CN115504520A - Layered sodium-ion battery positive electrode material and preparation method and application thereof - Google Patents

Layered sodium-ion battery positive electrode material and preparation method and application thereof Download PDF

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CN115504520A
CN115504520A CN202211180451.9A CN202211180451A CN115504520A CN 115504520 A CN115504520 A CN 115504520A CN 202211180451 A CN202211180451 A CN 202211180451A CN 115504520 A CN115504520 A CN 115504520A
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sodium
ion battery
positive electrode
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layered
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尹伊君
谭艳
钟毅
闫晓志
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Hunan Jinfuli New Energy Co ltd
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Abstract

The invention discloses a preparation method of a layered sodium-ion battery anode material, which comprises the following steps: step 1: stirring a sodium source, a metal source, a doping agent and a solvent together, and fully and uniformly mixing to obtain a metal salt solution; step 2: transferring the metal salt solution into an atomizer for atomization, and loading the metal salt solution into a roasting furnace for pyrolysis through carrier gas to obtain a precursor of the positive electrode material; and step 3: calcining the precursor of the positive electrode material at high temperature to obtain the positive electrode material of the layered single crystal sodium ion battery; the invention can overcome the problems that the operation is difficult, a large amount of ammonia waste liquid is generated in the synthesis process of the traditional coprecipitation method, the tail gas of the common dry spraying method is difficult to treat, the mixture of the precursor and the sodium source is uneven, the residual alkali is high and the like. Therefore, the sodium ion battery anode material which has the advantages of simple preparation method, easy tail gas treatment, high sodium source mixing degree, low residual alkali and good electrochemical performance is provided.

Description

Layered sodium-ion battery positive electrode material and preparation method and application thereof
Technical Field
The invention relates to the technical field of positive electrode materials of sodium-ion batteries, in particular to a layered positive electrode material of a sodium-ion battery, and a preparation method and application thereof.
Background
Sodium ion batteries are relatively slow to develop compared to lithium ion batteries. However, in practical application, due to the discovery of the problems of lithium resource scarcity, uneven distribution and the like, in recent years, many researchers and enterprises have turned their attention to sodium ion batteries. The working principle and the preparation process of the sodium ion battery are basically consistent with those of the lithium ion battery, and the sodium resource is rich and uniformly distributed, so that the sodium ion battery has the potential of large-scale production.
At present, the preparation process of the positive electrode material of the sodium-ion battery basically adopts a coprecipitation method and a solid phase method. The coprecipitation of metal salts such as iron, copper and the like is not easy to operate, and a large amount of ammonia wastewater generated in the production process does not accord with the environmental protection concept; and the capacity of the finished product obtained after the sodium source is added and the high-temperature calcination is not ideal, so that a method which is simple to operate and has good product capacity needs to be found to replace the traditional coprecipitation method.
The drying and spraying method can uniformly mix various metal salts on the atomic layer surface, and the sodium ion battery anode material is obtained by atomizing the salt solution and then pyrolyzing the atomized salt solution, so that the operation process is simple, and the method is considered to be an excellent alternative method of the traditional coprecipitation method. However, the sodium ion battery anode material prepared by the dry spraying method is generally prepared by two steps, most of organic salts, nitrates and the like are used in the process of synthesizing the precursor in the first step, and tail gas generated after pyrolysis is not easy to treat. In addition, the precursor obtained in the first step needs to be mixed with a sodium source and then calcined again, but the dry mixing time is long, the mixing is not uniform enough, and sodium sources such as sodium carbonate and the like are easy to corrode saggars, and excessive sodium sources are not completely sintered, so that the residual alkali is high.
Therefore, a method is needed to solve the problems of uneven mixing of the precursor and the sodium source, time consumption of mixing, high residual alkali and the like in tail gas treatment after spray pyrolysis, and the positive electrode material of the sodium-ion battery prepared by the method has good electrochemical performance.
Disclosure of Invention
In view of the defects, the invention provides a layered sodium-ion battery cathode material, and a preparation method and application thereof, and can overcome the problems that the operation is not easy, a large amount of ammonia waste liquid is generated, the tail gas of the conventional dry spraying method is not easy to treat, the mixing of a precursor and a sodium source is not uniform, the residual alkali is high and the like in the synthesis process of the conventional coprecipitation method. Therefore, the sodium ion battery anode material which has the advantages of simple preparation method, easy tail gas treatment, high sodium source mixing degree, low residual alkali and good electrochemical performance is provided.
