A quaternary sodium battery precursor material, a preparation method therefor and an application thereof

Abstract

The application provides a quaternary sodium battery precursor material and a preparation method and application thereof, and the preparation method comprises the following steps: introducing solution A and solution D into a base solution to perform a nucleation reaction; the base solution comprises a first complexing agent, the solution A comprises a nickel source and a manganese source, and the solution D comprises an alkali solution; after the nucleation reaction is completed, solution B and solution C are introduced to perform particle growth, and the quaternary sodium battery precursor material is obtained; the solution B comprises a ferric source and a second complexing agent, and the solution C comprises a copper source. According to the preparation method, only nickel salt and manganese salt are added to perform a reaction in the nucleation period, ferric salt and copper salt are added at the beginning of the growth period, and the reaction complexing agent is replaced at the same time, so that the crystallinity of the precursor is improved, the tap density of the precursor is improved, and the problem that the overall structure of the precursor is loose due to agglomeration in the nucleation period when the ferric source is ferric iron is solved.

Description

Technical Field

[0001] This invention belongs to the field of battery technology and relates to a quaternary sodium battery precursor material, its preparation method and application. Background Technology

[0002] Sodium-ion batteries have broad prospects in energy storage due to their good safety, abundant sodium resources, and low cost. CuFeNiMn quaternary sodium battery cathode materials have good air stability and good cycle stability. However, when using the traditional co-precipitation method to prepare quaternary precursors, uneven metal ion precipitation occurs, resulting in precursors with poor sphericity, poor crystallinity, and low tap density.

[0003] For example, CN 116750805A discloses a copper-containing multi-element sodium battery precursor and its preparation method, as well as a cathode material and a sodium-ion battery. The method includes: continuously adding a complexing agent, a soluble metal salt solution and a precipitant to a bottom liquid until the particle size of the obtained solid reaches a preset value; the complexing agent is of at least two types, and among the at least two complexing agents, there is a first complexing agent, and the complexing ability of the first complexing agent to copper ions in the soluble metal salt solution is higher than the complexing ability of the other complexing agents to copper ions.

[0004] In other words, existing technologies optimize the sphericity, tap density, and distribution density of precursors by selecting two or more complexing agents such as ammonia, EDTA, triethanolamine, and sodium citrate. This results in copper-containing quaternary sodium-ionized precursors with uniform dopant distribution, good sphericity, and high tap density. However, the complexing agents commonly used in existing technologies are generally weak in their ability to react with ferrous ions, making it easier for ferrous ions to precipitate in the system. This makes the primary particles of the precursor appear as fine flakes, and it is difficult to further improve the tap density.

[0005] Although ferric ions are relatively easy to precipitate compared to other metal ions, precipitation begins at around pH 2.0, they are highly selective for complexing agents. Furthermore, using ferric ions as an iron source during the nucleation stage can lead to particle agglomeration and excessively large nucleation particle size, resulting in a loose precursor structure and reduced tap density.

[0006] Based on the above research, there is a need to provide a method for preparing quaternary sodium-ionized precursor materials. This method can solve the problem that when trivalent iron is used as the iron source, the agglomeration during the nucleation period results in a loose overall structure of the precursor. Summary of the Invention

[0007] The purpose of this invention is to provide a quaternary sodium-ionized precursor material, its preparation method, and its application. The preparation method involves adding only nickel and manganese salts during the nucleation stage and adding iron and copper salts at the beginning of the growth stage, while changing the reaction complexing agent. This improves the crystallinity of the precursor, thereby increasing the tap density of the precursor. It also solves the problem that when ferric iron is used as the iron source, the agglomeration during the nucleation stage results in a loose overall structure of the precursor.

