CN115072695A - Preparation method of high-capacity lithium manganese iron phosphate material - Google Patents

Preparation method of high-capacity lithium manganese iron phosphate material Download PDF

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CN115072695A
CN115072695A CN202210801473.6A CN202210801473A CN115072695A CN 115072695 A CN115072695 A CN 115072695A CN 202210801473 A CN202210801473 A CN 202210801473A CN 115072695 A CN115072695 A CN 115072695A
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lithium
manganese
phosphate
ferric
precursor
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黄长靓
高伟
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Jiangsu Gcl Lithium Battery Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes

Abstract

The invention discloses a preparation method of a high-capacity lithium ferric manganese phosphate material, and belongs to the technical field of lithium ion battery anode materials. The chemical formula of the lithium ferric manganese phosphate precursor is Fe a Mn (1‑a‑b) A b P c O d (ii) a The chemical formula of the high-capacity lithium ferric manganese phosphate material is LiFe a Mn (1‑a‑b) A b PO 4 C, wherein 0.1<a<0.9，0<b≤0.04，0.1<1‑a‑b<0.9; a is selected from any one of titanium, magnesium, zirconium, niobium, strontium, nickel and vanadium. According to the invention, the metal element A is doped in the process of preparing the precursor, so that the effect of improving the performance of the iron phosphate manganese is achieved, the Fe, the Mn and the doped metal A are fully mixed and melted more uniformly through grinding and sintering, the doped element can enter the crystal lattice of the precursor more favorably, and finally, the improvement is achievedThe purpose of the electrochemical performance of the iron phosphate manganese.

Description

Preparation method of high-capacity lithium manganese iron phosphate material
Technical Field
The invention belongs to the technical field of lithium ion battery anode materials, and particularly relates to a preparation method of a high-capacity lithium manganese iron phosphate material, in particular to a preparation method of a lithium manganese iron phosphate precursor and the high-capacity lithium manganese iron phosphate material.
Background
Lithium iron phosphate is always favored by the market of power batteries due to the advantages of low price, high theoretical capacity ((170mAh/g), good safety performance, stable structure, good cycle performance and the like, and the application field of the lithium iron phosphate is limited due to the defect of low energy density of the lithium iron phosphate, and the lithium iron phosphate is also used as a positive material lithium manganese iron phosphate with an olivine structure, has all the advantages of the lithium iron phosphate, has higher working voltage (4.1V), has the theoretical energy density up to 21 percent higher than that of the lithium iron phosphate, and is considered as an upgraded version of the lithium iron phosphate, so that the lithium iron phosphate is more and more widely concerned by people.
At present, there are two main types of materials for synthesizing lithium ferric manganese phosphate. The other method is a solid phase method, and is prepared by taking the reference of a process for preparing lithium iron phosphate by using iron phosphate, physically and uniformly mixing a lithium source, an iron source, a manganese source and a phosphorus source, and then performing primary solid phase sintering. And the other method is a liquid phase method, and the lithium manganese iron phosphate is prepared by feeding materials according to the mol ratio of Li (Fe + Mn) to P (3: 1: 1), performing high-temperature and high-pressure reaction, then coating carbon again, and sintering. Because the existing precursor manganese iron phosphate has harsh preparation conditions and is difficult to industrially produce, the solid phase method can only use a lithium source, an iron source, a manganese source and a phosphorus source to physically and uniformly mix, but the method is difficult to ensure the uniform mixing of manganese iron element in molecular level to a certain extent, and the result of poor electrochemical performance is finally caused. The liquid phase method can achieve the mixing of ferro-manganese elements at a molecular level, but the production cost is too high due to the use of the tri-fold amount of lithium, and a large amount of waste water is generated in the washing process, so that the production cost is further increased.
For example, chinese patent application 201510847231.0 discloses a composite positive electrode material LiMn for lithium ion battery 1- x Fe x PO 4 A method for synthesizing the/C. The manganese source, the iron source, the phosphorus source and the organic carbon source are uniformly mixed and treated under a high-energy ball mill. The mixture is subjected to heat treatment at the temperature of 500 ℃ and 700 ℃ under the protection of inert atmosphere to obtain (Mn) 1-x Fe x ) 2 P 2 O 7 and/C. Then pyrophosphate/carbon is mixed with a lithium source and a carbon source, and the mixture is subjected to heat treatment at the temperature of 600-750 ℃ under the protection of inert atmosphere to obtain the lithium iron manganese phosphate/carbon cathode material with the composite conductive network. By addingThe organic carbon source, such as polystyrene, polypropylene, phenolic resin and the like, realizes the discharge capacity of 25.1-141.3mAh/g at 1C, and maintains 94-98% after circulating for 250 weeks.
The invention provides a novel preparation method of lithium iron manganese phosphate on the basis of the existing preparation method of lithium iron manganese phosphate. The method avoids the use of excessive lithium and the generation of a large amount of wastewater in the traditional liquid phase method, has simple process and is suitable for industrial industrialization, and the ferric manganese phosphate prepared by the process has better electrochemical performance.
Disclosure of Invention
The invention aims to provide a lithium manganese iron phosphate precursor and a preparation method of a lithium manganese iron phosphate material thereof.
In order to achieve the purpose, the technical scheme of the invention is as follows:
in one aspect, the invention provides a lithium ferric manganese phosphate precursor with a chemical formula of Fe a Mn (1-a-b) A b P c O d (ii) a Wherein, 0.1<a<0.9，0<b<0.04，0.1<1-a-b<0.9，1≤c≤4，1<d is less than or equal to 8; a is selected from any one of titanium, magnesium, zirconium, niobium, strontium, nickel and vanadium.
