CN113353907A - Ferric phosphate precursor and preparation method and application thereof - Google Patents
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Abstract
The invention discloses an iron phosphate precursor and a preparation method and application thereof, wherein the preparation method of the iron phosphate comprises the following steps: mixing and dissolving an iron source and a phosphorus source, adding a precipitation promoter, and stirring to obtain a metal liquid; heating the metal liquid for reaction, and filtering to obtain iron phosphate precipitate; taking the ferric phosphate precipitate for pulping, filtering, washing, grinding, washing again and filtering to obtain ferric phosphate dihydrate precipitate; and calcining the ferric phosphate dihydrate precipitate to obtain the anhydrous ferric phosphate. In a sulfate-containing system, a phosphorus source and an iron source are selected, and a precipitating accelerator is added, so that the system is precipitated in a heterogeneous manner, the heterogeneous precipitation is favorable for the rapid growth of iron phosphate, and the byproduct sulfate is not in time to be wrapped and precipitated, so that the flaky loosely-stacked ferric phosphate dihydrate is obtained.
Description
Technical Field
The invention belongs to the technical field of positive electrode material precursors, and particularly relates to an iron phosphate precursor and a preparation method and application thereof.
Background
With the heating of new energy automobile market, lithium iron phosphate has higher safety, and occupies a larger proportion in the battery matching of new energy special vehicles (including new energy logistics vehicles, new energy sanitation vehicles and new energy other special vehicles). The lithium iron phosphate has the advantages of good safety performance, long cycle life, environmental protection, safety, low manufacturing cost, higher energy density and the like, and particularly has good safety performance.
The method for producing titanium dioxide in China mainly uses a sulfuric acid method, and a large amount of dilute waste acid, acidic waste water and a byproduct ferrous sulfate heptahydrate are generated in the technical process. In order to more effectively utilize the byproduct ferrous sulfate generated in the titanium dioxide production process, a plurality of researchers research on the preparation of battery-grade iron phosphate by using the byproduct ferrous sulfate in the titanium dioxide production process as a raw material. However, in the process of preparing the iron phosphate by the ferrous sulfate system precipitation, iron phosphate crystal nuclei grow up continuously and can wrap by-product sulfate, so that the content of S in the iron phosphate is increased, and the electrochemical performance of the lithium iron phosphate battery is influenced by too high sulfur content. Generally, a water washing mode is adopted to reduce the sulfur content in the ferric phosphate product, but the process needs to consume a large amount of water, and the S can be washed clean by about 100-120 times at normal temperature, so that the environmental protection problems that a large amount of washing wastewater is difficult to treat and the like are caused.
In order to prepare low-sulfur lithium iron phosphate, Guoguang and Jiashuangzhu in the research on the preparation technology of spheroidal low-sulfur iron phosphate, ammonia water is added as a ligand to form an iron ammonium phosphate complex with central atomic iron, so that the formation of a byproduct sulfate is reduced, and the sulfur content of a ferric phosphate product is reduced. The method can effectively reduce the sulfur content, but the ammonia water is added, which can also cause the environmental protection problems of ammonia gas overflow, ammonia-containing wastewater difficult to treat and the like in the reaction process.
In order to solve the problems, the invention discloses an environment-friendly and simple process flow, and an iron phosphate precursor with low sulfur content is prepared mainly by controlling the shape of iron phosphate in a system containing a large amount of sulfate radicals.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. In a sulfate-containing system, a phosphorus source and an iron source are selectively added, and a precipitating accelerator is added, so that the system is precipitated in a heterogeneous manner, the heterogeneous precipitation is favorable for the rapid growth of the iron phosphate, and the sulfate serving as a byproduct cannot be wrapped and precipitated to obtain the flaky loose-packed ferric phosphate dihydrate.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of iron phosphate comprises the following steps:
s1, mixing and dissolving an iron source and a phosphorus source, adding a precipitation promoter, and stirring to obtain a metal liquid;
s2, heating the metal liquid for reaction, filtering and taking filter residue to obtain iron phosphate precipitate;
s3, pulping the ferric phosphate precipitate, filtering, washing, grinding, washing again, and filtering to obtain ferric phosphate dihydrate precipitate;
and S4, calcining the ferric phosphate dihydrate precipitate to obtain anhydrous ferric phosphate.
