Preparation method of low-nickel quaternary sodium ion battery layered oxide positive electrode material

Abstract

The invention relates to a preparation method of a low-nickel quaternary sodium ion battery layered oxide positive electrode material, which comprises the following steps: (1) uniformly mixing a sodium source, a nickel source, an iron source, a manganese source, a zinc salt and a lithium source in a ball milling tank, carrying out segmented sintering on the mixture in an air atmosphere, crushing, and sieving with a 400-mesh sieve; (2) uniformly mixing a certain amount of material obtained in the step (1) with oxide and hydroxide in a ball milling tank; and (3) carrying out secondary sintering on the product obtained in the step (2) in an air atmosphere, crushing, and sieving with a 400-mesh sieve to obtain the low-nickel quaternary sodium ion battery layered oxide positive electrode material jointly coated with the oxide and the hydroxide.

Description

Technical Field

[0001] This invention belongs to the field of sodium-ion battery cathode materials, specifically relating to a method for preparing a low-nickel quaternary sodium-ion battery layered oxide cathode material. Background Technology

[0002] With the rapid development of clean energy, sodium-ion batteries (SIBs) are gradually becoming one of the key technologies for next-generation energy storage systems. Due to their advantages such as low cost, high stability, and high safety, layered oxide cathode materials for sodium-ion batteries have attracted much attention. Layered oxide cathode materials possess high safety, stability, and cycle performance, among which sodium-ion layered oxide cathode materials have gradually become a research hotspot due to their low cost and good structural stability. Layered oxide cathode materials have a one-dimensional tunnel structure, facilitating the transport of sodium ions. In recent years, researchers at home and abroad have conducted extensive research on layered oxide cathode materials for sodium-ion batteries, achieving a series of important advances. For example, by changing the composition of transition metal elements, adjusting the material structure, and modifying the preparation process, the performance of layered oxide cathode materials for sodium-ion batteries has been improved. With the current state of the global energy structure and the rapid development of new energy vehicles, the application prospects of layered oxide cathode materials for sodium-ion batteries are very broad.

[0003] CN 117334890 A discloses an O3-type layered oxide sodium-ion battery cathode material and its preparation method. First, TM source, dopant, and sodium source powder are weighed. Then, the powder is placed in a ball mill with ethanol added for ball milling. After ball milling, the powder is dried to obtain a precursor. The precursor is then calcined in a sagger and cooled to obtain the O3-type layered oxide sodium-ion battery cathode material. The layered oxide sodium-ion battery cathode material provided by this invention has the characteristics of low strain, high capacity, stable cycle performance, and excellent rate performance.

[0004] CN 115207340A discloses a layered oxide cathode material for sodium-ion batteries, its preparation method, and its application. The method involves weighing and mixing manganese oxide, nickel oxide, metal oxide, and sodium salt according to a stoichiometric ratio; pressing the resulting mixed powder into sheets or blocks; subjecting the sheet or block mixed powder to segmented heat treatment; and after heat treatment, cooling, crushing, grinding, and sieving the sample to obtain the layered oxide cathode material for sodium-ion batteries. The sodium-ion battery cathode material prepared by this invention has high purity, with high-valence Ni elements activating the activity in the material, exhibiting high rate capability, long lifespan, and high specific capacity.

[0005] To optimize the electrochemical performance of materials, researchers are constantly exploring new preparation methods, such as reducing nickel content, doping, and coating. Element doping can improve the electrochemical performance of sodium-ion battery cathode materials. By adjusting the type and content of doping elements, the electrochemical activity of the material can be altered, improving the battery's charge-discharge efficiency and cycle life. Doping elements can also enhance the structural stability of the cathode material. During the charge-discharge process of sodium-ion batteries, the cathode material undergoes volume changes, leading to decreased structural stability. Element doping can prevent the collapse of the crystal structure during charge-discharge. Furthermore, doping elements can adjust the conductivity of the cathode material, which has a crucial impact on battery performance. Doping elements can improve the conductivity of the material, thereby enhancing the battery's rate performance. Summary of the Invention

