ion aqueous solution with the concentration of 0.05-2mol/L and phosphate radical aqueous solution into a reactor according to the stoichiometric ratio of ferrous ions and phosphate radical ions of 0.8-1.2: 1 and at the speed of 400-1000mL/h, and reacting for 0.2-2h under the conditions that the reaction temperature is 50-90 DEG C and the stirring speed is 400-1200rpm; adding hydrogen peroxide with excessive stoichiometry and reacting for 0.2-2h, and ageing for 2-8h, filtering, washing and drying to obtain iron phosphate powder with two crystallization water; and in the obtained iron phosphate, the total ferric content (Fe) is 29.5-30.5 percent, the P content is 16.0-16.9 percent, the particle size is 0.1-1Mum, and D50 is 1-5Mum. The invention has simple and convenient operation process, simple device, easy control, low energy consumption, even and fine particle size distribution and high reaction activity and is suitable for preparing the lithium ion battery cathode material lithium iron phosphate.
Description
Technical field
The present invention relates to a kind of preparation method of precursor iron phosphate of cathode material lithium iron phosphate of lithium ion battery.
Background technology
Ferric phosphate is because its low price, environmentally safe, and advantageous as anode material of lithium battery, Prosini etc. obtain amorphous FePO by coprecipitation
41.5H
2O; Hong etc. have studied amorphous FePO
4Synthesis condition.Croce etc. make the FePO of hexagonal structure by wet chemistry method
4FePO
42H
2O is pink monoclinic crystal, can be used as food and feed additive, is particularly useful for the preparation of lithium ion battery anode material lithium iron phosphate.Present industrial preparation method of ferric phosphate is synthetic by ferrite and phosphate pyroreaction, has the technological process complexity, working condition harshness, problems such as the difficult control of product composition.Chinese patent 200810049265.5 discloses a kind of preparation method who is used for positive material positive ferric phosphate of lithium battery, by ferrous sulfate heptahydrate, phosphoric acid, hydrogen peroxide or sodium chlorate, NaOH or sodium carbonate and water are feedstock production, the particle diameter of gained ferric orthophosphate is 1-2 μ m, and specific area is bigger, is 48-55.5m
2/ g, can make with the ferric phosphate is that the LiFePO4 capacity that presoma makes reduces relatively.The present invention is by adjusting source of iron and phosphorus source, and reducing cost, to optimize material and the protection environment is a purpose, each condition of control procedure obtains the ferric phosphate with two crystallizations water that particle diameter is moderate, be particularly suitable for preparing LiFePO4 need not regulating under the pH value prerequisite.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of precursor iron phosphate of cathode material lithium iron phosphate of lithium ion battery, to obtain ferric phosphate with two crystallizations water, operating process is easy, equipment is simple, be easy to control, energy consumption is low, the material particle size that obtains is evenly distributed, tiny, the reactivity height is applicable to preparation lithium ion battery material LiFePO4.
Technical scheme of the present invention may further comprise the steps:
(1) preparation of ferrous phosphate: the stoichiometric proportion by ferrous ion and phosphate anion is 0.8-1.2: 1, being the ferrous ion aqueous solution of 0.05-2mol/L and the phosphate radical aqueous solution with concentration adds in the reactor with the speed of 400-1000mL/h simultaneously, in reaction temperature is that 50-90 ℃, mixing speed are under the 400-1200rpm condition, reaction 0.2-2h;
(2) preparation of ferric phosphate: in above-mentioned reactor, add the excessive hydrogen peroxide of stoichiometry,, continue reaction 0.2-2h, behind ageing 2-8h, filter repeatedly and wash again, separate obtaining ferric phosphate to a large amount of white precipitates generations;
(3) put into air dry oven at temperature 60-140 ℃ of dry 5-20h, obtain dry FePO
42H
2The O powder.
The described ferrous ion aqueous solution is ferrous sulfate heptahydrate, ferrous nitrate, frerrous chloride, a kind of in ferrous acetate, ferrous lactate or the ferrous oxalate aqueous solution.
The described phosphate radical aqueous solution is a kind of in ammonium hydrogen phosphate or ammonium dihydrogen phosphate or the phosphate aqueous solution.
The concentration of described hydrogen peroxide is 30%.
