CN115566182A - Positive electrode active material, preparation method thereof, battery and power utilization device - Google Patents

Positive electrode active material, preparation method thereof, battery and power utilization device Download PDF

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CN115566182A
CN115566182A CN202211258260.XA CN202211258260A CN115566182A CN 115566182 A CN115566182 A CN 115566182A CN 202211258260 A CN202211258260 A CN 202211258260A CN 115566182 A CN115566182 A CN 115566182A
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nitrate
active material
positive electrode
oxide
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胡燚
陈巍
欧阳云鹏
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Sunwoda Electric Vehicle Battery Co Ltd
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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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/006—Compounds containing, besides manganese, two or more other elements, with the exception of oxygen or hydrogen
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—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

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Abstract

The application discloses a positive active material, a preparation method thereof, a battery and an electric device. When the sodium removal percentage of the positive active material is 10-85%, the maximum change rate delta a of the positive active cell parameter a max Satisfies the following conditions: delta a max Not more than 3.5 percent, and the maximum change rate Delta c of the parameter c of the active crystal cell of the positive electrode max Satisfies the following conditions: delta c max Less than or equal to 4.3 percent. The unit cell parameters are increased through doping, a sodium ion diffusion channel is widened, and the multiplying power performance is improved; by improving the uniformity of the doping elements, the volume expansion of the material is small, and the structural stability of the material is improvedAnd the cycle performance is improved.

Description

Positive electrode active material, preparation method thereof, battery and power utilization device
Technical Field
The application relates to the technical field of new energy, in particular to a positive electrode active material, a preparation method thereof, a battery and an electric device.
Background
At present, the application markets of the lithium ion battery in the power field and the energy storage field are wide, but the challenges faced by the lithium ion battery are also increasing, such as the problems of increasing shortage of lithium resources, increasing of material prices, low recycling rate of old batteries and the like. The sodium ion battery can realize charging and discharging by utilizing the process of deintercalation of sodium ions between the positive electrode and the negative electrode, the reserve of sodium resources is far higher than that of lithium resources, the cost advantage of the sodium resources is obvious, and the active material of the sodium electrode anode can not use noble metal cobalt, so that the cost of the sodium ion battery is obviously lower than that of a lithium ion battery.
Currently, the positive active materials used for sodium ion batteries mainly comprise three types, namely a transition metal oxide system, a polyanion compound and a prussian blue system. Among them, the layered transition metal oxide positive active material has a high specific capacity, and is considered as one of the most promising positive active materials for commercialization in a sodium ion battery.
However, the ion radius of the sodium ions is larger than that of the lithium ions, so that the diffusion difficulty of the sodium ions is higher, and the rate capability of the layered transition metal oxide positive electrode active material is poorer; and structural collapse easily occurs during the process of long-term sodium intercalation and the Jahn-Teller effect of manganese causes poor cycle performance.
Disclosure of Invention
The application provides a positive active material, a preparation method thereof, a battery and an electric device, and solves the problem that the rate capability and the cycle performance of a sodium ion battery adopting the conventional positive active material are poor.
According to the positive electrode active material provided by the first aspect of the present application, when the sodium removal percentage of the positive electrode active material is 10% to 85%, the maximum change rate of the positive electrode active cell parameter a is Δ a max % satisfying Δ a max Not more than 3.5, and the maximum change rate of the anode active unit cell parameter c is delta c max % satisfying Δ c max ≤4.3。
Alternatively, in other embodiments of the present application, the positive electrode active material includes a doping element M including at least one of Li, K, ni, mg, zn, ca, al, co, cr, V, sr, zr, ti, sn, mo, W, Y, nb, si, and Ru.
OptionallyIn other embodiments of the present application, the positive electrode active material includes Na having a chemical formula i Cu x Fe y Mn z Me p O 2 The compound of (1) is 0.5 < i < 1.5,0 < x < 0.3,0 < y < 0.5,0 < z < 0.5,0 < p < 0.2, x + y + z + p =1.
Optionally, in other embodiments of the present application, the mass concentration deviation of the doping element M is η%, and η ≦ 20 is satisfied.
Alternatively, in other embodiments of the present application, the positive electrode active material includes primary particles having an average particle diameter d μm satisfying 0.05. Ltoreq. D.ltoreq.7.
Alternatively, in other embodiments of the present application, the Dv50 of the positive electrode active material is 2 to 22 μm.
