CN114956211B - Manganese-nickel-copper precursor, sodium ion battery positive electrode material and preparation method thereof - Google Patents

Manganese-nickel-copper precursor, sodium ion battery positive electrode material and preparation method thereof Download PDF

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CN114956211B
CN114956211B CN202210919603.6A CN202210919603A CN114956211B CN 114956211 B CN114956211 B CN 114956211B CN 202210919603 A CN202210919603 A CN 202210919603A CN 114956211 B CN114956211 B CN 114956211B
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manganese
nickel
copper
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sodium
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张宁
万江涛
李子郯
王涛
张勇杰
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Svolt Energy Technology Co Ltd
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Abstract

The invention belongs to the technical field of sodium ion batteries, and particularly relates to a manganese-nickel-copper precursor with different morphologies, and further discloses a preparation method of the manganese-nickel-copper precursor, and applications of the manganese-nickel-copper precursor in preparation of a positive electrode material of a sodium ion battery and the sodium ion battery. The manganese-nickel-copper precursor is based on three metal elements of manganese, nickel and copper, and under the condition that the types and the element ratios of the three metal elements are determined, the precursor with better performance is obtained by regulating and controlling the appearance of the precursor, so that the precursor has higher tap density and simultaneously has sufficient ion de-intercalation channels, and has the advantages of low price and environmental friendliness.

Description

Manganese-nickel-copper precursor, sodium ion battery positive electrode material and preparation method thereof
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to manganese-nickel-copper precursors with different morphologies, and further discloses a preparation method of the manganese-nickel-copper precursors, and applications of the manganese-nickel-copper precursors in preparation of positive electrode materials of sodium ion batteries and sodium ion batteries.
Background
With the technical progress and the promotion of new national standards, the lithium battery has the advantages of environmental protection, long service life, relatively light weight and the like, is widely applied to the fields of electric bicycles, electric automobiles, electric tools, 3C digital products and the like, and is especially the first choice of portable electronic equipment and electric automobiles due to high energy density, long cycle life and excellent rate capability. At present, ternary lithium batteries are taken as main products in the lithium battery positive electrode material market, but the defects of poor low-temperature performance and the like exist, and the problem of using the ternary lithium batteries in cold regions is limited; moreover, cobalt has proven to have limited global reserves, and cobalt has radioactivity and toxicity, which brings a series of environmental related problems; in particular, the long-term high demand causes a large amount of lithium resource consumption, and the lithium price continuously and greatly rises, so that the overall cost of the lithium battery industry remains high. The above problems will severely restrict the rapid development of the lithium battery industry, and the solution to the above problems is to develop other kinds of positive electrode materials to match the preparation of the battery core.
Based on the above problems, sodium ion batteries have been produced. The sodium ion battery can just make up for the defects by virtue of the advantages of rich resources, low price and the like, and gradually becomes a research hotspot in the field of energy storage. However, sodium ions have a large ionic radius and a slow kinetic rate, so that charge and discharge deintercalation of the sodium ions are difficult; meanwhile, since the sodium ion battery material usually contains metal elements such as iron and copper, the tap density of the prepared material is low, the volume energy density of the material is seriously influenced, and the material becomes a main factor for restricting the development of the energy storage material. Therefore, how to prepare the positive electrode material of the sodium-ion battery with better performance becomes a problem to be solved urgently, and the development of the high-performance sodium-embedded positive electrode material is the key for improving the specific energy of the sodium-ion battery and promoting the application of the sodium-ion battery.
Disclosure of Invention
Therefore, the first purpose of the invention is to provide a manganese-nickel-copper precursor with different morphologies, which has both higher tap density and sufficient ion extraction channels;
the second purpose of the invention is to provide a positive electrode material of a sodium-ion battery, which has the advantages of low price, environmental friendliness and better performance;
the third purpose of the invention is to provide the preparation methods of the manganese-nickel-copper precursor and the positive electrode material of the sodium-ion battery.
In order to solve the technical problems, the invention provides a manganese-nickel-copper precursorThe manganese nickel copper precursor has Mn as x Ni y Cu 1-x-y (OH) 2 Chemical composition shown in the formula, wherein, 0.30<x≤0.50，0.25≤y<0.35；
The size S of primary particles of the manganese-nickel-copper precursor is 0.2-2 mu m, the thickness H of the primary particles is 0.05-1 mu m, and the specific surface area B is 10-150m 2 (ii)/g, tap density T is 0.5-1.5g/cm 3 . Wherein the primary particle size S is used for testing and characterizing the transverse dimension of primary particles in the precursor which exhibit a lamellar structure, and the primary particle thin thickness H is used for testing and characterizing the longitudinal dimension of the primary particles.
