CN101567441A - One-step preparation method of LiFePO4 powder coated with carbon - Google Patents
One-step preparation method of LiFePO4 powder coated with carbon Download PDFInfo
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- CN101567441A CN101567441A CNA200910069194XA CN200910069194A CN101567441A CN 101567441 A CN101567441 A CN 101567441A CN A200910069194X A CNA200910069194X A CN A200910069194XA CN 200910069194 A CN200910069194 A CN 200910069194A CN 101567441 A CN101567441 A CN 101567441A
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Abstract
The invention relates to a one-step preparation method of LiFePO4 powder coated with carbon. Lithium compounds, ferrite and phosphorous compounds are taken as raw materials, additive is antioxidant and glutin that accounts for 1-6% of the mass of theoretically generated lithium ferrous phosphate; the glutin is dissolved in de-ionized water which is then heated and stirred at the temperature of more than 40 DEG C to obtain the aqueous solution of the glutin. The prepared ferrite solution and the glutin solution are added to a Li3PO4 system to be mixed uniformly; the mixed solution reacts at the temperature of 120-170 DEG C for 2-5h; the obtained product is dry lithium ferrous phosphate powder coated with the glutin; the prepared powder is filled in a quartz crucible and calcined at the temperature of 550-750 DEG C under the protection of N2 atmosphere, and finally the lithium ferrous phosphate powder coated with carbon is obtained. The shape of the prepared lithium ferrous phosphate particles is uniform and columnar with the grain diameter being 400nm, the surface coating is thin and uniform amorphous carbon, has high tap density, is beneficial to improving the electrochemical performance of materials and is suitable for being used as anode material. The method has simple process route and no pollution and is suitable for scale production.
Description
Technical field
The present invention relates to the LiFePO that a kind of one-step method carbon coats
4The preparation method of powder belongs to the energy and material preparing technical field.
Background technology
LiFePO 4 (LiFePO
4) material has abundant raw material, low price, no hygroscopicity, nontoxic, environmentally friendly, characteristics such as specific capacity is higher (theoretical capacity is 170mAh/g), good stability, be a kind of anode material of lithium battery substitution material that has potentiality, be with a wide range of applications and the great market demand.Restrict LiFePO 4 and make the low conductivity that the main cause of positive electrode is ferrousphosphate lithium material itself.Low conductivity has had a strong impact on material charging and discharging currents density and specific capacity, has restricted the practical application of ferrous phosphate.Carry out a large amount of correlative studys in recent years and be intended to improve the ferrousphosphate lithium material conductivity.Improving the LiFePO 4 conductivity method at present comprises: doping, surface coating and refining grain size etc., wherein coating the raising conductivity of electrolyte materials by surface carbon is more effective a kind of method.Form effective carbon coating layer on the LiFePO 4 surface, can improve the surface conductivity of material significantly, thereby obtain comparatively desirable chemical property.In addition, carbon source becomes the carbon of loose structure at pyrolysis, can stop LiFePO
4Particle is grown up, and refinement product crystal grain is beneficial to and improves crystal structure.