In order to achieve the purpose, the invention provides a preparation method of a layered sodium-ion battery cathode material, which comprises the following steps:
step 1: stirring a sodium source, a metal source, a doping agent and a solvent together, and fully and uniformly mixing to obtain a metal salt solution;
step 2: transferring the metal salt solution to an atomizer for atomization, and then loading the metal salt solution into a roasting furnace for pyrolysis through carrier gas to obtain a positive electrode material precursor;
and step 3: and calcining the precursor of the positive electrode material at high temperature to obtain the layered single crystal sodium ion battery positive electrode material.
According to one aspect of the invention, the chemical general formula of the layered single crystal sodium-ion battery positive electrode material is as follows: M-NaNi a Cu b Fe c Mn d O 2 (ii) a Wherein M is a doping element provided by a dopant, and M is selected from one or more of Al, mg, zn, sr and Co; ni, cu, fe and Mn are metal elements provided by a metal source, a + b + c + d =1, a is more than or equal to 0 and less than 1, b is more than or equal to 0 and less than 1, c is more than or equal to 0 and less than 1, and d is more than or equal to 0 and less than or equal to 1.
In accordance with one aspect of the invention, the sodium source is a sodium halide; the metal source is a halide salt of the corresponding metal; the dopant is halide salt corresponding to the doped metal element.
According to one aspect of the invention, the sodium halide is one of NaF, naCl, naBr; the metal source comprises a nickel source, a copper source, an iron source and a manganese source, and the manganese source is MnF 2 、MnCl 2 、MnBr 2 The iron source is FeF 3 、FeCl 3 、FeBr 3 One of (a) and (b); the dopant is AlCl 3 、MgCl 2 、ZnCl 2 、SrCl 2 、CoCl 2 One kind of (1).
According to an aspect of the present invention, in the step 1, the solvent is one or more of deionized water, ethanol and methanol.
According to one aspect of the present invention, in the step 2, the pyrolysis temperature is 600 to 800 ℃, and the gas flow rate of the carrier gas is 5 to 20L/min.
In accordance with one aspect of the invention, the gases loaded into the furnace in step 2 are nitrogen and hydrogen.
According to one aspect of the invention, in the step 3, the temperature of the high-temperature calcination is 920-1050 ℃, and the time of the high-temperature calcination is 8-12 h.
Based on the same inventive concept, the invention also discloses the layered sodium-ion battery cathode material prepared by any one of the preparation methods.
Based on the same inventive concept, the invention also discloses a layered sodium-ion battery anode comprising the layered sodium-ion battery anode material prepared by any one of the preparation methods or the layered sodium-ion battery anode material.
Based on the same invention concept, the invention also discloses a layered sodium-ion battery positive electrode material prepared by any one of the preparation methods, a layered sodium-ion battery positive electrode material or a sodium-ion button battery of the layered sodium-ion battery positive electrode.
The invention has the beneficial effects that:
(1) According to the invention, firstly, sodium halide, nickel halide, copper halide, iron halide and manganese halide are dissolved in a solvent and uniformly mixed, and then spray pyrolysis is carried out to uniformly mix the materials at an atomic level, so that the nickel-copper-iron-manganese-sodium anode material is obtained, and a sodium source is not required to be added through dry mixing and secondary sintering.
(2) The hydrogen halide gas generated by pyrolysis of the invention can be treated with alkaline solution for tail gas treatment. And then further calcining the nickel-copper-iron-manganese-sodium cathode material obtained by spray pyrolysis at high temperature to improve the crystallinity, thereby obtaining the O3 phase layered sodium electric cathode with good performance.
(3) The method overcomes the defects that sodium sources such as sodium carbonate and the like and precursor mixed materials are easy to block and difficult to mix uniformly, the saggar is corroded after sintering, the yield is low, the productivity is low, the material residual alkali is high and the like.
(4) Compared with the traditional preparation method (a spray drying method using organic salt as a metal source after a precursor is obtained by a coprecipitation method and then is sintered at high temperature, and the like), the preparation method has the advantages of high mixing degree, high capacity, low residual alkali, difficulty in causing sagger corrosion, easiness in tail gas treatment, and good electrochemical performance.
