Phosphate-based materials having a nanoporous structure, methods for producing the same, and applications

Abstract

Phosphate-based material with nanoporous structure, its manufacturing method and use. The chemical formula of ferromanganese phosphate is Mn 1-x Fe x PO4, 0.01≦x≦0.99, particle size is 50nm or less, and it has a porous structure. The chemical formula is Mn 1-a-b Fe a M b PO4, wherein M is one or a combination of five or more selected from magnesium, titanium, vanadium, chromium, cobalt, nickel, zinc, gallium, aluminum, zirconium, niobium, molybdenum, tin, antimony, calcium, barium, strontium, boron, ruthenium, silicon, tellurium, niobium, copper, and lithium, and 0.01≦a≦0.98, 10 -4 ≦b≦10 -2 The particle size is 50 nm or less, and the material also has a porous structure. The material can be used to prepare manganese iron phosphate-based battery cathode materials, and the specific capacity, multiplication factor, and cyclability of the resulting cathode materials are improved.

Description

[Technical Field]

[0001] This invention relates to a phosphate-based material having a nanoporous structure, a method for producing the same, and its applications. [Background technology]

[0002] For the past decade or so, nanomaterials and porous materials have attracted the attention of scientific researchers as functional materials with special structures, demonstrating unique roles and value in many application fields such as photocatalysis, solar cells, electromagnetism, and optics. Ferromanganese phosphate material can be used as bonderite to provide rust and corrosion protection for steel products, and can also be used as an ion exchanger, sensor, adsorbent, and magnetic material, making it a very important non-metallic inorganic material. Furthermore, ferromanganese phosphate can be used as an important precursor material for manganese-iron phosphate cathode materials in lithium-ion batteries. In ferromanganese phosphate material, manganese and iron have a uniform degree of mixing at the atomic level, and when used in the manufacture of manganese-iron phosphate cathode materials, the distribution of manganese-iron metallic elements in the cathode material is also uniform at the atomic level, contributing to improved magnification performance and cycle stability of manganese-iron phosphate lithium-ion batteries, as well as improvements in voltage drop and manganese leaching.

[0003] Currently, there are few literature reports on the production of ferromanganese phosphate, and literature on ferromanganese phosphate with a nano-level porous structure is even rarer. Chinese Patent CN111908442A publishes ferromanganese phosphate and its production method, which involves reacting manganese dioxide, ferrous oxalate, and phosphoric acid in the presence of a reducing agent, (Mn 1-x Fe x ) a PO4·H2O crystals were obtained, and then amorphous (Mn) crystals with a particle size of approximately 2 μm were obtained by filtration, washing, and high-temperature sintering. 1-x Fe x ) aThe method requires obtaining PO4 powder, introducing a reducing agent during the manufacturing process, and heating during the reaction process. The resulting ferromanganese phosphate material particles are large, at the micron level, have high density, and lack pore structure.

[0004] There are some existing documents on the production of manganese phosphate using conventional techniques, including methods such as oxidation precipitation, reduction precipitation, and hydrothermal methods. However, the manganese phosphate particles obtained by these methods are macron-level, the particle size is too large, and the product solution contains many metal ions, resulting in low purity. Furthermore, when producing ferromanganese phosphate using methods for producing manganese phosphate, it is not always possible to obtain pure ferromanganese phosphate, but there is a possibility of obtaining a mixture of manganese phosphate and iron phosphate. [Overview of the Initiative]

[0005] In response to the shortcomings and deficiencies of the prior art, the present invention provides a nanoporous phosphate material having a nanoporous structure in which the particle size is small, at the nanoscale, and the particles exhibit a porous structure, and which can improve the specific capacity of the positive electrode material and improve the multiplier and cycle performance of the battery when used as a precursor for manganese iron phosphate-based battery positive electrode material.

[0006] The present invention further provides a method for producing a phosphate-based material having a nanoporous structure that does not require the use of a reducing agent and a soluble manganese salt, has mild reaction conditions, and can yield a high-purity phosphate-based material.

[0007] To achieve the above objectives, the technical solutions adopted in this invention are as follows.

[0008] The ferromanganese phosphate is, and the chemical formula of the ferromanganese phosphate is Mn 1-x Fe x The material is PO4, 0.01 ≤ x ≤ 0.99, and the phosphate ferromangan has a particle size of 50 nm or less and a porous structure.

[0009] In some embodiments, the particle size of the ferromanganese phosphate is 40 nm or less, more preferably 5 - 40 nm, and even more preferably 10 - 30 nm.

[0010] In some embodiments, the pore diameter of the ferromanganese phosphate is 2 - 10 nm, and preferably, the pore diameter of the ferromanganese phosphate is 3 - 5 nm.

[0011] In some embodiments, the specific surface area of the ferromanganese phosphate is 10 - 30 m 2 / g, and preferably, the specific surface area of the ferromanganese phosphate is 12 - 18 m 2 / g.

[0012] In some embodiments, 0.1 ≦ x ≦ 0.9, preferably, 0.2 ≦ x ≦ 0.5, and even more preferably, 0.3 ≦ x ≦ 0.4.

[0013] In some embodiments, the ferromanganese phosphate is in a monoclinic crystal form.

[0014] The present invention further provides a phosphate-based material, and the chemical formula of the phosphate-based material is Mn 1-a-b Fe a M b PO4, where M is one or a combination of more selected from magnesium, titanium, vanadium, chromium, cobalt, nickel, zinc, gallium, aluminum, zirconium, niobium, molybdenum, tin, antimony, calcium, barium, strontium, boron, ruthenium, silicon, tellurium, niobium, copper, and lithium, and 0.01 ≦ a ≦ 0.98, 10 -4 ≦ b ≦ 10 -2 and the phosphate-based material has a particle size of 50 nm or less and has a porous structure.

[0015] In some embodiments, the particle size of the phosphate-based material is 40 nm or less, more preferably 5 to 40 nm, and even more preferably 10 to 30 nm.

[0016] In some embodiments, the pore size of the phosphate-based material is 2 to 10 nm, preferably 3 to 5 nm.

[0017] In some embodiments, the specific surface area of ​​the phosphate-based material is 10 to 30 m². 2 The specific surface area of ​​the ferromanganese phosphate is preferably 12-18 m² / g. 2 It is / g.

[0018] In some embodiments, 0.2 ≤ a ≤ 0.5, 10 -3 ≤b ≤ 10 -2 That is the case.

[0019] In some embodiments, the phosphate-based material is in a monoclinic crystalline form.

[0020] In some embodiments, M is cobalt, or M is magnesium and boron, or M is molybdenum, niobium and boron, or M is cobalt, vanadium, nickel and boron, or M is magnesium, or M is vanadium and titanium. The phosphate material is a common doped ferromanganese phosphate material.

[0021] In some embodiments, the chemical formula of the phosphate material is Mn 1-a-b Fe a Co b PO4, or Mn 1-a-b Fe a Mg b1 B b2 PO4 is , and b1+b2=b, or Mn 1-a-b Fe a Mo b1Nb b2 B b3 PO4 is such that b1+b2+b3=b And, or Mn 1-a-b Fe a Co b1 V b2 Ni b3 B b4 PO4 is such that b1+b2+b3+b4=b, or Mn 1-a-b Fe a Mg b PO4, or Mn 1-a-b Fe a V b1 Ti b2 PO4 is , and b1+b2=b, 10 -4 ≤b1 ≤ 10 -2 , 10 -4 ≤b² ≤ 10 -2 , 10 -4 ≤b3 ≤ 10 -2 , 10 -4 ≤b4 ≤10 -2 That is the case.

[0022] In some embodiments, the chemical formula of the phosphate material is Mn 0.6 Fe 0.395 Co 0.005 PO4 or Mn 0.65 Fe 0.344 Mg 0.005 B 0.001 PO4 or Mn 0.7 Fe 0.293 Mo 0.003 Nb 0.003 B 0.001 PO4 or Mn 0.8 Fe 0.19 Co 0.005 V 0.001 Ni 0.001 B 0.003 PO4 or Mn 0.5 Fe 0.495 Mg 0.005 PO4 or Mn 0.65 Fe 0.34 V 0.005 Ti 0.005 PO 4である .

[0023] In some embodiments, M is five or more selected from magnesium, titanium, vanadium, chromium, cobalt, nickel, zinc, gallium, aluminum, zirconium, niobium, molybdenum, tin, antimony, calcium, barium, strontium, boron, ruthenium, silicon, tellurium, niobium, copper, and lithium. The phosphate-based material is a high-entropy doped manganese phosphate material.

[0024] In some embodiments, the chemical formula of the phosphate-based material is Mn 1-a-b Fe a Mg b1 V b2 Ti b3 Cr b4 Co b5 PO4, Mn 1-a-b Fe a Zn b1 Cu b2 Mg b3 Co b4 Ti b5 PO4, Mn 1-a-b Fe a Zn b1 Cu b2 Mg b3 Mo b4 Ti b5 PO4, Mn 1-a-b Fe a Mg b1 V[[ID=V]] b2 Ti b3 Cr b4 Mo b5 PO4, Mn 1-a-b Fe a Nb b1 B b2 Co b3 V b4 Al b5 PO4, Mn 1-a-b Fe a Co b1 V b2 Ni b3 B b4 Nb b5 PO4, Mn 1-a-b Fe a [[ID=9〗]Co b1 Ga b2 Bb3 Al b4 Sr b5 PO4 or Mn 1-a-b Fe a Mo b1 Co b2 Ni b3 V b4 Ca b5 PO4 is such that b1+b2+b3+b4+b5=b, and the range of b1 to b5 is 10 each. -4 ≤b1 ≤ 10 -2 , 10 -4 ≤b² ≤ 10 -2 , 10 -4 ≤b3 ≤ 10 -2 , 10 -4 ≤b4 ≤10 -2 , 10 -4 ≤b5 ≤10 -2 That is the case.

[0025] In some embodiments, the chemical formula of the phosphate material is Mn 0.7 Fe 0.293 Mg 0.015 V 0.001 Ti 0.0005 Cr 0.001 Co 0.003 PO4, Mn 0.6 Fe 0.395 Zn 0.001 Cu 0.0005 Mg 0.001 Co 0.002 Ti 0.0005 PO4, Mn 0.6 Fe 0.39 Zn 0.001 Cu 0.0005 Mg 0.005 Mo 0.003 Ti 0.0005 PO4, Mn 0.7 Fe 0.293 Mg 0.0015 V 0.001 Ti 0.0005 Cr 0.001 Mo 0.003 PO4, Mn 0.7 Fe 0.29 Nb 0.003 B 0.003 Co 0.001 V 0.002 Al 0.001 PO4, Mn 0.8 Fe0.19 Co 0.005 V 0.001 Ni 0.0005 B 0.003 Nb 0.0005 PO4, Mn 0.5 Fe 0.49 Co 0.0025 Ga 0.0005 B 0.003 Al 0.002 Sr 0.002 PO4 or Mn 0.65 Fe 0.34 Mo 0.003 Co 0.003 Ni 0.002 V 0.0015 Ca 0.0005 This is PO4.

[0026] The present invention further provides a method for producing a phosphate-based material, the production method comprising the following steps: 1) mixing manganese iron oxide and a compound of any element M with phosphoric acid to obtain a reaction mixture; 2) polishing the reaction mixture and reacting the reaction mixture to produce a phosphate, obtaining a slurry containing the phosphate, wherein the particle size of the phosphate in the slurry is 100 nm or less; 3) separating the slurry to obtain phosphate particles; and 4) the phosphate particles The phosphate-based material is obtained by drying and sintering, wherein M is one or more combinations selected from magnesium, titanium, vanadium, chromium, cobalt, nickel, zinc, gallium, aluminum, zirconium, niobium, molybdenum, tin, antimony, calcium, barium, strontium, boron, ruthenium, silicon, tellurium, niobium, copper, and lithium.

[0027] In some embodiments, the particle size of the manganese iron oxide is 1 to 20 μm, preferably 2 to 7 μm.