The patent of relevant carbon cladded ferrous lithium phosphate synthetic method is more, and as US 7371482, US 7390473, CN1410349A, CN1821062A, CN 1564343A etc.United States Patent (USP) 7371482 is with Fe (NO
3)
39H
2O and LiH
2PO
4Be raw material,, obtain the LiFePO of pure phase by the solution evaporation
4Material.Again with gained LiFePO
4Mix with the carbon source ball milling and to be incorporated in 500 ℃ of following processing and can to obtain the LiFePO 4 that carbon coats.Equally, Chinese patent 1821062A obtains lithium iron phosphate precursor with ferric phosphate, lithium acetate and reducing agent by the solution evaporation, makes LiFePO 4 through Overheating Treatment.Then LiFePO 4 is mixed in solution with carbon source, prepare the LiFePO 4 that carbon coats through heat treatment again.These class methods all are to prepare the LiFePO 4 of pure phase earlier, it are mixed again and then obtain having the LiFePO 4 of carbon coating with carbon source.Thisly coat the powder that obtains through follow-up carbon and need carry out secondary heat treatment, process complexity, and when heat treatment, the crystallization again that might cause crystal grain with grow up unusually, influence the crystal structure of material.Another kind of carbon coating method is directly to form the LiFePO 4 that carbon coats by carbon reduction, promptly realizes simultaneously that at the reduction ferric ion carbon coats.As Chinese patent 1410349A with Fe (Ac)
2, LiAc, NH
4H
2PO
4With organic acid be that initial feed is passed through sol-gel process synthesis type lithium iron phosphate precursor, gel is heat-treated can realize that LiFePO 4 carbon coats.Chinese patent 1564343A is with lithium salts, Fe
3+Compound and phosphate ball milling mix the back and add the high polymer carbon source, make the ferrousphosphate lithium material that carbon coats by heat treatment.United States Patent (USP) 7390473 is a raw material with dextran iron, iron containing compounds, lithium compound and phosphide, is solvent with acetone, and mechanical mixture is even; Under inert atmosphere protection, make the LiFePO 4 that carbon coats in 400～600 ℃ of calcinings.For guaranteeing Fe
3+Fully reduction, this type of course of reaction temperature requirement is higher, the cycle is long and need to introduce excessive carbon source, have a strong impact on the purity and the tap density of material, sometimes need secondary clacining, be difficult to control the batch stability of product, and carbon source is selected to have relatively high expectations, and these have all limited the suitability for industrialized production of material.Chinese patent CN101140985 has provided some important performance indexes of present domestic and international market LiFePO4 product, and concrete numerical value is as shown in table 1.
Table 1 is the performance index of existing LiFePO 4 product both at home and abroad
| U.S.'s product | Middle home made article | |
| Average grain diameter/μ m | 8±3 | 13±5 |
| Tap density/gcm -3 | 1.01 | 0.86 |
Summary of the invention
The LiFePO that the object of the present invention is to provide a kind of one-step method carbon to coat
4The preparation method of powder, according to the carbon cladded ferrous lithium phosphate powder of this method preparation, the granule-morphology homogeneous, particle size distribution is even, has desirable crystal structure; Carbon coating layer thickness is less than 6nm, and even structure can be used for the positive electrode of lithium battery.
The present invention is realized by the following technical programs, the LiFePO that a kind of one-step method carbon coats
4The preparation method of powder, step is as follows:
1) compound with compound, ferrous salt and the phosphorus of lithium is a raw material, and the mol ratio of three kinds of elements is 1～3: 1: 1; Additive is antioxidant and gelatin, and wherein antioxidant is reasonable by 1%～3% of synthesizing lithium ferrous phosphate quality, and the reasonable opinion of gelatin generates 1%～6% of LiFePO 4 quality; The compound of lithium, the compound of phosphorus are made into the aqueous solution respectively, and the solution that just prepares mixes precipitation, and the two fully reacts to continue to stir assurance, and this process pH value is controlled between 7～9, and sediment is Li
3PO
4
2) ferrous salt is dissolved in the aqueous solution of antioxidant; Gelatin is dissolved in deionized water, under greater than 40 ℃, adds the aqueous solution that thermal agitation obtains gelatin; With the ferrous salt solution that makes, the Li that gelatin solution joins step 1 gained successively
3PO
4Mix in the system; Mixed solution is placed closed reaction vessel, react 2～5h down in 120～170 ℃;
3) with step 2) product is with the abundant filtration washing of deionized water, and LiFePO4 intensive drying in vacuum drying chamber that the gained gelatin coats is cooled to room temperature again, and products therefrom be the ferrous phosphate lithium powder of dry gelatin coating;
4) powder that step 3) is made is packed in the silica crucible, at N
2In 550～750 ℃ of calcinings, insulation 3～5h obtains the ferrous phosphate powder for lithium that carbon coats under the atmosphere protection.
Described antioxidant is ascorbic acid or formaldehyde.