In another aspect, the present invention provides a method for preparing the lithium ferric manganese phosphate precursor, including the following steps:
(1) grinding and mixing a ferric iron source, a trivalent manganese source, a phosphorus source, a carbon source and a metal oxide or metal salt of a metal element A in a liquid phase system to obtain mixed slurry;
(2) drying the mixed slurry obtained in the step (1) to obtain dry powder, and sintering the dry powder in an inert atmosphere to obtain the lithium ferric manganese phosphate precursor Fe a Mn (1-a-b) A b P c O d 。
Preferably, in step (1), the ferric iron source is one or more of ferric hydroxide, ferric oxalate, ferric phosphate, ferric pyrophosphate, ferric hydroxide and ferric manganese phosphate; the trivalent manganese source is one or more of manganous oxide, manganese phosphate, manganese oxyhydroxide and manganese ferric phosphate; the phosphorus source is one or more of diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphate, iron manganese phosphate and manganese phosphate; the carbon source is any one or more of glucose, rock candy, sucrose, fructose, polyethylene glycol, cyclodextrin, starch, ascorbic acid, phenolic resin and cellulose; the metal oxide or metal salt doped with the metal element A is one or more of titanium dioxide, tetrabutyl titanate, magnesium acetate, magnesium titanate, magnesium nitrate, zirconium hydroxide, zirconium dioxide, niobium pentoxide, nickel acetate, nickel nitrate, nickel hydroxide, strontium oxide, strontium hydroxide, ammonium vanadate and vanadium pentoxide.
Preferably, in step (1), the medium of the liquid phase system is selected from at least one of water, methanol, acetone and ethanol.
Preferably, in the step (1), the metal element A is added in a molar amount of 0 to 4% based on the total metal (Fe + Mn + A) molar amount.
Preferably, in the step (1), the grinding is performed by coarse grinding to a particle size D50<1 μm, and then fine grinding to a particle size of 250-350 nm.
Preferably, in step (1), the molar ratio (Fe + Mn + a)/P is 0.96 to 0.985, while the molar ratio Fe/Mn is 1:9 to 9: 1.
Preferably, in step (2), the drying includes, but is not limited to, static drying, spray drying, and the like.
Preferably, in the step (2), the inert atmosphere gas is at least one of argon, helium, nitrogen and carbon dioxide.
Preferably, in the step (2), the sintering temperature is 500-700 ℃, and the sintering time is 3-6 h.
Preferably, in the step (2), the carbon content in the lithium ferric manganese phosphate precursor is 0.2-0.5 wt%.
In another aspect, the present invention provides a high capacity lithium manganese iron phosphate/carbon composite material having a chemical formula of LiFe a Mn (1-a-b) A b PO 4 C, wherein 0.1<a<0.9，0<b≤0.04，0.1<1-a-b<0.9; a is selected from any one of titanium, magnesium, zirconium, niobium, strontium, nickel and vanadium.
In a last aspect, the invention provides a preparation method of a high-capacity lithium ferric manganese phosphate material, which comprises the following steps:
s1, grinding, mixing and drying a lithium source, the lithium manganese iron phosphate precursor, a carbon source and an additive in a liquid phase system to obtain a lithium manganese iron phosphate/carbon composite material precursor;
s2, sintering the lithium ferric manganese phosphate/carbon composite material precursor obtained in the step S1 in an inert gas protection atmosphere to obtain LiFe with the structural formula a Mn (1-a-b) A b PO 4 High capacity lithium manganese iron phosphate per C.
Preferably, in step S1, the lithium source is one or more of lithium carbonate, lithium hydroxide, lithium acetate and lithium phosphate; the carbon source is any one or more of glucose, rock candy, sucrose, fructose, polyethylene glycol, cyclodextrin, starch, ascorbic acid, phenolic resin and cellulose.
Preferably, in step S1, the molar ratio Li/P is 1 to 1.06.
Preferably, in step S1, the medium of the liquid phase system is selected from at least one of water, methanol, acetone and ethanol.
Preferably, in step S1, the grinding is performed by coarse grinding to a particle size of D50<1 μm, and then fine grinding to a particle size of 250-350 nm.
Preferably, in step S1, the drying includes, but is not limited to, static drying, spray drying, and the like.
Preferably, in step S1, the metal element A is added in a molar amount of 0-4% based on the total metal (Fe + Mn + A) molar amount.
Preferably, in step S2, the inert atmosphere gas is at least one of argon, helium, nitrogen and carbon dioxide.
Preferably, in step S2, the sintering temperature is 650-780 ℃ and the sintering time is 8-10 hours.
Preferably, in step S2, the carbon content in the high-capacity lithium ferric manganese phosphate material is 1.5-2.5 wt%.
The invention has the beneficial effects that:
(1) the invention aims to provide a preparation method of a precursor for preparing lithium iron manganese phosphate, which is simple in process and environment-friendly. The ball milling nanocrystallization reduces the particle size of the raw materials, improves the reaction activity of the raw materials in high-temperature sintering, and is beneficial to improving the fusion and uniform mixing of iron and manganese elements; and a small amount of carbon source is added at one time, so that the formed residual carbon is beneficial to inhibiting the growth of lithium manganese iron phosphate precursor particles under the action of carbon thermal reduction, the uniform mixing of iron and manganese elements is further improved, and the reduction of Mn in the lithium manganese iron phosphate at the later stage is facilitated 3+ 、Fe 3+ Generation of impurity phases.
(2) The metal element A is doped in the process of preparing the precursor, so that the effect of improving the performance of the iron phosphate manganese is achieved. Through grinding and sintering, Fe, Mn and the doped metal A are fully mixed and melted more uniformly, so that the doped elements can enter the crystal lattices of the precursor more conveniently, and the aim of improving the electrochemical performance of the iron phosphate manganese is finally fulfilled.
(3) The invention abandons the use of excessive lithium and a large amount of water in the traditional liquid phase method, avoids the generation of waste water and reduces the production cost.
(4) Compared with the primary ball milling and sintering process of the traditional solid phase method, the invention is more beneficial to uniformly mixing lithium, iron, manganese, phosphorus and doped metal A through secondary ball milling, mixing and sintering; meanwhile, the secondary carbon source is added, so that the carbon source is more easily attached to the surface of the low-carbon lithium manganese iron phosphate precursor, and the uniform coating of the carbon source is more facilitated.