[0008] To achieve this objective, the present invention adopts the following technical solution:

[0009] In a first aspect, the present invention provides a method for preparing a quaternary sodium-electric precursor material, the method comprising the following steps:

[0010] (1) Pass solutions A and D into the bottom liquid to carry out a nucleation reaction;

[0011] The base solution includes a first complexing agent, solution A includes a nickel source and a manganese source, and solution D includes an alkaline solution;

[0012] (2) After the nucleation reaction described in step (1) is completed, solution B and solution C are introduced to carry out particle growth and obtain the quaternary sodium-electric precursor material.

[0013] Solution B includes a trivalent iron source and a second complexing agent, and solution C includes a copper source.

[0014] This invention divides the growth process of the precursor into a nucleation period (1) and a growth period (2). During the nucleation period, only nickel and manganese sources are introduced to obtain nickel-manganese binary crystal nuclei with high structural strength, avoiding the early particle agglomeration caused by the addition of all metal sources. Then, during the crystal growth period, iron and copper sources are introduced (solutions B and D are still introduced during the growth period), and a second complexing agent of a different type than the first complexing agent is used. This allows the quaternary system particles to continue to grow stably, improving the crystallinity of the precursor and thus increasing the tap density of the precursor. It also solves the problem of agglomeration during the nucleation period when trivalent iron is used as the iron source, which makes the overall structure of the precursor loose.

[0015] Preferably, in step (1), the first complexing agent comprises ammonia.

[0016] Preferably, in the base liquid of step (1), the concentration of the first complexing agent is 0.1-0.7 mol / L, for example, it can be 0.2 mol / L, 0.4 mol / L, 0.6 mol / L or 0.7 mol / L, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0017] This invention improves the timing of introducing the metal source solution and changes the method of complexing agent, so that only the co-precipitation of nickel and manganese needs to be considered during the nucleation period. It uses a complexing agent and complexing agent concentration that are more conducive to the growth of a stable structural framework of nickel and manganese during the nucleation period. Therefore, in step (1) of this invention, ammonia is used as a complexing agent. On the one hand, ammonia can be used to obtain stable crystal nuclei. On the other hand, the volatility of ammonia will not affect the growth period. At the same time, this invention only adds a specific concentration of ammonia to the bottom solution to ensure the precipitation of nickel and manganese and not affect the subsequent growth of particles.

[0018] Preferably, the nucleation reaction time in step (1) is 8-20h, for example, it can be 10h, 12h, 14h, 16h, 18h or 20h, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0019] In this invention, the nucleation reaction is carried out for a certain period of time before the iron and copper sources are introduced. If the nucleation reaction time is too short, sufficient crystallinity of the crystal nuclei will not be formed, resulting in Fe... 3+ If the nucleation reaction takes too long, highly crystalline nuclei will be generated, which will not be easy to transform into an iron-based morphological structure. At the same time, nuclei growth will also occur, resulting in high nickel and manganese content inside the precursor and increased iron content on the surface, which will reduce the cycle stability of the cathode.

[0020] Preferably, the temperature of the nucleation reaction in step (1) is 40-70℃, for example, 40℃, 50℃, 60℃ or 70℃, and the pH is 12.0-13.0, for example, 12.0, 12.5 or 13.0, but not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0021] Preferably, the flow rate of solution A in step (1) is 2-30 L / h, for example, it can be 5 L / h, 10 L / h, 15 L / h, 20 L / h, 25 L / h or 30 L / h, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0022] Preferably, the concentrations of the nickel source and manganese source in solution A in step (1) are independently 0.5-3 mol / L, for example, 1 mol / L, 1.5 mol / L, 2 mol / L, 2.5 mol / L or 3 mol / L, but not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0023] Preferably, the base liquid in step (1) further includes a precipitant and water.

[0024] Preferably, the precipitant comprises any one or a combination of at least two of sodium hydroxide, lithium hydroxide, potassium hydroxide, sodium carbonate, or sodium bicarbonate.