Preferably, the size S of the primary particles, the thickness H of the primary particles, the specific surface area B and the tap density T of the manganese-nickel-copper precursor satisfy the following relations: BXH/SXT is less than or equal to 50.
The invention also discloses a preparation method of the manganese-nickel-copper precursor, namely the precursor is prepared by a coprecipitation method, and the method comprises the steps of taking a soluble manganese source material, a nickel source material and a copper source material as raw materials according to the selected chemical composition, and adding a precipitator for reaction in the presence of a reducing agent and a complexing agent.
Specifically, the reducing agent comprises at least one of acetaldehyde, phenol or hydrazine hydrate; in the preparation process of the precursor, the reducing agent is continuously added, so that lattice misbehavior caused by system oxidation can be reduced, a material with complete lattices is obtained, and the size of primary particles is changed, and the winding mode of secondary particles is changed;
specifically, the addition amount of the reducing agent is not specifically limited, and only the whole reaction system is required to be in a reducing environment, and the reducing agent can be added in a mixture in each raw material liquid of the whole reaction, or can be added in the system when each raw material is mixed.
Specifically, the complexing agent comprises at least one of ammonia water, sodium fluoride and hydroxyethyl ethylene diamine triacetic acid.
Specifically, in the preparation process of the precursor, ammonia water can be selected as a complexing agent, and the adding modes of the ammonia water are divided into two modes: firstly, ammonia water is directly added into a copper sulfate solution to generate a precipitate, the ammonia water generates a solution again after being excessive, copper ions are complexed in advance, and then metal liquid and alkali are added simultaneously to react; secondly, adding ammonia water into alkali, then adding the metal liquid and the alkali into the alkali for reaction at the same time, wherein the reaction process and the complexing process are carried out at the same time, and the thickness of the primary particles can be adjusted through the operation;
similarly, in the precursor preparation method of the invention, sodium fluoride can be used as the complexing agent, the complexing agent is directly added into copper sulfate metal liquid for complexing in the precursor preparation process, then the metal liquid is added into the system for reaction, and the thickness of the primary particles and the winding mode of the secondary particles can be adjusted by replacing the complexing agent.
Specifically, the precipitant comprises an alkaline solution;
specifically, the alkaline solution comprises a sodium hydroxide solution and/or a potassium hydroxide solution.
Specifically, the manganese source material comprises a crystalline salt of metallic manganese;
specifically, the nickel source material includes a crystalline salt of metallic nickel;
specifically, the copper source material comprises a crystalline salt of metallic copper.
Preferably, the crystalline salt comprises a sulphate, chloride and/or nitrate salt.
The preparation method of the precursor of the present invention specifically includes, as an implementable embodiment: adding an aqueous solution as a base solution into a reaction kettle, adding a reducing agent to maintain a reducing atmosphere, and then adding a complexing agent for mixing; then respectively preparing metal liquid containing metal manganese, nickel and copper (preferably, controlling the molar concentration ratio of the manganese metal liquid to the nickel metal liquid to the copper metal liquid to be 0.25-0.50; preparing alkaline solution as precipitant, adding reducer and mixing. Finally, adding the prepared metal liquid and the alkali liquor into the base solution simultaneously for reaction; preferably, the temperature is controlled to be 25-60 ℃, and the reaction is continued for 40-80 hours by high-speed stirring at 200-1200 rpm.
The preparation method of the precursor of the invention specifically comprises the following steps: adding an aqueous solution into a reaction kettle as a base solution, adding a reducing agent to maintain a reducing atmosphere, then adding a complexing agent to mix, and then respectively preparing metal solutions containing metal manganese, nickel and copper (preferably, controlling the molar concentration ratio of the manganese metal solution, the nickel metal solution and the copper metal solution to be 0.30-0.50; preparing alkaline solution as precipitant, adding complexing agent and reducer, and mixing. And finally, adding the prepared metal liquid and alkali liquor into the base solution simultaneously for reaction, controlling the temperature of 25-60 ℃ in the process, and continuously reacting for 40-80 hours by matching with high-speed stirring at 200-1200 rpm.
