CN112736226A - Vanadium-doped carbon-coated lithium iron phosphate, and preparation method and application thereof - Google Patents
Vanadium-doped carbon-coated lithium iron phosphate, and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides vanadium-doped carbon-coated lithium iron phosphate, a preparation method and application thereof, wherein the preparation method of the vanadium-doped carbon-coated lithium iron phosphate comprises the following steps of: mixing ferric vanadate, an iron source, a phosphorus source, a lithium source and a carbon source, sanding, then spray-drying, and roasting under the protection of inert gas to prepare the vanadium-doped carbon-coated lithium iron phosphate. The invention also discloses a preparation method of the ferric vanadate, which comprises the steps of adding an iron source solution into a vanadium solution, adding ammonia water to adjust the pH value, filtering and washing to prepare a ferric vanadate precursor, and oxidizing and roasting the ferric vanadate precursor to prepare the ferric vanadate. The vanadium-doped carbon-coated lithium iron phosphate prepared by the invention has the advantages of good rate capability and high low-temperature capacity retention rate.
Description
Technical Field
The invention relates to a lithium iron phosphate technology, in particular to vanadium-doped carbon-coated lithium iron phosphate, a preparation method and application thereof.
Background
In the development process of new energy industry, lithium ion batteries occupy an important position, and compared with other secondary batteries, the lithium ion batteries have the advantages of high energy density, high open circuit voltage, high-current charge and discharge capacity, low self-discharge rate, no memory effect and the like.
As the anode material of the lithium ion battery, the lithium iron phosphate has the advantages of easily available raw materials, low cost, good safety performance, long cycle life and the like, and becomes one of the main choices of the anode material of the lithium ion battery.
In recent years, with the technical innovation of CTP technology and Biddi blade batteries in the Ningde era, compared with the strong regression of lithium iron phosphate with a ternary positive electrode material falling into the lower wind, the method attracts the attention of a plurality of enterprises again; after cooperation between Tesla and Nind era is achieved, the application of lithium iron phosphate to new energy automobiles gradually enters the good place, the cumulative loading of lithium iron phosphate batteries in 8 months exceeds 1 million, the battery loading capacity is 317.58MWh, the year-on-year increase is 178.41%, the total loading capacity of the lithium iron phosphate batteries accounts for 8.34% of the total loading capacity of a passenger automobile, the total loading capacity is increased by nearly 5 hundred points compared with 3.88% in the same period of the last year, and in addition, a domestic Model 3 automobile type carrying the lithium iron phosphate automobile type in the Nind era is on the road.
On the other hand, research and development and industrialization of lithium iron phosphate materials are supported by the national level. In 2020, the lithium iron phosphate energy storage battery is supported to be used on a large scale in a communication base station, the 5G high-quality development is promoted, and a good development opportunity is provided for a large number of lithium iron phosphate battery enterprises.
Disclosure of Invention
The invention aims to provide a preparation method of vanadium-doped carbon-coated lithium iron phosphate aiming at the problem of low conductivity of the current lithium iron phosphate cathode material.
In order to achieve the purpose, the invention adopts the technical scheme that: a preparation method of vanadium-doped carbon-coated lithium iron phosphate comprises the following steps: mixing ferric vanadate, an iron source, a phosphorus source, a lithium source and a carbon source, sanding, then spray-drying, and roasting under the protection of inert gas to prepare the vanadium-doped carbon-coated lithium iron phosphate.
Further, the iron source is one or two of ferrous oxalate and ferric phosphate; the phosphorus source is one or more of diammonium hydrogen phosphate, ammonium dihydrogen phosphate, lithium dihydrogen phosphate and lithium phosphate; the lithium source is one or more of lithium hydroxide, lithium sulfate, lithium bicarbonate, lithium carbonate, lithium chloride and lithium acetate; the carbon source is one or more of glucose, starch (soluble starch and amylopectin), graphite, acetylene black and citric acid.
Further, the ratio of ferric vanadate in the raw material: iron: phosphorus: the molar ratio of lithium is 0.005-0.045: 0.95-1.03: 0.97-1.05: 0.95-1.05, and the adding mass of the carbon source accounts for 5-25% of the total mass of the raw materials. Preferred iron vanadates: iron: phosphorus: the molar ratio of lithium is 0.010-0.020: 0.97 to 1.0: 1.0-1.03: 0.99-1.03, and the adding mass of the carbon source accounts for 15-20% of the total mass of the raw materials.
