WO2024207439A1 - 磷酸锰铁锂正极材料及其制备方法、磷酸锰铁前驱体及其制备方法、锂离子电池 - Google Patents

磷酸锰铁锂正极材料及其制备方法、磷酸锰铁前驱体及其制备方法、锂离子电池 Download PDF

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WO2024207439A1
WO2024207439A1 PCT/CN2023/086937 CN2023086937W WO2024207439A1 WO 2024207439 A1 WO2024207439 A1 WO 2024207439A1 CN 2023086937 W CN2023086937 W CN 2023086937W WO 2024207439 A1 WO2024207439 A1 WO 2024207439A1
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lithium
positive electrode
source
electrode material
manganese
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English (en)
French (fr)
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田鑫民
梁策
张朋立
刘亚飞
陈彦彬
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Beijing Easpring Material Technology Co Ltd
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Beijing Easpring Material Technology Co Ltd
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Priority to KR1020247040669A priority Critical patent/KR20250006302A/ko
Priority to PCT/CN2023/086937 priority patent/WO2024207439A1/zh
Priority to JP2024572729A priority patent/JP7792023B2/ja
Priority to EP23931500.5A priority patent/EP4525076A4/en
Publication of WO2024207439A1 publication Critical patent/WO2024207439A1/zh
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/11—Powder tap density
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to the technical field of lithium ion positive electrode material preparation, and in particular to a lithium iron manganese phosphate positive electrode material and a preparation method thereof, a manganese iron phosphate precursor and a preparation method thereof, and a lithium ion battery.
  • lithium-ion batteries are widely used in 3C products such as computers, communication tools and electronic tools, electric vehicles such as EV and PHEV, and energy storage systems.
  • lithium iron phosphate As a lithium-ion battery positive electrode material, lithium iron phosphate has the characteristics of good safety, good stability and low cost, which makes its market share continue to increase.
  • the shortcomings of lithium iron phosphate such as poor electronic conductivity, small lithium ion diffusion coefficient and low energy density limit its further development and application in the field of electric vehicles.
  • lithium iron manganese phosphate As an upgraded product of lithium iron phosphate, lithium iron manganese phosphate has the same specific capacity as lithium iron phosphate (theoretical capacity is 170mAh/g), but the introduction of manganese gives it a higher redox potential, thereby increasing the energy density of the material.
  • the synthesis methods of lithium manganese iron phosphate mainly include high-temperature solid phase method, hydrothermal method and co-precipitation method.
  • the high-temperature solid phase method has a simple process flow and is suitable for industrial production, but it is difficult to achieve uniform mixing of manganese and iron at the atomic level, poor consistency, and uneven particle morphology, which affects the compaction density and discharge capacity.
  • the main advantages of the co-precipitation method are uniform particle composition, adjustable size structure, simple operation and industrial production.
  • the preparation of manganese iron phosphate precursor is the key to synthesizing high-performance materials.
  • CN114057177A discloses a ferromanganese phosphate and a preparation method thereof.
  • a divalent manganese salt and a divalent iron salt are dissolved in water to obtain a mixed salt solution of manganese salt and iron salt; a phosphorus source is added to the mixed salt solution to obtain a precursor solution; an alkali coprecipitation is added to the precursor solution to obtain a ferromanganese phosphate slurry, wherein the ferromanganese phosphate slurry contains ferrous phosphate precipitation and ferromanganese phosphate precipitation; the ferromanganese phosphate slurry is washed, filtered, and dried to obtain ferromanganese phosphate.
  • the samples prepared by this method have phase separation of ferrous phosphate and manganese phosphate, resulting in an inhomogeneous structure; due to the large deviation in the ratio of metal to phosphorus, a phosphorus source needs to be supplemented in the process of preparing the positive electrode material, and it is not easy to regulate the ratio of metal to phosphorus, which limits the performance of the positive electrode material.
  • CN107697899A discloses a method for preparing ferromanganese phosphate, which first precipitates divalent ferromanganese under alkaline conditions, then adds an oxidant to oxidize the divalent ferromanganese into trivalent ferromanganese, and then adds a phosphorus source for phosphate conversion.
  • This preparation method has a complex process, there are too many phase transitions, it is easy to produce defects, and indicators such as precursor particle size and morphology are difficult to control.
  • the technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide a lithium iron manganese phosphate positive electrode material and a preparation method thereof, a ferromanganese phosphate precursor and a preparation method thereof, and a lithium ion battery.
  • the lithium iron manganese phosphate positive electrode material contains specific doping elements and has high purity, and the positive electrode material has a low volume resistivity.
  • the electrochemical performance of the lithium ion battery is effectively improved.
  • the lithium ion battery has a high specific capacity, a high cycle performance, and a high energy density.
  • the first aspect of the present invention provides a lithium iron manganese phosphate positive electrode material, wherein the positive electrode material has a composition shown in Formula I: Li d Mn 1-abc Fe a R b PO 4 /C Formula I;
  • R is selected from at least one of Al, Mg, Ca, Sr, V, Cr, Y, Mo, Nb, B, Al, W, La, Sm, Co, Ni, Cu, Zn, Zr and Ti;
  • the volume resistivity of the positive electrode material is 10-10 4 ⁇ cm
  • a second aspect of the present invention provides a method for preparing a lithium manganese iron phosphate positive electrode material, the preparation method comprising the following steps:
  • the third aspect of the present invention provides a lithium manganese iron phosphate positive electrode material prepared by the above preparation method.
  • a fourth aspect of the present invention provides a ferromanganese phosphate precursor material, wherein the precursor material has a composition shown in Formula II:
  • Mn1-xyFexR1yPzO4 ⁇ nH2O Formula II wherein 0.1 ⁇ x ⁇ 0.5, 0 ⁇ y ⁇ 0.04, 0.95 ⁇ z ⁇ 1.10, 0.95 ⁇ n ⁇ 1.5, and R1 is selected from at least one of Al, Mg, Ca, Sr, V, Cr, Y, Mo, Nb, B, Al, W, La, Sm, Co, Ni, Cu, Zn, Zr and Ti.
  • a fifth aspect of the present invention provides a method for preparing a ferromanganese phosphate precursor, the preparation method comprising the following steps:
  • the ferromanganese phosphate precursor is prepared according to the following steps:
  • a sixth aspect of the present invention provides a ferromanganese phosphate precursor prepared by the above preparation method.
  • a seventh aspect of the present invention provides a lithium-ion battery, comprising the above-mentioned lithium iron manganese phosphate positive electrode material or a positive electrode material made from the above-mentioned lithium iron manganese phosphate precursor.
  • the lithium iron manganese phosphate positive electrode material and its preparation method, the iron manganese phosphate precursor and its preparation method, and the lithium ion battery provided by the present invention achieve the following beneficial effects:
  • the lithium manganese iron phosphate positive electrode material provided by the present invention contains specific doping elements, and the positive electrode material has a low volume resistivity and high purity, which effectively avoids the generation of impurities.
  • the electrochemical properties of the lithium ion battery are effectively improved.
  • the lithium ion battery has a high specific capacity, a high cycle performance and a high energy density.
  • the manganese and iron elements in the lithium manganese iron phosphate positive electrode material provided by the present invention are evenly distributed, and the primary particles are small, the carbon coating is uniform, and the compaction density is high, which can further improve the electrochemical performance of the lithium ion battery.
  • a precursor with a specific composition is mixed with a lithium source, a carbon source and an R2 source and then calcined to obtain the material, wherein the precursor contains a special doping element R1, which can enter the metal site to form nanoparticles with a stable structure, thereby making the prepared lithium iron manganese phosphate positive electrode material have high purity and low volume resistivity.
  • manganese source, iron source, R1 source, phosphorus source and oxidant are used as raw materials, and in particular, a mixed salt solution containing manganese source, iron source, R1 source, phosphorus source solution and oxidant are added to the reactor in a parallel flow form, so that after the metal ions react and oxidize with the oxidant, they quickly combine with phosphate to form a precipitate, which can effectively avoid the disproportionation reaction of trivalent manganese ions in the aqueous solution, and realize oxidation and precipitation; at the same time, the parallel flow into the liquid can avoid the phenomenon of metal segregation caused by the excessive ion concentration in the solution, and realize the uniform co-precipitation of manganese and iron.
  • the metal stoichiometric ratio in the obtained ferromanganese phosphate precursor is stable; the molar ratio of phosphorus to metal P/Me is adjustable; the primary particles are small, the secondary particles are uniform, and the morphology is adjustable; the structure is stable; the synthesis process is simple, environmentally friendly and pollution-free, and suitable for industrial production.
  • the molar ratio K1 of the added amount of phosphorus source and metal manganese source, iron source and R1 source
  • the pH of the phosphorus source solution and the reaction temperature T the molar ratio K of phosphorus to metal in the ferromanganese phosphate precursor is regulated, and then the performance of the lithium iron manganese phosphate positive electrode material is regulated, so that the prepared lithium iron manganese phosphate positive electrode material has excellent electrochemical properties.
  • the preparation method of the lithium iron manganese phosphate positive electrode material provided by the present invention is non-toxic and harmless, has a simple process, readily available raw materials, low equipment requirements, is easy to promote and apply, and can be widely used in the industrial production of lithium iron manganese phosphate positive electrode materials.
  • FIG1 is an XRD diagram of the ferromanganese phosphate precursor prepared in Example 1 of the present invention.
  • FIG2 is a SEM image of the ferromanganese phosphate precursor prepared in Example 1 of the present invention.
  • FIG3 is an EDS distribution diagram of Mn and Fe elements in a cross-section of a manganese ferrophosphate precursor prepared in Example 1 of the present invention
  • FIG4 is an XRD diagram of the lithium iron manganese phosphate positive electrode material prepared in Example 1 of the present invention.
  • FIG. 5 is a SEM image of the lithium manganese iron phosphate positive electrode material prepared in Example 1 of the present invention.
  • any values of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values should be understood to include values close to these ranges or values.
  • the endpoint values of each range, the endpoint values of each range and the individual point values, and the individual point values can be combined with each other to obtain one or more new numerical ranges, which should be regarded as specifically disclosed in this article.
  • a first aspect of the present invention provides a lithium manganese iron phosphate positive electrode material, characterized in that the positive electrode material has a composition shown in Formula I: Li d Mn 1-abc Fe a R b PO 4 /C Formula I;
  • R is selected from at least one of Al, Mg, Ca, Sr, V, Cr, Y, Mo, Nb, B, Al, W, La, Sm, Co, Ni, Cu, Zn, Zr and Ti;
  • the volume resistivity of the positive electrode material is 10-10 4 ⁇ cm
  • the lithium manganese iron phosphate positive electrode material contains specific doping elements, and the positive electrode material has a low volume resistivity, and the positive electrode material has a high purity, and the manganese and iron elements in the lithium manganese iron phosphate positive electrode material are evenly distributed, which effectively avoids the generation of impurity phases.
  • the actual content ratio of the metal Mn element and the Fe element at any position is slightly different from the theoretical content ratio, indicating that the manganese and iron elements in the lithium manganese iron phosphate positive electrode material are evenly distributed without segregation.
  • the lithium manganese iron phosphate positive electrode material is used to prepare a lithium ion battery, the electrochemical performance of the lithium ion battery is effectively improved.
  • the lithium ion battery has a high specific capacity, a high cycle performance and a high energy density.
  • the actual content of Mn element and Fe element at any position in the positive electrode material is m”, which is measured by EDS method.
  • the area of the selected position accounts for 1-30% of the area of the selected positive electrode material particles.
  • it can not only ensure the feasibility of the test, but also effectively avoid the averaging effect, thereby better characterizing the uniformity of the distribution of the Mn element and the Fe element.
  • R is selected from at least one of Al, Co, Ni, Mg, Al, W, Nb, Zr and Ti.
  • R' is selected from at least one of Al, Cu, Zn, Zr and Ti;
  • R" is selected from at least one of Mg, Ca, Sr, V, Cr, Co, Ni,, Y, Mo, Nb, B, W, La and Sm.
  • R' is selected from at least one of Al, Zr and Ti; R" is selected from at least one of Co, Ni, Mg, Y, La, W and Nb.
  • the volume resistivity of the positive electrode material is 10-10 3 ⁇ cm.
  • volume resistivity of the positive electrode material is 10-500 ⁇ cm.
  • the carbon content is 0.5-5wt%.
  • the positive electrode material when the carbon content in the lithium manganese iron phosphate positive electrode material meets the above range, the positive electrode material can have good electronic conductivity, thereby improving the specific capacity, cycle performance and rate performance of the lithium ion battery made from the positive electrode material.
  • the carbon content is 1-3wt%.
  • the compaction density of the positive electrode material is 1.5-3.5 g/cm 3 , preferably 2-3 g/cm 3 .
  • the specific surface area of the positive electrode material is 10-60 m 2 /g, preferably 10-25 m 2 /g.
  • the lithium manganese iron phosphate positive electrode material has a secondary particle structure formed by primary particles.
  • the average particle size of the positive electrode material is 1-50 ⁇ m, preferably 7-15 ⁇ m.
  • the average particle size of the primary particles is 10-500 nm.
  • the positive electrode material has a small primary particle size, which shortens the lithium ion diffusion path and improves the ion conductivity of the positive electrode material. When used in a lithium ion battery, it can effectively improve the electrochemical performance of the lithium ion battery.
  • the average particle size of the primary particles is 10-200 nm.
  • a second aspect of the present invention provides a method for preparing a lithium manganese iron phosphate positive electrode material, characterized in that the preparation method comprises the following steps:
  • R1 and R2 are only used to distinguish the different timings of adding the R source, and do not limit the element type of the R source. Both the R1 source and the R2 source are used to introduce the R source into the positive electrode material.
  • a precursor with a specific composition is mixed with a lithium source, a carbon source and an R2 source and then calcined to obtain a material.
  • the precursor contains a special doping element R1, which can enter the metal site to form nanoparticles with a stable structure, thereby making the prepared lithium iron manganese phosphate positive electrode material have high purity and low volume resistivity.
  • manganese source, iron source, R1 source, phosphorus source and oxidant are used as raw materials.
  • a mixed salt solution containing manganese source, iron source and R1 source, a phosphorus source solution and an oxidant are added to a reactor in a parallel flow form, so that after the metal ions react and oxidize with the oxidant, they quickly combine with phosphate to form a precipitate, which can effectively avoid the disproportionation reaction of trivalent manganese ions in an aqueous solution, and achieve oxidation and precipitation; at the same time, the parallel flow into the liquid can avoid the phenomenon of metal segregation caused by the excessively high ion concentration in the solution, and achieve uniform co-precipitation of manganese and iron.
  • the metal stoichiometric ratio in the obtained ferromanganese phosphate precursor is stable; the molar ratio P/Me of phosphorus to metal is adjustable; the primary particles are small, the secondary particles are uniform, and the morphology is adjustable; the structure is stable; the synthesis process is simple, environmentally friendly and pollution-free, and suitable for industrial production.
  • the ferromanganese phosphate precursor has a composition shown in Formula II:
  • Mn1-xyFexR1yPzO4 ⁇ nH2O Formula II wherein 0.1 ⁇ x ⁇ 0.5, 0 ⁇ y ⁇ 0.04, 0.95 ⁇ z ⁇ 1.10, 0.95 ⁇ n ⁇ 1.5, and R1 is selected from at least one of Al, Mg, Ca, Sr, V, Cr, Y, Mo, Nb, B, Al, W, La, Sm, Co, Ni, Cu, Zn, Zr and Ti.
  • R1 is selected from at least one of Al, Co, Ni, Mg, Al, W, Nb, Zr and Ti.
  • the lithium manganese iron phosphate positive electrode material has a composition as described in Formula I: Li d Mn 1-abc Fe a R b PO 4 PO 4 /C Formula I;
  • R is selected from at least one of Al, Mg, Ca, Sr, V, Cr, Y, Mo, Nb, B, Al, W, La, Sm, Co, Ni, Cu, Zn, Zr and Ti.
  • R is selected from at least one of Al, Co, Ni, Mg, Al, W, Nb, Zr and Ti.
  • the manganese iron element is evenly distributed in the manganese iron phosphate precursor, especially, the metal Mn element and
  • the actual content ratio of the Fe element is slightly different from the theoretical content ratio, indicating that the manganese and iron elements are evenly distributed in the manganese iron phosphate precursor without segregation.
  • the precursor is used to prepare the positive electrode material, the manganese, iron and phosphorus elements in the positive electrode material can be evenly distributed, avoiding the segregation of elements in the positive electrode material, so that the capacity performance and cycle performance of the lithium-ion battery containing the manganese iron phosphate lithium positive electrode material are significantly improved.
  • the actual content of Mn element and Fe element at any position in the precursor is m' measured by EDS method.
  • the area of the selected position accounts for 1-30% of the area of the selected precursor particles.
  • the feasibility of the test can be guaranteed, and the averaging effect can be effectively avoided, so that the uniformity of the distribution of the Mn element and the Fe element can be better characterized.
  • the median particle size D 50 of the ferromanganese phosphate precursor is 0.5-10 ⁇ m, preferably 0.5-5 ⁇ m.
