CN107946591A - A kind of nickelic presoma of sodium-ion battery and its preparation method with positive electrode - Google Patents

Abstract

The invention discloses a high-nickel precursor of a sodium ion battery and a preparation method thereof and a positive electrode material, belonging to the technical field of sodium ion battery electrode materials. It is characterized in that: the chemical molecular formula of the positive electrode material is Na(Ni _{1‑x‑y‑z} Co _y Al _z Cu _z )O ₂ , where 0.2≥x+y+z, 0.1≥x≥0.05, 0.05≥y≥0.03 , 0.1≥z≥0.02, using controlled crystallization-co-precipitation technology, Ni, Cobalt, Aluminum and Copper four elements with uniform distribution and narrow particle size distribution Ni _{1‑x‑y‑z} Co _y Al _z Cu _z ( OH) ₂ micron sphere precursor, mix the precursor with sodium salt evenly, and obtain high-nickel Na(Ni _{1‑x‑y‑ z} Co _y Al _z Cu _z )O ₂ positive electrode material through high-temperature solid-state reaction. The invention is easy to operate, can be produced in batches continuously, and the product has the advantages of high specific capacity, good cycle performance, etc., and has high economic value and wide application prospect.

Description

A kind of high-nickel precursor of sodium ion battery and its preparation method with positive electrode material

technical field

The invention discloses a high-nickel precursor of a sodium ion battery and a preparation method thereof and a positive electrode material, belonging to the technical field of sodium ion battery electrode materials.

Background technique

In the field of energy storage, lithium-ion batteries have occupied the power supply market of portable electronic devices, and are gradually being applied to the power supply of new electric vehicles. At the same time, with the development of renewable energy such as solar energy, tidal energy, and wind energy, there is an urgent need to build a large-scale, low-cost, and high-security battery energy storage system to meet the needs of future renewable energy storage, power generation, and smart grid integration. The rapid development of the grid. However, constrained by lithium reserves in the earth's crust (if it is not recycled, it is estimated that it will be consumed within 65 years) and distribution (70% in South America), lithium resources are increasingly scarce and the cost remains high, seriously Restrict the development of lithium-ion batteries in the field of large-scale energy storage. Sodium and lithium belong to the same main group, and their physical and chemical properties are similar. Sodium-ion batteries have a similar working principle to lithium-ion batteries. At the same time, the reserves of sodium are more abundant (420 times that of lithium), and the distribution is uniform and the price is low. , Therefore, from the perspective of cost reduction, the development of sodium-ion batteries for large-scale energy storage has great potential and important practical significance.

At present, the development and development of sodium ion batteries are still far from practical and industrialization, mainly because of the large radius of sodium ions And the mass is heavy (22.99g mol ^-1 ), resulting in slow kinetics, which brings great challenges to the design of electrode materials, especially the positive electrode material that determines the basic characteristics of the battery. The development of cathode materials with high capacity, good stability, and low cost has become the focus of current research on sodium-ion batteries. At present, the research and development of cathode materials mainly focus on layered Na _x MO ₂ (M is Co, Ni, Mn, Fe, etc.) materials, tunnel metal oxides, polyanionic compounds, and Prussian blue compounds. Among them, the layered O ₃ -type Ni-based Na(Ni-M)O ₂ system has become a research hotspot because of its high specific capacity (~255mAh g ^-1 ), adjustable electrochemical active elements, and rich system. However, this type of material still has the following problems: (1) more phase transitions occur during the electrochemical reaction, resulting in poor cycle stability and rate performance; Reacts with moisture and carbon dioxide, resulting in higher storage costs; (3) The electrochemically active Ni element content is low (<80%), and does not show the characteristics of high specific capacity of O ₃ type Na(Ni-M)O ₂ materials; (4) There is no efficient preparation process to meet the requirements of macro-scale and controllable preparation of such materials. Therefore, it is necessary to seek effective strategies (element doping and micro-nano structure construction) to improve electrochemical performance and structural _stability , and to develop _macro -controllable preparation technologies. points and difficulties.