Drawings
FIG. 1 is an SEM image of the layered sodium-ion battery cathode material prepared in example 1 of the present invention;
FIG. 2 is an SEM image of the layered sodium-ion battery cathode material prepared in example 2 of the present invention;
FIG. 3 is an SEM image of the positive electrode material of the layered sodium-ion battery prepared in example 3 of the invention;
FIG. 4 is an SEM image of the layered sodium-ion battery positive electrode material prepared in comparative example 1 of the present invention;
FIG. 5 is an SEM image of a layered sodium-ion battery cathode material prepared by comparative example 2 of the invention;
fig. 6 is a charge-discharge curve diagram of a half cell made of the layered sodium-ion battery positive electrode material prepared in example 1 of the present invention.
Detailed Description
In order that the invention may be more readily understood, reference is now made to the following examples which are intended to illustrate the invention. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention, and it should be understood that the described examples are only a portion of the examples of the present invention, rather than the entire scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. Unless otherwise defined, the following terms used are intended to be consistent with the meaning understood by those skilled in the art; unless otherwise specified, the starting materials and reagents referred to herein may be purchased from commercial sources or prepared by known methods.
Example 1
28.51g of nickel chloride, 14.79g of copper chloride, 53.53g of ferric chloride, 42.78g of manganese chloride, 61.36g of sodium chloride and 0.65g of cobalt chloride are respectively weighed, poured into a 3L beaker, added with 1L of deionized water, and mechanically stirred at the rotating speed of 600r/min for 30min to obtain a uniformly mixed metal salt solution. And transferring the metal salt solution of the uniform solution into an atomizer for atomization, and carrying the mixed carrier gas of nitrogen and hydrogen at a rate of 10L/min into a roasting furnace for pyrolysis until the atomized gas is completely exhausted, wherein the antipyretic temperature is 700 ℃. Taking out a product (a precursor of the anode material) deposited in the roasting furnace, pouring the product into a sagger, marking a grid line, putting the sagger into a box furnace, and calcining in the air atmosphere at the calcining temperature of 1000 ℃ for 12h at the heating rate of 4 ℃/min. Obtaining a positive electrode material after the box furnace is cooled to below 100 ℃, wherein the positive electrode material is Co-doped sodium nickel copper iron manganese oxide Co-NaNi 0.22 Cu 0.11 Fe 0.33 Mn 0.34 O 2 ，Co-NaNi 0.22 Cu 0.11 Fe 0.33 Mn 0.34 O 2 Is shown in fig. 1.
Example 2
28.51g of nickel chloride, 14.79g of copper chloride, 53.53g of ferric chloride, 42.78g of manganese chloride, 61.36g of sodium chloride and 0.67g of aluminum chloride are respectively weighed, poured into a 3L beaker, added with 1L of deionized water, and mechanically stirred at the rotating speed of 600r/min for 30min to obtain a uniformly mixed metal salt solution. And transferring the metal salt solution of the uniform solution into an atomizer for atomization, and carrying the mixed carrier gas of nitrogen and hydrogen at a rate of 10L/min into a roasting furnace for pyrolysis until the atomized gas is completely exhausted, wherein the antipyretic temperature is 700 ℃. The product deposited in the furnace (positive electrode)Material precursor) is taken out and poured into a sagger, the grid lines are marked and put into a box furnace to be calcined in the air atmosphere, the calcining temperature is 1000 ℃, the calcining time is 12h, and the heating rate is 4 ℃/min. Obtaining the anode material after the box furnace is cooled to below 100 ℃, wherein the anode material is Al-doped nickel-copper-iron-sodium manganese Al-NaNi 0.22 Cu 0.11 Fe 0.33 Mn 0.34 O 2 ，Al-NaNi 0.22 Cu 0.11 Fe 0.33 Mn 0.34 O 2 Is shown in fig. 2.