(5) The invention provides a preparation method of lithium iron manganese phosphate; the lithium manganese iron phosphate with excellent performance can be prepared by mixing a self-made doped divalent low-carbon lithium manganese iron phosphate precursor, a lithium source and a carbon source and performing solid phase sintering, and particularly has better low-temperature performance.
Drawings
FIG. 1 is an SEM photograph of lithium manganese iron phosphate prepared in example 1;
fig. 2 is a graph showing a discharge curve of lithium manganese iron phosphate prepared in example 1.
Detailed Description
The following non-limiting examples will provide those of ordinary skill in the art with a more complete understanding of the present invention, but are not intended to limit the invention in any way. The following is merely an exemplary illustration of the scope of the invention as claimed, and various changes and modifications of the invention of the present application may be made by those skilled in the art based on the disclosure, which also fall within the scope of the invention as claimed.
The present invention will be further described below by way of specific examples. The various chemicals used in the examples of the present invention were obtained by conventional commercial routes unless otherwise specified. Unless otherwise specified, the contents are all mass contents hereinafter. Unless otherwise specified, it is understood to be carried out at room temperature.
Example 1
Preparing a lithium ferric manganese phosphate precursor:
preparing a lithium manganese iron phosphate precursor according to the raw material molar ratio (Fe + Mn + Ti)/P of 0.97. Adding 60.92g of iron phosphate, 90.39g of manganese phosphate, 6g of glucose and 0.81g of titanium dioxide into a 2L measuring cup containing 800mL of deionized water, placing the measuring cup into a basket mill for grinding for 1 hour, introducing the slurry into a sand mill for fine grinding after the slurry granularity reaches D50<1 mu m, performing spray drying after the slurry granularity reaches 250nm, placing the spray-dried powder into a muffle furnace for sintering at the sintering temperature of 500 ℃ for 4 hours after the drying is finished, taking out the powder after the sintering is finished to obtain 125g of a lithium manganese iron phosphate precursor with the carbon content of 0.4 percent, and detecting and analyzing the phosphorus content of the precursor to be 20.70 percent,
preparation of lithium iron manganese phosphate:
according to the raw material mol ratio Li: and feeding the mixture until the P is 1.06. 120g of lithium manganese iron phosphate precursor, 31.56g of lithium carbonate (purity 99.5%), 8.2g of glucose, 4.1g of PEG 20000 and 0.61g of titanium dioxide are sequentially added into a 2L measuring cup containing 800mL of water, the measuring cup is placed into a basket mill to be milled for 30 minutes at the rotating speed of 2000r/min, the slurry is led into a sand mill to be milled after the milling is finished, and the slurry is subjected to spray drying after the particle size of the slurry reaches 300 nm. And after the spray drying is finished, sintering the dried and crushed material in a tubular furnace in a nitrogen atmosphere at the sintering temperature of 700 ℃ for 10 hours. After the temperature of the tube furnace is naturally reduced to 80 ℃, the sintered material is crushed in a grading way to obtain LiFe with the carbon content of 1.7 percent 0.38 Mn 0.6 Ti 0.02 PO 4 a/C composite material.
To obtain LiFe 0.38 Mn 0.6 Ti 0.02 PO 4 The results of the observation of the/C composite powder by a scanning electron microscope are shown in FIG. 1. As can be seen from FIG. 1, the prepared lithium ferric manganese phosphate particles have different sizes, the size of the primary particle is about 0.1-0.5 μm, and most of the particles are mainly concentrated at about 0.3 μm.
To prepare LiFe 0.38 Mn 0.6 Ti 0.02 PO 4 the/C composite material is a positive electrode material, acetylene black is a conductive agent, polytetrafluoroethylene is a binder, and the mass ratio of the conductive agent to the polytetrafluoroethylene is 90: 5: 5 adding into NMP, mixing, coating on aluminum foil, drying at 100 deg.C under vacuum for 4 hr, rolling, and cutting into 12mm electrode sheet. And assembling the button cell by taking the electrode slice as a positive electrode and the metal lithium as a negative electrode. Under the conditions of 2-4.3V and 25 ℃, different charging and discharging current conditions are adopted for testing, the result of a discharging curve is shown in figure 2, the initial reversible capacity of charging and discharging with 0.2C is 154.9mAh/g, the first charging and discharging efficiency is 98.2%, the initial reversible capacity of charging and discharging with 1C is 148.8mAh/g, and the cycle retention rate is 98.5% after 1C for 250 weeks; at 25 ℃, charging at 0.2 ℃ and discharging at-20 ℃ at 0.2 ℃, wherein the low-temperature discharge capacity is up to 117.8. mAh/g.
Example 2
Preparing the lithium manganese iron phosphate precursor according to the raw material molar ratio (Fe + Mn + Mg)/P of 0.97. Adding 30.46g of iron phosphate, 135.55g of manganese phosphate, 5g of rock sugar and 0.45g of magnesium oxide into a 2L measuring cup containing 800mL of deionized water, placing the cup into a basket mill, grinding for 1 hour, introducing the slurry into a sand mill for fine grinding after the slurry particle size reaches D50<1 mu m, performing spray drying after the slurry particle size reaches 300nm, placing the spray-dried powder into a muffle furnace, sintering at the sintering temperature of 550 ℃ for 4 hours after the drying is completed, taking out after the sintering is completed, obtaining 128g of a lithium manganese iron phosphate precursor with the carbon content of 0.3%, and detecting and analyzing that the phosphorus content of the precursor is 20.60%.