[0025] The preparation method described in this invention is carried out in a reaction vessel with a volume of 100-1000L, such as 200L, 500L, 800L or 1000L. The amount of pure water added to the bottom liquid is 10-80% of the vessel volume, such as 20%, 40%, 60% or 80%, but not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0026] Preferably, the alkaline solution in step (1) comprises any one or a combination of at least two of sodium hydroxide, lithium hydroxide, potassium hydroxide, sodium carbonate, or sodium bicarbonate.

[0027] Preferably, the concentration of the alkaline solution in step (1) is 2-12 mol / L, for example, it can be 4 mol / L, 6 mol / L, 8 mol / L, 10 mol / L or 12 mol / L, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0028] Preferably, the nickel source in step (1) includes any one or a combination of at least two of nickel sulfate, nickel chloride, nickel acetate, nickel citrate or nickel oxalate.

[0029] Preferably, the manganese source in step (1) includes any one or a combination of at least two of manganese sulfate, manganese chloride, or manganese nitrate.

[0030] Preferably, in solution B of step (2), the concentration of the second complexing agent is 0.1-1 mol / L, for example, it can be 0.3 mol / L, 0.5 mol / L, 0.7 mol / L, 0.9 mol / L or 1 mol / L, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0031] Preferably, the second complexing agent in step (2) comprises any one or a combination of at least two of tartaric acid, sodium tartrate, succinic acid, citric acid, sodium citrate, acetylacetone, sodium acetylacetone, lactic acid, or sodium lactate.

[0032] The second complexing agent of this invention has good selectivity for ferric ions, which can achieve better co-precipitation of four metals.

[0033] Preferably, the trivalent iron source in step (2) includes any one or a combination of at least two of ferric chloride, ferric sulfate, ferric nitrate, or ferric phosphate.

[0034] Preferably, the iron source concentration in solution B in step (2) is 0.5-3 mol / L, for example, it can be 1 mol / L, 1.5 mol / L, 2 mol / L, 2.5 mol / L or 3 mol / L, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0035] Preferably, the concentration of copper source in solution C in step (2) is 0.5-3 mol / L, for example, it can be 1 mol / L, 1.5 mol / L, 2 mol / L, 2.5 mol / L or 3 mol / L, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0036] Preferably, the copper source in step (2) includes any one or a combination of at least two of copper sulfate, copper chloride, or copper nitrate.

[0037] Preferably, the temperature for particle growth in step (2) is 40-70℃, for example, 50℃, 60℃ or 70℃, and the pH is 11.0-12.0, for example, 11.0, 11.5 or 12.0, but not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0038] Preferably, the reaction is stopped after the particles in step (2) grow to a particle size D50 of 3-15 μm. For example, it can be 5 μm, 8 μm, 10 μm or 15 μm, but it is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0039] Preferably, the preparation method is carried out under a protective gas atmosphere.

[0040] Preferably, the flow rate of the protective gas is 2-25 L / min, for example, it can be 5 L / min, 10 L / min, 15 L / min, 20 L / min or 25 L / min, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0041] Preferably, the protective gas includes any one or a combination of at least two of helium, nitrogen, or argon.

[0042] As a preferred embodiment of the preparation method of the present invention, the preparation method includes the following steps:

[0043] (1) In a protective gas with a flow rate of 2-25 L / min, solution A and solution D are introduced into the bottom liquid, and the nucleation reaction is carried out at a temperature of 40-70℃ and a pH of 12.0-13.0 for 8-20 h.

[0044] The base liquid includes a first complexing agent, a precipitant, and water, wherein the first complexing agent includes ammonia water with a concentration of 0.1-0.7 mol / L;

[0045] Solution A includes a nickel source and a manganese source, and solution D includes an alkaline solution with a concentration of 2-12 mol / L;

[0046] (2) After the nucleation reaction described in step (1) is completed, solution B and solution C are introduced and particle growth is carried out at pH 11.0-12.0. The reaction is stopped after the particle size D50 is 3-15 μm to obtain the quaternary sodium-electric precursor material.

