CN102874788A - Process for preparing lithium iron phosphate material with co-precipitation method - Google Patents

Process for preparing lithium iron phosphate material with co-precipitation method Download PDF

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CN102874788A
CN102874788A CN2012103824466A CN201210382446A CN102874788A CN 102874788 A CN102874788 A CN 102874788A CN 2012103824466 A CN2012103824466 A CN 2012103824466A CN 201210382446 A CN201210382446 A CN 201210382446A CN 102874788 A CN102874788 A CN 102874788A
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lithium
iron
ratio
lifepo
phosphate
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刘涛涛
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Irico Group Corp
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a process for preparing a lithium iron phosphate material with a co-precipitation method. The process comprises the following steps of (1) preparing nanoscale lithium iron phosphate primary particles; (2) drying and carbon-coating the primary particles; and (3) sintering lithium iron phosphate: placing the obtained mixture in a nitrogen atmosphere or a mixing atmosphere with a volume ratio of nitrogen to hydrogen being 1-5 : 95-99, high-temperature roasting the mixture for 4-8 hours at a temperature of 500-800 DEG C, and thus the lithium iron phosphate cathode material is obtained. The process for preparing the lithium iron phosphate material with the co-precipitation method is provided. The process is rich is raw material source, low in cost, simple and practical in synthetic process and low in production cost and has high yield and no pollution to no environment. The product lithium ion battery cathode material LiFePO4 has relatively good electrochemical performance.

Description

Coprecipitation method prepares the technique of LiFePO 4 material
Technical field
The present invention relates to the technique that coprecipitation method prepares LiFePO 4 material.
Background technology
In lithium ion battery, positive electrode material occupies very important status, also is the emphasis of current lithium ion battery development.Traditional positive electrode material is to bore sour lithium, its advantage be energy height, good cycle, preparation simply, technology maturation, Technological adaptability be good, shortcoming is that price is too high, poor safety performance.The lithium manganate low price, but cycle performance and high-temperature behavior have much room for improvement./ 2nd materials with manganese and nickel part substituting cobalt are materials of the acid energy of lithium manganate and cobalt and price compromise, and its cobalt contents can not fall too low, and the price of nickel is also very high, so its cost performance is undesirable.And the iron lithium phosphate cost is low, aboundresources, good cycle, is desirable anode material for lithium-ion batteries.
LiFePO 4(LEP) positive electrode material also has very large defective, and its ion and electronic conductivity are not good, causes the charge-discharge magnification performance not good.This shortcoming has greatly affected LiFePO 4Replace LiCoO 2Become anode material for lithium-ion batteries of new generation.LiFePO 4This defective of positive electrode material can overcome by the preparation ultra-fine grain.By increasing the material specific surface area, promote being in contact with one another or the coated with conductive charcoal between the particle, can improve LiFePO 4The conductivity of positive electrode material.But thereupon a new problem arose again.Along with the increase of specific surface area, the amount that is coated with required caking agent and solvent also increases greatly, has brought very large difficulty for the coating of pole piece, and after pole piece is prepared into battery core or battery, is easy to occur falling the material phenomenon.At present, LiFePO 4 material ubiquity coating difficult problem.
The people such as J.B.Goodenough of U.S. Texas university in 1999 obtain the patent right of US PatentNo.591382de lithium battery anode LiFePO 4 material, low discharging current with 0.05mA/cm2, capacity is 110mAh/g, reach far away the theoretical capacity of 170mAh/g, reason is that iron lithium phosphate electronics and ionic conductivity are low.Be head it off, the people such as N.Ravet and M.Armand adopt charcoal coating, method metal-doped and that phosphate potential substitutes greatly to improve the iron lithium phosphate specific conductivity.The Yet-Ming Chiang of Massachusetts Institute Technology in 2002 etc. applies for a patent US2004/005265A1, and+2 above metal ions that mix in the lithium position can increase substantially electronic conductivity, thereby have improved the multiplying power property of iron lithium phosphate.More than provide fundamental basis for the application in the power lithium-ion battery.