[0028] In some embodiments, the phosphoric acid exists in the form of an aqueous phosphoric acid solution, the mass concentration of which is 10% to 70%, preferably 20% to 40%.

[0029] In some embodiments, the molecular formula of iron manganese oxide is (Mn x Fe y ) is 3O4, and 0.50≦x≦0.81 and 0.19≦y≦0.50.

[0030] In some embodiments, the molecular formula of iron manganese oxide is (Mn 0.60 Fe 0.40 )3O4, (Mn 0.61 Fe 0.39 )3O4, (Mn 0.65 Fe 0.35 )3O4, (Mn 0.70 Fe 0.30 )3O4, (Mn 0.71 Fe 0.29 )3O4, (Mn 0.81 Fe 0.19 )3O4, (Mn 0.50 Fe 0.50 )3O4, (Mn 0.51 Fe 0.49 )3O4 or (Mn 0.66 Fe 0.34 )3O4.

[0031] In some embodiments, in step 1), the mixing is carried out by mechanical stirring at a temperature of 20-40°C.

[0032] In some embodiments, the mixing time in step 1) is 1 to 12 hours.

[0033] In some embodiments, in step 2), the polishing is performed in a sand mill, and the polishing temperature is 20-40°C.

[0034] In some embodiments, the polishing time in step 2) is 0.5 to 3 hours.

[0035] In some embodiments, in step 4), the drying temperature is 100-120°C.

[0036] In some embodiments, the drying time in step 4) is 10 hours.

[0037] In some embodiments, the sintering temperature in step 4) is 300-400°C.

[0038] In some embodiments, the sintering time in step 4) is 1 to 4 hours.

[0039] In some embodiments, step 3) includes filtering and washing the phosphate slurry.

[0040] In some embodiments, step 4) includes drying the phosphate particles to obtain manganese ferric phosphate monohydrate crystals or doped manganese ferric phosphate monohydrate crystals having particles of 100 nm or less, and further sintering the manganese ferric phosphate monohydrate crystals or doped manganese ferric phosphate monohydrate crystals to obtain the phosphate-based material.

[0041] In some embodiments, the ratio of the total amount of the manganese iron oxide and the compound of element M to the amount of the phosphoric acid is 1:1 to 2.

[0042] In some embodiments, the manufacturing method further includes a step of pre-dispersing the iron manganese oxide in an aqueous dispersant solution before step 1).

[0043] In some embodiments, the dispersant is one or more combinations selected from polyvinylpyrrolidone, polyethylene glycol, and TC130 dispersant.

[0044] In some embodiments, the mass concentration of the dispersant aqueous solution is 0.01% to 5%.

[0045] In some embodiments, the manufacturing method further includes a step before step 1) in which phosphorus pentoxide is reacted with water to produce phosphoric acid. That is, the present invention may also use phosphoric acid or phosphorus pentoxide as a phosphorus source for manufacturing phosphate-based materials.

[0046] In some embodiments, the compound of element M is one or more combinations selected from magnesium compounds, titanium compounds, vanadium compounds, cobalt compounds, nickel compounds, zinc compounds, gallium compounds, aluminum compounds, zirconium compounds, niobium compounds, molybdenum compounds, tin compounds, antimony compounds, calcium compounds, barium compounds, strontium compounds, boron compounds, ruthenium compounds, silicon compounds, tellurium compounds, niobium compounds, copper compounds, and lithium compounds.

[0047] In some embodiments, the compound of element M is one or more combinations selected from oxides, carbonates, oxalates, nitrates, sulfates, chlorides, and organic acid salts of element M.

[0048] In some embodiments, the organic acid salt of element M is one or more combinations selected from organic phosphates, acetates, organic sulfons, alkyl salts, and ester salts of other metal elements.

[0049] Preferably, the compound of element M is an oxide, an acetate, or a carbonate.

[0050] In some embodiments, the compound of element M is cobalt chloride, or a combination of magnesium oxide and boric acid, or a combination of molybdenum trioxide, niobium oxalate and boric acid, or a combination of cobalt acetate, ammonium metavanadate, nickel sulfate and boric acid, or magnesium acetate, or a combination of vanadyl oxalate and titanium chloride.

[0051] In some embodiments, the compound of element M is a combination of five or more compounds selected from magnesium compounds, titanium compounds, vanadium compounds, cobalt compounds, nickel compounds, zinc compounds, gallium compounds, aluminum compounds, zirconium compounds, niobium compounds, molybdenum compounds, tin compounds, antimony compounds, calcium compounds, barium compounds, strontium compounds, boron compounds, ruthenium compounds, silicon compounds, tellurium compounds, niobium compounds, copper compounds, and lithium compounds.

[0052] In some embodiments, the compound of element M is a combination of magnesium acetate, ammonium metavanadate, titanium dioxide, cadmium oxide, and cobalt sulfate; or a combination of zinc sulfate, copper oxalate, cobalt acetate, magnesium nitrate, cobalt oxide, and n-butyl titanate; or a combination of zinc oxide, copper oxide, magnesium oxide, molybdenum oxide, and titanium dioxide; or magnesium oxide, ammonium metavanadate, and titanium dioxide. These are combinations of tungsten, chromium oxide, and molybdenum oxide; or niobium oxalate, boron oxide, cobalt acetate, ammonium metavanadate, and aluminum oxide; or cobalt acetate, ammonium metavanadate, nickel acetate, boric acid, and niobium oxalate; or cobalt chloride, gallium chloride, boric acid, chromium oxide, and strontium chloride; or molybdenum oxide, cobalt chloride, nickel chloride, vanadium oxalate, and calcium oxide.

[0053] The present invention further provides applications for using ferromanganese phosphate or a phosphate-based material or a phosphate-based material obtained by a method for producing the phosphate-based material in the manufacture of a battery cathode material.

[0054] The present invention further provides a manganese iron phosphate-based battery cathode material obtained by a high-temperature sintering reaction using raw materials comprising ferromanganese phosphate or a phosphate-based material or a phosphate-based material obtained by a method for producing the phosphate-based material, a lithium source compound, and an optional organic carbon source.

[0055] In some embodiments, the lithium source(s) compound is one or more combinations selected from lithium carbonate, lithium hydroxide, lithium chloride, lithium sulfate, lithium nitrate, lithium dihydrogen phosphate, dilithium hydrogen phosphate, and lithium acetate.

[0056] In some embodiments, the organic carbon source is one or more combinations selected from glucose, sucrose, fructose, citric acid, polyethylene glycol, polyvinylpyrrolidone, ethylenediaminetetraacetic acid, and ascorbic acid.

[0057] The present invention further provides a lithium-ion battery comprising a cathode material containing the manganese iron phosphate-based cathode material. The lithium-ion battery exhibits excellent cycle performance.

[0058] In some embodiments, the lithium-ion battery has a discharge ratio capacity of 145 mAh / g or more at 0.1C, a discharge ratio capacity of 135 mAh / g or more at 1C, and a capacity retention rate of 92% or more after 200 charge-discharge cycles at a 1C multiplier.

[0059] In some embodiments, the lithium-ion battery has a discharge ratio capacity of 145.2 mAh / g or more at 0.1C, a discharge ratio capacity of 135.7 mAh / g or more at 1C, and a capacity retention rate of 92.9% or more after 200 charge-discharge cycles at a 1C multiplier.

[0060] In some embodiments, the lithium-ion battery has a discharge ratio capacity of 150 mAh / g or more at 0.1C, a discharge ratio capacity of 140 mAh / g or more at 1C, and a capacity retention rate of 95.6% or more after 200 charge-discharge cycles at a 1C multiplier. [Effects of the Invention]

[0061] Compared to conventional technology, the present invention has the following advantages.

[0062] The ferromanganese phosphate material or phosphate-based material of the present invention has a nano-level particle size, is small in size, and has a porous structure. When the manganese iron phosphate-based battery cathode material obtained by manufacturing it as a precursor for a manganese iron phosphate-based battery cathode material is used in a lithium-ion battery, the specific capacity, magnification ratio, and cycle performance of the battery are all significantly improved. [Brief explanation of the drawing]

[0063] [Figure 1] Figure 1 is an XRD diagram of the manganese iron oxide raw material used in Example 1. [Figure 2] , [Figure 3] Figures 2 and 3 are SEM images of the manganese iron oxide raw materials used in Example 1, and the scales of the two are different. [Figure 4] Figure 4 is an XRD diagram of manganese ferric phosphate monohydrate in Example 1. [Figure 5] , [Figure 6] Figures 5 and 6 are SEM images of ferric manganese phosphate monohydrate in Example 1, with scales of 1 μm and 2 μm, respectively. [Figure 7] Figure 7 is an XRD diagram of ferromanganase phosphate produced and obtained in Example 1. [Figure 8] Figure 8 is an SEM image of ferromanganase phosphate produced and obtained in Example 1. [Figure 9] Figure 9 is an XRD diagram of the product from step 2) in Comparative Example 1. [Figure 10] , [Figure 11] Figures 10 and 11 are SEM images of the product from step 2) in Comparative Example 1, and the scales of the two are different. [Figure 12] This is the XRD diagram of the final product in Comparative Example 1. [Figure 13] Figure 13 is an SEM image of the final product in Comparative Example 1. [Figure 14] Figure 14 shows the adsorption and desorption curve of ferromanganese phosphate produced in Example 1. [Figure 15] Figure 15 shows the pore size distribution map of ferromanganese phosphate produced in Example 1. [Figure 16] , [Figure 17] Figures 16 and 17 are SEM images of the product from step 2) in Comparative Example 2, and the scales of the two are different. [Figure 18] Figure 18 is an SEM image of the final product in Comparative Example 2. [Figure 19] Figure 19 shows the magnification test results when Example 1 is used with a button battery. [Figure 20] Figure 20 shows the cycle test results using Example 1 with a button battery. [Figure 21] Figure 21 is an XRD diagram of the doped manganese ferric monohydrate in Example 8. [Figure 22] , [Figure 23] Figures 22-23 are SEM images of doped ferric manganese phosphate monohydrate in Example 8, with scales of 1 μm and 2 μm, respectively. [Figure 24] Figure 24 is an XRD diagram of the doped phosphate ferromangan obtained in Example 8. [Figure 25] Figure 25 is an SEM image of the doped phosphate ferromanganase obtained in Example 8. [Figure 26] Figure 26 is an XRD diagram of the product from step 2) in Comparative Example 4. [Figure 27] , [Figure 28] Figures 27 and 28 are SEM images of the product from step 2) in Comparative Example 4, and the scales of the two are different. [Figure 29] Figure 29 is an XRD diagram of the final product in Comparative Example 4. [Figure 30]Figure 30 is an SEM image of the final product in Comparative Example 4. [Figure 31] Figure 31 shows the adsorption / desorption curve of doped phosphate ferromanganese obtained in Example 8. [Figure 32] Figure 32 shows the pore size distribution map of doped phosphate ferromanganese obtained in Example 8. [Figure 33] Figure 33 shows the magnification test results when Example 8 is used with a button battery. [Figure 34] Figure 34 shows the cycle test results using Example 8 with a button battery. [Figure 35] Figure 35 is an XRD diagram of the manganese iron oxide raw material used in Example 14. [Figure 36] , [Figure 37] Figures 36-37 are SEM images of the manganese iron oxide raw materials used in Example 14, and the scales of the two are different. [Figure 38] Figure 38 is an XRD diagram of the manganese ferric phosphate monohydrate doped in Example 14. [Figure 39] , [Figure 40] Figures 39 to 40 are SEM images of ferric manganese phosphate monohydrate doped in Example 14, with scales of 1 μm and 2 μm, respectively. [Figure 41] Figure 41 is an XRD diagram of doped ferromanganase phosphate obtained in Example 14. [Figure 42] Figure 42 is an SEM image of the doped ferromanganase phosphate obtained in Example 14. [Figure 43] Figure 43 is an XRD diagram of the product from step 2) in Comparative Example 6. [Figure 44] , [Figure 45] Figures 44 and 45 are SEM images of the product from step 2) in Comparative Example 6, and the scales of the two are different. [Figure 46] Figure 46 is an XRD diagram of the final product in Comparative Example 6. [Figure 47]Figure 47 is an SEM image of the final product in Comparative Example 6. [Figure 48] Figure 48 shows the adsorption / desorption curve of doped ferromanganese phosphate obtained in Example 14. [Figure 49] Figure 49 shows the pore size distribution map of doped ferromanganese phosphate obtained in Example 14. [Figure 50] Figure 50 shows the magnification test results when Example 14 is used with a button battery. [Figure 51] Figure 51 shows the cycle test results using Example 14 with a button battery. [Modes for carrying out the invention]

[0064] This invention provides an improved ferromanganese phosphate, the main innovation of which is that its particle size is controlled to 50 nm or less and that it has a porous structure. In the prior art, ferromanganese phosphate is available, but its particle size is at the micron level, the particle size is large, and the particles of ferromanganese phosphate in the prior art are dense and usually have a non-porous structure. In this invention, when the ferromanganese phosphate with a small particle size and porous structure is used in the manufacture of a ferromanganese phosphate salt-based cathode material, the specific capacity, charge / discharge ratio, and cycle performance of the lithium-ion battery containing this cathode material are all significantly improved.

