CN114050257B - Manganese-iron-copper positive electrode precursor material and preparation method and application thereof - Google Patents

Manganese-iron-copper positive electrode precursor material and preparation method and application thereof Download PDF

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CN114050257B
CN114050257B CN202111342555.0A CN202111342555A CN114050257B CN 114050257 B CN114050257 B CN 114050257B CN 202111342555 A CN202111342555 A CN 202111342555A CN 114050257 B CN114050257 B CN 114050257B
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copper
iron
precursor material
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ferromanganese
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CN114050257A (en
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张宁
万江涛
李子郯
杨红新
张勇杰
刘海松
刘满库
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Svolt Energy Technology Co Ltd
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Abstract

The invention provides a manganese-iron-copper anode precursor material and a preparation method and application thereof. The shape of the positive electrode precursor material is spherical or sphere-like, and the chemical formula of the positive electrode precursor material is Mn X Cu Y Fe 1‑X‑Y (OH) 3‑X‑Y Wherein X is more than 0.3 and less than 0.45,0.1 and less than Y is less than 0.4. The preparation method of the precursor material is a coprecipitation method. The manganese-iron-copper anode precursor material is prepared by a coprecipitation method, the generation of impure phases caused by element segregation is overcome, the elements are uniformly distributed at an atomic level, and the sodium ion anode material prepared from the precursor material has a stable structure and excellent electrochemical performance.

Description

Manganese-iron-copper positive electrode precursor material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of sodium ion batteries, and relates to a manganese-iron-copper positive electrode precursor material, and a preparation method and application thereof.
Background
At present, ternary lithium batteries are taken as main products in the anode material market, however, the ternary lithium batteries also have many problems which cannot be solved, for example, the phenomenon of mixed discharging of nickel and lithium is serious, which directly causes a large amount of gas generation in the charging and discharging process, thereby leading to a series of safety problems, and simultaneously can also cause the capacity to be greatly attenuated, and when the content of nickel in the ternary materials is increased, the problem is more serious; the currently-proven global reserve of cobalt element is limited, so that the cobalt element is relatively high in price, and the cobalt element also has radioactivity and toxicity, which can bring a series of environmental protection problems. The above problems will seriously restrict the rapid development of the lithium battery industry, and in order to solve the above problems, other kinds of positive electrode materials need to be developed to match the preparation of the battery core.
With the continuous reduction of resources and the increasing destruction of the environment, the new energy industry develops rapidly. The lithium ion battery industry is rapidly developing, but the lithium ion battery industry also has some inherent problems, such as capacity attenuation and gas generation caused by lithium-nickel mixed emission, the problems that the global reserve of cobalt resources is limited and the environment is greatly influenced, and the price is greatly increased caused by the mismatch of lithium capacity and the existing demand are proved. Based on the above problems, the entire industry has looked at sodium ion batteries.
The positive electrode material of the sodium-ion battery mainly comprises polyanion compound phosphate, ternary transition metal oxide, organic materials and the like; the ternary transition metal oxide is doped with transition metal to improve the cycling stability and rate capability of the material. The preparation method of the sodium ion anode material comprises a high-temperature solid phase method, a sol-gel method, a hydrothermal method and a high-energy ball milling method. The high-temperature solid phase method is a traditional powder preparation process, has good filling property, low cost, high yield and simple preparation process, but has inherent defects such as high energy consumption, low efficiency, not fine powder, easy impurity mixing and the like. The sol-gel method requires lower reaction temperature, and raw materials can be uniformly mixed at a molecular level, but the method has expensive raw materials and overlong reaction period, so the method is not suitable for large-scale production. The hydrothermal method requires low reaction temperature, has high material purity and can obtain good and controllable morphology, however, the method requires high-temperature and high-pressure reaction in a long-time closed environment, has high operational risk, and requires repeated centrifugal washing and drying for a period of time in the later period, so that the reaction period is long. The high-energy ball milling method is a common method for preparing the electrode material of the lithium/sodium ion battery. The method is simple to operate, has strong adaptability to raw materials, and can realize nanoscale uniform mixing of the raw materials. However, the material synthesized by the method has uneven force distribution, is easy to introduce impurities, has large consumption of raw materials and has serious electric energy loss.