  • the primary particle size of the ferromanganese phosphate precursor is 20-200 nm, preferably 20-100 nm.
  • the tap density of the ferromanganese phosphate precursor is 0.50-1.50 g/cm 3 , preferably 0.80-1.50 g/cm 3 .
  • the specific surface area of the ferromanganese phosphate precursor is 10-100 m 2 /g, preferably 10-40 m 2 /g.
  • K is the ratio of n(P) to [n(Mn)+n(Fe)+n(R1)] in the manganese ferrophosphate precursor
  • K1 is the molar ratio of the amount of the phosphorus source added in terms of n1(P) to the total amount of the manganese source, the iron source and the R1 source added in terms of [n1(Mn)+n1(Fe)+n1(R1)]
  • L is the pH value of the phosphorus source solution
  • T is the temperature of the coprecipitation reaction.
  • the molar ratio K1 of the phosphorus source and the metal manganese source, iron source and R1 source
  • the pH of the phosphorus source solution and the reaction temperature T to satisfy a specific relationship
  • the molar ratio K of phosphorus to metal in the ferromanganese phosphate precursor is regulated, and then the performance of the lithium iron manganese phosphate positive electrode material is regulated, so that the prepared lithium iron manganese phosphate positive electrode material has excellent electrochemical properties.
  • the concentration of the mixed salt is 0.1-4 mol/L, preferably 0.2-2 mol/L.
  • the type of manganese source in step S1 there is no specific limitation on the type of manganese source in step S1, and conventional soluble manganese sources in the art may be used, including but not limited to divalent manganese salts.
  • the divalent manganese salt is selected from at least one of manganese sulfate, manganese chloride, manganese nitrate and manganese acetate.
  • the type of the iron source in step S1 is not specifically limited, and conventional soluble iron sources in the art can be used, including but not limited to ferrous iron salts.
  • the ferrous iron salt is selected from at least one of ferrous sulfate, ferrous chloride and ferrous nitrate.
  • R1 source and R2 source there is no specific limitation on the types of R1 source and R2 source.
  • Conventional soluble R-containing compounds in the art that can provide at least one of Al, Mg, Ca, Sr, V, Cr, Y, Mo, Nb, B, Al, W, La, Sm, Co, Ni, Cu, Zn, Zr and Ti can be used, including but not limited to at least one of R-containing sulfates, nitrates, acetates and chlorides.
  • the R source is selected from at least one of titanyl sulfate, zirconium nitrate and aluminum sulfate.
  • the types of R1 source and R2 source are different.
  • the R1 source is selected from a soluble R-containing compound that can provide at least one of Al, Cu, Zn, Zr and Ti;
  • the R2 source is selected from a compound that can provide at least one element among Mg, Ca, Sr, V, Cr, Co, Ni, Y, Mo, Nb, B, W, La and Sm.
  • the concentration of the phosphorus source solution is 0.2-20 mol/L, preferably 1-15 mol/L.
  • the type of phosphorus source in step S2 is not specifically limited, and a conventional soluble phosphorus source in the art can be used, including but not limited to one of phosphoric acid, sodium phosphate, sodium dihydrogen phosphate, sodium monohydrogen phosphate, ammonium dihydrogen phosphate and ammonium monohydrogen phosphate, preferably at least one selected from phosphoric acid, sodium dihydrogen phosphate and ammonium dihydrogen phosphate.
  • step S2 the pH value of the phosphorus source solution is 0-3, preferably, the pH value of the phosphorus source solution is 1.5-2.5.
  • the type of pH adjuster in step S2 is not specifically limited, as long as it can achieve the purpose of adjusting the pH value of the phosphorus source solution.
  • the pH adjuster is an acid solution or an alkaline solution.
  • the pH adjuster is selected from hydrogen At least one of sodium oxide, ammonia water, sulfuric acid, hydrochloric acid and nitric acid.
  • there is no particular limitation on the amount of the pH adjuster as long as the pH value of the phosphoric acid solution can meet the above range.
  • step S3 the molar ratio of the added amount of the phosphorus source measured in n1(P) to the total added amount of the manganese source, the iron source and the sources measured in [n1(Mn)+n1(Fe)+n1(R1)] is 1-5:1.
  • the molar ratio of P/Me in the positive electrode material can be controlled, thereby achieving the regulation of the performance of the lithium iron manganese phosphate positive electrode material, so that the prepared lithium iron manganese phosphate positive electrode material has excellent electrochemical properties.
  • step (3) the molar ratio of the added amount of the phosphorus source, measured as n1(P), to the total added amount of the manganese source, the iron source and the R1 source, measured as [n1(Mn)+n1(Fe)+n1(R1)], is 1-3:1.
  • step S3 the ratio of the amount of the oxidant added to the molar amount of the total amount of the manganese source, the iron source and the R1 source added calculated as [n1(Mn)+n1(Fe)+n1(R1)] is 1-10:1.
  • the lithium-ion batteries can have high specific capacity, high cycle performance and high energy density.
  • step S3 the molar ratio of the added amount of the oxidant to the total added amount of the manganese source, the iron source and the R1 source calculated as [n1(Mn)+n1(Fe)+n1(R1)] is 1-5:1.
  • the type of the oxidant in step S3 is not specifically limited, and conventional oxidants in the art can be used, including but not limited to ozone, potassium permanganate, sodium persulfate, ammonium persulfate, sodium hypochlorite, and sodium ferrate.
  • the oxidant is selected from at least one of ozone, potassium permanganate, sodium persulfate, and ammonium persulfate.
  • the speed at which the mixed salt solution, phosphorus source solution and oxidant flow into the reactor in step S3 is not specifically limited, and the conventional speed in the art can be used as long as ferromanganese can be uniformly co-precipitated.
  • the coprecipitation reaction is carried out under stirring conditions.
  • the stirring speed is 200-800 r/min, preferably 400-800 r/min.
  • an aging reaction is performed.
  • the conditions of the aging reaction include: an aging temperature of 30-90° C. and an aging time of 1-10 h.
  • the conditions of the aging reaction include: an aging temperature of 60-90° C. and an aging time of 3-6 h.
  • the washing detergent is water at 20-90°C.
  • the washing detergent is water at 60-90°C.
  • the detergent used for washing is pure water.
  • drying conditions include: drying temperature of 80-150° C. and drying time of 3-6 hours.
  • mixing is carried out in the presence of a solvent so that the manganese iron phosphate precursor, lithium source, carbon source and R2 source are fully and evenly mixed, so that the prepared manganese iron phosphate lithium positive electrode material has a higher purity and a low volume resistivity.
  • the solvent can be water, ethanol, etc.
  • the solvent is water.
  • the amount of the solvent which is also based on the ability to form a uniform slurry.
  • the lithium source is selected from at least one of lithium hydroxide, lithium carbonate, lithium dihydrogen phosphate, lithium oxalate, lithium nitrate and lithium acetate.
  • the lithium source is selected from at least one of lithium hydroxide, lithium carbonate and lithium dihydrogen phosphate.
  • the carbon source is selected from at least one of glucose, sucrose, fructose, cellulose, starch, citric acid, polyacrylic acid, polyethylene glycol and dopamine.
  • the carbon source is selected from at least one of glucose, sucrose, starch and cellulose.
  • the method for removing the solvent from the mixed slurry there is no particular limitation on the method for removing the solvent from the mixed slurry, and conventional methods in the art may be used.
  • the solvent in the mixed slurry may be removed by direct evaporation, and the evaporation temperature and process may adopt existing technologies known to those skilled in the art.
  • static drying or spray drying may be used to remove the solvent from the mixed slurry.
  • the calcination conditions include: a calcination temperature of 500-1000° C. and a calcination time of 4-20 hours.
  • the calcination conditions include: a calcination temperature of 600-800° C. and a calcination time of 6-12 h.
  • the protective atmosphere is selected from nitrogen atmosphere and/or argon atmosphere.
  • the third aspect of the present invention provides a lithium manganese iron phosphate positive electrode material obtained by the preparation method.
  • a fourth aspect of the present invention provides a ferromanganese phosphate precursor, characterized in that the precursor material has a composition shown in Formula II:
  • Mn1-xyFexR1yPzO4 ⁇ nH2O Formula II wherein 0.1 ⁇ x ⁇ 0.5, 0 ⁇ y ⁇ 0.04, 0.95 ⁇ z ⁇ 1.10, 0.95 ⁇ n ⁇ 1.5, and R1 is selected from at least one of Al, Mg, Ca, Sr, V, Cr, Y, Mo, Nb, B, Al, W, La, Sm, Co, Ni, Cu, Zn, Zr and Ti.
  • R is selected from at least one of Al, Co, Ni, Mg, Al, W, Nb, Zr and Ti.
  • the median particle size of the ferromanganese phosphate precursor is 0.5-10 ⁇ m, preferably 0.5-10 ⁇ m.
  • the primary particle size of the ferromanganese phosphate precursor is 20-200 nm, preferably 20-100 nm.
  • the tap density of the ferromanganese phosphate precursor is 0.5-1.5 g/cm 3 , preferably 0.8-1.5 g/cm 3 .
  • the specific surface area of the ferromanganese phosphate precursor is 10-100 m 2 /g, preferably 10-40 m 2 /g.
  • a fifth aspect of the present invention provides a method for preparing a ferromanganese phosphate precursor, characterized in that the preparation method comprises the following steps:
  • the ferromanganese phosphate precursor is prepared according to the following steps:
  • K is the ratio of n1(P) to [n1(Mn)+n1(Fe)+n1(R1)] in the manganese ferrophosphate precursor
  • K1 is the molar ratio of the amount of the phosphorus source added in terms of n1(P) to the total amount of the manganese source, the iron source and the R1 source added in terms of [n1(Mn)+n1(Fe)+n1(R1)]
  • L is the pH value of the phosphorus source solution
  • T is the temperature of the coprecipitation reaction.
  • the concentration of the mixed salt is 0.1-4 mol/L, preferably 0.2-2 mol/L.
  • the type of manganese source in step (1) is not specifically limited, and conventional soluble manganese sources in the art can be used, including but not limited to divalent manganese salts.
  • the divalent manganese salt is selected from at least one of manganese sulfate, manganese chloride, manganese nitrate and manganese acetate.
  • the type of the iron source in step (1) is not specifically limited, and conventional soluble iron sources in the art can be used, including but not limited to ferrous iron salts.
  • the ferrous iron salt is selected from at least one of ferrous sulfate, ferrous chloride and ferrous nitrate.
  • R1 source in step (1).
  • a conventional soluble R1 source capable of providing the M element in the art can be used, including but not limited to at least one of sulfates, nitrates, acetates and chlorides containing M.
  • the R1 source is selected from at least one of titanyl sulfate, zirconium nitrate and aluminum sulfate.
  • the concentration of the phosphorus source solution is 0.2-20 mol/L, preferably 1-15 mol/L.
  • the type of phosphorus source in step (2) is not specifically limited, and conventional soluble phosphorus sources in the art can be used, including but not limited to one of phosphoric acid, sodium phosphate, sodium dihydrogen phosphate, sodium monohydrogen phosphate, ammonium dihydrogen phosphate and ammonium monohydrogen phosphate, preferably at least one selected from phosphoric acid, sodium dihydrogen phosphate and ammonium dihydrogen phosphate.
  • the pH value of the phosphorus source solution is 0-3, preferably, the pH value of the phosphorus source solution is 1.5-2.5.
  • the type of pH adjuster in step (2) is not specifically limited, as long as the purpose of adjusting the pH value of the phosphorus source solution can be achieved.
  • the pH adjuster is an acid solution or an alkaline solution.
  • the pH adjuster is selected from at least one of sodium hydroxide, ammonia water, sulfuric acid, hydrochloric acid and nitric acid.
  • the amount of the pH adjuster is not particularly limited, as long as the pH value of the phosphoric acid solution can meet the above range.
  • step (3) the molar ratio of the added amount of the phosphorus source, measured as n1(P), to the total added amount of the manganese source, the iron source and the R1 source, measured as [n1(Mn)+n1(Fe)+n1(R1)], is 1-5:1, preferably 1-3:1.
  • step (3) the ratio of the amount of the oxidant added to the molar amount of the total amount of the manganese source, the iron source and the R1 source added calculated as [n1(Mn)+n1(Fe)+n1(R1)] is 1-10:1, preferably 1-5:1.
  • the type of the oxidant in step (3) is not specifically limited, and conventional oxidants in the art can be used, including but not limited to ozone, potassium permanganate, sodium persulfate, ammonium persulfate, sodium hypochlorite, sodium ferrate.
  • the oxidant is selected from at least one of ozone, potassium permanganate, sodium persulfate and ammonium persulfate.
  • the speed at which the mixed salt solution, phosphorus source solution and oxidant flow into the reactor in step (3) is not specifically limited, and the conventional speed in the art can be used as long as the ferromanganese can be uniformly co-precipitated.
  • the coprecipitation reaction is carried out under stirring conditions.
  • the stirring speed is 200-800 r/min, preferably 400-800 r/min.
  • an aging reaction is performed after the coprecipitation reaction.
  • the conditions of the aging reaction include: an aging temperature of 30-90° C. and an aging time of 1-10 h.
  • the conditions of the aging reaction include: an aging temperature of 60-90° C. and an aging time of 3-6 h.
  • the washing detergent is water at 20-90°C.
  • the washing detergent is water at 60-90°C.
  • the detergent used for washing is pure water.
  • the drying conditions include: drying temperature of 50-300° C., and drying time of 2-8 hours.
  • drying conditions include: drying temperature of 80-200° C. and drying time of 3-6 hours.
  • a sixth aspect of the present invention provides a ferromanganese phosphate precursor prepared by the above preparation method.
  • a seventh aspect of the present invention provides a lithium-ion battery, comprising the above-mentioned lithium iron manganese phosphate positive electrode material or a positive electrode material made from the above-mentioned lithium iron manganese phosphate precursor.
  • Particle size test measured using Malvern laser particle size analyzer Mastersizer 2000.
  • Morphology test measured by scanning electron microscope S-4800 of Hitachi HITACHI of Japan.
  • the actual content of Mn and Fe at any position in the cathode material precursor is m' and the actual content of Mn and Fe at any position in the cathode material is m", which are measured by the 50mm2 EDS test of the Oxford spectrometer manufacturer.
  • Specific surface area measured by the Tristar II3020 specific surface area tester of Micromertics, USA;
  • Tap density measured by the tap density tester of BT-30 of Baxter Company.
  • Compacted density Measured by Mitsubishi Chemical's MCP-PD51 compacted density meter.
  • the volume resistivity of the positive electrode material was measured using the MCP-PD51 powder compaction resistance tester produced by Mitsubishi Chemical of Japan.
  • Carbon content The carbon content in the positive electrode material is measured using the CS-i carbon-sulfur analyzer from Elt, Germany.
  • the content of each element in the positive electrode material and precursor was measured using Agilent’s 5800 ICP-OES spectrometer.
  • the raw materials used in the examples and comparative examples are all commercially available products.
  • reaction slurry is filtered and washed with pure water twice the volume of the slurry to obtain a filter cake.
  • the filter cake is dried at 105° C. for 3 hours to obtain a manganese iron phosphate precursor P1.
  • the composition of the ferromanganese phosphate precursor P1 is Mn 0.648 Fe 0.342 Ti 0.01 P 1.04 O 4 ⁇ H 2 O, the median particle size D 50 is 2.36 ⁇ m, the tap density is 0.96 g/cm 3 , and the specific surface area is 26.6 m 2 /g.
  • the composition of lithium manganese iron phosphate positive electrode material A1 is Li 1.04 Mn 0.642 Fe 0.339 Ti 0.01 Mg 0.01 PO 4 /C, the average particle size of its primary particles is 80 nm, the compaction density is 2.15 g/cm 3 , the specific surface area is 18.6 m 2 /g, and the carbon content is 1.84 wt %.
  • reaction slurry is filtered and washed with pure water twice the volume of the slurry to obtain a filter cake.
  • the filter cake is dried at 105° C. for 3 hours to obtain a manganese iron phosphate precursor P2.
  • the composition of the ferromanganese phosphate precursor P2 is Mn 0.652 Fe 0.338 Ti 0.01 P 1.09 O 4 ⁇ H 2 O, the median particle size D 50 is 1.65 ⁇ m, the tap density is 1.14 g/cm 3 , and the specific surface area is 26.5 m 2 /g.
  • the composition of lithium manganese iron phosphate positive electrode material A2 is Li 1.03 Mn 0.645 Fe 0.335 Ti 0.01 Mg 0.01 PO 4 /C, the average particle size of the primary particles is 60 nm, the compaction density is 2.20 g/cm 3 , the specific surface area is 21.2 m 2 /g, and the carbon content is 2.09 wt %.
  • reaction slurry is filtered and washed with pure water twice the volume of the slurry to obtain a filter cake.
  • the filter cake is dried at 105° C. for 3 hours to obtain a manganese iron phosphate precursor P3.