[0006] The purpose of this invention is to provide a method for preparing a low-nickel quaternary sodium-ion battery layered oxide cathode material, which is low in cost, simple in preparation process, has good reproducibility, and produces a cathode material with better rate performance and longer cycle life. The specific solution is as follows:

[0007] A method for preparing a low-nickel quaternary sodium-ion battery layered oxide cathode material, the preparation process includes the following steps:

[0008] (1) Sodium source, nickel source, iron source, manganese source, zinc salt and lithium source are mixed evenly in a ball mill jar, and the mixture is sintered in stages under air atmosphere, and then crushed and passed through a 400-mesh sieve; in step (1), the first stage sintering temperature is set at 300-600℃, the holding time is 1-5h, and the heating rate is 1-3℃ / min; the second stage sintering temperature is set at 900-1000℃, the sintering time is 12-18h, and the heating rate is 3-5℃ / min;

[0009] (2) Take a certain amount of the material obtained in step (1) and mix it evenly with oxides and hydroxides in a ball mill jar. Set the speed of the ball mill jar to 100-500 rpm and the milling time to 1-5 h.

[0010] (3) The product obtained in step (2) is sintered twice in air atmosphere, crushed and passed through a 400-mesh sieve to obtain a low-nickel quaternary sodium-ion battery layered oxide cathode material co-coated with oxide and hydroxide; the temperature of the second sintering in step (3) is 800-900℃, the holding time is 6-10h, and the heating rate is set to 2-5℃ / min.

[0011] The sodium source mentioned in step (1) is one or more of sodium oxide, sodium carbonate, sodium sulfate, sodium bicarbonate, sodium citrate, sodium nitrate, sodium hydroxide, sodium lactate, or sodium phosphate; the nickel salt is one or more of nickel chloride, nickel sulfate, nickel sulfite, nickel oxide, nickel tetroxide, or nickel trioxide; the iron salt is one or more of ferrous oxide, ferric oxide, ferric oxide, ferric tetroxide, ferric chloride, ferric sulfate, ferric nitrate, ferric bromide, ferric iodide, and ferric fluoride; the manganese salt is one or more of manganese oxide, manganese dioxide, manganese trioxide, manganese tetroxide, manganese sulfate, manganese carbonate, manganese nitrate, or manganese stearate; the zinc salt is one or more of zinc chloride, zinc sulfate, zinc nitrate, zinc fluorosilicate, zinc fluoroborate, zinc gluconate, and zinc acetate; and the lithium salt is one or more of lithium carbonate, lithium hydroxide, lithium oxide, lithium hydride, lithium chloride, lithium fluoride, lithium bromide, lithium nitrate, and lithium iodide.

[0012] In step (1), sodium salt, nickel salt, iron-manganese salt, and manganese salt are prepared according to Na... x Ni a Zn b Fe c Mn d The molar ratio of O2 is weighed and mixed, where x = 0.9–1.03, a = 0–0.2, b = 0–0.5, c = 0–0.5, d = 0–0.5, and a+b+c+d = 1; the doping amount of the lithium salt is 0–1.0 wt% of the total mass of the sodium source, nickel salt, iron salt, zinc salt, and manganese salt.

[0013] In step (2), the ball mill jar rotates at 100-500 rpm and the ball milling time is 1-5 hours.

[0014] In step (2), the oxide is one or more of magnesium oxide, zirconium oxide, calcium oxide, titanium oxide, aluminum oxide, and copper oxide; the hydroxide is one or more of lithium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, rubidium hydroxide, cesium hydroxide, francium hydroxide, and cobalt hydroxide.

[0015] The coating amount of oxides and hydroxides is 0 to 0.5 wt% of the weight of the cathode material.