According to a second aspect of the present application, there is provided a method for preparing a positive electrode active material, comprising:
mixing a copper source, an iron source and a manganese source, adding a precipitator and a complexing agent, and reacting to obtain a precursor;
and mixing the precursor, the doping element source and the sodium source, and performing primary sintering and secondary sintering to obtain the anode active material.
Optionally, in other embodiments herein, the copper source comprises at least one of copper acetate, copper nitrate, copper oxalate, or copper sulfate.
Optionally, in other embodiments herein, the iron source comprises at least one of iron acetate, iron nitrate, iron oxalate, or iron sulfate.
Optionally, in other embodiments herein, the source of manganese comprises at least one of manganese acetate, manganese nitrate, manganese oxalate, or manganese sulfate.
Optionally, in other embodiments of the present application, the source of the doping element comprises at least one of lithium oxide, lithium nitrate, potassium oxide, potassium nitrate, nickel oxide, nickel nitrate, magnesium oxide, magnesium nitrate, zinc oxide, zinc nitrate, calcium oxide, calcium nitrate, aluminum oxide, aluminum nitrate, cobalt oxide, cobalt nitrate, chromium oxide, chromium nitrate, vanadium oxide, vanadium nitrate, strontium oxide, strontium nitrate, zirconium dioxide, zirconium nitrate, titanium oxide, titanium nitrate, tin oxide, tin nitrate, molybdenum trioxide, molybdenum nitrate, tungsten oxide, tungsten nitrate, yttrium oxide, yttrium nitrate, niobium oxide, silicon oxide, ruthenium oxide, or ruthenium nitrate.
Optionally, in other embodiments herein, the sodium source comprises at least one of sodium carbonate, sodium hydroxide, sodium acetate, sodium nitrate, or sodium oxalate.
Optionally, in other embodiments of the present application, the temperature of the first sintering is 300 to 600 ℃, and the time of the first sintering is 5 to 12 hours.
Optionally, in other embodiments of the present application, the temperature of the second sintering is 700 to 1000 ℃, and the time of the second sintering is 6 to 24 hours.
According to the third aspect of the present application, a battery includes a positive electrode plate, the positive electrode plate includes a positive electrode current collector and a positive electrode active material layer disposed on the positive electrode current collector, and the positive electrode active material layer includes the positive electrode active material or the positive electrode active material prepared by the preparation method.
According to a fourth embodiment of the present application, an electric device includes the battery.
The positive electrode active material according to the embodiment of the application has at least the following technical effects:
the positive active material has small unit cell parameter change in the process of sodium deintercalation, and the maximum change rate delta a of the unit cell parameter a max Not more than 3.5%, and maximum change rate Delta c of unit cell parameter c max Less than or equal to 4.3 percent, is favorable for maintaining the structural stability of the material and improving the cycle performance.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Fig. 1 is an electron microscope characterization test chart of the surface morphology of the positive electrode active material obtained in example 1 of the present application;
FIG. 2 is a schematic diagram of sampling of doping uniformity in mass concentration deviation detection of examples and comparative examples of the present application;
fig. 3 is a graph comparing rate performance of batteries manufactured by the positive active materials of example 1 and comparative example 1 of the present application;
fig. 4 is a graph comparing cycle performance of batteries manufactured by the positive active materials of example 1 of the present application and comparative example 1.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The embodiment of the application provides a positive electrode active material, a preparation method thereof, a battery and an electric device. The following are detailed below. It should be noted that the following description of the embodiments is not intended to limit the preferred order of the embodiments.
In the present specification, the numerical range indicated by the term "to" means a range including numerical values described before and after the term "to" as the minimum value and the maximum value, respectively.
The embodiment of the application provides a positive active material, wherein when the sodium removal percentage of the positive active material is 10-85%, the maximum change rate of a positive active cell parameter a is delta a max % satisfies Δ a max Not more than 3.5, and the maximum change rate of the parameter c of the active crystal cell of the anode is Delta c max %, satisfies Δ c max Less than or equal to 4.3. The unit cell parameters a and c are the lengths of the unit translation vectors in the two crystal axis directions in the unit cell, respectively. Delta a max And may be 3.5, 3.4, 2.9, 2.8, 2.7, 2.6, or a range consisting of any two of these values. In some embodiments of the present application, Δ a max Less than or equal to 2.9. In some embodiments of the present application, Δ a max ≤2.7。△c max Can be 4.3, 4.2, 3.5, 3.3, 3.1, 3.0, or any two of the setsThe range of (A) to (B). In some embodiments of the present application, Δ c max Less than or equal to 3.5. In some embodiments of the present application, Δ c max Less than or equal to 3.0. The crystal cell parameter change of the anode active material is small, which is beneficial to keeping the structure of the material stable and improving the cycle performance. And obtaining the values a and c in each sodium removal state through an in-situ XRD test, and further calculating the change rates delta a and delta c of the values a and c.
