CN102244246A - Preparation method of lithium iron phosphate/carbon composite material - Google Patents
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- CN102244246A CN102244246A CN2011101544786A CN201110154478A CN102244246A CN 102244246 A CN102244246 A CN 102244246A CN 2011101544786 A CN2011101544786 A CN 2011101544786A CN 201110154478 A CN201110154478 A CN 201110154478A CN 102244246 A CN102244246 A CN 102244246A
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Abstract
The invention relates to a preparation method of a lithium iron phosphate/carbon composite material. The preparation method comprises the following steps: preparing amorphous iron phosphate through a coprecipitation method from a soluble ferrous iron source, a phosphorus source and an oxidant used as raw materials, and synthesizing the lithium iron phosphate/carbon cathode material on the basis of amorphous iron phosphate through a gel method by using oxalic acid and citric acid as carbon sources and lithium hydroxide as a lithium source, wherein by adjusting the ratio of the oxalic acid to the citric acid, the carbon content can be controlled, and ion doping can be easily carried out. The prepared lithium iron phosphate has the advantages of small particle size and narrow particle size distribution, thus reducing the ion diffusion path and maintaining high capacity and good rate performance of the product. In the preparation method provided by the invention, inexpensive ferrous sulfate is used as a raw material to synthesize amorphous ferric phosphate without preventing Fe<2+> from oxidation, thereby simplifying the process; ammonium salt waste liquid can be recycled as fertilizer, thereby reducing the cost; and water is used as the solvent in the preparation process, thereby generating no harmful gas. Thus, the preparation method is environmentally friendly, low in energy consumption, low in cost and suitable for industrial mass production.
Description
Technical field
The present invention relates to a kind of preparation method of lithium iron phosphate, can be used for anode material for lithium-ion batteries.Belong to the new energy materials technical field.
Background technology
Olivine-type LiFePO4 and LiCoO
2And other positive electrode compare have long service life, cost of material is low, thermal stability is high, fail safe is good and advantage such as environmentally friendly, makes one of its positive electrode that becomes tool potentiality.By the study on the modification to LiFePO4, carbon increases electronic conductivity and ion doping, minimizing particle size increase methods such as lithium ion conductive as adding, and the low-temperature conductive rate of LiFePO4 is improved, but performance has reached the level of practicability.
Method preparing phosphate iron lithium can be divided into " divalent iron salt method " and " ferric iron source method " according to the difference of synthetic route employing source of iron.Ferrous oxalate, ferrous acetate are " divalent iron salt method " sources of iron commonly used, but consider that divalence source of iron cost is higher, and oxidation easily in the building-up process, and then " ferric iron source method " becomes the main direction of research and development lithium iron phosphate positive material gradually.
" ferric iron source method " can be divided into solid reaction process again, liquid phase method and solid-liquid mixing method.(Feng Zerong etc. are the research that source of iron prepares the LiFePO4 reaction mechanism with the iron oxide, rare metal, 2009,33 (3): 361-365) and ferric phosphate (Wu Chunyang etc., a step solid phase method prepared in batches LiFePO with iron oxide
4The research of/C, power technology, 2011,35 (1): 18-21) be source of iron, adopt solid phase reaction to prepare LiFePO4/carbon positive electrode.This method technology is simple, easily large-scale production, but exist reactant to be difficult for mixing, product particle size distribution inequality, problems such as product lot quantity stability deficiency.For pattern and the particle size distribution of controlling LiFePO4 better; CN 101237043A and CN1305147C disclose a kind of ferric phosphate that synthesizes with coprecipitation as source of iron; add lithium source, carbon source mixing then, the method for solid phase reaction synthesizing iron lithium phosphate/carbon positive electrode under protective atmosphere.LiFePO4/material with carbon element that this method (can be described as the solid-liquid mixing method) obtains is compared with solid reaction process, in granule-morphology and particle size distribution control, be improved, but the process of synthesizing iron lithium phosphate still belongs to solid phase reaction in essence, has the deficiency of solid reaction process in varying degrees.