  • the composition of the ferromanganese phosphate precursor P3 is Mn 0.647 Fe 0.343 Ti 0.01 P 1.02 O 4 ⁇ H 2 O, the median particle size D 50 is 3.78 ⁇ m, the tap density is 1.02 g/cm 3 , and the specific surface area is 22.1 m 2 /g.
  • the composition of lithium manganese iron phosphate positive electrode material A3 is Li 1.03 Mn 0.640 Fe 0.340 Ti 0.01 Mg 0.01 PO 4 /C, the average particle size of the primary particles is 80 nm, the compaction density is 2.19 g/cm 3 , the specific surface area is 18.3 m 2 /g, and the carbon content is 2.08 wt %.
  • reaction slurry is filtered and washed with pure water twice the volume of the slurry to obtain a filter cake.
  • the filter cake is dried at 105° C. for 3 hours to obtain a manganese iron phosphate precursor P4.
  • the composition of the ferromanganese phosphate precursor P4 is Mn 0.748 Fe 0.242 Ti 0.01 P 0.99 O 4 ⁇ H 2 O, the median particle size D 50 is 2.12 ⁇ m, the tap density is 0.98 g/cm 3 , and the specific surface area is 23.6 m 2 /g.
  • the composition of lithium manganese iron phosphate positive electrode material A4 is Li 1.03 Mn 0.740 Fe 0.240 Ti 0.01 Mg 0.01 PO 4 /C, the average particle size of its primary particles is 80 nm, the compaction density is 2.26 g/cm 3 , the specific surface area is 18.4 m 2 /g, and the carbon content is 1.94 wt %.
  • reaction slurry is filtered and washed with pure water twice the volume of the slurry to obtain a filter cake.
  • the filter cake is dried at 105° C. for 3 hours to obtain a manganese iron phosphate precursor P5.
  • the composition of the manganese ferrophosphate precursor P5 is Mn 0.703 Fe 0.287 Al 0.01 P 0.99 O 4 ⁇ H 2 O, and the median particle size D 50 is 2.34 ⁇ m.
  • the tap density is 1.26 g/cm 3 and the specific surface area is 18.8 m 2 /g.
  • the composition of lithium manganese iron phosphate positive electrode material A5 is Li 1.03 Mn 0.696 Fe 0.284 Al 0.01 Nb 0.01 PO 4 /C, the average particle size of the primary particles is 90 nm, the compaction density is 2.15 g/cm 3 , the specific surface area is 18.3 m 2 /g, and the carbon content is 1.92 wt %.
  • reaction slurry is filtered and washed with pure water twice the volume of the slurry to obtain a filter cake.
  • the filter cake is dried at 105° C. for 3 hours to obtain a manganese iron phosphate precursor P6.
  • the composition of the ferromanganese phosphate precursor P6 is Mn 0.698 Fe 0.292 Zr 0.01 P 1.02 O 4 ⁇ H 2 O, the median particle size D 50 is 3.08 ⁇ m, the tap density is 1.18 g/cm 3 , and the specific surface area is 20.6 m 2 /g.
  • the chemical formula of lithium manganese iron phosphate positive electrode material A7 is Li 1.03 Mn 0.691 Fe 0.289 Zr 0.01 W 0.01 PO 4 /C, the average particle size of its primary particles is 120 nm, the compaction density is 2.23 g/cm 3 , the specific surface area is 15.8 m 2 /g, and the carbon content is 2.10 wt %.
  • reaction slurry is filtered and washed with pure water twice the volume of the slurry to obtain a filter cake.
  • the filter cake is dried at 105° C. for 3 hours to obtain a manganese iron phosphate precursor P7.
  • the composition of the ferromanganese phosphate precursor P7 is Mn 0.649 Fe 0.341 Ti 0.01 P 1.03 O 4 ⁇ H 2 O, the median particle size D 50 is 2.15 ⁇ m, the tap density is 0.93 g/cm 3 , and the specific surface area is 28.9 m 2 /g.
  • the composition of lithium manganese iron phosphate positive electrode material A7 is Li 1.04 Mn 0.642 Fe 0.338 Ti 0.01 Al 0.01 PO 4 /C, the average particle size of the primary particles is 85 nm, the compaction density is 2.10 g/cm 3 , the specific surface area is 19.7 m 2 /g, and the carbon content is 1.86 wt %.
  • reaction slurry is filtered and washed with pure water twice the volume of the slurry to obtain a filter cake.
  • the filter cake is dried at 105° C. for 3 hours to obtain a manganese iron phosphate precursor P8.
  • the composition of the ferromanganese phosphate precursor P8 is Mn 0.651 Fe 0.339 Ti 0.01 P 1.02 O 4 ⁇ H 2 O, the median particle size D 50 is 2.87 ⁇ m, the tap density is 0.99 g/cm 3 , and the specific surface area is 22.6 m 2 /g.
  • the composition of lithium manganese iron phosphate positive electrode material A8 is Li 1.04 Mn 0.644 Fe 0.336 Ti 0.01 Zr 0.01 PO 4 /C, the average particle size of the primary particles is 70 nm, the compaction density is 2.21 g/cm 3 , the specific surface area is 16.8 m 2 /g, and the carbon content is 1.80 wt %.
  • reaction slurry is filtered and washed with pure water twice the volume of the slurry to obtain a filter cake.
  • the filter cake is dried at 105° C. for 3 hours to obtain a manganese ferrophosphate precursor P9.
  • the composition of the ferromanganese phosphate precursor P9 is Mn 0.647 Fe 0.343 Ti 0.01 P 1.04 O 4 ⁇ H 2 O, the median particle size D 50 is 2.48 ⁇ m, the tap density is 0.97 g/cm 3 , and the specific surface area is 26.2 m 2 /g.
  • the composition of lithium manganese iron phosphate positive electrode material A9 is Li 1.04 Mn 0.647 Fe 0.343 Ti 0.01 PO 4 /C, the average particle size of the primary particles is 90 nm, the compaction density is 2.08 g/cm 3 , the specific surface area is 18.8 m 2 /g, and the carbon content is 1.78 wt %.
  • reaction slurry is filtered and washed with pure water twice the volume of the slurry to obtain a filter cake.
  • the filter cake is dried at 105° C. for 3 hours to obtain a manganese iron phosphate precursor P10.
  • the composition of the ferromanganese phosphate precursor P10 is Mn 0.650 Fe 0.348 P 1.04 O 4 ⁇ H 2 O, the median particle size D 50 is 4.88 ⁇ m, the tap density is 0.86 g/cm 3 , and the specific surface area is 23.2 m 2 /g.
  • the composition of lithium manganese iron phosphate positive electrode material A10 is Li 1.04 Mn 0.645 Fe 0.345 Mg 0.01 PO 4 /C, the average particle size of the primary particles is 250 nm, the compaction density is 2.05 g/cm 3 , the specific surface area is 24.8 m 2 /g, and the carbon content is 1.86 wt %.
  • reaction slurry is filtered and washed with pure water twice the volume of the slurry to obtain a filter cake.
  • the filter cake is dried at 105° C. for 3 hours to obtain a manganese iron phosphate precursor DP1.
  • the composition of the ferromanganese phosphate precursor DP1 is Mn 0.602 Fe 0.388 Ti 0.01 P 0.95 O 4 ⁇ H 2 O, the median particle size D 50 is 3.85 ⁇ m, the tap density is 0.88 g/cm 3 , and the specific surface area is 61.5 m 2 /g.
  • the composition of lithium manganese iron phosphate positive electrode material D1 is Li 1.04 Mn 0.596 Fe 0.384 Ti 0.01 Mg 0.01 PO 4 /C, the average particle size of primary particles is 1000 nm, the compaction density is 1.85 g/cm 3 , the specific surface area is 36.5 m 2 /g, and the carbon content is 1.75 wt %.
  • reaction slurry is filtered and washed with pure water twice the volume of the slurry to obtain a filter cake.
  • the filter cake is dried at 105° C. for 3 hours to obtain a manganese iron phosphate precursor DP2.
  • the composition of the ferromanganese phosphate precursor DP2 is Mn 0.613 Fe 0.377 Ti 0.01 P 0.92 O 4 ⁇ H 2 O, the median particle size D 50 is 3.65 ⁇ m, the tap density is 0.68 g/cm 3 , and the specific surface area is 52.5 m 2 /g.
  • the chemical formula of lithium manganese iron phosphate positive electrode material is Li 1.04 Mn 0.607 Fe 0.373 Ti 0.01 Mg 0.01 PO 4 /C, the average particle size of its primary particles is 600nm, the compaction density is 1.77g/cm 3 , the specific surface area is 32.5m 2 /g, and the carbon content is 1.18wt%.
  • reaction slurry is filtered and washed with pure water twice the volume of the slurry to obtain a filter cake.
  • the filter cake is dried at 105° C. for 3 hours to obtain a manganese ferrophosphate precursor DP3.
  • the composition of the ferromanganese phosphate precursor DP3 is (Mn 0.621 Fe 0.369 Ti 0.01 ) 3 (PO 4 ) 2 ⁇ H 2 O, the median particle size D 50 is 16.85 ⁇ m, the tap density is 0.34 g/cm 3 , and the specific surface area is 23.5 m 2 /g.
  • the composition of lithium manganese iron phosphate positive electrode material D3 is Li 1.04 Mn 0.615 Fe 0.365 Ti 0.01 Mg 0.01 PO 4 /C, the average particle size of the primary particles is 1.2 ⁇ m, the compaction density is 1.36 g/cm 3 , the specific surface area is 12.8 m 2 /g, and the carbon content is 1.32 wt %.
  • reaction slurry is filtered and washed with pure water twice the volume of the slurry to obtain a filter cake.
  • the filter cake is dried at 105° C. for 3 hours to obtain an iron phosphate precursor DP4.
  • the composition of the iron phosphate precursor DP4 is FePO 4 ⁇ 2H 2 O, the median particle size D 50 is 3.78 ⁇ m, the tap density is 0.78 g/cm 3 , and the specific surface area is 42.3 m 2 /g.
  • the composition of lithium manganese iron phosphate positive electrode material D4 is Li 1.04 Mn 0.643 Fe 0.347 Ti 0.01 PO 4 /C, the average particle size of primary particles is 600 nm, the compaction density is 1.65 g/cm 3 , the specific surface area is 32.8 m 2 /g, and the carbon content is 2.46 wt %.
  • the molar ratio of Mn and Fe at different positions in the precursor in Comparative Examples 1-2 is quite different from the theoretical value, and the ratio at different positions is also quite different. This is because compared with the preparation process of the precursor in Example 1, the precursor preparation process in Comparative Example 1 is to mix the mixed salt solution, the phosphorus source solution and the oxidant, and then perform the pH adjustment process.
  • compositions of the ferromanganese phosphate precursor and the lithium ferromanganese phosphate positive electrode material prepared in the embodiment and the comparative example are shown in Table 3.
  • the molar ratio of Mn and Fe at different positions in the positive electrode material precursor of Comparative Examples 1-2 is quite different from the theoretical value
  • the molar ratio of Mn and Fe at different positions in the positive electrode material of Comparative Examples 1-2 is quite different from the theoretical value, and the ratio at different positions is also quite different.
  • Comparative Example 3 needs to supplement the phosphorus source during the preparation of the positive electrode material, which will cause the ratio of metal and phosphorus to be unevenly distributed and not easy to control, and its volume resistivity is larger.
  • Comparative Example 4 is obtained by mixing iron phosphate and manganese tetraoxide, and the elements cannot be mixed at the atomic level, and the molar ratio of Mn and Fe also has a large deviation.
  • This test example is used to illustrate electrode materials, electrodes, lithium-ion batteries and their preparation methods.
  • (1) Preparation of positive electrode sheet The lithium manganese iron phosphate positive electrode material prepared in the above embodiment and comparative example, the conductive agent carbon nanotubes, and the NMP solution of the binder PVDF are mixed at a mass ratio of 90:5:5.
  • the specific method is: grind the dried positive electrode material and the conductive agent in a mortar for 15 minutes. After grinding evenly, add PVDF solution (mass fraction 5%) according to the proportion, and stir on a magnetic stirrer for 6 hours; evenly apply the obtained paste slurry on the current collector aluminum foil, and then dry it in a vacuum drying oven at 60°C for 20 hours, and then use a pressure of 100MPa to stamp it into a positive electrode sheet with a diameter of 12mm and a thickness of 120 ⁇ m. The pole pieces were placed in a vacuum drying oven at 120°C and dried for 12 hours.
  • a metal lithium sheet with a diameter of 17 mm and a thickness of 1 mm was used as the negative electrode, a polyethylene porous membrane coated with an alumina ceramic layer and a thickness of 25 ⁇ m was used as the separator, and an equal amount of a mixture of 1 mol/L LiPF6, ethylene carbonate (EC) and diethyl carbonate (DEC) was selected as the electrolyte.
  • the positive electrode sheet, separator, negative electrode sheet and electrolyte were assembled into a 2025-type button cell in an Ar gas glove box with a water content and an oxygen content of less than 5 ppm.
  • Electrochemical performance test The battery was charged and discharged using the LAND CT2001A charge and discharge instrument from Wuhan Rambo Electronics Co., Ltd. The charge and discharge voltage range was 2.5 to 4.4 V. The specific capacity of the assembled lithium-ion battery was tested at rates of 0.1C and 1C, respectively, and the cycle performance was tested at a rate of 1C. The test results are shown in Table 6.
  • the positive electrode material prepared by the present invention has good capacity performance, rate performance and cycle stability. This is because the precursor ferromanganese prepared by the present invention is evenly distributed, and the ratio of metal and phosphorus can be adjusted; the precursor doping improves the uniformity of the doping elements.
  • the positive electrode material prepared with the precursor of the present invention as the raw material has the characteristics of small primary particles, uniform carbon coating, low volume resistivity, etc.; it is conducive to the embedding and extraction of lithium ions, so that its 0.1C discharge specific capacity is greater than 150mAh/g, and the 1C discharge specific capacity is greater than 140mAh/g; the dual doping of the precursor and the positive electrode material ensures that its 80-week cycle retention rate is greater than 95%.
  • FIG1 is an XRD diagram of the ferromanganese phosphate precursor prepared in Example 1. It can be seen from FIG1 that the XRD of the ferromanganese phosphate precursor prepared in the present invention is completely consistent with the MnPO 4 ⁇ H 2 O standard card, indicating that phase separation and generation of other impurities do not occur.
  • Figure 2 is an SEM image of the ferromanganese phosphate precursor prepared in Example 1. It can be seen from Figure 2 that the primary particles of the ferromanganese phosphate precursor prepared by the present invention are relatively small. When it is used to prepare lithium ferromanganese phosphate positive electrode material, it is more conducive to uniform mixing with the lithium source and the carbon source, and can make the carbon source evenly coated on the surface of the positive electrode material.
  • FIG3 is an EDS distribution diagram of Mn and Fe in a cross section of the ferromanganese phosphate precursor prepared in Example 1. It can be seen from FIG3 that the ferromanganese in the ferromanganese phosphate precursor prepared in the present invention is evenly distributed.
  • FIG4 is an XRD diagram of the lithium iron manganese phosphate positive electrode material prepared in Example 1. It can be seen from FIG4 that the XRD of the lithium iron manganese phosphate positive electrode material prepared by the present invention corresponds to the standard spectrum, manganese iron does not form a phase separation, and no other impurities are generated.
  • FIG5 is a SEM image of the lithium iron manganese phosphate positive electrode material prepared in Example 1. It can be seen from FIG5 that the primary particles of the lithium iron manganese phosphate positive electrode material are small and uniform, and there is no carbon agglomeration on the surface, indicating that the carbon is evenly coated on the surface of the positive electrode material.

