CN104577088A - Lithium molybdate serving as secondary battery electrode material - Google Patents

Abstract

The invention discloses lithium molybdate serving as a secondary battery electrode material. In an execution mode, a chemical formula of the electrode material is Li (2-x)MoyMzO(3-u), wherein x is larger than or equal to minus 2 and smaller than or equal to 2, y is larger than 0 and smaller than or equal to 5, z is larger than or equal to 0 and smaller than or equal to 9, u is larger than or equal to minus 9 and smaller than or equal to 3, and M comprises one element selected from C, N, F, Na, Mg, Al, Si, P, S, Cl, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Br, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Cd, In, Sn, Sb, Te, I, Cs, Ba, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, Po, At, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu or combination of the elements. The electrode material is characterized by having very high specific capacity, excellent cycle performance, rate capability and safety.

Description

Secondary battery electrode material lithium molybdate

technical field

The invention belongs to the technical field of batteries, in particular to electrode materials for secondary batteries.

Background technique

With the gradual depletion of fossil energy such as coal, oil, and natural gas and the deteriorating environmental problems, clean energy has attracted much attention, such as solar energy, wind energy, and hydrogen energy. As the storage, transportation and use carrier of new clean energy, secondary batteries face huge development space. Among various secondary batteries, lithium-ion battery is an efficient electrical energy-chemical energy conversion device, which has been widely used in mobile phones, digital cameras, notebook computers and other portable electronic products and power tools. However, with the rapid development of electronic technology, increasingly powerful electronic products and power tools have gradually increased the performance requirements of lithium-ion batteries, while the development and development of electric vehicles and smart grids have placed increasing demands on the energy density and power density of lithium-ion batteries. , service life and safety and other performance put forward higher requirements.

Since the commercialization of lithium-ion batteries in 1991, the energy density of energy-type lithium-ion batteries has increased from the initial 90Wh/kg to 210Wh/kg, which still cannot reach the energy density (500Wh/kg) required by power batteries. Among them, the electrode material is an important factor that limits the improvement of the energy density of lithium-ion batteries. At present, the actual specific capacity of the positive electrode material has always hovered between 100-180mAh/g, which has become a bottleneck for improving the energy density of lithium-ion batteries. To improve the energy density of lithium-ion battery cathode materials, one method is to develop high-voltage (~5.0V) cathode materials, such as currently known LiMPO ₄ (M=Mn, Co, etc.), LiMn _1.5 Ni _0.5 O ₄ etc. Voltage materials; another approach is to look for cathode materials with high specific capacity (such as Mn-based lithium-rich cathode materials). Due to the lack of electrolytes that are well matched with high-voltage materials, the use of high-voltage electrode materials is limited, and their performance in many aspects is not conclusive. Therefore, materials with high specific capacity but also able to work at a slightly lower voltage have become the first choice for lithium-ion battery cathode materials.

Li ₂ MnO ₃ is currently known as the cathode material for lithium-ion batteries with the highest specific capacity and energy density. The theoretical specific capacity reaches 458mAh/g, so it has received extensive attention and in-depth research. The main disadvantage of this material is (1) high charging voltage. Only when charged to 4.8V and above, the specific capacity of the material can be fully exerted, and the material has basically no electrochemical activity below 4.5V; (2) Since Mn ⁴⁺ cannot continue to be oxidized below 4.8V, the material The capacity development must be accompanied by the precipitation of oxygen, which will cause a safety hazard in the actual battery; (3) in the first cycle, the structure of the material undergoes an irreversible change from layered to spinel structure, and the lithium released from charging cannot be completely Back to the parent material, which leads to lower first-time cycle efficiency; (4) Li ₂ MnO ₃ has low conductivity, and lithium-ion batteries using it as the positive electrode material can only cycle at a lower rate. Li ₂ MoO ₃ has a crystal structure similar to Li ₂ MnO ₃ and has a theoretical specific capacity of 339mAh/g. Compared with Li ₂ MnO ₃ , Li ₂ MoO ₃ has a series of advantages: (1) The delithiation potential is lower, and most of the current commercial electrolytes can meet the requirements. When charging and discharging between 2.0-4.5V, Li ₂ MoO ₃ can undergo a reversible oxidation-reduction reaction between Mo ⁴⁺ /Mo ⁶⁺ , which can provide a reversible specific capacity of more than 210mAh/g; (2) due to relying on Mo ⁴⁺ /Mo ⁶⁺ redox couple, so Li ₂ MoO ₃ can release capacity without the evolution of oxygen during cycling. Therefore, the lithium-ion battery with Li ₂ MoO ₃ as the positive electrode material has higher safety; (3) Since the structural change of Li ₂ MoO ₃ is completely reversible when cycling between 2.0-4.5V, the material whether it is It has very high Coulombic efficiency both in the first cycle and in subsequent cycles. For the first time, the Coulombic efficiency reached more than 98%; (4) Experiments and theory have proved that Li ₂ MoO ₃ has a higher conductivity than Li ₂ MnO ₃ , so Li-ion batteries composed of Li ₂ MoO ₃ will have better rate performance. Similarly, the lithium-rich molybdenum-based positive electrode material zLi ₂ MoO _{3 ·} (1-z)LiM'O ₂ (0<z _< 1.0, M'comprising Ni, Co, Mn, One of Al _{, Mo, Mg, Ru or a combination of them) than the lithium-rich manganese-based cathode material zLi 2 MnO 3 ·} (1-z)LiM′O ₂ (M 'same as above) also have higher security, rate performance and Coulombic efficiency. Therefore, the cathode material based on the Li ₂ MoO ₃ phase is more advantageous than the cathode material based on the Li ₂ MnO ₃ phase.