For addressing the above problem, liquid phase method is mutually even with its thing, and particle is little, and synthesis temperature is low, is easy to advantages such as doping and is used to the synthesized high-performance lithium iron phosphate positive material.With the ferric iron is in the liquid phase method of source of iron, more typically is exactly sol-gel process.Spong A D etc. are source of iron with the solubility ferric nitrate, lithium acetate is the lithium source, and phosphoric acid is the phosphorus source, and sucrose is carbon source, sol-gel process has been synthesized nano-grade lithium iron phosphate/carbon composite (et al, A solution-precursor synthesis of carbon-coated LiFePO
4For Li-ion cells, Journal of the electrochemical society, 2005,152 (12): A2376-A2382).But nitric acid material produces nitrogen oxide when calcining is synthetic, pollutes big.For this reason, Sun Y etc. are source of iron with the synthetic amorphous phosphoric acid iron of coprecipitation, and lithium hydroxide is the lithium source, citric acid is a chelating agent, polyethylene glycol is made carbon source, has synthesized LiFePO4/carbon positive electrode (Sun Y et al, the Synthesis of LiFePO of porous with sol-gal process
4Cathode materials by a chemical method, Advanced materials Research, 2011,197-198:1049-1052), relatively environmental protection, but porous calcium phosphate iron lithium/material with carbon element causes tap density too little, and the volume of battery specific capacity is on the low side.
Summary of the invention
The object of the invention be to provide a kind of with low cost, synthesis technique is simple, can control the LiFePO4 granule-morphology, and has the preparation method of the LiFePO4/carbon positive electrode of good electric chemical property.
The preparation method of lithium iron phosphate of the present invention comprises the steps:
1. the synthetic amorphous phosphoric acid iron of coprecipitation: it is water-soluble that Fe/P mol ratio 1: 1 is pressed in solubility divalence source of iron and phosphorus source, and the oxidant of adding capacity makes Fe
2+Be converted into Fe fully
3+, in solution, add precipitation reagent then, make pH=3.3～3.6; Behind filtration, the deionized water wash, sediment obtains amorphous phosphoric acid iron after 75～80 ℃ of oven dry;
2. gel method synthesizing iron lithium phosphate/carbon positive electrode:
Oxalic acid and citric acid are dissolved in deionized water get solution I; add lithium hydroxide then; acid-base neutralization reaction back adds the amorphous phosphoric acid iron that 1. step makes; wherein the mol ratio of lithium hydroxide and amorphous phosphoric acid iron is 1: 1, and the slip that obtains after the stirring is spray-dried, obtains gel particle; in protective atmosphere, calcine then; behind the insulation certain hour, cool to room temperature with the furnace, obtain lithium iron phosphate.
As one of the preferred technical solution of the present invention, the solubility divalence source of iron of above-mentioned steps in 1. is green vitriol, i.e. FeSO47H2O, and the phosphorus source is the phosphoric acid of 85wt% (mass percent), and oxidant is the hydrogen peroxide of 30wt%, and precipitation reagent is an ammoniacal liquor.The preferred Fe that uses
2+Concentration is 2mol/L; The preferred ammonia concn that uses is 2mol/L.
In arbitrary technical scheme of the invention described above, stirring behind the amorphous phosphoric acid iron of the 2. middle adding of step step is for reaction can fully be carried out, and according to the situation that feeds intake of the present invention, the inventor advises stirring after 8～15 hours and carries out subsequent operation.
Further in the optimal technical scheme, described step calcining heat 2. is 600～750 ℃, is incubated 4～10 hours.
Again in the optimized technical scheme, the described step 2. mol ratio of mesoxalic acid and citric acid is 1: 0.65～1.30, and the mol ratio of carboxylate radical total amount is 1: 1 in lithium hydroxide and the solution I.