The compound of described lithium is LiOHH
2O or Li
2CO
3
Described ferrous salt is FeSO
47H
2O or Fe (Ac)
2
The compound of described phosphorus is H
3PO
4, NH
4H
2PO
4Or (NH
4)
2HPO
4
The invention has the advantages that selected carbon source covering is an industrial gelatine, have wide material sources, characteristics such as with low cost.The distinctive charged group of gelatin molecule is the negative ions in the catching reaction system effectively, becomes the nucleation site of crystal growth, thereby realizes that gelatin contacts with the intermolecular point-to-point static of LiFePO 4, helps synthesizing the uniform powder of particle diameter.Simultaneously, the backbone of gelatin molecule can shrink gathering once more in dry run, thereby realizes the even coating to the ferrous phosphate lithium grain.Under inert atmosphere, gelatin cladded ferrous lithium phosphate presoma is heat-treated, impel gelatin to form carbon coating layer and obtain and have the LiFePO 4 that improves crystal structure, have the LiFePO 4 that even carbon coats thereby prepare once in LiFePO 4 surface cracking.This process can obtain the carbon coating layer of thickness at 1～6nm by strict control gelatin addition, can obtain tap density and reach 1.20～1.30g/cm
3Powder.In addition, be raw material with the divalent iron salt, avoid introducing too much organic substance because of the reduction ferric iron, guarantee that material has higher purity and tap density.
The LiFePO 4 granule-morphology homogeneous that the present invention is prepared is columnar shape, and particle diameter is less than 400nm, and surface coating layer approaches and is uniform amorphous, and has higher tap density, helps improving the chemical property of material, is suitable as positive electrode.Process route involved in the present invention is simple, and the cycle is short, and is pollution-free, very suitable large-scale production.
Description of drawings
The LiFePO that Fig. 1 embodiment 1 synthesizes
4The X ray diffracting spectrum of/C;
The nanometer LiFePO that Fig. 2 embodiment 2 synthesizes
4The sem photograph of/C;
The nanometer LiFePO that Fig. 3 embodiment 1 synthesizes
4The transmission electron microscope picture of/C.
Embodiment
Embodiment 1:
With phosphoric acid, a hydronium(ion) oxidation lithium, green vitriol, gelatin and ascorbic acid is raw material, mol ratio by a hydronium(ion) oxidation lithium, phosphoric acid and green vitriol is 3: 1: 1, accurately take by weighing 2.224g green vitriol, 1.001g one hydronium(ion) oxidation lithium, 0.55ml phosphoric acid (mass percent is 85%), take by weighing 0.08g gelatin and 0.04g antioxidants ascorbic acid, 6% and 3% of the two reasonable respectively opinion synthesizing lithium ferrous phosphate quality.Respectively above-mentioned substance is mixed with phosphoric acid solution, a hydronium(ion) oxidation lithium solution and an ascorbic acid solution, is dissolved in 40 ℃ the deionized water, obtain aqueous gelatin solution.Phosphoric acid solution and a hydronium(ion) oxidation lithium solution are evenly mixed acquisition lithium phosphate precipitation, and course of reaction pH is controlled at 7～9.Green vitriol is dissolved in ascorbic acid solution, again green vitriol is evenly mixed with the lithium phosphate precipitation with the ascorbic acid mixed solution, obtain blackish green suspension-turbid liquid, this suspension-turbid liquid and gelatin solution are transferred in the Pressure solution bullet, and evenly mix.Under 120 ℃, reaction 5h.With the products therefrom filtration washing, obtain the amorphous state lithium iron phosphate precursor powder that gelatin coats at 60 ℃ of following vacuumize 15h.