Preferably, in step S1, the phosphorus source is at least one of phosphoric acid, phosphorous acid, sodium hypophosphite, ammonium dihydrogen phosphate, phosphorous iron slag, or ammonium phosphate.
More preferably, the phosphorus source is phosphoric acid or phosphorous iron slag.
Preferably, in step S1, the iron source is at least one of elemental iron, ferrous salt, ferric salt, pyrite, sulfuric acid-dissolved ferrophosphorus slag, or sulfuric acid-dissolved ferrophosphorus.
Further preferably, the ferrous salt is at least one of ferrous chloride, ferrous sulfate or ferrous acetate.
Further preferably, the iron salt is at least one of ferric chloride, ferric nitrate or ferric phosphate.
Preferably, in step S1, the iron source is at least one of elemental iron or ferrous salt, and an oxidizing agent is further added after the mixing and dissolving.
Further preferably, the oxidant is at least one of hydrogen peroxide, sodium peroxide or ammonium persulfate.
More preferably, the oxidant is hydrogen peroxide.
More preferably, the iron source is at least one of ferrous sulfate, sulfuric acid dissolved ferrophosphorus slag, or sulfuric acid dissolved ferro-phosphorus ore.
Preferably, in step S1, the precipitation promoter is at least one of nickel sulfate, nickel chloride, nickel nitrate or nickel oxide.
More preferably, in step S1, the precipitation promoter is nickel sulfate.
Preferably, in step S1, the stirring speed is 300-500r/min, and more preferably 350-400 r/min.
Preferably, in step S2, the temperature of the heating reaction is not lower than 70 ℃, and more preferably 70 to 100 ℃.
Preferably, in step S3, the pulping is performed by using hot water, and the temperature of the hot water is 40-90 ℃, and more preferably 50-70 ℃.
Preferably, in step S3, the particle size of the milled iron phosphate is 2 to 6 μm, and more preferably 4 to 5 μm.
Preferably, in step S3, the washing and the re-washing are both performed using hot water having a temperature of 40 to 90 ℃, and more preferably 50 to 70 ℃.
More preferably, the conductivity of the filtrate after washing is 200. mu.s/cm or less.
More preferably, the conductivity of the filtrate after the second washing is 190. mu.s/cm or less.
Preferably, in step S4, the calcination temperature is 400-500 ℃, and the calcination time is 1-4 hours.
The iron phosphate is prepared by the preparation method.
Preferably, the microscopic morphology of the iron phosphate is in a flaky loose stack, the particle size Dv50 is 10-15 mu m, and the sulfur content is less than or equal to 300 ppm.
The invention also provides application of the iron phosphate in preparation of a lithium ion battery.
Compared with the prior art, the invention has the following beneficial effects:
1. in a sulfate-containing system, a phosphorus source and an iron source are selected, a precipitating accelerator is added, the system is subjected to heterogeneous precipitation, the heterogeneous precipitation is favorable for the rapid growth of the iron phosphate, a byproduct sulfate cannot be coated and precipitated, the thin paper sheet-shaped primary particles are obtained to form the ferric phosphate dihydrate with loose particles, and the ferric phosphate dihydrate is washed and calcined to obtain the anhydrous iron phosphate with the sulfur content of less than or equal to 300 ppm.
2. The ferric phosphate dihydrate prepared by the invention can be rapidly dehydrated in the calcining process, pore channels are left in the particles, and the ferric phosphate dihydrate has a plurality of internal voids, which are beneficial to the removal of sulfur from the inside of the particles so as to prepare the anhydrous ferric phosphate with low sulfur content (the sulfur content is less than or equal to 300ppm), and the anhydrous ferric phosphate obtained by the treatment at the temperature of 400 ℃ and 500 ℃ keeps higher activity.