In the technical scheme of the invention described above, to the mist that preferably hydrogen and high-purity argon gas, high pure nitrogen or the nitrogen of the protective atmosphere of step in are 2. formed, the volume content of hydrogen is 3～4% in the mist.
Highly preferred, technical scheme of the present invention comprises the steps:
1. the synthetic amorphous phosphoric acid iron of coprecipitation: it is water-soluble that the phosphoric acid of green vitriol and 85wt% is pressed Fe/P mol ratio 1: 1, makes Fe
2+Concentration is 2mol/L; The 30wt% hydrogen peroxide that adds capacity makes Fe
2+Be converted into Fe fully
3+, in solution, add 2mol/L ammoniacal liquor then, make pH=3.3～3.6; Behind filtration, the deionized water wash, sediment obtains amorphous phosphoric acid iron after 75～80 ℃ of oven dry;
2. gel method synthesizing iron lithium phosphate/carbon positive electrode:
Oxalic acid and citric acid are dissolved in deionized water according to mol ratio 1: 0.65～1.30 get solution I, add then with solution I in the lithium hydroxide of carboxylate radical total amount equal molar quantities, acid-base neutralization reaction back adds the amorphous phosphoric acid iron that 1. step makes, and wherein the mol ratio of lithium hydroxide and amorphous phosphoric acid iron is 1: 1; Stir after 8～15 hours, resulting slip is spray-dried, obtain gel particle, in protective atmosphere, to calcine then, calcining heat is 600～750 ℃, is incubated after 4～10 hours, cools to room temperature with the furnace, obtains lithium iron phosphate; Wherein calcining employed protective atmosphere is the mist that hydrogen and high-purity argon gas, high pure nitrogen or nitrogen are formed, and the volume content of hydrogen is 3～4% in the mist.
The invention has the beneficial effects as follows:
(1) the present invention is that raw material synthesizes amorphous trivalent ferric phosphate with the divalence ferrous sulfate of cheapness, need not anti-Fe
2+Technology has been simplified in the oxidation measure, and the ammonium salt waste liquid that produces in the synthetic ferric phosphate process can reclaim as fertilizer sources and use, and has reduced cost; With synthetic amorphous phosphoric acid iron is source of iron, and oxalic acid and citric acid are carbon source, and no pernicious gas produces in synthesizing iron lithium phosphate/carbon positive electrode process, and whole process of preparation all is to be solvent with water; Not only can control granule-morphology with spray drying, also can a step obtain gel particle, save the process that adds hot preparation colloidal sol.Therefore the present invention is a kind of Environmentally-sound technology, and less energy consumption, and cost is low, is fit to industrial large-scale production.
(2) the present invention has overcome the deficiency of solid reaction process, sol-gal process, the content of the ratio may command carbon by regulating oxalic acid and citric acid, and carry out ion doping easily.The LiFePO4 particle diameter of the method preparation is little, and narrow diameter distribution has dwindled the path of ions diffusion, helps overcoming the low shortcoming of ions diffusion rate, helps the raising of electrical property.Product capacity conservation rate height, high rate performance is better.
Description of drawings
Accompanying drawing 4 width of cloth of the present invention, wherein:
Fig. 1 is the SEM figure by the synthetic ferric phosphate of embodiment 1;
Fig. 2 is the XRD figure by the synthetic ferric phosphate of embodiment 1;
Fig. 3 is the SEM figure by the prepared lithium iron phosphate of embodiment 1;
Fig. 4 is the XRD figure by the prepared lithium iron phosphate of embodiment 1;
Fig. 5 is the SEM figure by the prepared lithium iron phosphate of embodiment 2;
Fig. 6 is the XRD figure by the prepared lithium iron phosphate of embodiment 2;
Fig. 7 is the SEM figure by the prepared lithium iron phosphate of embodiment 3;
Fig. 8 is the XRD figure by the prepared lithium iron phosphate of embodiment 3.