At N
2Under the atmosphere protection, the amorphous state ferrous phosphate lithium powder that above-mentioned gelatin is coated obtains the ferrous phosphate powder for lithium that good carbon coats at 600 ℃ of following heat treatment 5h, and its X-ray diffraction as shown in Figure 1.Diameter of particle is distributed between 200～300nm, and carbon coating layer thickness is between 4～6nm, and as shown in Figure 3, tap density is 1.22g/cm
3
Embodiment 2:
With phosphoric acid, a hydronium(ion) oxidation lithium, green vitriol, gelatin and ascorbic acid is raw material, mol ratio by a hydronium(ion) oxidation lithium, phosphoric acid and green vitriol is 3: 1: 1, accurately take by weighing 2.224g green vitriol, 1.001g one hydronium(ion) oxidation lithium, 0.55ml phosphoric acid (mass percent is 85%), take by weighing 0.013g gelatin and 0.040g antioxidants ascorbic acid, 1% and 3% of the two reasonable respectively opinion synthesizing lithium ferrous phosphate quality.Respectively above-mentioned substance is mixed with phosphoric acid solution, a hydronium(ion) oxidation lithium solution and an ascorbic acid solution, is dissolved in 40 ℃ the deionized water, obtain aqueous gelatin solution.Phosphoric acid solution and a hydronium(ion) oxidation lithium solution are evenly mixed acquisition lithium phosphate precipitation, and course of reaction pH is controlled at 7～9.Green vitriol is dissolved in ascorbic acid solution, again green vitriol is evenly mixed with the lithium phosphate precipitation with the mixed solution of ascorbic acid, obtain blackish green suspension-turbid liquid, this suspension-turbid liquid and gelatin solution are transferred in the Pressure solution bullet, and evenly mix.Under 170 ℃, reaction 3h.With the products therefrom filtration washing, obtain the amorphous state lithium iron phosphate precursor powder that gelatin coats at 70 ℃ of dry 12h of following vacuumize.
At N
2Under the atmosphere protection, the amorphous state ferrous phosphate lithium powder that above-mentioned gelatin is coated obtains the ferrous phosphate powder for lithium that good carbon coats at 750 ℃ of following heat treatment 3h.Diameter of particle is distributed between 300～600nm, and its SEM as shown in Figure 2.Carbon coating layer thickness is between 2～3nm.Tap density is 1.25g/cm
3
Embodiment 3:
With phosphoric acid, a hydronium(ion) oxidation lithium, green vitriol, gelatin and ascorbic acid is raw material, mol ratio by a hydronium(ion) oxidation lithium, phosphoric acid and green vitriol is 3: 1: 1, accurately take by weighing 2.224g green vitriol, 1.001g one hydronium(ion) oxidation lithium, 0.55ml phosphoric acid (mass percent is 85%), take by weighing 0.013g gelatin and 0.013g antioxidants ascorbic acid, 1% of the two all reasonable opinion synthesizing lithium ferrous phosphate quality.Respectively above-mentioned substance is mixed with phosphoric acid solution, a hydronium(ion) oxidation lithium solution and an ascorbic acid solution, is dissolved in 40 ℃ the deionized water, obtain aqueous gelatin solution.Phosphoric acid solution and a hydronium(ion) oxidation lithium solution are evenly mixed acquisition lithium phosphate precipitation, and course of reaction pH is controlled at 7～9.Green vitriol is dissolved in ascorbic acid solution.Green vitriol is evenly mixed with lithium phosphate with the mixed solution of ascorbic acid, obtain blackish green suspension-turbid liquid, this suspension-turbid liquid and gelatin solution are transferred in the Pressure solution bullet, and evenly mix.Under 150 ℃, reaction 5h.With the products therefrom filtration washing, dry 10h obtains the obviously amorphous state lithium iron phosphate precursor powder of glue coating in 80 ℃ of following vacuum drying chambers.