The total iron content of gained ferric phosphate of the present invention (Fe) is 29.5-30.5%, and P is 16.0-16.9%, and particle diameter is 0.1-1 μ m, D
50Be 1-5 μ m.The present invention is easy and simple to handle, equipment is simple, be easy to control, energy consumption is low, and the material particle size that obtains is evenly distributed, tiny, and the reactivity height is particularly useful for preparing the lithium ion battery material LiFePO4.
Description of drawings
The SEM collection of illustrative plates of the ferric phosphate that Fig. 1 obtains for embodiment 1;
The DSC-TGA collection of illustrative plates of the ferric phosphate that Fig. 2 obtains for embodiment 1.
Embodiment
Embodiment 1:
(1) takes by weighing ferrous sulfate heptahydrate 55.604g, take by weighing ammonium dihydrogen phosphate 23.004g, respectively it is dissolved in the deionized water of 0.2L, stir and make it dissolving; Copperas solution and ammonium dihydrogen phosphate are joined in the reactor with the speed of 800mL/h simultaneously, and open the stirring instrument and carry out strong stirring, control reaction temperature is 80 ℃, low whipping speed is under the 800r/min condition, reaction time is 0.5h, obtains the suspension of grey ferrous phosphate;
(2) get hydrogen peroxide 11.4mL and join in the above-mentioned suspension, have a large amount of white precipitates to produce at once, continue reaction 0.5h, behind ageing 6h, filter repeatedly and wash again, obtain the sediment ferric phosphate, color is a white.The total iron content of gained ferric phosphate (Fe) is 29.8%, and P is 16.5%, and particle diameter is about 300nm, D
50=2.5 μ m.
(3) ferric phosphate that the 2nd step was separated by prior art is put into air dry oven in 120 ℃ of dry 12h; Obtain dry FePO
42H
2The O powder.
Embodiment 2:
(1) takes by weighing ferrous sulfate heptahydrate 55.604g, take by weighing ammonium dihydrogen phosphate 23.004g, respectively it is dissolved in the deionized water of 2L, stir and make it dissolving; Copperas solution and ammonium dihydrogen phosphate are joined in the reactor with the speed of 600mL/h simultaneously, and open the stirring instrument and carry out strong stirring, control reaction temperature is 60 ℃, low whipping speed is under the 1000r/min condition, reaction time is 1h, obtains the suspension of light grey ferrous phosphate;
(2) get hydrogen peroxide 15.6mL and join in the above-mentioned suspension, have a large amount of white precipitates to produce at once, continue reaction 1h, behind ageing 8h, filter repeatedly and wash again, obtain the sediment ferric phosphate, color is light yellow.The total iron content of gained ferric phosphate (Fe) is 31.8%, and P is 17.2%, and particle diameter is about 100nm, D
50=1.8 μ m.
(3) ferric phosphate that the 2nd step was separated by prior art is put into air dry oven in 140 ℃ of dry 14h; Obtain dry FePO
42H
2The O powder.
Embodiment 3:
(1) takes by weighing ferrous sulfate heptahydrate 55.604g, take by weighing ammonium dihydrogen phosphate 23.004g, respectively it is dissolved in the deionized water of 0.1L, stir and make it dissolving; Copperas solution and ammonium dihydrogen phosphate are joined in the reactor with the speed of 1000mL/h simultaneously, and open the stirring instrument and stir, control reaction temperature is 90 ℃, low whipping speed is under the 600r/min condition, reaction time is 0.3h, obtains the suspension of light grey ferrous phosphate;
(2) get hydrogen peroxide 11.4mL and join in the above-mentioned suspension, have a large amount of white precipitates to produce at once, continue reaction 0.3h, behind ageing 4h, filter repeatedly and wash again, obtain the sediment ferric phosphate, color is a white.The total iron content of gained ferric phosphate (Fe) is 25.2%, and P is 13.7%, and particle diameter is about 1 μ m, D
50=4.3 μ m.
(3) ferric phosphate that the 2nd step was separated by prior art is put into air dry oven in 80 ℃ of dry 10h; Obtain dry FePO
42H
2The O powder.