Further, the sanding time is 0.5-5 h, preferably 1-3 h, and the spray drying temperature is 170-250 ℃, preferably 180-220 ℃.
Further, the inert gas is one or more of nitrogen, hydrogen, inert gas, carbon dioxide, carbon monoxide and acetylene.
Further, the roasting temperature is 600-800 ℃, and preferably 650-750 ℃; the roasting time is 1-10 hours, and preferably 2-8 hours.
Furthermore, grinding aid accounting for 1-2 percent of the total weight is added into the raw materials during mixing.
Further, the preparation method of the ferric vanadate comprises the following steps:
step 1, dissolving a vanadium source in water, heating in a water bath to dissolve until the vanadium source is clear, wherein the heating temperature is 40-100 ℃;
and step 5, oxidizing and roasting the ferric vanadate precursor at the roasting temperature of 550-850 ℃ for 1-4 h.
An example of the principle of the preparation of the iron vanadate
Fe2(SO4)3+2NH4VO3+4NH4OH→2FeVO4+3(NH4)2SO4+2H2O
Further, the heating temperature in the step 1 is 60-95 ℃.
Further, the vanadium source in step 1 is a pentavalent vanadium compound, preferably one or more of ammonium metavanadate, sodium metavanadate and vanadium pentoxide.
Further, the concentration of the ammonium metavanadate solution is 24 g/L-70 g/L, and V2O5The concentration is 18.7 g/L-54.4 g/L. Preferably, the concentration of the ammonium metavanadate solution is 40-45 g/L, V2O5The concentration is 31.1 g/L-35 g/L.
Further, the iron source in step 2 may be ferric chloride, ferric sulfate, ferric nitrate, or ferric salt generated by reacting ferrous salt such as ferrous sulfate, ferrous chloride with corresponding acid and oxidant.
Further, the molar ratio of iron to vanadium in the step 3 is 0.97-1.03: 0.97-1.03.
Further, the pH value in the step 4 is 4-5.
Further, in the step 5, the roasting temperature is 600-750 ℃, and the roasting time is 2-3 h.
The invention also discloses vanadium-doped carbon-coated lithium iron phosphate prepared by the method, and the general formula of the vanadium-doped carbon-coated lithium iron phosphate is as follows: LixFe1-yVy (PO4) x, wherein x is more than or equal to 0.97 and less than or equal to 1.03, and y is more than 0 and less than or equal to 0.1.
The invention also discloses application of the vanadium-doped carbon-coated lithium iron phosphate in the field of batteries.
Mixing the prepared vanadium-doped carbon-coated lithium iron phosphate, conductive carbon powder and a binder PVDF according to the mass ratio of 8:1:1, adding N-methylpyrrolidone as a solvent to prepare a slurry, coating the slurry on an aluminum current collector to prepare an electrode, drying the electrode slice in a vacuum oven at 120 ℃ for 24 hours, slicing and transferring the electrode slice into a glove box, and assembling the lithium iron phosphate electrode and a lithium slice into a half-cell for charge and discharge tests.
Compared with the prior art, the vanadium-doped carbon-coated lithium iron phosphate, the preparation method and the application thereof have the following advantages:
1) the doping of ferric vanadate in the lithium iron phosphate can effectively improve the charge-discharge performance and the rate performance of the carbon-coated lithium iron phosphate;
2) the doping of the ferric vanadate can improve the low-temperature performance of the lithium iron phosphate
3) The ferric vanadate does not introduce hetero atoms and can supplement the deficiency of the iron content in the raw material ferric phosphate
Drawings
FIG. 1 is an XRD spectrum of carbon-coated lithium iron phosphate doped with iron vanadate in example 1;
FIG. 2 is an SEM image of carbon-coated lithium iron phosphate doped with ferric vanadate in example 1;
FIG. 3 is an SEM image of carbon-coated lithium iron phosphate not doped with ferric vanadate in example 1;
FIG. 4 is a graph comparing the charge and discharge curves of carbon-coated lithium iron phosphate without ferric vanadate and carbon-coated lithium iron phosphate with ferric vanadate in example 1;
FIG. 5 is a graph showing the ratio of the carbon-coated lithium iron phosphate without ferric vanadate to the carbon-coated lithium iron phosphate with ferric vanadate in example 1;
FIG. 6 is a graph comparing the low temperature performance of carbon-coated lithium iron phosphate without ferric vanadate and carbon-coated lithium iron phosphate with ferric vanadate in example 1;
FIG. 7 is an SEM photograph of the iron vanadate prepared in example 1.