Embodiment
Following non-limiting example can make those of ordinary skill in the art more fully understand the present invention, but does not limit the present invention in any way.If no special instructions, raw materials such as the oxalic acid that reaches described in the present invention, citric acid, green vitriol, 85wt% phosphoric acid, lithium hydroxide, 30wt% hydrogen peroxide, ammoniacal liquor are more than the chemical pure level; Used aqueous solvent is deionized water.Carbon content adopts carbon and sulfur analytical instrument to measure, and lithium iron phosphate to discharge and recharge be by people such as Han Enshan (coprecipitation synthesizing iron lithium phosphate carbon dope composite positive pole, inorganic chemicals industry, 2008,40 (1): the sample preparation methods that 22-25) provides, with Wuhan blue light (LAND CT2001A) battery test system, temperature is 25 ℃ and measures down.
With 83.40g FeSO
47H
2O and 34.80g H
3PO
4Join in the 150ml deionized water, be stirred to fully dissolving after, add the H of 18.00g 30wt%
2O
2, stir and make its complete reaction, in solution, dropwise drip the about 321ml of 2M/L ammoniacal liquor, pH is about 3.65, continues to stir and treats that the pH value is basicly stable.Filter, wash the gained precipitation, 80 ℃ of oven dry obtain the precursor ferric phosphate.
Take by weighing citric acid 12.60g, oxalic acid 11.34g is dissolved in the 90g deionized water, takes by weighing 15.12gLiOHH
2O puts into acid solution, after reacting completely, pours the synthetic ferric phosphate of 45.26g into and mixes and stirred 15 hours.With reacted slip spray drying, obtain gel particle, 650 ℃ of calcinings under high-purity argon gas atmosphere then are incubated 6 hours, cool to room temperature with the furnace, obtain lithium iron phosphate.
Carbon content 1.38wt% in the material, particle diameter 0.3～0.8 μ m.
With the lithium sheet is negative pole, and the discharge capacity of this LiFePO4/carbon positive electrode 1C is 107mAg/h.
With 13.91gFeSO
47H
2O and 5.76g H
3PO
4Join in the 25ml deionized water, be stirred to fully dissolving after, add the H of 3.00g 30wt%
2O
2, stir and make its complete reaction, in solution, dropwise drip 2M/L ammoniacal liquor 55ml, pH is 3.50, continues to stir and treats that the pH value is basicly stable.Filter, wash the gained precipitation, 75 ℃ of oven dry obtain the precursor ferric phosphate.
Take by weighing citric acid 5.56g, oxalic acid 2.52g is dissolved in the 30g deionized water, takes by weighing 5.04gLiOHH
2O puts into acid solution, after reacting completely, pours the synthetic ferric phosphate mechanical agitation of 22.42g into 15 hours.With reacted slip spray drying, obtain gel particle, 650 ℃ of calcinings under high-purity argon gas atmosphere then are incubated 6 hours, cool to room temperature with the furnace, obtain lithium iron phosphate.
Carbon content 2.02wt% in the material, particle diameter 0.3～0.8 μ m.
With the lithium sheet is negative pole, and the discharge capacity of this LiFePO4/carbon positive electrode 1C can reach 136mAg/h.
Embodiment 3
With 27.80gFeSO
47H
2O, 11.60gH
3PO
4Add the 50ml deionized water, be stirred to dissolving fully after, add the H of 6.00g 30wt%
2O
2, stir and make its complete reaction, in solution, dropwise drip 2M/L ammoniacal liquor 107ml, control pH is about 3.38, continues to stir and treats that the pH value is basicly stable.Filter, wash the gained precipitation, 75 ℃ of oven dry obtain the precursor ferric phosphate.