At N
2Under the atmosphere protection, the amorphous state ferrous phosphate lithium powder that above-mentioned gelatin is coated obtains the ferrous phosphate powder for lithium that good carbon coats at 550 ℃ of following heat treatment 3h.Diameter of particle is distributed between 200～300nm, and carbon coating layer thickness is between 1～2nm.Tap density is 1.27g/cm
3
Embodiment 4:
With diammonium hydrogen phosphate, a hydronium(ion) oxidation lithium, ferrous acetate, gelatin and ascorbic acid is raw material, mol ratio by a hydronium(ion) oxidation lithium, diammonium hydrogen phosphate and green vitriol is 1: 1: 1, accurately take by weighing 1.392g ferrous acetate, 0.336g one hydronium(ion) oxidation lithium, 1.056g diammonium hydrogen phosphate, take by weighing 0.027g gelatin and 0.027g antioxidants ascorbic acid, 2% of the two all reasonable opinion synthesizing lithium ferrous phosphate quality.Respectively above-mentioned substance is mixed with ammonium dibasic phosphate solution, a hydronium(ion) oxidation lithium solution and an ascorbic acid solution, is dissolved in 45 ℃ the deionized water, obtain aqueous gelatin solution.Ammonium dibasic phosphate solution and a hydronium(ion) oxidation lithium solution are evenly mixed acquisition lithium phosphate precipitation, and course of reaction pH is controlled at 7～9.Ferrous acetate is dissolved in ascorbic acid solution.Ferrous acetate is evenly mixed with lithium phosphate with the mixed solution of ascorbic acid, obtain blackish green suspension-turbid liquid, this suspension-turbid liquid and gelatin solution are transferred in the Pressure solution bullet, and evenly mix.Under 120 ℃, reaction 5h.With the products therefrom filtration washing, at 60 ℃ of dry amorphous state lithium iron phosphate precursor powder that obtain the gelatin coating of following vacuumize.
At N
2Under the atmosphere protection, the amorphous state ferrous phosphate lithium powder that above-mentioned gelatin is coated obtains the ferrous phosphate powder for lithium that good carbon coats at 600 ℃ of following heat treatment 5h.Diameter of particle is distributed between 200～300nm.Carbon coating layer is between 3～4nm, and tap density is 1.25g/cm
3
Embodiment 5:
With ammonium dihydrogen phosphate, a hydronium(ion) oxidation lithium, green vitriol, gelatin and ascorbic acid is raw material, mol ratio by a hydronium(ion) oxidation lithium, diammonium hydrogen phosphate and green vitriol is 2: 1: 1, accurately take by weighing 2.224g green vitriol, 0.6714g one hydronium(ion) oxidation lithium, 0.92g ammonium dihydrogen phosphate, take by weighing 0.040g gelatin and 0.040g antioxidants ascorbic acid, 3% of the two all reasonable opinion synthesizing lithium ferrous phosphate quality.Respectively above-mentioned substance is mixed with ammonium dibasic phosphate solution, a hydronium(ion) oxidation lithium solution and an ascorbic acid solution, is dissolved in 50 ℃ the deionized water, obtain aqueous gelatin solution.Ammonium dibasic phosphate solution and a hydronium(ion) oxidation lithium solution are evenly mixed acquisition lithium phosphate precipitation, and course of reaction pH is controlled at 7～9.Green vitriol is dissolved in ascorbic acid solution.Green vitriol is evenly mixed with lithium phosphate with the mixed solution of ascorbic acid, obtain blackish green suspension-turbid liquid, this suspension-turbid liquid and gelatin solution are transferred in the Pressure solution bullet, and evenly mix.Under 170 ℃, reaction 2h.With the products therefrom filtration washing, at 70 ℃ of dry amorphous state lithium iron phosphate precursor powder that obtain the gelatin coating of following vacuumize.
At N
2Under the atmosphere protection, the amorphous state ferrous phosphate lithium powder that above-mentioned gelatin is coated obtains the ferrous phosphate powder for lithium that good carbon coats at 700 ℃ of following heat treatment 4h.Diameter of particle is distributed between 250～350nm.Carbon coating layer is between 3～4nm, and tap density is 1.30g/cm
3
Embodiment 6:
With phosphoric acid, lithium carbonate, green vitriol, gelatin and ascorbic acid is raw material, mol ratio by a hydronium(ion) oxidation lithium, diammonium hydrogen phosphate and ferrous acetate is 3: 2: 2, accurately take by weighing 2.2240g green vitriol, 0.5035g one hydronium(ion) oxidation lithium, 0.55ml phosphoric acid (mass percent is 85%), take by weighing 0.040g gelatin and 0.0277g antioxidants ascorbic acid, 3% and 2% of the two reasonable respectively opinion synthesizing lithium ferrous phosphate quality.