CN106340627A discloses a preparation method of a sodium ion battery anode material, which comprises the following steps: uniformly mixing a sodium source, an iron source and a manganese source to obtain a mixture; mixing the mixture with an oxidant, and carrying out an oxidation reaction through ultrasonic oscillation to obtain a reactant; drying and activating the reactant to obtain a precursor; calcining the precursor in air, and rapidly cooling to obtain the anode material; wherein the anode material is a hexagonal crystal sodium ion compound Na 2/3 Fe 1/2 Mn 1/2 O 2 . However, the high-temperature solid-phase method disclosed in this document has inherent disadvantages such as high energy consumption, low efficiency, insufficiently fine powder, and easy contamination with impurities.
CN103682320A discloses a preparation method of a sodium ion anode material, wherein the anode material is a composite material of a manganese oxide compound and a conductive polymer, the manganese oxide compound crystal is prepared through a hydrothermal reaction, and the surface of the manganese oxide compound crystal is coated by the conductive polymer to obtain the sodium ion anode material. However, the process is complex, and the hydrothermal reaction requires high-pressure equipment and is high in cost.
Therefore, how to obtain a sodium ion cathode material with excellent performance and simple preparation method is a technical problem to be solved urgently.
Disclosure of Invention
The invention aims to provide a manganese-iron-copper positive electrode precursor material, and a preparation method and application thereof. The manganese-iron-copper anode precursor material is prepared by a coprecipitation method, the generation of impure phases caused by element segregation is overcome, the elements are uniformly distributed at an atomic level, and the sodium ion anode material prepared from the precursor material has a stable structure and excellent electrochemical performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a ferromanganese-copper anode precursor material, wherein the shape of the anode precursor material is spherical or spheroidal, and the chemical formula of the anode precursor material is Mn X Cu Y Fe 1-X-Y (OH) 3-X-Y In which0.3 < X < 0.45,0.1 < Y < 0.4, for example, the X can be 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.4, 0.41, 0.42, 0.43, or 0.44, etc., and the Y can be 0.12, 0.15, 0.18, 0.2, 0.22, 0.25, 0.28, 0.3, 0.32, 0.35, 0.38, or 0.39, etc.
The manganese-iron-copper anode precursor material provided by the invention realizes uniform distribution of elements at atomic level, has no impure phase, uniform particles, small agglomeration and obvious sphericity, and the sodium ion anode material obtained by the precursor material has a stable structure and excellent electrochemical performance.
Preferably, the median particle diameter of the positive electrode precursor material is 7 to 10 μm, for example 7 μm, 8 μm, 9 μm, 10 μm or the like.
Preferably, the specific surface area of the positive electrode precursor material is 50-350 m 2 In terms of/g, e.g. 50m 2 /g、100m 2 /g、150m 2 /g、200m 2 /g、250m 2 /g、300m 2 G or 350m 2 And/g, etc.
Preferably, the tap density of the positive electrode precursor material is 0.8-1.3 g/cm 3 E.g. 0.8g/cm 3 、0.9g/cm 3 、1g/cm 3 、1.1g/cm 3 、1.2g/cm 3 Or 1.3g/cm 3 And the like.
In a second aspect, the present invention provides a method for preparing a ferromanganese copper positive electrode precursor material according to the first aspect, the method comprising:
mixing a manganese source, an iron source, a copper source, a reducing agent, a complexing agent and a precipitating agent, and carrying out coprecipitation reaction to obtain the ferromanganese-copper anode precursor material;
wherein the molar ratio of manganese, iron and copper in the manganese source, the iron source and the copper source to Mn X Cu Y Fe 1-X-Y (OH) 3-X-Y The stoichiometry of (A) is maintained consistent, 0.3 < X < 0.45,0.1 < Y < 0.4, e.g., X can be 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.4, 0.41, 0.42, 0.43, or 0.44, etc., and Y can be 0.12, 0.15, 0.18, 0.2, 0.22, 0.25, 0.28, 0.3, 0.32, 0.35, 0.38, or 0.39, etc.