[0016] Button cell fabrication: The carbon-coated low-nickel quaternary sodium-ion battery layered oxide cathode material obtained above is assembled into a button cell. The cathode material, conductive carbon black and PVDF are mixed in a mass ratio of 8:1:1. A certain amount of N-methylpyrrolidone (NMP) solution is added and the mixture is homogenized and stirred in a degassing machine to obtain a cathode material slurry. The slurry is then uniformly coated on aluminum foil and dried in a vacuum drying oven at 105°C for 6 hours. The cathode electrode is then obtained by rolling, cutting and weighing. A sodium sheet is used as the counter electrode, and a 1 mol / L NaClO4 solution of ethylene carbonate (EC) / dimethyl carbonate (DMC) (volume ratio 1:1) is used as the electrolyte. Glass fiber is used as the separator. The button cell is assembled in an argon-filled glove box.

[0017] Compared to existing technologies, the preparation method of carbon-coated low-nickel quaternary sodium-ion battery layered oxide cathode material described in this invention has the following advantages: Gradient sintering can improve the electrochemical and safety performance of the battery. Single-stage sintering, with a relatively slow heating rate, allows for more complete and uniform oxidation of the layered oxide cathode material during sintering. Furthermore, gradient sintering can improve material stability, reduce internal battery pressure, and thus extend battery cycle life. The layered oxide NFM system is doped with Zn. + It can improve the distortion of Ni-O octahedra during charging and discharging, enhance the structural reversibility of the material during charging and discharging, and improve the discharge specific capacity of the material; by introducing Li + This can increase the amount of Na in sodium-ion batteries. + It participates in the insertion and extraction during the charging and discharging process, increasing the specific capacity of the material and thus improving the energy density of the battery. Simultaneously, Li is doped... + It can suppress phase transitions in materials, thereby improving the electrochemical performance of the battery; the co-coating of oxides and peroxides can prevent damage to the electrode material structure during charge and discharge, improving the cycle stability of the battery. In addition, the coating layer also helps to mitigate side reactions between the electrode active material and the electrolyte, improving the battery's safety performance. Attached Figure Description

[0018] Figure 1 This is a SEM image of the low-nickel quaternary layered oxide cathode material of Example 1;

[0019] Figure 2 This is a SEM image of the low-nickel quaternary layered oxide cathode material from Example 5.

[0020] Figure 3 SEM image of the low-nickel quaternary layered oxide cathode material in Comparative Example 2;

[0021] Figure 4The figures (a) and (b) are charge-discharge curves and cycle performance diagrams of the low-nickel quaternary layered oxide cathode material of Example 5. Detailed Implementation

[0022] It should be noted that, unless otherwise specified, the embodiments and features described in this application can be combined with each other. To further understand this invention, the following description, in conjunction with the specification and specific preferred embodiments, will further illustrate the invention. These embodiments should not be construed as limiting the scope of protection claimed in this application.

[0023] Example 1

[0024] This embodiment provides a method for preparing a low-nickel quaternary sodium-ion battery layered oxide cathode material, the preparation method of which is as follows:

[0025] Sodium carbonate, nickel oxide, zinc oxide, ferric oxide, and manganese tetroxide were weighed and placed into a ball mill jar in a molar ratio of 0.95:0.20:0.05:0.35:0.40. Then, 0.3 wt% of lithium carbonate (based on the total weight of the positive electrode precursor) was added. The ball mill was set to a speed of 200 r / min and milled for 2 h. Then, under air conditions, the temperature was raised to 500 °C at a heating rate of 2 °C / min and held for 3 h. The temperature was then raised to 900 °C at a heating rate of 5 °C / min and held for 15 h. After pulverization, the material was passed through a 400-mesh sieve to obtain the primary sintered material. A certain amount of primary sintering material, 0.1 wt% of aluminum oxide and 0.05 wt% of cobalt hydroxide were mixed in a ball mill jar. The ball mill speed was set to 200 r / min and the mixture was milled for 2 hours. Then, secondary sintering was carried out in an air atmosphere. The temperature was raised to 850℃ at a heating rate of 2℃ / min and held for 8 hours for secondary sintering. After pulverization, the mixture was passed through a 400-mesh sieve to obtain a low-nickel quaternary layered oxide cathode material.