Among them, element doping in the Na(Ni-M)O ₂ system is more mature and more researched, and its advantages are (1) improving the stability of the sodium intercalation crystal structure, (2) improving the intercalation and desorption mechanism to enhance the sodium storage performance , but how to achieve uniform distribution and synergistic effect of various doping elements is still challenging; and the advantages of constructing micro-nano structures are (1) high activity of nanoparticles, which is conducive to particle/electronic conduction, (2) micron structure ensures the stability of the structure properties and provide high tap density, but there are few reports on Na(Ni-M)O ₂ micro-nano structure materials, and further research is urgently needed. In addition, it is of great significance and application prospect to develop a macro-controllable high-nickel Na(Ni-M)O ₂ (Ni>80%) preparation process while realizing the design of micro-nano structure and uniform distribution of multi-elements.

Contents of the invention

The technical problem to be solved by the present invention is: to overcome the deficiencies of the prior art, to provide a high-nickel precursor for sodium-ion batteries and its and the preparation method of the positive electrode material.

The technical solution adopted by the present invention to solve the technical problem is: the high-nickel precursor of the sodium ion battery, which is characterized in that the chemical formula is Na(Ni _1-xyz Co _y Al _z Cu _z )O ₂ , where 0.2≥x+ y+z, 0.1≥x≥0.03, 0.05≥y≥0.03, 0.1≥z≥0.02.

A preparation method for the high-nickel precursor of the above-mentioned sodium ion battery, characterized in that: comprising the following steps:

1) Prepare a nickel-cobalt-copper salt solution with a metal ion concentration of 0.3-6mol L ^-1 with nickel salt, cobalt salt, copper salt and aluminum salt; Ni:Co:Al in nickel salt, cobalt salt, copper salt and aluminum salt : The molar ratio of Cu is 0.80-0.90:0.03-0.10:0.03-0.05:0.02-0.1;

Prepare a mixed solution of aluminum metal ions and sodium hydroxide, wherein Al ³⁺ exists completely in the form of AlO ₂ ^- ;

Using a complexing agent to configure a complexing agent solution with a concentration of 0.5-7mol L ^-1 ;

Prepare a precipitant solution with a concentration of 0.5-10mol L ^-1 with a precipitant;

2) Add deionized water into the reaction kettle, stir mechanically, adjust the pH to 9-12 with complexing agent solution and precipitating agent solution, and control the temperature of the system to be constant at 30-60°C;

3) adding the nickel-cobalt-copper salt solution, the mixed solution of aluminum metal ions and sodium hydroxide and the complexing agent solution into the reaction kettle at the same time, and adding the precipitating agent solution to adjust the pH of the system to 9-12;

4) After the reaction, the obtained precipitate was filtered, washed, and dried in a vacuum oven at 70-200° C. for 4-12 hours to obtain a Ni _1-xyz Co _y Al _z Cu _z (OH) ₂ microsphere precursor.

Using controlled crystallization-co-precipitation technology, Ni _1-xyz Co _y Al _z Cu _z (OH) ₂ micron spherical precursor with uniform distribution of nickel, cobalt, aluminum and copper elements and narrow particle size distribution was prepared, among which the high The electrochemically active Ni content can provide high specific capacity, the coordination of non-electrochemically active Co and Al helps to improve the stability of the layered structure, and Cu can improve the stability of the material in air. Through the coordinated effect of high Ni content and co-doping of Co, Al, Cu, as well as controlling the microsphere morphology prepared by crystallization-co-precipitation, the layered O ₃ type high nickel Na(Ni _1-xyz Co _y Al _z Cu _z )O ₂ has high structural stability and excellent electrochemical performance. The invention has simple operation, realizes continuous batch production, and the product has the advantages of high specific capacity, good cycle performance, etc., and has high economic value and wide application prospect.

Preferably, the molar ratio of Ni:Co:Al:Cu in step 1) is 0.83-0.86:0.05-0.08:0.035-0.04:0.04-0.06. Under the preferred element ratio, the structure of the prepared battery cathode material is more stable.

Preferably, the nickel salt, cobalt salt, copper salt and aluminum salt described in step 1) are respectively one or more mixtures of acetic acid, sulfate, and nitrate containing corresponding elements; the complexing agent is One or more mixtures of ammonia water, citric acid, and EDTA; the precipitating agent is one or more mixtures of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, and sodium bicarbonate. The optimized material can ensure a more uniform distribution of elements, a better particle sphericity of the product, and a narrower particle size distribution.