Preparation of lithium iron manganese phosphate:
according to the raw material mol ratio Li: and feeding the mixture until the P is 1.06. 120g of lithium manganese iron phosphate precursor, 31.31g of lithium carbonate (purity is 99.5%), 8g of glucose, 2g of cyclodextrin and 1.33g of nickel acetate are sequentially added into a 2L measuring cup containing 800mL of ethanol, the measuring cup is placed in a basket mill to be milled for 30 minutes at the rotating speed of 2000r/min, after the milling is finished, the slurry is led into a sand mill to be milled, and after the granularity of the slurry reaches 300nm, the slurry is subjected to spray drying. And after the spray drying is finished, sintering the dried and crushed material in a tubular furnace in a nitrogen atmosphere at the sintering temperature of 700 ℃ for 10 hours. After the temperature of the tube furnace is naturally reduced to 80 ℃, the sintered material is crushed in a grading way to obtain LiFe with the carbon content of 1.9 percent 0.2 Mn 0.78 Ni 0.01 Mg 0.01 PO 4 a/C composite material.
To prepare LiFe 0.2 Mn 0.78 Ni 0.01 Mg 0.01 PO 4 the/C composite material is a positive electrode material, acetylene black is a conductive agent, polytetrafluoroethylene is a binder, and the mass ratio of the conductive agent to the polytetrafluoroethylene is 90: 5: 5 adding into NMP, mixing, coating on aluminum foil, drying at 100 deg.C under vacuum for 4 hr, rolling, and cutting into 12mm electrode sheet. And assembling the button cell by taking the electrode slice as a positive electrode and the metal lithium as a negative electrode. Under the conditions of 2-4.3V and 25 ℃, different charging and discharging current conditions are adopted for testing, the initial reversible capacity of charging and discharging at 0.2C is 154.5mAh/g, the first charging and discharging efficiency is 97.8 percent, and the charging and discharging at 1C are carried outThe initial reversible capacity is 147.3mAh/g, the capacity retention rate is 98.2 percent after 1C circulation for 250 weeks, the charging is carried out at 25 ℃ by 0.2C, the discharging is carried out at-20 ℃ by 0.2C, and the low-temperature discharging capacity is up to 110.1 mAh/g.
Example 3
Preparing the lithium manganese iron phosphate precursor according to the molar ratio (Fe + Mn + Zr)/P ═ 0.98 of the raw materials. Adding 64.51g of iron oxide (with the purity of 99.5%) and 95.67g of manganese oxide (with the purity of 99.5%), 117.84g of ammonium dihydrogen phosphate (with the purity of 99.6%), 1.23g of zirconium dioxide and 7.1g of cane sugar into a 2L measuring cup containing 800mL of deionized water, placing the measuring cup in a basket mill for grinding for 1 hour, introducing the slurry into a sand mill for fine grinding after the slurry particle size reaches D50<1 mu m, performing spray drying after the slurry particle size reaches 300nm, placing the spray-dried powder in a muffle furnace for sintering at the sintering temperature of 550 ℃ for 3 hours after the drying is completed, taking out the powder after the sintering is completed, obtaining 127g of a lithium manganese iron phosphate precursor with the content of 0.4%, and detecting and analyzing that the phosphorus content of the precursor is 20.80%.
Preparation of lithium iron manganese phosphate:
according to the raw material mol ratio Li: and feeding the mixture when the P is 1.05. Adding 120g of lithium ferric manganese phosphate precursor, 31.42g of lithium carbonate (purity is 99.5%), 7.5g of rock candy, 2g of cyclodextrin and 0.93g of zirconium dioxide into a 2L measuring cup containing 800mL of ethanol in sequence, placing the measuring cup in a basket mill, grinding for 30 minutes at the rotating speed of 2000r/min, introducing the slurry into a sand mill for grinding after grinding is finished, and performing spray drying on the slurry after the granularity of the slurry reaches 300 nm. And after the spray drying is finished, sintering the dried and crushed material in a tubular furnace in a nitrogen atmosphere at the sintering temperature of 720 ℃ for 10 hours. After the temperature of the tube furnace is naturally reduced to 80 ℃, the sintered material is crushed in a grading way to obtain LiFe with the carbon content of 1.7 percent 0.38 Mn 0.6 Zr 0.02 PO 4 a/C composite material.
To prepare LiFe 0.38 Mn 0.6 Zr 0.02 PO 4 the/C composite material is a positive electrode material, acetylene black is a conductive agent, polytetrafluoroethylene is a binder, and the mass ratio of the conductive agent to the polytetrafluoroethylene is 90: 5: 5 adding into NMP, mixing, coating on aluminum foil, and vacuum-drying at 100 deg.CDrying for 4 hours, and then rolling and cutting into electrode plates with the diameter of 12 mm. And assembling the button cell by taking the electrode slice as a positive electrode and the metal lithium as a negative electrode. Under the conditions of 2-4.3V and 25 ℃, different charging and discharging current conditions are adopted for testing, the initial reversible capacity of charging and discharging at 0.2C is 154.5mAh/g, the initial charging and discharging efficiency is 98.1%, the initial reversible capacity of charging and discharging at 1C is 145.6mAh/g, and the circulating capacity retention rate at 1C 250 weeks is 97.6%. At 25 ℃ with 0.2C, and-at 20 ℃ with 0.2C, the low-temperature discharge capacity of up to 115.1. mAh/g.
Example 4
Preparing a lithium ferric manganese phosphate precursor according to the raw material molar ratio (Fe + Mn + Nb)/P being 0.98. 26.78g of iron oxyhydroxide (with the purity of 99.5%) and 61.86g of manganese oxyhydroxide (with the purity of 99.5%), 117.84g of ammonium dihydrogen phosphate (with the purity of 99.6%), 1.32g of niobium pentoxide and 6g of glucose are added into a 2L measuring cup containing 800mL of deionized water, the measuring cup is placed into a basket mill for grinding for 1 hour, after the granularity of the slurry reaches D50<1 mu m, the slurry is led into a sand mill for fine grinding, after the granularity of the slurry reaches 300nm, spray drying is carried out, after drying is finished, the spray-dried powder is placed into a muffle furnace for sintering at the sintering temperature of 550 ℃ for 3 hours, after sintering is finished, the spray-dried powder is taken out to obtain 130g of a lithium manganese iron phosphate precursor with the carbon content of 0.3%, and the phosphorus content of the precursor is 20.65% through detection and analysis.
