Lithium nickel manganese phosphate positive electrode material and manufacturing method therefor

Abstract

A 5V high-voltage positive electrode material and a precursor material, the chemical general formulae of which are respectively LiaNibMndMePO4 / C, i.e., a lithium nickel manganese phosphate carbon-coated composite positive electrode material (LNMP), and NibMndMePO4, i.e., a lithium nickel manganese phosphate precursor (NMP). Upon calculation, the theoretical specific capacity of the positive electrode material is about 168.5 mAh / g, the theoretical voltage platform is about 5.1 V, the actual voltage platform is 5.1-5.3 V, and the positive electrode material belongs to a 5V high-voltage platform phosphate positive electrode material.

Description

A nickel manganese lithium phosphate positive electrode material and its manufacturing method Technical Field

[0001] The present application relates to a 5V high-voltage positive electrode material and a precursor material, namely, an olivine nickel manganese lithium phosphate positive electrode material and a method for making such a material. Background Art

[0002] With national policy support for new energy electric vehicles and their widespread commercialization, higher requirements are being placed on lithium batteries, the power source of electric vehicles. Crucially, the voltage platform and specific capacity of lithium batteries must be adapted to the development requirements of electric vehicles. Traditional lithium iron phosphate (LiFePO4) cells have a specific energy density of only 110-120 Wh / kg, and when assembled into a battery pack, the system energy density is less than 100 Wh / kg. While ternary materials offer a certain improvement in specific energy over LiFePO4, their thermal stability, safety, cycle life, processing difficulty, and cost do not meet the requirements of power batteries. Therefore, how to increase battery capacity, enhance safety, increase cycle life, and reduce costs—thus extending the range of electric vehicles while ensuring safety and optimizing cost-performance—has long been a major industry challenge. This patent application seeks to identify new lithium battery cathode materials with the goal of improving the voltage platform and thermal stability, while significantly increasing cycle life, reducing costs, and increasing specific energy, thereby significantly extending the range of electric vehicles and achieving ideal power battery performance. Technical Solutions

[0003] In view of the shortcomings of the performance and technology of existing lithium batteries, especially lithium iron phosphate and ternary materials, the technical problem to be solved by this application is to provide a phosphate battery material with a high voltage platform and specific capacity. The theoretical voltage platform of the nickel manganese lithium phosphate of this application can reach 5.1V, while the voltage platform of lithium iron phosphate is only 3.2V; the voltage platform of the ternary element 811 is also only 4.2V; in terms of specific capacity, nickel manganese lithium phosphate can reach 860WH / Kg, while lithium iron phosphate is only 540Wh / Kg, which is an increase of nearly 50%. This patent invention can be used to mass-produce the material through solid phase method, gel method, liquid phase method, and hydrothermal method. The raw materials are easy to obtain, the process can be implemented in a variety of ways, and the temperature and humidity of the environment during the production process are far less demanding than those of high nickel ternary materials. Nickel manganese phosphate lithium positive electrode battery materials can achieve high purity, low impurities, small and uniform particle size. The synthesized nickel manganese phosphate lithium battery has high gram capacity, good rate discharge performance, excellent high and low temperature performance, and the number of cycles is equivalent to that of lithium iron phosphate. The voltage platform is far superior to lithium iron phosphate and ternary, and the comprehensive electrical performance is far better than ternary.

[0004] The purpose of the present application is achieved as follows: a method for manufacturing a nickel manganese lithium phosphate positive electrode or precursor material;

[0005] 1. Solid phase method

[0006] Quasi-precursor / precursor: Manganese source, nickel source, phosphorus source and doping element raw materials are added in a stoichiometric ratio, and the particles are fully dispersed or refined in a crusher or sand mill. After reaching the designed particle size, the material can be dried or sintered in a high-temperature sintering furnace for dehydration and phase transformation to obtain nickel manganese phosphate material (abbreviated as: NMP) or nickel manganese oxide material (abbreviated as: NMO).

[0007] Positive electrode: Manganese source, nickel source, lithium source, carbon source, phosphorus source and doping element raw materials are added in proportion to the stoichiometric ratio, fully sand-milled and dispersed in a sand mill to reach the designed particle size, and then spray-dried. The dried material is sintered in an inert gas protection furnace for pyrolysis reaction and phase change to obtain carbon-coated nickel manganese lithium phosphate positive electrode material (abbreviated as: LNMP / C or LNMP@C).

[0008] 2. Liquid phase method / gel method:

[0009] Precursor: Manganese source and nickel source are fully dissolved in a certain concentration of phosphorus source aqueous solution in advance, filtered, and alkaline substances are added to adjust the pH value for precipitation and crystallization; the slurry is filtered to obtain a filter cake and the filter cake is fully washed with pure water; the filter cake is dried and sintered to obtain an NMP precursor substance.

[0010] Positive electrode: After determining the composition of the NMP precursor material in the previous step, add carbon source, lithium source and elemental doping material in proportion according to the stoichiometric ratio, fully grind and disperse in a sand mill, and after reaching the designed particle size requirement, spray dry it. The dried material is sintered in an inert gas protection furnace for pyrolysis reaction and phase change to obtain carbon-coated nickel manganese phosphate lithium positive electrode material (abbreviated: LNMP / C or LNMP@C).

[0011] 3. Hydrothermal method or critical hydrothermal method

[0012] NMP precursor material: Soluble manganese, nickel, and phosphorus sources are fully dissolved and filtered in stoichiometric proportions to obtain a clean solution. A hydrothermal reaction is carried out in a hydrothermal reactor at a specific pressure and temperature. After a period of OSTWALD reaction, the product is filtered to obtain a filter cake. The filter cake is dried, initially crushed, and classified. Based on test calculations, a certain amount of nickel, manganese, or phosphorus source is added to fine-tune the material to the required NMP specifications. This product can then be sintered at a high temperature of 200-800°C to obtain anhydrous NMP.

[0013] Cathode: Preliminary preparation: Soluble manganese source, nickel source, lithium source, carbon source, phosphorus source, and doping elements are fully dissolved and filtered according to stoichiometric ratios to obtain a clean solution. A hydrothermal reaction is carried out in a hydrothermal reactor at a specific pressure and temperature. After a period of OSTWALD reaction, the product is filtered to obtain a filter cake. The filter cake is then dried, initially crushed, graded, and finely mixed with a specific amount of carbon source and lithium source. Finally, the mixture is sintered under inert gas and then gas-pulverized to obtain the LNMP cathode material.

[0014] The SEM morphology of the precursor NMP obtained using the method provided in this application is plate-like, layered, spherical, olivine-like, strip-like, or fibrous, and its appearance is mainly light yellow or yellow-green. However, due to differences in particle size, morphology, and nickel-manganese content, the appearance color may vary to some extent. The SEM morphology of the prepared positive electrode material LNMP is a relatively rounded spherical olivine structure material. The product has high dispersibility and fluidity, and the vibration ratio can reach 0.95g / cm 3 Above, the impurity content is extremely low, S≤50ppm, Na≤50ppm, K≤50ppm, heavy metals such as Cu, Pb, Cd, Cr≤10ppm; Ca, Mg≤50ppm, magnetic substances≤1ppm; the voltage platform is about 5.25V, and the 0.1C gram capacity is about 160mAh / g.

[0015] The nickel manganese lithium phosphate product produced by the present application is easy to control in terms of the molar ratio of nickel, manganese and lithium elements, and the ratio of the three elements can be precisely controlled and adjusted arbitrarily; the impurity content is extremely low, the product has a high degree of dispersibility and fluidity, and the vibration ratio is above 0.95; the particle size distribution is within a relatively narrow range, wherein D 50 The particle size is stable at 0.5-2.0μm. SEM electron microscopy shows the product morphology to be plate-like or flaky, with extremely high compaction density. XRD also indicates that the resulting nickel manganese lithium phosphate product has a pure olivine structure. Testing of a buckle-charged simulated battery made from this material shows a voltage plateau of approximately 5.2V, and a 0.1C capacity of 160-161.5mAh / g. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] The present application will be further described below with reference to the accompanying drawings and examples.

[0017] FIG1 is an XDR (radiological diffraction) diagram of lithium nickel manganese phosphate prepared in Examples 1, 2, 3, and 4 of the present application.

[0018] FIG2 is a scanning electron microscope image (SEM image) of the nickel manganese phosphate obtained in Examples 1, 2, 3, and 4 of the present application.

[0019] FIG3 is a laser particle size distribution diagram of nickel manganese lithium phosphate obtained in Examples 1, 2, 3, and 4 of the present application.

[0020] FIG4 is a graph showing the electrical performance of lithium nickel manganese phosphate obtained in Examples 1, 2, 3, and 4 of the present application. Modes for Carrying Out the Invention

[0021] The implementation process of this application is as follows: manganese, nickel source, lithium source, carbon source, phosphorus source are set according to different process routes such as solid phase method, liquid phase method, hydrothermal method and nickel-manganese molar ratio, and then LNMP or NMP products are synthesized, wherein the positive electrode material molecular formula is Li a Ni b Mn d M e PO4 / C, in which the manganese valence is divalent;

[0022] The precursor is nickel manganese phosphate (NMP), and the general structural formula is Ni b Mn d M e PO4, in which the valence of nickel and manganese elements can be divalent or trivalent, and conductive agents such as CNT (carbon nanotubes) or GO (graphene oxide) can be added in advance during synthesis to improve material properties and optimize and enhance some electrical properties of the precursor itself.

[0023] A nickel manganese phosphate active material with an olivine structure, the general structural formula is Ni b Mn d M e PO4, b is 0.1-0.95, d is 0.05-0.9, and e is: 0≥e≤0.5; M is a doping element, and M is selected from one or more of Fe, Al, Co, Ca, Pb, Na, Ti, Zr, Mo, V, Nb, nickel, Sc, Cr, Cu, Zn, Be, La, Mg, N, and S. The nickel and manganese elements may have a divalent or trivalent valence.

