CN114835173A - Positive electrode material precursor, preparation method thereof and positive electrode material - Google Patents
Positive electrode material precursor, preparation method thereof and positive electrode material Download PDFInfo
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
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- 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
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- 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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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- 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
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- 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
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Abstract
The invention relates to the technical field of sodium ion batteries, in particular to a precursor of a positive electrode material, a preparation method thereof and the positive electrode material, wherein the preparation method comprises the following steps: and step S1: mixing an iron source, a copper source and a first complexing agent, and carrying out a complexing reaction to obtain a mixed solution; and step S2: the method of the invention can realize the uniform distribution of the four elements of manganese, iron, nickel and copper, fully play the synergistic effect of manganese, iron, nickel and copper, and remarkably improve the specific capacity of the anode material formed by the precursor by combining the control of the molar ratio of the four elements of manganese, iron, nickel and copper in the molecular formula.
Description
Technical Field
The invention relates to the technical field of sodium-ion batteries, in particular to a precursor of a positive electrode material, a preparation method of the precursor and the positive electrode material.
Background
In recent years, with the development of renewable resources such as solar energy, wind energy, tidal energy and the like, a battery energy storage system with large scale, low cost and high safety is urgently needed to meet the future requirements. The lithium ion battery industry is moving, however, the lithium ion battery has inherent problems, such as capacity attenuation and gas generation caused by lithium-nickel mixed discharge, and has proved that the global reserve of cobalt resources is limited and has a great influence on the environment, and the price is greatly increased due to the mismatch between the lithium capacity and the current demand. 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.
For example, chinese patent document CN109830679A discloses a novel positive electrode material precursor for sodium ion battery and a positive electrode material, which is prepared by dropping a metal solution containing an iron source, a manganese source, a nickel source and an M source selected from any one or a combination of at least two of an aluminum source, a copper source and a cobalt source into an alkaline solution and performing a heating precipitation reaction. In the prior art, M is a doping element and has low molar weight, when the four metal elements are added into alkali liquor together for coprecipitation reaction, the pH value of the solution is changed continuously, the precipitation speed of iron atoms and manganese atoms is greatly different from the precipitation speed of manganese atoms and nickel atoms, and the precipitation coefficient is different by 10-30 orders of magnitude, so that the precipitation speed of the metal elements cannot be maintained stably, uniform coprecipitation is not facilitated, the synergistic effect of the elements cannot be fully exerted, and the specific capacity of the product is influenced.
Disclosure of Invention
The invention aims to overcome the defect of low specific capacity of the anode material in the prior art, and provides a preparation method of an anode material precursor, which comprises the following steps:
and step S1: mixing a metal solution containing an iron source and a copper source with a first complexing agent, and carrying out a complexing reaction to obtain a mixed solution;
and step S2: mixing a reducing agent, a second complexing agent and water to obtain a base solution; adding a manganese source, a nickel source, the mixed solution prepared in the step S1 and an alkaline solution into the base solution to perform a precipitation reaction to prepare a precursor of the positive electrode material; wherein the molar ratio of the iron element in the iron source to the copper element in the copper source to the manganese element in the manganese source to the nickel element in the nickel source is 0.1-0.6: 0.1-0.2: 0.2-0.35: 0.1-0.35.
Further, the iron source is selected from at least one of ferric sulfate, ferrous sulfate, ferric chloride, ferrous chloride, ferric nitrate and ferrous nitrate; and/or the copper source is selected from at least one of copper sulfate, copper chloride and copper nitrate; and/or the manganese source is selected from at least one of manganese sulfate, manganese chloride and manganese nitrate; and/or, the nickel source is selected from at least one of nickel sulfate, nickel chloride and nickel nitrate; and/or, the first complexing agent and/or the second complexing agent is selected from at least one of sodium citrate, sodium fluoride and hydroxyethyl ethylene diamine triacetic acid; and/or, the reducing agent is selected from at least one of hydrazine hydrate, phenol and acetaldehyde; and/or the alkaline solution is selected from a sodium hydroxide aqueous solution and/or a potassium hydroxide aqueous solution.
Further, the molar ratio of the iron element in the iron source, the copper element in the copper source, the manganese element in the manganese source and the nickel element in the nickel source is 0.2-0.3: 0.1-0.2: 0.2-0.3: 0.2-0.3.
