CN102593452A - Method for preparing carbon-coated lithium iron phosphate material - Google Patents
Method for preparing carbon-coated lithium iron phosphate material Download PDFInfo
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- CN102593452A CN102593452A CN2012100775928A CN201210077592A CN102593452A CN 102593452 A CN102593452 A CN 102593452A CN 2012100775928 A CN2012100775928 A CN 2012100775928A CN 201210077592 A CN201210077592 A CN 201210077592A CN 102593452 A CN102593452 A CN 102593452A
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Abstract
The invention discloses a method for preparing a carbon-coated lithium iron phosphate material. The method comprises the following two steps of: 1, synthesizing an iron phosphate precursor; and 2, synthesizing a lithium iron phosphate material. The particle size and crystallinity of iron phosphate are controlled by methods of introducing a surfactant and calcining so as to control the performance of a final synthetic product. The material prepared by the method has low granularity, uniform particle size, excellent charging and discharging performance and high-rate discharge performance, and is easily implemented industrially.
Description
Technical field
The present invention relates to a kind of method for preparing anode material of lithium-ion battery, specifically is a kind of carbon-coated LiFePO 4 for lithium ion batteries preparation methods.
Background technology
Lithium ion battery has the power density height; Energy density height and high-temperature behavior excellent characteristics are widely used in mobile phone, laptop computer; Mobile devices such as video camera; Be used for space flight and aviation in addition, artificial satellite and military equipment communication field etc. also are the first-selections of following PHEV and pure electric vehicle.LiFePO4 does not contain precious metals such as cobalt, and cost of material is cheap, and earth reserves are abundant.It had after reversible embedding deviates from lithium since reports such as U.S. John. B. Goodenough in 1997; The higher steadily discharge platform that it has; Height ratio capacity, high security and excellent cycle performance win researchers' favor, are the positive electrodes that lithium ion battery has potentiality.
At present the main method of preparation LiFePO4 has the gel-sol method, spraying sputtering method, solid reaction process, liquid-phase coprecipitation, hydrothermal synthesis method and microwave, assisted synthesizing method such as ultrasonic.Solid-phase synthesis is the synthetic commonly used method of LiFePO4, and its key step is at first fully mixing initial feed, afterwards 300～400 ℃ of insulations, removes raw material and decomposes the ammonia that produces, carbon dioxide, steam etc., cooling grinding afterwards.Double sintering between 400～800 ℃.Its implementation is simple, obtains product easily.But because the abundant contact gear ratio of raw material is difficult, so impurity in products is more, and crystal grain is grown up easily, and particle is inhomogeneous, and the product electro-chemical activity is not high, and the growth ball milling time can be improved this shortcoming, but to the corresponding increase of expending of energy.
The carbothermic method of being come by the solid phase method development is a raw material with stable ferric iron, in course of reaction, ferric iron is reduced to ferrous iron, and has realized the carbon coating.Step is simple, and is easy to operate, is easy to realize, is a kind of method with big commercial production potentiality.But the material capacity and the high rate performance of this method preparation are on the low side than the material that the conventional solid state reaction method obtains.Ferric phosphate is a kind of comparatively excellent ferric iron source, can increase commercial cost but adopt commercial ferric phosphate to prepare LiFePO4 (CN201110072967.7), and can't optimize the performance of ferric phosphate.Adopting oxidation of divalent to prepare ferric phosphate (CN102244246A) then increases production stage, and the amount of oxidant is not easy control.
Hydrothermal synthesis method is a kind of quick, and cost is low, and the method for conserve energy.Realize than be easier to that the product that obtains is thinner, better performances in the laboratory.But its industrialization not only large-size reactor is difficult to realize that danger is big, and prepares the strict controlled atmospher of needs in the process at precursor, increases cost.And with this synthetic method the Fe inconsistent phenomenon takes place in forming olivine structural easily, influence chemical property.
With householder method microwave, ultrasonic introducing commercial production (CN10180792A), production cost and production stage have been increased.