In other embodiments of the present application, the positive electrode active material includes a doping element M including at least one of Li, K, ni, mg, zn, ca, al, co, cr, V, sr, zr, ti, sn, mo, W, Y, nb, si, and Ru. The positive active material is doped with doping elements, and the doping can increase unit cell parameters, promote the migration of sodium ions and improve the rate capability.
Optionally, in other embodiments of the present application, the positive electrode active material comprises Na i Cu x Fe y Mn z Me p O 2 The compound of (1) is 0.5 < i < 1.5,0 < x < 0.3,0 < y < 0.5,0 < z < 0.5,0 < p < 0.2, x + y + z + p =1. The proportion of the main element and the doping element in the anode active material is regulated and controlled, so that the main element and the doping element are promoted to play a synergistic effect, and the performance of the material is improved.
In some embodiments of the present application, the mass concentration deviation of the doping element is η%, satisfying η ≦ 20.η may be 20, 19, 14, 13, 12, 10, 8, 7, 5, 3 or a range of any two of these values. In some embodiments of the present application, η ≦ 19. In some embodiments of the present application, η ≦ 10. Eta = (M) max －M min )/M mean Wherein, M is max M represents the maximum value of the mass fraction of the doping element in any 21 regions in the cross section of the positive electrode active material min M represents the minimum value of the mass fraction of the doping element of any 21 regions in the cross section of the positive electrode active material mean Represents the average value of the mass fractions of the doping elements of any 21 regions in the cross section of the positive electrode active material. The mass concentration deviation of the doping elements is small, the doping elements have better uniformity, and the internal stress of the material can be better relieved and released, so that the material is removedThe crystal cell parameter change in the sodium insertion process is small, the volume expansion is small, the structural stability of the material is facilitated, and the cycle performance is improved.
In some embodiments of the present application, the positive electrode active material includes primary particles, which refer to crystalline particles of the layered metal oxide, different from particles (secondary particles) formed after the crystalline particles are agglomerated. The average particle diameter of the primary particles is d mu m, and d is more than or equal to 0.05 and less than or equal to 7. For example, the concentration may be 0.05, 1, 2, 3, 4, 5, 6, 7, or any two of them. In some embodiments of the present application, 1 ≦ d ≦ 6. In some embodiments of the present application, 2 ≦ d ≦ 5. When the cumulative volume distribution percentage of the positive electrode active material reaches 50%, the corresponding particle size value is Dv50 μm, and satisfies that Dv50 is not less than 2 and not more than 22. For example, it may be 2, 4.1, 4.3, 4.5, 5, 10, 15, 20, 22 or any two of these ranges. In some embodiments of the present application, 4.1 ≦ Dv50 ≦ 20. In some embodiments of the present application, 4.5 ≦ Dv50 ≦ 15.Dv50 was tested using a malvern laser granulometer. The grain size is regulated and controlled through doping, the grain size is smaller, the sodium ion diffusion path is favorably shortened, and the multiplying power performance is improved.
Correspondingly, the embodiment of the application also provides a preparation method of the positive active material, which comprises the following steps: mixing a copper source, an iron source and a manganese source, adding a precipitator and a complexing agent, and reacting to obtain a precursor; and mixing the precursor, the doping element source and the sodium source, and performing primary sintering and secondary sintering to obtain the anode active material. The method improves the uniformity of the doping elements by increasing the sintering temperature, the sintering time, the sintering process and the like.
In some embodiments of the present application, the copper source comprises at least one of copper acetate, copper nitrate, copper oxalate, or copper sulfate.
In some embodiments of the present application, the iron source comprises at least one of iron acetate, iron nitrate, iron oxalate, or iron sulfate.