Preparation of lithium iron manganese phosphate:
according to the raw material mol ratio Li: and feeding the mixture with P being 1.04. Adding 120g of lithium manganese iron phosphate precursor, 30.89g of lithium carbonate (with the purity of 99.5%), 9g of rock candy, 2g of starch and 0.6g of magnesium oxide into a 2L measuring cup containing 800mL of ethanol in sequence, placing the measuring cup in a basket mill, grinding for 30 minutes at the rotating speed of 2000r/min, introducing the slurry into a sand mill for grinding after the grinding is finished, and performing spray drying on the slurry after the particle size of the slurry reaches 350 nm. And after the spray drying is finished, sintering the dried and crushed material in a tube furnace in a nitrogen atmosphere at the sintering temperature of 710 ℃ for 10 hours. After the temperature of the tube furnace is naturally reduced to 80 ℃, the sintered material is crushed in a grading way to obtain LiFe with the carbon content of 1.8 percent 0.27 Mn 0.7 Nb 0.01 Mg 0.02 PO 4 a/C composite material.
To prepare LiFe 0.27 Mn 0.7 Nb 0.01 Mg 0.02 PO 4 the/C composite material is a positive electrode material, acetylene black is a conductive agent, polytetrafluoroethylene is a binder, and the mass ratio of the conductive agent to the polytetrafluoroethylene is 90: 5: 5 adding into NMP, mixing, coating on aluminum foil, drying at 100 deg.C under vacuum for 4 hr, rolling, and cutting into 12mm electrode sheet. And assembling the button cell by taking the electrode slice as a positive electrode and the metal lithium as a negative electrode. Under the conditions of 2-4.3V and 25 ℃, different charging and discharging current conditions are adopted for testing, the initial reversible capacity of charging and discharging at 0.2C is 153.5mAh/g, the first charging and discharging efficiency is 98.3%, the initial reversible capacity of charging and discharging at 1C is 144.1mAh/g, and the capacity retention rate of 1C circulating for 250 weeks is 97.9%. Charging at 0.2C, discharging at-20 deg.C at 0.2C, and low-temperature discharge capacity up to 114.3. mAh/g.
Example 5
Preparing a lithium ferric manganese phosphate precursor:
preparing a lithium ferric manganese phosphate precursor according to the raw material molar ratio (Fe + Mn + Nb)/P of 0.97. Adding 60.92g of ferric phosphate, 90.39g of manganese phosphate, 6g of glucose and 1.33g of niobium pentoxide into a 2L measuring cup containing 800mL of deionized water, placing the cup into a basket mill, grinding the cup for 1 hour, introducing the slurry into a sand mill for fine grinding after the particle size of the slurry reaches D50<1 mu m, carrying out spray drying after the particle size of the slurry reaches 250nm, placing the spray-dried powder into a muffle furnace to sinter for 4 hours at the sintering temperature of 500 ℃, taking out the powder after the sintering is finished to obtain 126g of lithium manganese ferric phosphate precursor with the carbon content of 0.4%, and detecting and analyzing the phosphorus content of the precursor to be 20.71%,
preparation of lithium iron manganese phosphate:
according to the raw material mol ratio Li: and feeding the mixture until the P is 1.06. Adding 120g of lithium manganese iron phosphate precursor, 31.58g of lithium carbonate (purity is 99.5%), 8.2g of glucose, 4.1g of PEG 20000 and 0.93g of ammonium vanadate into a 2L measuring cup containing 800mL of water in sequence, grinding for 30 minutes in a basket grinder at the rotating speed of 2000r/min, introducing the slurry into a sand mill for grinding after grinding is finished, and grinding until the granularity of the slurry reaches 300nmThe slurry is spray dried. And after the spray drying is finished, sintering the dried and crushed material in a tubular furnace in a nitrogen atmosphere at the sintering temperature of 700 ℃ for 10 hours. After the temperature of the tube furnace is naturally reduced to 80 ℃, the sintered material is crushed in a grading way to obtain LiFe with the carbon content of 1.7 percent 0.38 Mn 0.6 Nb 0.01 V 0.01 PO 4 a/C composite material.
To prepare LiFe 0.38 Mn 0.6 Nb 0.01 V 0.01 PO 4 the/C composite material is a positive electrode material, acetylene black is a conductive agent, polytetrafluoroethylene is a binder, and the mass ratio of the conductive agent to the polytetrafluoroethylene is 90: 5: 5 adding into NMP, mixing, coating on aluminum foil, drying at 100 deg.C under vacuum for 4 hr, rolling, and cutting into 12mm electrode sheet. And assembling the button cell by taking the electrode slice as a positive electrode and the metal lithium as a negative electrode. Under the conditions of 2-4.3V and 25 ℃, different charging and discharging current conditions are adopted for testing, the initial reversible capacity of charging and discharging at 0.2C is 155.0mAh/g, the first charging and discharging efficiency is 98.4%, the initial reversible capacity of charging and discharging at 1C is 148.2mAh/g, and the cycle retention rate at 1C 200 weeks is 98.7%. The charge is carried out at 0.2C, the discharge is carried out at 0.2C at the temperature of minus 20 ℃, and the low-temperature discharge capacity is up to 119.5 mAh/g.
Comparative example 1
The difference from example 3 is that, instead of preparing the precursor separately, the raw materials were mixed together to prepare lithium manganese iron phosphate.