Preferably, the stirring speed of the mechanical stirring described in step 2) is 300-900 rpm, and the temperature of the system is controlled at 40-50°C. The optimal system stirring and temperature conditions can make the particle sphericity of the product better.

Preferably, in step 3), a peristaltic pump is used to control the inflow flow rate when adding the precipitant solution. Allows for more precise pH control.

A sodium-ion battery cathode material prepared by using the above-mentioned high-nickel precursor, characterized in that: the chemical molecular formula is Ni _1-xyz Co _y Al _z Cu _z (OH) ₂ , wherein 0.2≥x+y+z, 0.1≥x ≥0.03, 0.05≥y≥0.03, 0.1≥z≥0.02.

A method for preparing anode materials for sodium-ion batteries using the above-mentioned high-nickel precursors, characterized in that: uniformly mix Ni _1-xyz Co _y Al _z Cu _z (OH) ₂ precursors with sodium salts, and first heat the Calcining for 2-9 hours, heating up, and then calcining at 600-800°C for 5-15 hours, the calcining atmosphere is air, oxygen or mixed gas, cooling down, grinding and sieving the obtained product to obtain Na(Ni _1-xyz Co _y Al _z Cu _z ) O ₂ type sodium ion battery cathode material.

The present invention provides a sodium ion battery to solve the problems of macro controllable preparation, low energy density, fast capacity fading and high storage cost of the layered _O3 type Na(Ni-M) _O2 cathode material of the existing sodium ion battery. The preparation method of the layered O ₃ -type cobalt-aluminum-copper co-doped high-nickel positive precursor of the battery is to mix the precursor uniformly with the sodium salt, and then obtain the high-nickel Na(Ni _1-xyz Co _y Al _z Cu _z )O ₂ cathode material. The method is suitable for industrialized production, has high automation procedures and stable product quality. The prepared positive electrode material has uniform distribution of elements, good electrochemical performance and high tap density, which is helpful to promote the practical development of sodium-ion batteries.

Preferably, the sodium salt is sodium nitrate, sodium carbonate, sodium hydroxide, sodium peroxide, sodium superoxide or a mixture of two or more, and in the sodium salt, Na and Ni _1-xyz Co _y Al _z Cu _z The molar ratio of the total amount of Ni, Co, Al, and Cu in the (OH) ₂ precursor is 0.95-1.05:1. The optimal material ratio can ensure higher tap density, better particle sphericity and narrower particle size distribution of the positive electrode material.

Preferably, the heating rate of the heating is 1-15°C·min ^-1 ; the cooling rate of the cooling is 5-20°C·min ^-1 for quenching or controlled rate. The optimal heating and cooling rate can ensure better particle sphericity and narrower particle size distribution of the positive electrode material.

Compared with the prior art, the beneficial effects of a high-nickel precursor for a sodium ion battery of the present invention and its preparation method with positive electrode materials are: (1) prepared Na(Ni _1-xyz Co _y Al _z Cu _z ) O ₂ microsphere material has uniform distribution of elements, high tap density, good particle sphericity and narrow particle size distribution.

(2) The preparation method has a relatively simple process, specific adjustable and controllable parameters in production, low energy consumption, and is very suitable for industrial mass and continuous production.

(3) The synergistic effect of co-doping of multiple elements can significantly improve the structural stability of the material, maintain the stability during charge and discharge, and maintain the high capacity characteristics of high-nickel materials. The layered O prepared by this method _{The 3-} type high-nickel Na(Ni _1-xyz Co _y Al _z Cu _z )O ₂ sodium ion cathode material has application prospects in the field of large-scale energy storage of secondary batteries.

Description of drawings

Fig. 1 is a scanning electron microscope image of the Ni _0.8 Co _0.1 Al _0.05 Cu _0.05 (OH) ₂ microsphere precursor obtained in Example 1 of the present invention.

Fig. 2 is a scanning electron microscope image of the Na Ni _0.8 Co _0.1 Al _0.05 Cu _0.05 O ₂ positive electrode material obtained in Example 1 of the present invention. It can be seen from the figure that after calcination, the product still maintains the spherical shape of the precursor.