Embodiment 4:
(1) takes by weighing ferrous nitrate 36g, take by weighing ammonium hydrogen phosphate 26.4g, respectively it is dissolved in the deionized water of 0.4L, stir and make it dissolving; Ferrous nitrate solution and ammonium hydrogen phosphate solution are joined in the reactor with the speed of 800mL/h simultaneously, and open the stirring instrument and stir, control reaction temperature is 80 ℃, low whipping speed is under the 800r/min condition, reaction time is 1h, obtains the suspension of light grey ferrous phosphate;
(2) get hydrogen peroxide 11.4mL and join in the above-mentioned suspension, have a large amount of white precipitates to produce at once, continue reaction 1h, behind ageing 4h, filter repeatedly and wash again, obtain the sediment ferric phosphate, color is a white.The total iron content of gained ferric phosphate (Fe) is 29.1%, and P is 15.9%, and particle diameter is about 200nm, D
50=2.2 μ m.
(3) ferric phosphate that the 2nd step was separated by prior art is put into air dry oven in 140 ℃ of dry 10h; Obtain dry FePO
42H
2The O powder.
Embodiment 5:
(1) takes by weighing the ferrous 36g of oxalic acid dihydrate, take by weighing ammonium dihydrogen phosphate 23.004g, respectively it is dissolved in the deionized water of 150mL, stir and make it dissolving; Oxalic acid dihydrate ferrous iron solution and ammonium dihydrogen phosphate are joined in the reactor with the speed of 800mL/h simultaneously, and open the stirring instrument and stir, control reaction temperature is 80 ℃, low whipping speed is under the 800r/min condition, reaction time is 0.5h, obtains the suspension of light grey ferrous phosphate;
(2) get hydrogen peroxide 11.4mL and join in the above-mentioned suspension, have a large amount of white precipitates to produce at once, continue reaction 0.5h, behind ageing 6h, filter repeatedly and wash again, obtain the sediment ferric phosphate, color is a white.The total iron content of gained ferric phosphate (Fe) is 30.6%, and P is 17.1%, and particle diameter is about 500nm, D
50=3.2 μ m.
(3) ferric phosphate that the 2nd step was separated by prior art is put into air dry oven in 120 ℃ of dry 14h, obtains dry FePO
42H
2The O powder.
Claims (4)
1. the preparation method of a precursor iron phosphate of cathode material lithium iron phosphate of lithium ion battery is characterized in that, may further comprise the steps:
(1) preparation of ferrous phosphate: the stoichiometric proportion by ferrous ion and phosphate anion is 0.8-1.2: 1, being the ferrous ion aqueous solution of 0.05-2mol/L and the phosphate radical aqueous solution with concentration adds in the reactor with the speed of 400-1000mL/h simultaneously, in reaction temperature is that 50-90 ℃, mixing speed are under the 400-1200rpm condition, reaction 0.2-2h;
(2) preparation of ferric phosphate: in above-mentioned reactor, add the excessive hydrogen peroxide of stoichiometry,, continue reaction 0.2-2h, behind ageing 2-8h, filter repeatedly and wash again, separate obtaining ferric phosphate to a large amount of white precipitates generations;
(3) put into air dry oven at temperature 60-140 ℃ of dry 5-20h, obtain dry FePO42H2O powder.
2. the preparation method of precursor iron phosphate of cathode material lithium iron phosphate of lithium ion battery according to claim 1, it is characterized in that the described ferrous ion aqueous solution is ferrous sulfate heptahydrate, ferrous nitrate, frerrous chloride, a kind of in ferrous acetate, ferrous lactate or the ferrous oxalate aqueous solution.
3. the preparation method of precursor iron phosphate of cathode material lithium iron phosphate of lithium ion battery according to claim 1 is characterized in that, the described phosphate radical aqueous solution is a kind of in ammonium hydrogen phosphate or ammonium dihydrogen phosphate or the phosphate aqueous solution.