In some embodiments of the present application, the source of manganese comprises at least one of manganese acetate, manganese nitrate, manganese oxalate, or manganese sulfate.
In some embodiments of the present application, the source of doping elements comprises at least one of lithium oxide, lithium nitrate, potassium oxide, potassium nitrate, nickel oxide, nickel nitrate, magnesium oxide, magnesium nitrate, zinc oxide, zinc nitrate, calcium oxide, calcium nitrate, aluminum oxide, aluminum nitrate, cobalt oxide, cobalt nitrate, chromium oxide, chromium nitrate, vanadium oxide, vanadium nitrate, strontium oxide, strontium nitrate, zirconium dioxide, zirconium nitrate, titanium oxide, titanium nitrate, tin oxide, tin nitrate, molybdenum trioxide, molybdenum nitrate, tungsten oxide, tungsten nitrate, yttrium oxide, yttrium nitrate, niobium oxide, silicon oxide, ruthenium oxide, or ruthenium nitrate.
In some embodiments of the present application, the sodium source comprises at least one of sodium carbonate, sodium hydroxide, sodium acetate, sodium nitrate, or sodium oxalate.
Specifically, the precipitant comprises one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide.
Specifically, the complexing agent comprises one or more of ammonia water, ammonium bicarbonate, ammonium sulfate, ammonium carbonate, citric acid and disodium ethylene diamine tetraacetate.
Further, the temperature of the first sintering can be 300-600 ℃, also can be 350-550 ℃, and also can be 400-500 ℃; the time for the first sintering can be 5-12 hours, 6-11 hours and 8-10 hours. By controlling the time and temperature of the first sintering within the above ranges, the uniformity of the doping elements can be improved.
Furthermore, the temperature of the second sintering can be 700-1000 ℃, also can be 750-960 ℃, and also can be 800-900 ℃; the time for the second sintering can be 6-24 h, 10-20 h, and 12-15 h. The time and temperature of the second sintering are controlled within the above ranges, and the uniformity of the doping elements can be improved.
In specific implementation, the preparation method of the positive electrode active material comprises the following steps:
(1) Weighing a copper source, an iron source and a manganese source according to a certain molar ratio, respectively dissolving the copper source, the iron source and the manganese source in deionized water, and synthesizing a precursor by controlling the process conditions such as ammonia water concentration, pH value, stirring speed, reaction time, reaction temperature and the like.
(2) And (2) uniformly mixing the precursor obtained in the step (1), a doping element source and a sodium source, performing primary sintering and secondary sintering on the mixture, cooling to room temperature, and crushing to obtain the anode active material.
In addition, the embodiment of the application also provides a battery, which comprises a positive pole piece, wherein the positive pole piece comprises a positive pole current collector and a positive active material layer arranged on the positive pole current collector, and the positive active material layer comprises the positive active material or the positive active material prepared by the preparation method. The battery adopting the positive active material has better rate performance and cycle performance.
In specific implementation, the positive electrode active material or the positive electrode active material prepared by the method is uniformly stirred with a conductive agent, a binder and a solvent, and is subjected to coating, rolling, tabletting and other processes to prepare the positive electrode piece.
Specifically, the battery comprises a positive pole piece, a negative pole piece, an isolating membrane and electrolyte, wherein the positive pole piece is the positive pole piece. In specific implementation, the positive pole piece, the negative pole piece, the isolating membrane, the electrolyte and the like are assembled into the lithium ion battery. The negative active material used by the negative pole piece can be one or more of natural graphite, artificial graphite, mesophase micro carbon spheres (MCMB), hard carbon and soft carbon.
Further, the separator is not particularly limited, and any known separator having a porous structure with electrochemical stability and chemical stability may be used, and may be, for example, a single-layer or multi-layer film of one or more of glass fiber, nonwoven fabric, polyethylene, polypropylene, and polyvinylidene fluoride.
Further, the electrolyte may include an organic solvent and an electrolyte sodium salt. As an example, the organic solvent may be one or more of Ethylene Carbonate (EC), propylene Carbonate (PC), ethyl Methyl Carbonate (EMC), and diethyl carbonate (DEC); the sodium salt of the electrolyte may be NaPF 6 、NaClO 4 、NaBCl 4 、NaSO 3 CF 3 And Na (CH) 3 )C 6 H 4 SO 3 One or more of (a).
The embodiment of the application also provides an electric device which comprises the battery.