Summary of the invention
In order to overcome defective of the prior art; Improve the performance of LiFePO 4 material; The present invention provides a kind of preparation method, and liquid-phase coprecipitation and carbothermic method are combined, and is the synthetic carbon-coated LiFePO 4 for lithium ion batteries material of initial feed with the ferric phosphate; Control the performance and the later stage sintering parameter of precursor ferric phosphate emphatically, use the LiFePO 4 material that obtains excellent performance.
Technical scheme of the present invention is following: a kind of carbon-coated LiFePO 4 for lithium ion batteries preparation methods may further comprise the steps:
(1) ferric phosphate is synthetic: in deionized water, add nonionic surface active agent, be stirred to it and form homogeneous solution, then with water-soluble ferric iron compound, dissolve in above-mentioned homogeneous solution; Add phosphoric acid solution or ammonium dihydrogen phosphate again; Dropping ammonia is regulated pH value to 1.5～4 then, generates the ferric phosphate deposition; With sintering behind the deposition centrifugal drying that generates 0～20 hour;
(2) LiFePO 4 material is synthetic: with the precursor ferric phosphate and the lithium source of above-mentioned preparation, and the carbon source ball mill mixing, dry back sintering under atmosphere protection obtains end product carbon-coated LiFePO 4 for lithium ion batteries material.
Further, the lithium source is lithium acetate, lithium carbonate, lithium hydroxide or lithium oxalate, and iron lithium mol ratio is 1: (0.5～1.5).
Further, said carbon source is glucose, sucrose, citric acid or acetylene black, the amount of carbon source be ferric phosphate and lithium salts quality and 5～30%.
Further, sintering temperature is 350～450 ℃ in the step (1); Step is sintered to double sintering in (2), at first 350～450 ℃ of sintering 3～8 hours, 650～750 ℃ of calcinings 8～15 hours, all adopts atmosphere protection in the sintering process afterwards.
Further, said atmosphere be nitrogen or argon gas or hydrogen volume content be 1～15% hydrogen nitrogen mixed gas or hydrogen volume content be 1～15% hydrogen-argon-mixed.
Further, also added manganese acetate or cobalt acetate or magnesium acetate during step (2) ball milling, the mol ratio of ferrimanganic, iron cobalt or iron magnesium is 1: (0.05～0.1).
Further, dropping ammonia is regulated pH value to 2～3 in the step (1).
Further, surfactant is tween or molecular weight less than 600000 polyoxyethylene in the step (1), and its consumption is 5～15% of a ferric iron compound quality.
Further, in the step (1), the mol ratio of iron phosphorus is 1: (0.8～1.2).
Further, in the step (1), ferric iron compound is ferric nitrate, ferric trichloride or ferric sulfate.
Compared with prior art, of the present invention have a following advantage:
(1) among the preparation method of the present invention, the synthetic employing liquid-phase coprecipitation of ferric phosphate can be so that raw material be uniformly dispersed, and can under cryogenic conditions, synthesize, and is a kind of comparatively desirable method for preparing the precursor ferric phosphate.
(2) the inventive method is simple to operate, be easy in the industry realize, and homogeneity of product can be excellent.Be fit to produce in enormous quantities.And in building-up process, reduced inert atmosphere protection, reduced energy loss.
Introduce surfactant when (3) presoma is synthetic in the inventive method, can effectively reduce the granular precursor size, make LiFePO4 in sintering process, can fully contact, and the end product particle size is less with the lithium source.Help material and obtain excellent high-rate discharge ability.
(4) the present invention is when synthetic composite lithium iron phosphate material, and synthetic method is simple, can improve the lithium ion diffusion rate and the conductivity of LiFePO4.
Description of drawings
Fig. 1 is the multiplying power discharging figure of the LiFePO 4 material of embodiment 1 preparation;
Fig. 2 is the sem photograph of the LiFePO 4 material of embodiment 1 preparation.