In the invention, three metal elements with precipitation coefficients different by 10-30 orders of magnitude, namely manganese, iron and copper, are subjected to coprecipitation to obtain the ferromanganese copper anode precursor material, the impure phase generation caused by element segregation is overcome, the elements are uniformly distributed at the atomic level, the price is low, the environment is friendly, and the sodium ion anode material prepared from the precursor material has a stable structure and excellent electrochemical performance.
According to the preparation method provided by the invention, the reducing agent is added, so that the system oxidation can be effectively prevented, and if the reducing agent is not added, a large amount of manganese elements are oxidized in the initial reaction nucleation stage, so that a large amount of lattice defects are increased, and the stable growth of a subsequent precursor is not facilitated.
Preferably, the source of manganese comprises any one of manganese sulphate, manganese chloride or manganese nitrate, or a combination of at least two of these.
Preferably, the manganese source is a divalent manganese source.
Preferably, the iron source is a ferric iron source.
According to the invention, the ferric iron source is selected, so that the preparation of the anode material with stable iron valence state is facilitated, the anode material with stable structure is obtained, and the electrochemical performance of the anode material is further improved.
Preferably, the iron source comprises any one of iron sulphate, iron chloride or iron nitrate or a combination of at least two thereof.
Preferably, the copper source comprises any one of copper sulfate, copper chloride or copper nitrate or a combination of at least two thereof.
Preferably, the reducing agent comprises any one of phenol, hydrazine hydrate or acetaldehyde or a combination of at least two thereof.
Preferably, the complexing agent comprises any one of sodium fluoride, sodium citrate or hydroxyethylethylenediaminetriacetic acid or a combination of at least two thereof.
Preferably, the precipitating agent comprises sodium hydroxide and/or potassium hydroxide.
Preferably, the mass concentration of the reducing agent is 1 to 20g/L, such as 1g/L, 2g/L, 3g/L, 4g/L, 5g/L, 6g/L, 7g/L, 8g/L, 9g/L, 10g/L, 11g/L, 12g/L, 13g/L, 14g/L, 15g/L, 16g/L, 17g/L, 18g/L, 19g/L, or 20g/L.
Preferably, the mass concentration of the complexing agent is 20-100 g/L, such as 20g/L, 30g/L, 40g/L, 50g/L, 60g/L, 70g/L, 80g/L, 90g/L or 100g/L.
Preferably, the sum of the molar concentrations of the manganese source, the iron source and the copper source is 2 to 4mol/L, such as 2mol/L, 2.5mol/L, 3mol/L, 3.5mol/L or 4mol/L.
Preferably, the molar concentration of the precipitant is 2 to 5mol/L, such as 2mol/L, 3mol/L, 4mol/L, or 5mol/L.
Preferably, the method of mixing comprises:
mixing an iron source, a copper source and a complexing agent to obtain a metal complexing solution, and adding the metal complexing solution, a manganese source and a precipitator into a base solution in a parallel flow manner, wherein the base solution comprises a reducing agent and the complexing agent.
In the invention, the reducing agent is only added into the base solution at the initial stage of the reaction, and the addition amount of the reducing agent is small, so that the adverse effect of the large amount of oxidation of the divalent manganese on the subsequent reaction in the initial nucleation stage is prevented, and therefore, the addition amount of the reducing agent does not reduce the iron in the trivalent iron source into the divalent iron in a large amount.
In the invention, the iron-copper metal complex solution is prepared firstly, and then is subjected to coprecipitation reaction with the manganese source and the precipitator in the base solution, so that uniform coprecipitation of manganese-iron-copper elements can be better realized, and if the manganese source, the iron source, the copper source, the complexing agent and the precipitator are directly subjected to reaction in the base solution, element segregation can occur, and the electrochemical performance of the prepared anode material is influenced finally.