Example 3
28.51g of nickel chloride, 14.79g of copper chloride, 53.53g of ferric chloride, 42.78g of manganese chloride, 61.36g of sodium chloride and 0.48g of magnesium chloride are respectively weighed, poured into a 3L beaker, added with 1L of deionized water, and mechanically stirred at the rotating speed of 600r/min for 30min to obtain a uniformly mixed metal salt solution. Transferring the metal salt solution of the uniform solution to an atomizer for atomization, and carrying the mixed carrier gas of nitrogen and hydrogen at a rate of 10L/min into a roasting furnace for pyrolysis until the atomized gas is completely consumed, wherein the antipyretic temperature is 700 ℃. Taking out a product (a precursor of the anode material) deposited in the roasting furnace, pouring the product into a sagger, marking a grid line, putting the sagger into a box furnace, and calcining in the air atmosphere at the calcining temperature of 1000 ℃ for 12h at the heating rate of 4 ℃/min. Obtaining the anode material after the box furnace is cooled to below 100 ℃, wherein the anode material is Mg-doped nickel-copper-iron-sodium manganese Mg-NaNi 0.22 Cu 0.11 Fe 0.33 Mn 0.34 O 2 ，Mg-NaNi 0.22 Cu 0.11 Fe 0.33 Mn 0.34 O 2 Is shown in fig. 3.
Comparative example 1
100g of nickel-copper-iron-manganese precursor obtained by coprecipitation, 61.19g of sodium carbonate and 0.25g of alumina are weighed and poured into a mixer, and the mixture is mixed for 20min under the condition of the rotating speed of 800 r/min. And pouring the mixed materials into a sagger, and drawing grid lines to ensure air circulation. And then putting the sagger with the material into a box furnace, and calcining in an air atmosphere. The temperature is raised to 1000 ℃ at the temperature raising rate of 4 ℃/min and kept for 12h. Naturally cooling the box furnace to below 100 ℃ to obtain the anode material, wherein the anode material is Al-doped nickelCopper iron sodium manganate Al-NaNi 0.22 Cu 0.11 Fe 0.33 Mn 0.34 O 2 ，Al-NaNi 0.22 Cu 0.11 Fe 0.33 Mn 0.34 O 2 Is shown in fig. 4.
Comparative example 2
28.51g of nickel chloride, 14.79g of copper chloride, 53.53g of ferric chloride, 42.78g of manganese chloride and 0.67g of aluminum chloride are respectively weighed, poured into a 3L beaker, added with 1L of deionized water, and mechanically stirred for 30min at the rotating speed of 600r/min to obtain a uniform solution. And transferring the uniform solution into an atomizer for atomization, and loading the uniform solution into a roasting furnace by mixed carrier gas of nitrogen and hydrogen at a rate of 10L/min for pyrolysis until the atomized gas is completely consumed, wherein the antipyretic temperature is 700 ℃, so as to obtain the aluminum-doped nickel-copper-iron-manganese precursor. 100g of the precursor and 61.19g of sodium carbonate are weighed and poured into a mixer, and the mixture is mixed for 20min under the condition of the rotating speed of 800 r/min. And pouring the mixed materials into a sagger, and drawing grid lines to ensure air circulation. And then, putting the saggar with the materials into a box furnace, and calcining in an air atmosphere. The temperature is raised to 1000 ℃ at the temperature raising rate of 4 ℃/min and kept for 12h. Naturally cooling the box furnace to below 100 ℃ to obtain the anode material, wherein the anode material is Al-doped sodium nickel copper iron manganese oxide Al-NaNi 0.22 Cu 0.11 Fe 0.33 Mn 0.34 O 2 ，Al-NaNi 0.22 Cu 0.11 Fe 0.33 Mn 0.34 O 2 Is shown in fig. 5.
Performance testing
As can be seen from the SEM images of the sodium ion cathode materials prepared in examples 1 to 3 and comparative examples 1 to 2, the morphology of the sodium ion cathode material prepared in examples 1 to 3 was more uniform, while the sodium ion cathode material prepared in comparative examples 1 to 2 was not uniform enough and had too many small particles, which affected the stability of the material.