[0065] Another innovative aspect of the present invention is that a doped ferromanganese phosphate material is obtained by doping ferromanganese phosphate with five or more doping metals, and then a high-entropy doped ferromanganese phosphate cathode material is obtained by high-temperature sintering of the doped ferromanganese phosphate material with a lithium source and an organic carbon source. In the cathode material structure, the ferromanganese active element site is occupied by five or more doped metal elements, and the cathode material exhibits a high-entropy effect, specifically: 1) the high-entropy material composed of multiple elements forms a single-phase solid solution rather than a mixture of separate phases or multiple solid solutions, making the material more thermodynamically stable; 2) each atom within the high-entropy material is randomly distributed within the crystal lattice, with different metal atomic radii, significantly different chemical bonds, and different surrounding environments and sites for each atom, resulting in greater strain and defects within the crystal lattice than in the crystal lattices of conventional one- or two-component phosphate materials, thus increasing the material's activity and thus its electrochemical activity; 3) there is a dynamic hysteresis diffusion effect, meaning the internal diffusion and phase change rates of the high-entropy material are very slow; and 4) the high-entropy material exhibits more complex properties due to the fundamental properties of various components and their interactions, resulting in a richer range of material performance. Therefore, due to the high-entropy effect, the performance of high-entropy doped phosphate-based cathode materials is far superior to that of binary metal element cathode materials such as ferromanganese phosphate-based cathode materials. High-entropy doped ferromanganese phosphate-based cathode materials have a more stable crystal structure, thus making it more difficult for metal ions such as manganese to dissolve, and can further improve the material's cycling performance, as well as the presence of multiple active metals. The cooperative action between the active metals increases the number of electrochemical platforms in the cathode material, and the interconnections between these platforms become smoother, eliminating the abrupt drop at the edge of the discharge platform. Furthermore, the electron and ion conduction rates of high-entropy doped ferromanganese phosphate cathode materials are also increased, potentially leading to improved late-stage magnification performance when used in lithium-ion batteries.

[0066] Another innovative aspect of the present invention lies in the manufacturing process of ferromanganese phosphate. In this invention, manganese iron oxide is directly mixed with phosphoric acid, and then the reaction speed of both is accelerated by polishing. The two are reacted to produce a nanoscale phosphate slurry, and after separating the particles from the slurry, the particles are dried to obtain nanoscale manganese ferric monohydrate crystals. Finally, by sintering, the nanoporous structure ferromanganese phosphate of the present invention can be obtained. Compared to conventional techniques, this manufacturing process does not require a reducing agent or a soluble ferrous salt as a reaction raw material. However, by directly reacting phosphoric acid with manganese iron oxide, a compound that uniformly mixes manganese iron elements at the atomic level, high-purity ferromanganese phosphate can be obtained, and the process is simple. The reaction speed can be accelerated by the polishing; without polishing, the reaction between manganese iron oxide and phosphoric acid is very slow, the reaction cycle is very long, and it is difficult to react thoroughly.

[0067] Another innovative aspect of the present invention is that by changing the concentration of phosphoric acid, the dissolution rate of iron manganese oxide and the nucleation rate of ferromanganese phosphate can be adjusted, and the crystal particle size of ferromanganese phosphate can also be adjusted. The phosphoric acid here can also be obtained by reacting phosphorus pentoxide with water; that is, when producing ferromanganese phosphate according to the present invention, either phosphoric acid or phosphorus pentoxide may be used as the phosphorus source.

[0068] Another innovative aspect of the present invention is that compounds of at least five other doped metal elements and iron manganese oxide can be mixed with phosphoric acid and carried out in subsequent processes, thereby enabling the production and acquisition of the doped ferromanganese phosphate material of the present invention. [Examples]

[0069] The present invention will be further described below with reference to examples. However, the present invention is not limited to the following examples. The conditions of implementation adopted in the examples can be further adjusted according to different requirements of specific use, and conditions of implementation not explicitly stated are general conditions in the industry. The technical features of the various embodiments of the present invention can be combined with each other, insofar as they do not conflict with each other. Example 1

[0070] In this embodiment, the chemical formula is Mn 0.6 Fe 0.4 A nanoporous structure of ferromanganese phosphate, which is PO4, is provided, and its manufacturing process is as follows.

[0071] 1) Add concentrated phosphoric acid solution and deionized water sequentially to a glass beaker, stir uniformly, and prepare a 35% phosphoric acid aqueous solution by mass. The total molar ratio of Mn and Fe is 1:1.5, and 50 g of micron-level iron manganese oxide (molecular formula (Mn 0.60 Fe 0.40 )3O4, purchased from Sichuan Qingyuan New Materials Co., Ltd., with an average particle size of 7 μm, is poured in and mechanically stirred for 12 hours to obtain the reaction mixture.

[0072] 2) The reaction mixture is poured into a sand mill and sanded for 1 hour to obtain a dark green slurry. The slurry is filtered and washed to obtain particles, and these particles are then dried at 100°C to obtain dark green ferric manganese phosphate monohydrate.

[0073] 3) Ferric manganese phosphate monohydrate is sintered in a muffle furnace at 400°C for 2 hours to obtain ferromanganese phosphate, which has a reddish-brown nanoporous structure.

[0074] The XRD and SEM images of manganese iron oxide are shown in Figures 1, 2-3, respectively, and as can be seen, manganese iron oxide has a crystalline structure. The XRD and SEM images of manganese ferric monohydrate obtained in step 2) are shown in Figures 4, 5-6, respectively, and as can be seen, its crystalline phase is MnPO4·H2O with a monoclinic structure. The particle size of manganese ferric monohydrate was measured using a scanning electron microscope (SEM) test method and is 20 nm. Figures 7 and 8 show the XRD and SEM images of the ferromanganese phosphate obtained in step 3). As can be seen, the ferromanganese phosphate has a certain degree of crystallinity, and a large amount of porous structure is distributed between the particles. As can be seen from the XRD test, the crystalline phase remains a monoclinic phase structure. The particle size of the ferromanganese phosphate was measured using the scanning electron microscope (SEM) method and was found to be 40 nm. At the same time, adsorption and desorption tests and analysis were performed on the ferromanganese phosphate using a specific surface area and aperture tester. As can be seen from Figures 14 and 15, the ferromanganese phosphate material has a mesoporous structure, with pore sizes mainly distributed at about 3-5 nm, and its specific surface area is 15 m². 2 It is approximately / g

[0075] In this embodiment, the chemical formula is Mn 0.85 Fe 0.15 A nanoporous structure of ferromanganese phosphate, which is PO4, is provided, and its manufacturing process is as follows.

[0076] 1) Add concentrated phosphoric acid solution and deionized water sequentially to a glass beaker, stir uniformly, and prepare a 70% mass concentration phosphoric acid aqueous solution. Add polyvinylpyrrolidone and deionized water sequentially to the other glass beaker, stir uniformly, and prepare a 0.1% mass concentration polyvinylpyrrolidone aqueous solution. The total molar ratio of Mn and Fe is 1:1.5, and 76.4 g of micron-level iron manganese oxide (molecular formula (Mn 0.85 Fe 0.15 )3O4, purchased from Sichuan Qingyuan New Materials Co., Ltd., with an average particle size of 7 μm, is poured in and mechanically stirred for 30 minutes to obtain a black suspension aqueous solution. 210 g of the above phosphoric acid solution is slowly poured into the suspension solution, and after all of the phosphoric acid solution has been poured in, the mixed solution is mechanically stirred for 12 hours to obtain the reaction mixture.

[0077] 2) The reaction mixture is poured into a sand mill and sanded for 1 hour to obtain a dark green slurry. The slurry is filtered and washed to obtain particles, and these particles are then dried at 100°C to obtain dark green ferric manganese phosphate monohydrate.

[0078] 3) Ferric manganese phosphate monohydrate is sintered in a muffle furnace at 400°C for 2 hours to obtain ferromanganese phosphate, which has a reddish-brown nanoporous structure.

[0079] Tests and analyses revealed that the obtained manganese ferric monohydrate was MnPO4·H2O with a monoclinic phase structure and a particle size of 25 nm. After heat treatment, the ferromanganese phosphate exhibited a certain degree of crystallinity, maintaining a monoclinic phase structure. A large amount of porous structure was distributed between the particles, resulting in a particle size of 45 nm. The ferromanganese phosphate material had a mesoporous structure with pore sizes mainly distributed at approximately 4-5 nm, and a specific surface area of ​​14.5 m². 2 It is approximately / g Example 3

[0080] In this embodiment, the chemical formula is Mn 0.72 Fe 0.28A nanoporous structure of ferromanganese phosphate, which is PO4, is provided, and its manufacturing process is as follows.

[0081] 1) Add concentrated phosphoric acid solution and deionized water to the glass beaker in order, and stir uniformly. Prepare a 60% phosphoric acid aqueous solution by mass, then sequentially add polyethylene glycol and deionized water to the other glass beaker, stir uniformly, and prepare a 5% polyethylene glycol aqueous solution by mass, with a total of Mn and Fe, and a P element molar ratio of 1:1.5, and add 76.52 g of micron-level manganese iron oxide (molecular formula (Mn 0.72 Fe 0.28 )3O4, purchased from Sichuan Qingyuan New Materials Co., Ltd., with an average particle size of 7 μm, is poured in and mechanically stirred for 30 minutes to obtain a black suspension aqueous solution. 245 g of the above phosphoric acid solution is slowly poured into the suspension solution, and after all of the phosphoric acid solution has been poured in, the mixed solution is mechanically stirred for 12 hours to obtain the reaction mixture.

[0082] 2) The reaction mixture is poured into a sand mill and sanded for 1 hour to obtain a dark green slurry. The slurry is filtered and washed to obtain particles, and these particles are then dried at 100°C to obtain dark green ferric manganese phosphate monohydrate.

[0083] 3) Ferric manganese phosphate monohydrate is sintered in a muffle furnace at 400°C for 2 hours to obtain ferromanganese phosphate, which has a reddish-brown nanoporous structure.

[0084] Tests and analyses revealed that the obtained manganese ferric monohydrate was MnPO4·H2O with a monoclinic phase structure and a particle size of 20 nm. After heat treatment, the ferromanganese phosphate exhibited a certain degree of crystallinity, maintaining a monoclinic phase structure. A large amount of porous structure was distributed between the particles, resulting in a particle size of 40 nm. The ferromanganese phosphate material had a mesoporous structure with pore sizes mainly distributed at approximately 3-5 nm, and a specific surface area of ​​15.1 m². 2 It is approximately / g Example 4

[0085] In this embodiment, the chemical formula is Mn 0.65 Fe 0.35 A nanoporous structure of ferromanganese phosphate, which is PO4, is provided, and its manufacturing process is as follows.