[0026] Example 2

[0027] Sodium carbonate, nickel oxide, zinc oxide, ferric oxide, and manganese tetroxide were weighed and placed into a ball mill jar in a molar ratio of 1.00:0.20:0.05:0.35:0.40. Then, 0.3 wt% of lithium carbonate (based on the total weight of the positive electrode substrate) was added. The ball mill was set to a speed of 200 r / min and milled for 2 h. Then, under air conditions, the temperature was raised to 500 °C at a heating rate of 2 °C / min and held for 3 h. The temperature was then raised to 900 °C at a heating rate of 5 °C / min and held for 15 h. After pulverization, the material was passed through a 400-mesh sieve to obtain the primary sintered material. A certain amount of primary sintering material, 0.1 wt% of aluminum oxide and 0.05 wt% of cobalt hydroxide were mixed in a ball mill jar. The ball mill speed was set to 200 r / min and the mixture was milled for 2 hours. Then, secondary sintering was carried out in an air atmosphere. The temperature was raised to 850℃ at a heating rate of 2℃ / min and held for 8 hours for secondary sintering. After pulverization, the mixture was passed through a 400-mesh sieve to obtain a low-nickel quaternary layered oxide cathode material.

[0028] Example 3

[0029] Sodium carbonate, nickel oxide, zinc oxide, ferric oxide, and manganese tetroxide were weighed and placed into a ball mill jar in a molar ratio of 1.03:0.20:0.05:0.35:0.40. Then, 0.3 wt% of lithium carbonate (based on the total weight of the positive electrode substrate) was added. The ball mill was set to a speed of 200 r / min and milled for 2 hours. Then, under air conditions, the temperature was raised to 500°C at a heating rate of 2°C / min and held for 3 hours. The temperature was then raised to 900°C at a heating rate of 5°C / min and held for 15 hours. After pulverization, the material was passed through a 400-mesh sieve to obtain the primary sintered material. A certain amount of primary sintering material, 0.1 wt% of aluminum oxide and 0.05 wt% of cobalt hydroxide were mixed in a ball mill jar. The ball mill speed was set to 200 r / min and the mixture was milled for 2 hours. Then, secondary sintering was carried out in an air atmosphere. The temperature was raised to 850℃ at a heating rate of 2℃ / min and held for 8 hours for secondary sintering. After pulverization, the mixture was passed through a 400-mesh sieve to obtain a low-nickel quaternary layered oxide cathode material.

[0030] Example 4

[0031] Sodium carbonate, nickel oxide, zinc oxide, ferric oxide, and manganese tetroxide were weighed and placed into a ball mill jar in a molar ratio of 1.00:0.20:0.05:0.35:0.40. Then, 0.5 wt% of lithium carbonate (based on the total weight of the positive electrode precursor) was added. The ball mill was set to a speed of 200 r / min and milled for 2 h. Then, under air conditions, the temperature was raised to 500 °C at a heating rate of 2 °C / min and held for 3 h. The temperature was then raised to 900 °C at a heating rate of 5 °C / min and held for 15 h. After pulverization, the material was passed through a 400-mesh sieve to obtain the primary sintered material. A certain amount of primary sintering material, 0.1 wt% of aluminum oxide and 0.05 wt% of cobalt hydroxide were mixed in a ball mill jar. The ball mill speed was set to 200 r / min and the mixture was milled for 2 hours. Then, secondary sintering was carried out in an air atmosphere. The temperature was raised to 850℃ at a heating rate of 2℃ / min and held for 8 hours for secondary sintering. After pulverization, the mixture was passed through a 400-mesh sieve to obtain a low-nickel quaternary layered oxide cathode material.