The sodium ion positive electrode materials prepared in the examples 1-3 and the comparative examples 1-2 are used as positive electrode active materials to prepare a positive electrode piece, metal Na is used as a negative electrode to obtain a button electric battery, and the electrochemical performance of the battery provided in the examples 1-3 and the comparative examples 1-2 is tested: the voltage is 2-4V, the first cycle charging and discharging multiplying power is 0.1C, the first charging and discharging specific capacity is measured, and the first effect is obtained, and fig. 6 is a charging and discharging curve diagram of a half-cell made of the layered sodium-ion battery anode material in example 1. Meanwhile, the physical and chemical properties of pH were also tested in examples 1 to 3 and comparative examples 1 to 2. The test results are shown in table 1:
first cycle specific charge capacity Specific capacity of first cycle discharge First effect pH
Example 1 152.4 137.2 90.00 7.51
Example 2 151.8 136.8 90.12 7.47
Example 3 150.8 136.5 90.52 7.55
Comparative example 1 150.9 127.4 84.43 12.83
Comparative example 2 149.8 130.6 87.18 12.86
As can be seen from table 1 and fig. 6, the specific capacity and the first efficiency of the half-cells prepared from the positive electrode materials of examples 1 to 3 are significantly improved as compared with the positive electrode material prepared by the co-precipitation method of comparative example 1 or comparative example 2. This is because the positive electrode materials in examples 1 to 3 were layered sodium ion battery materials obtained by spray drying and then calcining at high temperature. In addition, the pH values of the examples 1 to 3 are all lower than those of the comparative examples 1 to 2 (the pH values are relatively low, which indicates that the residual alkali is relatively low), because the conventional sodium carbonate or sodium hydroxide and the like are not adopted as the sodium source in the examples 1 to 3, but sodium chloride is adopted as the sodium source, so that the problems of overhigh residual alkali, sagger corrosion and the like caused by the conventional sodium source can be effectively reduced.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention disclosed herein should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.

Claims (10)

1. The preparation method of the layered sodium-ion battery positive electrode material is characterized by comprising the following steps of:
step 1: stirring a sodium source, a metal source, a doping agent and a solvent together, and fully and uniformly mixing to obtain a metal salt solution;
step 2: transferring the metal salt solution to an atomizer for atomization, and then loading the metal salt solution into a roasting furnace for pyrolysis through carrier gas to obtain a positive electrode material precursor;
and step 3: and (3) calcining the precursor of the positive electrode material at high temperature to obtain the layered single crystal sodium ion battery positive electrode material.
2. The preparation method of the layered sodium-ion battery cathode material according to claim 1, wherein the layered single-crystal sodium-ion battery cathode material has a chemical general formula: M-NaNi a Cu b Fe c Mn d O 2 (ii) a Wherein M is a doping element provided by a dopant, and M is selected from one or more of Al, mg, zn, sr and Co; ni, cu, fe and Mn are metal elements provided by a metal source, a + b + c + d =1, a is more than or equal to 0 and less than 1, b is more than or equal to 0 and less than 1, c is more than or equal to 0 and less than 1, and d is more than or equal to 0 and less than or equal to 1.
3. The method for preparing the layered sodium-ion battery cathode material according to claim 1, wherein the sodium source is sodium halide; the metal source is a halide salt of the corresponding metal; the dopant is halide salt corresponding to the doped metal element.
4. The method for preparing the layered sodium-ion battery cathode material according to claim 3, wherein the sodium halide is one of NaF, naCl and NaBr; the metal source comprises a nickel source, a copper source, an iron source and a manganese source, and the manganese source is MnF 2 、MnCl 2 、MnBr 2 The iron source is FeF 3 、FeCl 3 、FeBr 3 One of (a) and (b); the dopant is AlCl 3 、MgCl 2 、ZnCl 2 、SrCl 2 、CoCl 2 One kind of (1).
5. The preparation method of the layered sodium-ion battery cathode material as claimed in claim 1, wherein in the step 2, the pyrolysis temperature is 600-800 ℃, and the gas flow rate of the carrier gas is 5-20L/min.
6. The method for preparing the layered sodium-ion battery cathode material as claimed in claim 1, wherein in the step 2, the gases loaded into the baking furnace are nitrogen and hydrogen.
7. The preparation method of the layered sodium-ion battery cathode material as claimed in claim 1, wherein in the step 3, the high-temperature calcination temperature is 920-1050 ℃, and the high-temperature calcination time is 8-12 h.
8. The layered positive electrode material for the sodium-ion battery is characterized by being prepared by the preparation method of any one of claims 1 to 7.
9. The layered sodium-ion battery positive electrode is characterized by comprising the layered sodium-ion battery positive electrode material prepared by the preparation method according to any one of claims 1 to 7 or the layered sodium-ion battery positive electrode material according to claim 8.
10. A sodium ion button cell, which is characterized by comprising the layered sodium ion cell positive electrode material prepared by the preparation method of any one of claims 1 to 7, the layered sodium ion cell positive electrode material of claim 8 or the layered sodium ion cell positive electrode of claim 9.
CN202211180451.9A 2022-09-27 2022-09-27 Layered sodium-ion battery positive electrode material and preparation method and application thereof Pending CN115504520A (en)

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