[0024] In some embodiments, the structural formula Ni b Mn d M e In PO4, b is 0.5 to 0.95, d is 0.2 to 0.9, and e is 0.05 to 0.5.

[0025] In some embodiments, the structural formula Ni b Mn d M e In PO4, b is 0.5 to 0.8, d is 0.2 to 0.5, and e is 0.05 to 0.15.

[0026] In some embodiments, the structural formula Ni b Mn d M eIn PO4, b is 0.5, 0.6, 0.7, or 0.8;

[0027] d is 0.2, 0.3, 0.4, or 0.5;

[0028] e is 0, 0.05, 0.1, or 0.15.

[0029] In some embodiments, the structural formula Ni b Mn d M e In PO4, b is 0.8, d is 0.2, and e is 0.05, 0.1, or 0.15; or b is 0.7, d is 0.3, and e is 0.05, 0.1, or 0.15; or b is 0.6, d is 0.4, and e is 0.05, 0.1, or 0.15; or b is 0.5, d is 0.5, and e is 0.05, 0.1, or 0.15.

[0030] In some embodiments, the present application prepares a nickel manganese phosphate active material having a structural formula of Ni 0.8 Mn 0.2 PO4, Ni 0.8 Mn 0.2 M 0.05 PO4, Ni 0.8 Mn 0.2 M 0.1 PO4, Ni 0.8 Mn 0.2 M 0.15 PO4,

[0031] Ni 0.7 Mn 0.3 PO4, Ni 0.7 Mn 0.3 M 0.05 PO4, Ni 0.7 Mn 0.3 M 0.1 PO4, Ni 0.7 Mn 0.3 M 0.15 PO4,

[0032] Ni 0.6 Mn 0.4 PO4, Ni 0.6 Mn 0.4 M 0.05 PO4, Ni 0.6 Mn 0.4 M 0.1 PO4, Ni 0.6 Mn 0.4 M 0.15 PO4,

[0033] Ni 0.5 Mn 0.5 PO4, Ni 0.5 Mn 0.5 M 0.05 PO4, Ni 0.5 Mn 0.5 M 0.1 PO4, Ni 0.5 Mn 0.5 M 0.15 PO4, M is any one of Fe, Co, Ca, Pb, Na, Ti, Zr, Mo, V, Nb, Sc, Cr, Cu, Zn, Be, La, and Mg.

[0034] The manganese source used in the synthesis process of the above materials is selected from one or more combinations of metallic manganese, manganese monoxide, manganese dioxide, manganese tetraoxide, manganese carbonate, manganese citrate, manganese acetate, manganese oxalate, manganese sulfate, manganese nitrate, and manganese chloride.

[0035] The nickel source is selected from one or more combinations of nickel metal, nickel hydroxide, nickel sulfate, nickel oxalate, nickel carbonate, nickel nitrate, and nickel chloride.

[0036] The raw material of the doping element M is selected from one or more combinations of sulfates, phosphates, nitrates, chlorides, oxalates, acetates, and carbonates of any one of Fe, Co, Ca, Pb, Na, Ti, Zr, Mo, V, Nb, Sc, Cr, Cu, Zn, Be, La, and Mg.

[0037] The particle size of the nickel manganese phosphate active material with olivine structure is D 50 0.5-2.0 μm, more preferably D 50 1.0-1.6 μm, more preferably D 50 1.2-1.55μm.

[0038] In view of the above technical solution, the present application also provides a carbon-coated nickel manganese lithium phosphate composite material, the structural formula of the carbon-coated nickel manganese lithium phosphate composite material includes the structural formula of the nickel manganese phosphate active material, and the structural formula of the carbon-coated nickel manganese lithium phosphate composite material is Li a Ni b Mn d M e PO4 / C, a is 0.01~1.05, and the sum of (a+b+d+e) is equal to PO4 3- The ratio of the root molar value is 0.90-1.05, and the values ​​of b, d, and e are taken from Ni b Mn d M e The value in the PO4 general formula.

[0039] As a preferred embodiment, a is 1.025 to 1.035, more preferably any one of 1.025, 1.026, 1.027, 1.028, 1.029, 1.030, 1.031, 1.032, 1.033, 1.034, or 1.035;

[0040] When 0<a<1.025, nickel manganese phosphate pre-embedded with lithium is obtained.

[0041] The carbon source in the carbon-coated composite material is selected from one or more of organic carbon, artificial or natural graphite, graphene, carbon nanotubes or Super P, acetylene black, or other conductive carbons; the carbon content is 0.1-10%. In this application, the introduction of carbon is to increase conductivity, but it is not the only method. Low carbon can be used in combination with other conductive agents. High carbon content can lead to poor processing performance, difficulty in moisture control, and low specific capacity.

[0042] The present application also provides a 5V high voltage platform phosphate positive electrode material, which is a combination of any one or more of the nickel manganese phosphate active material with an olivine structure or the carbon-coated nickel manganese lithium phosphate composite material.

[0043] Another technical solution of the present application is to synthesize LNMP or NMP products by setting different process routes such as solid phase method, liquid phase method, hydrothermal method and nickel-manganese molar ratio of manganese, nickel, lithium, carbon and phosphorus sources, wherein the positive electrode material molecular formula is Li a Ni b Mn d M e PO4 / C, where the manganese valence is divalent, the specific technical solution is as follows:

[0044] A method for preparing a nickel-manganese phosphate active material having an olivine structure comprises adding a manganese source, a nickel source, a phosphorus source, and a doping element raw material in proportion to the element stoichiometric ratio in the above structural formula, fully sand-grinding and dispersing the material in a sand mill to achieve the required particle size, spray drying the material, and sintering and dehydrating the dried material in a high-temperature sintering furnace for phase transformation to obtain the nickel-manganese phosphate material.

[0045] Alternatively, the manganese source, nickel source, lithium source, carbon source, phosphorus source and doping element raw materials are added in proportion to the element stoichiometric ratio in the above structural formula, fully sand-milled and dispersed in a sand mill, and after reaching the particle size requirement, spray-dried, and the dried material is sintered and dehydrated in a high-temperature sintering furnace to undergo phase change to obtain a carbon-coated nickel manganese lithium phosphate positive electrode material.

[0046] The manganese source is selected from one or more combinations of metallic manganese, manganese monoxide, manganese dioxide, manganese tetraoxide, manganese carbonate, manganese citrate, manganese acetate, manganese oxalate, manganese sulfate, manganese nitrate, and manganese chloride;

[0047] The nickel source is selected from one or more of nickel metal, nickel hydroxide, nickel sulfate, nickel oxalate, nickel carbonate, nickel nitrate, and nickel chloride;

[0048] The lithium source is selected from one or more combinations of lithium carbonate, lithium bicarbonate, lithium sulfate, lithium phosphate, lithium oxalate, and lithium hydroxide;

[0049] The phosphorus source is selected from a combination of one or more of ammonium phosphate, lithium phosphate, sodium phosphate, phosphoric acid, and hypophosphorous acid;

[0050] The raw material of the doping element M is selected from one or more combinations of sulfates, phosphates, nitrates, chlorides, oxalates, acetates, and carbonates of any one of Fe, Co, Ca, Pb, Na, Ti, Zr, Mo, V, Nb, Sc, Cr, Cu, Zn, Be, La, and Mg;

[0051] The carbon source is selected from one or more combinations of organic carbon, artificial or natural graphite, graphene, carbon nanotubes or Super P, acetylene black or other conductive carbons.

[0052] In the above steps, the manganese source, nickel source, phosphorus source and doping element raw materials are mixed, or the manganese source, nickel source, lithium source, carbon source, phosphorus source and doping element raw materials are mixed and water is added to form a slurry, a surfactant is added, and the temperature is raised to 90-120° C. to react for 2-4 hours. After the reaction, the nickel manganese lithium phosphate filter cake obtained by filtration is dried and then ball milled.

[0053] The surfactant is a mixture of allyl polyethylene glycol, pyridine, polyvinyl pyridine, PVP and the like in a mass ratio of 4:2-3:0.5-2.

[0054] Carbon source and lithium source are added during the ball milling process, so that the product structure contains Li a Ni b Mn d M e PO4 / C, the molar amount of lithium is 0.01-1.05, and the carbon content is 0.1-10%.

[0055] In the process of preparing nickel manganese phosphate material, the doping element M is selectively added, and the addition amount of each raw material is controlled according to the atomic ratio of each raw material in the doping element M of manganese source, nickel source and phosphorus source, so that the structure of nickel manganese phosphate active material is Ni b Mn d M ePO4, b is 0.1-0.95, d is 0.05-0.9, and e is 0≤e≤0.5; M is a doping element, and M is selected from one or more combinations of Fe, Al, Co, Ca, Pb, Na, Ti, Zr, Mo, V, Nb, Sc, Cr, Cu, Zn, Be, La, Mg, N, S or Al.

[0056] In some specific embodiments, the nickel manganese phosphate active material prepared has the structural formula Ni 0.8 Mn 0.2 PO4, Ni 0.7 Mn 0.3 PO4, Ni 0.6 Mn 0.4 PO4 or Ni 0.5 Mn 0.5 PO4, M is any one of Fe, Co, Ca, Pb, Na, Ti, Zr, Mo, V, Nb, Sc, Cr, Cu, Zn, Be, La, and Mg.

[0057] The particle size requirement is D of a single group of materials. 50 The nanomaterial is within 400 nm, more preferably within 200 nm, and even more preferably within 100 nm. The nanomaterial has good gram capacity and rate characteristics, and the cycle performance is more excellent.