Preferably, the mass concentration of the complexing agent in the base solution is 5-20 g/L, such as 5g/L, 10g/L, 15g/L or 20g/L.
Preferably, the reaction temperature of the coprecipitation reaction is 50 to 70 ℃, for example, 50 ℃, 55 ℃, 60 ℃, 65 ℃, or 70 ℃.
In the invention, the reaction temperature of the coprecipitation reaction is too low, the reaction speed is too slow, and if the temperature is too high, the reaction is too fast, which is not favorable for the smooth reaction.
Preferably, the stirring speed in the coprecipitation reaction is 200 to 1000rpm, for example 200rpm, 300rpm, 400rpm, 500rpm, 600rpm, 700rpm, 800rpm, 900rpm, 1000rpm, or the like.
In the invention, the stirring speed in the coprecipitation reaction is too low to be beneficial to uniform mixing, the stirring speed is too high, the reaction system is unstable and the energy consumption is increased.
Preferably, the reaction time of the coprecipitation reaction is 40 to 80h, such as 40h, 45h, 50h, 55h, 60h, 65h, 70h, 75h, or 80h, and the like.
Preferably, the product after the coprecipitation reaction is washed 3 to 5 times, for example 3, 4 or 5 times with water.
Preferably, the pH in the co-precipitation reaction is 7.5 to 12, such as 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5 or 12, etc.
As a preferred technical solution, the preparation method comprises:
mixing an iron source, a copper source and a complexing agent to obtain a metal complex solution, adding the metal complex solution, a manganese source and a precipitator into a base solution in a concurrent flow manner, keeping the pH value to be 7.5-12, carrying out a coprecipitation reaction at a stirring speed of 200-1000 rpm at 50-70 ℃ for 40-80 h, and then washing a product after the coprecipitation reaction for 3-5 times; obtaining the manganese-iron-copper anode precursor material;
wherein the base solution comprises a reducing agent and a complexing agent; the mass concentration of the reducing agent is 1-20 g/L; the mass concentration of the complexing agent is 20-100 g/L; the sum of the molar concentrations of the manganese source, the iron source and the copper source is 2-4 mol/L; the molar concentration of the precipitant is 2-5 mol/L; the mass concentration of the complexing agent in the base solution is 5-20 g/L; molar ratio of manganese, iron and copper in manganese source, iron source and copper source to Mn X Cu Y Fe 1-X-Y (OH) 3-X-Y The stoichiometric ratio of (A) is consistent, X is more than 0.3 and less than 0.45,0.1 and less than Y is less than 0.4.
In a third aspect, the invention provides a sodium ion positive electrode material, which is obtained by mixing the ferromanganese-copper positive electrode precursor material of the first aspect with a sodium source and then sintering.
The sodium ion anode material prepared from the ferromanganese copper anode precursor material provided by the invention has more excellent electrochemical performance.
Compared with the sodium ion anode material prepared by the conventional solid phase method, the precursor is prepared by the coprecipitation method, and then the sodium ion anode material is further obtained, wherein the metal elements can be uniformly mixed at the atomic level, so that the electrochemical performance of the material is improved.
Preferably, the molar addition amount of sodium in the sodium source is 1 to 2 times, for example, 1 time, 1.1 times, 1.2 times, 1.3 times, 1.4 times, 1.5 times, 1.6 times, 1.7 times, 1.8 times, 1.9 times, 2 times, or the like, of the total molar amount of the metal elements in the ferromanganese copper positive electrode precursor material.
Preferably, the sintering includes sequentially performing a primary sintering and a secondary sintering.
Preferably, the temperature of the primary sintering is 500 to 800 ℃, for example, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, or 800 ℃ or the like.
Preferably, the time for the first sintering is 2 to 14h, such as 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h or 14h, etc.
Preferably, the temperature of the secondary sintering is 700 to 900 ℃, for example 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃ or the like.