4. the preparation method of precursor iron phosphate of cathode material lithium iron phosphate of lithium ion battery according to claim 1 is characterized in that, the concentration of described hydrogen peroxide is 30%.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101820062A (en) * | 2010-05-05 | 2010-09-01 | 黄铭 | Multi-solvent preparation method of lithium iron phosphate |
| CN102101662A (en) * | 2011-04-01 | 2011-06-22 | 四川大学 | Preparation method and product of ferric phosphate |
| CN102126713A (en) * | 2011-03-01 | 2011-07-20 | 四川大学 | High-purity iron phosphate used for producing lithium ion battery positive-pole material and preparation method thereof |
| CN102431988A (en) * | 2011-10-12 | 2012-05-02 | 浙江南都电源动力股份有限公司 | New process for preparing low-cost cell-grade iron phosphate material from basic iron acetate |
| CN102479944A (en) * | 2010-11-22 | 2012-05-30 | 海洋王照明科技股份有限公司 | Preparation method and application of lithium iron phosphate composite material |
| CN102760880A (en) * | 2012-08-07 | 2012-10-31 | 杨志宽 | High power iron phosphate ion battery material and preparation method thereof |
| CN104362341A (en) * | 2014-09-23 | 2015-02-18 | 深圳市贝特瑞新能源材料股份有限公司 | High-density nano-lithium iron phosphate material and preparation method thereof |
| CN105470504A (en) * | 2014-09-29 | 2016-04-06 | 住友大阪水泥股份有限公司 | Cathode material, method for producing cathode materials, cathode, and lithium ion battery |
| CN105895914A (en) * | 2016-05-11 | 2016-08-24 | 上海应用技术学院 | Preparation method of iron phosphate dihydrate |
| CN108183234A (en) * | 2018-01-05 | 2018-06-19 | 乳源东阳光磁性材料有限公司 | Preparation method of lithium iron phosphate/carbon composite material |
| CN109721041A (en) * | 2019-03-18 | 2019-05-07 | 中南大学 | A kind of preparation method of high-tap density ferric phosphate |
-
2009
- 2009-09-09 CN CN200910306742A patent/CN101640268A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101820062A (en) * | 2010-05-05 | 2010-09-01 | 黄铭 | Multi-solvent preparation method of lithium iron phosphate |
| CN102479944A (en) * | 2010-11-22 | 2012-05-30 | 海洋王照明科技股份有限公司 | Preparation method and application of lithium iron phosphate composite material |
| CN102126713B (en) * | 2011-03-01 | 2012-10-03 | 四川大学 | High-purity iron phosphate used for producing lithium ion battery positive-pole material and preparation method thereof |
| CN102126713A (en) * | 2011-03-01 | 2011-07-20 | 四川大学 | High-purity iron phosphate used for producing lithium ion battery positive-pole material and preparation method thereof |
| CN102101662A (en) * | 2011-04-01 | 2011-06-22 | 四川大学 | Preparation method and product of ferric phosphate |
| CN102101662B (en) * | 2011-04-01 | 2012-09-05 | 四川大学 | Preparation method and product of ferric phosphate |
| CN102431988A (en) * | 2011-10-12 | 2012-05-02 | 浙江南都电源动力股份有限公司 | New process for preparing low-cost cell-grade iron phosphate material from basic iron acetate |
| CN102431988B (en) * | 2011-10-12 | 2013-05-29 | 浙江南都电源动力股份有限公司 | New process for preparing low-cost cell-grade iron phosphate material from basic iron acetate |
| CN102760880A (en) * | 2012-08-07 | 2012-10-31 | 杨志宽 | High power iron phosphate ion battery material and preparation method thereof |
| CN104362341A (en) * | 2014-09-23 | 2015-02-18 | 深圳市贝特瑞新能源材料股份有限公司 | High-density nano-lithium iron phosphate material and preparation method thereof |
| CN105470504A (en) * | 2014-09-29 | 2016-04-06 | 住友大阪水泥股份有限公司 | Cathode material, method for producing cathode materials, cathode, and lithium ion battery |
| CN105895914A (en) * | 2016-05-11 | 2016-08-24 | 上海应用技术学院 | Preparation method of iron phosphate dihydrate |
| CN108183234A (en) * | 2018-01-05 | 2018-06-19 | 乳源东阳光磁性材料有限公司 | Preparation method of lithium iron phosphate/carbon composite material |
| CN108183234B (en) * | 2018-01-05 | 2020-10-20 | 乳源东阳光磁性材料有限公司 | Preparation method of lithium iron phosphate/carbon composite material |
| CN109721041A (en) * | 2019-03-18 | 2019-05-07 | 中南大学 | A kind of preparation method of high-tap density ferric phosphate |
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Application publication date: 20100203 |