The preparation method of the precursor of the invention specifically comprises the following steps: adding an aqueous solution into a reaction kettle to serve as a base solution, adding a reducing agent to maintain a reducing atmosphere, adding a complexing agent to mix, and then respectively preparing metal solutions containing metal manganese, nickel and copper (preferably, controlling the molar concentration ratio of the manganese metal solution, the nickel metal solution and the copper metal solution to be 0.30-0.50; the complexing agent can be added into the prepared copper metal liquid; preparing alkaline solution as precipitant. And finally, simultaneously adding the metal liquid and the alkali liquor into the base solution for reaction, controlling the temperature to be 25-60 ℃ in the process, and continuously reacting for 40-80 hours by matching with high-speed stirring at 200-1200 rpm.
The invention also discloses a sodium-ion battery anode material prepared based on the manganese-nickel-copper precursor, and the anode material has NaMn x Ni y Cu 1-x-y O 2 Chemical composition shown in the specification, wherein, 0.30<x≤0.50，0.25≤y<0.35；
Preferably, the reversible capacity of the cathode material is 110-150mAh/g.
The invention also discloses a method for preparing the positive electrode material of the sodium-ion battery, which comprises the step of taking the manganese-nickel-copper precursor and the sodium salt as raw materials and sintering the raw materials in an air atmosphere;
preferably, the molar ratio of the manganese-nickel-copper precursor to the sodium salt is 1:0.5 to 1;
preferably, the sintering step comprises a step of performing first sintering at 500-800 ℃ for 2-14h, and a step of performing second sintering at 700-900 ℃ for 10-20 h.
The invention also discloses application of the manganese-nickel-copper precursor or the positive electrode material of the sodium ion battery in preparation of the sodium ion battery.
The invention also discloses a sodium-ion battery prepared on the basis of the manganese-nickel-copper precursor or the positive electrode material of the sodium-ion battery.
The chemical composition of the manganese-nickel-copper precursor is Mn x Ni y Cu 1-x-y (OH) 2 The size S of primary particles of the manganese-nickel-copper precursor is 0.2-2 mu m, the thickness H of the primary particles is 0.05-1 mu m, and the specific surface area B is 10-150m 2 The tap density T is 0.5-1.5g/cm 3 And the size S of the primary particles, the thickness H of the primary particles, the specific surface area B and the tap density T satisfy the following relationship: BXH/SXT is less than or equal to 50. The manganese-nickel-copper precursor is based on three metal elements of manganese, nickel and copper, and under the condition that the types and the element ratios of the three metal elements are determined, the precursor with better performance is obtained by regulating and controlling the appearance of the precursor, wherein the precursor comprises primary particles with different thicknesses (characterized by specific surface area) and secondary particles with different winding modes (characterized by tap density), so that the precursor has a high tap density and simultaneously has sufficient ion extraction channels, and the precursor has the advantages of low price and environmental friendliness.
According to the precursor, the mode that primary particles of the precursor material are finer and smaller and secondary particles are loosely wound is controlled, the ion migration path is shortened, the electrochemical performance release is facilitated, the defect that the radius of sodium ions is larger than that of lithium ions is effectively overcome, and the precursor with better performance is obtained; meanwhile, the precursor material has tap density performance, the problem that the electrochemical performance is not released due to overhigh tap density of the material and the cycle performance of the material is influenced due to overlow tap density is effectively solved, and all parameters of the precursor material are ideally matched.
According to the preparation method of the manganese-nickel-copper precursor, the sodium ion battery precursor is prepared through a coprecipitation method, hydroxide is used as a precipitator, acetaldehyde is used as a reducing agent, sodium fluoride and ammonia water are used as complexing agents, and the preparation process is adjusted to prepare the precursors with different shapes.
According to the preparation method of the manganese-nickel-copper precursor, the reducing agent is continuously added in the preparation process of the precursor, so that lattice misbehavior caused by system oxidation is effectively reduced, a material with complete lattices is obtained, and the sizes of primary particles are changed, the thicknesses of the primary particles are changed, and the winding mode of secondary particles is changed.
According to the preparation method of the manganese-nickel-copper precursor, ammonia water is selected as a complexing agent in the preparation process of the precursor, and the adding modes of the ammonia water are divided into two modes: firstly, ammonia water is directly added into a copper sulfate solution to generate a precipitate, the ammonia water generates a solution again after being excessive, copper ions are complexed in advance, and then metal liquid and alkali are added simultaneously to react; the second method is to add ammonia water into alkali, then add metal liquid and alkali into the reaction at the same time, the reaction process and the complexing process are carried out at the same time, and the thickness of the primary particles can be adjusted by the operation.