In some embodiments, the electricity consuming device of the present application is, but not limited to, a backup power source, an electric motor, an electric car, an electric motorcycle, a power assisted bicycle, a bicycle, an electric tool, a household large-sized battery, and the like.
The following description will be given with reference to specific examples.
Examples 1,
This example provides methods for preparing positive electrode active materials and batteries.
The preparation of the positive active material comprises the following steps:
1) According to the element mole ratio Cu: fe: mn =0.2:0.35: weighing copper sulfate, ferric sulfate and manganese sulfate according to the proportion of 0.45, respectively dissolving in deionized water, conveying each metal solution to a reaction kettle through a pipeline to form a mixed metal solution, introducing nitrogen as a protective gas, adding a NaOH aqueous solution as a precipitator into the mixed metal solution, adding ammonia water as a complexing agent, adjusting the pH value of the solution to 11, and reacting for 10 hours to obtain a precursor.
2) The precursor, sodium carbonate, alumina and titanium oxide are uniformly mixed, the sodium ratio is controlled to be 1:1, and the weight ratio of the alumina to the precursor is 0.75wt% and the weight ratio of the titanium oxide to the precursor is 0.34wt%, respectively.
3) Transferring the mixed materials to a sintering process, wherein the sintering process comprises two stages: the first stage is sintered for 8 hours at 550 ℃; the second stage was sintered at 960 ℃ for 12h.
4) And crushing, screening and removing iron from the sintered material to obtain the anode active material.
The preparation method of the battery comprises the following steps:
1) The positive electrode active material, the conductive agent, the binder and the solvent are stirred and mixed uniformly, and the positive electrode plate is prepared through the working procedures of sieving, coating, rolling, slitting, cutting and the like.
2) And assembling the parts such as the positive pole piece, the negative pole piece, the isolating membrane, the electrolyte and the like into the lithium ion battery.
Fig. 1 is an electron microscope characterization test chart of the surface morphology of the positive electrode active material obtained in example 1.
The material preparation flow of examples 2-15 and comparative examples 1-7 is substantially the same as that of example 1, the main difference is the difference of doping elements, sintering temperature, sintering time and main element ratio, the specific parameters of specific different materials are shown in table 1, and the electrical property data are shown in table 2.
Among them, the method for testing the uniformity of the doping element is that the anode active material is cut by argon ion, and the cross section of the anode active material is arbitrarily tested by EDS, EDX and the like for the content of Na, fe, mn and the doping element, and the sampling position can refer to the position shown in FIG. 2, and the mass concentration deviation eta of the doping element is = (M is the mass concentration deviation eta of the doping element =) max －M min )/M mean ，M max The maximum value of the mass fraction of the doping element in any 21 regions in the cross section of the positive electrode active material, M min Is the minimum value of the mass fraction of the doping element of any 21 regions in the cross section of the positive electrode active material, M mean Is the average value of the mass fractions of the doping elements of any 21 regions in the cross section of the positive electrode active material.
The crystal cell parameter change delta a and delta c from 10% sodium removal state overcharge to 85% sodium removal state is obtained by obtaining a value and c value in each sodium removal state through an in-situ XRD test, and then calculating the change rate delta a and the change rate delta c of the a value, wherein the specific test conditions of the in-situ XRD test are as follows: range of diffraction angle 2 θ: 10-90 °, scan rate: 5 deg/min. The in situ XRD was tested via the following procedure: 1) After the voltage is charged to 4.7V at 0.1C, the voltage is charged to 0.02C at constant voltage; 2) Standing for 10min; 3) 0.1C to 2.0V; 4) Standing for 10min; 5) After the voltage is charged to 4.7V at 0.1C, the voltage is charged to 0.02C at constant voltage; 6) Standing for 10min.
The multiplying power test flow is as follows: at a temperature of 25 ℃, the battery was charged to 4.25V at 1/3C, and then discharged at rates of 1/3C, 1C, 2C, 5C, and 10C, respectively.
The cycle test flow is as follows: after the battery is clamped, standing for 30min, discharging to 2.0V at a constant current of 1C, standing for 10min, charging to 4.25V at a constant current of 1C, keeping constant voltage to 0.05C, standing for 10min, and stopping when the capacity retention rate is less than or equal to 80%.