[0032] Example 5

[0033] Sodium carbonate, nickel oxide, zinc oxide, ferric oxide, and manganese tetroxide were weighed and placed into a ball mill jar in a molar ratio of 1.00:0.20:0.05:0.35:0.40. Then, 0.5 wt% of lithium carbonate (based on the total weight of the positive electrode precursor) was added. The ball mill was set to a speed of 200 r / min and milled for 2 hours. Then, under air conditions, the temperature was raised to 500°C at a heating rate of 2°C / min and held for 3 hours. The temperature was then raised to 950°C at a heating rate of 5°C / min and held for 15 hours. After pulverization, the material was passed through a 400-mesh sieve to obtain the primary sintered material. A certain amount of primary sintering material, 0.1 wt% of aluminum oxide and 0.05 wt% of cobalt hydroxide were mixed in a ball mill jar. The ball mill speed was set to 200 r / min and the mixture was milled for 2 hours. Then, secondary sintering was carried out in an air atmosphere. The temperature was raised to 850℃ at a heating rate of 2℃ / min and held for 8 hours for secondary sintering. After pulverization, the mixture was passed through a 400-mesh sieve to obtain a low-nickel quaternary layered oxide cathode material.

[0034] Example 6

[0035] Sodium carbonate, nickel oxide, zinc oxide, ferric oxide, and manganese tetroxide were weighed and placed into a ball mill jar in a molar ratio of 1.00:0.20:0.05:0.35:0.40. Then, 0.5 wt% of lithium carbonate (based on the total weight of the positive electrode precursor) was added. The ball mill was set to a speed of 200 r / min and milled for 2 hours. Then, under air conditions, the temperature was raised to 500°C at a heating rate of 2°C / min and held for 3 hours. The temperature was then raised to 1000°C at a heating rate of 5°C / min and held for 15 hours. After pulverization, the material was passed through a 400-mesh sieve to obtain the primary sintered material. A certain amount of primary sintering material, 0.1 wt% of aluminum oxide and 0.05 wt% of cobalt hydroxide were mixed in a ball mill jar. The ball mill speed was set to 200 r / min and the mixture was milled for 2 hours. Then, secondary sintering was carried out in an air atmosphere. The temperature was raised to 850℃ at a heating rate of 2℃ / min and held for 8 hours for secondary sintering. After pulverization, the mixture was passed through a 400-mesh sieve to obtain a low-nickel quaternary layered oxide cathode material.

[0036] Comparative Example 1

[0037] Sodium carbonate, nickel oxide, zinc oxide, ferric oxide, and manganese tetroxide were weighed and placed into a ball mill jar in a molar ratio of 0.95:0.20:0.05:0.35:0.40. The ball mill was set to a speed of 200 r / min and milled for 2 hours. Then, under air conditions, the temperature was raised to 500℃ at a heating rate of 2℃ / min and held for 3 hours. The temperature was then raised to 950℃ at a heating rate of 5℃ / min and held for 15 hours. After pulverization, the material was passed through a 400-mesh sieve to obtain the primary sintered material. A certain amount of primary sintering material, 0.1 wt% of aluminum oxide and 0.05 wt% of cobalt hydroxide were mixed in a ball mill jar. The ball mill speed was set to 200 r / min and the mixture was milled for 2 hours. Then, secondary sintering was carried out in an air atmosphere. The temperature was raised to 850℃ at a heating rate of 2℃ / min and held for 8 hours for secondary sintering. After pulverization, the mixture was passed through a 400-mesh sieve to obtain a low-nickel quaternary layered oxide cathode material.