Sony company adopts Li 3PO and Fe 3(PO) 2-8H 20 is raw material, adds together ball milling of amorphous carbon black or carbon precursor, prepares iron lithium phosphate below 6000C.The advantage of the method maximum is to only have water to discharge in the tail gas, and productive rate is high, but need to prepare first the ferrous phosphate presoma, and if other elements that mix need to add in addition in proportion the balance that phosphoric acid could keep each element metering ratio.
Based on pyrocarbon thermal reduction synthetic technology, the cheap ferric iron sources such as ferric oxide of U.S. Valence Technology Inc. company, it is excessive to add weight ratio 100% when starting material mix, and is prepared iron lithium phosphate in ferric iron by the amorphous carbon black that carbon black is reduced to ferrous consumption.
Prior art generally adopts solid phase method or wet chemical method to prepare positive active material LiFeP04, and for example publication number is that the Chinese patent of CN 1401559A discloses a kind of iron lithium phosphate (LiFePO 4) the preparation method, the method with lithium salts, ferrous salt and phosphoric acid salt ground and mixed evenly after high-temperature calcination, calcine complete rear adding conductive agent ground and mixed and make iron lithium phosphate.But during the employing solid phase method, various solids components are difficult to fully mix, and especially the conductive agent dispersion is inhomogeneous for various compositions in the iron phosphate lithium positive pole active substance that therefore obtains, and directly affects the electroconductibility of positive active material.
Summary of the invention
The purpose of this invention is to provide the technique that a kind of coprecipitation method prepares LiFePO 4 material, this raw materials technology source is abundant, cheap, and synthesis technique is simple.
A kind of coprecipitation method prepares the technique of LiFePO 4 material, and its special feature is, comprises the steps:
(1) preparation nano-scale lithium iron phosphate primary particle:
Mol ratio according to three kinds of salt is P: Fe: Li=1: 0.7～1.2: 2.5～3.5 ratio takes by weighing phosphoric acid salt, molysite, lithium salts, be dissolved in water respectively to 0.5～2mol/L, then under 200-800r/min, stir 0.5-2h respectively, be dissolved to after the stirring and obtain settled solution;
Then three kinds of solution are mixed, it is 6.5～8.6 that the re-adjustment pH value makes the PH scope of mixing solutions, temperature remains on 120～180C, add airtight and logical nitrogen atmosphere in the reaction vessel, nitrogen outlet keeps dividing potential drop 0.02～0.08Mpa, to prevent oxidation of divalent, and adding molysite mass ratio is 3% xitix, pass through 1-5 hour heating, temperature is controlled at 80-120C again, until form blackish green precipitation, filter through separating funnel, then will precipitate with 5-10 times of weight deionized water and mix, pass through again the separating funnel filtering separation, obtain the ferric lithium phosphate precursor nano particle;
(2) oven dry and carbon coat:
The ferric lithium phosphate precursor nano particle that obtains is put into baking oven, keep 70～80 ℃ and dry, drying time 24～48 hours;
Ferric lithium phosphate precursor nano particle after the oven dry is carried out carbon coat, covering amount adds carbon black according to the weight of precipitation 2～8%, carries out ball milling after the mixing, and 400-600 rev/min of control rotating speed ball milling 20-40 minute, fully grinds stirring and evenly mixing with mixture;
(3) iron lithium phosphate sintering:
The mixture that obtains is placed nitrogen atmosphere, or in nitrogen and the mixed atmosphere of hydrogen with volume ratio 1-5: 95-99, through 500-800C high-temperature roasting 4-8 hour, obtain lithium iron phosphate positive material.
Molysite adopts ferrous salt in the step (1).
Lithium salts adopts Quilonum Retard, lithium hydroxide or lithium fluoride in the step (1); Molysite adopts Iron diacetate, Iron nitrate or iron protochloride; Phosphoric acid salt adopts monometallic, primary ammonium phosphate or phosphoric acid.
Also to revise phosphorus, iron, elemental lithium ratio in the step (2), specifically get oven dry rear section ferric lithium phosphate precursor nano particle as sample, be sample phosphate radical, iron, lithium ion state according to the acidolysis of dissolution sample universal method, carry out the test of element ratio, whether the molar ratio of investigating phosphorus, iron, three kinds of elements of lithium meets 1: 1: 1, if element ratio does not meet, replenishing Minor element to final phosphorus, iron, lithium ratio is 1: 1: 1; The complementary element material is Quilonum Retard, Ferrox, primary ammonium phosphate.