Detailed Description
The invention is further illustrated by the following examples:
example 1
The embodiment discloses a preparation method of iron vanadate doped carbon-coated lithium iron phosphate, and the performance of the iron vanadate doped carbon-coated lithium iron phosphate is compared with that of carbon-coated lithium iron phosphate without vanadium doping.
Dissolving 60g ammonium metavanadate in 2L water, heating in water bath to dissolve until the solution is clear, wherein the heating temperature is 80 ℃, and the concentration of the ammonium metavanadate solution is 30g/L (V)2O5The concentration is 23.3g/L), 102.5g of ferric sulfate is dissolved in 1L of water, the mixture is stirred until the ferric sulfate is completely dissolved, the solution is clarified, the ferric sulfate solution is slowly added into the vanadium solution, the feeding speed is 8mol/h, the molar ratio of iron to vanadium is 1.03:0.97, ammonia water is added to adjust the pH value of the solution to 6, the filtration is carried out, deionized water is used for washing a filter cake, the sulfur content in the filter cake is 183ppm, and the filter cake is dried in an air-blast drying oven at 70 ℃ for 24h to obtain a ferric vanadate precursor; and (3) roasting the ferric vanadate precursor in an air atmosphere by using a muffle furnace, wherein the roasting temperature is 600 ℃, and the roasting time is 3 hours, so as to obtain a ferric vanadate product.
Weighing iron phosphate, lithium carbonate, starch and ferric vanadate and mixing, wherein the molar ratio of the ferric vanadate to the iron phosphate to the lithium carbonate is 0.015: 0.97: 1.01, adding 15 percent of carbon source by mass based on the total mass of the raw materials, adding water for mixing to ensure that the solid content of the system is 30 percent, and sanding by using a horizontal sand mill for 2 hours at the spray drying temperature of 200 ℃.
And (3) placing the spray-dried precursor in a tubular furnace, roasting in nitrogen atmosphere at 700 ℃ for 3h, cooling to room temperature along with the furnace after roasting, and taking out.
Mixing the prepared vanadium-doped carbon-coated lithium iron phosphate, conductive carbon powder and a binder PVDF according to the mass ratio of 8:1:1, adding N-methylpyrrolidone as a solvent to prepare a slurry, coating the slurry on an aluminum current collector to prepare an electrode, drying the electrode slice in a vacuum oven at 120 ℃ for 24 hours, slicing and transferring the electrode slice into a glove box, and assembling the lithium iron phosphate electrode and a lithium slice into a half-cell for charge and discharge tests.
For comparison, a carbon-coated lithium iron phosphate without vanadium doping was also prepared as a comparison.
Weighing iron phosphate, lithium carbonate, starch and ferric vanadate, and mixing, wherein the molar ratio of the ferric vanadate to the iron phosphate to the lithium carbonate is 0.015: 0.97: 1.01, adding 15 percent of carbon source by mass based on the total mass of the raw materials, adding water, mixing to ensure that the solid content of the system is 30 percent, sanding by using a horizontal sand mill for 2 hours, and spray drying at the spray drying temperature of 200 ℃.
And (3) placing the spray-dried precursor in a tubular furnace, roasting in nitrogen atmosphere at 700 ℃ for 3h, cooling to room temperature along with the furnace after roasting, and taking out.
Mixing the prepared vanadium-doped carbon-coated lithium iron phosphate with conductive carbon powder and a binder PVDF according to a mass ratio of 8:1:1, adding N-methylpyrrolidone as a solvent to prepare a slurry, coating the slurry on an aluminum current collector to prepare an electrode, drying the electrode slice in a vacuum oven at 120 ℃ for 24 hours, slicing the electrode slice into a glove box, assembling the lithium iron phosphate electrode and a lithium slice into a half-cell, and performing charge-discharge test to prepare the vanadium-doped carbon-coated lithium iron phosphate, wherein the specific charge capacity of a first circle is 160.6mAh/g, the specific discharge capacity of the first circle is 159.6mAh/g, and the efficiency of the first circle is 99.4%; under the 5C discharge condition, the discharge specific capacity is 131.2 mAh/g; the capacity retention at-30 ℃ was 37.23%.