Figure 3 is the X-ray diffraction pattern of the Ni _0.8 Co _0.1 Al _0.05 Cu _0.05 (OH) ₂ microsphere precursor obtained in Example 1 of the present invention. It is found that the diffraction peaks in the figure are consistent with the standard PDF card of nickel hydroxide.

Fig. 4 is the X-ray diffraction pattern of the Na Ni _0.8 Co _0.1 Al _0.05 Cu _0.05 O ₂ positive electrode material obtained in Example 1 of the present invention. It is found that each diffraction peak in the figure is consistent with the standard PDF card of sodium nickelate.

Fig. 5 is the first-cycle charge-discharge curve at a rate of 0.1C after the CR2032 button battery is assembled into a CR2032 button battery using the NaNi _0.8 Co _0.1 Al _0.05 Cu _0.05 O ₂ positive electrode material obtained in Example 1 of the present invention.

Detailed ways

The present invention will be further described below in conjunction with specific examples, wherein Example 1 is the best implementation.

Example 1

Step (1): Prepare a transition metal ion solution with a concentration of 3.5 mol·L ^-1 , wherein the nickel-cobalt-aluminum-copper salt is nickel sulfate, cobalt sulfate, aluminum sulfate, copper sulfate, nickel ion, cobalt ion, aluminum ion, copper The molar ratio of ions is 0.85:0.06:0.038:0.05; the complexing agent ammonia solution is 3mol L ^-1 solution, the precipitant sodium hydroxide solution is 5mol L ^-1 solution; put the solution on the stirrer Thoroughly stir to dissolve the solute completely;

Step (2): Add 200ml of deionized water to the 2L reaction kettle, set the stirring speed of the stirring paddle to 700rpm, control the temperature of the system at 45°C, add 3ml of concentrated ammonia water to initially adjust the pH, and then use the precipitant sodium hydroxide Adjust the pH of the solution to 10.7; after the system is stable, use a peristaltic pump to pump the transition metal ion solution, the complexing agent ammonia and the precipitant sodium hydroxide solution into the reaction kettle at the same time, and adjust the feed rate of the precipitant sodium hydroxide solution during this period. , to stabilize the pH at 10.7;

Step (3): After the feeding is completed, age for 1 hour, take out part of the reaction solution from the reaction kettle, filter and wash it several times with deionized water until the pH is nearly neutral, dry it in a vacuum oven at 100°C for 10 hours, and obtain sufficient Dried Ni _0.85 Co _0.06 Al _0.038 Cu _0.05 (OH) ₂ precursor;

Step (4): Take 1 g of fully dried Ni _0.85 Co _0.06 Al _0.038 Cu _0.05 (OH) ₂ precursor to prepare positive electrode material, use agate mortar and sodium carbonate to fully mix, wherein Na:(Ni+Co+Al+ Cu)=1:1, put an oxygen atmosphere into the tube furnace, raise the temperature to 500°C at a heating rate of 5°C min ^-1 and keep it for 5 hours, then raise the temperature to 750°C at the same heating rate, and hold it for 12 hours, After cooling to room temperature, the calcined product was ground and sieved to obtain Na Ni _0.85 Co _0.06 Al _0.038 Cu _0.05 O ₂ cathode material.

Example 2

Step (1): Prepare a transition metal ion solution with a concentration of 2mol L ^-1 , wherein the nickel-cobalt-aluminum-copper salt is a mixture of nickel chloride, cobalt chloride, aluminum chloride, and copper chloride, nickel ions, cobalt ions , the molar ratio of aluminum ion and copper ion is 0.83:0.08:0.035:0.06; the solution with complexing agent EDTA concentration of 5mol L ^-1 and the precipitant sodium hydroxide concentration of 2mol L ^-1 solution; the solution Put it on a stirrer and stir it fully to dissolve the solute completely;

Step (2): Add 300ml of deionized water into the 2L reactor, set the stirring speed of the stirring paddle to 450rpm, control the temperature of the system at 55°C, and adjust the pH to 11.5 with the precipitating agent sodium hydroxide solution; after the system is stable, Use a peristaltic pump to pump the transition metal ion solution, the complexing agent EDTA solution and the precipitating agent sodium hydroxide solution into the reaction kettle at the same time, during which the pH is stabilized at 11.5 by adjusting the feeding speed of the precipitating agent sodium hydroxide solution;