Take by weighing citric acid 5.04g, oxalic acid 3.02g is dissolved in the 30g deionized water, takes by weighing 5.04g LiOHH
2O puts into acid solution, after reacting completely, adds the synthetic ferric phosphate ball milling of 22.44g and mixes 10 hours.With the slip spray drying, obtain gel particle, 700 ℃ of calcinings under high pure nitrogen atmosphere then are incubated 6 hours, cool to room temperature with the furnace, obtain lithium iron phosphate.
Carbon content 1.73wt% in the material, particle diameter 0.5～0.8um.
With the lithium sheet is negative pole, and the discharge capacity of this LiFePO4/carbon positive electrode 1C is 119mAg/h.
Claims (8)
1. the preparation method of lithium iron phosphate comprises the steps:
1. the synthetic amorphous phosphoric acid iron of coprecipitation: it is water-soluble that Fe/P mol ratio 1: 1 is pressed in solubility divalence source of iron and phosphorus source, and the oxidant of adding capacity makes Fe
2+Be converted into Fe fully
3+, in solution, add precipitation reagent then, make pH=3.3～3.6; Behind filtration, the deionized water wash, sediment obtains amorphous phosphoric acid iron after 75～80 ℃ of oven dry;
2. gel method synthesizing iron lithium phosphate/carbon positive electrode:
Oxalic acid and citric acid are dissolved in deionized water get solution I; add lithium hydroxide then; acid-base neutralization reaction back adds the amorphous phosphoric acid iron that 1. step makes; wherein the mol ratio of lithium hydroxide and amorphous phosphoric acid iron is 1: 1, and the slip that obtains after the stirring is spray-dried, obtains gel particle; in protective atmosphere, calcine then; behind the insulation certain hour, cool to room temperature with the furnace, obtain lithium iron phosphate.
2. the described method of claim 1 is characterized in that the solubility divalence source of iron during described step 1. is a green vitriol, and the phosphorus source is the phosphoric acid of 85wt%, and oxidant is the hydrogen peroxide of 30wt%, and precipitation reagent is an ammoniacal liquor.
3. the described method of claim 2 is characterized in that described Fe
2+Concentration and ammonia concn are 2mol/L.
4. the described method of claim 1 is characterized in that stirring 8～15 hours behind the amorphous phosphoric acid iron of the 2. middle adding of described step.
5. the described method of claim 1 is characterized in that described step calcining heat 2. is 600～750 ℃, is incubated 4～10 hours.
6. the described method of claim 1, it is characterized in that described step 2. the mol ratio of mesoxalic acid and citric acid be 1: 0.65～1.30, the mol ratio of carboxylate radical total amount is 1: 1 in lithium hydroxide and the solution I.
7. the described method of claim 1 is characterized in that the protective atmosphere during described step 2. is the mist that hydrogen and high-purity argon gas, high pure nitrogen or nitrogen are formed, and the volume content of hydrogen is 3～4% in the mist.