Further, the manganese source, the nickel source, the mixed solution prepared in the step S1, and the alkaline solution are simultaneously added dropwise to the base solution in the step S2.
Further, the step S2 satisfies at least one of the following (1) to (5):
(1) the dropping speed of at least one of the manganese source, the nickel source and the mixed liquid prepared in the step S1 is 60-300 mL/h;
(2) the manganese source and the nickel source are independently dripped into the base solution or dripped into the base solution in the form of mixed metal solution containing the manganese source and the nickel source;
(3) the ratio of the total molar concentration of metal elements contained in the mixed solution prepared in the manganese source, the nickel source and the S1 step to the molar concentration of the alkaline solution is 2-4: 2-5;
(4) in the process of precipitation reaction, the rotation speed is controlled to be 200-1000rpm, the temperature of the reaction liquid is 50-70 ℃, the pH value of the reaction liquid is 7.5-12, and the reaction time is 40-80 h;
(5) in the preparation process of the base solution, the ratio of the volume of the added reducing agent to the volume of water is 1-20: 1000, parts by weight; and/or the ratio of the mass of the added second complexing agent to the volume of water is 5-100 g/L.
Further, the step of S1 satisfies at least one of the following a-C:
A. the total molar concentration of the metal elements in the mixed solution is 1-2 mol/L;
B. in the preparation process of the mixed liquid, the mixed liquid containing an iron source and a copper source is mixed with a first complexing agent, wherein the concentration of the first complexing agent in the mixed liquid is 20-100 g/L;
C. the temperature of the complex reaction is 20-40 ℃ and the time is 0.5-3 hours.
The precursor of the positive electrode material can be cleaned for 3-5 times by using ultrapure water.
The invention provides a precursor of the cathode material prepared by any one of the preparation methods. The chemical formula of the precursor of the anode material is Mn a Ni b Cu c Fe (1-a-b-c) (OH) 2 Or Mn a Ni b Cu c Fe (1-a-b-c) (OH) (3-a-b-c) (ii) a Wherein a is more than or equal to 0.20 and less than or equal to 0.35, b is more than or equal to 0.1 and less than or equal to 0.35, and c is more than or equal to 0.1 and less than or equal to 0.2.
Furthermore, a is more than or equal to 0.20 and less than or equal to 0.30, and b is more than or equal to 0.2 and less than or equal to 0.30.
Further, the precursor of the cathode material is spherical or spheroidal particles; and/or the median particle diameter D50 of the precursor of the positive electrode material is 6-10 mu m, and the specific surface area B is 50-200 m 2 (ii)/g; and/or the tap density T of the precursor of the positive electrode material is 0.6-1.3 g/cm 3 。
The invention also provides a cathode material, and the preparation raw material of the cathode material comprises the cathode material precursor prepared by any one of the preparation methods or the cathode material precursor, and also comprises a sodium source.
Further, the positive electrode material satisfies at least one of the following 1) to 5):
1) the molecular formula of the cathode material is as follows: NaMn a Ni b Cu c Fe (1-a-b-c) O 2 Wherein a is more than or equal to 0.20 and less than or equal to 0.35, b is more than or equal to 0.10 and less than or equal to 0.35, and c is more than or equal to 0.10 and less than or equal to 0.20;
2) the first discharge specific capacity G of the positive electrode material is 90-140 mAh/G;
3) the relation among the median particle diameter D50, the specific surface area B, the tap density T and the first discharge specific capacity G of the anode material precursor satisfies the following conditions: (B multiplied by D50 multiplied by T)/G is more than or equal to 1.43 and less than or equal to 15;
4) the specific surface area of the positive electrode material is 0.5-5m 2 (ii) g, tap density of 0.9-1.7g/cm 3 ；
5) The relation between the specific surface area B and the tap density T of the precursor of the positive electrode material and the relation between the specific surface area C and the tap density D of the positive electrode material satisfy that B/C + T/D is more than or equal to 10 and less than or equal to 100.
The specific first discharge capacity G refers to the specific first discharge capacity obtained by performing a charge-discharge test in a potential window of 2.0-4.05V at a charge-discharge speed of 0.1C.
The invention also provides a preparation method of the cathode material, which comprises the steps of mixing the precursor of the cathode material with a sodium source, and calcining to obtain the cathode material.
Preferably, the calcination comprises a first calcination and a second calcination, wherein the temperature of the first calcination is 500-800 ℃ for 2-14 hours, and the temperature of the second calcination is 700-900 ℃ for 10-20 hours.