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Abstract

本发明涉及锂离子正极材料制备技术领域，公开了一种磷酸锰铁锂正极材料及其制备方法、磷酸锰铁前驱体及制备方法、锂离子电池。该正极材料具有式I所示的组成： LidMn1-a-b-cFeaRbPO4/C 式I；其中，0.1≤a≤0.5，0≤b≤0.08，0.9<d≤1.2，R选自Al、Mg、Ca、Sr、V、Cr、Y、Mo、Nb、B、Al、W、La、Sm、Co、Ni、Cu、Zn、Zr和Ti中的至少一种；该正极材料的体积电阻率为10-104Ω·cm。该正极材料中包含特定的掺杂元素，并且正极材料具有低的体积电阻率，将其用于制备锂离子电池时，有效改善了锂离子电池的电化学性能。

Description

磷酸锰铁锂正极材料及其制备方法、磷酸锰铁前驱体及其制备方法、锂离子电池 技术领域
技术领域
本发明涉及锂离子正极材料制备技术领域，具体涉及一种磷酸锰铁锂正极材料及其制备方法、磷酸锰铁前驱体及其制备方法、锂离子电池。
背景技术
锂离子电池作为重要的电源系统，广泛地应用于计算机、通讯工具和电子工具等3C产品，EV、PHEV等电动汽车领域以及能源储存系统。磷酸铁锂作为一种锂离子电池正极材料，具有安全性好、稳定性好、成本低等特点，使其市场占有率不断提升。然而磷酸铁锂电子电导率差、锂离子扩散系数小、能量密度低等缺点，限制了其在电动汽车领域的进一步发展和应用。磷酸锰铁锂作为磷酸铁锂的升级产品，与磷酸铁锂具有相同的比容量(理论容量为170mAh/g)，但锰的引入使其具有更高的氧化还原电位，从而提高了材料的能量密度。
目前磷酸锰铁锂的合成方法主要包括高温固相法、水热法和共沉淀法等，其中高温固相法工艺流程简单，适合工业化生产，但很难实现锰铁原子级均匀混合、一致性差、颗粒形貌不均一，从而影响压实密度和放电容量。共沉淀法主要的优点是颗粒组分均匀，尺寸结构可调控，操作简单可工业化生产，磷酸锰铁前驱体的制备是合成高性能材料的关键。
目前人们对于磷酸锰铁前驱体的研究比较广泛，CN114057177A公开了一种磷酸亚锰铁及其制备方法，将二价锰盐和二价铁盐溶于水中，得到锰盐和铁盐的混合盐溶液；向所述混合盐溶液中加入磷源，得到前驱体溶液；向所述前驱体溶液中加入碱共沉淀，得到磷酸亚铁锰浆料，所述磷酸亚铁锰浆料中包含磷酸亚铁沉淀及磷酸锰铁沉淀；对所述磷酸亚铁锰浆料进行水洗、过滤、干燥，得到磷酸亚铁锰。该方法制备的样品出现磷酸亚铁和磷酸锰的分相，导致结构不均一；由于金属和磷的比例有较大偏差，在制备正极材料过程中需要补充磷源，不易调控金属和磷的比例，对正极材料性能的发挥有限制。
CN107697899A公开了一种磷酸锰铁的制备方法，首先在碱性条件下进行二价锰铁沉淀，再加入氧化剂将二价锰铁氧化为三价锰铁，随后加入磷源进行磷酸盐转化。此制备方法流程复杂，存在过多物相之间的转变，容易产生缺陷，且前驱体粒度和形貌等指标不易控制。
发明内容
本发明要解决的技术问题是克服现有技术的不足，提供一种磷酸锰铁锂正极材料及其制备方法、磷酸锰铁前驱体及其制备方法、锂离子电池。该磷酸锰铁锂正极材料中包含特定的掺杂元素，具有高的纯度，并且正极材料具有低的体积电阻率，将其用于制备锂离子电池时，有效改善了锂离子电池的电化学性能，具体地，锂离子电池具有高的比容量、高的循环性能以及高的能量密度。
为了实现上述目的，本发明第一方面提供一种磷酸锰铁锂正极材料，所述正极材料具有式I所示的组成：
LidMn1-a-b-cFeaRbPO4/C   式I；
其中，0.1≤a≤0.5，0≤b≤0.08，0.9<d≤1.2，R选自Al、Mg、Ca、Sr、V、Cr、Y、Mo、Nb、B、Al、W、La、Sm、Co、Ni、Cu、Zn、Zr和Ti中的至少一种；
所述正极材料的体积电阻率为10-104Ω·cm；
所述正极材料中任意位置处Mn元素和Fe元素的实际摩尔含量比m”与所述正极材料中任意位置处Mn元素和Fe元素的理论摩尔含量比m之间满足以下关系：
Δmc＝︱m”-m︱/m≤5％。
本发明第二方面提供一种磷酸锰铁锂正极材料的制备方法，所述制备方法包括以下步骤：
S1、将锰源、铁源、R1源与水混合，得到混合盐溶液；
S2、将磷源与水混合，加入pH调节剂，得到磷源溶液；
S3、将所述混合盐溶液、所述磷源溶液和氧化剂以并流的形式加入到反应釜中，进行共沉淀反应，经过滤、洗涤、干燥得到所述磷酸锰铁前驱体；
S4、将所述磷酸锰铁前驱体、锂源、碳源、R2源进行混合，得到混合料；
S5、在保护性气氛的存在下，将混合料进行煅烧，得到所述磷酸锰铁锂正极材料。
本发明第三方面提供一种由上述制备方法制得的磷酸锰铁锂正极材料。
本发明第四方面提供一种磷酸锰铁前驱体材料，所述前驱体材料具有式II所示的组成：
Mn1-x-yFexR1yPzO4·nH2O式II，其中，0.1≤x≤0.5，0≤y≤0.04，0.95≤z≤1.10，0.95≤n≤1.5，R1选自Al、Mg、Ca、Sr、V、Cr、Y、Mo、Nb、B、Al、W、La、Sm、Co、Ni、Cu、Zn、Zr和Ti中的至少一种。
本发明第五方面提供一种磷酸锰铁前驱体的制备方法，所述制备方法包括以下步骤：
所述磷酸锰铁前驱体按照以下步骤制备：
(1)将锰源、铁源、R1源与水混合，得到混合盐溶液；
(2)将磷源与水混合，加入pH调节剂，得到磷源溶液；
(3)将所述混合盐溶液、所述磷源溶液和氧化剂以并流的形式加入到反应釜中，进行共沉淀反应，经过滤、洗涤、干燥得到所述磷酸锰铁前驱体。
本发明第六方面提供一种由上述制备方法制得的磷酸锰铁前驱体。
本发明第七方面提供一种锂离子电池，所述锂离子电池包括上述磷酸锰铁锂正极材料或由上述磷酸锰铁前驱体制得的正极材料。
通过上述技术方案，本发明提供的磷酸锰铁锂正极材料及其制备方法、磷酸锰铁前驱体及其制备方法、锂离子电池获得以下有益的效果：
1、本发明提供的磷酸锰铁锂正极材料中包含特定的掺杂元素，并且正极材料具有低的体积电阻率，且该正极材料具有高的纯度，有效避免了杂相的生成，将其用于制备锂离子电池时，有效改善了锂离子电池的电化学性能，具体地，锂离子电池具有高的比容量、高的循环性能以及高的能量密度。
进一步地，本发明提供的磷酸锰铁锂正极材料中锰铁元素分布均匀，且一次颗粒小、碳包覆均匀、压实密度高，能够进一步改善锂离子电池的电化学性能。
2、本发明提供的磷酸锰铁锂正极材料的制备方法中，将具有特定组成的前驱体与锂源、碳源以及R2源经混合后煅烧制得，其中，前驱体中包含特地的掺杂元素R1，该掺杂元素能够进入金属位点形成具有稳定结构的纳米颗粒，进而使得制得的磷酸锰铁锂正极材料具有高的纯度，并且具有低的体积电阻率。
进一步地，本发明中，以锰源、铁源、R1源、磷源和氧化剂为原料，特别地，将包含锰源、铁源、R1源的混合盐溶液、磷源溶液和氧化剂以并流的形式加入到反应釜中，使金属离子与氧化剂反应氧化后，迅速与磷酸根结合形成沉淀，能够有效避免三价锰离子在水溶液中的歧化反应，实现边氧化边沉淀；同时并流进液能够避免因溶液中离子浓度过高而产生的锰铁先后沉淀，导致金属偏析的现象，实现锰铁进行均匀共沉淀。且制得的磷酸锰铁前驱体中金属化学计量比稳定；磷与金属的摩尔比P/Me可调控；一次颗粒小，二次颗粒均匀，形貌可调控；结构稳定；合成工艺简单，环境友好无污染，适用于工业化生产。
更进一步地，通过控制磷源与金属(锰源、铁源和R1源)的加入量摩尔比K1、磷源溶液的pH以及反应温度T之间满足特定的关系，实现对磷酸锰铁前驱体中磷与金属的摩尔比K的调控，进而实现了对磷酸锰铁锂正极材料性能的调控，使得制得的磷酸锰铁锂正极材料具有优异的电化学性能。
本发明的提供的磷酸锰铁锂正极材料的制备方法无毒无害，工艺简单，原料易得，设备需求低，易于推广和应用，可广泛应用于磷酸锰铁锂正极材料的工业化生产中。
附图说明
图1为本发明实施例1制备得到的磷酸锰铁前驱体XRD图；
图2为本发明实施例1制备得到的磷酸锰铁前驱体SEM图；
图3为本发明实施例1制备得到的磷酸锰铁前驱体剖面Mn、Fe元素EDS分布图；
图4为本发明实施例1制备得到的磷酸锰铁锂正极材料XRD图；
图5为本发明实施例1制备得到的磷酸锰铁锂正极材料SEM图。
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
本发明第一方面提供一种磷酸锰铁锂正极材料，其特征在于，所述正极材料具有式I所示的组成：
LidMn1-a-b-cFeaRbPO4/C  式I；
其中，0.1≤a≤0.5，0≤b≤0.08，0.9<d≤1.2，R选自Al、Mg、Ca、Sr、V、Cr、Y、Mo、Nb、B、Al、W、La、Sm、Co、Ni、Cu、Zn、Zr和Ti中的至少一种；
所述正极材料的体积电阻率为10-104Ω·cm；
所述正极材料中任意位置处Mn元素和Fe元素的实际摩尔含量比m”与所述正极材料中任意位置处Mn元素和Fe元素的理论摩尔含量比m之间满足以下关系：
Δmc＝︱m”-m︱/m≤5％。
本发明中，磷酸锰铁锂正极材料中包含特定的掺杂元素，并且正极材料具有低的体积电阻率，且该正极材料具有高的纯度，并且磷酸锰铁锂正极材料中锰铁元素分布均匀，有效避免了杂相的生成，具体地，任意位置处金属Mn元素和Fe元素的实际含量比值与理论含量比值相差较小，表明磷酸锰铁锂正极材料中锰铁元素均分布，未发生偏析现象，将其用于制备锂离子电池时，有效改善了锂离子电池的电化学性能，具体地，锂离子电池具有高的比容量、高的循环性能以及高的能量密度。
本发明中，所述正极材料中任意位置处Mn元素和Fe元素的实际含量为m”采用EDS方法测得。
本发明中，所述正极材料中任意位置处Mn元素和Fe元素的理论含量摩尔含量比m＝(1-a-b-c)/a。
本发明，Mn元素和Fe元素的实际含量w”测试时，所选自位置的面积占所选正极材料颗粒的面积的1-30％。本发明中，确保测试Mn元素和Fe元素的实际含量m”时所选位置的面积满足上述范围时，既能保证测试的可行性，又能有效地避免平均化效应，从而更能表征出Mn元素和Fe元素的分布的均匀程度。
进一步地，式I中，0.15≤a≤0.45，0<b≤6，0.95<d≤1.15。
进一步地，式I中，R选自Al、Co、Ni、Mg、Al、W、Nb、Zr和Ti中的至少一种。
本发明的一个具体实施方式中，所述磷酸锰铁锂正极材料中包含两种以上不同种类的元素R。具体地，所述磷酸锰铁锂正极材料具有式II所示的组成：
LidMn1-a-b-cFeaR’bR”cPO4/C  式II；
其中，0.1≤a≤0.5，0≤b≤0.04，0≤c≤0.04，0.9<d≤1.2，R’选自Al、Cu、Zn、Zr和Ti中的至少一种；R”选自Mg、Ca、Sr、V、Cr、Co、Ni、、Y、Mo、Nb、B、W、La和Sm中的至少一种。
本发明的一个具体实施方式中，式II中，0.15≤a≤0.45，0<b≤0.03，0<c≤0.03，0.95<d≤1.15。
本发明的一个具体实施方式中，式II中，R’选自Al、Zr和Ti中的至少一种；R”选自Co、Ni、Mg、Y、La、W、Nb中的至少一种。
进一步地，所述正极材料的体积电阻率为10-103Ω·cm。
更进一步地，所述正极材料的体积电阻率为10-500Ω·cm。
根据本发明，以所述磷酸锰铁锂正极材料的总重量为基准，碳含量为0.5-5wt％。
本发明中，当磷酸锰铁锂正极材料中，碳含量满足上述范围时，能够使得正极材料具有良好的电子导电性，进而提高由该正极材料制得的锂离子电池的比容量、循环性能和倍率性能。
进一步地，以所述磷酸锰铁锂正极材料的总重量为基准，碳含量为1-3wt％。
进一步地，Δmc＝︱m”-m︱/m≤3％。
根据本发明，所述正极材料的压实密度为1.5-3.5g/cm3，优选为2-3g/cm3。
根据本发明，所述正极材料的比表面积为10-60m2/g，优选为10-25m2/g。
根据本发明，所述磷酸锰铁锂正极材料具有由一次颗粒形成的二次颗粒结构。
根据本发明，所述正极材料的平均粒度为1-50μm，优选为7-15μm。
根据本发明，所述一次颗粒的平均粒度为10-500nm。
本发明中，所述正极材料具有小的一次颗粒粒径，缩短了锂离子扩散路径，提高了正极材料的离子电导率，将其用于锂离子电池时，能够有效改善锂离子电池的电化学性能。
进一步地，所述一次颗粒的平均粒度为10-200nm。
本发明第二方面提供一种磷酸锰铁锂正极材料的制备方法，其特征在于，所述制备方法包括以下步骤：
S1、将锰源、铁源、R1源与水混合，得到混合盐溶液；
S2、将磷源与水混合，加入pH调节剂，得到磷源溶液；
S3、将所述混合盐溶液、所述磷源溶液和氧化剂以并流的形式加入到反应釜中，进行共沉淀反应，经过滤、洗涤、干燥得到所述磷酸锰铁前驱体；
S4、将所述磷酸锰铁前驱体、锂源、碳源、R2源进行混合，得到混合料；
S5、在保护性气氛的存在下，将混合料进行煅烧，得到所述磷酸锰铁锂正极材料。
本发明中，R1和R2只是为了区分R源加入时机的不同，并不对R源的元素种类进行限定。R1源和R2源均为了在正极材料中引入R源。
本发明中，将具有特定组成的前驱体与锂源、碳源以及R2源经混合后煅烧制得，其中，前驱体中包含特地的掺杂元素R1，该掺杂元素能够进入金属位点形成具有稳定结构的纳米颗粒，进而使得制得的磷酸锰铁锂正极材料具有高的纯度，并且具有低的体积电阻率，将制得的磷酸锰铁锂正极材料用于锂离子电池时，能够有效改善锂离子电池的电化学性能，具体地，使得锂离子电池具有高的比容量、高的循环性能以及高的能量密度。
本发明中，以锰源、铁源、R1源、磷源和氧化剂为原料，特别地，将包含锰源、铁源、R1源的混合盐溶液、磷源溶液和氧化剂以并流的形式加入到反应釜中，使金属离子与氧化剂反应氧化后，迅速与磷酸根结合形成沉淀，能够有效避免三价锰离子在水溶液中的歧化反应，实现边氧化边沉淀；同时并流进液能够避免因溶液中离子浓度过高而产生的锰铁先后沉淀，导致金属偏析的现象，实现锰铁进行均匀共沉淀。且制得的磷酸锰铁前驱体中金属化学计量比稳定；磷与金属的摩尔比P/Me可调控；一次颗粒小，二次颗粒均匀，形貌可调控；结构稳定；合成工艺简单，环境友好无污染，适用于工业化生产。
根据本发明，所述磷酸锰铁前驱体具有式II所示的组成：
Mn1-x-yFexR1yPzO4·nH2O式II，其中，0.1≤x≤0.5，0≤y≤0.04，0.95≤z≤1.10，0.95≤n≤1.5，R1选自Al、Mg、Ca、Sr、V、Cr、Y、Mo、Nb、B、Al、W、La、Sm、Co、Ni、Cu、Zn、Zr和Ti中的至少一种。
进一步地，式II中，0.15≤x≤0.45，0＜y≤0.03，0.95≤z≤1.05，0.95≤n≤1.2，R1选自Al、Co、Ni、Mg、Al、W、Nb、Zr和Ti中的至少一种。
根据本发明，所述磷酸锰铁锂正极材料具有式I所述的组成：
LidMn1-a-b-cFeaRbPO4PO4/C  式I；
其中，0.1≤a≤0.5，0≤b≤0.08，0.9<d≤1.2，R选自Al、Mg、Ca、Sr、V、Cr、Y、Mo、Nb、B、Al、W、La、Sm、Co、Ni、Cu、Zn、Zr和Ti中的至少一种。