Under the discharge condition of 0.1C of the prepared carbon-coated lithium iron phosphate, the charging specific capacity of the first circle is 146.2mAh/g, the discharging specific capacity of the first circle is 145mAh/g, and the efficiency of the first circle is 99.2%; under the 5C discharge condition, the discharge specific capacity is 96.8 mAh/g; the capacity retention at-30 ℃ was 24.12%.
The results of the experiment are shown in FIGS. 1-7:
fig. 1 is an XRD spectrogram of iron vanadate-doped carbon-coated lithium iron phosphate in the example, comparing with the XRD spectrogram of lithium iron phosphate, no impurity peak appears when doping lithium iron phosphate, which indicates that the doping amount is low, and the doping atoms are dissolved in the crystal lattice of lithium iron phosphate, which does not affect the crystal structure of lithium iron phosphate itself;
fig. 2 is an SEM image of carbon-coated lithium iron phosphate doped with ferric vanadate in the example, and it can be seen from the image that the prepared doped lithium iron phosphate is spherical, and meanwhile, compared with the SEM image of undoped lithium iron phosphate, the presence of pores on the surface of doped lithium iron phosphate is more beneficial to the wetting of the electrolyte and the movement of ions;
fig. 3 is an SEM image of carbon-coated lithium iron phosphate that is not doped with ferric vanadate in the example, and it can be seen from the figure that the undoped lithium iron phosphate is a spherical structure, and compared with the SEM image of doped lithium iron phosphate, the surface of the undoped lithium iron phosphate is relatively dense;
fig. 4, fig. 5 and fig. 6 are comparisons of electrochemical performances of the carbon-coated lithium iron phosphate not doped with iron vanadate and the carbon-coated lithium iron phosphate doped with iron vanadate in the embodiments, including comparison of charge and discharge performances, rate performance and low temperature performance, and it can be seen from the figures that after the iron vanadate is doped with the lithium iron phosphate, the charge and discharge performances, rate performance and low temperature performance of the lithium iron phosphate are all improved, because of the introduction of the iron vanadate, on one hand, the conductivity of the lithium iron phosphate is increased, and the electron conduction performance of the lithium iron phosphate is improved under a large current, and on the other hand, the introduction of the hetero atoms can increase a lithium ion conduction channel, which is beneficial to the insertion and extraction;
fig. 7 is an SEM image of the obtained ferric vanadate, and it can be seen from the SEM image that the obtained ferric vanadate is a nano-sized particle, and the nano-sized particle is more beneficial to the mixing and doping process with the material, and has an effect of promoting the doping effect.
Example 2
The embodiment discloses a preparation method of iron vanadate doped carbon-coated lithium iron phosphate
Dissolving 0g ammonium metavanadate in L water, heating in water bath to dissolve until the solution is clearThe heating temperature is 95 ℃, and the concentration of the ammonium metavanadate solution is g/L (V)2O5The concentration is 23.3g/L), dissolving g of ferrous sulfate in L water, mixing with g of concentrated sulfuric acid and excessive hydrogen peroxide, stirring until the ferrous sulfate is completely dissolved, clarifying the solution, slowly adding the mixed solution into a vanadium solution, wherein the feeding speed is 10mol/h, the iron-vanadium molar ratio is 0.99:1.02, adding ammonia water to adjust the pH solution to 5, filtering, washing a filter cake by using deionized water, the sulfur content in the filter cake is 158ppm, and drying for 24 hours at 70 ℃ in an air blast drying oven to obtain an iron vanadate precursor; and (3) roasting the ferric vanadate precursor in an air atmosphere by using a muffle furnace, wherein the roasting temperature is 700 ℃, and the roasting time is 2 hours, so as to obtain the ferric vanadate product.