According to the raw material mol ratio Li: and preparing a lithium manganese iron phosphate precursor, wherein P is 1.05, and (Fe + Mn + Zr)/P is 0.98. 39.78g of lithium carbonate (purity 99.5%), 64.51g of iron oxide (purity 99.5%) and 95.67g of manganese sesquioxide (purity 99.5%), 117.84g of ammonium dihydrogen phosphate (purity 99.6%), 7.1g of sucrose, 8g of rock candy, 2.3g of cyclodextrin and 2.36g of zirconium dioxide are added into a 2L measuring cup containing 800mL of ethanol, the measuring cup is placed in a basket mill and ground for 30 minutes at the rotation speed of 2000r/min, after the grinding is finished, the slurry is led into a sand mill and ground, and after the particle size of the slurry reaches 300nm, the slurry is subjected to spray drying. After the spray drying is finished, the dried and crushed material is placed in a tube furnace under the nitrogen atmosphere for sintering, the sintering temperature is 720 ℃, and the constant temperature is kept for 10 hours. After the temperature of the tube furnace is naturally reduced to 80 ℃, the sintered material is crushed in a grading way to obtain LiFe with the carbon content of 1.7 percent 0.38 Mn 0.6 Zr 0.02 PO 4 a/C composite material.
To prepare LiFe 0.38 Mn 0.6 Zr 0.02 PO 4 the/C composite material is a positive electrode material, acetylene black is a conductive agent, polytetrafluoroethylene is a binder, and the mass ratio of the conductive agent to the polytetrafluoroethylene is 90: 5: 5 adding into NMP, mixing, coating on aluminum foil, drying at 100 deg.C under vacuum for 4 hr, rolling, and cutting into 12mm electrode sheet. And assembling the button cell by taking the electrode slice as a positive electrode and the metal lithium as a negative electrode. Under the conditions of 2-4.3V and 25 ℃, different charging and discharging current conditions are adopted to test that the initial reversible capacity of charging and discharging at 0.2C is 149.7mAh/g, the initial charging and discharging efficiency is 96.5%, the initial reversible capacity of charging and discharging at 1C is 137.5mAh/g, the capacity retention ratio is 93.2% after 1C circulation for 250 weeks, the charging is carried out at 0.2C, the discharging is carried out at-20 ℃ at 0.2C, and the low-temperature discharging capacity is 91.3 mAh/g.
Comparative example 2
The difference from the example 1 is that the doping metal element Ti is not added in the precursor preparation process, and the rest is the same as the example 1.
Preparing a lithium ferric manganese phosphate precursor:
preparing a lithium manganese iron phosphate precursor according to the raw material molar ratio (Fe + Mn)/P of 0.97. Adding 60.92g of ferric phosphate, 90.39g of manganese phosphate and 6g of glucose into a 2L measuring cup containing 800mL of deionized water, placing the cup into a basket mill for grinding for 1 hour, introducing the slurry into a sand mill for fine grinding after the particle size of the slurry reaches D50<1 mu m, performing spray drying after the particle size of the slurry reaches 300nm, placing the spray-dried powder into a muffle furnace for sintering at the sintering temperature of 500 ℃ for 4 hours after the drying is finished, taking out the powder after the sintering is finished to obtain 125g of a lithium manganese ferric phosphate precursor with the carbon content of 0.4 percent, and detecting and analyzing that the phosphorus content of the precursor is 20.70 percent,
preparation of lithium iron manganese phosphate:
according to the raw material mol ratio Li: and feeding the mixture until the P is 1.06. 120g of lithium manganese iron phosphate precursor and 31.56g of the precursor are sequentially mixedAdding lithium carbonate (purity 99.5%), 8.2g glucose and 4.1g PEG 20000 into a 2L measuring cup containing 800mL water, placing the measuring cup in a basket mill, grinding for 30 minutes at the rotating speed of 2000r/min, introducing the slurry into a sand mill for grinding after the grinding is finished, and carrying out spray drying on the slurry after the granularity of the slurry reaches 350 nm. And after the spray drying is finished, sintering the dried and crushed material in a tubular furnace in a nitrogen atmosphere at the sintering temperature of 700 ℃ for 10 hours. After the temperature of the tube furnace is naturally reduced to 80 ℃, the sintered material is crushed in a grading way to obtain LiFe with the carbon content of 1.7 percent 0.4 Mn 0.6 PO 4 a/C composite material.
To prepare LiFe 0.4 Mn 0.6 PO 4 the/C composite material is a positive electrode material, acetylene black is a conductive agent, polytetrafluoroethylene is a binder, and the mass ratio of the conductive agent to the polytetrafluoroethylene is 90: 5: 5 adding into NMP, mixing, coating on aluminum foil, drying at 100 deg.C under vacuum for 4 hr, rolling, and cutting into 12mm electrode sheet. And assembling the button cell by taking the electrode slice as a positive electrode and the metal lithium as a negative electrode. Under the conditions of 2-4.3V and 25 ℃, different charging and discharging current conditions are adopted for testing, the result of a discharging curve is shown in figure 2, the initial reversible capacity of charging and discharging with 0.2C is 150.5mAh/g, the first charging and discharging efficiency is 96.1%, the initial reversible capacity of charging and discharging with 1C is 140.6mAh/g, and the cycle retention rate of 1C for 250 weeks is 94.1%. Charging at 0.2C, discharging at-20 deg.C at 0.2C, and discharging at low temperature up to 100.5 mAh/g.
Comparative example 3
The difference from example 3 was that the molar ratio of (Fe + Mn + Zr)/P as the starting material was different.
Preparing a lithium manganese iron phosphate precursor according to the raw material molar ratio (Fe + Mn + Zr)/P ═ 1. Adding 64.51g of iron oxide (with the purity of 99.5%) and 95.67g of manganese oxide (with the purity of 99.5%), 115.5g of ammonium dihydrogen phosphate (with the purity of 99.6%), 1.23g of zirconium dioxide and 7.1g of cane sugar into a 2L measuring cup containing 800mL of deionized water, placing the measuring cup in a basket mill for grinding for 1 hour, introducing the slurry into a sand mill for fine grinding after the particle size of the slurry reaches D50<2 mu m, performing spray drying after the particle size of the slurry reaches 300nm, placing the spray-dried powder in a muffle furnace for sintering at the sintering temperature of 550 ℃ for 3 hours after the drying is completed, taking out the powder after the sintering is completed, obtaining 128g of a 0.38% lithium manganese iron phosphate precursor, and detecting and analyzing the phosphorus content of the precursor to be 20.92%.