Preferably, the time of the secondary sintering is 10 to 20 hours, such as 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours or 20 hours, and the like.
In a fourth aspect, the present invention also provides a sodium ion battery comprising the sodium ion positive electrode material according to the third aspect.
Compared with the prior art, the invention has the following beneficial effects:
the manganese-iron-copper anode precursor material is prepared by a coprecipitation method, the generation of impure phases caused by element segregation is overcome, the elements are uniformly distributed at an atomic level, and the sodium ion anode material prepared from the precursor material has a stable structure and better electrochemical performance. The sodium ion battery provided by the invention has a specific discharge capacity of more than 97mAh/g in a reversible capacity test at 0.2C.
Drawings
Fig. 1 is an SEM image of the ferromanganese copper positive electrode precursor material provided in example 1.
FIG. 2 is a distribution diagram of Mn element obtained by EDS spectrum scanning of FIG. 1.
Fig. 3 is a distribution diagram of Fe element obtained by performing EDS spectrum scanning on fig. 1.
Fig. 4 is a distribution diagram of Cu element obtained by performing EDS spectrum scanning on fig. 1.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The present embodiment provides a spherical ferromanganese-copper positive electrode precursor material, where the chemical formula of the positive electrode precursor material is Mn 0.35 Cu 0.35 Fe 0.3 (OH) 2.3 。
The preparation method of the manganese-iron-copper anode precursor material comprises the following steps: (the molar ratio of manganese, iron and copper is ensured to be consistent with the chemical formula in the preparation process)
Mixing a ferric sulfate solution, a copper sulfate solution and a sodium fluoride solution (55 g/L) to obtain a metal complex solution;
adding a metal complex solution, a manganese sulfate solution and sodium hydroxide (the molar concentration is 4 mol/L) in a parallel flow mode (the flow rate is 240 ml/h), keeping the pH value at 11, and carrying out coprecipitation reaction for 80h at the temperature of 50 ℃ at the stirring speed of 900rpm to obtain the ferromanganese copper anode precursor material;
the preparation method of the base solution comprises the following steps:
4L of water, 5g of phenol and 30g of sodium fluoride were mixed in a reaction vessel to prepare a base solution.
Fig. 1 shows an SEM image of the positive electrode precursor material of ferromanganese, provided in example 1, and it can be seen from fig. 1 that the positive electrode precursor material of ferromanganese, has better sphericity and more uniform particles.
Fig. 2, fig. 3 and fig. 4 respectively show distribution diagrams of Mn element, fe element and Cu element obtained by performing EDS spectrum scanning on fig. 1, and it can be seen from fig. 2, fig. 3 and fig. 4 that the elements in the ferromanganese-copper positive electrode precursor material are distributed more uniformly, and no obvious element segregation occurs.
Example 2
The embodiment provides a sphere-like ferromanganese-copper anode precursor material, and the chemical formula of the anode precursor material is Mn 0.40 Cu 0.40 Fe 0.20 (OH) 2.20 。
The preparation method of the manganese-iron-copper anode precursor material comprises the following steps: (the molar ratio of manganese, iron and copper is ensured to be consistent with the chemical formula in the preparation process)
Mixing a ferric sulfate solution, a copper sulfate solution and a sodium fluoride solution (100 g/L) to obtain a metal complex solution;
adding a metal complex solution, a manganese sulfate solution and sodium hydroxide (the molar concentration is 3 mol/L) into the base solution in a concurrent flow mode (the flow rate is 240 ml/h), keeping the pH value to be 8, and carrying out a coprecipitation reaction at the stirring speed of 500rpm for 40h at the temperature of 70 ℃ to obtain the ferromanganese-copper anode precursor material;
the preparation method of the base solution comprises the following steps:
4L of water, 5g of phenol and 30g of sodium fluoride were mixed in a reaction vessel to prepare a base solution.