[0047] Solution B comprises a ferric iron source with a concentration of 0.5-3 mol / L and a second complexing agent with a concentration of 0.1-1 mol / L. The second complexing agent comprises any one or a combination of at least two of tartaric acid, sodium tartrate, succinic acid, citric acid, sodium citrate, acetylacetone, sodium acetylacetone, lactic acid, or sodium lactate.

[0048] The solution C includes a copper source with a concentration of 0.5-3 mol / L.

[0049] In a second aspect, the present invention provides a quaternary sodium-electric precursor material, which is prepared by the preparation method described in the first aspect.

[0050] Preferably, the chemical formula of the quaternary sodium-electric precursor material is Ni. a Fe b Mn c Cu d (OH)2, where a+1.5b+c+d=1, 0.2<a<0.6, for example, it can be 0.3, 0.4 or 0.5, 0.15<b<0.45, for example, it can be 0.2, 0.3 or 0.4, 0.2<c<0.6, for example, it can be 0.3, 0.4 or 0.5, 0.04<d<0.15, for example, it can be 0.08, 0.1 or 0.13, but not limited to the listed values, other unlisted values ​​within the range are also applicable.

[0051] Thirdly, the present invention provides a quaternary sodium-ion cathode material, wherein the quaternary sodium-ion cathode material is obtained by mixing and sintering a sodium source and the quaternary sodium-ion precursor material described in the second aspect.

[0052] Fourthly, the present invention provides a sodium-ion battery, the sodium-ion battery comprising the quaternary sodium-ion cathode material as described in the third aspect.

[0053] Compared with the prior art, the present invention has the following beneficial effects:

[0054] This invention, by adding only nickel and manganese salts during the nucleation stage and omitting iron and copper salts, only considers the co-precipitation of nickel and manganese, which is more conducive to the growth of a stable structural framework of nickel and manganese during the nucleation stage and avoids early particle agglomeration. Then, iron and copper salts are added at the beginning of the crystal growth stage, and the complexing agent is changed, so that the quaternary system can continue to grow stably, achieving better co-precipitation of metals in the quaternary system, resulting in a more uniform distribution of precursor metal elements and an improved tap density. Detailed Implementation

[0055] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0056] Example 1

[0057] This embodiment provides a method for preparing a quaternary sodium-electric precursor material, the method comprising the following steps:

[0058] (1) In nitrogen gas with a flow rate of 15 L / min, solution A and solution D were introduced into the bottom liquid, and the nucleation reaction was carried out at a temperature of 50 °C and a pH of 12.7 for 12 h.

[0059] The base liquid includes a first complexing agent, sodium hydroxide and pure water. The first complexing agent is ammonia water with a concentration of 0.3 mol / L. The amount of pure water added is 20% of the volume of the reactor, and the volume of the reactor is 500L.

[0060] The flow rate of solution A is 18 L / h, and it includes nickel sulfate and manganese sulfate with a concentration of 0.7 mol / L. Solution D includes sodium hydroxide with a concentration of 7 mol / L.

[0061] (2) After the nucleation reaction described in step (1) is completed, solutions B and C are introduced again, while solutions A and D continue to be introduced. Particle growth is carried out at pH 11.8 until the particle size D50 reaches 4.7 μm, at which point the reaction is stopped, yielding the quaternary sodium-ion precursor material. The chemical formula of the quaternary sodium-ion precursor material is Ni. 0.33 Fe 0.153 Mn 0.31 Cu 0.13 (OH)2;

[0062] Solution B comprises ferric chloride at a concentration of 0.7 mol / L and a second complexing agent at a concentration of 0.2 mol / L, wherein the second complexing agent is sodium citrate and sodium lactate in a molar ratio of 1:1, and solution C comprises copper sulfate solution at a concentration of 0.7 mol / L.

[0063] Example 2

[0064] This embodiment provides a method for preparing a quaternary sodium-electric precursor material, the method comprising the following steps:

[0065] (1) In nitrogen gas with a flow rate of 25 L / min, solution A and solution D were introduced into the bottom liquid, and the nucleation reaction was carried out at a temperature of 40 °C and a pH of 13.0 for 8 h.