Embodiment
Embodiment 1
Tween 80 is added in the 100ml deionized water, add 0.03molFeCl
3.6H
2O stirs and makes its dissolving, and the consumption of Tween 80 is FeCl
3.6H
215% of O quality.With 0.03molNH
4H
2PO
4Be dissolved in the 100ml deionized water, stir and make its dissolving.With NH
4H
2PO
4Solution dropwise adds in the ferric chloride solution that contains tween, stirs 10min.PH value with the ammoniacal liquor regulator solution is 2.3, has a large amount of faint yellow precipitations to occur.The powerful 3h that stirs.Centrifugal drying obtains nanoscale FePO
4.2H
2O.
With the faint yellow FePO that obtains
4.2H
2O mixes with lithium acetate, and then adding glucose ball milling 5h makes its abundant mixing.90 ℃ of dryings are 12 hours afterwards.Mol ratio is Fe:Li=1:1.2, and the consumption of glucose is FePO
4.2H
2The quality of O and lithium acetate and 25%.
The drying composite that obtains at first 350 ℃ of sintering 3 hours, 650 ℃ of calcinings 10 hours, promptly obtains the carbon-coated LiFePO 4 for lithium ion batteries positive electrode afterwards under nitrogen protection.
Fig. 1 is the multiplying power discharging figure of the LiFePO 4 material of present embodiment preparation, and Fig. 2 is the sem photograph of the LiFePO 4 material of present embodiment preparation, and as can beappreciated from fig. 2, sample particle is evenly distributed, and on average about 200nm.As shown in Figure 1, after synthetic sample is assembled into button cell, 5 (not shown)s of activation under the 0.1C multiplying power, afterwards respectively at 3C, 5C discharges and recharges respectively under 8C and the 10C 20 times.As can beappreciated from fig. 1, this sample has good high-rate discharge ability.
Embodiment 2
Polysorbas20 is added in the 100ml deionized water, add 0.03mol Fe
2(SO
4)
3, stirring and make its dissolving, the consumption of polysorbas20 is Fe
2(SO
4)
310% of quality.With 0.03molNH
4H
2PO
4Be dissolved in the 100ml deionized water, stir and make its dissolving.With NH
4H
2PO
4Solution dropwise adds in the ferrum sulfuricum oxydatum solutum that contains tween, stirs 10min.PH value with the ammoniacal liquor regulator solution is 3, has a large amount of faint yellow precipitations to occur.The powerful 3h that stirs.Centrifugal drying obtains nanoscale FePO
4.2H
2O.
With the faint yellow FePO that obtains
4.2H
2O in tube furnace at 3%H
2/ N
2The following 350 ℃ of sintering 5h of (hydrogen volume content is 3% hydrogen nitrogen mixed gas) atmosphere protection mix with lithium oxalate afterwards, and then adding glucose ball milling 5h makes its abundant mixing.90 ℃ of dryings are 12 hours afterwards.Mol ratio is Fe:Li=1:0.5, and the consumption of glucose is FePO
4.2H
225% of the gross mass of O and lithium oxalate.
The drying composite that obtains is at 3%H
2/ N
2At first 450 ℃ of sintering 5 hours, 750 ℃ of calcinings 8 hours, promptly obtain the carbon-coated LiFePO 4 for lithium ion batteries positive electrode afterwards under the atmosphere protection.Test shows, the battery of being assembled by the lithium iron phosphate positive material of present embodiment preparation has good high-rate discharge ability.
Embodiment 3
Tween 80 is added in the 100ml deionized water, add 0.05molFe (NO
3)
3.H
2O stirs and makes its dissolving, and the consumption of Tween 80 is Fe (NO
3)
3.H
25% of O quality.With 0.05molNH
4H
2PO
4Be dissolved in the 100ml deionized water, stir and make its dissolving.With NH
4H
2PO
4Solution dropwise adds in the iron nitrate solution that contains tween, stirs 10min.Using the pH value of PH meter regulator solution is 2.3, has a large amount of faint yellow depositions to occur.The powerful 3h that stirs.Centrifugal drying obtains nanoscale FePO
4.2H
2O.