[0058] The sand grinding particle size D50 is controlled at 0.2~0.8μm;

[0059] The particle size of the product obtained after the spray drying is recommended to be 15-25 μm, more preferably 10-15 μm;

[0060] The carbon coating sintering temperature is: the low-temperature coke removal section temperature is set to 250-650°C, more preferably 400-500°C, and the high-temperature phase change section temperature is 680-800°C, more preferably 700-790°C.

[0061] A nickel manganese phosphate active material with an olivine structure is prepared by one of the methods to obtain a nickel manganese phosphate positive electrode material or a carbon-coated nickel manganese phosphate positive electrode material. The active material has a 5V high voltage platform as a phosphate positive electrode material.

[0062] A 5V high voltage platform phosphate positive electrode material, prepared by one of the methods described above to obtain a nickel manganese phosphate positive electrode material or a carbon-coated nickel manganese phosphate positive electrode material, the structural formula of the nickel manganese phosphate positive electrode material is Ni b Mn d M ePO4, b is 0.1-0.95, d is 0.05-0.9, and e is 0≤e≤0.5; M is a doping element, and M is selected from one or more combinations of Fe, Al, Co, Ca, Pb, Na, Ti, Zr, Mo, V, Nb, Sc, Cr, Cu, Zn, Be, La, Mg, N, S or Al.

[0063] The general structural formula Ni b Mn d M e In PO4, b is 0.5 to 0.95, d is 0.2 to 0.9, and e is 0.05 to 0.5.

[0064] In the preferred embodiment, the general structural formula Ni b Mn d M e In PO4, b is 0.5 to 0.8, d is 0.2 to 0.5, and e is 0 to 0.15.

[0065] A further preferred structural formula is Ni b Mn d M e In PO4, b is 0.5, 0.6, 0.7, or 0.8;

[0066] d is 0.2, 0.3, 0.4, or 0.5; e is 0, 0.05, 0.1, or 0.15.

[0067] A further preferred structural formula is Ni b Mn d M e In PO4, b is 0.8, d is 0.2, and e is 0.05, 0.1, or 0.15; or b is 0.7, d is 0.3, and e is 0.05, 0.1, or 0.15; or b is 0.6, d is 0.4, and e is 0.05, 0.1, or 0.15; or b is 0.5, d is 0.5, and e is 0, 0.05, 0.1, or 0.15.

[0068] In a further preferred general structural formula, the structural formula of the nickel manganese phosphate active material is Ni 0.8 Mn 0.2 M 0.05 PO4, Ni 0.8 Mn 0.2 M 0.1 PO4, Ni 0.8 Mn 0.2 M 0.15 PO4, Ni 0.7 Mn 0.3 M 0.05 PO4, Ni 0.7 Mn0.3 M 0.1 PO4, Ni 0.7 Mn 0.3 M 0.15 PO4, Ni 0.6 Mn 0.4 M 0.05 PO4, Ni 0.6 Mn 0.4 M 0.1 PO4, Ni 0.6 Mn 0.4 M 0.15 PO4, Ni 0.5 Mn 0.5 M 0.05 PO4, Ni 0.5 Mn 0.5 M 0.1 PO4, Ni 0.5 Mn 0.5 M 0.15 PO4, M is any one of Fe, Co, Ca, Pb, Na, Ti, Zr, Mo, V, Nb, Sc, Cr, Cu, Zn, Be, La, and Mg.

[0069] The carbon-coated nickel manganese lithium phosphate cathode material prepared by one of the methods has the structural formula Li a Ni b Mn d M e PO4 / C, a is 0.01~1.05, and the sum of (a+b+d+e) is equal to PO4 3- The ratio of root molar values ​​is 0.90-1.05.

[0070] The a is 1.025 to 1.035, more preferably any one of 1.025, 1.026, 1.027, 1.028, 1.029, 1.030, 1.031, 1.032, 1.033, 1.034, or 1.035;

[0071] When 0<a<1.025, nickel manganese phosphate pre-embedded with lithium is obtained.

[0072] A second method for preparing a nickel-manganese phosphate active material having an olivine structure comprises dissolving a manganese source and a nickel source in a phosphorus source aqueous solution of a certain concentration, filtering, and adding an alkaline substance to adjust the pH value to 2-9 for precipitation and crystallization; filtering the crystallized slurry to obtain a filter cake, and washing the filter cake with pure water; drying and sintering the filter cake to obtain the nickel-manganese phosphate active material having an olivine structure;

[0073] Alternatively, a carbon source, a lithium source and a doping element are added to the nickel manganese phosphate active material, the particles are spray dried after grinding and dispersion, and the dried material is sintered to obtain a carbon-coated nickel manganese lithium phosphate positive electrode material with an olivine structure.

[0074] In the preparation of nickel manganese phosphate active material, the amount of each raw material added is according to the structural formula Ni b Mn d M e PO4, b is 0.1~0.95, d is 0.05~0.9, e is 0≤e≤0.5 and can be reasonably adjusted. Or according to the structural formula Li a Ni b Mn d M e PO4 / C, a is 0.01~1.05, and the sum of (a+b+d+e) is equal to PO4 3- The contract adjustment is made when the ratio of the root molar value is 0.90-1.05.

[0075] The alkaline substance is selected from any one of sodium hydroxide, lithium hydroxide, ammonia water, cesium carbonate, sodium carbonate, sodium bicarbonate, sodium methoxide, potassium ethoxide, and potassium tert-butoxide.

[0076] An alkaline substance is added to adjust the pH value to 1-5, preferably 1.5-5, and more preferably 3.5-4.5.

[0077] The crystallization of the material occurs in an environment where the elements can effectively form crystals, avoiding the situation where some of the necessary elements in the material remain in an ionic state, and at the same time obtaining a material with a purer crystal phase and higher crystallinity.

[0078] The precipitation and crystallization time is 1-48 h, preferably 12-16 h, more preferably 8-10 h, and most preferably 4-6 h.

[0079] The manganese source is selected from one or more combinations of metallic manganese, manganese monoxide, manganese dioxide, manganese tetraoxide, manganese carbonate, manganese citrate, manganese acetate, manganese oxalate, manganese sulfate, manganese nitrate, and manganese chloride;

[0080] The nickel source is selected from one or more of nickel metal, nickel hydroxide, nickel sulfate, nickel oxalate, nickel carbonate, nickel nitrate, and nickel chloride;

[0081] The lithium source is selected from one or more combinations of lithium carbonate, lithium bicarbonate, lithium sulfate, lithium phosphate, lithium oxalate, and lithium hydroxide;

[0082] The phosphorus source is selected from a combination of one or more of ammonium phosphate, lithium phosphate, sodium phosphate, phosphoric acid, and hypophosphorous acid;

[0083] The raw material of the doping element M is selected from one or more combinations of sulfates, phosphates, nitrates, chlorides, oxalates, acetates, and carbonates of any one of Fe, Co, Ca, Pb, Na, Ti, Zr, Mo, V, Nb, Sc, Cr, Cu, Zn, Be, La, and Mg;

[0084] The carbon source is selected from one or more combinations of organic carbon, artificial or natural graphite, graphene, carbon nanotubes or Super P, acetylene black or other conductive carbons.

[0085] The sand grinding particle size D50 is controlled at 0.2~0.8μm;

[0086] The particle size of the product obtained after the spray drying is recommended to be 15-25 μm, more preferably 10-15 μm;

[0087] The carbon coating sintering temperature is: the low-temperature coke removal section temperature is set to 250-650°C, more preferably 400-500°C, and the high-temperature phase change section temperature is 680-800°C, more preferably 700-790°C.

[0088] A nickel manganese phosphate active material with an olivine structure is prepared by the second method to obtain a nickel manganese phosphate positive electrode material or a carbon-coated nickel manganese phosphate positive electrode material. The active material has a 5V high voltage platform as a phosphate positive electrode material.

[0089] A 5V high voltage platform phosphate positive electrode material is prepared by the second method to obtain a nickel manganese phosphate positive electrode material or a carbon-coated nickel manganese phosphate positive electrode material. The structural formula of the nickel manganese phosphate positive electrode material is Ni b Mn d M e PO4, b is 0.1-0.95, d is 0.05-0.9, and e is 0≤e≤0.5 (M is a doping element, and M is selected from one or more combinations of Fe, Al, Co, Ca, Pb, Na, Ti, Zr, Mo, V, Nb, Sc, Cr, Cu, Zn, Be, La, Mg, N, and S).

[0090] The general structural formula Ni b Mn d M e In PO4, b is 0.5 to 0.95, d is 0.2 to 0.9, and e is 0.05 to 0.5.

[0091] In the preferred embodiment, the general structural formula Ni b Mn d M e In PO4, b is 0.5 to 0.8, d is 0.2 to 0.5, and e is 0 to 0.15.

[0092] A further preferred structural formula is Ni b Mn d M e In PO4, b is 0.5, 0.6, 0.7, or 0.8; d is 0.2, 0.3, 0.4, or 0.5; and e is 0, 0.05, 0.1, or 0.15.

[0093] A further preferred structural formula is Ni b Mn d M e In PO4, b is 0.8, d is 0.2, and e is 0.05, 0.1, or 0.15; or b is 0.7, d is 0.3, and e is 0.05, 0.1, or 0.15; or b is 0.6, d is 0.4, and e is 0.05, 0.1, or 0.15; or b is 0.5, d is 0.5, and e is 0, 0.05, 0.1, or 0.15.

