Preparation of copper-doped nickel-manganese-sodium-based ion composite oxide material

Abstract

The invention discloses a copper-doped nickel-manganese-sodium ion composite oxide material, and belongs to the technical field of new energy materials. The general formula of the material is Na < 1-x > Mn < 1-y > Ni < 1-z > WO < 2 >, 0 < = x < = 0.7, 0.8 < = y < 1, 0.5 < = z < = 0.9 (W: Cu: Fe: Co: Cr). The preparation method comprises the following steps: weighing sodium carbonate, manganese dioxide, nickel oxide and a copper oxide compound according to a molar ratio of Na: Mn: Ni: Cu of (0.5-1.0): (0-0.6): (0.1-0.4): (0.1-0.3), putting into a ball mill, grinding, uniformly mixing, sintering and synthesizing at 500-1000 DEG C for 6-24 hours, naturally cooling to room temperature, and finally mixing and crushing in mixing and grinding equipment to obtain the copper-doped nickel-manganese-sodium-based ion composite oxide material. The copper-doped nickel-manganese-sodium-based ion composite oxide material prepared by the method has good rate capability and cycle performance, the 1C half-battery discharge gram volume is 100.0-140.0 mAh / g, and the 10C discharge gram volume is greater than 100.0 mAh / g. The method has the advantages of simple process, low raw material cost, wide distribution, short period and low energy consumption, and can be used for large-scale production.

Description

Technical Field

[0001] The present invention belongs to the technical field of new energy materials and relates to a method for preparing a copper-doped nickel-manganese-sodium based ion composite oxide material. Background Art

[0002] In recent years, sodium-ion batteries have been considered to be the best and most promising complement to lithium-ion batteries due to their rich sodium resource reserves, wide distribution, low price, green and sustainable development, safety and stability, high integrated efficiency, excellent fast charging performance, and good low-temperature performance. They are also one of the most promising systems for the future development of large-scale electrochemical energy storage. However, factors that hinder the development of sodium-ion batteries are that the cathode material system structure is prone to phase change, the discharge specific capacity is not high enough, and the cycle performance is not good enough. In the future development process, we should strengthen the further improvement of the micro- and macro-structures, expand the types of multi-element and multi-site doping, doping ratios, and matching types of materials, etc. Sodium-ion batteries are expected to be used in the field of large-scale energy storage in the future. Summary of the invention

[0003] The present invention uses sodium carbonate, manganese dioxide, nickel oxide and copper oxide as raw materials to prepare a copper-doped nickel-manganese-sodium based ion composite oxide material by a high temperature solid phase method. The preparation steps are as follows:

[0004] (1) Weigh sodium carbonate, manganese dioxide, nickel oxide and copper oxide compound according to the molar ratio of Na:Mn:Ni:Cu (0.5-1.0):(0-0.6):(0.1-0.4):(0.1-0.3);

[0005] (2) The weighed materials are put into a ball mill, ground and uniformly mixed, and then sintered at a temperature of 500 to 1000° C. for 6 to 24 hours to form a sintered product;

[0006] (3) The mixture is then naturally cooled to room temperature, and finally mixed and crushed in a mixing and grinding device to obtain a copper-doped nickel-manganese-sodium based ion composite oxide material. BRIEF DESCRIPTION OF THE DRAWINGS

[0007] Figure 1 , Figure 2 This is an electron microscope image of the copper-doped nickel-manganese-sodium based ion composite oxide material;

[0008] Figure 3 It is the charge and discharge curves of the first three times of the invented copper-doped nickel-manganese-sodium based ion composite oxide material;

[0009] Figure 4 This is a performance diagram of the first few 1C charge and discharge cycles of the invented copper-doped nickel-manganese-sodium based ion composite oxide material. DETAILED DESCRIPTION

[0010] The present invention is further described below in conjunction with the examples, which are merely further supplements and explanations of the present invention, rather than limitations of the invention.

[0011] Example 1

[0012] Sodium carbonate, manganese dioxide, nickel oxide and copper oxide were weighed according to the molar ratio of Na:Mn:Ni:Cu of 0.86:0.48:0.40:0.12, and put into a planetary ball mill for ball milling for 1 hour. The mixture was pressed into tablets and annealed in a tube furnace under high temperature conditions. This process is divided into two steps: first, the temperature was heated to 500°C at a heating rate of 5°C / min and kept warm for 5 hours; then the temperature was heated to 1000°C at the same heating rate and kept warm for 15 hours; finally, the temperature was cooled to room temperature at a rate of 3°C / min, taken out and ground, so that the material Na 0.86 Mn 0.48 Ni 0.4 Cu 0.12 O2.

[0013] This method can produce Na 0.86 Mn 0.48 Ni 0.4 Cu 0.12 O2 material. The gram capacity of the first discharge at 1C is 124.16mAh / g, and the gram capacity of the first discharge at 0.5C is 140.36mAh / g.