TABLE 1
Figure BDA0003889498210000081
Figure BDA0003889498210000091
Figure BDA0003889498210000101
TABLE 2
Figure BDA0003889498210000102
Examples 1 to 5, comparative examples 1 to 2 and comparative example 6, or example 13 and comparative example 3 compare the relevant parameters and electrical properties of the material with different mass concentration deviations of the doped element, and it can be seen that, compared with comparative example 1, the capacity retention ratio of 10C and the capacity retention ratio of 1000 cycles at 25 ℃ in examples 1 to 5 are higher, and the rate capability and the cycle performance of undoped comparative example 6 are the worst, indicating that doping can increase cell parameters, widen a sodium ion diffusion channel, improve the rate capability, and doping is beneficial to improving the structural stability of the material and the cycle performance. The 10C capacity retention and 25℃ cycle 1000 cycle capacity retention of example 13 are higher relative to comparative example 3. The mass concentration deviations of comparative example 1 and comparative example 3 were high, indicating that controlling the mass concentration deviations within the ranges provided herein helps to improve the rate performance and cycle performance of the battery.
The rate performance of the batteries manufactured from the positive active materials of example 1 and comparative example 1 is shown in fig. 3, and the cycle performance of the batteries manufactured from the positive active materials of example 1 and comparative example 1 is shown in fig. 4. As can be seen, the capacity retention rate of the battery 10C and the capacity retention rate of the battery at 25 ℃ after 1000 cycles are both significantly higher than those of the battery in comparative example 1, which indicates that the cycle performance and the rate performance of the battery made of the cathode active material in example 1 are higher.
Examples 1, 6, 7 and comparative example 4, or example 13 and comparative example 5, compare the material-related parameters and electrical properties for different dopant element contents, and it can be seen that, relative to comparative example 4, the 10C capacity retention is higher for examples 1, 6, 7, and the capacity retention is 1000 cycles at 25 ℃: example 6 > example 1 > example 7 > comparative example 4, which shows that the amount of doping elements in the cathode material has a great influence on the rate and cycle of the battery, and the appropriate doping amount needs to be selected to ensure the rate and cycle performance of the battery. The data relating to example 13 and comparative example 5 also illustrate the above conclusions.
Examples 1, 8, 9, 10 compare the material-related parameters and electrical properties of different Dv50, and it can be seen that the rate and cycle performance of examples 9 and 10 are inferior compared to example 1, and the 10C capacity retention: example 1 > example 9 > example 10, capacity retention at 25 ℃ cycling 1000 cycles: example 1 > example 9 > example 10, demonstrating that the size of the material Dv50 has an effect on the rate and cycling of the cell, primarily because the size of Dv50 affects the diffusion path length of sodium ions.
Compared with the relevant parameters and the electrical properties of materials of different doping element types in examples 1, 11 and 12 and comparative example 7, it can be seen that the capacity retention rates of 10C in examples 1, 11 and 12 are similar, and the capacity retention rates of 1000 cycles at 25 ℃ are similar and are obviously better than those in comparative example 7, which shows that the technical effects achieved after different doping elements are combined in the technical scheme are basically similar, but the electrical properties of the element doped materials which are not in the doping element range in the technical scheme are poor, and further shows the feasibility of the technical scheme.
Examples 1, 13, 14 and 15 compare the relevant parameters and electrical properties of materials with different main element ratios, and it can be seen that the adjustment of the main element ratio has no obvious influence on the cycle performance and rate performance of the battery.
The unit cell parameters are increased through doping, a sodium ion diffusion channel is widened, and the multiplying power performance is improved; the particle size is regulated and controlled by doping, so that the sodium ion diffusion path is shortened, and the rate capability is improved; the sodium-electricity power is realized by regulating and controlling the doping uniformity of the doping elements of the positive active material, namely the mass concentration deviation of any one doping element is less than or equal to 20 percentThe change of the cell parameter of the anode material is small in the process of sodium extraction, and the maximum change rate delta a of the cell parameter a max Not more than 3.5%, and maximum change rate Delta c of unit cell parameter c max Less than or equal to 4.3 percent, is favorable for maintaining the structural stability of the material and improving the cycle performance.
The positive active material, the preparation method thereof, the battery and the electric device provided by the present application are described in detail above, and the principle and the embodiment of the present application are explained by applying specific examples, and the description of the above examples is only used to help understanding the method and the core concept of the present application; meanwhile, for those skilled in the art, according to the idea of the present application, the specific implementation manner and the application scope may be changed, and in summary, the content of the present specification should not be construed as a limitation to the present application.