3. The loose granular ferric phosphate dihydrate prepared by the invention is washed (hot water) and ground again, so that sulfate carried on the surface of the washed ferric phosphate dihydrate is favorably reduced in sulfur content, and the ferric phosphate precursor prepared by the preparation method has the advantages of low cost, simple operation and low sulfur content.
Drawings
The invention is further described with reference to the following figures and examples, in which:
FIG. 1 is an SEM photograph of iron phosphate dihydrate of example 1 of the present invention;
FIG. 2 is an SEM photograph of the interior of a sliced iron phosphate dihydrate according to example 1 of the present invention;
FIG. 3 is an XRD pattern of iron phosphate dihydrate of example 1 of the present invention;
FIG. 4 is an SEM photograph of comparative example 1 iron phosphate dihydrate of the present invention;
FIG. 5 is an SEM photograph of comparative example 4 of iron phosphate dihydrate according to the present invention.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1
The preparation method of iron phosphate of this embodiment includes the following steps:
s1, weighing 10.87kg of ferrophosphorus slag, adding the ferrophosphorus slag into 45L of sulfuric acid with the concentration of 1.2mol/L, stirring to fully dissolve, adding 8.5kg of nickel sulfate hexahydrate, and stirring to fully dissolve to obtain a metal liquid;
s2, measuring 50L of metal liquid, adding the metal liquid into a reaction kettle, heating to 90 ℃ at a speed of 310r/min, reacting for 6 hours to obtain slurry containing ferric phosphate, and filtering the slurry containing ferric phosphate after the reaction is finished to obtain ferric phosphate precipitate;
s3, pulping the ferric phosphate precipitate by using hot water at 60 ℃, stirring for 1h, then filtering, pulping and washing for 2 times according to the same method, wherein the filtrate is 192 mu S/cm;
s4, grinding the washed iron phosphate precipitate to 4 mu m, washing the iron phosphate precipitate with 60 ℃ hot water for one time, and filtering to obtain 180us/cm filtrate to obtain ferric phosphate dihydrate precipitate;
and S5, calcining the ferric phosphate dihydrate precipitate obtained in the step S4 at 450 ℃ for 4h to obtain the battery-grade ferric phosphate.
Example 2
The preparation method of iron phosphate of this embodiment includes the following steps:
s1, weighing 14.97kg of ferrous sulfate, adding the ferrous sulfate into 24.3L of phosphoric acid with the concentration of 2.48mol/L, gradually adding 33.17kg of hydrogen peroxide in the stirring process, stirring to fully dissolve, adding 8.5kg of nickel sulfate hexahydrate, and stirring to fully dissolve to obtain metal liquid;
s2, measuring 50L of metal liquid, adding the metal liquid into a reaction kettle, heating to 90 ℃ at a speed of 310r/min, reacting for 6 hours to obtain slurry containing ferric phosphate, and filtering the slurry containing ferric phosphate after the reaction is finished to obtain ferric phosphate precipitate;
s3, pulping the ferric phosphate precipitate by using hot water at 60 ℃, stirring for 1h, filtering, pulping and washing for 2 times according to the same method, wherein the filtrate is 196 mu S/cm;
s4, grinding the washed iron phosphate precipitate to 4 mu m, washing the iron phosphate precipitate again by using hot water slurry at 60 ℃, and filtering to obtain filtrate of 180us/cm to obtain ferric phosphate dihydrate precipitate;
and S5, calcining the ferric phosphate dihydrate precipitate after the secondary pulp washing at 450 ℃ for 4h to obtain the battery-grade ferric phosphate.