Weighing iron phosphate, lithium carbonate, starch and ferric vanadate and mixing, wherein the molar ratio of the ferric vanadate to the iron phosphate to the lithium carbonate is 0.030: 1.00: 1.03, adding 17 percent of carbon source by mass based on the total mass of the raw materials, adding water for mixing to ensure that the solid content of the system is 43 percent, and sanding by using a horizontal sand mill for 3 hours at a spray drying temperature of 180 ℃.
And (3) placing the spray-dried precursor into a tubular furnace, roasting in an argon atmosphere at the roasting temperature of 650 ℃ for 6 hours, cooling to room temperature along with the furnace after roasting, and taking out.
Mixing the prepared vanadium-doped carbon-coated lithium iron phosphate, conductive carbon powder and a binder PVDF according to the mass ratio of 8:1:1, adding N-methylpyrrolidone as a solvent to prepare a slurry, coating the slurry on an aluminum current collector to prepare an electrode, drying the electrode slice in a vacuum oven at 120 ℃ for 24 hours, slicing and transferring the electrode slice into a glove box, and assembling the lithium iron phosphate electrode and a lithium slice into a half-cell for charge and discharge tests.
Under the discharge condition of 0.1C of the prepared vanadium-doped carbon-coated lithium iron phosphate, the specific charge capacity of the first circle is 159.5mAh/g, the specific discharge capacity of the first circle is 156.6mAh/g, and the efficiency of the first circle is 98.2 percent; under the 5C discharge condition, the discharge specific capacity is 129.8 mAh/g; the capacity retention at-30 ℃ was 38.24%.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of vanadium-doped carbon-coated lithium iron phosphate is characterized by comprising the following steps of: mixing ferric vanadate, an iron source, a phosphorus source, a lithium source and a carbon source, sanding, then spray-drying, and roasting under the protection of inert gas to prepare the vanadium-doped carbon-coated lithium iron phosphate.
2. The preparation method of the vanadium-doped carbon-coated lithium iron phosphate according to claim 1, wherein the iron source is one or both of ferrous oxalate and iron phosphate; the phosphorus source is one or more of diammonium hydrogen phosphate, ammonium dihydrogen phosphate, lithium dihydrogen phosphate and lithium phosphate; the lithium source is one or more of lithium hydroxide, lithium sulfate, lithium bicarbonate, lithium carbonate, lithium chloride and lithium acetate; the carbon source is one or more of glucose, starch, graphite, acetylene black and citric acid.
3. The method for preparing vanadium-doped carbon-coated lithium iron phosphate according to claim 1, wherein the ratio of ferric vanadate: iron: phosphorus: the molar ratio of lithium is 0.005-0.045: 0.95-1.03: 0.97-1.05: 0.95-1.05, and the adding mass of the carbon source accounts for 5-25% of the total mass of the raw materials.
4. The preparation method of the vanadium-doped carbon-coated lithium iron phosphate as claimed in claim 1, wherein the sanding time is 0.5-5 h, and the spray drying temperature is 170-250 ℃.
5. The preparation method of the vanadium-doped carbon-coated lithium iron phosphate according to claim 1, wherein the roasting temperature is 600 ℃ to 800 ℃; the roasting time is 1-10 h.
6. The method for preparing vanadium-doped carbon-coated lithium iron phosphate according to claim 1, wherein the method for preparing iron vanadate comprises the following steps:
step 1, dissolving a vanadium source in water, and heating to dissolve until the vanadium source is clear, wherein the heating temperature is 40-100 ℃;
step 2, dissolving an iron source in water until the solution is clear;
step 3, adding the iron source solution into the vanadium solution, wherein the molar ratio of iron to vanadium is 0.95-1.05: 0.95-1.05;
step 4, adding ammonia water to adjust the pH value of the solution to 4-7, filtering and washing until the sulfur content in the filter cake is less than or equal to 200ppm, and preparing to obtain an iron vanadate precursor;
and step 5, oxidizing and roasting the ferric vanadate precursor at the roasting temperature of 550-850 ℃ for 1-4 h.
7. The method for preparing vanadium-doped carbon-coated lithium iron phosphate according to claim 6, wherein the vanadium source in step 1 is a pentavalent vanadium compound.