[0066] The base liquid includes a first complexing agent, sodium hydroxide and pure water. The first complexing agent includes ammonia water with a concentration of 0.7 mol / L. The amount of pure water added is 40% of the volume of the reactor, and the volume of the reactor is 500L.

[0067] The flow rate of solution A is 2 L / h, and it includes nickel sulfate with a concentration of 1.5 mol / L and manganese sulfate with a concentration of 1.6 mol / L. Solution D includes sodium hydroxide with a concentration of 12 mol / L.

[0068] (2) After the nucleation reaction described in step (1) is completed, solutions B and C are introduced, while solutions A and D are continuously introduced. Particle growth is carried out at pH 12.0 until the particle size D50 reaches 3 μm, at which point the reaction is stopped, yielding the quaternary sodium-ion precursor material. The chemical formula of the quaternary sodium-ion precursor material is Ni. 0.25 Fe 0.3 Mn 0.25 Cu 0.05 (OH)2;

[0069] Solution B comprises ferric chloride at a concentration of 3 mol / L and a second complexing agent at a concentration of 1 mol / L, wherein the second complexing agent is citric acid; solution C comprises copper sulfate solution at a concentration of 0.5 mol / L.

[0070] Example 3

[0071] This embodiment provides a method for preparing a quaternary sodium-electric precursor material, the method comprising the following steps:

[0072] (1) In nitrogen gas with a flow rate of 2 L / min, solution A and solution D were introduced into the bottom liquid, and the nucleation reaction was carried out at a temperature of 70 °C and a pH of 12.0 for 20 h.

[0073] The base liquid includes a first complexing agent, sodium hydroxide and pure water. The first complexing agent includes ammonia water with a concentration of 0.1 mol / L. The amount of pure water added is 80% of the volume of the reactor, and the volume of the reactor is 500L.

[0074] The flow rate of solution A is 30 L / h, and it includes nickel sulfate and manganese sulfate with a concentration of 0.7 mol / L. Solution D includes sodium hydroxide with a concentration of 2 mol / L.

[0075] (2) After the nucleation reaction described in step (1) is completed, solutions B and C are introduced, while solutions A and D are continuously introduced. Particle growth is carried out at pH 11.0 until the particle size D50 reaches 6 μm, at which point the reaction is stopped, yielding the quaternary sodium-ion battery precursor material. The chemical formula of the quaternary sodium-ion battery precursor material is Ni. 0.33 Fe 0.153 Mn 0.31 Cu 0.13 (OH)2;

[0076] Solution B comprises ferric chloride at a concentration of 0.7 mol / L and a second complexing agent at a concentration of 0.1 mol / L, wherein the second complexing agent is sodium citrate and sodium lactate in a molar ratio of 2:1; solution C comprises copper sulfate solution at a concentration of 0.7 mol / L.

[0077] Example 4

[0078] This embodiment provides a method for preparing a quaternary sodium-ion precursor material. Except for the ammonia concentration of 0.05 mol / L in step (1), the preparation method is the same as in Example 1.

[0079] Example 5

[0080] This embodiment provides a method for preparing a quaternary sodium-ion precursor material. Except for the ammonia concentration of 0.9 mol / L in step (1), the preparation method is the same as in Example 1.

[0081] Example 6

[0082] This embodiment provides a method for preparing a quaternary sodium-ion precursor material. The preparation method is the same as in Example 1, except that the concentration of ammonia in step (1) is replaced with EDTA.

[0083] Example 7

[0084] This embodiment provides a method for preparing a quaternary sodium-ion precursor material. Except for the nucleation reaction time of 6 hours in step (1), the preparation method is the same as that in Example 1.

[0085] Example 8

[0086] This embodiment provides a method for preparing a quaternary sodium-ion precursor material. Except for the nucleation reaction time of 23 hours in step (1), the preparation method is the same as that in Example 1.