Preferably, the molar quantity of the sodium source is 0.5-1.0 time of that of the precursor of the positive electrode material;
preferably, the sodium source comprises sodium carbonate.
The technical scheme of the invention has the following advantages:
1. the preparation method of the precursor of the cathode material provided by the invention comprises the following steps: and step S1: mixing a metal solution containing an iron source and a copper source with a first complexing agent, and carrying out a complexing reaction to obtain a mixed solution; mixing a reducing agent, a second complexing agent and water to obtain a base solution; and step S2: adding a manganese source, a nickel source, a mixed solution and an alkaline solution into the base solution to perform a precipitation reaction to obtain a precursor of the positive electrode material, wherein the molar ratio of iron element in the iron source, copper element in the copper source, manganese element in the manganese source and nickel element in the nickel source is 0.1-0.6: 0.1-0.2: 0.2-0.35: 0.1-0.35; the invention reduces the using amount of manganese and nickel by using iron and copper with low price, and the iron and copper are bound by carrying out complex reaction on a first complexing agent, an iron source and a copper source, and then the first complexing agent, a manganese source, a nickel source and an alkaline solution are added into a base solution containing a reducing agent and a second complexing agent, so that the four elements of manganese, iron, nickel and copper can be uniformly distributed at an atomic level, the synergistic effect of manganese, iron, nickel and copper is fully exerted, and the specific capacity of an anode material formed by the precursor is remarkably improved by combining the control of the molar ratio of the four elements of manganese, iron, nickel and copper in a molecular formula.
In addition, the preparation method is combined with the control of the molar quantity of the four elements of manganese, iron, nickel and copper in the molecular formula, so that the preparation of the micron-sized spherical or sphere-like precursor of the quaternary metal element is realized, the shape is regular, the tap density of the precursor is favorably improved, the cycle stability of the anode material is improved, and the gas generation of the anode material is reduced.
2. According to the preparation method of the precursor of the anode material, provided by the invention, the anode material prepared by selecting ferric sulfate as a raw material has higher specific capacity, which is probably because trivalent iron has no valence change in the calcining process compared with divalent iron, a stable structure is more favorably formed, and the synergistic effect of elements is exerted.
3. The preparation method of the precursor of the cathode material provided by the invention comprises the following steps of (1) enabling the molar ratio of the iron element in the iron source, the copper element in the copper source, the manganese element in the manganese source and the nickel element in the nickel source to be 0.2-0.3: 0.1-0.2: 0.2-0.3: 0.2-0.3, the obtained anode material has higher specific capacity.
4. According to the preparation method of the precursor of the cathode material, provided by the invention, the manganese source, the nickel source, the mixed solution prepared in the step S1 and the alkaline solution are added into the base solution in the step S2 in a dropwise manner, so that the pH value of the reaction solution can be well controlled, the pH value in the whole reaction process is kept consistent, and the distribution of metal elements in the reaction product is more uniform.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is an SEM plane electron micrograph of a precursor of the cathode material prepared in example 3 of the present invention;
FIG. 2 is a sectional electron microscope image of a precursor of the positive electrode material prepared in example 3 of the present invention;
FIG. 3 is a cross-sectional energy spectrum (Cu, Mn, Ni and Fe) of the precursor of the positive electrode material obtained in example 3 of the present invention;
FIG. 4 is an SEM electron micrograph of the precursor of the cathode material prepared in example 2 of the present invention;
fig. 5 is a cycle curve of the positive electrode material obtained in example 3 of experimental example 2 of the present invention.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
The embodiment provides a preparation method of a precursor of a positive electrode material and the precursor:
(1) weighing manganese sulfate and nickel sulfate, mixing, and dissolving with water to obtain a mixed metal solution of manganese sulfate (with a concentration of 0.90mol/L) and nickel sulfate (with a concentration of 0.60 mol/L). Weighing ferric sulfate and copper sulfate, mixing, and dissolving with water to obtain a mixed metal solution of ferric sulfate (with a concentration of 0.45mol/L) and copper sulfate (with a concentration of 0.60 mol/L). Weighing sodium hydroxide, adding deionized water to prepare a sodium hydroxide solution with the concentration of 4 mol/L.