Claims (11)

1. The positive active material is characterized in that when the sodium removal percentage of the positive active material is 10-85%, the maximum change rate of a parameter a of a positive active cell is delta a max % satisfies Δ a max Not more than 3.5, and the maximum change rate of the parameter c of the active crystal cell of the anode is Delta c max %, satisfies Δ c max ≤4.3。
2. The positive electrode active material according to claim 1, comprising a doping element M comprising at least one of Li, K, ni, mg, zn, ca, al, co, cr, V, sr, zr, ti, sn, mo, W, Y, nb, si and Ru.
3. The positive electrode active material according to claim 1, wherein the positive electrode active material comprises Na having a chemical formula i Cu x Fe y Mn z Me p O 2 The compound of (1) is 0.5 < i < 1.5,0 < x < 0.3,0 < y < 0.5,0 < z < 0.5,0 < p < 0.2, x + y + z + p =1.
4. The positive electrode active material according to claim 2, wherein the mass concentration deviation of the doping element M is η%, and η ≦ 20 is satisfied.
5. The positive electrode active material according to claim 1, wherein the positive electrode active material comprises primary particles having an average particle diameter d μm satisfying 0.05. Ltoreq. D.ltoreq.7.
6. The positive electrode active material according to claim 1, wherein the Dv50 of the positive electrode active material is 2 to 22 μm.
7. A method for producing a positive electrode active material according to any one of claims 1 to 6, comprising:
mixing a copper source, an iron source and a manganese source, adding a precipitator and a complexing agent, and reacting to obtain a precursor;
and mixing the precursor, the doping element source and the sodium source, and performing primary sintering and secondary sintering to obtain the anode active material.
8. The method for producing a positive electrode active material according to claim 7, wherein the copper source includes at least one of copper acetate, copper nitrate, copper oxalate, and copper sulfate; and/or the presence of a gas in the gas,
the iron source comprises at least one of iron acetate, iron nitrate, iron oxalate and iron sulfate; and/or the presence of a gas in the gas,
the manganese source comprises at least one of manganese acetate, manganese nitrate, manganese oxalate and manganese sulfate; and/or the presence of a gas in the gas,
the doping element source comprises at least one of lithium oxide, lithium nitrate, potassium oxide, potassium nitrate, nickel oxide, nickel nitrate, magnesium oxide, magnesium nitrate, zinc oxide, zinc nitrate, calcium oxide, calcium nitrate, aluminum oxide, aluminum nitrate, cobalt oxide, cobalt nitrate, chromium oxide, chromium nitrate, vanadium oxide, vanadium nitrate, strontium oxide, strontium nitrate, zirconium dioxide, zirconium nitrate, titanium oxide, titanium nitrate, tin oxide, tin nitrate, molybdenum trioxide, molybdenum nitrate, tungsten oxide, tungsten nitrate, yttrium oxide, yttrium nitrate, niobium oxide, silicon oxide, ruthenium oxide and ruthenium nitrate; and/or the presence of a gas in the gas,
the sodium source comprises at least one of sodium carbonate, sodium hydroxide, sodium acetate, sodium nitrate or sodium oxalate.
9. The method for preparing a positive electrode active material according to claim 7, wherein the temperature of the first sintering is 300 to 600 ℃, and the time of the first sintering is 5 to 12 hours; and/or the presence of a gas in the gas,
the temperature of the second sintering is 700-1000 ℃, and the time of the second sintering is 6-24 h.
10. A battery, comprising a positive electrode sheet, wherein the positive electrode sheet comprises a positive electrode current collector and a positive electrode active material layer disposed on the positive electrode current collector, and the positive electrode active material layer comprises the positive electrode active material according to any one of claims 1 to 6; or, a positive electrode active material produced by the production method according to any one of claims 7 to 9.
11. An electric device comprising the battery according to claim 10.
CN202211258260.XA 2022-10-13 2022-10-13 Positive electrode active material, preparation method thereof, battery and power utilization device Pending CN115566182A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116885096A (en) * 2023-09-06 2023-10-13 中创新航科技集团股份有限公司 Lithium ion battery

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116885096A (en) * 2023-09-06 2023-10-13 中创新航科技集团股份有限公司 Lithium ion battery

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