Example 3
The preparation method of iron phosphate of this embodiment includes the following steps:
s1, weighing 3.2kg of iron powder, adding the iron powder into 24.3L of phosphoric acid with the concentration of 2.5mol/L, gradually adding 33.5kg of hydrogen peroxide in the stirring process, adding 8kg of nickel sulfate hexahydrate, and stirring to completely dissolve the nickel sulfate hexahydrate to obtain metal liquid;
s2, measuring 50L of metal liquid, adding the metal liquid into a reaction kettle, heating to 96 ℃ at the speed of 400r/min, reacting for 6 hours to obtain slurry containing ferric phosphate, and filtering the slurry containing ferric phosphate after the reaction is finished to obtain ferric phosphate precipitate;
s3, pulping the ferric phosphate precipitate by using hot water at 50 ℃, stirring for 1h, then filtering, pulping and washing for 2 times according to the same method, wherein the filtrate is 196 mu S/cm;
s4, grinding the washed iron phosphate precipitate to 4 mu m, washing with hot water of 50 ℃ once, and filtering to obtain 185us/cm filtrate to obtain ferric phosphate dihydrate precipitate;
and S5, calcining the ferric phosphate dihydrate precipitate after the secondary pulp washing at 450 ℃ for 4h to obtain the battery-grade ferric phosphate.
Example 4
The preparation method of iron phosphate of this embodiment includes the following steps:
s1, weighing 14.97kg of ferrous sulfate, slowly adding the ferrous sulfate into 24.3L of phosphoric acid with the concentration of 2.48mol/L, gradually adding 33.17kg of hydrogen peroxide in the stirring process, adding 7.6kg of nickel sulfate hexahydrate, and stirring to completely dissolve the mixture to obtain a metal liquid;
s2, measuring 50L of metal liquid, adding the metal liquid into a reaction kettle, heating to 94 ℃ at the speed of 350r/min, reacting for 6 hours to obtain slurry containing ferric phosphate, and filtering the slurry containing ferric phosphate after the reaction is finished to obtain ferric phosphate precipitate;
s3, pulping the ferric phosphate precipitate by using hot water at 70 ℃, stirring for 1h, then filtering, pulping and washing for 2 times according to the same method, wherein the filtrate is 190 Mus/cm;
s4, grinding the washed iron phosphate precipitate to 4 mu m, washing with 60 ℃ hot water slurry once, and filtering to obtain 185us/cm filtrate to obtain ferric phosphate dihydrate precipitate;
and S5, calcining the ferric phosphate dihydrate precipitate after the secondary pulp washing at 450 ℃ for 4h to obtain the battery-grade ferric phosphate.
Comparative example 1
The method for preparing iron phosphate of comparative example 1, comprising the steps of:
s1, weighing 4kg of iron phosphate waste, adding the iron phosphate waste into 50L of sulfuric acid with the concentration of 1.2mol/L, stirring to fully dissolve, adding 7.6kg of nickel sulfate hexahydrate, and stirring to fully dissolve to obtain metal liquid;
s2, measuring 50L of metal liquid, adding the metal liquid into a reaction kettle, heating to 90 ℃ at a speed of 310r/min, reacting for 6 hours to obtain slurry containing ferric phosphate, and filtering the slurry containing ferric phosphate after the reaction is finished to obtain ferric phosphate precipitate;
s3, pulping the ferric phosphate precipitate with hot water at 60 ℃, stirring for 1h, filtering, taking the precipitate, continuously pulping and washing with hot water at 60 ℃ for 2 times, wherein the filtrate is 180 mu S/cm;
s4, grinding the washed iron phosphate precipitate to 4 mu m, washing the iron phosphate precipitate with 60 ℃ hot water for one time, and filtering to obtain 180us/cm filtrate to obtain ferric phosphate dihydrate precipitate;
and S5, calcining the ferric phosphate dihydrate precipitate after the slurry washing at 450 ℃ for 4h to obtain the battery-grade ferric phosphate.