8. the described method of claim 1 is characterized in that comprising the steps:
1. the synthetic amorphous phosphoric acid iron of coprecipitation: it is water-soluble that the phosphoric acid of green vitriol and 85wt% is pressed Fe/P mol ratio 1: 1, makes Fe
2+Concentration is 2mol/L; The 30wt% hydrogen peroxide that adds capacity makes Fe
2+Be converted into Fe fully
3+, in solution, add 2mol/L ammoniacal liquor then, make pH=3.3～3.6; Behind filtration, the deionized water wash, sediment obtains amorphous phosphoric acid iron after 75～80 ℃ of oven dry;
2. gel method synthesizing iron lithium phosphate/carbon positive electrode:
Oxalic acid and citric acid are dissolved in deionized water according to mol ratio 1: 0.65～1.30 get solution I, add then with solution I in the lithium hydroxide of carboxylate radical total amount equal molar quantities, acid-base neutralization reaction back adds the amorphous phosphoric acid iron that 1. step makes, and wherein the mol ratio of lithium hydroxide and amorphous phosphoric acid iron is 1: 1; Stir after 8～15 hours, resulting slip is spray-dried, obtain gel particle, in protective atmosphere, to calcine then, calcining heat is 600～750 ℃, is incubated after 4～10 hours, cools to room temperature with the furnace, obtains lithium iron phosphate; Wherein calcining employed protective atmosphere is the mist that hydrogen and high-purity argon gas, high pure nitrogen or nitrogen are formed, and the volume content of hydrogen is 3～4% in the mist.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103078114A (en) * | 2013-01-18 | 2013-05-01 | 青岛科技大学 | Porous lithium iron phosphate/carbon composite microspheres and preparation method thereof |
| CN103280692A (en) * | 2013-06-03 | 2013-09-04 | 哈尔滨工业大学 | 2-micrometer solid laser device operating based on polarization beam combining manner |
| CN108461720A (en) * | 2018-02-01 | 2018-08-28 | 北大先行科技产业有限公司 | A kind of preparation method of anode material for lithium-ion batteries |
| CN111146439A (en) * | 2018-11-06 | 2020-05-12 | 北京泰丰先行新能源科技有限公司 | Preparation method of lithium iron phosphate cathode material |
| CN111704122A (en) * | 2020-07-24 | 2020-09-25 | 艾姆新能源(江苏)有限公司 | Preparation method of lithium iron phosphate cathode material of lithium ion battery |
| CN112289991A (en) * | 2020-10-20 | 2021-01-29 | 合肥国轩高科动力能源有限公司 | Ni and Cr co-doped carbon-coated lithium iron phosphate and preparation method and application thereof |
| CN112678792A (en) * | 2020-12-28 | 2021-04-20 | 大连博融新材料有限公司 | Iron phosphate, preparation method and application thereof |
| CN114613965A (en) * | 2022-03-22 | 2022-06-10 | 宜昌邦普循环科技有限公司 | Preparation method and application of lithium iron phosphate/carbon composite material |
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Cited By (11)
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| CN103078114A (en) * | 2013-01-18 | 2013-05-01 | 青岛科技大学 | Porous lithium iron phosphate/carbon composite microspheres and preparation method thereof |
| CN103280692A (en) * | 2013-06-03 | 2013-09-04 | 哈尔滨工业大学 | 2-micrometer solid laser device operating based on polarization beam combining manner |
| CN103280692B (en) * | 2013-06-03 | 2015-06-10 | 哈尔滨工业大学 | 2-micrometer solid laser device operating based on polarization beam combining manner |
| CN108461720A (en) * | 2018-02-01 | 2018-08-28 | 北大先行科技产业有限公司 | A kind of preparation method of anode material for lithium-ion batteries |
| CN108461720B (en) * | 2018-02-01 | 2021-11-09 | 北大先行科技产业有限公司 | Preparation method of lithium ion battery anode material |
| CN111146439A (en) * | 2018-11-06 | 2020-05-12 | 北京泰丰先行新能源科技有限公司 | Preparation method of lithium iron phosphate cathode material |
| CN111704122A (en) * | 2020-07-24 | 2020-09-25 | 艾姆新能源(江苏)有限公司 | Preparation method of lithium iron phosphate cathode material of lithium ion battery |
| CN112289991A (en) * | 2020-10-20 | 2021-01-29 | 合肥国轩高科动力能源有限公司 | Ni and Cr co-doped carbon-coated lithium iron phosphate and preparation method and application thereof |
| CN112678792A (en) * | 2020-12-28 | 2021-04-20 | 大连博融新材料有限公司 | Iron phosphate, preparation method and application thereof |
| CN112678792B (en) * | 2020-12-28 | 2022-05-13 | 大连博融新材料有限公司 | Iron phosphate, preparation method and application thereof |
| CN114613965A (en) * | 2022-03-22 | 2022-06-10 | 宜昌邦普循环科技有限公司 | Preparation method and application of lithium iron phosphate/carbon composite material |
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