[0086] 1) Add concentrated phosphoric acid solution and deionized water sequentially to a glass beaker, stir uniformly, and prepare a 40% mass concentration phosphoric acid aqueous solution. The total molar ratio of Mn and Fe is 1:2, and 76.59 g of micron-level iron manganese oxide (molecular formula (Mn 0.65 Fe 0.35 )3O4, purchased from Sichuan Qingyuan New Materials Co., Ltd., with an average particle size of 7 μm, is poured in and mechanically stirred for 12 hours to obtain the reaction mixture.

[0087] 2) The reaction mixture is poured into a sand mill and sanded for 1 hour to obtain a dark green slurry. The slurry is filtered and washed to obtain particles, and these particles are then dried at 100°C to obtain dark green ferric manganese phosphate monohydrate.

[0088] 3) Ferric manganese phosphate monohydrate is sintered in a muffle furnace at 400°C for 2 hours to obtain ferromanganese phosphate, which has a reddish-brown nanoporous structure.

[0089] Tests and analyses revealed that the obtained manganese ferric monohydrate was MnPO4·H2O with a monoclinic phase structure and a particle size of 10 nm. After heat treatment, the ferromanganese phosphate exhibited a certain degree of crystallinity, maintaining a monoclinic phase structure. A large amount of porous structure was distributed between the particles, resulting in a particle size of 20 nm. The ferromanganese phosphate material had a mesoporous structure with pore sizes mainly distributed at approximately 2-4 nm and a specific surface area of ​​17 m². 2 It is approximately / g

[0090] In this embodiment, the chemical formula is Mn 0.99 Fe 0.01A nanoporous structure of ferromanganese phosphate, which is PO4, is provided, and its manufacturing process is as follows.

[0091] 1) Add concentrated phosphoric acid solution and deionized water sequentially to a glass beaker, stir uniformly, and prepare a 20% phosphoric acid aqueous solution by mass. Set the molar ratio of element P to 1:1.2 for the total of Mn and Fe, and add 72.3 g of micron-level iron manganese oxide (molecular formula (Mn 0.99 Fe 0.01 )3O4, purchased from Sichuan Qingyuan New Materials Co., Ltd., with an average particle size of 7 μm, is poured in and mechanically stirred for 12 hours to obtain the reaction mixture.

[0092] 2) The reaction mixture is poured into a sand mill and sanded for 1 hour to obtain a dark green slurry. The slurry is filtered and washed to obtain particles, and these particles are then dried at 100°C to obtain dark green ferric manganese phosphate monohydrate.

[0093] 3) Ferric manganese phosphate monohydrate is sintered in a muffle furnace at 400°C for 2 hours to obtain ferromanganese phosphate, which has a reddish-brown nanoporous structure.

[0094] Tests and analyses revealed that the obtained manganese ferric monohydrate was MnPO4·H2O with a monoclinic phase structure and a particle size of 30 nm. After heat treatment, the ferromanganese phosphate exhibited a certain degree of crystallinity, maintaining a monoclinic phase structure. A large amount of porous structure was distributed between the particles, with a particle size of 50 nm. The ferromanganese phosphate material had a mesoporous structure, with pore sizes mainly distributed at approximately 5-8 nm, and a specific surface area of ​​13.8 m². 2 It is approximately / g Example 6

[0095] In this embodiment, the chemical formula is Mn 0.5 Fe 0.5 A nanoporous structure of ferromanganese phosphate, which is PO4, is provided, and its manufacturing process is as follows.

[0096] 1) Add concentrated phosphoric acid solution and deionized water sequentially to a glass beaker, stir uniformly, and prepare a 30% phosphoric acid aqueous solution by mass. Set the molar ratio of element P to 1:1.5 for the total of Mn and Fe, and add 76.72 g of micron-level iron manganese oxide (molecular formula (Mn 0.5 Fe 0.5 )3O4, purchased from Sichuan Qingyuan New Materials Co., Ltd., with an average particle size of 7 μm, is poured in and mechanically stirred for 12 hours to obtain the reaction mixture.

[0097] 2) The reaction mixture is poured into a sand mill and sanded for 1 hour to obtain a dark green slurry. The slurry is filtered and washed to obtain particles, and these particles are then dried at 100°C to obtain dark green ferric manganese phosphate monohydrate.

[0098] 3) Ferric manganese phosphate monohydrate is sintered in a muffle furnace at 400°C for 2 hours to obtain ferromanganese phosphate, which has a reddish-brown nanoporous structure.

[0099] Tests and analyses revealed that the obtained manganese ferric monohydrate was MnPO4·H2O with a monoclinic phase structure and a particle size of 15 nm. After heat treatment, the ferromanganese phosphate exhibited a certain degree of crystallinity, maintaining a monoclinic phase structure. A large amount of porous structure was distributed between the particles, with a particle size of 30 nm. The ferromanganese phosphate material had a mesoporous structure, with pore sizes mainly distributed at approximately 3-5 nm, and a specific surface area of ​​16.4 m². 2 It is approximately / g Example 7

[0100] In this embodiment, the chemical formula is Mn 0.01 Fe 0.99 A nanoporous structure of ferromanganese phosphate, which is PO4, is provided, and its manufacturing process is as follows.

[0101] 1) Add concentrated phosphoric acid solution and deionized water sequentially to a glass beaker, stir uniformly, and prepare a 40% mass concentration phosphoric acid aqueous solution. The molar ratio of element P is calculated based on the total of Mn and Fe. Mix 77.16 g of micron-level iron manganese oxide (molecular formula (Mn)) in 294 mL of the above phosphoric acid aqueous solution at a ratio of 1:1.2. 0.01 Fe 0.99 )3O4, purchased from Sichuan Qingyuan New Materials Co., Ltd., with an average particle size of 7 μm, is poured in and mechanically stirred for 12 hours to obtain the reaction mixture.

[0102] 2) The reaction mixture is poured into a sand mill and sanded for 1 hour to obtain a dark green slurry. The slurry is filtered and washed to obtain particles, and these particles are then dried at 100°C to obtain dark green ferric manganese phosphate monohydrate.

[0103] 3) Ferric manganese phosphate monohydrate is sintered in a muffle furnace at 400°C for 2 hours to obtain ferromanganese phosphate, which has a reddish-brown nanoporous structure.

[0104] Tests and analyses revealed that the obtained manganese ferric monohydrate was MnPO4·H2O with a monoclinic phase structure and a particle size of 25 nm. After heat treatment, the ferromanganese phosphate exhibited a certain degree of crystallinity, maintaining a monoclinic phase structure. A large amount of porous structure was distributed between the particles, with a particle size of 50 nm. The ferromanganese phosphate material had a mesoporous structure, with pore sizes mainly distributed at approximately 3-5 nm, and a specific surface area of ​​15.4 m². 2 It is approximately / g Comparative Example 1

[0105] This comparative example provides a phosphate material for comparison, and its manufacturing process is basically the same as in Example 1, specifically as follows.

[0106] 1) Add concentrated phosphoric acid solution and deionized water sequentially to a glass beaker and stir uniformly to prepare a 35% phosphoric acid aqueous solution. The total molar ratio of Mn and Fe is set to 1:1.5. Add a mixture of 34.38 g of manganese oxide and 15.62 g of iron oxide (with a molar ratio of Mn to Fe of 6.9:3.1 and particle sizes of both manganese oxide and iron oxide of 7 μm) to 265 mL of the above phosphoric acid aqueous solution, and stir mechanically for 12 hours to obtain the reaction mixture.

[0107] 2) Pour the reaction mixture into a sand mill and sand for 1 hour to obtain a dark brown slurry. Filter the slurry to wash and obtain particles. Further dry the particles at 100°C to obtain a dark brown product.

[0108] 3) The product from step 2) is sintered in a muffle furnace at 400°C for 2 hours to obtain the final dark brown product.

[0109] Figures 9, 10-11 show the XRD and SEM images of the product obtained in step 2), respectively. As can be seen, the product is a mixture of manganese phosphate monohydrate (MnPO4·H2O) and iron oxide, and the particle size distribution of the product is not uniform, ranging from 50 to 1000 nm. Smaller particles of about 50 nm are MnPO4·H2O, and larger particles of about 1000 nm are iron oxide. Figures 12 and 13 show the XRD and SEM images of the final product obtained in step 3), respectively. As can be seen, the final product is a mixture of manganese phosphate and iron oxide with low crystallinity, and the particle size distribution of the final product is also not uniform, mainly ranging from 50 to 1000 nm. There are many pore structures between the small particles, but the density of the large particles is relatively high. Comparative Example 2

[0110] This comparative example provides a phosphate material for comparison, and its manufacturing process is basically the same as in Example 1, specifically as follows.

[0111] 1) Add concentrated phosphoric acid solution and deionized water sequentially to a glass beaker and stir uniformly to prepare a 35% phosphoric acid aqueous solution. The total molar ratio of Mn and Fe is set to 1:1.5. Add a mixture of 47.36 g of manganese(III) oxide and 31.94 g of iron(III) oxide (both manganese oxide and iron oxide have particle sizes of 7 μm, and the molar ratio of Mn to Fe is 6:4) to 420 mL of the above phosphoric acid aqueous solution, and stir mechanically for 12 hours to obtain the reaction mixture.

[0112] 2) Pour the reaction mixture into a sand mill and sand for 1 hour to obtain a dark brown slurry. Filter the slurry to wash and obtain particles. Further dry the particles at 100°C to obtain a dark brown product.

[0113] 3) The product from step 2) is sintered in a muffle furnace at 400°C for 2 hours to obtain the final dark brown product.

[0114] The product obtained in step 2) is a mixture of manganese phosphate monohydrate (MnPO4·H2O) and iron oxide. The particle size distribution of the product is not uniform, ranging from 30 to 1000 nm. Smaller particles of about 30 nm are MnPO4·H2O, while larger particles of about 1000 nm are iron oxide. SEM images of this mixture are shown in Figures 16 and 17. The final product obtained in step 3) is a mixture of manganese phosphate and iron oxide with low crystallinity. An SEM image of the final product is shown in Figure 18. As can be seen from this, the primary particle size distribution of the final product is also not uniform, mainly ranging from 50 to 800 nm. There are many pore structures between the small particles, but the density of the large particles is relatively high. Comparative Example 3

[0115] This comparative example provides a phosphate material for comparison, and its manufacturing process is basically the same as in Example 1, with the only difference being that polishing is not performed in step 2). The manufacturing process is specifically as follows.

[0116] 1) Add concentrated phosphoric acid solution and deionized water sequentially to a glass beaker, stir uniformly, and prepare a 35% phosphoric acid aqueous solution by mass. The total molar ratio of Mn and Fe is 1:1.5, and 50 g of micron-level iron manganese oxide (molecular formula (Mn 0.60 Fe 0.40 )3O4, purchased from Sichuan Qingyuan New Materials Co., Ltd., with an average particle size of 7 μm, is poured in and mechanically stirred for 12 hours to obtain the reaction mixture.

[0117] 2) The reaction mixture is filtered and washed to obtain particles, and these particles are then dried at 100°C to obtain a black powder material.

[0118] 3) The black powder material is sintered in a muffle furnace at 400°C for 2 hours to obtain a brown-black powder material.

[0119] Regarding the black powder material obtained in step 2), the main component of the material remains manganese iron oxide, with a small amount of manganese ferric monohydrate. Regarding the brown-black powder material obtained in step 3), the main component is also manganese iron oxide, with a small amount of ferromanganese phosphate. Example 8

[0120] In this embodiment, the chemical formula is Mn 0.6 Fe 0.395 Co 0.005 A doped ferromanganese phosphate with a nanoporous structure, which is PO4, is provided, and its manufacturing process is as follows.