According to the preparation method of the manganese-nickel-copper precursor, sodium fluoride is used as a complexing agent in the preparation process of the precursor, the complexing agent is directly added into copper sulfate metal liquid for complexing, then the metal liquid is added into a system for reaction, and the thickness of primary particles and the winding mode of secondary particles can be adjusted by adding the complexing agent.
The composition of the sodium ion manganese nickel copper anode material is NaMn x Ni y Cu 1-x-y O 2 The three metal elements of manganese, nickel and copper are combined, the manufacturing and production cost of the precursor and the anode material is reduced, the reversible capacity of the material reaches 110-150mAh/g, and the material has the advantages of low price, environmental friendliness and ideal application performance.
Drawings
In order that the manner in which the disclosure of the present invention is attained and can be more readily understood, a more particular description of the invention briefly described above will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings, wherein,
FIGS. 1 to 3 are SEM test results of the precursors obtained in examples 1 to 3, respectively;
FIG. 4 shows the EDS test results of the precursor obtained in example 2, in which Ch1 and Mn are on the first row from left to right and Cu and Ni are on the second row from left to right.
Detailed Description
Example 1
The chemical composition of the manganese-nickel-copper precursor in this example is Mn 0.50 Ni 0.25 Cu 0.25 (OH) 2 According to the composition ratio, mixed metal liquid containing manganese sulfate with the concentration of 1.0mol/L and nickel sulfate with the concentration of 0.50mol/L and copper sulfate metal liquid with the concentration of 0.50mol/L are prepared, and sodium fluoride serving as a complexing agent (the addition amount is 30 g/L) is added into the copper sulfate metal liquid for later use.
Preparing a sodium hydroxide solution with the concentration of 4mol/L, adding acetaldehyde serving as a reducing agent, wherein the adding amount is 10ml/L for later use.
Adding 4L of aqueous solution into a reaction kettle to serve as reaction base solution, adding 10ml of acetaldehyde to maintain a reduction atmosphere, and adding 10g of sodium fluoride to serve as base solution, wherein the acetaldehyde is used for providing the reduction atmosphere, and the sodium fluoride serves as a complexing agent; and then, adding the prepared manganese nickel sulfate mixed metal solution and copper sulfate metal solution and sodium hydroxide solution into the base solution at the speed of 300ml/h to react, controlling the temperature at 45 ℃ in the reaction process, and regulating the pH to 10.50 by matching with high-speed stirring at 1200rpm, and continuously reacting for 60 hours.
The SEM test results of the precursor described in this example (EHT =10.00KV, WD =4.4mm, mag =50.00 kx, signal = InLens) are shown in fig. 1, where EHT denotes extra high pressure, WD denotes working distance, mag denotes magnification, and Signal = InLens denotes Signal in InLens mode. And the contour and the shape are displayed according to the test result, and the sphericity of the product is judged to be better by visual inspection.
Continuously mixing the prepared precursor and sodium carbonate according to the molar ratio of 1:1, fully mixing, calcining for 12 hours at 800 ℃ in air atmosphere, crushing, then carrying out secondary sintering treatment, controlling the temperature to be 900 ℃ and the calcining time to be 10 hours, and generating a ternary cathode material NaMn 0.50 Ni 0.25 Cu 0.25 O 2 。
Mixing the material with SP (carbon black conductive agent), CNT (carbon nano tube) and PVDF (polyvinylidene fluoride), wherein the mass ratio of the precursor material, SP + CNT and PVDF is controlled to be 90:5: and 5, using NMP (N-methylpyrrolidone) as a solvent, and pulping and stirring for several hours to prepare the sodium-ion battery anode.
Example 2
The chemical composition of the manganese-nickel-copper precursor in this example is Mn 0.50 Ni 0.25 Cu 0.25 (OH) 2 According to the composition ratio, mixed metal liquid containing manganese sulfate with the concentration of 1.0mol/L and nickel sulfate with the concentration of 0.50mol/L and copper sulfate metal liquid with the concentration of 0.50mol/L are prepared for later use.
Preparing a sodium hydroxide solution with the concentration of 4mol/L, adding ammonia water serving as a complexing agent in an amount of 60ml/L, adding acetaldehyde serving as a reducing agent in an amount of 10ml/L for later use.