Comparative example 2 (without addition of precipitation promoter)
The method for preparing iron phosphate of comparative example 2, comprising the steps of:
s1, weighing 16.75kg of ferrous sulfate, adding into 48L of 1.31mol/L phosphoric acid, and uniformly stirring to obtain a metal liquid;
s2, measuring 50L of metal liquid, adding the metal liquid into a reaction kettle, heating to 95 ℃ at the speed of 350r/min, continuously introducing oxygen in the reaction process, reacting for 12 hours to obtain slurry containing ferric phosphate, and filtering the slurry containing ferric phosphate after the reaction is finished to obtain ferric phosphate precipitate;
s3, pulping the ferric phosphate precipitate with hot water at 60 ℃, stirring for 1h, filtering, taking the precipitate, continuously pulping and washing with hot water at 60 ℃ for 2 times, wherein the filtrate is 198 mus/cm;
and S4, precipitating the ferric phosphate dihydrate subjected to the secondary pulp washing at 450 ℃ for 4h, and calcining to obtain the battery-grade ferric phosphate.
Comparative example 3 (reaction temperature lower than 70 ℃ C.)
The method for preparing the iron phosphate precursor of comparative example 3, comprising the steps of:
s1, weighing 10.87kg of iron phosphate waste, slowly adding the iron phosphate waste into 45L of sulfuric acid with the concentration of 1.2mol/L, stirring and fully dissolving, adding 8.5kg of nickel sulfate hexahydrate, and stirring and fully dissolving to obtain metal liquid;
s2, measuring 50L of metal liquid, adding the metal liquid into a reaction kettle, heating to 40 ℃ at the speed of 310r/min, reacting for 24h, and filtering the slurry to obtain almost no filter residue, namely almost no iron phosphate is generated.
Comparative example 4 (addition of sodium hydroxide solution as precipitant)
The method for preparing iron phosphate of comparative example 4, comprising the steps of:
s1, weighing 5.45kg of iron phosphate waste, adding the iron phosphate waste into 45L of sulfuric acid with the concentration of 1.2mol/L, stirring to fully dissolve, adding 9.9kg of nickel sulfate hexahydrate, and stirring to fully dissolve to obtain metal liquid;
s2, dissolving sodium hydroxide in water to prepare a sodium hydroxide solution as a precipitator;
s3, measuring 50L of metal liquid, adding the metal liquid into a reaction kettle, heating the metal liquid to 45 ℃ at the speed of 310r/min, adding a sodium hydroxide solution into the reaction kettle, aging the solution for 3 to 6 hours after the reaction is finished, filtering iron phosphate slurry after the aging is finished to obtain iron phosphate precipitate, and repeatedly washing the iron phosphate precipitate for 1 to 2 times by pure water, wherein the filtrate is 180 mu S/cm;
and S4, calcining the washed ferric phosphate dihydrate precipitate at 450 ℃ to obtain the battery-grade ferric phosphate.
TABLE 1
As can be seen from table 1 above, the anhydrous iron phosphates prepared by the preparation methods of examples 1 to 4 of the present invention have low S content, and the iron phosphates dihydrate in different morphologies were prepared in comparative example 1. Comparative example 2 no precipitation promoter was added and the resulting iron phosphate dihydrate wrapped in sulfate, resulting in a high sulfur content. The reaction temperature of comparative example 3 was lower than 70 c, and iron phosphate precipitates were hardly generated. Comparative example 4 adds sodium hydroxide solution as precipitant, and the ferric phosphate dihydrate of comparative example 4 comprises once thin slice granule, and the granule dispersion is loose moreover, is unfavorable for obtaining the high lithium iron phosphate material of density, uses sodium hydroxide solution as precipitant to have sodium salt waste water to produce in addition, difficult processing.