进一步地，式I中，0.15≤a≤0.45，0<b≤0.06，0.95<d≤1.15。
进一步地，式I中，R选自Al、Co、Ni、Mg、Al、W、Nb、Zr和Ti中的至少一种。
根据本发明，所述磷酸锰铁前驱体中任意位置处Mn元素和Fe元素的实际摩尔含量比m'与所述磷酸锰铁锂前驱体中任意位置处Mn元素和Fe元素的理论摩尔含量比m0之间满足以下关系：
Δmp＝︱m'-m0︱/m0≤5％。
本发明中，所述磷酸锰铁前驱体中锰铁元素分布均匀，特别地，任意位置处金属Mn元素和 Fe元素的实际含量比值与理论含量比值相差较小，表明磷酸锰铁前驱体中锰铁元素均分布，未发生偏析现象，将该前驱体用于制备正极材料时，能够使得正极材料中锰铁磷元素实现均匀分布，避免正极材料中的元素发生偏析现象，使得包含该磷酸锰铁锂正极材料的锂离子电池的容量性能以及循环性能得到显著改善。
本发明中，磷酸锰铁锂前驱体中任意位置处Mn元素和Fe元素的理论摩尔含量比m0＝(1-x-y)/x。
本发明中，所述前驱体中任意位置处Mn元素和Fe元素的实际含量为m'采用EDS方法测得。
本发明，Mn元素和Fe元素的实际含量m'测试时，所选自位置的面积占所选前驱体颗粒的面积的1-30％。本发明中，确保测试Mn元素和Fe元素的的实际含量m'时所选位置的面积满足上述范围时，既能保证测试的可行性，又能有效地避免平均化效应，从而更能表征出Mn元素和Fe元素的分布的均匀程度。
进一步地，Δmp＝︱m'-m0︱/m0≤3％。
根据本发明，所述磷酸锰铁前驱体的中值粒径D50为0.5-10μm，优选为0.5-5μm。
根据本发明，所述磷酸锰铁前驱体的一次颗粒尺寸为20-200nm，优选为20-100nm。
根据本发明，所述磷酸锰铁前驱体的振实密度为0.50-1.50g/cm3，优选为0.80-1.50g/cm3。
根据本发明，所述磷酸锰铁前驱体的比表面积为10-100m2/g，优选为10-40m2/g。
本发明中，磷酸锰铁前驱体中磷含量与总金属摩尔量的比例K＝0.95-1.10，即式II中的z值。
根据本发明，所述磷酸锰铁前驱体的制备方法满足以下关系：
K＝(0.033K1+0.5)·L-0.3·T0.2-0.05  式III；
其中，K为磷酸锰铁前驱体中n(P)与[n(Mn)+n(Fe)+n(R1)]之比；K1为以n1(P)计所述磷源的加入量，与以[n1(Mn)+n1(Fe)+n1(R1)]计所述锰源、所述铁源和所述R1源的总加入量的摩尔量之比；L为所述磷源溶液的pH值；T为所述共沉淀反应的温度。
本发明中，通过控制磷源与金属(锰源、铁源和R1源)的加入量摩尔比K1、磷源溶液的pH以及反应温度T之间满足特定的关系，实现对磷酸锰铁前驱体中磷与金属的摩尔比K的调控，进而实现了对磷酸锰铁锂正极材料性能的调控，使得制得的磷酸锰铁锂正极材料具有优异的电化学性能。
根据本发明，式III中，0.9≤K1≤2，0＜L≤3，30℃≤T≤90℃。
进一步地，式III中，1≤K1≤1.5，1.5≤L≤2.5，60℃≤T≤90℃。
根据本发明，步骤S1中，所述混合盐的浓度为0.1-4mol/L，优选为0.2-2mol/L。
本发明中，对于步骤S1中锰源的种类不做具体的限定，可以采用本领域中常规的可溶性锰源，包括但不限制于二价锰盐，优选地，所述二价锰盐选自硫酸锰、氯化锰、硝酸锰和醋酸锰中的至少一种。
本发明中，对步骤S1中铁源的种类不做具体的限定，可以采用本领域中常规的可溶性铁源，包括但不限于二价铁盐，优选地，所述二价铁盐选自硫酸亚铁、氯化亚铁和硝酸亚铁中的至少一种。
本发明中，对于R1源和R2源的种类不做具体的限定，可以采用本领域中常规的能够提供Al、Mg、Ca、Sr、V、Cr、Y、Mo、Nb、B、Al、W、La、Sm、Co、Ni、Cu、Zn、Zr和Ti中的至少一种的可溶性含R化合物，包括但不限于含有R的硫酸盐、硝酸盐、乙酸盐和氯化物中的至少一种，优选地，所述R源选自硫酸氧钛、硝酸锆和硫酸铝中的至少一种。
本发明的一个具体实施方式中，R1源和R2源的种类不同，具体地，R1源选自能提供Al、、Cu、Zn、Zr和Ti中的至少一种的可溶性含R化合物；R2源选自能够提供Mg、Ca、Sr、、V、Cr、Co、Ni、、Y、Mo、Nb、B、W、La和Sm中的至少一种元素的化合物。
根据本发明，步骤S2中，所述磷源溶液的浓度为0.2-20mol/L，优选为1-15mol/L。
本发明中，对于步骤S2中磷源的种类不做具体的限定，可以采用本领域中常规的可溶性磷源，包括但不限于磷酸、磷酸钠、磷酸二氢钠、磷酸一氢钠、磷酸二氢铵和磷酸一氢铵中的一种，优选选自磷酸、磷酸二氢钠和磷酸二氢铵中的至少一种。
本发明中，步骤S2中，所述磷源溶液的pH值为0-3，优选地，所述磷源溶液的pH值为1.5-2.5。
本发明中，对于步骤S2中的pH调节剂的种类不做具体的限定，只要能够实现调节磷源溶液的pH值的目的即可，例如，所述pH调节剂为酸溶液或碱溶液，优选地，所述pH调节剂选自氢 氧化钠、氨水、硫酸、盐酸和硝酸中的至少一种。本发明中，对于pH调节剂的用量也没有特别限定，只要能够使得磷酸溶液的pH值满足上述范围即可。
根据本发明，步骤S3中，以n1(P)计所述磷源的加入量，与以[n1(Mn)+n1(Fe)+n1(R1)]计所述锰源、所述铁源和所述源的总加入量的摩尔量之比为1-5:1。
本发明中，通过控制磷源与锰源、铁源以及R1源的总加入量满足上述范围时，能够实现对正极材料中P/Me的摩尔比的可控调节，进而实现了对磷酸锰铁锂正极材料性能的调控，使得制得的磷酸锰铁锂正极材料具有优异的电化学性能。
进一步地，步骤(3)中，以n1(P)计所述磷源的加入量，与以[n1(Mn)+n1(Fe)+n1(R1)]计所述锰源、所述铁源和所述R1源的总加入量的摩尔量之比为1-3:1。
根据本发明，步骤S3中，所述氧化剂的加入量，与以[n1(Mn)+n1(Fe)+n1(R1)]计所述锰源、所述铁源和所述R1源的总加入量的摩尔量之比为1-10:1。
进一步地，控制氧化剂与锰源、铁源以及R1源的总加入量满足上述关系时，能够实现对正极材料中金属元素氧化程度的控制，使得制得的磷酸锰铁锂正极材料具有低的体积电阻率、以及高的纯度，将其用于锂离子电池时，能够使得锂离子电池具有高的比容量、高的循环性能以及高的能量密度。
进一步地，步骤S3中，所述氧化剂的加入量与以[n1(Mn)+n1(Fe)+n1(R1)]计，所述锰源、所述铁源和所述R1源的总加入量的摩尔量之比为1-5:1。
本发明中，对步骤S3中氧化剂的种类不做具体的限定，可以采用本领域中常规的氧化剂，包括但不限于臭氧、高锰酸钾、过硫酸钠、过硫酸铵、次氯酸钠、高铁酸钠，优选地，所述氧化剂选自臭氧、高锰酸钾、过硫酸钠和过硫酸铵中的至少一种。
本发明中，对步骤S3中混合盐溶液、磷源溶液和氧化剂并流进入反应釜的速度不做具体限定，可以采用本领域中的常规速度，只要能够使得锰铁实现均匀共沉淀即可。
根据本发明，在搅拌条件下，进行所述共沉淀反应。
根据本发明，所述搅拌的转速为200-800r/min，优选为400-800r/min。
根据本发明，在所述共沉淀反应之后，进行陈化反应。
根据本发明，所述陈化反应的条件包括：陈化温度为30-90℃，陈化时间为1-10h。
进一步地，所述陈化反应的条件包括：陈化温度为60-90℃，陈化时间为3-6h。
根据本发明，所述洗涤用的洗涤剂为20-90℃的水。
进一步地，所述洗涤用的洗涤剂为60-90℃的水。
本发明中，洗涤用的洗涤剂为纯水。
根据本发明，所述干燥的条件包括：干燥温度为50-200℃，干燥时间为2-8h。
进一步地，所述干燥的条件包括：干燥温度为80-150℃，干燥时间为3-6h。
根据本发明，步骤S4中，在溶剂的存在下，进行所述混合，得到混合浆料，除去混合浆料中的溶剂后，得到所述混合料。
本发明中，优选地，在溶剂的存在下，进行混合能够使得磷酸锰铁前驱体、锂源、碳源和R2源充分混合均匀，使得制得的磷酸锰铁锂正极材料具有较高的纯度，且具有低的体积电阻率。
本发明中，对于溶剂的种类没有特别限定，只要能够使得混合后的物料形成均匀的浆料即可，例如，所述溶剂可以为水、乙醇等，优选地，所述溶剂为水；对所述溶剂的用量也不做具体的限定，同样以能够形成均匀的浆料为准。
根据本发明，所述锂源选自氢氧化锂、碳酸锂、磷酸二氢锂、草酸锂、硝酸锂和乙酸锂中的至少一种，优选地，所述锂源选自氢氧化锂、碳酸锂和磷酸二氢锂中的至少一种；
根据本发明，所述碳源选自选自葡萄糖、蔗糖、果糖、纤维素、淀粉、柠檬酸、聚丙烯酸、聚乙二醇和多巴胺中的至少一种，优选地，所述碳源选自葡萄糖、蔗糖、淀粉和纤维素中的至少一种。
本发明中，对于除去混合浆料中的溶剂的方式没有特别限定，可以采用本领域中常规的方式，例如，可以采用直接蒸发的方式除去所述混合浆料中的溶剂，蒸发的温度和工艺可以采用本领域技术人员所公知的现有技术，例如，可以采用静态干燥或喷雾干燥以除去所述混合浆料中的溶剂。
根据本发明，步骤S5中，所述煅烧的条件包括：煅烧温度为500-1000℃，煅烧时间为4-20h。
进一步地，步骤S5中，所述煅烧的条件包括：煅烧温度为600-800℃，煅烧时间为6-12h。
本发明中，所述保护性气氛选自氮气气氛和/或氩气气氛
本发明第三方面提供一种由制备方法制得的磷酸锰铁锂正极材料。
本发明第四方面提供一种磷酸锰铁前驱体，其特征在于，所述前驱体材料具有式II所示的组成：
Mn1-x-yFexR1yPzO4·nH2O式II，其中，0.1≤x≤0.5，0≤y≤0.04，0.95≤z≤1.10，0.95≤n≤1.5，R1选自Al、Mg、Ca、Sr、V、Cr、Y、Mo、Nb、B、Al、W、La、Sm、Co、Ni、Cu、Zn、Zr和Ti中的至少一种。
进一步地，式II中，0.15≤x≤0.45，0＜y≤0.03，0.95≤z≤1.05，0.95≤n≤1.2，R选自Al、Co、Ni、Mg、Al、W、Nb、Zr和Ti中的至少一种。
本发明中，所述磷酸锰铁前驱体中任意位置处Mn元素和Fe元素的实际摩尔含量比m'与所述磷酸锰铁锂前驱体中任意位置处Mn元素和Fe元素的理论摩尔含量比m0之间满足以下关系：
Δmp＝︱m'-m0︱/m0≤5％。
进一步地，Δmp＝︱m'-m0︱/m0≤3％。
本发明中，所述磷酸锰铁前驱体的中值粒径为0.5-10μm，优选为0.5-10μm。
本发明中，所述磷酸锰铁前驱体的一次颗粒尺寸为20-200nm，优选为20-100nm。
本发明中，所述磷酸锰铁前驱体的振实密度为0.5-1.5g/cm3，优选为0.8-1.5g/cm3。
本发明中，所述磷酸锰铁前驱体的比表面积为10-100m2/g，优选为10-40m2/g。
本发明第五方面提供一种磷酸锰铁前驱体的制备方法，其特征在于，所述制备方法包括以下步骤：
所述磷酸锰铁前驱体按照以下步骤制备：
(1)将锰源、铁源、R1源与水混合，得到混合盐溶液；
(2)将磷源与水混合，加入pH调节剂，得到磷源溶液；
(3)将所述混合盐溶液、所述磷源溶液和氧化剂以并流的形式加入到反应釜中，进行共沉淀反应，经过滤、洗涤、干燥得到所述磷酸锰铁前驱体。
本发明中，所述磷酸锰铁前驱体的制备方法满足以下关系：
K＝(0.033K1+0.5)·L-0.3·T0.2-0.05   式III；
其中，K为磷酸锰铁前驱体中n1(P)与[n1(Mn)+n1(Fe)+n1(R1)]之比；K1为以n1(P)计，所述磷源的加入量与以[n1(Mn)+n1(Fe)+n1(R1)]计，所述锰源、所述铁源和所述R1源的总加入量的摩尔量之比；L为所述磷源溶液的pH值；T为所述共沉淀反应的温度。
本发明中，式III中，0.9≤K1≤2，0＜L≤3，30℃≤T≤90℃。
进一步地，式III中，1≤K1≤1.5，1.5≤L≤2.5，60℃≤T≤90℃。
根据本发明，步骤(1)中，所述混合盐的浓度为0.1-4mol/L，优选为0.2-2mol/L。
本发明中，对于步骤(1)中锰源的种类不做具体的限定，可以采用本领域中常规的可溶性锰源，包括但不限制于二价锰盐，优选地，所述二价锰盐选自硫酸锰、氯化锰、硝酸锰和醋酸锰中的至少一种。
本发明中，对步骤(1)中铁源的种类不做具体的限定，可以采用本领域中常规的可溶性铁源，包括但不限于二价铁盐，优选地，所述二价铁盐选自硫酸亚铁、氯化亚铁和硝酸亚铁中的至少一种。
本发明中，对于步骤(1)中R1源的种类不做具体的限定，可以采用本领域中常规的能够提供M元素的可溶性R1源，包括但不限于含有M的硫酸盐、硝酸盐、乙酸盐和氯化物中的至少一种，优选地，所述R1源选自硫酸氧钛、硝酸锆和硫酸铝中的至少一种。
本发明中，步骤(2)中，所述磷源溶液的浓度为0.2-20mol/L，优选为1-15mol/L。
本发明中，对于步骤(2)中磷源的种类不做具体的限定，可以采用本领域中常规的可溶性磷源，包括但不限于磷酸、磷酸钠、磷酸二氢钠、磷酸一氢钠、磷酸二氢铵和磷酸一氢铵中的一种，优选选自磷酸、磷酸二氢钠和磷酸二氢铵中的至少一种。
本发明中，步骤(2)中，所述磷源溶液的pH值为0-3，优选地，所述磷源溶液的pH值为 1.5-2.5。
本发明中，对于步骤(2)中的pH调节剂的种类不做具体的限定，只要能够实现调节磷源溶液的pH值的目的即可，例如，所述pH调节剂为酸溶液或碱溶液，优选地，所述pH调节剂选自氢氧化钠、氨水、硫酸、盐酸和硝酸中的至少一种。本发明中，对于pH调节剂的用量也没有特别限定，只要能够使得磷酸溶液的pH值满足上述范围即可。
本发明中，步骤(3)中，以n1(P)计所述磷源的加入量，与以[n1(Mn)+n1(Fe)+n1(R1)]计所述锰源、所述铁源和所述R1源的总加入量的摩尔量之比为1-5:1，优选为1-3:1。
本发明中，步骤(3)中，所述氧化剂的加入量，与以[n1(Mn)+n1(Fe)+n1(R1)]计所述锰源、所述铁源和所述R1源的总加入量的摩尔量之比为1-10:1，优选为1-5:1。
本发明中，对步骤(3)中氧化剂的种类不做具体的限定，可以采用本领域中常规的氧化剂，包括但不限于臭氧、高锰酸钾、过硫酸钠、过硫酸铵、次氯酸钠、高铁酸钠，优选地，所述氧化剂选自臭氧、高锰酸钾、过硫酸钠和过硫酸铵中的至少一种。
本发明中，对步骤(3)中混合盐溶液、磷源溶液和氧化剂并流进入反应釜的速度不做具体限定，可以采用本领域中的常规速度，只要能够使得锰铁实现均匀共沉淀即可。
本发明中，在搅拌条件下，进行所述共沉淀反应。
本发明中，所述搅拌的转速为200-800r/min，优选为400-800r/min。
本发明中，在所述共沉淀反应之后，进行陈化反应。
本发明中，所述陈化反应的条件包括：陈化温度为30-90℃，陈化时间为1-10h。
进一步地，所述陈化反应的条件包括：陈化温度为60-90℃，陈化时间为3-6h。
本发明中，所述洗涤用的洗涤剂为20-90℃的水。
进一步地，所述洗涤用的洗涤剂为60-90℃的水。
本发明中，洗涤用的洗涤剂为纯水。
本发明中，所述干燥的条件包括：干燥温度为50-300℃，干燥时间为2-8h。
进一步地，所述干燥的条件包括：干燥温度为80-200℃，干燥时间为3-6h。
本发明第六方面提供一种由上述制备方法制得的磷酸锰铁前驱体。