[0038] Comparative Example 2

[0039] Sodium carbonate, nickel oxide, zinc oxide, ferric oxide, and manganese tetroxide were weighed and placed into a ball mill jar in a molar ratio of 1.00:0.20:0.05:0.35:0.40. The ball mill was set to a speed of 200 r / min and milled for 2 hours. Then, under air conditions, the temperature was raised to 500℃ at a heating rate of 2℃ / min and held for 3 hours. The temperature was then raised to 950℃ at a heating rate of 5℃ / min and held for 15 hours. After pulverizing, the material was passed through a 400-mesh sieve to obtain the primary sintered material. A certain amount of primary sintering material, 0.1 wt% of aluminum oxide and 0.05 wt% of cobalt hydroxide were mixed in a ball mill jar. The ball mill speed was set to 200 r / min and the mixture was milled for 2 hours. Then, secondary sintering was carried out in an air atmosphere. The temperature was raised to 850℃ at a heating rate of 2℃ / min and held for 8 hours for secondary sintering. After pulverization, the mixture was passed through a 400-mesh sieve to obtain a low-nickel quaternary layered oxide cathode material.

[0040] Comparative Example 3

[0041] Sodium carbonate, nickel oxide, zinc oxide, ferric oxide, and manganese tetroxide were weighed and placed into a ball mill jar in a molar ratio of 1.03:0.20:0.05:0.35:0.40. The ball mill was set to a speed of 200 r / min and milled for 2 hours. Then, under air conditions, the temperature was raised to 500℃ at a heating rate of 2℃ / min and held for 3 hours. The temperature was then raised to 950℃ at a heating rate of 5℃ / min and held for 15 hours. After pulverization, the material was passed through a 400-mesh sieve to obtain the primary sintered material. A certain amount of primary sintering material, 0.1 wt% of aluminum oxide and 0.05 wt% of cobalt hydroxide were mixed in a ball mill jar. The ball mill speed was set to 200 r / min and the mixture was milled for 2 hours. Then, secondary sintering was carried out in an air atmosphere. The temperature was raised to 850℃ at a heating rate of 2℃ / min and held for 8 hours for secondary sintering. After pulverization, the mixture was passed through a 400-mesh sieve to obtain a low-nickel quaternary layered oxide cathode material.

[0042] Comparative Example 4

[0043] Sodium carbonate, nickel oxide, zinc oxide, ferric oxide, and manganese tetroxide were weighed and placed into a ball mill jar in a molar ratio of 0.95:0.20:0.05:0.35:0.40. Lithium carbonate (0.5 wt% of the total weight of the cathode precursor) was then added. The ball mill was set to 200 r / min and milled for 2 hours. Then, under air conditions, the mixture was heated to 500℃ at a heating rate of 2℃ / min and held for 3 hours. The temperature was then increased to 950℃ at a further heating rate of 5℃ / min and held for 15 hours. The resulting material was pulverized and passed through a 400-mesh sieve to obtain the primary sintered material. A certain amount of the primary sintered material was placed in a crucible and then subjected to secondary sintering under air atmosphere. The temperature was increased to 850℃ at a heating rate of 2℃ / min and held for 8 hours. The resulting material was pulverized and passed through a 400-mesh sieve to obtain the low-nickel quaternary layered oxide cathode material.

[0044] The experimental results are recorded in Table 1 below:

[0045] Table 1

[0046]

[0047] Analysis of Example 5 and Comparative Example 2 shows that with the doping of lithium, the initial coulombic efficiency and rate performance of the battery increase. This may be because lithium can be doped with Na+. + More of the material remains in the alkali metal layer during charging and discharging, which is more beneficial to the electrochemical performance of the material. As can be seen from Examples 5 and 6, the initial coulombic efficiency of the battery decreases with the increase of sintering temperature. The possible reason is that the increase of temperature causes the primary particles of the material to increase in size, thus reducing the specific surface area of ​​the material and consequently reducing the initial coulombic efficiency.