With the faint yellow FePO that obtains
4.2H
2O mixes with lithium carbonate, and then adds glucose and manganese acetate (mol ratio Fe:Mn=1:0.1) ball milling 5h makes its abundant mixing.90 ℃ of dryings are 12 hours afterwards.Mol ratio is Fe:Li=1:1.5, and the consumption of glucose is FePO
4.2H
225% of the gross mass of O and lithium carbonate.
The drying composite that obtains at first 400 ℃ of sintering 5 hours, afterwards 700 ℃ of calcinings 10 hours, promptly obtains carbon and coats compound phosphoric acid ferrimanganic lithium anode material under the Ar atmosphere protection.Test shows, the battery of being assembled by the lithium iron phosphate positive material of present embodiment preparation has good high-rate discharge ability.
Embodiment 4
Polysorbas20 is added in the 100ml deionized water, add 0.03molFe
2(SO
4)
3, stirring and make its dissolving, the consumption of polysorbas20 is Fe
2(SO
4)
38% of quality.With 0.024molNH
4H
2PO
4Be dissolved in the 100ml deionized water, stir and make its dissolving.With NH
4H
2PO
4Solution dropwise adds in the ferrum sulfuricum oxydatum solutum that contains tween, stirs 10min.Using the pH value of PH meter regulator solution is 2, has a large amount of faint yellow depositions to occur.The powerful 3h that stirs.Centrifugal drying obtains nanoscale FePO
4.2H
2O.
With the faint yellow FePO that obtains
4.2H
2O sintering in tube furnace mixes with lithium carbonate, and then adding sucrose ball milling 5h makes its abundant mixing.90 ℃ of dryings are 12 hours afterwards.Mol ratio is Fe:Li=1:1.5, and the consumption of sucrose is FePO
4.2H
230% of the gross mass of O and lithium carbonate.
The drying composite that obtains is at 3%H
2At first 350 ℃ of sintering 8 hours,, promptly obtain carbon and coat compound phosphoric acid iron cobalt lithium anode material under the/Ar atmosphere protection afterwards 750 ℃ of calcinings 15 hours.Test shows, the battery of being assembled by the lithium iron phosphate positive material of present embodiment preparation has good high-rate discharge ability.
Embodiment 5
With molecular weight is that 50000 polyoxyethylene adds in the 100ml deionized water, adds 0.03molFeCl
3.6H
2O stirs and makes its dissolving.With 0.036molH
3PO
4Be dissolved in the 100ml deionized water, stir and make its dissolving.With H
3PO
4Solution dropwise adds and contains in the polyoxyethylated ferric chloride solution, stirs 10min.Using the pH value of PH meter regulator solution is 4, has a large amount of faint yellow depositions to occur.The powerful 3h that stirs.Centrifugal drying obtains nanoscale FePO
4.2H
2O.
With the faint yellow FePO that obtains
4.2H
2O mixes with lithium hydroxide, and then adds acetylene black and magnesium acetate (mol ratio Fe:Mg=1:0.05) ball milling 5h makes its abundant mixing.90 ℃ of dryings are 12 hours afterwards.Mol ratio is Fe:Li=1:1.2, and the consumption of acetylene black is FePO
4.2H
2The quality of O and lithium hydroxide and 5%.
The drying composite that obtains is at 1%H
2/ N
2At first 350 ℃ of sintering 8 hours,, promptly obtain carbon and coat compound phosphoric acid iron magnesium lithium anode material under the atmosphere protection afterwards 750 ℃ of calcinings 10 hours.Test shows, the battery of being assembled by the lithium iron phosphate positive material of present embodiment preparation has good high-rate discharge ability.