Example 3
The present embodiment provides a spheroidal manganese-iron-copper positive electrode precursor material, wherein the chemical formula of the positive electrode precursor material is Mn 0.40 Cu 0.35 Fe 0.25 (OH) 2.25 。
The preparation method of the manganese-iron-copper anode precursor material comprises the following steps: (the molar ratio of manganese, iron and copper is ensured to be consistent with the chemical formula in the preparation process)
Mixing a ferric sulfate solution, a copper sulfate solution and a sodium fluoride solution (20 g/L) to obtain a metal complex solution;
adding a metal complex solution, a manganese sulfate solution and sodium hydroxide (the molar concentration is 3.5 mol/L) into the base solution in a concurrent flow mode (the flow rates are 240 ml/h), keeping the pH value to be 10, and carrying out a coprecipitation reaction at the stirring speed of 200rpm and the temperature of 60 ℃ for 65 hours to obtain the ferromanganese-copper anode precursor material;
the preparation method of the base solution comprises the following steps:
4L of water, 5g of phenol and 30g of sodium fluoride were mixed in a reaction vessel to prepare a base solution.
Example 4
This example differs from example 1 in that ferric sulphate is replaced by ferrous sulphate, a divalent iron source.
The remaining preparation methods and parameters were in accordance with example 1.
Example 5
This example differs from example 1 in that in this example, a ferric sulfate solution, a copper sulfate solution, a sodium fluoride solution, a manganese sulfate solution and a sodium hydroxide solution are added together in parallel to the base solution.
The remaining preparation methods and parameters were in accordance with example 1.
Comparative example 1
The comparative example provides a sodium ion positive electrode material prepared by a solid phase method, and the chemical formula is NaMn 0.35 Cu 0.35 Fe 0.30 O 2 The preparation method comprises the following steps:
grinding manganese sesquioxide, iron sesquioxide and copper oxide according to a molar ratio of 0.35 to 0.30, then mixing and grinding the ground mixed material and sodium carbonate (wherein the ratio of the total molar amount of metal elements to the molar amount of sodium ions in the sodium carbonate is 1:1), then sintering for 12 hours at 800 ℃ in an air atmosphere, then crushing, and sintering for 10 hours at 900 ℃ to obtain the sodium ion ternary cathode material.
The chemical formula, median particle diameter, specific surface area and tap density of the ferromanganese copper positive electrode precursor materials provided in examples 1-5 are listed in table 1.
TABLE 1
Figure BDA0003352703070000111
The positive electrode precursors of ferromanganese copper provided in examples 1 to 5 were mixed with sodium carbonate (wherein the ratio of the total molar amount of metal ions to the molar amount of sodium ions in the sodium carbonate was 1:1), and then subjected to primary sintering at 800 ℃ for 12 hours in an air atmosphere, followed by crushing and secondary sintering at 900 ℃ for 10 hours, to obtain a sodium ion ternary positive electrode material.
The sodium ion positive electrode materials provided in examples 1 to 5 and comparative example 1 were mixed with carbon black conductive agent (SP), carbon Nanotube (CNT), polyvinylidene fluoride (PVDF), slurried and stirred with N-methylpyrrolidone (NMP) as a solvent to prepare a sodium ion half cell, and the sodium ion half cell was subjected to electrochemical performance test in which reversible capacity test was discharged at 0.2C, and the results are shown in table 2.
TABLE 2
Specific discharge capacity (mAh/g)
Example 1 112
Example 2 109
Example 3 105
Example 4 98
Example 5 97
Comparative example 1 90
From the data results of examples 1 and 4, it is understood that the electrochemical performance is deteriorated when the ferrous iron source is used as the raw material.
From the data results of example 1 and example 5, it can be seen that the raw materials are directly mixed for the co-precipitation reaction, and the reaction speed is poorly controlled during the co-precipitation process, so that the performance of the positive electrode material prepared by sintering the precursor prepared by the method is poor.
From the data results of the embodiment 1 and the comparative example 1, it can be known that, compared with the sodium ion cathode material prepared by the solid phase method, the battery prepared by the material provided by the invention can better realize the synergistic effect of three metal elements of manganese, iron and copper, and can exert better electrochemical performance.