(2) And adding sodium citrate into the mixed metal solution of ferric sulfate and copper sulfate to ensure that the concentration of the sodium citrate in the solution is 20g/L, and carrying out a complex reaction at the temperature of 25 ℃ for 1 h.
(3) Adding 4L of water into a reaction kettle, adding 5mL of hydrazine hydrate, adding 30g of sodium citrate to prepare a base solution, dropwise adding the mixed metal solution of manganese sulfate and nickel sulfate prepared in the step (1) and the mixed metal solution of ferric sulfate and copper sulfate obtained after the complex reaction in the step (2) into the base solution together with a sodium hydroxide solution at the speed of 240mL/h, simultaneously performing dropwise addition and precipitation reaction, controlling the temperature in the reaction kettle to be 50 ℃, the rotating speed to be 900rpm, and the pH value of the reaction solution to be 11.0, continuously dropwise adding for 80 hours, and obtaining the precursor of the cathode material after the reaction is finished. Wherein the molecular formula of the precursor of the positive electrode material is Mn 0.3 Ni 0.2 Cu 0.2 Fe 0.3 (OH) 2.3 Tap density of 1.25g/mL 3 The specific surface area B was 171.04m 2 The volume ratio of D50 is 6.38 μm, the precursor of the positive electrode material is spherical or spheroidal particle, and the sphericity is good.
Example 2
The embodiment provides a preparation method of a precursor of a positive electrode material and the precursor:
(1) weighing manganese sulfate and nickel sulfate, mixing, and dissolving with water to obtain a mixed metal solution of manganese sulfate (with a concentration of 0.90mol/L) and nickel sulfate (with a concentration of 0.60 mol/L). Weighing ferrous sulfate and copper sulfate, mixing, and dissolving with water to obtain a mixed metal solution of ferrous sulfate (with a concentration of 0.90mol/L) and copper sulfate (with a concentration of 0.60 mol/L). Sodium hydroxide is weighed and added into deionized water to prepare 4mol/L sodium hydroxide solution.
(2) And adding sodium citrate into the mixed metal solution of ferric sulfate and copper sulfate to ensure that the concentration of the sodium citrate in the solution is 20g/L, and carrying out a complex reaction at the temperature of 25 ℃ for 1 h.
(3) Adding 4L of water into a reaction kettle, adding 5mL of hydrazine hydrate, adding 30g of sodium citrate to prepare a base solution, dropwise adding the mixed metal solution of manganese sulfate and nickel sulfate prepared in the step (1), the mixed metal solution of ferric sulfate and copper sulfate after the complexing reaction in the step (2) and a sodium hydroxide solution into the base solution at the speed of 240mL/h, dropwise adding and performing a precipitation reaction at the same time, controlling the temperature in the reaction kettle to be 50 ℃, the rotating speed to be 900rpm, and the pH value of the reaction solution to be 11.0, continuously dropwise adding for 80 hours, and obtaining the precursor of the anode material after the reaction is finished. Wherein the molecular formula of the precursor of the positive electrode material is Mn 0.3 Ni 0.2 Cu 0.2 Fe 0.3 (OH) 2 Tap density of 1.12g/mL 3 The specific surface area B was 92.45m 2 The volume ratio of D50 is 6.43 μm, and as shown in FIG. 4, the precursor of the positive electrode material is spherical or spheroidal particle, with better sphericity.
Example 3
The embodiment provides a preparation method of a precursor of a positive electrode material and the precursor:
(1) weighing manganese sulfate and nickel sulfate, mixing, and dissolving with water to obtain a mixed metal solution of manganese sulfate (with a concentration of 0.60mol/L) and nickel sulfate (with a concentration of 0.90 mol/L). Weighing ferric sulfate and copper sulfate, mixing, and dissolving with water to obtain a mixed metal solution of ferric sulfate (with a concentration of 0.45mol/L) and copper sulfate (with a concentration of 0.60 mol/L). Weighing sodium hydroxide, adding deionized water to prepare a sodium hydroxide solution with the concentration of 4 mol/L.
(2) And (2) adding sodium citrate into the mixed metal solution of ferric sulfate and copper sulfate prepared in the step (1) to enable the concentration of the sodium citrate in the solution to be 20g/L, and carrying out a complex reaction at the temperature of 25 ℃ for 1 h.