Embodiment 6
Tween 80 is added in the 100ml deionized water, add 0.03mol Fe
2(SO
4)
3, stirring and make its dissolving, the consumption of Tween 80 is Fe
2(SO
4)
312% of quality.With 0.03molNH
4H
2PO
4Be dissolved in the 100ml deionized water, stir and make its dissolving.With NH
4H
2PO
4Solution dropwise adds in the ferrum sulfuricum oxydatum solutum that contains tween, stirs 10min.PH value with the ammoniacal liquor regulator solution is 1.5, has a large amount of faint yellow precipitations to occur.The powerful 3h that stirs.Centrifugal drying obtains nanoscale FePO
4.2H
2O.
With the faint yellow FePO that obtains
4.2H
2O in tube furnace at 15%H
2/ N
2At 450 ℃ of sintering 20h, mix with lithium oxalate afterwards under the atmosphere protection, and then adding citric acid ball milling 5h makes its abundant mixing.90 ℃ of dryings are 12 hours afterwards.Mol ratio is Fe:Li=1:0.5, and the consumption of citric acid is FePO
4.2H
2The quality of O and lithium oxalate and 25%.
The drying composite that obtains is at 15%H
2/ N
2At first 450 ℃ of sintering 8 hours, 700 ℃ of calcinings 15 hours, promptly obtain the carbon-coated LiFePO 4 for lithium ion batteries positive electrode afterwards under the atmosphere protection.Test shows, the battery of being assembled by the lithium iron phosphate positive material of present embodiment preparation has good high-rate discharge ability.
Embodiment 7
With molecular weight is that 30000 polyoxyethylene adds in the 100ml deionized water, adds 0.03molFeCl
3.6H
2O stirs and makes its dissolving.With 0.03molH
3PO
4Be dissolved in the 100ml deionized water, stir and make its dissolving.With H
3PO
4Solution dropwise adds and contains in the polyoxyethylated ferric chloride solution, stirs 10min.Using the pH value of PH meter regulator solution is 3.5, has a large amount of faint yellow depositions to occur.The powerful 3h that stirs.Centrifugal drying obtains nanoscale FePO
4.2H
2O.
With the faint yellow FePO that obtains
4.2H
2O mixes with lithium hydroxide, and then adds acetylene black and cobalt acetate (mol ratio Fe:Co=1:0.08) ball milling 5h makes its abundant mixing.90 ℃ of dryings are 12 hours afterwards.Mol ratio is Fe:Li=1:1.2, and the consumption of acetylene black is FePO
4.2H
2The quality of O and lithium hydroxide and 20%.
The drying composite that obtains is at 15%H
2At first 350 ℃ of sintering 8 hours,, promptly obtain carbon and coat compound phosphoric acid iron magnesium lithium anode material under the/Ar atmosphere protection afterwards 750 ℃ of calcinings 10 hours.Test shows, the battery of being assembled by the lithium iron phosphate positive material of present embodiment preparation has good high-rate discharge ability.
Embodiment 8
Polysorbas20 is added in the 100ml deionized water, add 0.03mol Fe
2(SO
4)
3, stirring and make its dissolving, the consumption of polysorbas20 is Fe
2(SO
4)
315% of quality.With 0.03molNH
4H
2PO
4Be dissolved in the 100ml deionized water, stir and make its dissolving.With NH
4H
2PO
4Solution dropwise adds in the ferrum sulfuricum oxydatum solutum that contains tween, stirs 10min.PH value with the ammoniacal liquor regulator solution is 3, has a large amount of faint yellow precipitations to occur.The powerful 3h that stirs.Centrifugal drying obtains nanoscale FePO
4.2H
2O.
With the faint yellow FePO that obtains
4.2H
2O in tube furnace at 1%H
2/ Ar (hydrogen volume content be 1% hydrogen-argon-mixed) the following 400 ℃ of sintering 10h of atmosphere protection mix with lithium oxalate afterwards, and then add glucose ball milling 5h and make its abundant mixing.90 ℃ of dryings are 12 hours afterwards.Mol ratio is Fe:Li=1:0.5, and the consumption of glucose is FePO
4.2H
220% of the gross mass of O and lithium oxalate.