Preparation of lithium iron manganese phosphate:
according to the raw material mol ratio Li: and feeding the mixture when the P is 1.05. 120g of lithium manganese iron phosphate precursor, 31.60g of lithium carbonate (purity is 99.5%), 7.5g of rock candy, 2g of cyclodextrin and 0.93g of zirconium dioxide are sequentially added into a 2L measuring cup containing 800mL of ethanol, the measuring cup is placed in a basket mill to be milled for 30 minutes at the rotating speed of 2000r/min, after the milling is finished, the slurry is led into a sand mill to be milled, and after the granularity of the slurry reaches 300nm, the slurry is subjected to spray drying. And after the spray drying is finished, sintering the dried and crushed material in a tubular furnace in a nitrogen atmosphere at the sintering temperature of 720 ℃ for 10 hours. After the temperature of the tube furnace is naturally reduced to 80 ℃, the sintered material is crushed in a grading way to obtain LiFe with the carbon content of 1.7 percent 0.38 Mn 0.6 PZr 0.02 O 4 a/C composite material.
To prepare LiFe 0.38 Mn 0.6 PZr 0.02 O 4 the/C composite material is a positive electrode material, acetylene black is a conductive agent, polytetrafluoroethylene is a binder, and the mass ratio of the conductive agent to the polytetrafluoroethylene is 90: 5: 5 adding into NMP, mixing, coating on aluminum foil, drying at 100 deg.C under vacuum for 4 hr, rolling, and cutting into 12mm electrode sheet. And assembling the button cell by taking the electrode slice as a positive electrode and the metal lithium as a negative electrode. The method is characterized in that different charging and discharging current conditions are adopted for testing at 25 ℃ under 2-4.3V, the initial reversible capacity of charging and discharging at 0.2C is 150.1mAh/g, the initial charging and discharging efficiency is 95.6%, the initial reversible capacity of charging and discharging at 1C is 138.5mAh/g, the capacity retention rate is 93.8% after 1C circulation for 250 weeks, charging is carried out at 0.2C, discharging is carried out at 0.2C under-20 ℃, and the low-temperature discharging capacity of the method is up to 102.5 mAh/g.
Comparative example 4
The difference from example 1 is that the grinding particle size is increased during two mixing processes, and other experimental steps are the same as example 1.
Preparing a lithium ferric manganese phosphate precursor:
preparing a lithium manganese iron phosphate precursor according to the raw material molar ratio (Fe + Mn + Ti)/P of 0.97. Adding 60.92g of ferric phosphate, 90.39g of manganese phosphate, 6g of glucose and 0.81g of titanium dioxide into a 2L measuring cup containing 800mL of deionized water, placing the measuring cup into a basket type grinding machine for grinding for 1 hour, introducing the slurry into a sand mill for fine grinding after the particle size of the slurry reaches D50<1 mu m, performing spray drying after the particle size of the slurry reaches 500nm, placing the spray-dried powder into a muffle furnace for sintering at the sintering temperature of 500 ℃ for 4 hours after the drying is finished, taking out the powder after the sintering is finished to obtain 125g of a lithium manganese ferric phosphate precursor with the carbon content of 0.4 percent, and detecting and analyzing the phosphorus content of the precursor to be 20.70 percent,
preparation of lithium iron manganese phosphate:
according to the raw material mol ratio Li: and feeding the mixture until the P is 1.06. 120g of lithium manganese iron phosphate precursor, 31.56g of lithium carbonate (purity 99.5 percent), 8.2g of glucose and 4.1g of PEG 20000 are sequentially added, 0.61g of titanium dioxide is added into a 2L measuring cup containing 800mL of water, the measuring cup is placed into a basket mill to be milled for 30 minutes at the rotating speed of 2000r/min, the slurry is led into a sand mill to be milled after the milling is finished, and the slurry is subjected to spray drying after the particle size of the slurry reaches 500 nm. And after the spray drying is finished, sintering the dried and crushed material in a tubular furnace in a nitrogen atmosphere at the sintering temperature of 700 ℃ for 10 hours. After the temperature of the tube furnace is naturally reduced to 80 ℃, the sintered material is crushed in a grading way to obtain LiFe with the carbon content of 1.7 percent 0.38 Mn 0.6 Ti 0.02 PO 4 a/C composite material.
To prepare LiFe 0.38 Mn 0.6 Ti 0.02 PO 4 the/C composite material is a positive electrode material, acetylene black is a conductive agent, polytetrafluoroethylene is a binder, and the mass ratio of the conductive agent to the polytetrafluoroethylene is 90: 5: 5 adding into NMP, mixing, coating on aluminum foil, drying at 100 deg.C under vacuum for 4 hr, rolling, and cutting into 12mm electrode sheet. And assembling the button cell by taking the electrode slice as a positive electrode and the metal lithium as a negative electrode. Under the conditions of 2-4.3V and 25 ℃, different charging and discharging current conditions are adopted for testing, the result of a discharging curve is shown in figure 2, the initial reversible capacity of charging and discharging with 0.2C is 147.5mAh/g, and the charging and discharging are carried out for the first timeThe electric efficiency is 95.2%, the initial reversible capacity of charging and discharging with 1C is 132.2mAh/g, the cycle retention rate of 1C 250 is 92.1%, the charging is carried out with 0.2C, the discharging is carried out with 0.2C at-20 ℃, and the low-temperature discharging capacity is 81.3 mAh/g.