(3) Adding 4L of water into a reaction kettle, adding 5mL of hydrazine hydrate, adding 30g of sodium citrate to prepare a base solution, and mixing the manganese sulfate and nickel sulfate mixed metal solution prepared in the step (1) and the ferric sulfate and copper sulfate mixed metal solution after the complexing reaction in the step (2) at the same speed of 240mL/hAnd dropwise adding the solution and a sodium hydroxide solution into the base solution, wherein the dropwise adding and the precipitation reaction are carried out simultaneously, the temperature in the reaction kettle is controlled to be 50 ℃, the rotating speed is 900rpm, the pH value of the reaction solution is 11.0, the dropwise adding is continuously carried out for 60 hours, and the anode material precursor is prepared in the whole reaction process through testing. Wherein the molecular formula of the precursor of the positive electrode material is Mn 0.2 Ni 0.3 Cu 0.2 Fe 0.3 (OH) 2.3 Tap density of 1.28g/mL 3 The specific surface area B is 168.93m 2 The volume ratio of D50 is 7.08 μm, and as shown in FIG. 1, the precursor of the positive electrode material is spherical or spheroidal particle, and the sphericity is better.
Example 4
The embodiment provides a preparation method of a positive electrode precursor material and a precursor:
(1) weighing and mixing manganese chloride and nickel chloride, and dissolving the mixture by water to prepare a mixed metal liquid of manganese chloride (with the concentration of 0.70mol/L) and nickel chloride (with the concentration of 0.30 mol/L). Weighing ferric chloride and copper nitrate, mixing, and dissolving with water to obtain a mixed metal liquid of ferric chloride (with the concentration of 0.60mol/L) and copper nitrate (with the concentration of 0.40 mol/L). Weighing potassium hydroxide, adding deionized water to prepare a 2mol/L sodium hydroxide solution.
(2) And adding sodium citrate into the mixed metal liquid of the ferric chloride and the copper nitrate to ensure that the concentration of the sodium citrate in the solution is 100g/L, and carrying out a complex reaction at the temperature of 25 ℃ for 1 h.
(3) Adding 4L of water into a reaction kettle, adding 80mL of phenol, adding 400g of sodium fluoride to prepare a base solution, dropwise adding the mixed metal solution of manganese chloride and nickel chloride prepared in the step (1) and the mixed metal solution of iron chloride and copper nitrate obtained after the complexing reaction in the step (2) into the base solution at the same speed of 60mL/h, dropwise adding the mixed metal solution of iron chloride and copper nitrate and the sodium hydroxide solution into the base solution at the same time, performing dropwise adding and precipitation reaction at the same time, controlling the temperature in the reaction kettle to be 70 ℃, the rotating speed to be 600rpm, and the pH value of the reaction solution to be 11.0, continuously dropwise adding for 40 hours, and obtaining the anode precursor material after the reaction is finished. Wherein the molecular formula of the anode precursor material is Mn 0.35 Ni 0.15 Cu 0.20 Fe 0.30 (OH) 2.30 Tap density of 1.18g/mL 3 Specific surface area of 182.35m 2 D50 is 6.21m, and the sphericity is better.
Comparative example 1
The embodiment provides a preparation method of a precursor of a positive electrode material and the precursor:
(1) weighing manganese sulfate and nickel sulfate, mixing, and dissolving with water to obtain a mixed metal solution of manganese sulfate (with a concentration of 0.90mol/L) and nickel sulfate (with a concentration of 0.60 mol/L). Weighing ferric sulfate and copper sulfate, mixing, and dissolving with water to obtain a mixed metal solution of ferric sulfate (with a concentration of 0.45mol/L) and copper sulfate (with a concentration of 0.60 mol/L). Weighing sodium hydroxide, adding deionized water to prepare a sodium hydroxide solution with the concentration of 4 mol/L.
(2) Adding 4L of water into a reaction kettle, adding 5mL of hydrazine hydrate, adding 30g of sodium citrate to prepare a base solution, dropwise adding the mixed metal solution of manganese sulfate and nickel sulfate prepared in the step (1), the mixed metal solution of ferric sulfate and copper sulfate obtained after the complex reaction in the step (2) and a sodium hydroxide solution into the base solution at the same speed of 240mL/h, simultaneously performing dropwise addition and precipitation reaction, controlling the temperature in the reaction kettle to be 50 ℃, the rotating speed to be 900rpm, and the pH value of the reaction solution to be 11.0, continuously dropwise adding for 80 hours, and obtaining the precursor of the cathode material after the reaction is finished. Wherein the molecular formula of the precursor of the positive electrode material is Mn 0.3 Ni 0.2 Cu 0.2 Fe 0.3 (OH) 2.3 Tap density 0.68g/mL 3 The specific surface area B is 191.07m 2 The concentration/g and the D50 are 7.30 mu m, and the prepared precursor of the cathode material is an agglomerate of large and small particles.