The drying composite that obtains is at 1%H
2At first 450 ℃ of sintering 5 hours, 750 ℃ of calcinings 8 hours, promptly obtain the carbon-coated LiFePO 4 for lithium ion batteries positive electrode afterwards under the/Ar atmosphere protection.Test shows, the battery of being assembled by the lithium iron phosphate positive material of present embodiment preparation has good high-rate discharge ability.
Claims (10)
1. carbon-coated LiFePO 4 for lithium ion batteries preparation methods is characterized in that may further comprise the steps:
(1) ferric phosphate is synthetic: in deionized water, add nonionic surface active agent, be stirred to it and form homogeneous solution, then with water-soluble ferric iron compound, dissolve in above-mentioned homogeneous solution; Add phosphoric acid solution or ammonium dihydrogen phosphate again; Dropping ammonia is regulated pH value to 1.5～4 then, generates the ferric phosphate deposition; With sintering behind the deposition centrifugal drying that generates 0～20 hour;
(2) LiFePO 4 material is synthetic: with the precursor ferric phosphate and the lithium source of above-mentioned preparation, and the carbon source ball mill mixing, dry back sintering under atmosphere protection obtains end product carbon-coated LiFePO 4 for lithium ion batteries material.
2. preparation method according to claim 1 is characterized in that said lithium source is lithium acetate, lithium carbonate, lithium hydroxide or lithium oxalate, and iron lithium mol ratio is 1: (0.5～1.5).
3. preparation method according to claim 2 is characterized in that said carbon source is glucose, sucrose, citric acid or acetylene black, the amount of carbon source be ferric phosphate and lithium salts quality and 5～30%.
4. preparation method according to claim 3 is characterized in that: sintering temperature is 350～450 ℃ in the step (1); Step is sintered to double sintering in (2), at first 350～450 ℃ of sintering 3～8 hours, 650～750 ℃ of calcinings 8～15 hours, all adopts atmosphere protection in the sintering process afterwards.
5. preparation method according to claim 4, it is characterized in that said atmosphere be nitrogen or argon gas or hydrogen volume content be 1～15% hydrogen nitrogen mixed gas or hydrogen volume content be 1～15% hydrogen-argon-mixed.
6. preparation method according to claim 5 has also added manganese acetate or cobalt acetate or magnesium acetate when it is characterized in that step (2) ball milling, and the mol ratio of ferrimanganic, iron cobalt or iron magnesium is 1: (0.05～0.1).
7. according to each described preparation method of claim 1 to 6, it is characterized in that dropping ammonia is regulated pH value to 2～3 in the step (1).
8. according to each described preparation method of claim 1 to 6, it is characterized in that surfactant in the step (1) is tween or molecular weight less than 600000 polyoxyethylene, its consumption is 5～15% of a ferric iron compound quality.
9. according to each described preparation method of claim 1 to 6, it is characterized in that in the step (1), the mol ratio of iron phosphorus is 1: (0.8～1.2).