FIG. 1 is an SEM photograph of iron phosphate dihydrate of example 1 of the present invention; it can be seen from FIG. 1 that the iron phosphate dihydrate prepared in example 1 is composed of thin and fine primary particles in the form of a sheet, and the particles are loosely distributed and not densely arranged. FIG. 2 is an SEM photograph of the interior of a sliced iron phosphate dihydrate of example 1 of the present invention; it can be seen from fig. 2 that the iron phosphate dihydrate prepared in example 1 has many voids inside, and these voids are favorable for sulfur removal during calcination. FIG. 3 is an XRD pattern of iron phosphate dihydrate of example 1 of the present invention; it can be seen from figure 3 that the example preparation yielded a pure phase of iron phosphate dihydrate. FIG. 4 is an SEM photograph of iron phosphate dihydrate of comparative example 1 of the present invention; it can be seen from fig. 4 that the iron phosphate dihydrate of comparative example 1 is a particle composed of larger and thicker primary particles, and the primary particles are arranged regularly and densely. FIG. 5 is an SEM image of ferric phosphate dihydrate prepared by a conventional alkali precipitation process in comparative example 4; it can be seen from fig. 5 that the ferric phosphate dihydrate of comparative example 4 is composed of primary flake particles, and the particles are dispersed and loose, which is not favorable for obtaining a high-compactness lithium iron phosphate material (the loose of example 1 and the loose of comparative example 4 can be greatly distinguished from the morphology, the morphology of example 1 is that the primary particles are distributed loosely and agglomerated into large particles, which is dense compared with comparative example 4, and the dispersed primary particles of comparative example 4 are difficult to form large particles).
TABLE 2
The lithium iron phosphate prepared by the iron phosphate prepared in the examples 1 to 2 and the comparative examples 1 and 4 according to the present invention was prepared by a conventional method, and the table above shows electrochemical properties of the lithium iron phosphate and the compacted density of the powder. It can be seen from table 2 that in comparative example 4, the iron phosphate made of loose flake iron phosphate is used as a precursor to prepare a lithium iron phosphate material powder with low compacted density and low specific discharge capacity.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the embodiments, and various changes can be made without departing from the gist of the present invention within the knowledge of those skilled in the art. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (10)
1. The preparation method of the iron phosphate is characterized by comprising the following steps:
s1, mixing and dissolving an iron source and a phosphorus source, adding a precipitation promoter, and stirring to obtain a metal liquid;
s2, heating the metal liquid for reaction, filtering and taking filter residue to obtain iron phosphate precipitate;
s3, pulping the ferric phosphate precipitate, filtering, washing, grinding, washing again, and filtering to obtain ferric phosphate dihydrate precipitate;
and S4, calcining the ferric phosphate dihydrate precipitate to obtain anhydrous ferric phosphate.
2. The method according to claim 1, wherein in step S1, the phosphorus source is at least one of phosphoric acid, phosphorous acid, sodium hypophosphite, ammonium dihydrogen phosphate, phosphorous iron slag, or ammonium phosphate.
3. The method according to claim 1, wherein in step S1, the iron source is at least one of elemental iron, ferrous salts, ferric salts, pyrite, sulfuric acid-dissolved ferrophosphorus slag, and sulfuric acid-dissolved iron phosphorus ore.
4. The method according to claim 3, wherein the iron source in step S1 is at least one of elemental iron or ferrous salt, and an oxidizing agent is added after the mixing and dissolving.
5. The method according to claim 1, wherein in step S1, the precipitation promoter is at least one of nickel sulfate, nickel chloride, nickel nitrate or nickel oxide.
6. The method according to claim 1, wherein the temperature of the heating reaction in step S2 is 70 to 100 ℃.
7. The method as claimed in claim 1, wherein in step S4, the calcination temperature is 400-500 ℃ and the calcination time is 1-4 hours.
8. Iron phosphate, characterized by being produced by the production method according to any one of claims 1 to 7.
9. The iron phosphate according to claim 8, characterized in that the iron phosphate has a microscopic morphology of loose packing in the form of sheets and a particle size Dv50 of 10-15 μm and a sulfur content of 300ppm or less.