[0094] In a further preferred general structural formula, the structural formula of the nickel manganese phosphate active material is Ni 0.8 Mn 0.2 M 0.05 PO4, Ni 0.8 Mn 0.2 M 0.1 PO4, Ni 0.8 Mn 0.2 M 0.15 PO4, Ni 0.7 Mn 0.3 M 0.05 PO4, Ni 0.7 Mn 0.3 M 0.1 PO4, Ni 0.7 Mn 0.3 M 0.15 PO4, Ni 0.6 Mn 0.4 M 0.05 PO4, Ni 0.6 Mn 0.4 M 0.1 PO4, Ni 0.6 Mn 0.4 M 0.15 PO4, Ni 0.5 Mn 0.5 M 0.05 PO4, Ni 0.5 Mn 0.5 M 0.1 PO4, Ni 0.5 Mn 0.5 M 0.15PO4, M is any one of Fe, Co, Ca, Pb, Na, Ti, Zr, Mo, V, Nb, Sc, Cr, Cu, Zn, Be, La, and Mg.

[0095] The structural formula of the carbon-coated nickel manganese lithium phosphate cathode material prepared by the second method is Li a Ni b Mn d M e PO4 / C, a is 0.01~1.05, and the sum of (a+b+d+e) is equal to PO4 3- The ratio of root molar values ​​is 0.90-1.05.

[0096] The a is 1.025 to 1.035, more preferably any one of 1.025, 1.026, 1.027, 1.028, 1.029, 1.030, 1.031, 1.032, 1.033, 1.034, or 1.035;

[0097] When 0<a<1.025, nickel manganese phosphate pre-embedded with lithium is obtained.

[0098] Another technical solution of the present application is to provide a third method for preparing a nickel manganese phosphate active material having an olivine structure, comprising: fully dissolving a soluble manganese source, a nickel source, and a phosphorus source in a stoichiometric ratio and filtering to obtain a clean solution; conducting a hydrothermal reaction in a hydrothermal kettle at a certain pressure and temperature; after a period of hydrothermal reaction, filtering the discharged material to obtain a filter cake; and drying and sintering the filter cake to obtain a nickel manganese phosphate active material having an olivine structure;

[0099] Alternatively, a soluble manganese source, nickel source, lithium source, phosphorus source, carbon source and doping elements are fully dissolved and filtered in a stoichiometric ratio to obtain a clean solution, and a hydrothermal reaction is carried out in a hydrothermal kettle at a certain pressure and temperature. After a period of hydrothermal reaction, the material is discharged and filtered to obtain a filter cake. The filter cake is dried and sintered to obtain a carbon-coated nickel manganese phosphate active material with an olivine structure.

[0100] The stoichiometry is based on the general structural formula Ni b Mn d M e PO4, b is 0.1~0.95, d is 0.05~0.9, 0≤e≤0.5 (there is no M in the structural formula in the embodiment, so can it be 0 here??) Make reasonable adjustments. Or according to Li a Ni b Mn d M e PO4 / C, a is 0.01~1.05, and the sum of (a+b+d+e) is equal to PO4 3-The ratio of the root molar value is adjusted appropriately to 0.90-1.05.

[0101] The hydrothermal reaction temperature is 120-200°C, and the hydrothermal reaction pressure is 5-20 MPa. The sintering temperature is 400-600°C, more preferably 450-500°C. It is recommended to analyze why the hydrothermal reaction temperature and pressure conditions can produce the active product described, and what kind of environment the hydrothermal reaction provides for the various raw materials. What effects do excessively high hydrothermal temperatures and pressures have on the structural characteristics of the product?

[0102] The manganese source is selected from one or more combinations of metallic manganese, manganese monoxide, manganese dioxide, manganese tetraoxide, manganese carbonate, manganese citrate, manganese acetate, manganese oxalate, manganese sulfate, manganese nitrate, and manganese chloride;

[0103] The nickel source is selected from one or more of nickel metal, nickel hydroxide, nickel sulfate, nickel oxalate, nickel carbonate, nickel nitrate, and nickel chloride;

[0104] The lithium source is selected from one or more combinations of lithium carbonate, lithium bicarbonate, lithium sulfate, lithium phosphate, lithium oxalate, and lithium hydroxide;

[0105] The phosphorus source is selected from a combination of one or more of ammonium phosphate, lithium phosphate, sodium phosphate, phosphoric acid, and hypophosphorous acid;

[0106] The raw material of the doping element M is selected from one or more combinations of sulfates, phosphates, nitrates, chlorides, oxalates, acetates, and carbonates of any one of Fe, Co, Ca, Pb, Na, Ti, Zr, Mo, V, Nb, Sc, Cr, Cu, Zn, Be, La, and Mg;

[0107] The carbon source is selected from one or more combinations of organic carbon, artificial or natural graphite, graphene, carbon nanotubes or Super P, acetylene black or other conductive carbons.

[0108] A nickel manganese phosphate active material with an olivine structure is prepared by the third method to obtain a nickel manganese phosphate positive electrode material or a carbon-coated nickel manganese phosphate positive electrode material. The active material has a 5V high voltage platform as a phosphate positive electrode material.

[0109] A 5V high voltage platform phosphate positive electrode material is prepared by the third method to obtain a nickel manganese phosphate positive electrode material or a carbon-coated nickel manganese phosphate positive electrode material. The structural formula of the nickel manganese phosphate positive electrode material is Ni b Mn d M ePO4, b is 0.1-0.95, d is 0.05-0.9, 0≤e≤0.5; M is a doping element, and M is selected from one or more combinations of Fe, Co, Ca, Pb, Na, Ti, Zr, Mo, V, Nb, Sc, Cr, Cu, Zn, Be, La, Mg, N, S or Al.

[0110] The general structural formula Ni b Mn d M e In PO4, b is 0.5 to 0.95, d is 0.2 to 0.9, and e is 0.05 to 0.5.

[0111] In the preferred embodiment, the general structural formula Ni b Mn d M e In PO4, b is 0.5 to 0.8, d is 0.2 to 0.5, and e is 0 to 0.15.

[0112] A further preferred structural formula is Ni b Mn d M e In PO4, b is 0.5, 0.6, 0.7, or 0.8; d is 0.2, 0.3, 0.4, or 0.5; and e is 0, 0.05, 0.1, or 0.15.

[0113] A further preferred structural formula is Ni b Mn d M e In PO4, b is 0.8, d is 0.2, and e is 0.05, 0.1, or 0.15; or b is 0.7, d is 0.3, and e is 0.05, 0.1, or 0.15; or b is 0.6, d is 0.4, and e is 0.05, 0.1, or 0.15; or b is 0.5, d is 0.5, and e is 0, 0.05, 0.1, or 0.15.

[0114] In a further preferred general structural formula, the structural formula of the nickel manganese phosphate active material is Ni 0.8 Mn 0.2 M 0.05 PO4, Ni 0.8 Mn 0.2 M 0.1 PO4, Ni 0.8 Mn 0.2 M 0.15 PO4, Ni 0.7 Mn 0.3 M 0.05 PO4, Ni 0.7 Mn 0.3 M 0.1 PO4, Ni0.7 Mn 0.3 M 0.15 PO4, Ni 0.6 Mn 0.4 M 0.05 PO4, Ni 0.6 Mn 0.4 M 0.1 PO4, Ni 0.6 Mn 0.4 M 0.15 PO4, Ni 0.5 Mn 0.5 M 0.05 PO4, Ni 0.5 Mn 0.5 M 0.1 PO4, Ni 0.5 Mn 0.5 M 0.15 PO4, M is any one of Fe, Co, Ca, Pb, Na, Ti, Zr, Mo, V, Nb, Sc, Cr, Cu, Zn, Be, La, and Mg.

[0115] The structural formula of the carbon-coated nickel manganese lithium phosphate cathode material prepared by the third method is Li a Ni b Mn d M e PO4 / C, a is 0.01~1.05, and the sum of (a+b+d+e) is equal to PO4 3- The ratio of root molar values ​​is 0.90-1.05.

[0116] The a is 1.025 to 1.035, more preferably any one of 1.025, 1.026, 1.027, 1.028, 1.029, 1.030, 1.031, 1.032, 1.033, 1.034, or 1.035;

[0117] When 0<a<1.025, nickel manganese phosphate pre-embedded with lithium is obtained.

[0118] The present invention relates to a 5V high-voltage lithium battery electrode, comprising a battery electrode made of the positive electrode material, namely a carbon-coated nickel manganese lithium phosphate composite positive electrode material electrode, wherein the positive electrode material composition contains 1-100wt% of a carbon-coated nickel manganese lithium phosphate positive electrode material, and the structural formula of the carbon-coated nickel manganese lithium phosphate positive electrode material is Li a Ni b Mn d M e PO4 / C, a is 0.01~1.05, and the sum of (a+b+d+e) is equal to PO4 3- The ratio of root molar values ​​is 0.90-1.05.

[0119] The a is 1.025 to 1.035, more preferably any one of 1.025, 1.026, 1.027, 1.028, 1.029, 1.030, 1.031, 1.032, 1.033, 1.034, or 1.035;

[0120] When 0<a<1.025, nickel manganese phosphate pre-embedded with lithium is obtained.

[0121] The positive electrode material composition contains 1-90wt% of carbon-coated nickel manganese lithium phosphate positive electrode material, preferably the positive electrode material composition contains 10-80wt% of carbon-coated nickel manganese lithium phosphate positive electrode material, preferably the positive electrode material composition contains 20-70wt% of carbon-coated nickel manganese lithium phosphate positive electrode material, preferably the positive electrode material composition contains 30-70wt% of carbon-coated nickel manganese lithium phosphate positive electrode material, preferably the positive electrode material composition contains 30-60wt% of carbon-coated nickel manganese lithium phosphate positive electrode material.

[0122] When the carbon-coated nickel manganese lithium phosphate positive electrode material is less than 100%, it also contains other positive electrode materials, and the other positive electrode materials are selected from any one of lithium cobalt oxide, lithium manganese oxide, lithium nickel manganese phosphate, nickel cobalt manganese, and nickel cobalt manganese ternary polymer materials.