Comparative example 2
The embodiment provides a preparation method of a precursor of a positive electrode material and the precursor:
(1) weighing manganese sulfate and nickel sulfate, mixing, and dissolving with water to obtain a mixed metal solution of manganese sulfate (with a concentration of 0.90mol/L) and nickel sulfate (with a concentration of 0.6 mol/L). Weighing ferric sulfate and copper sulfate, mixing, and dissolving with water to obtain a mixed metal solution of ferric sulfate (with a concentration of 0.60mol/L) and copper sulfate (with a concentration of 0.30 mol/L). Weighing sodium hydroxide, adding deionized water to prepare a sodium hydroxide solution with the concentration of 4 mol/L.
(2) And adding sodium citrate into the mixed metal solution of ferric sulfate and copper sulfate to ensure that the concentration of the sodium citrate in the solution is 20g/L, and carrying out a complex reaction at the temperature of 25 ℃ for 1 h.
(3) Adding 4L of water into a reaction kettle, adding 5mL of hydrazine hydrate, adding 30g of sodium citrate to prepare a base solution, dropwise adding the mixed metal solution of manganese sulfate and nickel sulfate prepared in the step (1) and the mixed metal solution of ferric sulfate and copper sulfate obtained after the complex reaction in the step (2) into the base solution together with a sodium hydroxide solution at the speed of 240mL/h, simultaneously performing dropwise addition and precipitation reaction, controlling the temperature in the reaction kettle to be 50 ℃, the rotating speed to be 900rpm, and the pH value of the reaction solution to be 11.0, continuously dropwise adding for 80 hours, and obtaining the precursor of the cathode material after the reaction is finished. Wherein the molecular formula of the precursor of the positive electrode material is Mn 0.3 Ni 0.2 Cu 0.05 Fe 0.45 (OH) 2.45 Tap density of 1.07g/mL 3 The specific surface area B is 185.46m 2 The volume ratio of D50 is 6.26 μm, the precursor of the positive electrode material is spherical or spheroidal particle, and the sphericity is good.
Comparative example 3
The embodiment provides a preparation method of a precursor of a positive electrode material and the precursor:
(1) weighing manganese sulfate and nickel sulfate, mixing, and dissolving with water to obtain a mixed metal solution of manganese sulfate (with a concentration of 0.90mol/L) and nickel sulfate (with a concentration of 0.60 mol/L). Weighing ferric sulfate and copper sulfate, mixing, and dissolving with water to obtain a mixed metal solution of ferric sulfate (with a concentration of 0.06mol/L) and copper sulfate (with a concentration of 1.38 mol/L). Weighing sodium hydroxide, adding deionized water to prepare a sodium hydroxide solution with the concentration of 4 mol/L.
(2) And adding sodium citrate into the mixed metal solution of ferric sulfate and copper sulfate to ensure that the concentration of the sodium citrate in the solution is 20g/L, and carrying out a complex reaction at the temperature of 25 ℃ for 1 h.
(3) Adding 4L of water into a reaction kettle, adding 5mL of hydrazine hydrate, adding 30g of sodium citrate to prepare a base solution, dropwise adding the mixed metal solution of manganese sulfate and nickel sulfate prepared in the step (1) and the mixed metal solution of iron sulfate and copper sulfate obtained after the complex reaction in the step (2) into the base solution together with a sodium hydroxide solution at the speed of 240mL/h, and simultaneously performing dropwise addition and precipitation reaction, wherein the temperature in the reaction kettle is controlled to be 50 DEG CThe rotating speed is 900rpm, the pH value of the reaction solution is 11.0, and the dropwise addition is continuously carried out for 80 hours, so that the precursor of the anode material is prepared after the reaction is finished. Wherein the molecular formula of the precursor of the positive electrode material is Mn 0.3 Ni 0.2 Cu 0.46 Fe 0.04 (OH) 2.04 Tap density 0.97g/mL 3 The specific surface area B is 186.31m 2 The volume ratio of the precursor to the positive electrode material is 6.29 mu m, the D50 is spherical or spheroidal, and the sphericity is good.