In conclusion, the ferromanganese-iron-copper anode precursor material is prepared by a coprecipitation method, the generation of impurity phases caused by element segregation is avoided, the elements are uniformly distributed at an atomic level, and the sodium ion anode material prepared from the precursor material has a stable structure and excellent electrochemical performance. The sodium ion battery provided by the invention has a specific discharge capacity of more than 97mAh/g in a reversible capacity test at 0.2C.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims (30)

1. The manganese-iron-copper anode precursor material is characterized in that the anode precursor material is spherical or sphere-like in shape, and the anode precursor material is changed into a sphere-like shapeChemical formula is Mn X Cu Y Fe 1-X-Y (OH) 3-X-Y Wherein X is more than 0.3 and less than 0.45,0.1 and less than Y is less than 0.4; the median particle diameter of the positive electrode precursor material is 7-10 mu m;
the manganese-iron-copper positive electrode precursor material is prepared by the following preparation method, and the preparation method comprises the following steps:
mixing an iron source, a copper source and a complexing agent to obtain a metal complexing solution, adding the metal complexing solution, a manganese source and a precipitator into a base solution in a parallel flow manner, wherein the base solution comprises a reducing agent and the complexing agent, and carrying out a coprecipitation reaction to obtain the ferromanganese-copper anode precursor material;
wherein the molar ratio of manganese, iron and copper in the manganese source, the iron source and the copper source to Mn X Cu Y Fe 1-X-Y (OH) 3-X-Y The stoichiometric ratio of (a) is kept consistent.
2. The ferromanganese-iron-copper positive electrode precursor material according to claim 1, wherein the specific surface area of the positive electrode precursor material is 50 to 350m 2 /g。
3. The ferromanganese-copper positive electrode precursor material according to claim 1, wherein the tap density of the positive electrode precursor material is 0.8-1.3 g/cm 3 。
4. A method for preparing a ferromanganese copper positive electrode precursor material according to any one of claims 1 to 3, comprising:
mixing an iron source, a copper source and a complexing agent to obtain a metal complexing solution, adding the metal complexing solution, a manganese source and a precipitator into a base solution in a parallel flow manner, wherein the base solution comprises a reducing agent and the complexing agent, and performing a coprecipitation reaction to obtain a ferromanganese-copper anode precursor material;
wherein the molar ratio of manganese, iron and copper in the manganese source, the iron source and the copper source to Mn X Cu Y Fe 1-X-Y (OH) 3-X-Y The stoichiometric ratio of (A) is kept consistent, X is more than 0.3 and less than 0.45,0.1 and less than Y and less than 0.4.
5. The method of preparing a ferromanganese copper positive precursor material according to claim 4, wherein the manganese source comprises any one of manganese sulfate, manganese chloride, or manganese nitrate, or a combination of at least two thereof.
6. The method of preparing a ferromanganese-iron-copper positive precursor material according to claim 4, wherein the iron source is a trivalent iron source.
7. The method of preparing a ferromanganese-iron-copper positive precursor material according to claim 6, wherein the iron source comprises any one of iron sulfate, iron chloride, or iron nitrate, or a combination of at least two thereof.
8. The method of preparing a ferromanganese copper positive precursor material according to claim 4, wherein the copper source comprises any one of copper sulfate, copper chloride, or copper nitrate, or a combination of at least two thereof.
9. The method of preparing a ferromanganese copper positive electrode precursor material according to claim 4, wherein the reducing agent comprises any one of phenol, hydrazine hydrate, or acetaldehyde, or a combination of at least two thereof.
10. The method of preparing a ferromanganese copper positive precursor material according to claim 4, wherein the complexing agent comprises any one of sodium fluoride, sodium citrate, or hydroxyethylethylenediaminetriacetic acid, or a combination of at least two thereof.
11. The method of preparing a ferromanganese-iron-copper positive precursor material according to claim 4, wherein the precipitant comprises sodium hydroxide and/or potassium hydroxide.