[0123] In some implementation cases, the present application provides a 5V high-voltage lithium battery, which includes the corresponding laminates, square aluminum shells, cylindrical windings or other lithium batteries of different shapes and structures made from the 5V high-voltage lithium battery pole pieces, and the lithium battery contains at least one lithium element electrolyte solution.

[0124] The manganese sources described in this application, namely elemental manganese, manganese monoxide, manganese dioxide, manganese tetraoxide, manganese carbonate, manganese citrate, manganese acetate, manganese oxalate, manganese sulfate, manganese nitrate, and manganese chloride, are all materials of analytical grade or higher.

[0125] The nickel sources, namely elemental nickel, nickel hydroxide, nickel sulfate, nickel oxalate, nickel carbonate, nickel nitrate and nickel chloride, are all analytically pure or higher.

[0126] The lithium sources, namely lithium carbonate, lithium bicarbonate, lithium sulfate, lithium phosphate, lithium oxalate and lithium hydroxide, are all analytically pure or higher.

[0127] The phosphorus sources, namely phosphorus pentoxide, phosphoric acid and hypophosphorous acid, are all analytically pure or higher.

[0128] The raw materials of the doping element M, that is, sulfates, phosphates, nitrates, chlorides, oxalates, acetates, and carbonates of any one of Fe, Co, Ca, Pb, Na, Ti, Zr, Mo, V, Nb, Sc, Cr, Cu, Zn, Be, La, and Mg, are all analytically pure or higher.

[0129] The carbon sources, namely organic carbon, artificial or natural graphite, graphene, carbon nanotubes or Super P, acetylene black or other conductive carbons, are all materials of analytical grade or above.

[0130] Among the surfactants of the present application, the surfactant is a mixture of allyl polyethylene glycol, polyvinyl pyridine and PVP. Example 1

[0131] 1. First, weigh 2000g of 16% dilute phosphoric acid solution with a Baume degree of 10.5-11°Bé; 178.5g of analytical grade nickel hydroxide, 0.5g of battery-grade titanium oxide, 64g of battery-grade manganese tetraoxide, 57.9g of lithium carbonate, and 15g of 5% graphene oxide slurry, and add them to the reactor in sequence. Stir thoroughly for 10 minutes, and then add 15g of a high-efficiency surfactant (a mixture of allyl polyethylene glycol, polyvinyl pyridine, and PVP in a mass ratio of 4:3:2). Raise the temperature to about 90°C, stir, and fully react for 2-4 hours.

[0132] 2. Filter the solution from the previous step through a plate and frame filter to obtain a nickel manganese lithium phosphate filter cake, which is ready for use;

[0133] 3. The damp product was dried in a CT hot air circulation oven at 140°C for 2.5 hours. The obtained dry product was crushed, sieved, and then the components were determined. The quality of the organic carbon source and the optimized lithium amount were calculated based on the component content, stoichiometric ratio, and carbon content in LNMP. The added amounts of organic carbon sources glucose and PEG6000 were 20.33 g and 12.4 g, respectively; and the added amount of lithium carbonate was 1.59 g.

[0134] 4. Control the solid-liquid ratio of the previous material to 40-45% and the viscosity to 4000-5000 Pa.S. Stir thoroughly in the batching tank for 10 minutes, pump into the sand mill for sand grinding, and control the particle size D 50 =500nm, the main engine speed is set to 1200r / min;

[0135] 5. Spray dry the sand-milled slurry;

[0136] 6. The material from step 5 was sintered in an N2 gas inert furnace. The low-temperature sintering temperature was controlled at 450°C, the high-temperature sintering temperature was controlled at 760°C, and the temperature rise rate of each section was controlled at 3°C / min.

[0137] 7. Grind the material from step 6 by air flow to a particle size of D 50 The particle size was controlled at 1.27 μm, and after screening, grading and packaging, 260.7 g of carbon-coated lithium nickel manganese phosphate (LNMP / C) finished product was obtained: LiMn 0.4 Ni 0.6 PO4 / C (nickel-manganese molar ratio of 6:4). This step allows the material to be tested for carbon content, compaction, and electrical properties. (Li is present in the material only as a percentage by mass, typically 4.2-4.5%)

[0138] 8. Mix the LNMP / C powder material, PVDF, and conductive carbon black in a mass ratio of 95:5:5, and then disperse and adjust the slurry with N-methylpyrrolidone dispersant. To ensure uniform dispersion, a double planetary agitator can be used for strong dispersion. The semi-dispersed slurry is evenly coated on carbon-coated aluminum foil using a coating machine and dried;

[0139] 9. The dried semi-finished electrode pieces are extruded twice by a roller machine; the extruded electrode pieces are cut by a punching machine to obtain φ32mm circular electrode pieces for use as positive electrode pieces in button battery assembly.

[0140] 10. Assemble the electrodes into 2032 button batteries according to the requirements of the simulated battery for electrical performance measurement.

[0141] The test results of the finished product are shown in the table below:

[0142]

[0143] Example 2

[0144] 1. Weigh 300 g of battery-grade nickel sulfate and 300 g of 85% industrial phosphoric acid, dissolve them in 2500 g of pure water at about 80°C, then add 140.7 g of battery-grade manganese sulfate monohydrate, 90.2 g of battery-grade lithium hydroxide, and 20 g of 5% graphene oxide slurry, add them to the reactor in sequence, stir thoroughly for 10 minutes, and then add 15 g of high-efficiency surfactant (ethylene propyl polyethylene glycol: polyvinyl pyridine: PVP = 4:3:2); raise the temperature to about 95°C, stir, and fully react for 60 minutes; adjust the pH value to 3.5-4.5 with ammonia water and continue to keep warm and react for 120 minutes.

[0145] 2. Filter the solution from the previous step through a plate and frame filter or a PP barrel type precision filter to obtain a nickel manganese phosphate filter cake, which is ready for use.

[0146] 3. Dry the damp NMP product in a CT hot air circulation oven at 140°C for 2.5 hours, crush the dry product, screen it, and determine its components. Based on the component content, the quality of the organic carbon source and the optimized lithium amount are calculated by the stoichiometric ratio and the carbon content in LNMP. The added amounts of organic carbon sources glucose and PEG6000 are 23.5 g and 15.7 g, respectively; the added amount of lithium carbonate is 2.37 g.

[0147] 4. Control the solid-liquid ratio of the previous material to 40-45% and the viscosity to 4000-5000 Pa·S. Stir thoroughly in the batching tank for 15 minutes, pump into the sand mill for sand grinding, and control the particle size D 50 =400nm, the main engine speed is set to 900r / min.

[0148] 5. Spray dry the sanding slurry.

[0149] 6. The material from step 5 is sintered in an inert furnace under the protection of high-purity N2 gas. The low-temperature sintering temperature is controlled at 450°C, the high-temperature sintering temperature is controlled at 730°C, and the temperature rise rate of each section is controlled at 3°C / min.

[0150] 7. Grind the material from step 6 by air flow to a particle size of D 50 The particle size was controlled at 1.34 μm, and after screening, grading and packaging, 410.9 g of carbon-coated lithium nickel manganese phosphate (LNMP / C) finished product was obtained: LiMn 0.2 Ni 0.8 PO4 (nickel-manganese molar ratio is 8:2). In this step, the material can be tested for carbon content, compaction, and electrical properties.

[0151] 8. Mix the LNMP / C powder material, PVDF, and conductive carbon black from step 7 in a ratio of 95:5:5, and then disperse and slurry with N-methylpyrrolidone dispersant. To ensure uniform dispersion, a double planetary agitator can be used for strong dispersion. The semi-dispersed slurry is evenly coated on carbon-coated aluminum foil using a coating machine and dried.

[0152] 9. The dried semi-finished electrode pieces are extruded twice by a roller machine; the extruded electrode pieces are cut by a punching machine to obtain φ32mm circular electrode pieces for use as positive electrode pieces in button battery assembly.

[0153] 10. Assemble the electrodes into 2032 button batteries according to the requirements of the simulated battery for electrical performance measurement.

[0154] The test results of the finished product are shown in the table below:

[0155]

[0156] Example 3

[0157] 1. Weigh 550 g of analytical grade nickelous nitrate and 332 g of 85% industrial phosphoric acid, dissolve them in 2000 g of pure water at about 75°C, then add 212.5 g of battery grade manganese nitrate, 71.5 g of battery grade lithium hydroxide, and 7 g of CNT. Add them to a 5000 L hydrothermal reactor in sequence, set the temperature to 180 ± 2°C, and control the pressure in the reactor at 1.35 ± 0.1 MPa; fully react for 240 min.

[0158] 2. Filter the slurry from the previous step through a plate and frame filter to obtain a nickel manganese lithium phosphate filter cake, i.e., LNMP wet product for standby use.

[0159] 3. Dry the damp LNMP product in a CT hot air circulation oven at 160°C for 2.5 hours, crush the dry product, screen it, and determine its components. Based on the component content, the quality of the organic carbon source and the optimized lithium amount are calculated by the stoichiometric ratio and the carbon content in LNMP. The added amounts of organic carbon sources glucose and PEG6000 are 22.7 g and 12.5 g, respectively; the added amount of lithium carbonate is 1.89 g.

[0160] 4. Control the solid-liquid ratio of the previous material to 40-45% and the viscosity to 4000-5000 Pa.S. Stir thoroughly in the batching tank for 15 minutes, pump into the sand mill for sand grinding, and control the particle size D 50 =600nm, the main engine speed is set to 900r / min.

[0161] 5. Spray dry the sanding slurry.

[0162] 6. The material from step 5 was sintered in an inert furnace under the protection of high-purity N2 gas. The low-temperature sintering temperature was controlled at 450°C, the high-temperature sintering temperature was controlled at 770°C, and the temperature rise rate of each section was controlled at 3°C / min.