[0121] 1) Add concentrated phosphoric acid solution and deionized water to the glass beaker in order, and stir uniformly. Prepare a 35% phosphoric acid aqueous solution, with a total molar ratio of Mn and Fe of P being 1:1.5, and add 114.95 g of micron-level iron manganese oxide (molecular formula (Mn 0.60 Fe 0.403O4 (purchased from Sichuan Qingyuan New Materials Co., Ltd., with an average particle size of 7 μm), 1.190 g of cobalt chloride hexahydrate was added and the mixture was mechanically stirred for 12 hours to obtain the reaction mixture.

[0122] 2) The reaction mixture is poured into a sand mill and sanded for 1 hour to obtain a dark green slurry. The slurry is filtered and washed to obtain particles, and these particles are then dried at 100°C to obtain a dark green powder (manganese iron cobalt phosphate monohydrate).

[0123] 3) Manganese iron cobalt phosphate monohydrate is sintered in a muffle furnace at 400°C for 2 hours to obtain reddish-brown powdered ferromanganese cobalt phosphate.

[0124] The XRD and SEM images of the manganese iron cobalt phosphate monohydrate obtained in step 2) are shown in Figures 21 and 22-23, respectively. As can be seen from these images, its crystal phase is MnPO4·H2O with a monoclinic structure. The particle size of the manganese iron cobalt phosphate monohydrate was measured using a scanning electron microscope (SEM) and found to be 20 nm. Figures 24 and 25 show the XRD and SEM images of the ferromanganese cobalt phosphate obtained in step 3). As can be seen, the ferromanganese cobalt phosphate has a certain degree of crystallinity, and a large amount of porous structure is distributed between the particles. As can be seen from the XRD test, the crystalline phase remains a monoclinic phase structure. The particle size of the ferromanganese cobalt phosphate was measured using the scanning electron microscope (SEM) method and was found to be 40 nm. At the same time, adsorption and desorption tests and analysis were performed on the ferromanganese cobalt phosphate using a specific surface area and aperture tester. As can be seen from Figures 31 and 32, the ferromanganese cobalt phosphate material has a mesoporous structure, with pore sizes mainly distributed at about 3-5 nm, and its specific surface area is 15.1 m². 2 It is approximately / g Example 9

[0125] In this embodiment, the chemical formula is Mn 0.65 Fe 0.344 Mg 0.005 B 0.001There is provided a doped and modified ferromanganese phosphate with a nanoporous structure of PO4, and its manufacturing process is as follows.

[0126] 1) Concentrated phosphoric acid solution and deionized water were sequentially added into a glass beaker, and after uniformly stirring, it was prepared into an aqueous phosphoric acid solution with a mass concentration of 30%. In total for Mn and Fe, the molar ratio of P element was 1:1.5. 114.88 g of micron-level manganese iron oxide (molecular formula (Mn 0.65 Fe 0.35 )3O4, purchased from Sichuan Qingyuan New Materials Co., Ltd., with an average particle size of 7 μm), 0.201 g of magnesium oxide, and 0.062 g of boric acid were poured in, and mechanically stirred for 12 hours to obtain a reaction mixture.

[0127] 2) The reaction mixture was poured into a sand mill and sanded for 1 hour to obtain a dark green slurry. The slurry was filtered and washed to obtain particles, and the particles were further dried at 100 °C to obtain a dark green powder (magnesium boron-doped ferric manganese phosphate monohydrate).

[0128] 3) The magnesium boron-doped ferric manganese phosphate monohydrate was sintered in a muffler furnace at 400 °C for 2 hours to obtain a reddish-brown powder.

[0129] As a result of testing and analysis, the obtained magnesium boron-doped ferric manganese phosphate monohydrate is MnPO4·H2O with a monoclinic phase structure, the particle size is 25 nm, and the magnesium boron-doped ferromanganese phosphate after heat treatment has a certain degree of crystallinity and the crystal phase remains as a monoclinic phase structure without change. A large number of porous structures are distributed among the particles, the particle size is 45 nm, the magnesium boron-doped ferromanganese phosphate material has a mesoporous structure, the pore size distribution is mainly about 4 - 6 nm, and its specific surface area is about 14.8 m 2 / g. Example 10

[0130] This example has a chemical formula of Mn0.7 Fe 0.293 Mo 0.003 Nb 0.003 B 0.001 A doped ferromanganese phosphate with a nanoporous structure, which is PO4, is provided, and its manufacturing process is as follows.

[0131] 1) Add concentrated phosphoric acid solution and deionized water sequentially to a glass beaker, stir uniformly, and prepare a 25% mass concentration phosphoric acid aqueous solution. The total molar ratio of Mn and Fe is set to 1:1.5, and 114.81 g of micron-level iron manganese oxide (molecular formula (Mn 0.70 Fe 0.30 3O4 (purchased from Sichuan Qingyuan New Materials Co., Ltd., average particle size 7 μm), 0.432 g molybdenum trioxide, 1.614 g niobium oxalate, and 0.062 g boric acid are added, and the mixture is mechanically stirred for 12 hours to obtain the reaction mixture.

[0132] 2) The reaction mixture is poured into a sand mill and sanded for 1 hour to obtain a dark green slurry. The slurry is filtered and washed to obtain particles, and these particles are then dried at 100°C to obtain a dark green powder (molybdenum nioboboron-doped manganese ferric phosphate monohydrate).

[0133] 3) Manganese ferric monohydrate doped with molybdenum niobboron is sintered in a muffle furnace at 400°C for 2 hours to obtain a reddish-brown powder.

[0134] Tests and analyses revealed that the obtained molybdenum niobboron-doped manganese ferric monohydrate was MnPO4·H2O with a monoclinic phase structure and a particle size of 30 nm. After heat treatment, the molybdenum niobboron-doped ferromanganese phosphate exhibited a certain degree of crystallinity, maintaining a monoclinic phase structure with a large amount of porous structure distributed between particles, resulting in a particle size of 50 nm. The molybdenum niobboron-doped ferromanganese phosphate material had a mesoporous structure, with pore sizes mainly distributed at approximately 4-6 nm, and a specific surface area of ​​14.1 m².2 It is approximately / g Example 11

[0135] In this embodiment, the chemical formula is Mn 0.8 Fe 0.19 Co 0.005 V 0.001 Ni 0.001 B 0.003 A doped ferromanganese phosphate with a nanoporous structure, which is PO4, is provided, and its manufacturing process is as follows.

[0136] 1) Add concentrated phosphoric acid solution and deionized water sequentially to a glass beaker, stir uniformly, and prepare a 30% phosphoric acid aqueous solution by mass. Set the molar ratio of element P to 1:1.5 for the total of Mn and Fe, and add 114.66 g of micron-level iron manganese oxide (molecular formula (Mn 0.81 Fe 0.19 3O4 (purchased from Sichuan Qingyuan New Materials Co., Ltd., average particle size 7 μm), 1.245 g of cobalt acetate tetrahydrate, 0.117 g of ammonium metavanadate, 0.263 g of nickel sulfate hexahydrate, and 0.185 g of boric acid are added, and the mixture is mechanically stirred for 12 hours to obtain the reaction mixture.

[0137] 2) Pour the reaction mixture into a sand mill and sand for 1 hour to obtain a dark green slurry. Filter and wash the slurry to obtain particles. Further dry the particles at 100°C to obtain a dark green powder (cobalt vanadium nickel boron-doped phosphorus). Obtain manganese ferric monohydrate.

[0138] 3) Cobalt vanadium nickel boron-doped manganese ferric monohydrate is sintered in a muffle furnace at 400°C for 2 hours to obtain a reddish-brown powder.

[0139] Tests and analyses revealed that the obtained cobalt vanadium nickel boron-doped manganese ferric monohydrate was MnPO4·H2O with a monoclinic phase structure and a particle size of 20 nm. After heat treatment, the cobalt vanadium nickel boron-doped ferromanganese phosphate exhibited a certain degree of crystallinity, maintaining a monoclinic phase structure with a large amount of porous structure distributed between particles, resulting in a particle size of 40 nm. The cobalt vanadium nickel boron-doped ferromanganese phosphate material had a mesoporous structure, with pore sizes mainly distributed at approximately 3-5 nm, and a specific surface area of ​​15.8 m². 2 It is approximately / g Example 12

[0140] In this embodiment, the chemical formula is Mn 0.5 Fe 0.495 Mg 0.005 A doped ferromanganese phosphate with a nanoporous structure, which is PO4, is provided, and its manufacturing process is as follows.

[0141] 1) Add concentrated phosphoric acid solution and deionized water sequentially to a glass beaker, stir uniformly, and prepare a 25% mass concentration aqueous phosphoric acid solution. Set the molar ratio of element P to 1:1.5 for the total of Mn and Fe, and add 115.08 g of micron-level iron manganese oxide (molecular formula (Mn 0.50 Fe 0.50 3O4 (purchased from Sichuan Qingyuan New Materials Co., Ltd., with an average particle size of 7 μm), 1.072 g of magnesium acetate tetrahydrate is added and the mixture is mechanically stirred for 12 hours to obtain the reaction mixture.

[0142] 2) The reaction mixture is poured into a sand mill and sanded for 1 hour to obtain a dark green slurry. The slurry is filtered and washed to obtain particles, and these particles are then dried at 100°C to obtain a dark green powder (magnesium ferromanganese phosphate monohydrate).

[0143] 3) A magnesium ferromanganese phosphate monohydrate is sintered in a muffle furnace at 400°C for 2 hours to obtain a reddish-brown powder.

[0144] As a result of testing and analysis, the obtained manganese iron magnesium phosphate monohydrate is MnPO4·H2O with a monoclinic phase structure, having a particle size of 25 nm. After heat treatment, the manganese iron magnesium phosphate has a certain degree of crystallinity, and the crystal phase remains as the monoclinic phase structure without phase change. A large amount of porous structures are distributed among the particles, with a particle size of 45 nm. The manganese iron magnesium phosphate has a mesoporous structure, and the pore size is mainly distributed around 4 - 6 nm, and its specific surface area is about 15.1 m 2 / g. Example 13

[0145] This example provides a doped and modified manganese iron phosphate with a nanoporous structure having the chemical formula Mn 0.65 Fe 0.34 V 0.005 Ti 0.005 PO4, and its manufacturing process is as follows.

[0146] 1) Concentrated phosphoric acid solution and deionized water are sequentially added into a glass beaker. After uniformly stirring, it is prepared as an aqueous phosphoric acid solution with a mass concentration of 25%. In total for Mn and Fe, the molar ratio of P element is 1:1.5. To 882 mL of the above aqueous phosphoric acid solution, 114.87 g of micron-level manganese iron oxide (molecular formula (Mn 0.66 Fe 0.34 )3O4, purchased from Sichuan Qingyuan New Materials Co., Ltd., with an average particle size of 7 μm), 1.225 g of vanadyl oxalate, and 0.948 g of titanium chloride are poured, and mechanically stirred for 12 hours to obtain a reaction mixture.

[0147] 2) The reaction mixture is poured into a sand mill and sanded for 1 hour to obtain a dark green slurry. The slurry is filtered and washed to obtain particles, and the particles are further dried at 100 °C to obtain a dark green powder (manganese ferric phosphate monohydrate doped with vanadium and titanium).

[0148] 3) The manganese ferric phosphate monohydrate doped with vanadium and titanium is sintered in a muffler furnace at 400 °C for 2 hours to obtain a reddish-brown powder.

[0149] Tests and analyses revealed that the resulting vanadium-titanium doped manganese ferric monohydrate was MnPO4·H2O with a monoclinic phase structure and a particle size of 25 nm. After heat treatment, the vanadium-titanium doped ferromanganese phosphate exhibited a certain degree of crystallinity, maintaining a monoclinic phase structure with a large amount of porous structure distributed between particles, resulting in a particle size of 45 nm. The vanadium-titanium doped ferromanganese phosphate had a mesoporous structure, with pore sizes mainly distributed at approximately 4-6 nm, and a specific surface area of ​​14.8 m². 2 It is approximately / g Comparative Example 4

[0150] This comparative example provides a comparative phosphate material, the manufacturing process of which is basically the same as in Example 8, and is specifically as follows.