Utilize inductive coupling plasma emission spectrograph ICP-AES to carry out the test of element ratio.
Regulating the ammoniacal liquor of pH value employing 10～50% or the nitric acid of 0.5～2mol/L in the step (1) adjusts.
The invention provides the technique that a kind of coprecipitation method prepares LiFePO 4 material, the raw material sources of this technique are abundant, cheap, synthesis technique is simple, safe and reliable, production cost is low, productive rate is high, non-environmental-pollution, product lithium ion anode material LiFePO 4Has preferably chemical property.
Description of drawings
Fig. 1 is X-ray diffraction (XRD) figure of the iron lithium phosphate of example 1 preparation;
Fig. 2 is X-ray diffraction (XRD) figure of the iron lithium phosphate of example 2 preparations;
Fig. 3 is X-ray diffraction (XRD) figure of the iron lithium phosphate of example 3 preparations;
Fig. 4 is scanning electron microscope (SEM) photograph (SEM) figure of the iron lithium phosphate of example 1 preparation;
Fig. 5 is scanning electron microscope (SEM) photograph (SEM) figure of the iron lithium phosphate of example 2 preparations;
Fig. 6 is scanning electron microscope (SEM) photograph (SEM) figure of the iron lithium phosphate of example 3 preparations.
Embodiment
In the synthetic LFP process of coprecipitation method, side reaction occuring easily in the aqueous solution, cause the existence of a lot of dephasigns, so the ratio of element is easy to occur deviation, causes the purity of product of final LFP undesirable.Technique of the present invention by the element ratio that adds three kinds of elements changes and correct mistakes, has improved the purity of LFP product before sintering.
Molysite of the present invention should use ferrous salt, reduces simultaneously the time of ferrous salt solution stirring and evenly mixing, reduces Fe 2+The degree of oxidation by air.Simultaneously, when reaction, should add xitix, suppress Fe 2+Oxidation.
The conductive capability of LFP material of the present invention is undesirable, wraps carbon by the preparation presoma around particulate, improves intergranular conductive capability.Simultaneously, bag carbon amount is very large on the electrical property impact of material.
In the synthetic LFP process of coprecipitation method of the present invention, side reaction occurs easily in the aqueous solution, cause the existence of a lot of dephasigns, so the ratio of element is easy to occur deviation, the purity of the product of final LFP is undesirable.Before sintering process, the element ratio that changes and correct mistakes by adding three kinds of elements, then the purity of LFP product is very high.
The iron lithium phosphate that this method of the present invention obtains is nano-scale particle, can greatly improve the utilising efficiency of Li+, and heavy-current discharge performance is greatly improved.
PH value of the present invention is very large on the impact of final product purity, notes using soda acid to carry out the adjusting of pH value in building-up process.
The nitrogen that utilizes of the present invention carries out atmosphere protection, suppresses Fe 2+Oxidation, nitrogen outlet should be placed the dividing potential drop table, control reaction vessel interior pressure, different pressure has certain influence to the purity of product.
Ball milling presoma particle size were of the present invention is larger on the impact of the electrical property of material, should consider to make the coating operation requirement of battery, regulates the ball milling parameter, makes the grain diameter behind the ball milling satisfy the electrical property needs as far as possible.
Embodiment 1:
Utilize analytical balance accurately to take by weighing respectively (NH 4) 3PO 4Be 149g, Fe (NO 3) 2Be 180g, LiF is 25g, is dissolved in respectively in the 500ml water, utilizes under the mechanical stirring 200r/min to stir 2h and fully dissolve and mix.Treat that medicine dissolves fully, and without the visible crystals particle.At this moment, under mechanical stirring slurry (rotating speed=300 rev/min) effect, while stirring according to (NH 4) 3PO 4, LiF, Fe (NO 3) 2Pour three kinds of solution that prepare into reaction vessel successively.Utilize oil bath to heat, keep 150 ℃ of temperature of reaction, the reaction times is 3h.In heating, airtight and logical 99.9% nitrogen of reaction vessel carries out atmosphere protection, and nitrogen outlet keeps dividing potential drop 0.05Mpa, adds xitix (amount of molysite mass ratio 3%) inhibited oxidation again.Utilize mechanical stirrer (rotating speed=300 rev/min) to stir the reaction homogeneous phase is carried out.Be the PH=7.5 of the add-on conditioned reaction system of 20% ammoniacal liquor and 1mol/L nitric acid by regulating concentration.After reaction is finished, filter mixed liquor with separating funnel and be precipitated, will precipitate with 5 times of weight deionized waters and mix also agitation and filtration, repeat resolution of precipitate washing and filtering 4 times is finally obtained presoma.