[0163] 7. Grind the material from step 6 by air flow to a particle size of D 50 The particle size was controlled at 1.51 μm, and after screening, grading and packaging, 410.9 g of carbon-coated lithium nickel manganese phosphate (LNMP / C) finished product was obtained: LiMn 0.3 Ni 0.7 PO4 (nickel-manganese molar ratio is 7:3). In this step, the material can be tested for carbon content, compaction, and electrical properties.

[0164] 8. Mix the LNMP / C powder material, PVDF, and conductive carbon black from step 7 in a ratio of 95:5:5, and then disperse and slurry with N-methylpyrrolidone dispersant. To ensure uniform dispersion, a double planetary agitator can be used for strong dispersion. The semi-dispersed slurry is evenly coated on carbon-coated aluminum foil using a coating machine and dried.

[0165] 9. The dried semi-finished electrode pieces are extruded twice by a roller machine; the extruded electrode pieces are cut by a punching machine to obtain φ32mm circular electrode pieces for use as positive electrode pieces in button battery assembly.

[0166] 10. Assemble the electrodes into 2032 button batteries according to the requirements of the simulated battery for electrical performance measurement.

[0167] The test results of the finished product are shown in the table below:

[0168]

[0169] Example 4

[0170] 1. Weigh 350 g of analytically pure nickel oxalate monohydrate, 555.5 g of ammonium dihydrogen phosphate, and 1500 g of pure water. Then add 98.5 g of battery-grade manganese carbonate, 66.5 g of battery-grade lithium carbonate, 15 g of 5% graphene oxide slurry, 25 g of glucose, 23 g of PEG6000, and 10 g of high-efficiency surfactant (allyl polyethylene glycol: fatty alcohol and ethylene oxide condensate: ether phosphate = 4:3:2). Add them to a 3000 L beaker in sequence and stir thoroughly for 10 minutes to disperse.

[0171] 2. Control the solid-liquid ratio of the material in the previous step to 40~45%, and the viscosity to 4000~5000Pa.S. The pure water volume can be controlled and pumped into the sand mill for sand grinding to control the particle size D 50 =300nm, the main engine speed is set to 1500r / min.

[0172] 3. Spray dry the sanding slurry.

[0173] 4. The material from step 5 is sintered in an inert furnace under the protection of high-purity N2 gas. The low-temperature sintering temperature is controlled at 450°C, the high-temperature sintering temperature is controlled at 750°C, and the temperature rise rate of each section is controlled at 3°C / min.

[0174] 5. Grind the material from step 4 by air flow to a particle size of D 50 The particle size was controlled at 1.55 μm, and after screening, grading and packaging, 267.4 g of carbon-coated lithium nickel manganese phosphate (LNMP / C) finished product was obtained: LiMn 0.5 Ni 0.5 PO4 (nickel-manganese molar ratio of 5:5). In this step, the material can be tested for carbon content, compaction, and electrical properties.

[0175] 8. Mix the LNMP / C powder material, PVDF, and conductive carbon black from step 7 in a ratio of 95:5:5, and then disperse and slurry with N-methylpyrrolidone dispersant. To ensure uniform dispersion, a double planetary agitator can be used for strong dispersion. The semi-dispersed slurry is evenly coated on carbon-coated aluminum foil using a coating machine and dried.

[0176] 9. The dried semi-finished electrode pieces are extruded twice by a roller machine; the extruded electrode pieces are cut by a punching machine to obtain φ32mm circular electrode pieces for use as positive electrode pieces in button battery assembly.

[0177] 10. Assemble the electrodes into 2032 button batteries according to the requirements of the simulated battery for electrical performance measurement.

[0178] The test results of the finished product are shown in the table below:

[0179]

[0180] Example 5

[0181] The method and steps are the same as those in Example 1, except that 0.3g of magnesium nitrate and 0.3g of zinc nitrate are added to the raw materials in step 1. After all the raw materials are mixed, they are subjected to high-energy ball milling at 1200r / min for 5h. Finally, 327.58g of carbon-coated lithium nickel manganese phosphate (LNMP / C) product is obtained: LiMn 0.4 Ni 0.6 Mg 0.01 Zn 0.07 PO4 / C (nickel-manganese molar ratio is 6:4).

[0182] The test results of the finished product are shown in the table below:

[0183]

[0184] Example 6

[0185] The method and steps are the same as those in Example 1, except that 0.5g of vanadium pentoxide and 0.5g of beryllium chloride are added to the raw materials in step 1. After all the raw materials are mixed, they are subjected to high-energy ball milling at 1200r / min for 5h. Finally, 371.99g of carbon-coated lithium nickel manganese phosphate (LNMP / C) product is obtained: LiMn 0.4 Ni 0.6 V 0.022 Be 0.012 PO4 / C (nickel-manganese molar ratio is 6:4).

[0186] The test results of the finished product are shown in the table below:

[0187]

[0188] Example 7

[0189] The method and steps are the same as those in Example 1, except that 1.5 g of cobalt chloride is added to the raw materials in step 1. After all the raw materials are mixed, they are subjected to high-energy ball milling at 1200 r / min for 5 h. Finally, 376.82 g of carbon-coated lithium nickel manganese phosphate (LNMP / C) product is obtained: LiMn 0.4 Ni 0.6 Co 0.15 PO4 / C (nickel-manganese molar ratio is 6:4).

[0190] The test results of the finished product are shown in the table below:

[0191]

[0192] Example 8

[0193] The method and steps are the same as those in Example 2, except that 0.8 g of copper sulfate is added to the raw materials in step 1. After all the raw materials are mixed, the pH value is adjusted to 2.0-3.0, and finally 413.65 g of carbon-coated lithium nickel manganese phosphate (LNMP / C) finished product is obtained: LiMn 0.2 Ni 0.8 Cu 0.05 PO4 / C (nickel-manganese molar ratio is 8:2)

[0194] The test results of the finished product are shown in the table below:

[0195]

[0196] Example 9

[0197] The method and steps are the same as those in Example 2, except that lithium carbonate is added to 143.7 g in step 3, and finally 412.1 g of carbon-coated lithium nickel manganese phosphate (LNMP / C) product is obtained: Li 1.025 Mn 0.2 Ni 0.8 PO4 / C (nickel-manganese molar ratio is 8:2).

[0198] The test results of the finished product are shown in the table below:

[0199]

[0200] Example 10

[0201] The method and steps are the same as those in Example 3, except that lithium carbonate is added to 136.54 g in step 3, and finally 381.32 g of carbon-coated lithium nickel manganese phosphate (LNMP / C) product is obtained: Li 1.035 Mn 0.3 Ni 0.7 PO4 / C (nickel-manganese molar ratio is 7:3).

[0202] The test results of the finished product are shown in the table below:

[0203]

[0204] Example 11

[0205] The method and steps were the same as those in Example 4, except that in step 8, the obtained LNMP / C powder material, 622 ternary material, PVDF, and conductive carbon black were mixed in a ratio of 80:10:5:5. After dispersion and slurry preparation, a double planetary agitator was used to vigorously disperse the slurry to ensure uniform dispersion. The semi-dispersed slurry was evenly coated on a carbon-coated aluminum foil using a coating machine and dried.

[0206] The test results of the finished product are shown in the table below:

[0207]

[0208] Example 12

[0209] The method and steps are the same as those in Example 4, except that in step 8, the obtained LNMP / C powder material, lithium manganate, PVDF, and conductive carbon black are mixed in a ratio of 75:15:5:5. After dispersion and slurry adjustment, a double planetary agitator is used to vigorously disperse the slurry to ensure uniform dispersion. The semi-dispersed slurry is evenly coated on a carbon-coated aluminum foil using a coating machine and dried.

[0210] The test results of the finished product are shown in the table below:

[0211]

[0212] It should also be noted that the various specific technical features described in the above specific embodiments are willing to be combined in any appropriate manner unless there is any contradiction. In order to avoid unnecessary repetition, this application does not describe each possible combination one by one.

[0213] The above-described embodiments are merely preferred embodiments for the purpose of fully illustrating this application, and the scope of protection of this application is not limited thereto. Any equivalent substitutions or modifications made by persons skilled in the art based on this application are within the scope of protection of this application. The scope of protection of this application shall be determined by the claims.

Claims

1. A nickel manganese phosphate active material having an olivine structure, characterized in that: The general structural formula is Ni b Mn d M e PO4, b is 0.1≤b≤0.95, 0.05≤d≤0.900, 0≤e≤0.5; M is a doping element, and M is selected from one or more combinations of Fe, Al, Co, Ca, Pb, Na, Ti, Zr, Mo, V, Nb, Sc, Cr, Cu, Zn, Be, La, Mg, N, S or Al.

2. The nickel manganese phosphate active material having an olivine structure according to claim 1, characterized in that: The structural formula Ni b Mn d M e In PO4, b is 0.1 to 0.95, d is 0.05 to 0.9, and e is 0≤e≤0.

5.

3. The nickel manganese phosphate active material having an olivine structure according to claim 2, characterized in that: The structural formula Ni b Mn d M e In PO4, b is 0.5-0.8, d is 0.2-0.5, and e is 0≤e≤0.

5.

4. The nickel manganese phosphate active material having an olivine structure according to claim 3, characterized in that: The structural formula Ni b Mn d M e In PO4, b is 0.5, 0.6, 0.7, or 0.8; d is 0.2, 0.3, 0.4, or 0.5; e is 0, 0.05, 0.1, or 0.

15.

5. The nickel manganese phosphate active material having an olivine structure according to claim 4, characterized in that: The structural formula Ni b Mn d M e In PO4, b is 0.8, d is 0.2, and e is 0.05, 0.1, or 0.15; or b is 0.7, d is 0.3, and e is 0.05, 0.1, or 0.15; or b is 0.6, d is 0.4, and e is 0.05, 0.1, or 0.15; or b is 0.5, d is 0.5, and e is 0, 0.05, 0.1, or 0.