Respectively above-mentioned substance is mixed with phosphorus solution, lithium carbonate solution and ascorbic acid solution, is dissolved in 40 ℃ the deionized water, obtain aqueous gelatin solution.Phosphoric acid solution and lithium carbonate solution are evenly mixed acquisition lithium phosphate precipitation, and course of reaction pH is controlled at 7～9.Green vitriol is dissolved in ascorbic acid solution.Green vitriol is evenly mixed with lithium phosphate with the mixed solution of ascorbic acid, obtain blackish green suspension-turbid liquid, this suspension-turbid liquid and gelatin solution are transferred in the Pressure solution bullet, and evenly mix.Under 170 ℃, reaction 3h.With the products therefrom filtration washing, obtain the amorphous state lithium iron phosphate precursor powder that gelatin coats at 70 ℃ of dry 15h of following vacuumize.
At N
2Under the atmosphere protection, the amorphous state ferrous phosphate lithium powder that above-mentioned gelatin is coated obtains the ferrous phosphate powder for lithium that good carbon coats at 650 ℃ of following heat treatment 4h.Diameter of particle is distributed between 200～350nm.Carbon coating layer is between 3～4nm, and tap density is 1.24g/cm
3
The LiFePO that a kind of one-step method carbon that the present invention proposes coats
4The preparation method of powder is described by embodiment, and person skilled obviously can be changed or suitably change and combination content as herein described in not breaking away from content of the present invention, spirit and scope, realizes the present invention.Special needs to be pointed out is, the replacement that all are similar and change apparent to those skilled in the artly, they are regarded as being included in spirit of the present invention, scope and the content.
Claims (5)
1. the LiFePO that coats of an one-step method carbon
4The preparation method of powder is characterized in that step is as follows:
1) compound with compound, ferrous salt and the phosphorus of lithium is a raw material, and the mol ratio of three kinds of elements is 1～3: 1: 1; Additive is antioxidant and gelatin, and wherein antioxidant is reasonable by 1%～3% of synthesizing lithium ferrous phosphate quality, and the reasonable opinion of gelatin generates 1%～6% of LiFePO 4 quality; The compound of lithium, the compound of phosphorus are made into the aqueous solution respectively, and the solution that just prepares mixes precipitation, and the two fully reacts to continue to stir assurance, and this process pH value is controlled between 7～9, and sediment is Li
3PO
4
2) ferrous salt is dissolved in the aqueous solution of antioxidant; Gelatin is dissolved in deionized water, under greater than 40 ℃, adds the aqueous solution that thermal agitation obtains gelatin; With the ferrous salt solution that makes, the Li that gelatin solution joins step 1 gained successively
3PO
4Mix in the system; Mixed solution is placed closed reaction vessel, react 2～5h down in 120～170 ℃;
3) with step 2) product is with the abundant filtration washing of deionized water, and LiFePO4 intensive drying in vacuum drying chamber that the gained gelatin coats is cooled to room temperature again, and products therefrom be the ferrous phosphate lithium powder of dry gelatin coating;
4) powder that step 3) is made is packed in the silica crucible, at N
2In 550～750 ℃ of calcinings, insulation 3～5h obtains the ferrous phosphate powder for lithium that carbon coats under the atmosphere protection.
2. the LiFePO that one-step method carbon as claimed in claim 1 coats
4The preparation method of powder, the described antioxidant of its feature is ascorbic acid or formaldehyde.