The LFP presoma that obtains is put into baking oven, keep 80C to dry, oven dry kept 36 hours, the quality of weighing presoma, and add carbon black according to 3% precursor weight and carry out carbon and coat.
The LFP presoma of getting 5g carries out conventional acidolysis, the acid hydrolysate of ionic condition is utilized inductive coupling plasma emission spectrograph (ICP-AES, carry out the test of element ratio down together), if phosphorus, iron, lithium molar ratio are not 1: 1: 1, not enough element then carries out the adjustment of element ratio by adding Quilonum Retard, Ferrox, primary ammonium phosphate.
With mixture (LFP presoma, carbon black, element ratio add medicine) ball milling in planetary ball mill, select 400 rev/mins of rotating speeds, ball milling 40 minutes fully grinds stirring with presoma.
Place tube furnace to carry out roasting powder, pass into the mixed gas of 94% nitrogen and 6% hydrogen in tube furnace, be warmed up to 700C with the speed of 3C/min, keep temperature 5h, stove naturally cools to room temperature, obtains LiFePO 4 material.
LiFePO 4 material is carried out SEM and XRD detection, obtain the LiFePO 4 material of pure phase, grain diameter is nano level.
Embodiment 2:
Utilize analytical balance accurately to take by weighing respectively (NH 4) 3PO 4Be 14.9g, Fe (NO 3) 2Be 18g, LiF is 2.5g, is dissolved in respectively in the 50ml water, utilizes under the mechanical stirring 600r/min to stir 0.5h and be charged into fully dissolving and mixing of row.Treat that medicine dissolves fully, and without the visible crystals particle.At this moment, under mechanical stirring slurry (rotating speed=200 rev/min) effect, while stirring successively according to (NH 4) 3PO 4, LiF, Fe (NO 3) 2Pour three kinds of solution that prepare into reaction vessel.Utilize oil bath to heat, keep the 140C temperature of reaction, the reaction times is 4h.In heating, airtight and logical 99.9% nitrogen of reaction vessel carries out atmosphere protection, and nitrogen outlet keeps dividing potential drop 0.05Mpa, adds the amount inhibited oxidation of molysite mass ratio 3% xitix.Utilize mechanical stirrer (rotating speed=350 rev/min) to stir the reaction homogeneous phase is carried out.Be the PH=7.7 of the add-on conditioned reaction system of 50% ammoniacal liquor and 2mol/L nitric acid by regulating concentration.After reaction is finished, filter mixed liquor with separating funnel and be precipitated, will precipitate with deionized water and mix and agitation and filtration according to mass ratio 1:10, repeatedly use washed with de-ionized water 4 times, finally obtain presoma.
The LFP presoma is put into baking oven, keep 75 ℃ and dry, oven dry kept 30 hours, the quality of weighing presoma, and add carbon black according to the quality of precursor 3% and carry out carbon and coat.
The LFP presoma of getting 5g carries out acidolysis, utilize ICP-AES to carry out the test of element ratio the acid hydrolysate of ionic condition, if phosphorus, iron, lithium ratio are not 1: 1: 1, then carry out the adjustment of element ratio by adding Quilonum Retard, Ferrox, primary ammonium phosphate.
With mixture (LFP presoma, carbon black, element ratio add medicine) ball milling in planetary ball mill, select 400 rev/mins of rotating speeds, ball milling 40 minutes fully grinds stirring with presoma.
Place tube furnace to carry out roasting powder, pass into the mixed gas of 94% nitrogen and 6% hydrogen in tube furnace, be warmed up to 600C with the speed of 3C/min, keep temperature 7h, stove naturally cools to room temperature, obtains LiFePO 4 material.