15.

6. The nickel manganese phosphate active material having an olivine structure according to claim 5, characterized in that: The structural formula of the nickel manganese phosphate active material is Ni 0.8 Mn 0.2 M 0.05 PO4, Ni 0.8 Mn 0.2 M 0.1 PO4, Ni 0.8 Mn 0.2 M 0.15 PO4, Ni 0.7 Mn 0.3 M 0.05 PO4, Ni 0.7 Mn 0.3 M 0.1 PO4, Ni 0.7 Mn 0.3 M 0.15 PO4, Ni 0.6 Mn 0.4 M 0.05 PO4, Ni 0.6 Mn 0.4 M 0.1 PO4, Ni 0.6 Mn 0.4 M 0.15 PO4, Ni 0.5 Mn 0.5 M 0.05 PO4, Ni 0.5 Mn 0.5 M 0.1 PO4, Ni 0.5 Mn 0.5 M 0.15 Any one of PO4, MFe, Co, Ca, Pb, Na, Ti, Zr, Mo, V, Nb, Sc, Cr, Cu, Zn, Be, La, Mg.

7. The nickel manganese phosphate active material having an olivine structure according to claim 6, characterized in that: The manganese source is selected from one or more combinations of metallic manganese, manganese monoxide, manganese dioxide, manganese tetraoxide, manganese carbonate, manganese citrate, manganese acetate, manganese oxalate, manganese sulfate, manganese nitrate, and manganese chloride.

8. The nickel manganese phosphate active material having an olivine structure according to claim 7, characterized in that: The nickel source is selected from one or more combinations of nickel metal, nickel hydroxide, nickel sulfate, nickel oxalate, nickel carbonate, nickel nitrate and nickel chloride.

9. The nickel manganese phosphate active material having an olivine structure according to claim 8, characterized in that: The raw material of the doping element M is selected from one or more combinations of sulfates, phosphates, nitrates, chlorides, oxalates, acetates, and carbonates of any one of Fe, Co, Ca, Pb, Na, Ti, Zr, Mo, V, Nb, Sc, Cr, Cu, Zn, Be, La, and Mg.

10. The nickel manganese phosphate active material having an olivine structure according to claim 9, characterized in that: The particle size of the nickel manganese phosphate active material having an olivine structure is D 50 0.5-2.0 μm, more preferably D 50 1.0-1.6 μm, more preferably D 50 1.2-1.55μm.

11. A carbon-coated nickel manganese lithium phosphate composite material, characterized in that: The structural formula of the carbon-coated nickel manganese lithium phosphate composite material includes the structural formula of the nickel manganese phosphate active material according to any one of claims 1 to 10, and the structural formula of the carbon-coated nickel manganese lithium phosphate composite material is Li a Ni b Mn d M e PO4 / C, a is 0.01~1.05, and the sum of (a+b+d+e) and PO4 3- The ratio of root molar values ​​is 0.90-1.

05.

12. The carbon-coated nickel manganese lithium phosphate composite material according to claim 11, characterized in that: The a is 1.025-1.035, more preferably any one of 1.025, 1.026, 1.027, 1.028, 1.029, 1.030, 1.031, 1.032, 1.033, 1.034, or 1.035, and the carbon content is 1-3%; When 0<a<1.025, nickel manganese phosphate pre-embedded with lithium or precursor material nickel manganese phosphate (abbreviated code: NMP) is obtained.

13. The carbon-coated nickel manganese lithium phosphate composite material according to claim 12, characterized in that: The carbon-coated carbon source is selected from one or more combinations of organic carbon, artificial or natural graphite, graphene, carbon nanotubes or Super P, acetylene black or other conductive carbons; the carbon content is 0.1-10%.

14. A 5V high voltage platform phosphate positive electrode material, characterized in that: The material is any one or more combinations of the carbon-coated nickel manganese lithium phosphate composite material with an olivine structure as described in any one of claims 1 to 13.

15. A method for preparing a nickel manganese phosphate active material having an olivine structure, characterized in that: The manganese source, nickel source, phosphorus source and doping element raw materials are added in a stoichiometric ratio, fully sand-ground and dispersed in a sand mill, and spray-dried after reaching the particle size requirement, and the dried material is sintered and dehydrated in a high-temperature sintering furnace for phase change to obtain nickel manganese phosphate material; Alternatively, the manganese source, nickel source, lithium source, carbon source, phosphorus source and doping element raw materials are added in a stoichiometric ratio, fully dispersed by sand grinding in a sand mill, spray dried after reaching the particle size requirement, and the dried material is sintered and dehydrated in a high-temperature sintering furnace for phase change to obtain a carbon-coated nickel manganese lithium phosphate positive electrode material.

16. The method for preparing the nickel manganese phosphate active material having an olivine structure according to claim 15, characterized in that: The manganese source is selected from one or more combinations of metallic manganese, manganese monoxide, manganese dioxide, manganese tetraoxide, manganese carbonate, manganese citrate, manganese acetate, manganese oxalate, manganese sulfate, manganese nitrate, and manganese chloride; The nickel source is selected from one or more combinations of nickel metal, nickel hydroxide, nickel sulfate, nickel oxalate, nickel carbonate, nickel nitrate, and nickel chloride; The lithium source is selected from one or more combinations of lithium carbonate, lithium bicarbonate, lithium sulfate, lithium phosphate, lithium oxalate and lithium hydroxide; The phosphorus source is selected from one or more combinations of ammonium phosphate, lithium phosphate, sodium phosphate, phosphoric acid, and hypophosphorous acid; The raw material of the doping element M is selected from one or more combinations of sulfates, phosphates, nitrates, chlorides, oxalates, acetates, and carbonates of any one of Fe, Co, Ca, Pb, Na, Ti, Zr, Mo, V, Nb, Sc, Cr, Cu, Zn, Be, La, and Mg; The nickel manganese raw material for synthesizing the nickel manganese lithium phosphate positive material can also be nickel manganese oxide (abbreviated code: NMO) or nickel manganese hydroxide (abbreviated code: NMOH) or precursor nickel manganese phosphate (NMP); The carbon source is selected from one or more combinations of organic carbon, artificial or natural graphite, graphene, carbon nanotubes or Super P, acetylene black or other conductive carbon, PEG, and glucose.

17. The method for preparing the nickel manganese phosphate active material having an olivine structure according to claim 16, characterized in that: After the manganese source, nickel source, phosphorus source and doping element raw materials are mixed, or after the manganese source, nickel source, lithium source, carbon source, phosphorus source and doping element raw materials are mixed, water is added to form a slurry, a surfactant is added, and the temperature is raised to 90-120° C. to react for 2-4 hours. After the reaction, the nickel manganese lithium phosphate filter cake obtained by filtering is dried and ball milled.

18. The method for preparing the nickel manganese phosphate active material having an olivine structure according to claim 17, characterized in that: The surfactant is any one of allyl polyethylene glycol, polyvinyl pyridine and PVP, in a mixture with a mass ratio of 4:2-3:0.5-2.

19. The method for preparing the nickel manganese phosphate active material having an olivine structure according to claim 18, characterized in that: During the ball milling process, a carbon source and a lithium source are added so that the product structure is LiaNibMndMePO4 / C, the molar amount of lithium is 0.01-1.05, the carbon content is 0.1-10%, the solid-liquid ratio is adjusted to 40-45%, the viscosity is controlled at 4000-5000 Pa·s, and the product is ground to a particle size D50 of 200-800 nm and then spray-dried.

20. The method for preparing the nickel manganese phosphate active material having an olivine structure according to claim 19, characterized in that: The particle size requirement is D of a single group of materials. 50 It is within 200 nm, more preferably within 100 nm.

21. The method for preparing the nickel manganese phosphate active material having an olivine structure according to claim 20, characterized in that: The sand grinding particle size is controlled at D50 of 0.2~0.8μm; The particle size of the product obtained after the spray drying is 15-25 μm, more preferably 10-15 μm; The carbon coating sintering temperature is: the low-temperature coke removal section temperature is set to 250-650°C, more preferably 350-550°C, and the high-temperature phase change section temperature is 680-850°C, more preferably 700-790°C.

22. A nickel manganese phosphate active material having an olivine structure, characterized in that: A nickel manganese phosphate positive electrode material or a carbon-coated nickel manganese phosphate positive electrode material is prepared by the method described in any one of claims 15 to 18. The active material has a 5V high voltage platform as a phosphate positive electrode material.

23. A 5V high voltage platform phosphate positive electrode material, characterized in that: A nickel manganese phosphate positive electrode material or a carbon-coated nickel manganese phosphate positive electrode material is prepared by the method described in any one of claims 15 to 18, wherein the structural formula of the nickel manganese phosphate positive electrode material is any one of claims 1 to 10; The structural formula of the carbon-coated nickel manganese lithium phosphate positive electrode material is any one of claims 11-13.

24. A method for preparing a nickel manganese phosphate active material having an olivine structure, characterized in that: The manganese source and the nickel source are fully dissolved in a certain concentration of a phosphorus source aqueous solution, and an alkaline substance is added to adjust the pH value to 2-10 for precipitation and crystallization; the slurry after crystallization is filtered to obtain a filter cake and the filter cake is fully washed with pure water; the filter cake is dried and sintered to obtain a nickel manganese phosphate active material with an olivine structure; Alternatively, a carbon source, a lithium source and a doping element are added to the nickel manganese phosphate active material, and after grinding and dispersion, the particle size is spray-dried, and the dried material is sintered to obtain a carbon-coated nickel manganese lithium phosphate positive electrode material with an olivine structure.