8. The method for preparing vanadium-doped carbon-coated lithium iron phosphate according to claim 6, wherein the iron source in step 2 is ferric chloride, ferric sulfate, ferric nitrate or the like, or ferric salt generated by reacting ferrous salt such as ferrous sulfate, ferrous chloride with corresponding acid and an oxidant.
9. A vanadium-doped carbon-coated lithium iron phosphate characterized by being prepared by the method of any one of claims 1 to 8.
10. An application of the vanadium-doped carbon-coated lithium iron phosphate as defined in claim 9 in the field of batteries.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113735091A (en) * | 2021-09-07 | 2021-12-03 | 湖北云翔聚能新能源科技有限公司 | Preparation method of nano spherical lithium iron phosphate and lithium iron phosphate material |
| CN114024055A (en) * | 2021-11-05 | 2022-02-08 | 江西省科学院应用化学研究所 | Short-process recovery method for waste lithium iron phosphate battery material |
| WO2023142677A1 (en) * | 2022-01-28 | 2023-08-03 | 宜昌邦普循环科技有限公司 | Doped iron(iii) phosphate, method for preparing same, and use thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102299303A (en) * | 2011-09-01 | 2011-12-28 | 深圳科雷拉能源科技有限公司 | Method for preparing lithium iron phosphate-lithium vanadium phosphate cathode material of lithium ion battery |
| CN102583300A (en) * | 2012-02-29 | 2012-07-18 | 华南理工大学 | Fluorine and vanadium ion-doped lithium iron phosphate material and preparation method thereof |
| US20120308892A1 (en) * | 2010-02-25 | 2012-12-06 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | High-power lithium-ion storage battery |
| CN104103832A (en) * | 2014-07-23 | 2014-10-15 | 中南大学 | Preparation method for LiFePO4-LiVPO4F for cathode material for lithium ion battery |
| CN105261732A (en) * | 2015-09-02 | 2016-01-20 | 武汉理工力强能源有限公司 | Vanadium doped lithium iron phosphate/carbon three-dimensional porous electrode material and preparation method therefor |
-
2020
- 2020-12-28 CN CN202011575832.8A patent/CN112736226A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120308892A1 (en) * | 2010-02-25 | 2012-12-06 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | High-power lithium-ion storage battery |
| CN102299303A (en) * | 2011-09-01 | 2011-12-28 | 深圳科雷拉能源科技有限公司 | Method for preparing lithium iron phosphate-lithium vanadium phosphate cathode material of lithium ion battery |
| CN102583300A (en) * | 2012-02-29 | 2012-07-18 | 华南理工大学 | Fluorine and vanadium ion-doped lithium iron phosphate material and preparation method thereof |
| CN104103832A (en) * | 2014-07-23 | 2014-10-15 | 中南大学 | Preparation method for LiFePO4-LiVPO4F for cathode material for lithium ion battery |
| CN105261732A (en) * | 2015-09-02 | 2016-01-20 | 武汉理工力强能源有限公司 | Vanadium doped lithium iron phosphate/carbon three-dimensional porous electrode material and preparation method therefor |
Non-Patent Citations (1)
| Title |
|---|
| TOMASZ K. PIETRZAK等: ""Nanocrystallisation in vanadate phosphate and lithium iron vanadate phosphate glasses"", 《PHYS. CHEM. GLASSES: EUR. J. GLASS SCI. TECHNOL. B》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113735091A (en) * | 2021-09-07 | 2021-12-03 | 湖北云翔聚能新能源科技有限公司 | Preparation method of nano spherical lithium iron phosphate and lithium iron phosphate material |
| CN113735091B (en) * | 2021-09-07 | 2023-06-02 | 湖北云翔聚能新能源科技有限公司 | Preparation method of nano spherical lithium iron phosphate and lithium iron phosphate material |
| CN114024055A (en) * | 2021-11-05 | 2022-02-08 | 江西省科学院应用化学研究所 | Short-process recovery method for waste lithium iron phosphate battery material |
| WO2023142677A1 (en) * | 2022-01-28 | 2023-08-03 | 宜昌邦普循环科技有限公司 | Doped iron(iii) phosphate, method for preparing same, and use thereof |
| GB2619869A (en) * | 2022-01-28 | 2023-12-20 | Yichang Brunp Recycling Tech Co Ltd | Doped iron(III) phosphate, method for preparing same, and use thereof |
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