本发明第七方面提供一种锂离子电池，所述锂离子电池包括上述磷酸锰铁锂正极材料或由上述磷酸锰铁前驱体制得的正极材料。
以下将通过实施例对本发明进行详细描述。以下实施例中，
粒度测试：采用马尔文激光粒度仪Mastersizer 2000测试测得。
形貌测试：通过日本日立HITACHI公司的S-4800型号的扫描电子显微镜测试测得。
正极材料前驱体中任意位置处Mn元素和Fe元素的实际含量为m'以及正极材料中任意位置处Mn元素和Fe元素的实际含量为m”，通过牛津能谱厂家的50mm2型号的EDS测试测得。
比表面积：通过美国Micromertics公司的Tristar II3020型号的比表面测试仪测试测得；
振实密度：通过百特公司的BT-30型号的振实密度测试仪测试测得。
压实密度：通过日本三菱化学的MCP-PD51型号压实密度仪测试测得。
正极材料的体积电阻率采用日本三菱化学的MCP-PD51型号粉末压实电阻仪测试测得。
碳含量：正极材料中碳含量采用德国埃尔特的CS-i碳硫分析仪测试测得。
正极材料以及前驱体中各元素的含量采用美国安捷伦的5800 ICP-OES光谱仪测试测得。
实施例以及对比例所用原料均为市售品。
实施例1
(1)按照n(Mn):n(Fe):n(Ti)＝65:34:1的摩尔比，称取一定质量的硫酸锰、硫酸亚铁、硫酸氧钛溶于去离子水中，配制得到2mol/L的混合盐溶液。
(2)称取一定质量的磷酸二氢钠，溶于去离子水，加入浓度为30wt％的稀硫酸调节溶液pH为2，配制得到2.8mol/L的磷源溶液。
(3)将等体积的混合盐溶液、磷源溶液和过硫酸钠溶液(2mol/L)并流加入到反应釜中，进 行共沉淀反应，反应温度为90℃，搅拌转速为500r/min，3h完成进液。进液结束后，进行陈化反应，陈化温度为90℃，搅拌转速为500r/min，陈化反应时间为3h。其中，n(氧化剂)/[n1(Mn)+n1(Fe)+n1(M)]＝1，K1＝n1(P)/[n1(Mn)+n1(Fe)+n1(M)]＝1.4。
(4)反应结束后，将反应浆料进行过滤，用浆料两倍体积纯水进行洗涤得到滤饼。将滤饼在105℃下烘干3小时，得到磷酸锰铁前驱体P1。
其中，磷酸锰铁前驱体P1的组成为Mn0.648Fe0.342Ti0.01P1.04O4·H2O，中值粒径D50为2.36μm，振实密度为0.96g/cm3，比表面积为26.6m2/g。磷酸锰铁前驱体中锰铁钛比例为n(Mn):n(Fe):n(Ti)＝64.8:34.2:1，测量得到磷含量与总金属量的摩尔量之比K＝n(P)/[n(Mn)+n(Fe)+n(M)]＝1.04。
(5)将上述制备得到的磷酸锰铁前驱体、碳酸锂(Li2CO3)、碳酸镁和(以C计)葡萄糖按照1：0.52：0.01：0.7的摩尔比与纯水混合，通过机械搅拌混合均匀，得到浆料；
(6)将浆料在加热炉料盘中蒸干，再放入85℃的真空烘箱中干燥4h后得到干料；将干料在氮气气氛下于650℃煅烧10h，筛分后，得到磷酸锰铁锂正极材料A1。
磷酸锰铁锂正极材料A1的组成为Li1.04Mn0.642Fe0.339Ti0.01Mg0.01PO4/C，其一次颗粒的平均粒度为80nm，压实密度为2.15g/cm3，比表面积为18.6m2/g，碳含量为1.84wt％。
实施例2
(1)按照n(Mn):n(Fe):n(Ti)＝65:34:1的摩尔比，称取一定质量的硫酸锰、硫酸亚铁、硫酸氧钛溶于去离子水中，配制得到1mol/L的混合盐溶液。
(2)称取一定质量的浓磷酸，加去离子水稀释，加入浓度为40wt％的氢氧化钠调节溶液pH为1.5，配制得到1.3mol/L的磷源溶液。
(3)将等体积的混合盐溶液、磷源溶液和过硫酸铵溶液(1.5mol/L)并流加入到反应釜中，进行共沉淀反应，反应温度为60℃，搅拌转速为500r/min，3h完成进液。进液结束后，进行陈化反应，陈化温度为90℃，搅拌转速为500r/min，陈化反应时间为3h。n(氧化剂)/[n1(Mn)+n1(Fe)+n1(M)]＝1.5；K1＝n1(P)/[n1(Mn)+n1(Fe)+n1(M)]＝1.3。
(4)反应结束后，将反应浆料进行过滤，用浆料两倍体积纯水进行洗涤得到滤饼。将滤饼在105℃下烘干3小时，得到磷酸锰铁前驱体P2。
其中，磷酸锰铁前驱体P2的组成为Mn0.652Fe0.338Ti0.01P1.09O4·H2O，中值粒径D50为1.65μm，振实密度为1.14g/cm3，比表面积为26.5m2/g。磷酸锰铁前驱体中锰铁钛比例为n(Mn):n(Fe):n(Ti)＝65.2:33.8:1，测量得到磷含量与总金属量的摩尔量之比K＝n(P)/[n(Mn)+n(Fe)+n(M)]＝1.04。
(5)将上述制备得到的磷酸锰铁前驱体、氢氧化锂、碳酸镁和(以C计)蔗糖按照1：1.03：0.01：0.7的摩尔比与纯水混合，通过机械搅拌混合均匀，得到浆料；
(6)将浆料在加热炉料盘中蒸干，再放入85℃的真空烘箱中干燥4h后得到干料；将干料在氮气气氛下于650℃煅烧10h，筛分后，得到磷酸锰铁锂正极材料A2。
磷酸锰铁锂正极材料A2的组成为Li1.03Mn0.645Fe0.335Ti0.01Mg0.01PO4/C，其一次颗粒的平均粒度为60nm，压实密度为2.20g/cm3，比表面积为21.2m2/g，碳含量为2.09wt％。
实施例3
(1)按照n(Mn):n(Fe):n(Ti)＝65:34:1的摩尔比，称取一定质量的氯化锰、硫酸亚铁、硫酸氧钛溶于去离子水中，配制得到2mol/L的混合盐溶液。
(2)称取一定质量的磷酸二氢铵，溶于去离子水，加入浓度为30wt％的稀硫酸溶液pH为2.2，配制得到3mol/L的磷源溶液。
(3)将等体积的混合盐溶液、磷源溶液和高锰酸钠溶液(2mol/L)并流加入到反应釜中，进行共沉淀反应，反应温度为90℃，搅拌转速为500r/min，3h完成进液。进液结束后，进行陈化反应，陈化温度为90℃，搅拌转速为500r/min，陈化反应时间为3h。其中，n(氧化剂)/[n1(Mn)+n1(Fe)+n1(M)]＝1，K1＝n1(P)/[n1(Mn)+n1(Fe)+n1(M)]＝1.5。
(4)反应结束后，将反应浆料进行过滤，用浆料两倍体积纯水进行洗涤得到滤饼。将滤饼在105℃下烘干3小时，得到磷酸锰铁前驱体P3。
其中，磷酸锰铁前驱体P3的组成为Mn0.647Fe0.343Ti0.01P1.02O4·H2O，中值粒径D50为3.78μm，振实密度为1.02g/cm3，比表面积为22.1m2/g。磷酸锰铁前驱体中锰铁钛比例为n(Mn):n(Fe):n(Ti)＝64.7:34.3:1测量得到磷含量与总金属量的摩尔量之比K＝n(P)/[n(Mn)+n(Fe)+n(M)]＝1.02。
(5)将上述制备得到的磷酸锰铁前驱体、氢氧化锂、碳酸镁和(以C计)蔗糖按照1：1.03：0.01：0.7的摩尔比与纯水混合，通过机械搅拌混合均匀，得到浆料；
(6)将浆料在加热炉料盘中蒸干，再放入85℃的真空烘箱中干燥4h后得到干料；将干料在氮气气氛下于650℃煅烧10h，筛分后，得到磷酸锰铁锂正极材料A3。
磷酸锰铁锂正极材料A3的组成为Li1.03Mn0.640Fe0.340Ti0.01Mg0.01PO4/C，其一次颗粒的平均粒度为80nm，压实密度为2.19g/cm3，比表面积为18.3m2/g，碳含量为2.08wt％。
实施例4
(1)按照n(Mn):n(Fe):n(Ti)＝75:24:1的摩尔比，称取一定质量的氯化锰、氯化铁、硫酸氧钛溶于去离子水中，配制得到1.8mol/L的混合盐溶液。
(2)称取一定质量的磷酸二氢钠，溶于去离子水，加入浓度为30wt％的稀硫酸溶液pH为1.8，配制得到1.8mol/L的磷源溶液。
(3)将混合盐溶液、磷源溶液和过硫酸钠溶液(2.7mol/L)并流加入到反应釜中，进行共沉淀反应，反应温度为70℃，搅拌转速为500r/min，3h完成进液。进液结束后，进行陈化反应，陈化温度为90℃，搅拌转速为500r/min，陈化反应时间为3h。n(氧化剂)/[n1(Mn)+n1(Fe)+n1(M)]＝1.5；K1＝n1(P)/[n1(Mn)+n1(Fe)+n1(M)]＝1。
(4)反应结束后，将反应浆料进行过滤，用浆料两倍体积纯水进行洗涤得到滤饼。将滤饼在105℃下烘干3小时，得到磷酸锰铁前驱体P4。
其中，磷酸锰铁前驱体P4的组成为Mn0.748Fe0.242Ti0.01P0.99O4·H2O，中值粒径D50为2.12μm，振实密度为0.98g/cm3，比表面积为23.6m2/g。磷酸锰铁前驱体中锰铁钛比例为n(Mn):n(Fe):n(Ti)＝74.8:24.2:1，测量得到磷含量与总金属量的摩尔量之比K＝n(P)/[n(Mn)+n(Fe)+n(M)]＝0.99。
(5)将上述制备得到的磷酸锰铁前驱体、氢氧化锂、碳酸镁和(以C计)蔗糖按照1：1.03：0.01：0.6的摩尔比与纯水混合，通过机械搅拌混合均匀，得到浆料；
(6)将浆料在加热炉料盘中蒸干，再放入85℃的真空烘箱中干燥4h后得到干料；将干料在氮气气氛下于650℃煅烧10h，筛分后，得到磷酸锰铁锂正极材料A4。
磷酸锰铁锂正极材料A4的组成为Li1.03Mn0.740Fe0.240Ti0.01Mg0.01PO4/C，其一次颗粒的平均粒度为80nm，压实密度为2.26g/cm3，比表面积为18.4m2/g，碳含量为1.94wt％。
实施例5
(1)按照n(Mn):n(Fe):n(Al)＝70:29:1的摩尔比，称取一定质量的氯化锰、硫酸亚铁、硫酸铝溶于去离子水中，配制得到2mol/L的混合盐溶液。
(2)称取一定质量的磷酸一氢钠，溶于去离子水，加入浓度为50wt％的稀硝酸溶液pH为2，配制得到2mol/L的磷源溶液。
(3)将混合盐溶液、磷源溶液和过硫酸钠溶液(1.5mol/L)并流加入到反应釜中，进行共沉淀反应，反应温度为80℃，搅拌转速为500r/min，3h完成进液。进液结束后，进行陈化反应，陈化温度为90℃，搅拌转速为500r/min，陈化反应时间为3h。n(氧化剂)/[n1(Mn)+n1(Fe)+n1(M)]＝0.75；K1＝n1(P)/[n1(Mn)+n1(Fe)+n1(M)]＝1。
(4)反应结束后，将反应浆料进行过滤，用浆料两倍体积纯水进行洗涤得到滤饼。将滤饼在105℃下烘干3小时，得到磷酸锰铁前驱体P5。
其中，磷酸锰铁前驱体P5的组成为Mn0.703Fe0.287Al0.01P0.99O4·H2O，中值粒径D50为2.34μm， 振实密度为1.26g/cm3，比表面积为18.8m2/g。磷酸锰铁前驱体中锰铁铝比例为n(Mn):n(Fe):n(Al)＝70.3:28.7:1，测量得到磷含量与总金属量的摩尔量之比K＝n(P)/[n(Mn)+n(Fe)+n(M)]＝0.99。
(5)将上述制备得到的磷酸锰铁前驱体、氢氧化锂、五氧化二铌和纤维素按照1：1.03：0.005：0.7的摩尔比与纯水混合，通过机械搅拌混合均匀，得到浆料；
(6)将浆料在加热炉料盘中蒸干，再放入85℃的真空烘箱中干燥4h后得到干料；将干料在氮气气氛下于650℃煅烧10h，筛分后，得到磷酸锰铁锂正极材料A5。
磷酸锰铁锂正极材料A5的组成为Li1.03Mn0.696Fe0.284Al0.01Nb0.01PO4/C，其一次颗粒的平均粒度为90nm，压实密度为2.15g/cm3，比表面积为18.3m2/g，碳含量为1.92wt％。
实施例6
(1)按照n(Mn):n(Fe):n(Zr)＝70:29:1的摩尔比，称取一定质量的氯化锰、硫酸亚铁、硝酸锆溶于去离子水中，配制得到2mol/L的混合盐溶液。
(2)称取一定质量的磷酸一氢钠，溶于去离子水，加入浓度为50wt％的稀硝酸溶液pH为1.8，配制得到2.2mol/L的磷源溶液。
(3)将混合盐溶液、磷源溶液和过硫酸铵溶液(1.5mol/L)并流加入到反应釜中，进行共沉淀反应，反应温度为75℃，搅拌转速为500r/min，3h完成进液。进液结束后，进行陈化反应，陈化温度为90℃，搅拌转速为500r/min，陈化反应时间为3h。n(氧化剂)/[n1(Mn)+n1(Fe)+n1(M)]＝0.75；K1＝n1(P)/[n1(Mn)+n1(Fe)+n1(M)]＝1.1。
(4)反应结束后，将反应浆料进行过滤，用浆料两倍体积纯水进行洗涤得到滤饼。将滤饼在105℃下烘干3小时，得到磷酸锰铁前驱体P6。
磷酸锰铁前驱体P6的组成为Mn0.698Fe0.292Zr0.01P1.02O4·H2O，中值粒径D50为3.08μm，振实密度为1.18g/cm3，比表面积为20.6m2/g。磷酸锰铁前驱体中锰铁铝比例为n(Mn):n(Fe):n(Zr)＝69.8:29.2:1，测量得到磷含量与总金属量的摩尔量之比K＝n(P)/[n(Mn)+n(Fe)+n(M)]＝1.02。
(5)将上述制备得到的磷酸锰铁前驱体、氢氧化锂、氧化钨和(以C计)蔗糖按照1：1.03：0.01：0.7的摩尔比与纯水混合，通过机械搅拌混合均匀，得到浆料；
(6)将浆料在加热炉料盘中蒸干，再放入85℃的真空烘箱中干燥4h后得到干料；将干料在氮气气氛下于650℃煅烧10h，筛分后，得到磷酸锰铁锂正极材料A7。
磷酸锰铁锂正极材料A7的化学式为Li1.03Mn0.691Fe0.289Zr0.01W0.01PO4/C，其一次颗粒的平均粒度为120nm，压实密度为2.23g/cm3，比表面积为15.8m2/g，碳含量为2.10wt％。
实施例7
(1)按照n(Mn):n(Fe):n(Ti)＝65:34:1的摩尔比，称取一定质量的硫酸锰、硫酸亚铁、硫酸氧钛溶于去离子水中，配制得到2mol/L的混合盐溶液。
(2)称取一定质量的磷酸二氢钠，溶于去离子水，加入浓度为30wt％的稀硫酸调节溶液pH为2，配制得到2.5mol/L的磷源溶液。
(3)将等体积的混合盐溶液、磷源溶液和过硫酸钠溶液(2mol/L)并流加入到反应釜中，进行共沉淀反应，反应温度为90℃，搅拌转速为500r/min，3h完成进液。进液结束后，进行陈化反应，陈化温度为90℃，搅拌转速为500r/min，陈化反应时间为3h。其中，n(氧化剂)/[n1(Mn)+n1(Fe)+n1(M)]＝1，K1＝n1(P)/[n1(Mn)+n1(Fe)+n1(M)]＝1.25。
(4)反应结束后，将反应浆料进行过滤，用浆料两倍体积纯水进行洗涤得到滤饼。将滤饼在105℃下烘干3小时，得到磷酸锰铁前驱体P7。
其中，磷酸锰铁前驱体P7的组成为Mn0.649Fe0.341Ti0.01P1.03O4·H2O，中值粒径D50为2.15μm，振实密度为0.93g/cm3，比表面积为28.9m2/g。磷酸锰铁前驱体中锰铁钛比例为n(Mn):n(Fe):n(Ti)＝64.9:34.1:1，测量得到磷含量与总金属量的摩尔量之比K＝n(P)/[n(Mn)+n(Fe)+n(M)]＝1.03。
(5)将上述制备得到的磷酸锰铁前驱体、碳酸锂(Li2CO3)、三氧化二铝和(以C计)葡萄糖按照1：0.52：0.005：0.7的摩尔比与纯水混合，通过机械搅拌混合均匀，得到浆料；