3. the LiFePO that one-step method carbon as claimed in claim 1 coats
4The preparation method of powder, the compound of the described lithium of its feature is LiOHH
2O or Li
2CO
3
4. the LiFePO that one-step method carbon as claimed in claim 1 coats
4The preparation method of powder, the described ferrous salt of its feature is FeSO
47H
2O or Fe (Ac)
2
5. the LiFePO that one-step method carbon as claimed in claim 1 coats
4The preparation method of powder, the compound of the described phosphorus of its feature is H
3PO
4, NH
4H
2PO
4Or (NH
4)
2HPO
4
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|---|---|---|---|
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|---|---|---|---|
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| CN101567441B CN101567441B (en) | 2011-11-30 |
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ID=41283499
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102299334A (en) * | 2011-07-15 | 2011-12-28 | 北京化工大学 | Carbon coated LiFePO4 porous anode and preparation method thereof |
| CN102598388A (en) * | 2009-10-30 | 2012-07-18 | 第一工业制药株式会社 | Lithium secondary battery |
| CN102709558A (en) * | 2012-06-08 | 2012-10-03 | 中南大学 | Method for preparing lithium iron phosphate from vivianite |
| CN102757236A (en) * | 2012-06-28 | 2012-10-31 | 航天材料及工艺研究所 | Wrapping method of ceramic powder |
| CN102910611A (en) * | 2012-10-15 | 2013-02-06 | 彩虹集团公司 | Method for preparing ferrous phosphate-based lithium salt |
| CN103296256A (en) * | 2013-05-13 | 2013-09-11 | 北京化工大学 | Method for preparing LiFePO4/C composite material by using sol-gel method |
| CN103918109A (en) * | 2011-10-04 | 2014-07-09 | 魁北克电力公司 | Positive-electrode materials: methods for their preparation and use in lithium secondary batteries |
| EP2562857A4 (en) * | 2010-04-21 | 2015-08-05 | Lg Chemical Ltd | Lithium iron phosphate with carbon-coated olivine crystal structure and lithium secondary battery using the same |
| CN106887589A (en) * | 2015-12-12 | 2017-06-23 | 中国科学院大连化学物理研究所 | A kind of method for preparing carbon coating phosphoric acid vanadium lithium using biological carbon source |
| CN115020855A (en) * | 2022-06-24 | 2022-09-06 | 广东邦普循环科技有限公司 | Recycling method of waste lithium iron phosphate battery |
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| EP2562857A4 (en) * | 2010-04-21 | 2015-08-05 | Lg Chemical Ltd | Lithium iron phosphate with carbon-coated olivine crystal structure and lithium secondary battery using the same |
| US9331329B2 (en) | 2010-04-21 | 2016-05-03 | Lg Chem, Ltd. | Carbon-coated lithium iron phosphate of olivine crystal structure and lithium secondary battery using the same |
| CN102299334A (en) * | 2011-07-15 | 2011-12-28 | 北京化工大学 | Carbon coated LiFePO4 porous anode and preparation method thereof |
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| CN103918109A (en) * | 2011-10-04 | 2014-07-09 | 魁北克电力公司 | Positive-electrode materials: methods for their preparation and use in lithium secondary batteries |
| CN102709558A (en) * | 2012-06-08 | 2012-10-03 | 中南大学 | Method for preparing lithium iron phosphate from vivianite |
| CN102709558B (en) * | 2012-06-08 | 2014-04-09 | 中南大学 | Method for preparing lithium iron phosphate from vivianite |
| CN102757236A (en) * | 2012-06-28 | 2012-10-31 | 航天材料及工艺研究所 | Wrapping method of ceramic powder |
| CN102757236B (en) * | 2012-06-28 | 2014-03-26 | 航天材料及工艺研究所 | Wrapping method of ceramic powder |
| CN102910611A (en) * | 2012-10-15 | 2013-02-06 | 彩虹集团公司 | Method for preparing ferrous phosphate-based lithium salt |
| CN103296256A (en) * | 2013-05-13 | 2013-09-11 | 北京化工大学 | Method for preparing LiFePO4/C composite material by using sol-gel method |
| CN106887589A (en) * | 2015-12-12 | 2017-06-23 | 中国科学院大连化学物理研究所 | A kind of method for preparing carbon coating phosphoric acid vanadium lithium using biological carbon source |
| CN115020855A (en) * | 2022-06-24 | 2022-09-06 | 广东邦普循环科技有限公司 | Recycling method of waste lithium iron phosphate battery |
| CN115020855B (en) * | 2022-06-24 | 2023-10-17 | 广东邦普循环科技有限公司 | Recycling method of lithium iron phosphate waste batteries |
| CN116639674A (en) * | 2023-05-31 | 2023-08-25 | 河南工程学院 | Preparation method of low-cost high-capacity lithium iron phosphate positive electrode material |
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