12. The method for preparing a ferromanganese-iron-copper positive electrode precursor material according to claim 4, wherein the mass concentration of the reducing agent is 1 to 20g/L.
13. The preparation method of the ferromanganese-iron-copper positive precursor material according to claim 4, wherein the mass concentration of the complexing agent is 20 to 100g/L.
14. The method for preparing a ferromanganese-copper positive electrode precursor material according to claim 4, wherein the sum of molar concentrations of the manganese source, the iron source, and the copper source is 2 to 4mol/L.
15. The method for preparing a ferromanganese-copper positive electrode precursor material according to claim 4, wherein the molar concentration of the precipitant is 2 to 5mol/L.
16. The method for preparing a ferromanganese-iron-copper positive precursor material according to claim 4, wherein the mass concentration of the complexing agent in the base solution is 5 to 20g/L.
17. The preparation method of the ferromanganese-iron-copper positive precursor material according to claim 4, wherein the reaction temperature of the coprecipitation reaction is 50-70 ℃.
18. The method for preparing a ferromanganese-iron-copper positive precursor material according to claim 4, wherein a stirring speed in the coprecipitation reaction is 200 to 1000rpm.
19. The preparation method of the ferromanganese-iron-copper positive precursor material according to claim 4, wherein the reaction time of the coprecipitation reaction is 40-80 hours.
20. The method for preparing a ferromanganese-iron-copper positive electrode precursor material according to claim 4, wherein a product obtained after the coprecipitation reaction is washed with water for 3 to 5 times.
21. The method for preparing a ferromanganese-iron-copper positive precursor material according to claim 4, wherein the pH value in the coprecipitation reaction is 7.5 to 12.
22. The method for preparing a ferromanganese-iron-copper positive precursor material according to claim 4, comprising:
mixing an iron source, a copper source and a complexing agent to obtain a metal complex solution, adding the metal complex solution, a manganese source and a precipitator into a base solution in a concurrent flow manner, keeping the pH value to be 7.5-12, carrying out a coprecipitation reaction at a stirring speed of 200-1000 rpm at 50-70 ℃ for 40-80 h, and then washing a product after the coprecipitation reaction for 3-5 times; obtaining the ferromanganese copper anode precursor material;
wherein the base solution comprises a reducing agent and a complexing agent; the mass concentration of the reducing agent is 1-20 g/L; the mass concentration of the complexing agent is 20-100 g/L; the sum of the molar concentrations of the manganese source, the iron source and the copper source is 2-4 mol/L; the molar concentration of the precipitant is 2-5 mol/L; the mass concentration of the complexing agent in the base solution is 5-20 g/L; molar ratio of manganese, iron and copper in manganese source, iron source and copper source to Mn X Cu Y Fe 1-X-Y (OH) 3-X-Y The stoichiometric ratio of (A) is consistent, X is more than 0.3 and less than 0.45,0.1 and less than Y is less than 0.4.
23. A sodium ion positive electrode material, characterized in that the sodium ion positive electrode material is obtained by mixing the ferromanganese copper positive electrode precursor material according to any one of claims 1 to 3 with a sodium source and then sintering.
24. The sodium ion positive electrode material of claim 23, wherein the molar amount of sodium added in the sodium source is 1-2 times the total molar amount of metal elements in the ferromanganese copper positive electrode precursor material.
25. The sodium ion positive electrode material according to claim 23, wherein the sintering comprises performing a primary sintering and a secondary sintering in this order.
26. The sodium ion positive electrode material according to claim 25, wherein the temperature of the primary sintering is 500 to 800 ℃.
27. The sodium ion positive electrode material according to claim 25, wherein the time for the primary sintering is 2 to 14 hours.
28. The sodium ion positive electrode material according to claim 25, wherein the secondary sintering temperature is 700 to 900 ℃.
29. The sodium ion cathode material according to claim 25, wherein the secondary sintering time is 10 to 20 hours.
30. A sodium-ion battery, characterized in that the sodium-ion battery comprises a sodium-ion positive electrode material according to any one of claims 23-29.
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