Experimental example 1
The precursors of the positive electrode materials prepared in the examples and the comparative examples were used to prepare sodium ion half cells according to the following methods. Taking a precursor of the anode material and sodium carbonate, fully mixing the precursor and the sodium carbonate according to a molar ratio of 1:1, calcining the mixture for 12 hours at the temperature of 800 ℃ in an air atmosphere, and then crushing and carrying out secondary calcination treatment at the temperature of 900 ℃ for 10 hours to obtain the anode material.
Mixing the positive electrode material with SP (carbon black conductive agent) and PVDF (polyvinylidene fluoride) according to a mass ratio of 90: 5: 5, mixing, stirring for 4 hours by using NMP (N-methyl pyrrolidone) as a solvent to prepare slurry, coating the slurry on an aluminum foil, drying to prepare a positive pole piece, and preparing the sodium-ion half-cell by using metal sodium as a negative pole piece. And (3) carrying out charging and discharging test on the first discharging specific capacity G of the anode material in a potential window of 2.0-4.05V at a charging and discharging speed of 0.1C.
TABLE 1 specific surface area, tap density and specific first discharge capacity of the positive electrode material
Experimental example 2
The precursors of the positive electrode materials prepared in the examples and the comparative examples are respectively prepared into the sodium ion half-cell by the method of experiment example 1, the battery cycle performance test is carried out, 50 times of charging and discharging are carried out in a potential window of 2.0-4.05V at a charging and discharging speed of 1.0C, and the results are shown in the following table.
TABLE 2 Capacity conservation Rate of Positive electrode Material
| Item | Capacity retention at 50 weeks |
| Example 1 | 85.0％ |
| Example 2 | 86.7％ |
| Example 3 | 90.3％ |
| Example 4 | 86.9％ |
| Comparative example 1 | 73.4％ |
| Comparative example 2 | 82.6％ |
| Comparative example 3 | 83.7％ |
As can be seen from the above table, the capacity retention rate of the cathode material of each embodiment of the present invention is significantly improved, in particular, in embodiment 3, referring to fig. 5, the capacity retention rate of the cathode material formed by the cathode material precursor of embodiment 3 is 90.3% after 50 cycles.
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 (10)
1. A preparation method of a precursor of a positive electrode material is characterized by comprising the following steps:
and step S1: mixing an iron source, a copper source and a first complexing agent, and carrying out a complexing reaction to obtain a mixed solution;
and step S2: mixing a reducing agent, a second complexing agent and water to obtain a base solution, and adding a manganese source, a nickel source, the mixed solution prepared in the step S1 and an alkaline solution into the base solution to perform a precipitation reaction to obtain a precursor of the positive electrode material; wherein the molar ratio of the iron element in the iron source to the copper element in the copper source to the manganese element in the manganese source to the nickel element in the nickel source is 0.1-0.6: 0.1-0.2: 0.2-0.35: 0.1-0.35.
2. The method for preparing a precursor of a positive electrode material according to claim 1, wherein the iron source is at least one selected from the group consisting of iron sulfate, ferrous sulfate, iron chloride, ferrous chloride, iron nitrate, and ferrous nitrate; and/or the copper source is selected from at least one of copper sulfate, copper chloride and copper nitrate; and/or the manganese source is selected from at least one of manganese sulfate, manganese chloride and manganese nitrate; and/or, the nickel source is selected from at least one of nickel sulfate, nickel chloride and nickel nitrate; and/or, the first complexing agent and/or the second complexing agent is selected from at least one of sodium citrate, sodium fluoride and hydroxyethyl ethylene diamine triacetic acid; and/or, the reducing agent is selected from at least one of hydrazine hydrate, phenol and acetaldehyde; and/or the alkaline solution is selected from a sodium hydroxide aqueous solution and/or a potassium hydroxide aqueous solution.
3. The method for producing a precursor for a positive electrode material according to claim 1 or 2, wherein a molar ratio of an iron element in the iron source, a copper element in the copper source, a manganese element in the manganese source, and a nickel element in the nickel source is 0.2 to 0.3: 0.1-0.2: 0.2-0.3: 0.2-0.3.