10. Use of the iron phosphate according to any one of claims 8 to 9 for the preparation of lithium ion batteries.
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| CN202110694414.9A CN113353907A (en) | 2021-06-22 | 2021-06-22 | Ferric phosphate precursor and preparation method and application thereof |
| PCT/CN2021/142946 WO2022267420A1 (en) | 2021-06-22 | 2021-12-30 | Iron phosphate precursor, preparation method therefor and use thereof |
| HU2200337A HUP2200337A1 (en) | 2021-06-22 | 2021-12-30 | Iron phosphate precursor and preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113845100A (en) * | 2021-11-16 | 2021-12-28 | 湖北融通高科先进材料有限公司 | Iron phosphate and preparation method and application thereof |
| CN114477121A (en) * | 2022-02-25 | 2022-05-13 | 湖南长宏新能源材料有限责任公司 | Production of battery-grade iron phosphate from iron-containing waste residues |
| CN115092903A (en) * | 2022-07-28 | 2022-09-23 | 福建紫金锂元材料科技有限公司 | Preparation method of high-compaction-density lithium iron phosphate |
| WO2022267420A1 (en) * | 2021-06-22 | 2022-12-29 | 广东邦普循环科技有限公司 | Iron phosphate precursor, preparation method therefor and use thereof |
| CN115849319A (en) * | 2022-12-07 | 2023-03-28 | 河南佰利新能源材料有限公司 | Preparation method and application of iron phosphate |
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| CN116621141B (en) * | 2023-04-25 | 2023-12-26 | 浙江友山新材料科技有限公司 | Preparation method of low-manganese magnesium ferric phosphate |
| CN116443835A (en) * | 2023-05-25 | 2023-07-18 | 河南佰利新能源材料有限公司 | Ferric phosphate and preparation method and application thereof |
| CN117566716B (en) * | 2023-11-23 | 2024-05-17 | 新洋丰农业科技股份有限公司 | Preparation method of low-impurity high-performance ferric manganese phosphate and ferric manganese lithium phosphate |
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| CN112645299A (en) * | 2020-12-03 | 2021-04-13 | 广东邦普循环科技有限公司 | Preparation method and application of iron phosphate |
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| CN112624077A (en) * | 2020-12-15 | 2021-04-09 | 广东邦普循环科技有限公司 | Battery-grade iron phosphate and preparation method and application thereof |
| CN113353907A (en) * | 2021-06-22 | 2021-09-07 | 广东邦普循环科技有限公司 | Ferric phosphate precursor and preparation method and application thereof |
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| CN110615418A (en) * | 2019-06-28 | 2019-12-27 | 湖北虹润高科新材料有限公司 | Preparation method for preparing battery-grade iron phosphate from iron powder |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022267420A1 (en) * | 2021-06-22 | 2022-12-29 | 广东邦普循环科技有限公司 | Iron phosphate precursor, preparation method therefor and use thereof |
| CN113845100A (en) * | 2021-11-16 | 2021-12-28 | 湖北融通高科先进材料有限公司 | Iron phosphate and preparation method and application thereof |
| CN114477121A (en) * | 2022-02-25 | 2022-05-13 | 湖南长宏新能源材料有限责任公司 | Production of battery-grade iron phosphate from iron-containing waste residues |
| CN115092903A (en) * | 2022-07-28 | 2022-09-23 | 福建紫金锂元材料科技有限公司 | Preparation method of high-compaction-density lithium iron phosphate |
| CN115092903B (en) * | 2022-07-28 | 2023-10-24 | 福建紫金锂元材料科技有限公司 | Preparation method of high-compaction-density lithium iron phosphate |
| CN115849319A (en) * | 2022-12-07 | 2023-03-28 | 河南佰利新能源材料有限公司 | Preparation method and application of iron phosphate |
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| WO2022267420A1 (en) | 2022-12-29 |
| HUP2200337A1 (en) | 2023-04-28 |
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