10. according to each described preparation method of claim 1 to 6, it is characterized in that in the step (1), ferric iron compound is ferric nitrate, ferric trichloride or ferric sulfate.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103996829A (en) * | 2014-05-29 | 2014-08-20 | 西安交通大学 | Nano-micro composite structure lithium iron phosphate positive material and coprecipitation preparation method thereof |
| CN105870443A (en) * | 2016-04-28 | 2016-08-17 | 深圳市力为锂能科技有限公司 | Lithium iron phosphate composite material and preparation method thereof |
| CN105967161A (en) * | 2016-06-23 | 2016-09-28 | 成都翔羽科技有限公司 | Method for continuously preparing low-cost battery grade ferric phosphate by utilizing iron filings |
| CN109103433A (en) * | 2018-08-22 | 2018-12-28 | 江苏元景锂粉工业有限公司 | A kind of nitrogen mixes carbon-coated lithium iron phosphate composite and preparation method thereof |
| CN109904423A (en) * | 2019-02-27 | 2019-06-18 | 湖北锂诺新能源科技有限公司 | Fluorine-ion-doped and lithium fluoride coated LiFePO 4 for lithium ion batteries positive electrode preparation method |
| CN110085855A (en) * | 2019-06-06 | 2019-08-02 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of method that LiFePO4 is modified |
| CN110857216A (en) * | 2019-09-29 | 2020-03-03 | 湖南雅城新材料有限公司 | Battery-grade iron phosphate precursor, lithium iron phosphate, and preparation method and application thereof |
| CN110914194A (en) * | 2017-07-19 | 2020-03-24 | 纳诺万材料公司 | Improved synthesis of olivine-type lithium metal phosphate positive electrode materials |
| CN114976020A (en) * | 2022-07-19 | 2022-08-30 | 蜂巢能源科技股份有限公司 | Modified lithium iron phosphate, preparation method thereof and lithium ion battery |
| CN116281932A (en) * | 2023-04-18 | 2023-06-23 | 上海量孚新能源科技有限公司 | Lithium iron manganese phosphate and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103996829A (en) * | 2014-05-29 | 2014-08-20 | 西安交通大学 | Nano-micro composite structure lithium iron phosphate positive material and coprecipitation preparation method thereof |
| CN105870443A (en) * | 2016-04-28 | 2016-08-17 | 深圳市力为锂能科技有限公司 | Lithium iron phosphate composite material and preparation method thereof |
| CN105870443B (en) * | 2016-04-28 | 2018-11-09 | 深圳市力为锂能科技有限公司 | A kind of composite ferric lithium phosphate material and preparation method thereof |
| CN105967161A (en) * | 2016-06-23 | 2016-09-28 | 成都翔羽科技有限公司 | Method for continuously preparing low-cost battery grade ferric phosphate by utilizing iron filings |
| CN105967161B (en) * | 2016-06-23 | 2018-01-09 | 成都翔羽科技有限公司 | A kind of method that low-cost cell-grade ferric orthophosphate is continuously prepared using iron filings |
| CN110914194A (en) * | 2017-07-19 | 2020-03-24 | 纳诺万材料公司 | Improved synthesis of olivine-type lithium metal phosphate positive electrode materials |
| CN109103433A (en) * | 2018-08-22 | 2018-12-28 | 江苏元景锂粉工业有限公司 | A kind of nitrogen mixes carbon-coated lithium iron phosphate composite and preparation method thereof |
| CN109103433B (en) * | 2018-08-22 | 2021-09-14 | 江苏元景锂粉工业有限公司 | Nitrogen-doped carbon-coated lithium iron phosphate composite material and preparation method thereof |
| CN109904423A (en) * | 2019-02-27 | 2019-06-18 | 湖北锂诺新能源科技有限公司 | Fluorine-ion-doped and lithium fluoride coated LiFePO 4 for lithium ion batteries positive electrode preparation method |
| CN110085855A (en) * | 2019-06-06 | 2019-08-02 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of method that LiFePO4 is modified |
| CN110857216A (en) * | 2019-09-29 | 2020-03-03 | 湖南雅城新材料有限公司 | Battery-grade iron phosphate precursor, lithium iron phosphate, and preparation method and application thereof |
| CN110857216B (en) * | 2019-09-29 | 2021-11-12 | 湖南雅城新材料有限公司 | Battery-grade iron phosphate precursor, lithium iron phosphate, and preparation method and application thereof |
| CN114976020A (en) * | 2022-07-19 | 2022-08-30 | 蜂巢能源科技股份有限公司 | Modified lithium iron phosphate, preparation method thereof and lithium ion battery |
| CN116281932A (en) * | 2023-04-18 | 2023-06-23 | 上海量孚新能源科技有限公司 | Lithium iron manganese phosphate and preparation method and application thereof |
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