Step (3): After the feeding is completed, age for 1 hour, take out part of the reaction solution from the reaction kettle, filter and wash it several times with deionized water until the pH is nearly neutral, dry it in a vacuum oven at 150°C for 5 hours, and obtain sufficient Dried Ni _0.83 Co _0.08 Al _0.035 Cu _0.06 (OH) ₂ precursor;

Step (4): Take 1 g of fully dried Ni _0.83 Co _0.08 Al _0.035 Cu _0.06 (OH) ₂ precursor to prepare the positive electrode material, and use an agate mortar to fully mix it with sodium hydroxide, where Na:(Ni+Co+Al +Cu)=1.02:1, put an oxygen atmosphere into the tube furnace, raise the temperature to 520°C at a rate of 10°C min ^-1 and keep it for 3.5 hours, then raise the temperature to 650°C at the same rate and keep it for 13 hours After that, it was quenched to room temperature, and the roasted product was ground and sieved to obtain NaNi _0.83 Co _0.08 Al _0.035 Cu _0.06 O ₂ positive electrode material.

Example 3

Step (1): Prepare a transition metal ion solution with a concentration of 4mol·L ^-1 , wherein the nickel-cobalt-aluminum-copper salt is nickel sulfate, cobalt sulfate, aluminum sulfate, copper sulfate, nickel ions, cobalt ions, aluminum ions, copper ions The molar ratio is 0.86:0.05:0.04:0.04; the complexing agent EDTA concentration is 1.5mol L ^-1 solution, the precipitating agent sodium hydroxide concentration is 7mol L ^-1 solution; put the solution on the stirrer Thoroughly stir to dissolve the solute completely;

Step (2): Add 200ml of deionized water into the 2L reactor, set the stirring speed of the stirring paddle to 800rpm, control the temperature of the system at 45°C, and adjust the pH to 10.2 with the precipitating agent sodium hydroxide solution; after the system is stable, Use a peristaltic pump to pump the transition metal ion solution, the complexing agent EDTA solution and the precipitating agent sodium hydroxide solution into the reactor at the same time, during which the pH is stabilized at 10.2 by adjusting the feeding speed of the precipitating agent sodium hydroxide solution;

Step (3): After the feeding is completed, age for 1 hour, take out part of the reaction solution from the reaction kettle, filter and wash it several times with deionized water until the pH is nearly neutral, dry it in a vacuum oven at 85°C for 11 hours, and obtain sufficient Dry Ni _0.86 Co _0.05 Al _0.04 Cu _0.04 (OH) ₂ precursor;

Step (4): Take 1 g of fully dried Ni _0.86 Co _0.05 Al _0.04 Cu _0.04 (OH) ₂ precursor to prepare the positive electrode material, and use an agate mortar to fully mix it with sodium peroxide, where Na:(Ni+Co+Al +Cu)=0.98:1, put an oxygen atmosphere into the tube furnace, raise the temperature to 350°C at a heating rate of 2°C min ^-1 and keep it for 8 hours, then raise the temperature to 750°C at the same heating rate, and keep it for 8 hours , at a rate of 15°C min ^-1 to room temperature, the roasted product was ground and sieved to obtain the NaNi _0.86 Co _0.05 Al _0.04 Cu _0.04 O ₂ cathode material.

Example 4

Step (1): Prepare a transition metal ion solution with a concentration of 6mol·L ^-1 , wherein the nickel-cobalt-aluminum-copper salt is a mixture of nickel nitrate, cobalt nitrate, aluminum nitrate, copper nitrate, nickel ions, cobalt ions, aluminum ions, The molar ratio of copper ions is 0.80:0.10:0.03:0.1; the complexing agent citric acid concentration is 0.5mol L ^-1 solution, the precipitating agent sodium hydroxide concentration is 10mol L ^-1 solution; the solution is placed in Fully stir on the stirrer to completely dissolve the solute;