Adding 4L of aqueous solution into a reaction kettle, and adding 10ml of acetaldehyde and 20ml of ammonia water as base solution, wherein acetaldehyde provides a reduction atmosphere, and the ammonia water is used as a complexing agent; and then, adding the prepared manganese nickel sulfate mixed metal solution and copper sulfate metal solution and sodium hydroxide solution into the base solution at the speed of 300ml/h to react, controlling the temperature at 45 ℃ in the reaction process, and regulating the pH to 10.50 by matching with high-speed stirring at 1200rpm, and continuously reacting for 60 hours.
The SEM test results (EHT =10.00KV, WD =4.8mm, mag =20.00 kx, signal = InLens) of the precursor described in this example are shown in fig. 2, and the outline and morphology are shown based on the test results, and the sphericity of the product is judged to be good by visual inspection. The EDS test results of the precursor obtained in this example (HV =10KV, WD =9.1mm, mag = 5000X, unit scale: 4 μm) are shown in fig. 4, HV representing high voltage, WD representing working distance, and Mag representing magnification. It can be seen that the three metal elements of manganese, nickel and copper are uniformly distributed at atomic level.
Continuously mixing the prepared precursor and sodium carbonate according to the molar ratio of 1:1, calcining at 800 ℃ for 12 hours in an air atmosphere, and then crushingThen secondary sintering treatment is carried out, the temperature is controlled at 900 ℃, the calcination time is 10 hours, and the ternary cathode material NaMn is generated 0.50 Ni 0.25 Cu 0.25 O 2 。
Mixing the material with SP (carbon black conductive agent), CNT (carbon nano tube) and PVDF (polyvinylidene fluoride), wherein the mass ratio of the precursor material, SP + CNT and PVDF is controlled to be 90:5: and 5, using NMP (N-methyl pyrrolidone) as a solvent, and pulping and stirring for several hours to prepare the sodium-ion battery anode.
Example 3
The chemical composition of the manganese-nickel-copper precursor in this example is Mn 0.50 Ni 0.25 Cu 0.25 (OH) 2 According to the composition ratio, mixed metal liquid containing manganese sulfate with the concentration of 1.0mol/L, nickel sulfate with the concentration of 0.50mol/L and copper sulfate metal liquid with the concentration of 0.50mol/L are prepared, and ammonia water is added into copper sulfate metal liquid for complexing, wherein the addition amount is 80ml/L for later use.
Preparing a sodium hydroxide solution with the concentration of 4mol/L, adding acetaldehyde serving as a reducing agent, wherein the adding amount is 10ml/L for later use.
Adding 4L of aqueous solution into a reaction kettle, and adding 10ml of acetaldehyde and 20ml of ammonia water as base solution, wherein acetaldehyde provides a reducing atmosphere, and the ammonia water is used as a complexing agent; and then, adding the prepared manganese nickel sulfate mixed metal solution and copper sulfate metal solution and sodium hydroxide solution into the base solution at the speed of 300ml/h to react, controlling the temperature at 45 ℃ in the reaction process, and regulating the pH to 10.50 by matching with high-speed stirring at 1200rpm, and continuously reacting for 60 hours.
The SEM test results (EHT =10.00KV, WD =3.8mm, mag =20.00 kx, signal = InLens) of the precursor described in this example are shown in fig. 3, and the outline and morphology are shown from the test results, and the sphericity of the product is judged to be good visually.
Continuously mixing the prepared precursor and sodium carbonate according to the molar ratio of 1:1, fully mixing, calcining for 12 hours at 800 ℃ in air atmosphere, crushing, then carrying out secondary sintering treatment, controlling the temperature to be 900 ℃ and the calcining time to be 10 hours, and generating a ternary cathode material NaMn 0.50 Ni 0.25 Cu 0.25 O 2 。
Mixing the material with SP (carbon black conductive agent), CNT (carbon nano tube) and PVDF (polyvinylidene fluoride), wherein the mass ratio of the precursor material, SP + CNT and PVDF is controlled to be 90:5: and 5, using NMP (N-methyl pyrrolidone) as a solvent, and pulping and stirring for several hours to prepare the sodium-ion battery anode.
Comparative example 1
The preparation method of the manganese nickel copper precursor in the comparative example is the same as that in example 1, except that the acetaldehyde reducing agent is not added to the reaction liquid system.
Comparative example 2
The preparation method of the manganese-nickel-copper precursor in the comparative example is the same as that in example 1, except that the sodium fluoride complexing agent is not added to the reaction solution system.