(6)将浆料在加热炉料盘中蒸干，再放入85℃的真空烘箱中干燥4h后得到干料；将干料在氮气气氛下于650℃煅烧10h，筛分后，得到磷酸锰铁锂正极材料A7。
磷酸锰铁锂正极材料A7的组成为Li1.04Mn0.642Fe0.338Ti0.01Al0.01PO4/C，其一次颗粒的平均粒度为85nm，压实密度为2.10g/cm3，比表面积为19.7m2/g，碳含量为1.86wt％。
实施例8
(1)按照n(Mn):n(Fe):n(Ti)＝65:34:1的摩尔比，称取一定质量的硫酸锰、硫酸亚铁、硫酸氧钛溶于去离子水中，配制得到2mol/L的混合盐溶液。
(2)称取一定质量的磷酸二氢钠，溶于去离子水，加入浓度为30wt％的稀硫酸调节溶液pH为2，配制得到2.8mol/L的磷源溶液。
(3)将等体积的混合盐溶液、磷源溶液和过硫酸钠溶液(2mol/L)并流加入到反应釜中，进行共沉淀反应，反应温度为80℃，搅拌转速为500r/min，3h完成进液。进液结束后，进行陈化反应，陈化温度为90℃，搅拌转速为500r/min，陈化反应时间为3h。其中，n(氧化剂)/[n1(Mn)+n1(Fe)+n1(M)]＝1，K1＝n1(P)/[n1(Mn)+n1(Fe)+n1(M)]＝1.4。
(4)反应结束后，将反应浆料进行过滤，用浆料两倍体积纯水进行洗涤得到滤饼。将滤饼在105℃下烘干3小时，得到磷酸锰铁前驱体P8。
其中，磷酸锰铁前驱体P8的组成为Mn0.651Fe0.339Ti0.01P1.02O4·H2O，中值粒径D50为2.87μm，振实密度为0.99g/cm3，比表面积为22.6m2/g。磷酸锰铁前驱体中锰铁钛比例为n(Mn):n(Fe):n(Ti)＝65.1:33.9:1，测量得到磷含量与总金属量的摩尔量之比K＝n(P)/[n(Mn)+n(Fe)+n(M)]＝1.02。
(5)将上述制备得到的磷酸锰铁前驱体、碳酸锂(Li2CO3)、氧化锆和(以C计)葡萄糖按照1：0.52：0.01：0.7的摩尔比与纯水混合，通过机械搅拌混合均匀，得到浆料；
(6)将浆料在加热炉料盘中蒸干，再放入85℃的真空烘箱中干燥4h后得到干料；将干料在氮气气氛下于650℃煅烧10h，筛分后，得到磷酸锰铁锂正极材料A8。
磷酸锰铁锂正极材料A8的组成为Li1.04Mn0.644Fe0.336Ti0.01Zr0.01PO4/C，其一次颗粒的平均粒度为70nm，压实密度为2.21g/cm3，比表面积为16.8m2/g，碳含量为1.80wt％。
实施例9
(1)按照n(Mn):n(Fe):n(Ti)＝65:34:1的摩尔比，称取一定质量的硫酸锰、硫酸亚铁溶于去离子水中，配制得到2mol/L的混合盐溶液。
(2)称取一定质量的磷酸二氢钠，溶于去离子水，加入浓度为30wt％的稀硫酸调节溶液pH为2，配制得到2.8mol/L的磷源溶液。
(3)将等体积的混合盐溶液、磷源溶液和过硫酸钠溶液(2mol/L)并流加入到反应釜中，进行共沉淀反应，反应温度为90℃，搅拌转速为500r/min，反应时间为1h。随后进行陈化反应，陈化温度为90℃，搅拌转速为500r/min，陈化反应时间为3h。n(氧化剂)/[n1(Mn)+n1(Fe)+n1(M)]＝1；K1＝n1(P)/[n1(Mn)+n1(Fe)+n1(M)]＝1.4。
(4)反应结束后，将反应浆料进行过滤、用浆料两倍体积纯水进行洗涤得到滤饼。将滤饼在105℃下烘干3小时，得到磷酸亚锰铁前驱体P9。
其中，磷酸锰铁前驱体P9的组成为Mn0.647Fe0.343Ti0.01P1.04O4·H2O，中值粒径D50为2.48μm，振实密度为0.97g/cm3，比表面积为26.2m2/g。磷酸锰铁前驱体中锰铁比例为n(Mn):n(Fe):n(Ti)＝64.7:34.3:1，测量得到磷含量与总金属量的摩尔量之比K＝n(P)/[n(Mn)+n(Fe)+n(M)]＝1.04。
(5)将上述制备得到的磷酸锰铁前驱体、碳酸锂和(以C计)葡萄糖按照1：0.52：0.7的摩尔比与纯水混合，通过机械搅拌混合均匀，得到浆料；
(6)将浆料在加热炉料盘中蒸干，再放入85℃的真空烘箱中干燥4h后得到干料；将干料在 氮气气氛下于650℃煅烧10h，筛分后，得到磷酸锰铁锂正极材料A9。
磷酸锰铁锂正极材料A9的组成为Li1.04Mn0.647Fe0.343Ti0.01PO4/C，其一次颗粒的平均粒度为90nm，压实密度为2.08g/cm3，比表面积为18.8m2/g，碳含量为1.78wt％。
实施例10
(1)按照n(Mn):n(Fe)＝65:35的摩尔比，称取一定质量的硫酸锰、硫酸亚铁溶于去离子水中，配制得到2mol/L的混合盐溶液。
(2)称取一定质量的磷酸二氢钠，溶于去离子水，加入浓度为30wt％的稀硫酸调节溶液pH为2，配制得到2.8mol/L的磷源溶液。
(3)将混合盐溶液、磷源溶液和过硫酸钠溶液(2mol/L)并流加入到反应釜中，进行共沉淀反应，反应温度为90℃，搅拌转速为500r/min，3h完成进液。进液结束后，进行陈化反应，陈化温度为90℃，搅拌转速为500r/min，陈化反应时间为3h。其中，n(氧化剂)/[n1(Mn)+n1(Fe)]＝1；K1＝n1(P)/[n1(Mn)+n1(Fe)]＝1.4。
(4)反应结束后，将反应浆料进行过滤，用浆料两倍体积纯水进行洗涤得到滤饼。将滤饼在105℃下烘干3小时，得到磷酸锰铁前驱体P10。
其中，磷酸锰铁前驱体P10的组成为Mn0.650Fe0.348P1.04O4·H2O，中值粒径D50为4.88μm，振实密度为0.86g/cm3，比表面积为23.2m2/g。磷酸锰铁前驱体中锰铁比例为n(Mn):n(Fe)＝65.2:34.8，测量得到磷含量与总金属量的摩尔量之比K＝n(P)/[n(Mn)+n(Fe)]＝1.04。
(5)将上述制备得到的磷酸锰铁前驱体、碳酸锂、碳酸镁和(以C计)葡萄糖按照1：0.52：0.01：0.7的摩尔比与纯水混合，通过机械搅拌混合均匀，得到浆料；
(6)将浆料在加热炉料盘中蒸干，再放入85℃的真空烘箱中干燥4h后得到干料；将干料在氮气气氛下于650℃煅烧10h，筛分后，得到磷酸锰铁锂正极材料A10。
磷酸锰铁锂正极材料A10的组成为Li1.04Mn0.645Fe0.345Mg0.01PO4/C，其一次颗粒的平均粒度为250nm，压实密度为2.05g/cm3，比表面积为24.8m2/g，碳含量为1.86wt％。
对比例1
(1)按照n(Mn):n(Fe):n(Ti)＝65:34:1的摩尔比，称取一定质量的硫酸锰、硫酸亚铁、硫酸氧钛溶于去离子水中，配制得到2mol/L的混合盐溶液。
(2)称取一定质量的磷酸二氢钠，溶于去离子水，配制得到2.8mol/L的磷源溶液。
(3)将等体积的混合盐溶液、磷源溶液和过硫酸钠溶液(2mol/L)混合，加入浓度为30wt％的稀硫酸调节溶液pH为2，将混合溶液直接加入到反应釜中，进行共沉淀反应，反应温度为90℃，搅拌转速为500r/min，反应时间为1h。随后进行陈化反应，陈化温度为90℃，搅拌转速为500r/min，陈化反应时间为3h。n(氧化剂)/[n1(Mn)+n1(Fe)+n1(M)]＝1，K1＝n1(P)/[n1(Mn)+n1(Fe)+n1(M)]＝1.4。
(4)反应结束后，将反应浆料进行过滤，用浆料两倍体积纯水进行洗涤得到滤饼。将滤饼在105℃下烘干3小时，得到磷酸锰铁前驱体DP1。
磷酸锰铁前驱体DP1的组成为Mn0.602Fe0.388Ti0.01P0.95O4·H2O，中值粒径D50为3.85μm，振实密度为0.88g/cm3，比表面积为61.5m2/g。磷酸锰铁前驱体中锰铁钛比例为n(Mn):n(Fe):n(Ti)＝60.2:38.8:1，测量得到磷含量与总金属量的摩尔量之比K＝n(P)/[n(Mn)+n(Fe)+n(M)]＝0.95。
(5)将上述制备得到的磷酸锰铁前驱体、碳酸锂、碳酸镁和(以C计)葡萄糖按照1：0.52：0.01：0.7的摩尔比与纯水混合，通过机械搅拌混合均匀，得到浆料；
(6)将浆料在加热炉料盘中蒸干，再放入85℃的真空烘箱中干燥4h后得到干料；将干料在氮气气氛下于650℃煅烧10h，筛分后，得到磷酸锰铁锂正极材料D1。
磷酸锰铁锂正极材料D1的组成为Li1.04Mn0.596Fe0.384Ti0.01Mg0.01PO4/C，其一次颗粒的平均粒度为1000nm，压实密度为1.85g/cm3，比表面积为36.5m2/g，碳含量为1.75wt％。
对比例2
(1)按照n(Mn):n(Fe):n(Ti)＝65:34:1的摩尔比，称取一定质量的硫酸锰、硫酸亚铁、硫酸氧钛溶于去离子水中，配制得到2mol/L的混合盐溶液。
(2)称取一定质量的磷酸二氢钠，溶于去离子水，加入浓度为30wt％的稀硫酸调节溶液pH为2，配制得到2.8mol/L的磷源溶液。
(3)将等体积的混合盐溶液和磷源溶液混合，将混合溶液直接加入到反应釜中，对混合溶液进行加热搅拌，反应温度为90℃，搅拌转速为500r/min，再向混合溶液中加入相同体积的过硫酸钠溶液(2mol/L)，3h完成进液。进液结束后，进行陈化反应，陈化温度为90℃，搅拌转速为500r/min，陈化反应时间为3h。其中，n(氧化剂)/[n1(Mn)+n1(Fe)+n1(M)]＝1；K1＝n1(P)/[n1(Mn)+n1(Fe)+n1(M)]＝1.4。
(4)反应结束后，将反应浆料进行过滤，用浆料两倍体积纯水进行洗涤得到滤饼。将滤饼在105℃下烘干3小时，得到磷酸锰铁前驱体DP2。
磷酸锰铁前驱体DP2的组成为Mn0.613Fe0.377Ti0.01P0.92O4·H2O，中值粒径D50为3.65μm，振实密度为0.68g/cm3，比表面积为52.5m2/g。磷酸锰铁前驱体中锰铁钛比例为n(Mn):n(Fe):n(Ti)＝61.3:37.7:1，测量得到磷含量与总金属量的摩尔量之比K＝n(P)/[n(Mn)+n(Fe)+n(M)]＝0.92。
(5)将上述制备得到的磷酸锰铁前驱体、碳酸锂、碳酸镁和(以C计)葡萄糖按照1：0.52：0.01：0.7的摩尔比与纯水混合，通过机械搅拌混合均匀，得到浆料；
(6)将浆料在加热炉料盘中蒸干，再放入85℃的真空烘箱中干燥4h后得到干料；将干料在氮气气氛下于650℃煅烧10h，筛分后，得到磷酸锰铁锂正极材料D2。
磷酸锰铁锂正极材料的化学式为Li1.04Mn0.607Fe0.373Ti0.01Mg0.01PO4/C，其一次颗粒的平均粒度为600nm，压实密度为1.77g/cm3，比表面积为32.5m2/g，碳含量为1.18wt％。
对比例3
(1)按照n(Mn):n(Fe):n(Ti)＝65:34:1的摩尔比，称取一定质量的硫酸锰、硫酸亚铁、硫酸氧钛溶于去离子水中，配制得到2mol/L的混合盐溶液。
(2)称取一定质量的磷酸二氢钠，溶于去离子水，加入浓度为30％的稀硫酸调节溶液pH为2，配制得到2.8mol/L的磷源溶液。
(3)将等体积的混合盐溶液和磷源溶液并流加入到反应釜中，反应温度为90℃，搅拌转速为500r/min，加碱调节pH值，3h完成进液。进液结束后，进行陈化反应，陈化温度为90℃，搅拌转速为500r/min，陈化反应时间为3h。其中，K1＝n1(P)/[n1(Mn)+n1(Fe)+n1(M)]＝1.4。
(4)反应结束后，将反应浆料进行过滤，用浆料两倍体积纯水进行洗涤得到滤饼。将滤饼在105℃下烘干3小时，得到磷酸亚锰铁前驱体DP3。
磷酸亚锰铁前驱体DP3的组成为(Mn0.621Fe0.369Ti0.01)3(PO4)2·H2O，中值粒径D50为16.85μm，振实密度为0.34g/cm3，比表面积为23.5m2/g。磷酸锰铁前驱体中锰铁钛比例为n(Mn):n(Fe):n(Ti)＝62.1:36.9:1，测量得到磷含量与总金属量的摩尔量之比K＝n(P)/[n(Mn)+n(Fe)+n(M)]＝0.67。
(5)将上述制备得到的磷酸亚锰铁前驱体、碳酸锂、磷酸二氢锂、碳酸镁和葡萄糖按照1：0.02：1：0.01：0.7的摩尔比与纯水混合，通过机械搅拌混合均匀，得到浆料；
(6)将浆料在加热炉料盘中蒸干，再放入85℃的真空烘箱中干燥4h后得到干料；将干料在氮气气氛下于650℃煅烧10h，筛分后，得到磷酸锰铁锂正极材料D3。
磷酸锰铁锂正极材料D3的组成为Li1.04Mn0.615Fe0.365Ti0.01Mg0.01PO4/C，其一次颗粒的平均粒度为1.2μm，压实密度为1.36g/cm3，比表面积为12.8m2/g，碳含量为1.32wt％。
对比例4
(1)称取一定质量的硫酸亚铁，溶于去离子水中，配制得到2mol/L的混合盐溶液。
(2)称取一定质量的磷酸二氢钠，溶于去离子水，加入浓度为30％的稀硫酸调节溶液pH为2，配制得到2.8mol/L的磷源溶液。
(3)将1L混合盐溶液、1L磷源溶液和1L过硫酸钠溶液(2mol/L)并流加入到5L反应釜中，进行共沉淀反应，反应温度为90℃，搅拌转速为500r/min，进液时间为1h。进液结束后，进行陈化反应，陈化温度为90℃，搅拌转速为500r/min，陈化反应时间为3h。其中，n(氧化剂)/n1(Fe)＝1；K1＝n1(P)/n1(Fe)＝1.4。
(4)反应结束后，将反应浆料进行过滤，用浆料两倍体积纯水进行洗涤得到滤饼。将滤饼在105℃下烘干3小时，得到磷酸铁前驱体DP4。
其中，磷酸铁前驱体DP4的组成为FePO4·2H2O，中值粒径D50为3.78μm，振实密度为0.78g/cm3，比表面积为42.3m2/g。测量得到磷含量与总金属量的摩尔量之比K＝n(P)/n(Fe)＝1。
(5)将上述制备得到的磷酸铁前驱体、四氧化三锰、碳酸锂、二氧化钛和(以C计)葡萄糖按照1：0.62：0.52：0.01：0.7的摩尔比与纯水混合，通过机械搅拌混合均匀，得到浆料；
(6)将浆料在加热炉料盘中蒸干，再放入85℃的真空烘箱中干燥4h后得到干料；将干料在氮气气氛下于650℃煅烧10h，筛分后，得到磷酸锰铁锂正极材料D4。
磷酸锰铁锂正极材料D4的组成为Li1.04Mn0.643Fe0.347Ti0.01PO4/C，其一次颗粒的平均粒度为600nm，压实密度为1.65g/cm3，比表面积为32.8m2/g，碳含量为2.46wt％。
随机选取上述所制备磷酸锰铁前驱体的任意两个位置，采用EDS测试分别每个位置金属Mn和Fe的实际摩尔含量比值m'，测得的数值如表1所示。所述磷酸锰铁前驱体中金属Mn和Fe的理论摩尔含量比值m。
表1
对比例1-2中前驱体中不同位置处Mn和Fe的摩尔比值与理论值差别较大，且不同位置的比值也差别较大。这是因为与实施例1中前驱体的制备过程相比，对比例1中前驱体制备过程中是将混合盐溶液、磷源溶液以及氧化剂混合后，再进行pH的调节过程，这种一锅法加入原料的方式，会导致反应不均匀，容易出现锰铁偏析的现象；对比例2中是将混合盐溶液和磷源溶液混合反应后，再加入氧化剂，导致部分金属和磷已经反应生成沉淀，从而未实现完全氧化，同时影响锰铁均匀分布；对比例3中则完全没有加入氧化剂，生成磷酸亚锰铁，其中金属和磷的含量偏差较大。
对实施例以及对比例制得的磷酸锰铁前驱体的中值粒径D50、振实密度、比表面积进行测试，结果如表2所示。
表2