[0048] The applicant declares that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. A method for preparing a low nickel quaternary sodium-ion battery layered-oxide cathode material, characterized in that, The preparation process comprises the following steps: (1) uniformly mixing a sodium source, a nickel source, an iron source, a manganese source, a zinc salt and a lithium source in a ball mill jar, and performing stepwise sintering on the mixture under an air atmosphere, crushing and then passing through a 400-mesh sieve; in the step (1), a first-stage sintering temperature is set to 300-600 ℃, a holding time is 1-5 h, and a heating rate is 1-3 ℃ / min; a second-stage sintering temperature is set to 900-1000 ℃, a sintering time is 12-18 h, and a heating rate is set to 3-5 ℃ / min; (2) uniformly mixing a certain amount of the material obtained in the step (1) with oxides and hydroxides in a ball mill jar; (3) performing secondary sintering on the product obtained in the step (2) under an air atmosphere, crushing and then passing through a 400-mesh sieve to obtain a low-nickel quaternary sodium-ion battery layered oxide positive electrode material coated with oxides and hydroxides; in the step (3), a secondary sintering temperature is 800-900 ℃, a holding time is 6-10 h, and a heating rate is set to 2-5 ℃ / min.

2. The method for preparing a low-nickel quaternary sodium-ion battery layered oxide cathode material as described in claim 1, characterized in that: In the step (1), the sodium source is one or more of sodium oxide, sodium carbonate, sodium sulfate, sodium bicarbonate, sodium citrate, sodium nitrate, sodium hydroxide, sodium lactate or sodium phosphate; the nickel salt is one or more of nickel chloride, nickel sulfate, nickel sulfite, nickel protoxide, triniickel tetroxide or dinickel trioxide; the iron salt is one or more of ferrous oxide, diiron oxide, diiron trioxide, triiron tetroxide, iron chloride, iron sulfate, iron nitrate, iron bromide, iron iodide and iron fluoride; the manganese salt is one or more of manganese oxide, dimanganese oxide, dimanganese trioxide, trimanganese tetroxide, manganese sulfate, manganese carbonate, manganese nitrate or manganese stearate; the zinc salt is one or more of zinc chloride, zinc sulfate, zinc nitrate, zinc fluorosilicate, zinc fluoroborate, zinc gluconate and zinc acetate; and the lithium salt is one or more of lithium carbonate, lithium hydroxide, lithium oxide, lithium hydride, lithium chloride, lithium fluoride, lithium bromide, lithium nitrate and lithium iodide.

3. The method for preparing a low-nickel quaternary sodium-ion battery layered oxide cathode material as described in claim 1, characterized in that: The sodium salt, nickel salt, iron-manganese, manganese salt in step (1) is weighed and mixed according to the molar ratio of Na x Ni a Zn b Fe c Mn d O2, wherein x = 0.9-1.03, a = 0-0.2, b = 0-0.5, c = 0-0.5, d = 0-0.5, and a+b+c+d = 1; the doping amount of the lithium salt is 0-1.0 wt% of the total mass of the sodium source, nickel salt, iron salt, zinc salt, and manganese salt.

4. The method for preparing a low-nickel quaternary sodium-ion battery layered oxide cathode material as described in claim 1, characterized in that: In the step (2), the rotation speed of the ball mill jar is 100-500 rpm, and the ball milling time is 1-5 h.

5. The method for preparing a low-nickel quaternary sodium-ion battery layered oxide cathode material as described in claim 1, characterized in that: In the step (2), the oxides are one or more of magnesium oxide, zirconium oxide, calcium oxide, titanium oxide, di-aluminum trioxide and copper oxide; and the hydroxides are one or more of lithium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, rubidium hydroxide, cesium hydroxide, francium hydroxide and cobalt hydroxide.

6. The method of preparing a low nickel quaternary sodium-ion battery layered oxide cathode material according to claim 5, characterized in that: The coating amount of the oxides and the hydroxides is 0-0.5 wt% of the weight of the positive electrode material.

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