Examples of the experiments
1. Precursor parameter characterization
The parameters of the precursors prepared in examples 1 to 3 and comparative examples 1 to 2 were measured and the results are reported in table 1 below.
TABLE 1 characteristics of manganese-nickel-copper precursors
Figure 552696DEST_PATH_IMAGE001
As can be seen from the data in the above table, the primary particle size and the primary particle combination mode of the precursors prepared by adding different complexing agents are different from those in examples 1 to 3; as can be seen from examples 2 and 3, the way of adding the complexing agent also changes the size of the primary particles.
As can be seen from the example 1 and the comparative example 1, if a corresponding reducing agent is not added in the reaction process, the lattice of the product is increased, the size of primary particles is reduced, the thickness of the primary particles is not changed greatly, the tap density is reduced, and the specific surface area is increased; as can be seen from example 1 and comparative example 2, if no complexing agent is added in the reaction process, the product has no specific morphology, the tap density is greatly reduced, and the specific surface is greatly reduced.
2. Sodium ion battery performance test results
The performance of the sodium ion batteries obtained in examples 1 to 3 and comparative examples 1 to 2 was measured, and the results are reported in table 2 below.
Table 2 sodium ion battery performance test results
Figure 394750DEST_PATH_IMAGE002
As can be seen from the data in the table above, the electrochemical properties of the positive electrode materials prepared from the precursors with different morphologies according to the scheme of the present invention have large differences from each other according to the data in examples 1 to 3. In the embodiment 1 and the proportion 1, the electrochemical performance of the positive electrode material prepared by preparing the precursor without adding the reducing agent in the reaction process is relatively poor; as can be seen from example 1 and comparative example 2, the electrochemical performance of the positive electrode material prepared from the precursor having no specific morphology is greatly reduced.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.

Claims (9)

1. A manganese nickel copper precursor, characterized in that the manganese nickel copper precursor has Mn as x Ni y Cu 1-x-y (OH) 2 Chemical composition shown in the formula, wherein, 0.30<x≤0.50，0.25≤y<0.35；
The size S of primary particles of the manganese-nickel-copper precursor is 0.2-2 mu m, the thickness H of the primary particles is 0.05-1 mu m, and the specific surface area B is 10-150m 2 (ii)/g, tap density T is 0.5-1.5g/cm 3 ；
The size S of the primary particles, the thickness H of the primary particles, the specific surface area B and the tap density T of the manganese-nickel-copper precursor satisfy the following relations: BXH/SXT is less than or equal to 50.
2. A method for preparing a manganese-nickel-copper precursor according to claim 1, comprising the step of taking a soluble manganese source material, a nickel source material and a copper source material as raw materials according to a selected chemical composition, and adding a precipitant to react in the presence of a reducing agent and a complexing agent.
3. The method of claim 2, wherein the reducing agent comprises at least one of acetaldehyde, phenol, or hydrazine hydrate.
4. The method according to claim 3, wherein the complexing agent comprises at least one of ammonia, sodium fluoride, or hydroxyethylethylenediaminetriacetic acid.
5. The method of claim 4, wherein the precipitating agent comprises an alkaline solution.
6. The method for preparing a manganese-nickel-copper precursor according to any one of claims 2 to 5, characterized in that:
the manganese source material comprises a crystalline salt of manganese metal;
the nickel source material comprises a crystalline salt of metallic nickel;
the copper source material includes a crystalline salt of metallic copper.
7. A positive electrode material of a sodium-ion battery prepared on the basis of the manganese-nickel-copper precursor as claimed in claim 1, wherein the positive electrode material has NaMn x Ni y Cu 1-x-y O 2 Chemical composition shown in the specification, wherein, 0.30<x≤0.50，0.25≤y<0.35。
8. The method for preparing the positive electrode material of the sodium-ion battery of claim 7 is characterized by comprising the steps of taking the manganese-nickel-copper precursor and the sodium salt as raw materials, and sintering the raw materials in an air atmosphere;
the molar ratio of the manganese-nickel-copper precursor to the sodium salt is 1:0.5 to 1;
the sintering step comprises a step of performing primary sintering at 500-800 ℃ for 2-14h, and a step of performing secondary sintering at 700-900 ℃ for 10-20 h.
9. Use of the manganese nickel copper precursor according to claim 1 or the positive electrode material for sodium-ion batteries according to claim 8 for the preparation of sodium-ion batteries.
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