[0151] 1) Add concentrated phosphoric acid solution and deionized water sequentially to a glass beaker, stir uniformly, and prepare a 35% phosphoric acid aqueous solution by mass. The total molar ratio of Mn and Fe is set to 1:1.5. Add a mixture of 47.36 g of manganese(III) oxide and 31.94 g of iron(III) oxide (both with particle sizes of 7 μm) and 1.190 g of cobalt chloride hexahydrate to 420 mL of the above phosphoric acid aqueous solution, and stir mechanically for 12 hours to obtain the reaction mixture.

[0152] 2) Pour the reaction mixture into a sand mill and sand for 1 hour to obtain a dark brown slurry. Filter the slurry to wash and obtain particles. Further dry the particles at 100°C to obtain a dark brown product.

[0153] 3) The product from step 2) is sintered in a muffle furnace at 400°C for 2 hours to obtain the final dark brown product.

[0154] Figures 26 and 27-28 show the XRD and SEM images of the product obtained in step 2), respectively. As can be seen, the product is a mixture of cobalt-doped manganese phosphate monohydrate (MnPO4·H2O) and iron oxide. The particle size distribution of the product is not uniform, ranging from 30 to 2000 nm. Smaller particles of about 30 nm are cobalt-doped manganese phosphate monohydrate, while larger particles of about 2000 nm are iron oxide. Figures 29 and 30 show the XRD and SEM images of the final product obtained in step 3), respectively. As can be seen, the final product is a mixture of cobalt-doped manganese phosphate and iron oxide with low crystallinity. The particle size distribution of the final product is also not uniform, mainly ranging from 50 to 2000 nm. There are many pore structures between the small particles, but the density of the large particles is relatively high. Comparative Example 5

[0155] This comparative example provides a phosphate material for comparison, and its manufacturing process is basically the same as in Example 8, the only difference being that cobalt chloride hexahydrate is not added in step 1). The manufacturing process is specifically as follows.

[0156] 1) Add concentrated phosphoric acid solution and deionized water sequentially to a glass beaker, stir uniformly, and prepare a 35% phosphoric acid aqueous solution by mass. Set the molar ratio of element P to 1:1.5 for the total of Mn and Fe, and add 114.85 g of micron-level iron manganese oxide (molecular formula (Mn 0.60 Fe 0.40 )3O4, purchased from Sichuan Qingyuan New Materials Co., Ltd., with an average particle size of 7 μm, is poured in and mechanically stirred for 12 hours to obtain the reaction mixture.

[0157] 2) The reaction mixture is poured into a sand mill and sanded for 1 hour to obtain a dark green slurry. The slurry is filtered and washed to obtain particles, and these particles are then dried at 100°C to obtain a dark green powder (ferric manganese phosphate monohydrate).

[0158] 3) Ferric manganese phosphate monohydrate is sintered in a muffle furnace at 400°C for 2 hours to obtain reddish-brown powdered ferromanganese phosphate.

[0159] The dark green powder obtained in step 2) was subjected to XRD and SEM testing and analysis, and the results showed that the crystalline phase of the material is MnPO4·H2O with a monoclinic structure and a particle size of 20 nm.

[0160] The reddish-brown powder obtained in step 3) underwent XRD and SEM testing and analysis. The results showed that the crystalline phase of the material remained monoclinic, with a particle size of 40 nm. The ferromanganese phosphate material has a mesoporous structure, with pore sizes mainly distributed at approximately 3-5 nm, and a specific surface area of ​​15.0 m². 2 It is approximately / g Example 14

[0161] In this embodiment, the chemical formula is Mn 0.6 Fe 0.39 Zn 0.001 Cu 0.0005 Mg 0.005 Mo 0.003 Ti 0.0005 A doped ferromanganese phosphate with a nanoporous structure, which is PO4, is provided, and its manufacturing process is as follows.

[0162] 1) Add concentrated phosphoric acid solution and deionized water sequentially to a glass beaker, stir uniformly, and prepare a 25% phosphoric acid aqueous solution by mass. Set the molar ratio of element P to 1:1.5 for the total of Mn and Fe, and add 114.93 g of micron-level iron manganese oxide (molecular formula (Mn 0.61 Fe 0.39 3O4 (purchased from Sichuan Qingyuan New Materials Co., Ltd., average particle size 7 μm), 0.081 g zinc oxide, 0.040 g copper oxide, 0.20 g magnesium oxide, 0.432 g molybdenum oxide, and 0.040 g titanium dioxide are added and mechanically stirred for 12 hours to obtain the reaction mixture.

[0163] 2) The reaction mixture is poured into a sand mill and sanded for 1 hour to obtain a dark green slurry. The slurry is filtered and washed to obtain particles, and these particles are then dried at 100°C to obtain a dark green powder (doped ferric manganese phosphate monohydrate).

[0164] 3) The doped manganese ferric monohydrate is sintered in a muffle furnace at 400°C for 2 hours to obtain a reddish-brown powder.

[0165] XRD and SEM images of manganese iron oxide are shown in Figures 35 and 36-37, respectively, and as can be seen, manganese iron oxide has a crystalline structure. XRD and SEM images of the doped manganese ferric monohydrate obtained in step 2) are shown in Figures 38 and 39-40, respectively, and as can be seen, its crystal phase is MnPO4·H2O with a monoclinic structure. The particle size of the doped manganese ferric monohydrate was measured by scanning electron microscopy (SEM) and found to be 25 nm. The doped phosphate obtained in step 3) XRD and SEM images of ferromanganese phosphate are shown in Figures 41 and 42, respectively. As can be seen, the doped ferromanganese phosphate has a certain degree of crystallinity, and a large amount of porous structure is distributed between the particles. As can be seen from the XRD test, the crystalline phase remains a monoclinic phase structure. The particle size of the doped ferromanganese phosphate was measured using the scanning electron microscope (SEM) method and was found to be 35 nm. Adsorption and desorption tests and analysis were also performed on the doped ferromanganese phosphate using a specific surface area and aperture tester. As can be seen from Figures 48 and 49, the doped ferromanganese phosphate material has a mesoporous structure, with pore sizes mainly distributed at around 4-6 nm, and its specific surface area is 15.1 m². 2 It is approximately / g Example 15

[0166] In this embodiment, the chemical formula is Mn 0.7 Fe 0.293 Mg 0.0015 V 0.001 Ti 0.0005 Cr 0.001Mo 0.003 A doped ferromanganese phosphate with a nanoporous structure, which is PO4, is provided, and its manufacturing process is as follows.

[0167] 1) Add concentrated phosphoric acid solution and deionized water sequentially to a glass beaker, stir uniformly, and prepare a 25% mass concentration phosphoric acid aqueous solution. The total molar ratio of Mn and Fe is set to 1:1.5, and 114.81 g of micron-level iron manganese oxide (molecular formula (Mn 0.70 Fe 0.30 3O4 (purchased from Sichuan Qingyuan New Materials Co., Ltd., average particle size 7 μm), 0.060 g of magnesium oxide, 0.117 g of ammonium metavanadate, 0.399 g of titanium dioxide, 0.152 g of chromium oxide, and 0.432 g of molybdenum oxide were added and the mixture was mechanically stirred for 12 hours to obtain the reaction mixture.

[0168] 2) The reaction mixture is poured into a sand mill and sanded for 1 hour to obtain a dark green slurry. The slurry is filtered and washed to obtain particles, and these particles are then dried at 100°C to obtain a dark green powder (doped ferric manganese phosphate monohydrate).

[0169] 3) The doped manganese ferric monohydrate is sintered in a muffle furnace at 400°C for 2 hours to obtain a reddish-brown powder.

[0170] Tests and analyses revealed that the obtained doped manganese ferric monohydrate was MnPO4·H2O with a monoclinic phase structure and a particle size of 25 nm. After heat treatment, the doped ferromanganese phosphate exhibited a certain degree of crystallinity, maintaining a monoclinic phase structure with a large amount of porous structure distributed between particles, resulting in a particle size of 35 nm. The doped ferromanganese phosphate material had a mesoporous structure with pore sizes mainly distributed at approximately 4-6 nm and a specific surface area of ​​14.8 m². 2 It is approximately / g Example 16

[0171] In this embodiment, the chemical formula is Mn 0.7 Fe 0.29 Nb 0.003 B 0.003 Co 0.001 V 0.002 Al 0.001 A doped ferromanganese phosphate with a nanoporous structure, which is PO4, is provided, and its manufacturing process is as follows.

[0172] 1) Add concentrated phosphoric acid solution and deionized water sequentially to a glass beaker, stir uniformly, and prepare a 30% phosphoric acid aqueous solution by mass. Set the molar ratio of element P to 1:1.5 for the total of Mn and Fe, and add 114.80 g of micron-level iron manganese oxide (molecular formula (Mn 0.71 Fe 0.29 3O4 (purchased from Sichuan Qingyuan New Materials Co., Ltd., average particle size 7 μm), 1.614 g of niobium oxalate, 0.104 g of boron oxide, 0.177 g of cobalt acetate, 0.234 g of ammonium metavanadate, and 0.051 g of aluminum oxide are poured in and the mixture is mechanically stirred for 12 hours to obtain the reaction mixture.

[0173] 2) The reaction mixture is poured into a sand mill and sanded for 1 hour to obtain a dark green slurry. The slurry is filtered and washed to obtain particles, and these particles are then dried at 100°C to obtain a dark green powder (doped ferric manganese phosphate monohydrate).

[0174] 3) The doped manganese ferric monohydrate is sintered in a muffle furnace at 400°C for 2 hours to obtain a reddish-brown powder.

[0175] Tests and analyses revealed that the obtained doped manganese ferric monohydrate was MnPO4·H2O with a monoclinic phase structure and a particle size of 20 nm. After heat treatment, the doped ferromanganese phosphate exhibited a certain degree of crystallinity, maintaining a monoclinic phase structure with a large amount of porous structure distributed between particles, resulting in a particle size of 30 nm. The doped ferromanganese phosphate material had a mesoporous structure with pore sizes mainly distributed at approximately 3-5 nm and a specific surface area of ​​16.5 m². 2 It is approximately / g Example 17

[0176] In this embodiment, the chemical formula is Mn 0.8 Fe 0.19 Co 0.005 V 0.001 Ni 0.0005 B 0.003 Nb 0.0005 A high-entropy doped ferromanganese phosphate with a nanoporous structure, which is PO4, is provided, and its manufacturing process is as follows.

[0177] 1) Add concentrated phosphoric acid solution and deionized water sequentially to a glass beaker, stir uniformly, and prepare a 30% phosphoric acid aqueous solution by mass. Set the molar ratio of element P to 1:1.5 for the total of Mn and Fe, and add 114.66 g of micron-level iron manganese oxide (molecular formula (Mn 0.81 Fe 0.19 3O4 (purchased from Sichuan Qingyuan New Materials Co., Ltd., average particle size 7 μm), 0.885 g cobalt acetate, 0.117 g ammonium metavanadate, 0.088 g nickel acetate, 0.186 g boric acid, and 0.269 g niobium oxalate are added and the mixture is mechanically stirred for 12 hours to obtain the reaction mixture.

[0178] 2) The reaction mixture is poured into a sand mill and sanded for 1 hour to obtain a dark green slurry. The slurry is filtered and washed to obtain particles, and these particles are then dried at 100°C to obtain a dark green powder (doped ferric manganese phosphate monohydrate).

[0179] 3) The doped manganese ferric monohydrate is sintered in a muffle furnace at 400°C for 2 hours to obtain a reddish-brown powder.

[0180] Tests and analyses revealed that the obtained doped manganese ferric monohydrate was MnPO4·H2O with a monoclinic phase structure and a particle size of 20 nm. After heat treatment, the doped ferromanganese phosphate exhibited a certain degree of crystallinity, maintaining a monoclinic phase structure with a large amount of porous structure distributed between particles, resulting in a particle size of 30 nm. The doped ferromanganese phosphate material had a mesoporous structure with pore sizes mainly distributed at approximately 4-5 nm and a specific surface area of ​​16.8 m². 2 It is approximately / g Example 18

[0181] In this embodiment, the chemical formula is Mn 0.5 Fe 0.49 Co 0.0025 Ga 0.0005 B 0.003 Al 0.002 Sr 0.002 A doped ferromanganese phosphate with a nanoporous structure, which is PO4, is provided, and its manufacturing process is as follows.