LiFePO 4 material is carried out SEM and XRD detection, obtain the LiFePO 4 material of pure phase, grain diameter is nano level.
Embodiment 3:
Utilize analytical balance accurately to take by weighing respectively (NH 4) 3PO 4Be 1490g, Fe (NO 3) 2Be 1800g, LiF is 250g, is dissolved in respectively in the 5000ml water, utilizes under the mechanical stirring 400r/min to stir 1h and fully dissolve and mix.Treat that medicine dissolves fully, and without the visible crystals particle.At this moment, under mechanical stirring slurry (rotating speed=300 rev/min) effect, pour three kinds of solution that prepare into reaction vessel successively while stirring.Utilize oil bath to heat, keep the 150C temperature of reaction, the reaction times is 5h.In heating, airtight and logical 99.9% nitrogen of reaction vessel carries out atmosphere protection, and nitrogen outlet keeps dividing potential drop 0.03Mpa, adds the amount inhibited oxidation of molysite mass ratio 3% xitix.Utilize mechanical stirrer (rotating speed=300 rev/min) to stir the reaction homogeneous phase is carried out.Be the PH=7.3 of the add-on conditioned reaction system of 10% ammoniacal liquor and 0.5mol/L nitric acid by regulating concentration.After reaction is finished, filter mixed liquor and be precipitated, will precipitate and mix with deionized water and mix and agitation and filtration according to mass ratio 1:8, repeatedly use washed with de-ionized water 4 times, finally obtain presoma.
The LFP presoma is put into baking oven, keep 70C to dry, oven dry kept 40 hours, the quality of weighing presoma, and add carbon black according to 3% of precursor quality and carry out carbon and coat.
The LFP presoma of getting 5g carries out acidolysis, utilize ICP-AES to carry out the test of element ratio the acid hydrolysate of ionic condition, if phosphorus, iron, lithium ratio are not 1: 1: 1, then carry out the adjustment of element ratio by adding Quilonum Retard, Ferrox, primary ammonium phosphate.
With mixture (LFP presoma, carbon black, element ratio add medicine) ball milling in planetary ball mill, select 400 rev/mins of rotating speeds, ball milling 40 minutes fully grinds stirring with presoma.
Place tube furnace to carry out roasting powder, pass into the mixed gas of 94% nitrogen and 6% hydrogen in tube furnace, be warmed up to 650C with the speed of 3 ℃/min, keep temperature 5h, stove naturally cools to room temperature, obtains LiFePO 4 material.
LiFePO 4 material is carried out SEM and XRD detection, obtain the LiFePO 4 material of pure phase, grain diameter is nano level.

Claims (6)

1. a coprecipitation method prepares the technique of LiFePO 4 material, it is characterized in that, comprises the steps:
(1) preparation nano-scale lithium iron phosphate primary particle:
Mol ratio according to three kinds of salt is P: Fe: Li=1: 0.7～1.2: 2.5～3.5 ratio takes by weighing phosphoric acid salt, molysite, lithium salts, be dissolved in water respectively to 0.5～2mol/L, then under 200-800r/min, stir 0.5-2h respectively, be dissolved to after the stirring and obtain settled solution;
Then three kinds of solution are mixed, it is 6.5～8.6 that the re-adjustment pH value makes the PH scope of mixing solutions, temperature remains on 120～180C, add airtight and logical nitrogen atmosphere in the reaction vessel, nitrogen outlet keeps dividing potential drop 0.02～0.08Mpa, to prevent oxidation of divalent, and adding molysite mass ratio is 3% xitix, pass through 1-5 hour heating, temperature is controlled at 80-120 ℃ again, until form blackish green precipitation, filter through separating funnel, then will precipitate with 5-10 times of weight deionized water and mix, pass through again the separating funnel filtering separation, obtain the ferric lithium phosphate precursor nano particle;
(2) oven dry and carbon coat:
The ferric lithium phosphate precursor nano particle that obtains is put into baking oven, keep 70～80C to dry drying time 24～48 hours;
Ferric lithium phosphate precursor nano particle after the oven dry is carried out carbon coat, covering amount adds carbon black according to the weight of precipitation 2～8%, carries out ball milling after the mixing, and 400-600 rev/min of control rotating speed ball milling 20-40 minute, fully grinds stirring and evenly mixing with mixture;
(3) iron lithium phosphate sintering:
The mixture that obtains is placed nitrogen atmosphere, or in nitrogen and the mixed atmosphere of hydrogen with volume ratio 1-5: 95-99, through 500-800C high-temperature roasting 4-8 hour, obtain lithium iron phosphate positive material.