实施例以及对比例制得的磷酸锰铁前驱体和磷酸锰铁锂正极材料的组成如表3所示。
表3
随机选取上述所制备磷酸锰铁锂正极材料的任意两个位置，采用EDS测试分别每个位置金属Mn和Fe的实际摩尔含量比值m”，测得的数值如表4所示。所述磷酸锰铁锂正极材料体中金属Mn和Fe的理论摩尔含量比值m。
表4

对实施例以及对比例制得的磷酸锰铁锂正极材料中一次颗粒的平均粒度、压实密度、比表面积、碳含量和体积电阻率进行测试，结果表5所示。
表5
由表1-表5可以看出，相比于对比例1-4，实施例1-10中正极材料以及其前驱体中不同位置处Mn和Fe的摩尔比值与理论值差别较小，表明正极材料以及其前驱体中铁锰分布均匀，不存在偏析现象，由此制得的正极材料具有低的体积电阻率，以及小的一次颗粒，将其用于锂离子电池时，能够显著改善锂离子电池的电化学性能。
具体地，由于对比例1-2的正极材料前驱体中不同位置处Mn和Fe的摩尔比值与理论值差别较大，导致对比例1-2正极材料中不同位置处Mn和Fe的摩尔比值与理论值差别较大，且不同位置的比值也差别较大。与此同时正是由于对比例1前驱体锰铁偏析分布不均匀，对比例2前驱体氧化反应不完全存在杂相，导致对比例1-2正极材料中一次颗粒偏大，体积电阻率偏大。对比例3在制备正极材料阶段需要补充磷源，会导致其金属和磷的比例分布不均匀且不容易控制，其体积电阻率偏大。对比例4是通过磷酸铁和四氧化三锰通过混合，元素不能实现原子级混合，其Mn和Fe的摩尔比值也存在较大偏差。
测试例
本测试例用于说明电极材料、电极、锂离子电池及其制备方法。
(1)正极极片的制备：分别将上述实施例和对比例制备所得的磷酸锰铁锂正极材料，导电剂碳纳米管，粘结剂PVDF的NMP溶液以质量比90：5：5进行混合。具体方法为：将干燥后的正极材料和导电剂在研钵中研磨15分钟，研磨均匀后，按照比例加入PVDF溶液(质量分数5％)，在磁力搅拌器上搅拌6小时；将得到的膏状浆液均匀涂布在集流体铝箔上，然后在60℃的真空干燥箱中干燥20小时，再用100MPa的压力冲压成型为直径12mm、厚度120μm的正极极片，将正 极极片放入120℃的真空干燥箱中干燥12h。
(2)电池组装：以直径为17mm、厚度为1mm的金属锂片为负极，以表面涂覆有氧化铝陶瓷层、厚度为25μm的聚乙烯多孔膜为隔膜，选取1mol/L的LiPF6、碳酸乙烯酯(EC)和碳酸二乙酯(DEC)的等量混合液为电解液，将正极极片、隔膜、负极极片及电解液在水含量与氧含量均小于5ppm的Ar气手套箱内组装成2025型扣式电池。
(3)电化学性能测试：使用武汉兰博电子有限公司的蓝电LAND CT2001A充放电仪对电池进行充放电测试，充放电电压范围为2.5到4.4V，分别在0.1C和1C的倍率下对组装的锂离子电池进行比容量测试，并在1C倍率下进行循环性能测试，测试结果如表6所示。
表6
由表6能够看出，本发明制备的正极材料具有较好的容量性能、倍率性能和循环稳定性。这是由于本发明制备的前驱体锰铁分布均匀，金属和磷的比例可以调控；前驱体掺杂提高了掺杂元素的均匀性。由本发明的前驱体为原料制备的正极材料具有一次颗粒小，碳包覆均匀，体积电阻率低等特点；有利于锂离子的嵌入与脱出，从而使其0.1C放电比容量大于150mAh/g，1C放电比容量大于140mAh/g；前驱体和正极材料双掺杂确保其80周循环保持率大于95％。
图1是实施例1制得的磷酸锰铁前驱体的XRD图，由图1可以看出本发明制备的磷酸锰铁前驱体XRD与MnPO4·H2O标准卡片完全对应一致，表明并未发生分相以及其他杂质的生成。
图2是实施例1制得的磷酸锰铁前驱体的SEM图，由图2可以看出本发明制备的磷酸锰铁前驱体一次颗粒较小，将其用于制备磷酸锰铁锂正极材料时，更有利于与锂源和碳源的均匀混合，并且能够使得碳源均匀包覆于正极材料的表面。
图3是实施例1制备的磷酸锰铁前驱体剖面Mn、Fe的EDS分布图，由图3可以看出，本发明制备的磷酸锰铁前驱体锰铁分布均匀。
图4是实施例1制得的磷酸锰铁锂正极材料的XRD图，由图4可以看出，本发明制备的磷酸锰铁锂正极材料XRD与标准谱图对应一致，锰铁并没有形成分相，并且无其他杂质的生成。
图5为实施例1制备得到的磷酸锰铁锂正极材料SEM图，由图5可以看出，该磷酸锰铁锂正极材料一次颗粒较小且均匀，且表面不存在碳团聚的现象，表明在正极材料表面，碳实现了均匀包覆。

Claims (15)

  1. 一种磷酸锰铁锂正极材料，其特征在于，所述正极材料具有式I所示的组成：
    LidMn1-a-b-cFeaRbPO4/C   式I；
    其中，0.1≤a≤0.5，0≤b≤0.08，0.9<d≤1.2，R选自Al、Mg、Ca、Sr、V、Cr、Y、Mo、Nb、B、Al、W、La、Sm、Co、Ni、Cu、Zn、Zr和Ti中的至少一种；
    所述正极材料的体积电阻率为10-104Ω·cm；
    所述正极材料中任意位置处Mn元素和Fe元素的实际摩尔含量比m”与所述正极材料中任意位置处Mn元素和Fe元素的理论摩尔含量比m之间满足以下关系：
    Δmc＝︱m”-m︱/m≤5％。
  2. 根据权利要求1所述的磷酸锰铁锂正极材料，其中，0.15≤a≤0.45，0<b≤0.06，0.95<d≤1.15；
    优选地，R选自Al、Co、Ni、Mg、Al、W、Nb、Zr和Ti中的至少一种；
    优选地，所述正极材料的体积电阻率为10-103Ω·cm；进一步优选地，所述正极材料的体积电阻率为10-500Ω·cm；
    优选地，以所述磷酸锰铁锂正极材料的总重量为基准，碳含量为0.5-5wt％，优选为1-3wt％。
  3. 根据权利要求1或2所述的磷酸锰铁锂正极材料，其中，Δmc＝︱m”-m︱/m≤3％。
  4. 根据权利要求1-3中任意一项所述的磷酸锰铁锂正极材料，其中，所述正极材料的压实密度为1.5-3.5g/cm3，优选为2-3g/cm3；
    优选地，所述正极材料的比表面积为10-60m2/g，优选为10-25m2/g；
    优选地，所述磷酸锰铁锂正极材料具有由一次颗粒形成的二次颗粒结构；
    优选地，所述正极材料的平均粒度为1-50μm，优选为7-15μm；
    优选地，所述一次颗粒的平均粒度为10-500nm，优选为10-200nm。
  5. 一种磷酸锰铁锂正极材料的制备方法，其特征在于，所述制备方法包括以下步骤：
    S1、将锰源、铁源、R1源与水混合，得到混合盐溶液；
    S2、将磷源与水混合，加入pH调节剂，得到磷源溶液；
    S3、将所述混合盐溶液、所述磷源溶液和氧化剂以并流的形式加入到反应釜中，进行共沉淀反应，经过滤、洗涤、干燥得到所述磷酸锰铁前驱体；
    S4、将所述磷酸锰铁前驱体、锂源、碳源、R2源进行混合，得到混合料；
    S5、在保护性气氛的存在下，将混合料进行煅烧，得到所述磷酸锰铁锂正极材料；
    优选地，所述磷酸锰铁前驱体具有式II所示的组成：
    Mn1-x-yFexR1yPzO4·nH2O式II，其中，0.1≤x≤0.5，0≤y≤0.04，0.95≤z≤1.10，0.95≤n≤1.5，R1选自Al、Mg、Ca、Sr、V、Cr、Y、Mo、Nb、B、Al、W、La、Sm、Co、Ni、Cu、Zn、Zr和Ti中的至少一种；优选地，所述磷酸锰铁锂正极材料具有式I所述的组成：
    LidMn1-a-b-cFeaRbPO4PO4/C  式I；
    其中，0.1≤a≤0.5，0≤b≤0.08，0.9<d≤1.2，R选自Al、Mg、Ca、Sr、V、Cr、Y、Mo、Nb、B、Al、W、La、Sm、Co、Ni、Cu、Zn、Zr和Ti中的至少一种。
  6. 根据权利要求5所述的制备方法，其中，所述磷酸锰铁前驱体中任意位置处Mn元素和Fe元素的实际摩尔含量比m'与所述磷酸锰铁锂前驱体中任意位置处Mn元素和Fe元素的理论摩尔含量比m0之间满足以下关系：
    Δmp＝︱m'-m0︱/m0≤5％，优选地，Δmp＝︱m'-m0︱/m0≤3％；
    优选地，所述磷酸锰铁前驱体的中值粒径为0.5-10μm，优选为0.5-5μm；
    优选地，所述磷酸锰铁前驱体的一次颗粒尺寸为20-200nm，优选为20-100nm；
    优选地，所述磷酸锰铁前驱体的振实密度为0.50-1.50g/cm3，优选为0.80-1.50g/cm3；
    优选地，所述磷酸锰铁前驱体的比表面积为10-100m2/g，优选为10-40m2/g。
  7. 根据权利要求5或6所述的制备方法，其中，所述磷酸锰铁前驱体的制备方法满足以下关系：
    K＝(0.033K1+0.5)·L-0.3·T0.2-0.05   式III；
    其中，K为磷酸锰铁前驱体中n(P)与[n(Mn)+n(Fe)+n(M)]之比；K1为以n1(P)计所述磷源的加入量，与以[n1(Mn)+n1(Fe)+n1(M)]计所述锰源、所述铁源和所述R1源的总加入量的摩尔量之比；L为所述磷源溶液的pH值；T为所述共沉淀反应的温度；
    优选地，0.9≤K1≤2，0<L≤3，30℃≤T≤90℃；
    优选地，1≤K1≤1.5，1.5≤L≤2.5，60℃≤T≤90℃。
  8. 根据权利要求5-7中任意一项所述的制备方法，其中，所述R1源和所述R2源各自独立地选自能够提供Al、Mg、Ca、Sr、V、Cr、Y、Mo、Nb、B、Al、W、La、Sm、Co、Ni、Cu、Zn、Zr和Ti中的至少一种元素的化合物；
    优选地，所述锂源选自氢氧化锂、碳酸锂、磷酸二氢锂、草酸锂、硝酸锂和乙酸锂中的至少 一种；
    优选地，所述碳源选自葡萄糖、蔗糖、果糖、纤维素、淀粉、柠檬酸、聚丙烯酸、聚乙二醇和多巴胺中的至少一种。
  9. 根据权利要求5-8中任意一项所述的制备方法，其中，步骤S1中，所述混合盐的浓度为0.1-4mol/L，优选为0.2-2mol/L；
    优选地，步骤S2中，所述磷源溶液的浓度为0.2-20mol/L，优选为1-15mol/L；
    优选地，步骤S3中，以n1(P)计所述磷源的加入量，与以[n1(Mn)+n1(Fe)+n1(R1)]计所述锰源、所述铁源和所述R1源的总加入量的摩尔量之比为1-5:1，优选为1-3:1；
    优选地，步骤S3中，所述氧化剂的加入量，与以[n1(Mn)+n1(Fe)+n1(R1)]计所述锰源、所述铁源和所述R1源的总加入量的摩尔量之比为1-10:1，优选为1-5:1。
  10. 根据权利要求5-9中任意一项所述的制备方法，其中，在搅拌条件下，进行所述共沉淀反应；
    优选地，所述搅拌的转速为200-800r/min，优选为400-800r/min；
    优选地，在所述共沉淀反应之后，进行陈化反应；
    优选地，所述陈化反应的条件包括：陈化温度为30-90℃，陈化时间为1-10h；
    优选地，所述洗涤用的洗涤剂为20-90℃的水；
    优选地，所述干燥的条件包括：干燥温度为50-200℃，干燥时间为2-8h；
    优选地，步骤S4中，在溶剂的存在下，进行所述混合，得到混合浆料，除去混合浆料中的溶剂后，得到所述混合料；
    优选地，步骤S5中，所述煅烧的条件包括：煅烧温度为500-1000℃，煅烧时间为4-20h。
  11. 由权利要求5-10中任意一项所述的制备方法制得的磷酸锰铁锂正极材料。
  12. 一种磷酸锰铁前驱体，其特征在于，所述前驱体材料具有式II所示的组成：
    Mn1-x-yFexR1yPzO4·nH2O式II，其中，0.1≤x≤0.5，0≤y≤0.04，0.95≤z≤1.10，0.95≤n≤1.5，R1选自Al、Mg、Ca、Sr、V、Cr、Y、Mo、Nb、B、Al、W、La、Sm、Co、Ni、Cu、Zn、Zr和Ti中的至少一种；
    优选地，所述磷酸锰铁前驱体中任意位置处Mn元素和Fe元素的实际摩尔含量比m'与所述磷酸锰铁锂前驱体中任意位置处Mn元素和Fe元素的理论摩尔含量比m0之间满足以下关系：
    Δmp＝︱m'-m0︱/m0≤5％；
    优选地，所述磷酸锰铁前驱体的中值粒径为0.5-10μm，优选为0.5-5μm；
    优选地，所述磷酸锰铁前驱体的一次颗粒尺寸为20-200nm，优选为20-100nm；
    优选地，所述磷酸锰铁前驱体的振实密度为0.50-1.50g/cm3，优选为0.80-1.50g/cm3；
    优选地，所述磷酸锰铁前驱体的比表面积为10-100m2/g，优选为10-40m2/g。
  13. 一种磷酸锰铁前驱体的制备方法，其特征在于，所述制备方法包括以下步骤：
    所述磷酸锰铁前驱体按照以下步骤制备：
    (1)将锰源、铁源、R1源与水混合，得到混合盐溶液；
    (2)将磷源与水混合，加入pH调节剂，得到磷源溶液；
    (3)将所述混合盐溶液、所述磷源溶液和氧化剂以并流的形式加入到反应釜中，进行共沉淀反应，经过滤、洗涤、干燥得到所述磷酸锰铁前驱体；
    优选地，所述磷酸锰铁前驱体的制备方法满足以下关系：
    K＝(0.033K1+0.5)·L-0.3·T0.2-0.05式III；
    其中，K为磷酸锰铁前驱体中n(P)与[n(Mn)+n(Fe)+n(R1)]之比；K1为以n1(P)计所述磷源的加入量，与以[n1(Mn)+n1(Fe)+n1(R1)]计所述锰源、所述铁源和所述R1源的总加入量的摩尔量之比；L为所述磷源溶液的pH值；T为所述共沉淀反应的温度；
    优选地，0.9≤K1≤2，0＜L≤3，30℃≤T≤90℃。
  14. 由权利要求13所述的制备方法制得的磷酸锰铁前驱体。
  15. 一种锂离子电池，其特征在于，所述锂离子电池包括权利要求1-4和11中任意一项所述的磷酸锰铁锂正极材料或由权利要求12或14所述的磷酸锰铁前驱体制得的正极材料。
PCT/CN2023/086937 2023-04-07 2023-04-07 磷酸锰铁锂正极材料及其制备方法、磷酸锰铁前驱体及其制备方法、锂离子电池 Ceased WO2024207439A1 (zh)

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JP2024572729A JP7792023B2 (ja) 2023-04-07 2023-04-07 リン酸マンガン鉄リチウム正極材料及びその調製方法、リン酸マンガン鉄前駆体及びその調製方法、リチウムイオン電池
EP23931500.5A EP4525076A4 (en) 2023-04-07 2023-04-07 Iron-lithium-manganese phosphate positive electrode material and its preparation process, iron-manganese phosphate precursor and its preparation process, and lithium-ion battery

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