[0182] 1) Add concentrated phosphoric acid solution and deionized water to the glass beaker in order, and stir uniformly. Prepare a 25% phosphoric acid aqueous solution, with a total molar ratio of Mn and Fe of P at 1:1.5, and add 115.07 g of micron-level iron manganese oxide (molecular formula (Mn 0.51 Fe 0.49 3O4 (purchased from Sichuan Qingyuan New Materials Co., Ltd., with an average particle size of 7 μm), 0.325 g of cobalt chloride, 0.088 g of gallium chloride, 0.186 g of boric acid, 0.102 g of chromium oxide, and 0.317 g of strontium chloride were added and the mixture was mechanically stirred for 12 hours to obtain the reaction mixture.

[0183] 2) The reaction mixture is poured into a sand mill and sanded for 1 hour to obtain a dark green slurry. The slurry is filtered and washed to obtain particles, and these particles are then dried at 100°C to obtain a dark green powder (doped ferric manganese phosphate monohydrate).

[0184] 3) The doped manganese ferric monohydrate is sintered in a muffle furnace at 400°C for 2 hours to obtain a reddish-brown powder.

[0185] Tests and analyses revealed that the obtained doped manganese ferric monohydrate was MnPO4·H2O with a monoclinic phase structure and a particle size of 25 nm. After heat treatment, the doped ferromanganese phosphate exhibited a certain degree of crystallinity, maintaining a monoclinic phase structure with a large amount of porous structure distributed between particles, resulting in a particle size of 35 nm. The doped ferromanganese phosphate material had a mesoporous structure with pore sizes mainly distributed at approximately 4-6 nm and a specific surface area of ​​14.5 m². 2 It is approximately / g Example 19

[0186] In this embodiment, the chemical formula is Mn 0.65 Fe 0.34 Mo 0.003 Co 0.003 Ni 0.002 V 0.0015 Ca 0.0005 A doped ferromanganese phosphate with a nanoporous structure, which is PO4, is provided, and its manufacturing process is as follows.

[0187] 1) Add concentrated phosphoric acid solution and deionized water sequentially to a glass beaker, stir uniformly, and prepare a 25% mass concentration aqueous phosphoric acid solution. The total molar ratio of Mn and Fe is set to 1:1.5, and 114.87 g of micron-level iron manganese oxide (molecular formula (Mn 0.66 Fe 0.343O4 (purchased from Sichuan Qingyuan New Materials Co., Ltd., average particle size 7 μm), 0.432 g molybdenum oxide, 0.389 g cobalt chloride, 0.259 g nickel chloride, 0.4 g vanadium oxalate, and 0.028 g calcium oxide are added and the mixture is mechanically stirred for 12 hours to obtain the reaction mixture.

[0188] 2) The reaction mixture is poured into a sand mill and sanded for 1 hour to obtain a dark green slurry. The slurry is filtered and washed to obtain particles, and these particles are then dried at 100°C to obtain a dark green powder (doped ferric manganese phosphate monohydrate).

[0189] 3) The doped manganese ferric monohydrate is sintered in a muffle furnace at 400°C for 2 hours to obtain a reddish-brown powder.

[0190] Tests and analyses revealed that the obtained doped manganese ferric monohydrate was MnPO4·H2O with a monoclinic phase structure and a particle size of 25 nm. After heat treatment, the doped ferromanganese phosphate exhibited a certain degree of crystallinity, maintaining a monoclinic phase structure with a large amount of porous structure distributed between particles, resulting in a particle size of 35 nm. The doped ferromanganese phosphate material had a mesoporous structure with pore sizes mainly distributed at approximately 4-6 nm and a specific surface area of ​​14.7 m². 2 It is approximately / g Comparative Example 6

[0191] This comparative example provides a phosphate material for comparison, and its manufacturing process is basically the same as in Example 14, specifically as follows.

[0192] 1) Add concentrated phosphoric acid solution and deionized water sequentially to a glass beaker and stir uniformly to prepare a 25% phosphoric acid aqueous solution. The total molar ratio of Mn and Fe is set to 1:1.5. Add a mixture of 48.15 g of manganese(III) oxide and 31.14 g of iron(III) oxide (both with particle sizes of 7 μm), 0.081 g of zinc oxide, 0.040 g of copper oxide, 0.20 g of magnesium oxide, 0.432 g of molybdenum oxide, and 0.040 g of titanium dioxide to 882 mL of the above phosphoric acid aqueous solution, and stir mechanically for 12 hours to obtain the reaction mixture.

[0193] 2) Pour the reaction mixture into a sand mill and sand for 1 hour to obtain a dark brown slurry. Filter the slurry to wash and obtain particles. Further dry the particles at 100°C to obtain a dark brown product.

[0194] 3) The product from step 2) is sintered in a muffle furnace at 400°C for 2 hours to obtain the final dark brown product.

[0195] The XRD and SEM images of the product obtained in step 2) are shown in Figures 43 and 44-45, respectively. As can be seen from these, the product is manganese phosphate monohydrate (Mn) doped with zinc copper magnesium molybdenum titanium. 0.9839 Zn 0.0016 Cu 0.0008 Mg 0.0081 Mo 0.0048 Ti 0.0008 ) is a mixture of PO4·H2O and iron oxide, and the particle size distribution of the product is not uniform, ranging from 50 to 2000 nm. Smaller particles of about 50 nm are zinc copper magnesium molybdenum titanium-doped manganese phosphate monohydrate, and larger particles of about 2000 nm are iron oxide. The XRD and SEM images of the final product obtained in step 3) are shown in Figures 46 and 47, respectively. As can be seen from these, the final product is low-crystallinity zinc copper magnesium molybdenum titanium-doped manganese phosphate (Mn 0.9839 Zn 0.0016 Cu 0.0008 Mg 0.0081Mo 0.0048 Ti 0.0008 It is a mixture of PO4 and iron oxide, and the particle size distribution of the final product is not uniform, mainly distributed between 50 and 2000 nm. There are many pore structures between the small particles, but the larger particles have a relatively high density. Comparative Example 7

[0196] This comparative example provides a phosphate material for comparison, and its manufacturing process is basically the same as in Example 14, the only difference being that only the compound of four doping elements is added in step 1), and the manufacturing process is specifically as follows.

[0197] 1) Add concentrated phosphoric acid solution and deionized water sequentially to a glass beaker, stir uniformly, and prepare a 25% phosphoric acid aqueous solution by mass. Set the molar ratio of element P to 1:1.5 for the total of Mn and Fe, and add 114.93 g of micron-level iron manganese oxide (molecular formula (Mn 0.61 Fe 0.39 3O4 (purchased from Sichuan Qingyuan New Materials Co., Ltd., average particle size 7 μm), 0.081 g zinc oxide, 0.040 g copper oxide, 0.20 g magnesium oxide, and 0.040 g titanium dioxide are added and mechanically stirred for 12 hours to obtain the reaction mixture.

[0198] 2) The reaction mixture is poured into a sand mill and sanded for 1 hour to obtain a dark green slurry. The slurry is filtered and washed to obtain particles, and these particles are then dried at 100°C to obtain a dark green powder (doped ferric manganese phosphate monohydrate).

[0199] 3) The doped manganese ferric monohydrate is sintered in a muffle furnace at 400°C for 2 hours to obtain a reddish-brown powder.

[0200] Tests and analyses revealed that the obtained doped manganese ferric monohydrate was MnPO4·H2O with a monoclinic phase structure and a particle size of 25 nm. After heat treatment, the doped ferromanganese phosphate exhibited a certain degree of crystallinity, maintaining a monoclinic phase structure with a large amount of porous structure distributed between particles, resulting in a particle size of 35 nm. The doped ferromanganese phosphate material had a mesoporous structure with pore sizes mainly distributed at approximately 4-6 nm and a specific surface area of ​​15 m². 2 It is approximately / g Application Example 1

[0201] The ferromanganese phosphate or doped ferromanganese phosphate obtained in Examples 1-19, Comparative Examples 1-2, and Comparative Examples 4-7 were used in the production of lithium ferromanganese phosphate, and the specific procedure is as follows.

[0202] 1) According to the elemental molar ratio of Li:(Mn+Fe):P of 1.02:1:1, 113g lithium carbonate and 450.9g ferromanganese phosphate (Mn 0.6 Fe 0.4 Weigh out 68.3g each of the raw materials, including PO4 and glucose.

[0203] 2) Pour 2.5 kg of water and the measured glucose into the sand mill and mechanically stir for 10 minutes until the glucose is completely dissolved.

[0204] 3) Pour the measured ferromanganese phosphate and lithium carbonate into the sand mill and perform sanding dispersion for 2 hours.

[0205] 4) The slurry obtained by the above sanding dispersion can be spray-dried to obtain a precursor powder of lithium ferromanganese phosphate (LMFP) / C.

[0206] 5) The LMFP / C precursor powder is first pre-baked at 350°C for 2 hours in an inert atmosphere, and then secondary sintered at 600°C for 10 hours to finally obtain the LMFP / C cathode material.

[0207] The above LMFP / C cathode material, conductive carbon nanotubes, conductive carbon black, adhesive polyvinylidene fluoride, and solvent N-methylpyrrolidone are arranged as a cathode slurry, with a mass ratio of 91.5:1.5:1.0:6. The cathode slurry is applied to aluminum foil, then vacuum-fired and punched out to produce an LMFP / C cathode piece. Using the LMFP / C as the cathode, the lithium piece as the anode, and a 1 mol / LLiPF6 ethylene carbonate EC / dimethyl carbonate DMC / methyl ethyl carbonate EMC solution as the electrolyte, a button cell is assembled, and a charge-discharge test (charge-discharge window 2.5V~4.3V) is performed on the battery to obtain the electrical performance of lithium ferromanganese phosphate. The results are shown in Table 1 below, the results for Example 1 are shown in Figures 19-20, the results for Example 8 are shown in Figures 33-34, and the results for Example 14 are shown in Figures 50-51.

[0208] [Table 1]

[0209] The above embodiments are merely for illustrating the technical idea and features of the present invention, and their purpose is to enable a person familiar with this art to understand and implement the present invention, but not to limit the scope of protection of the present invention. Any substantially equivalent modifications or alterations made in accordance with the idea of ​​the present invention should be included within the scope of protection of the present invention.

Claims

1. The chemical formula is Mn １－ｘ Fe ｘ PO ４ It is ferromanganese phosphate, 0.01 ≤ x ≤ 0.99, and the ferromanganese phosphate has a particle size of 50 nm or less and a porous structure. The ferromanganese phosphate has a specific surface area of ​​10 to 30 m² / g and a pore size of 2 to 10 nm. Ferromanganese phosphate, characterized by its features.

2. The particle size of the ferromanganese phosphate is 40 nm or less. Ferromanganase phosphate according to claim 1, characterized by the feature.

3. The particle size of the ferromanganese phosphate is 5 to 40 nm. Ferromanganase phosphate according to claim 1, characterized by the feature.

4. The ferromanganese phosphate has a specific surface area of ​​12 to 18 m². ２ The pore size is 3-5 nm, and the pore size is 3-5 nm. Ferromanganase phosphate according to claim 1, characterized by the feature.

5. 0.1 ≤ x ≤ 0.9, and / or the ferromanganese phosphate is in a monoclinic crystalline form. Ferromanganase phosphate according to claim 1, characterized by the feature.