4. The method for producing a precursor of a positive electrode material according to any one of claims 1 to 3, wherein the manganese source, the nickel source, the mixed solution obtained in the step S1, and the alkaline solution are simultaneously added dropwise to the base solution in the step S2; preferably, the S2 step satisfies at least one of the following (1) to (5):
(1) the dropping speed of at least one of the manganese source, the nickel source and the mixed liquid prepared in the step S1 is 60-300 mL/h;
(2) the manganese source and the nickel source are independently dripped into the base solution or dripped into the base solution in the form of mixed metal solution containing the manganese source and the nickel source;
(3) the ratio of the total molar concentration of metal elements contained in the mixed solution prepared in the manganese source, the nickel source and the S1 step to the molar concentration of the alkaline solution is 2-4: 2-5;
(4) in the process of precipitation reaction, the rotation speed is controlled to be 200-1000rpm, the temperature of the reaction liquid is 50-70 ℃, the pH value of the reaction liquid is 7.5-12, and the reaction time is 40-80 h;
(5) in the preparation process of the base solution, the ratio of the volume of the added reducing agent to the volume of water is 1-20: 1000, parts by weight; and/or the ratio of the mass of the added second complexing agent to the volume of water is 5-100 g/L.
5. The method for producing a positive electrode material precursor according to any one of claims 1 to 4, wherein the step S1 satisfies at least one of the following A to C:
A. the total molar concentration of the metal elements in the mixed solution is 1-2 mol/L;
B. in the preparation process of the mixed liquid, mixed metal liquid containing an iron source and a copper source is mixed with a first complexing agent, preferably, the concentration of the first complexing agent in the mixed metal liquid is 20-100 g/L;
C. the temperature of the complex reaction is 20-40 ℃ and the time is 0.5-3 hours.
6. The positive electrode material precursor prepared by the preparation method according to any one of claims 1 to 5, preferably the positive electrode material precursorThe chemical formula of the body is Mn a Ni b Cu c Fe (1-a-b-c) (OH) 2 Or Mn a Ni b Cu c Fe (1-a-b-c) (OH) (3-a-b-c) (ii) a Wherein a is more than or equal to 0.20 and less than or equal to 0.35, b is more than or equal to 0.1 and less than or equal to 0.35, and c is more than or equal to 0.1 and less than or equal to 0.2.
7. The positive electrode material precursor according to claim 6, wherein the positive electrode material precursor is spherical or spheroidal particles; and/or the median particle diameter D50 of the precursor of the positive electrode material is 6-10 mu m, and the specific surface area B is 50-200 m 2 (ii)/g; and/or the tap density T of the precursor of the positive electrode material is 0.6-1.3 g/cm 3 。
8. A positive electrode material, characterized in that a raw material for production thereof comprises a positive electrode material precursor produced by the production method according to any one of claims 1 to 5 or the positive electrode material precursor according to claim 6 or 7, and further comprises a sodium source.
9. The positive electrode material according to claim 8, wherein the positive electrode material satisfies at least one of the following 1) to 5):
1) the molecular formula of the cathode material is as follows: NaMn a Ni b Cu c Fe (1-a-b-c) O 2 Wherein a is more than or equal to 0.20 and less than or equal to 0.35, b is more than or equal to 0.10 and less than or equal to 0.35, and c is more than or equal to 0.10 and less than or equal to 0.20;
2) the first discharge specific capacity G of the positive electrode material is 90-140 mAh/G;
3) the relation among the median particle diameter D50, the specific surface area B, the tap density T and the first discharge specific capacity G of the anode material precursor satisfies the following conditions: (B multiplied by D50 multiplied by T)/G is more than or equal to 1.43 and less than or equal to 15;
4) the specific surface area of the cathode material is 0.5-5m 2 (ii) g, tap density of 0.9-1.7g/cm 3 ；
5) The relation between the specific surface area B and the tap density T of the precursor of the positive electrode material and the relation between the specific surface area C and the tap density D of the positive electrode material satisfy that B/C + T/D is more than or equal to 10 and less than or equal to 100.
10. A method for preparing the anode material of claim 8 or 9, the anode material precursor is taken to be mixed with a sodium source and calcined to prepare the anode material,
preferably, the calcination comprises a first calcination and a second calcination, wherein the temperature of the first calcination is 500-800 ℃ for 2-14 hours, and the temperature of the second calcination is 700-900 ℃ for 10-20 hours;
preferably, the molar quantity of the sodium source is 0.5-1.0 time of that of the precursor of the positive electrode material;
preferably, the sodium source comprises sodium carbonate.
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