Step (2): Add 200ml of deionized water into the 2L reaction kettle, set the stirring speed of the stirring paddle to 900rpm, control the temperature of the system at 60°C, and adjust the pH to 9 with the precipitating agent sodium hydroxide solution; after the system is stable, Use a peristaltic pump to pump the transition metal ion solution, the complexing agent EDTA solution and the precipitating agent sodium hydroxide solution into the reaction kettle at the same time, during which the pH is stabilized at 9 by adjusting the feeding speed of the precipitating agent sodium hydroxide solution;

Step (3): After the feeding is completed, age for 1 hour, take out part of the reaction solution from the reaction kettle, filter and wash it several times with deionized water until the pH is nearly neutral, dry it in a vacuum oven at 70°C for 12 hours, and obtain sufficient Dried Ni _0.8 Co _0.1 Al _0.03 Cu _0.1 (OH) ₂ precursor;

Step (4): Take fully dried Ni _0.8 Co _0.1 Al _0.03 Cu _0.1 (OH) ₂ precursor 1g to prepare positive electrode material, use agate mortar and sodium peroxide to fully mix, wherein Na:(Ni+Co+Al +Cu)=0.95, put an oxygen atmosphere into the tube furnace, raise the temperature to 250°C for 9 hours at a rate of 1°C·min ^-1 , and then raise the temperature to 600°C with the same rate of increase for 15 hours. From 20°C min ^-1 to room temperature, the roasted product was ground and sieved to obtain NaNi _0.8 Co _0.1 Al _0.03 Cu _0.1 O ₂ cathode material.

Example 4

Step (1): Prepare a transition metal ion solution with a concentration of 0.3mol·L ^-1 , wherein the nickel-cobalt-aluminum-copper salt is a mixture of nickel acetate, cobalt acetate, aluminum acetate, and copper acetate, and nickel ions, cobalt ions, and aluminum ions , the molar ratio of copper ions is 0.90:0.03:0.05:0.02; the complexing agent citric acid concentration is 7mol L ^-1 solution, the precipitating agent sodium hydroxide concentration is 0.5mol L ^-1 solution; the solution is placed Fully stir on the stirrer to completely dissolve the solute;

Step (2): Add 200ml of deionized water into the 2L reactor, set the stirring speed of the stirring paddle to 300rpm, control the temperature of the system at 30°C, and adjust the pH to 12 with the precipitating agent sodium hydroxide solution; after the system is stable, Use a peristaltic pump to pump the transition metal ion solution, the complexing agent EDTA solution and the precipitating agent sodium hydroxide solution into the reaction kettle at the same time, during which the pH is stabilized at 12 by adjusting the feeding speed of the precipitating agent sodium hydroxide solution;

Step (3): After the feeding is completed, age for 1 hour, take out part of the reaction solution from the reaction kettle, filter and wash it several times with deionized water until the pH is nearly neutral, dry it in a vacuum oven at 200°C for 4 hours, and obtain sufficient Dried Ni _0.9 Co _0.03 Al _0.05 Cu _0.02 (OH) ₂ precursor;

Step (4): Take 1 g of fully dried Ni _0.9 Co _0.03 Al _0.05 Cu _0.02 (OH) ₂ precursor to prepare the positive electrode material, and use an agate mortar to fully mix it with sodium peroxide, where Na:(Ni+Co+Al +Cu)=1.05, put an oxygen atmosphere into the tube furnace, raise the temperature to 550°C at a rate of 15°C·min ^-1 and keep it for 2 hours, then raise the temperature to 800°C at the same rate of increase, and hold it for 5 hours, then 5 ^℃ min ^-1 rate to room temperature, the product obtained by roasting was ground and sieved to obtain NaNi _0.9 Co _0.03 Al _0.05 Cu _0.02 O ₂ cathode material.

The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention to other forms. Any skilled person who is familiar with this profession may use the technical content disclosed above to change or modify the equivalent of equivalent changes. Embodiment; But all without departing from the content of the technical solution of the present invention, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention still belong to the protection scope of the technical solution of the present invention.