TABLE 1 electrochemical Performance results for samples of examples and comparative examples
Figure BDA0003733981080000131
Figure BDA0003733981080000141
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. The lithium ferric manganese phosphate precursor is characterized in that the chemical formula is Fe a Mn (1-a-b) A b P c O d (ii) a Wherein, 0.1<a<0.9，0<b<0.04，0.1<1-a-b<0.9，1≤c≤4，1<d is less than or equal to 8; a is selected from any one of titanium, magnesium, zirconium, niobium, strontium, nickel and vanadium.
2. The method for preparing a lithium manganese iron phosphate precursor according to claim 1, comprising the steps of:
(1) grinding and mixing a ferric iron source, a trivalent manganese source, a phosphorus source, a carbon source and a metal oxide or metal salt of a metal element A in a liquid phase system to obtain mixed slurry;
(2) drying the mixed slurry obtained in the step (1) to obtain dry powder, and sintering the dry powder in an inert atmosphere to obtain the lithium ferric manganese phosphate precursor Fe a Mn (1-a-b) A b P c O d 。
3. The preparation method according to claim 2, wherein in the step (1), the ferric iron source is one or more of ferric hydroxide, ferric oxalate, ferric phosphate, ferric pyrophosphate, ferric hydroxide and ferric manganese phosphate; the trivalent manganese source is one or more of manganous oxide, manganese phosphate, manganese oxyhydroxide and manganese ferric phosphate; the phosphorus source is one or more of diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphate, iron manganese phosphate and manganese phosphate; the carbon source is any one or more of glucose, rock candy, sucrose, fructose, polyethylene glycol, cyclodextrin, starch, ascorbic acid, phenolic resin and cellulose; the metal oxide or metal salt doped with the metal element A is one or more of titanium dioxide, tetrabutyl titanate, magnesium acetate, magnesium titanate, magnesium nitrate, zirconium hydroxide, zirconium dioxide, niobium pentoxide, nickel acetate, nickel nitrate, nickel hydroxide, strontium oxide, strontium hydroxide, ammonium vanadate and vanadium pentoxide.
4. The method according to claim 2, wherein in the step (1), the medium of the liquid phase system is at least one selected from water, methanol, acetone and ethanol; the grinding is to grind the slurry to a particle size of 250-350nm after grinding the slurry to a particle size D50<1 μm.
5. The process according to claim 2, wherein in step (1), the metal element (a) is added in a molar amount of 0 to 4% based on the total metal (Fe + Mn + a), and the molar ratio (Fe + Mn + a)/P is 0.96 to 0.985, while the molar ratio Fe/Mn is 1:9 to 9: 1.
6. The method as claimed in claim 2, wherein the sintering temperature in step (2) is 500-700 ℃ and the sintering time is 3-6 h.
7. The preparation method according to claim 2, wherein in the step (2), the carbon content in the lithium ferric manganese phosphate precursor is 0.2-0.5 wt%.
8. The high-capacity lithium ferric manganese phosphate material is characterized in that the chemical formula of the material is LiFe a Mn (1-a-b) A b PO 4 C, wherein 0.1<a<0.9，0<b≤0.04，0.1<1-a-b<0.9; a is selected from any one of titanium, magnesium, zirconium, niobium, strontium, nickel and vanadium.
9. The method for preparing the high-capacity lithium ferric manganese phosphate material according to claim 8, which is characterized by comprising the following steps:
s1, grinding, mixing and drying a lithium source, the lithium manganese iron phosphate precursor, a carbon source and an additive in a liquid phase system to obtain a lithium manganese iron phosphate/carbon composite material precursor;
s2, sintering the lithium ferric manganese phosphate/carbon composite material precursor obtained in the step S1 in an inert gas protection atmosphere to obtain LiFe with the structural formula a Mn (1-a-b) A b PO 4 A high-capacity lithium ferric manganese phosphate material of/C,
preferably, in step S1, the lithium source is one or more of lithium carbonate, lithium hydroxide, lithium acetate and lithium phosphate; the carbon source is any one or more of glucose, rock candy, sucrose, fructose, polyethylene glycol, cyclodextrin, starch, ascorbic acid, phenolic resin and cellulose,
preferably, in step S1, the medium of the liquid phase system is at least one selected from water, methanol, acetone and ethanol,
preferably, in step S1, the grinding is performed by coarse grinding to a particle size D50<1 μm, then fine grinding is performed to a particle size of 250-350nm,
preferably, in step S1, the metal element A is added in a molar amount of 0 to 4% based on the total metal (Fe + Mn + A) molar amount,
preferably, in step S2, the sintering temperature is 650-780 ℃ and the sintering time is 8-10 hours.
10. The method of claim 2, wherein in step S1, the molar ratio Li/P is 1-1.06, the metal element a is added in a molar amount of 0-4% of the total metal (Fe + Mn + a), and in step S2, the high capacity lithium manganese iron phosphate material has a carbon content of 1.5-2.5 wt%.
CN202210801473.6A 2022-07-07 2022-07-07 Preparation method of high-capacity lithium manganese iron phosphate material Pending CN115072695A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115583642A (en) * 2022-10-25 2023-01-10 西安合升汇力新材料有限公司 LiFe x Mn y D z PO 4 @ C and preparation and application of precursor thereof
WO2024082539A1 (en) * 2022-10-21 2024-04-25 广东邦普循环科技有限公司 Lithium iron manganese phosphate positive electrode material and preparation method therefor and use thereof
CN115583642B (en) * 2022-10-25 2024-05-10 西安合升汇力新材料有限公司 LiFexMnyDzPO4Preparation and application of @ C and precursor thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024082539A1 (en) * 2022-10-21 2024-04-25 广东邦普循环科技有限公司 Lithium iron manganese phosphate positive electrode material and preparation method therefor and use thereof
CN115583642A (en) * 2022-10-25 2023-01-10 西安合升汇力新材料有限公司 LiFe x Mn y D z PO 4 @ C and preparation and application of precursor thereof
CN115583642B (en) * 2022-10-25 2024-05-10 西安合升汇力新材料有限公司 LiFexMnyDzPO4Preparation and application of @ C and precursor thereof

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