[0087] Comparative Example 1

[0088] This comparative example provides a method for preparing a quaternary sodium-ion precursor material. The preparation method is the same as in Example 1, except that solutions B and C in step (2) are simultaneously and concurrently introduced into the base liquid as solutions A and D in step (1).

[0089] Comparative Example 2

[0090] This comparative example provides a method for preparing a quaternary sodium-ion precursor material. Except for step (2), in which the second complexing agent is the same as the first complexing agent (ammonia water), the preparation method is the same as in Example 1.

[0091] The tap densities of the quaternary sodium-ion battery precursor materials obtained in the above embodiments and comparative examples are shown in Table 1. The quaternary sodium-ion battery precursor materials obtained in the above embodiments and comparative examples were mixed with sodium carbonate and sintered to obtain the P2 type sodium-ion battery cathode material Na. 2 / 3 MO2 was used to prepare the sodium electrode material into a positive electrode sheet, which was then assembled into a half-cell with a sodium sheet, a glass fiber separator, and an electrolyte. The electrolyte was 1M NaPF6 / EC+DEC+PC (volume ratio, 2:3:5). The electrochemical performance of the battery was then tested under the following conditions: 2.0-4.0V 1C for 500 cycles.

[0092] The test results are shown in Table 1:

[0093] Table 1

[0094]

[0095] As can be seen from Table 1:

[0096] The quaternary sodium-ion precursor material obtained by this invention has high tap density and excellent electrochemical performance. As shown in Example 1 and Comparative Examples 1-2, this invention avoids agglomeration and improves the tap density of the material by introducing the iron and copper sources only during the nucleation period. At the same time, by changing the complexing agent, this invention promotes the co-precipitation of metals and avoids the first complexing agent affecting subsequent particle growth. As shown in Example 1 and Examples 4-5, the ammonia concentration of this invention affects the nucleation of nickel and manganese and subsequent particle growth. As shown in Example 1 and Example 6, this invention uses volatile ammonia as the first complexing agent, which avoids its influence on subsequent particle growth and thus promotes metal co-precipitation. As shown in Example 1 and Examples 7-8, the nucleation reaction time of this invention affects the nucleus strength and subsequent particle growth, thereby affecting the material properties.

[0097] In summary, this invention provides a quaternary sodium-ion precursor material, its preparation method, and its application. The preparation method involves adding only nickel and manganese salts during the nucleation stage and adding iron and copper salts at the beginning of the growth stage, while simultaneously changing the reaction complexing agent. This improves the crystallinity of the precursor, thereby increasing the tap density of the precursor. It also solves the problem of loose overall precursor structure caused by agglomeration during the nucleation stage when ferric iron is used as the iron source.

[0098] 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 quaternary sodium-ionized precursor material, characterized in that, The preparation method includes the following steps: (1) Introduce solutions A and D into the bottom liquid to carry out the nucleation reaction; The base solution includes a first complexing agent, solution A includes a nickel source and a manganese source, and solution D includes an alkaline solution; Step (1) The first complexing agent includes ammonia; In the base solution described in step (1), the concentration of the first complexing agent is 0.1-0.7 mol / L; The nucleation reaction in step (1) takes 8-20 hours; The nucleation reaction in step (1) is carried out at a temperature of 40-70℃ and a pH of 12.0-13.

0. (2) After the nucleation reaction in step (1) is completed, solution B and solution C are introduced to carry out particle growth and obtain the quaternary sodium-electric precursor material; Solution B includes a trivalent iron source and a second complexing agent, and solution C includes a copper source; In solution B described in step (2), the concentration of the second complexing agent is 0.1-1 mol / L; Step (2) The second complexing agent includes any one or a combination of at least two of tartaric acid, sodium tartrate, succinic acid, citric acid, sodium citrate, acetylacetone, sodium acetylacetone, lactic acid, or sodium lactate.

2. The preparation method according to claim 1, characterized in that, The flow rate of solution A in step (1) is 2-30 L / h.