[0014] Example 2

[0015] The molar ratio of Na:Mn:Ni:Cu is 0.86:0.48:0.40:0.12. Sodium carbonate, manganese trioxide, nickel oxide and copper oxide are weighed and put into a planetary ball mill for ball milling for 1 hour. The mixture is pressed into tablets and annealed in a tube furnace under high temperature conditions. This process is divided into two steps: first, the temperature is heated to 500°C at a heating rate of 5°C / min and kept warm for 5 hours; then the temperature is raised to 1000°C at the same heating rate and kept warm for 15 hours; finally, it is cooled to room temperature at a rate of 3°C / min, taken out and ground, so that the material Na 0.86 Mn 0.48 Ni 0.4 Cu 0.12 O2.

[0016] This method can produce Na 0.86 Mn 0.48 Ni 0.4 Cu 0.12 O2 material. The gram capacity of the first discharge at 0.5C is 133.08mAh / g, and the gram capacity of the first discharge at 1C is 120.49mAh / g.

[0017] Example 3

[0018] The molar ratio of Na: Mn: Ni: Cu is 0.86: 0.48: 0.40: 0.12. Sodium carbonate, manganese tetraoxide, nickel oxide and copper oxide are weighed and put into a planetary ball mill for ball milling for 1 hour. The mixture is pressed into tablets and annealed in a tube furnace under high temperature conditions. This process is divided into two steps: first, the temperature is heated to 500°C at a heating rate of 5°C / min and kept warm for 5 hours; then the temperature is heated to 1000°C at the same heating rate and kept warm for 15 hours; finally, it is cooled to room temperature at a rate of 3°C / min, taken out and ground, so that the material Na 0.86 Mn 0.48 Ni 0.4 Cu 0.12 O2.

[0019] This method can produce Na 0.86 Mn 0.48 Ni 0.4 Cu 0.12 O2 material. The 1C first discharge capacity is 118.54 mAh / g, and the 5C first discharge capacity is 103.71 mAh / g.

[0020] Example 4

[0021] The molar ratio of Na:Mn:Ni:Cu is 1.0:0.48:0.40:0.12. Sodium carbonate, manganese tetraoxide, nickel oxide and copper oxide are weighed and put into a planetary ball mill for ball milling for 1 hour. The mixture is pressed into tablets and annealed in a tube furnace under high temperature conditions. This process is divided into two steps: first, the temperature is heated to 500°C at a heating rate of 5°C / min and kept warm for 5 hours; then the temperature is raised to 1000°C at the same heating rate and kept warm for 15 hours; finally, it is cooled to room temperature at a rate of 3°C / min, taken out and ground, so that the material Na 0.86 Mn 0.48 Ni 0.4 Cu 0.12 O2.

[0022] This method can produce Na 0.86 Mn 0.48 Ni 0.4 Cu 0.12 O2 material. The gram capacity of the first discharge at 1C is 136.08mAh / g, and the gram capacity of the first discharge at 5C is 100.65mAh / g.

Claims

1. Prepare a copper-doped nickel-manganese-sodium based ion composite oxide material, the preparation method comprising the following steps: (1) Weigh sodium carbonate, manganese dioxide, nickel oxide and copper oxide compound according to the molar ratio of Na:Mn:Ni:Cu (0.5-1.0):(0-0.6):(0.1-0.4):(0.1-0.3); (2) The weighed materials are put into a ball mill for grinding and uniform mixing, and then sintered at a temperature of 500-1000°C for 6-24 hours to form a sintered product; (3) The mixture is then naturally cooled to room temperature and finally mixed and crushed in a mixing and grinding device to obtain a copper-doped nickel-manganese-sodium based ion composite oxide material.

2. The copper-doped nickel-manganese-sodium based ion composite oxide material according to claim 1, characterized in that , the sodium source is one of sodium carbonate and sodium acetate.

3. The copper-doped nickel-manganese-sodium based ion composite oxide material according to claim 1, characterized in that , the manganese source is one of manganese dioxide, manganese trioxide, and manganese tetraoxide.

4. The copper-doped nickel-manganese-sodium based ion composite oxide material according to claim 1, characterized in that , the nickel source is one of nickel oxide, nickel hydroxide, and nickel trioxide.

5. The copper-doped nickel-manganese-sodium based ion composite oxide material according to claim 1, characterized in that , the copper source is one of cupric oxide and cuprous oxide.

6. The copper-doped nickel-manganese-sodium based ion composite oxide material according to claim 1, characterized in that: Na:Mn:Ni:Cu molar ratio (0.5~1.0):(0~0.6):(0.1~0.4):(0.1~0.3).

7. The copper-doped nickel-manganese-sodium based ion composite oxide material according to claim 1, characterized in that: Sinter at 500~1000℃ for 6~24h.

Images