25. The method for preparing the nickel manganese phosphate active material having an olivine structure according to claim 24, characterized in that: After the manganese source, nickel source and phosphorus source are mixed, or the manganese source, nickel source, lithium source, carbon source, phosphorus source and doping element raw materials are mixed, water is added to form a slurry, a surfactant is added, the temperature is raised to 90-120° C. to react for 1-4 hours, an alkaline substance is added to adjust the pH value to 2-10, and the reaction is continued by keeping the temperature for 2-4 hours. After the reaction, a nickel manganese lithium phosphate filter cake is obtained by filtration.

26. The method for preparing the nickel manganese phosphate active material having an olivine structure according to claim 25, characterized in that: The alkaline substance is selected from any one of sodium hydroxide, lithium hydroxide, ammonia water, cesium carbonate, sodium carbonate, sodium bicarbonate, sodium methoxide, potassium ethoxide, and potassium tert-butoxide, and the alkaline substance is added to adjust the pH value to 1-5, preferably 1.5-5, preferably 3.5-4.5; The surfactant is a mixture of allyl polyethylene glycol, allyl polyethylene glycol, polyvinyl pyridine and PVP in a mass ratio of 4:2-3:0.5-2.

27. The method for preparing the nickel manganese phosphate active material having an olivine structure according to claim 26, characterized in that: After drying, carbon source and lithium source are added to make the product structure Li a Ni b Mn d M e PO4 / C, the molar amount of lithium is 0.01-1.05, the carbon content is 0.1-10%, the solid-liquid ratio is adjusted to 40-45%, the viscosity is controlled at 4000-5000 Pa·s, and the powder is ground to a particle size of D50 of 200-800 nm and then spray-dried.

28. The method for preparing the nickel manganese phosphate active material having an olivine structure according to claim 27, characterized in that: The manganese source is selected from one or more combinations of metallic manganese, manganese monoxide, manganese dioxide, manganese tetraoxide, manganese carbonate, manganese citrate, manganese acetate, manganese oxalate, manganese sulfate, manganese nitrate, and manganese chloride; The nickel source is selected from one or more combinations of nickel metal, nickel hydroxide, nickel sulfate, nickel oxalate, nickel carbonate, nickel nitrate, and nickel chloride; The lithium source is selected from one or more combinations of lithium carbonate, lithium bicarbonate, lithium sulfate, lithium phosphate, lithium oxalate and lithium hydroxide; The phosphorus source is selected from a combination of one or more of ammonium phosphate, lithium phosphate, sodium phosphate, phosphoric acid, and hypophosphorous acid; The raw material of the doping element M is selected from one or more combinations of sulfates, phosphates, nitrates, chlorides, oxalates, acetates, and carbonates of any one of Fe, Co, Ca, Pb, Na, Ti, Zr, Mo, V, Nb, Sc, Cr, Cu, Zn, Be, La, and Mg; The carbon source is selected from one or more combinations of organic carbon, artificial or natural graphite, graphene, carbon nanotubes or Super P, acetylene black or other conductive carbons.

29. The method for preparing the nickel manganese phosphate active material having an olivine structure according to claim 28, characterized in that: The ball mill speed is 800-1200r / min; The particle size of the product obtained after the spray drying is 15-25 μm, more preferably 10-15 μm; the sintering temperature is 400-600°C, more preferably 450°C-500°C.

30. A nickel manganese phosphate active material having an olivine structure, characterized in that: A nickel manganese phosphate positive electrode material or a carbon-coated nickel manganese phosphate positive electrode material is prepared by the method described in any one of claims 21 to 26. The active material has a 5V high voltage platform as a phosphate positive electrode material.

31. A 5V high voltage platform phosphate positive electrode material, characterized in that: A nickel manganese phosphate positive electrode material or a carbon-coated nickel manganese phosphate positive electrode material is prepared by the method described in any one of claims 21 to 26, wherein the structural formula of the nickel manganese phosphate positive electrode material is any one of claims 1 to 10; The structural formula of the carbon-coated nickel manganese lithium phosphate positive electrode material is any one of claims 11-13.

32. A method for preparing a nickel manganese phosphate active material having an olivine structure, characterized in that: The soluble manganese source, nickel source and phosphorus source are fully dissolved and filtered according to the stoichiometric ratio to obtain a clean solution, and a hydrothermal reaction is carried out in a hydrothermal kettle at a certain pressure and temperature. After a period of hydrothermal reaction, the discharged material is filtered to obtain a filter cake, and the filter cake is dried and sintered to obtain a nickel manganese phosphate active material with an olivine structure; Alternatively, a soluble manganese source, a nickel source, a lithium source, a phosphorus source, a carbon source and doping elements are fully dissolved and filtered according to a stoichiometric ratio to obtain a clean solution, and a hydrothermal reaction is carried out in a hydrothermal kettle at a certain pressure and temperature. After a period of hydrothermal reaction, the material is filtered to obtain a filter cake, and the filter cake is dried and sintered to obtain a carbon-coated nickel manganese phosphate active material with an olivine structure.

33. The method for preparing the nickel manganese phosphate active material having an olivine structure according to claim 32, characterized in that: The hydrothermal reaction temperature is 120-200°C, and the hydrothermal reaction pressure is 5-20MPa; After the hydrothermal reaction, the product is dried, and a carbon source and a lithium source are added so that the product structure is Li a Ni b Mn d M e PO4 / C, the molar amount of lithium is 0.01-1.05, the carbon content is 0.1-10%, the solid-liquid ratio is adjusted to 40-45%, the viscosity is controlled at 4000-5000 Pa·s, and the powder is ground to a particle size of D50 of 200-800 nm and then spray-dried.

34. The method for preparing the nickel manganese phosphate active material having an olivine structure according to claim 32, characterized in that: The manganese source is selected from one or more combinations of metallic manganese, manganese monoxide, manganese dioxide, manganese tetraoxide, manganese carbonate, manganese citrate, manganese acetate, manganese oxalate, manganese sulfate, manganese nitrate, and manganese chloride; The nickel source is selected from one or more combinations of nickel metal, nickel hydroxide, nickel sulfate, nickel oxalate, nickel carbonate, nickel nitrate, and nickel chloride; The lithium source is selected from one or more combinations of lithium carbonate, lithium bicarbonate, lithium sulfate, lithium phosphate, lithium oxalate and lithium hydroxide; The phosphorus source is selected from a combination of one or more of ammonium phosphate, lithium phosphate, sodium phosphate, phosphoric acid, and hypophosphorous acid; The raw material of the doping element M is selected from one or more combinations of sulfates, phosphates, nitrates, chlorides, oxalates, acetates, and carbonates of any one of Fe, Co, Ca, Pb, Na, Ti, Zr, Mo, V, Nb, Sc, Cr, Cu, Zn, Be, La, and Mg; The carbon source is selected from one or more combinations of organic carbon, artificial or natural graphite, graphene, carbon nanotubes or Super P, acetylene black or other conductive carbons.

35. The method for preparing the nickel manganese phosphate active material having an olivine structure according to claim 34, characterized in that: The sintering temperature is 400-600°C, more preferably 450°C-500°C.

36. A nickel manganese phosphate active material having an olivine structure, characterized in that: A nickel manganese phosphate positive electrode material or a carbon-coated nickel manganese phosphate positive electrode material is prepared by the method described in any one of claims 29 to 32. The active material has a 5V high voltage platform as a phosphate positive electrode material.

37. A 5V high voltage platform phosphate positive electrode material, characterized in that: A nickel manganese phosphate positive electrode material or a carbon-coated nickel manganese phosphate positive electrode material is prepared by the method described in any one of claims 29 to 32, wherein the structural formula of the nickel manganese phosphate positive electrode material is any one of claims 1 to 10; The structural formula of the carbon-coated nickel manganese lithium phosphate positive electrode material is any one of claims 11-13.

38. A 5V high voltage lithium battery pole piece, characterized in that: A battery pole piece made of the positive electrode material, i.e., a carbon-coated nickel manganese lithium phosphate composite positive electrode material pole piece, wherein the positive electrode material component contains 1-100wt% of the carbon-coated nickel manganese lithium phosphate positive electrode material, and the structural formula of the carbon-coated nickel manganese lithium phosphate positive electrode material is any one of claims 11-13.

39. The 5V high voltage lithium battery pole piece according to claim 38, characterized in that: The positive electrode material composition contains 1-90wt% of carbon-coated nickel manganese lithium phosphate positive electrode material, preferably the positive electrode material composition contains 10-80wt% of carbon-coated nickel manganese lithium phosphate positive electrode material, preferably the positive electrode material composition contains 20-70wt% of carbon-coated nickel manganese lithium phosphate positive electrode material, preferably the positive electrode material composition contains 30-70wt% of carbon-coated nickel manganese lithium phosphate positive electrode material, preferably the positive electrode material composition contains 30-60wt% of carbon-coated nickel manganese lithium phosphate positive electrode material.

40. The 5V high voltage lithium battery pole piece according to claim 38, characterized in that: When the carbon-coated nickel manganese lithium phosphate positive electrode material is less than 100%, it also contains other positive electrode materials, and the other positive electrode materials are selected from any one of lithium cobalt oxide, lithium manganese oxide, nickel cobalt aluminum ternary polymer material, nickel cobalt manganese ternary polymer material, and nickel manganese phosphate active material with olivine structure; the structural formula of the nickel manganese phosphate active material with olivine structure is selected from any one of claims 1-10.

41. A 5V high voltage lithium battery, characterized in that: The lithium battery includes a corresponding laminate, a square aluminum shell, a cylindrical winding or other lithium batteries of different shapes and structures made from the 5V high-voltage lithium battery pole piece described in any one of claims 38-40, and the lithium battery contains at least one lithium element electrolyte solution.

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