3. The preparation method according to claim 1 or 2, characterized in that, The base liquid in step (1) also includes a precipitant and water.

4. The preparation method according to claim 1 or 2, characterized in that, The alkaline solution in step (1) includes any one or a combination of at least two of sodium hydroxide, lithium hydroxide, potassium hydroxide, sodium carbonate, or sodium bicarbonate.

5. The preparation method according to claim 1 or 2, characterized in that, The concentration of the alkaline solution in step (1) is 2-12 mol / L.

6. The preparation method according to claim 1, characterized in that, The trivalent iron source in step (2) includes any one or a combination of at least two of ferric chloride, ferric sulfate, ferric nitrate, or ferric phosphate.

7. The preparation method according to claim 1 or 2, characterized in that, The iron source concentration in solution B in step (2) is 0.5-3 mol / L.

8. The preparation method according to claim 1, characterized in that, The concentration of the copper source in solution C in step (2) is 0.5-3 mol / L.

9. The preparation method according to claim 1 or 2, characterized in that, The copper source in step (2) includes any one or a combination of at least two of copper sulfate, copper chloride, or copper nitrate.

10. The preparation method according to claim 1 or 2, characterized in that, The temperature for particle growth in step (2) is 40-70℃ and the pH is 11.0-12.

0.

11. The preparation method according to claim 1 or 2, characterized in that, The reaction is stopped after the particles in step (2) grow to a particle size D50 of 3-15 μm.

12. The preparation method according to claim 1, characterized in that, The preparation method is carried out under a protective gas atmosphere.

13. The preparation method according to claim 12, characterized in that, The flow rate of the protective gas is 2-25 L / min.

14. The preparation method according to claim 12, characterized in that, The protective gas includes any one or a combination of at least two of helium, nitrogen, or argon.

15. The preparation method according to claim 1, characterized in that, The preparation method includes the following steps: (1) In a protective gas with a flow rate of 2-25 L / min, solution A and solution D are introduced into the bottom liquid, and the nucleation reaction is carried out at a temperature of 40-70℃ and a pH of 12.0-13.0 for 8-20 h; The base liquid includes a first complexing agent, a precipitant, and water, wherein the first complexing agent includes ammonia water with a concentration of 0.1-0.7 mol / L; Solution A includes a nickel source and a manganese source, and solution D includes an alkaline solution with a concentration of 2-12 mol / L; (2) After the nucleation reaction described in step (1) is completed, solution B and solution C are introduced and particle growth is carried out at pH 11.0-12.

0. The reaction is stopped after the particle size D50 is 3-15 μm to obtain the quaternary sodium-electric precursor material. Solution B comprises a ferric iron source with a concentration of 0.5-3 mol / L and a second complexing agent with a concentration of 0.1-1 mol / L. The second complexing agent comprises any one or a combination of at least two of tartaric acid, sodium tartrate, succinic acid, citric acid, sodium citrate, acetylacetone, sodium acetylacetone, lactic acid, or sodium lactate. The solution C includes a copper source with a concentration of 0.5-3 mol / L.

16. A quaternary sodium-electric precursor material, characterized in that, The quaternary sodium-ion precursor material is prepared using the preparation method described in any one of claims 1-15.

17. The quaternary sodium-electric precursor material according to claim 16, characterized in that, The chemical formula of the quaternary sodium-ion precursor material is Ni. a Fe b Mn c Cu d (OH)2, where a+1.5b+c+d=1, 0.2<a<0.6, 0.15<b<0.45, 0.2<c<0.6, 0.04<d<0.

15.

18. A quaternary sodium-ion cathode material, characterized in that, The quaternary sodium-ion cathode material is obtained by mixing and sintering a sodium source and the quaternary sodium-ion precursor material as described in claim 16 or 17.

19. A sodium-ion battery, characterized in that, The sodium-ion battery includes the quaternary sodium-ion cathode material as described in claim 18.

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