Claims (9)

1. A high-nickel precursor for a sodium-ion battery, characterized in that the chemical formula is Ni _1-xyz Co _y Al _z Cu _z (OH) ₂ , wherein 0.2≥x+y+z, 0.1≥x≥0.03, 0.05 ≥y≥0.03, 0.1≥z≥0.02. 2. a preparation method of the high-nickel precursor of sodium ion battery according to claim 1, is characterized in that: comprises the following steps: 1) Prepare a nickel-cobalt-copper salt solution with a metal ion concentration of 0.3-6mol L ^-1 with nickel salt, cobalt salt, copper salt and aluminum salt; Ni:Co:Al in nickel salt, cobalt salt, copper salt and aluminum salt : The molar ratio of Cu is 0.80-0.90:0.03-0.10:0.03-0.05:0.02-0.1; Prepare a mixed solution of aluminum metal ions and sodium hydroxide, wherein Al ³⁺ exists completely in the form of AlO ₂ ^- ; Using a complexing agent to configure a complexing agent solution with a concentration of 0.5-7mol L ^-1 ; Prepare a precipitant solution with a concentration of 0.5-10mol L ^-1 with a precipitant; 2) Add deionized water into the reaction kettle, stir mechanically, adjust the pH to 9-12 with complexing agent solution and precipitating agent solution, and control the temperature of the system to be constant at 30-60°C; 3) adding the nickel-cobalt-copper salt solution, the mixed solution of aluminum metal ions and sodium hydroxide and the complexing agent solution into the reaction kettle at the same time, and adding the precipitating agent solution to adjust the pH of the system to 9-12; 4) After the reaction, the obtained precipitate was filtered, washed, and dried in a vacuum oven at 70-200° C. for 4-12 hours to obtain a Ni _1-xyz Co _y Al _z Cu _z (OH) ₂ microsphere precursor. 3. the preparation method of a kind of high-nickel precursor of sodium ion battery according to claim 2, is characterized in that: the molar ratio of Ni:Co:Al:Cu described in step 1) is 0.83-0.86:0.05- 0.08:0.035-0.04:0.04-0.06. 4. the preparation method of a kind of high-nickel precursor according to claim 2 is characterized in that: step 1) described nickel salt, cobalt salt, copper salt and aluminum salt are respectively the acetic acid that contains corresponding element, vitriol , one or more mixtures of nitrates; the complexing agent is one or more mixtures of ammonia, citric acid, EDTA; the precipitating agent is sodium hydroxide, potassium hydroxide, lithium hydroxide , sodium carbonate, sodium bicarbonate or a mixture of two or more. 5. the preparation method of a kind of high-nickel precursor of sodium ion battery according to claim 2, is characterized in that: the stirring speed of the mechanical stirring described in step 2) is 300-900rpm, and system temperature is controlled at 40-50 ℃. 6. A sodium-ion battery cathode material prepared by using the high-nickel precursor according to claim 1, characterized in that: the chemical molecular formula is Na(Ni _1-xyz Co _y Al _z Cu _z )O ₂ , wherein 0.2≥x +y+z, 0.1≥x≥0.03, 0.05≥y≥0.03, 0.1≥z≥0.02. 7. A method utilizing the high-nickel precursor as claimed in claim 1 to prepare anode material for sodium ion battery, characterized in that: Ni _1-xyz Co _y Al _z Cu _z (OH) ₂ precursor and sodium salt are mixed uniformly , first calcined at 250-550°C for 2-9h, raised the temperature, and then calcined at 600-800°C for 5-15h, the calcining atmosphere was air, oxygen or mixed gas, lowered the temperature, and ground and sieved the obtained product to obtain Na(Ni _{1- xyz} Co _y Al _z Cu _z )O ₂ type sodium ion battery cathode material. 8. the method for preparing sodium ion battery cathode material according to claim 7, is characterized in that: described sodium salt is sodium nitrate, sodium carbonate, sodium hydroxide, sodium peroxide, sodium superoxide one or both For the above mixture, the molar ratio of Na in the sodium salt to the total amount of Ni, Co, Al and Cu in the Ni _1-xyz Co _y Al _z Cu _z (OH) ₂ precursor is 0.95-1.05:1. 9. The method for preparing the positive electrode material of a sodium ion battery according to claim 7, characterized in that: the heating rate of the heating is 1-15°C·min ⁻¹ ; the cooling rate of the cooling is divided into quenching or controlled cooling. Speed 5～20℃·min ^-1 .