6. Phosphate-based materials, The chemical formula of the phosphate-based material is Mn １－ａ－ｂ Fe ａ M ｂ PO ４ where M is one or a combination of more than one selected from magnesium, titanium, vanadium, chromium, cobalt, nickel, zinc, gallium, aluminum, zirconium, niobium, molybdenum, tin, antimony, calcium, barium, strontium, boron, ruthenium, silicon, tellurium, niobium, copper and lithium, and 0.01 ≦ a ≦ 0.98, 10 －４ ≦ b ≤ 10 －２ The phosphate-based material has a particle size of 50 nm or less and a porous structure. A phosphate-based material characterized by the following features.

7. The particle size of the phosphate-based material is 40 nm or less. The phosphate-based material according to feature 6.

8. The particle size of the phosphate-based material is 5 to 40 nm. The phosphate-based material according to feature 6.

9. The aforementioned phosphate-based material has a specific surface area of ​​10 to 30 m². ２ / g, pore size 2-10 nm The phosphate-based material according to feature 6.

10. The phosphate-based material has a specific surface area of ​​12 to 18 m² / g and a pore size of 3 to 5 nm. The phosphate-based material according to feature 6.

11. 0.2 ≤ a ≤ 0.5, 10 －３ ≤ b ≤ 10 －２ And / or, the phosphate-based material is in a monoclinic crystalline form. The phosphate-based material according to feature 6.

12. The M is cobalt, or the M is magnesium and boron, or the M is molybdenum, niobium and boron, or the M is cobalt, vanadium, nickel and boron, or the M is magnesium, or the M is vanadium and titanium. The phosphate-based material according to feature 6.

13. The chemical formula of the aforementioned phosphate material is Mn １－ａ－ｂ Fe ａ Co ｂ PO ４ And, or Mn １－ａ－ｂ Fe ａ Mg ｂ１ B ｂ２ PO ４ And b1 + b2 = b, or Mn １－ａ－ｂ Fe ａ Mo ｂ１ Nb ｂ２ B ｂ３ PO ４ And b1 + b2 + b3 = b, or Mn １－ａ－ｂ Fe ａ Co ｂ１ V ｂ２ Ni ｂ３ B ｂ４ PO ４ And b1 + b2 + b3 + b4 = b, or Mn １－ａ－ｂ Fe ａ Mg ｂ PO ４ And, or Mn １－ａ－ｂ Fe ａ V ｂ１ Ti ｂ２ PO ４ And b1 + b2 = b, 10 －４ ≤ b1 ≤ 10 －２ , 10 －４ ≤ b² ≤ 10 －２ , 10 －４ ≤ b3 ≤ 10 －２ , 10 －４ ≤ b4 ≤ 10 －２ That is The phosphate-based material according to feature 6.

14. The chemical formula of the aforementioned phosphate material is Mn ０．６ Fe ０．３９５ Co ０．００５ PO ４ or Mn ０．６５ Fe ０．３４４ Mg ０．００５ B ０．００１ PO ４ or Mn ０．７ Fe ０．２９３ Mo ０．００３ Nb ０．００３ B ０．００１ PO ４ or Mn ０．８ Fe ０．１９ Co ０．００５ V ０．００１ Ni ０．００１ B ０．００３ PO ４ or Mn ０．５ Fe ０．４９５ Mg ０．００５ PO ４ or Mn ０．６５ Fe ０．３４ V ０．００５ Ti ０．００５ PO ４ That is The phosphate-based material according to feature 6.

15. The aforementioned M is five or more selected from magnesium, titanium, vanadium, chromium, cobalt, nickel, zinc, gallium, aluminum, zirconium, niobium, molybdenum, tin, antimony, calcium, barium, strontium, boron, ruthenium, silicon, tellurium, niobium, copper, and lithium. The phosphate-based material according to feature 6.

16. The chemical formula of the phosphate-based material is Mn １－ａ－ｂ Fe ａ Mg ｂ１ V ｂ２ Ti ｂ３ Cr ｂ４ Co ｂ５ PO ４ , Mn １－ａ－ｂ Fe ａ Zn ｂ１ Cu ｂ２ Mg ｂ３ Co ｂ４ Ti ｂ５ PO ４ , Mn １－ａ－ｂ Fe ａ Zn ｂ１ Cu ｂ２ Mg ｂ３ Mo ｂ４ Ti ｂ５ PO ４ , Mn １－ａ－ｂ Fe ａ Mg ｂ１ V ｂ２ Ti ｂ３ Cr ｂ４ Mo ｂ５ PO ４ 、Mn １－ａ－ｂ Fe ａ Nb ｂ１ B[[ID=…]]​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​Therefore, b1 + b2 + b3 + b4 + b5 = b, and the range of b1 to b5 is 10 each. －４ ≤ b1 ≤ 10 －２ , 10 －４ ≤ b² ≤ 10 －２ , 10 －４ ≤ b3 ≤ 10 －２ , 10 －４ ≤ b4 ≤ 10 －２ , 10 －４ ≤ b5 ≤ 10 －２ That is The phosphate-based material according to feature 6.

17. The chemical formula of the aforementioned phosphate material is Mn ０．７ Fe ０．２９３ Mg ０．０１５ V ０．００１ Ti ０．０００５ Cr ０．００１ Co ０．００３ PO ４ Mn ０．６ Fe ０．３９５ Zn ０．００１ Cu ０．０００５ Mg ０．００１ Co ０．００２ Ti ０．０００５ PO ４ Mn ０．６ Fe ０．３９ Zn ０．００１ Cu ０．０００５ Mg ０．００５ Mo ０．００３ Ti ０．０００５ PO ４ Mn ０．７ Fe ０．２９３ Mg ０．００１５ V ０．００１ Ti ０．０００５ Cr ０．００１ Mo ０．００３ PO ４ Mn ０．７ Fe ０．２９ Nb ０．００３ B ０．００３ Co ０．００１ V ０．００２ Al ０．００１ PO ４ Mn ０．８ Fe ０．１９ Co ０．００５ V ０．００１ Ni ０．０００５ B ０．００３ Nb ０．０００５ PO ４ Mn ０．５ Fe ０．４９ Co ０．００２５ Ga ０．０００５ B ０．００３ Al ０．００２ Sr ０．００２ PO ４ or Mn ０．６５ Fe ０．３４ Mo ０．００３ Co ０．００３ Ni ０．００２ V ０．００１５ Ca ０．０００５ PO ４ That is The phosphate-based material according to feature 6.

18. A method for producing phosphate-based materials, The aforementioned manufacturing method is Step 1) A step of obtaining a reaction mixture by mixing manganese iron oxide and a compound of any element M with phosphoric acid, Step 2) A step of polishing the reaction mixture, reacting the reaction mixture to produce phosphate, and obtaining a slurry containing phosphate, wherein the particle size of the phosphate in the slurry is 100 nm or less. Step 3) A step of separating the slurry and obtaining phosphate particles, Step 4) A step of drying and sintering the phosphate particles to obtain the phosphate-based material, The element M is one or more combinations selected from magnesium, titanium, vanadium, chromium, cobalt, nickel, zinc, gallium, aluminum, zirconium, niobium, molybdenum, tin, antimony, calcium, barium, strontium, boron, ruthenium, silicon, tellurium, niobium, copper, and lithium. A method for producing phosphate-based materials characterized by the following:

19. The average particle size of the manganese iron oxide is 1 to 20 μm, and / or the phosphoric acid exists in the form of an aqueous phosphoric acid solution, the mass concentration of the aqueous phosphoric acid solution is 10% to 70%. A method for producing a phosphate-based material according to feature 18.

20. In step 1), the mixing is carried out by mechanical stirring at a temperature of 20 to 40°C, and / or, In step 2), the polishing is performed in a sand mill, the polishing temperature is 20 to 40°C, and / or In step 4), the drying temperature is 100 to 120°C, and / or, In step 4), the sintering temperature is 300 to 400°C, and / or, Step 3) includes a step of filtering and washing the slurry. A method for producing a phosphate-based material according to feature 18.

21. Step 4) includes drying the phosphate particles to obtain manganese ferric phosphate monohydrate crystals or doped manganese ferric phosphate monohydrate crystals having a particle size of 100 nm or less, and further sintering the manganese ferric phosphate monohydrate crystals or doped manganese ferric phosphate monohydrate crystals to obtain the phosphate-based material. A method for producing a phosphate-based material according to feature 18.

22. The ratio of the total amount of the manganese iron oxide and the compound of element M to the amount of the phosphoric acid is 1:1 to 2. A method for producing a phosphate-based material according to feature 18.

23. The above manufacturing method further includes, before step 1), a step of pre-dispersing the iron manganese oxide in an aqueous dispersant solution. A method for producing a phosphate-based material according to feature 18.

24. The aqueous dispersant solution is one or more combinations selected from polyvinylpyrrolidone and polyethylene glycol, and / or the mass concentration of the aqueous dispersant solution is 0.01% to 5%. A method for producing a phosphate-based material according to claim 23, characterized by the above.

25. The above manufacturing method further includes, before step 1), a step of reacting phosphorus pentoxide with water to produce the phosphoric acid. A method for producing a phosphate-based material according to feature 18.

26. The compound of element M is one or more combinations selected from magnesium compounds, titanium compounds, vanadium compounds, cobalt compounds, nickel compounds, zinc compounds, gallium compounds, aluminum compounds, zirconium compounds, niobium compounds, molybdenum compounds, tin compounds, antimony compounds, calcium compounds, barium compounds, strontium compounds, boron compounds, ruthenium compounds, silicon compounds, tellurium compounds, niobium compounds, copper compounds, and lithium compounds. A method for producing a phosphate-based material according to any one of claims 18 to 25, characterized by the above.

27. The compound of element M is one or more combinations selected from oxides, carbonates, oxalates, nitrates, sulfates, chlorides, and organic acid salts of element M. A method for producing a phosphate-based material according to any one of claims 18 to 25, characterized by the above.

28. The compound of element M is cobalt chloride, or a combination of magnesium oxide and boric acid, or a combination of molybdenum trioxide, niobium oxalate and boric acid, or a combination of cobalt acetate, ammonium metavanadate, nickel sulfate and boric acid, or magnesium acetate, or a combination of vanadyl oxalate and titanium chloride. A method for producing a phosphate-based material according to any one of claims 18 to 25, characterized by the above.

29. A method for producing a phosphate-based material according to any one of claims 18 to 25, characterized in that the compound of element M is a combination of five or more selected from magnesium compounds, titanium compounds, vanadium compounds, cobalt compounds, nickel compounds, zinc compounds, gallium compounds, aluminum compounds, zirconium compounds, niobium compounds, molybdenum compounds, tin compounds, antimony compounds, calcium compounds, barium compounds, strontium compounds, boron compounds, ruthenium compounds, silicon compounds, tellurium compounds, niobium compounds, copper compounds, and lithium compounds.

30. The compound of element M is a combination of magnesium acetate, ammonium metavanadate, titanium dioxide, cadmium oxide, and cobalt sulfate; or a combination of zinc sulfate, copper oxalate, cobalt acetate, magnesium nitrate, cobalt oxide, and n-butyl titanate; or a combination of zinc oxide, copper oxide, magnesium oxide, molybdenum oxide, and titanium dioxide; or a combination of magnesium oxide, ammonium metavanadate, titanium dioxide, chromium oxide, and molybdenum oxide; or a combination of niobium oxalate, boron oxide, cobalt acetate, ammonium metavanadate, and aluminum oxide; or a combination of cobalt acetate, ammonium metavanadate, nickel acetate, boric acid, and niobium oxalate; or a combination of cobalt chloride, gallium chloride, boric acid, chromium oxide, and strontium chloride; or a combination of molybdenum oxide, cobalt chloride, nickel chloride, vanadium oxalate, and calcium oxide. A method for producing a phosphate-based material according to any one of claims 18 to 25, characterized by the above.

31. Applications of using a phosphate-based material obtained by a method for producing ferromanganese phosphate according to any one of claims 1 to 5, a phosphate-based material according to any one of claims 6 to 17, or a phosphate-based material according to a method for producing a phosphate-based material according to any one of claims 18 to 25, in the manufacture of a battery cathode material.

Images