2. a kind of coprecipitation method as claimed in claim 1 prepares the technique of LiFePO 4 material, it is characterized in that: molysite adopts ferrous salt in the step (1).
3. a kind of coprecipitation method as claimed in claim 1 prepares the technique of LiFePO 4 material, it is characterized in that: lithium salts adopts Quilonum Retard, lithium hydroxide or lithium fluoride in the step (1); Molysite adopts Iron diacetate, Iron nitrate or iron protochloride; Phosphoric acid salt adopts monometallic, primary ammonium phosphate or phosphoric acid.
4. a kind of coprecipitation method as claimed in claim 1 prepares the technique of LiFePO 4 material, it is characterized in that: also will be to phosphorus in the step (2), iron, the elemental lithium ratio is revised, specifically get oven dry rear section ferric lithium phosphate precursor nano particle as sample, be sample phosphate radical according to the acidolysis of dissolution sample universal method, iron, the lithium ion state, carry out the test of element ratio, investigate phosphorus, iron, whether the molar ratio of three kinds of elements of lithium meets 1: 1: 1, if element ratio does not meet, replenish Minor element to final phosphorus, iron, the lithium ratio is 1: 1: 1; The complementary element material is Quilonum Retard, Ferrox, primary ammonium phosphate.
5. a kind of coprecipitation method as claimed in claim 4 prepares the technique of LiFePO 4 material, it is characterized in that: utilize inductive coupling plasma emission spectrograph ICP-AES to carry out the test of element ratio.
6. a kind of coprecipitation method as claimed in claim 1 prepares the technique of LiFePO 4 material, it is characterized in that: regulate the ammoniacal liquor of pH value employing 10～50% or the nitric acid of 0.5～2mol/L in the step (1) and adjust.
CN2012103824466A 2012-10-10 2012-10-10 Process for preparing lithium iron phosphate material with co-precipitation method Pending CN102874788A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108539132A (en) * 2018-01-26 2018-09-14 澳洋集团有限公司 A kind of preparation method of zinc oxide-lithium iron phosphate composite anode material
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
CN115818610A (en) * 2022-12-07 2023-03-21 合肥国轩科宏新能源科技有限公司 Liquid-phase synthesis method of lithium iron phosphate
CN116143091A (en) * 2022-12-06 2023-05-23 四川思特瑞锂业有限公司 Method for producing battery grade lithium dihydrogen phosphate from brine lithium chloride

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102522549A (en) * 2011-12-23 2012-06-27 彩虹集团公司 Preparation method of carbon-coated and doped lithium-iron phosphate
CN102556998A (en) * 2011-12-23 2012-07-11 彩虹集团公司 Preparation method of lithium iron phosphate material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102522549A (en) * 2011-12-23 2012-06-27 彩虹集团公司 Preparation method of carbon-coated and doped lithium-iron phosphate
CN102556998A (en) * 2011-12-23 2012-07-11 彩虹集团公司 Preparation method of lithium iron phosphate material

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN108539132A (en) * 2018-01-26 2018-09-14 澳洋集团有限公司 A kind of preparation method of zinc oxide-lithium iron phosphate composite anode material
CN108539132B (en) * 2018-01-26 2021-05-11 澳洋集团有限公司 Preparation method of zinc oxide composite lithium iron phosphate cathode material
CN116143091A (en) * 2022-12-06 2023-05-23 四川思特瑞锂业有限公司 Method for producing battery grade lithium dihydrogen phosphate from brine lithium chloride
CN116143091B (en) * 2022-12-06 2023-09-12 四川思特瑞锂业有限公司 Method for producing battery grade lithium dihydrogen phosphate from brine lithium chloride
CN115818610A (en) * 2022-12-07 2023-03-21 合肥国轩科宏新能源科技有限公司 Liquid-phase synthesis method of lithium iron phosphate

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Application publication date: 20130116