In addition, compared with lithium-ion batteries, sodium-ion batteries have been widely studied due to their low raw material cost, compatibility with electrolytes with low decomposition voltages, and high safety, while magnesium-ion batteries have been the most popular choice so far due to their higher energy density. The most theoretically promising new green battery for electric vehicles. However, electrode materials are also an important factor restricting the development of sodium-ion batteries and magnesium-ion batteries.

The fundamental difference between secondary batteries such as secondary lithium batteries and secondary sodium batteries and the corresponding lithium-ion batteries and sodium-ion batteries is that the former use the corresponding metal element or alloy as the negative electrode (anode) of the battery, and they are also controlled Due to the current low capacity of cathode materials and other limitations.

Contents of the invention

The purpose of the present invention is to break through the limitations of existing secondary battery electrode materials and provide a secondary battery electrode material Li _2-x Mo _y M _z O with high specific capacity, high rate performance, high Coulombic efficiency and high safety _3-u .

Technical scheme of the present invention is as follows:

The chemical formula of the secondary battery electrode material in the present invention is Li _2-x Mo _y M _z O _3-u , wherein, -2≤x≤2, 0<y≤5, 0≤z≤9, -9≤u ≤3. M contains selected from C, N, F, Na, Mg, Al, Si, P, S, Cl, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Br, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Cd, In, Sn, Sb, Te, I, Cs, Ba, Ta, W, Re, One of Os, Ir, Pt, Au, Hg, Pb, Bi, Po, At, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu or combination between them.

The electrode material Li _2-x Mo _y M _z O _3-u can be used alone as a secondary battery electrode material, or can be combined with other materials in a certain proportion as a secondary battery electrode material.

The combination of the electrode material Li _2-x Mo _y M _z O _3-u and other materials includes solid solution, superstructure, composite, mixing and covering.

The electrode material can be used as the positive electrode material and additive material of the secondary battery.

The electrode material Li _2-x Mo _y M _z O _3-u can be used in lithium-ion batteries when 0≤x<2, 0<y≤5, 0≤z≤9, -9≤u≤3 or secondary lithium batteries.

The electrode material Li _2-x Mo _y M _z O _3-u , when -2≤x≤2, 0<y≤5, 0≤z≤9, -9≤u≤3, and M is Na, It can be used in sodium ion battery or secondary sodium battery.

The electrode material Li _2-x Mo _y M _z O _3-u , when -2≤x≤2, 0<y≤5, 0≤z≤9, -9≤u≤3, and M is Mg, Can be used in magnesium ion batteries.

The advantages of the secondary battery electrode material Li _2-x Mo _y M _z O _3-u provided by the invention are:

(1) High specific capacity

When the lithium ion battery made of Li _2-x Mo _y M _z O _3-u described in the present invention is the positive electrode material, when charging and discharging between 2.0-4.5V, the reversible specific capacity reaches 270mAh/g, the current high specific capacity Lithium-ion battery cathode materials, such as Mn-based lithium-rich cathode materials, can only obtain a specific capacity of 250mAh/g when charged to 4.8V or above. Therefore, Li _2-x Mo _y M _z O _3-u has excellent specific capacity when used as a cathode material. When Li _2-x Mo _y M _z O _3-u is used as an additive material for electrode materials, the specific capacity of lithium-ion batteries can be significantly improved.

(2) Coulombic efficiency is high

The coulombic efficiency _of the lithium ion battery made of the Li2 _{-xMoyMzO3 - u} material of the present invention as _the positive electrode material is greater than 99.8%, far superior to that of the parent material _Li2MnO3 of the Mn-based lithium-rich positive electrode material. Coulombic efficiency (about 66%).

(3) Stable cycle performance

Compared with the parent material Li ₂ MnO ₃ of the Mn-based lithium-rich positive electrode material, the Li _2-x Mo _y M _z O _3-u described in the present invention is used as the positive electrode material without oxygen precipitation during the delithiation process, so it has more Good cycle stability. Due to the low working voltage, most of the current commercial electrolyte materials can meet the requirements of Li-ion batteries with Li _2-x Mo _y M _z O _3-u as the cathode material. The lithium-ion battery made of Li _2-x Mo _y M _z O _3-u as the positive electrode material can maintain a capacity retention rate of more than 90% in a normal cycle of more than 500 cycles. When Li _2-x Mo _y M _z O _3-u is used as the electrode material of sodium ion battery and magnesium ion battery, it also has excellent cycle performance.

(4) Good magnification performance

Compared with the parent material Li ₂ MnO ₃ of the Mn-based lithium-rich positive electrode material with lower conductivity, the Li _2-x Mo _y M _z O _3-u described in the present invention has high conductivity, and it is used as an electrode material or electrode The lithium-ion battery prepared by the additive material of the material has good rate performance.

(5) High security

The Li _2-x Mo _y M _z O _3-u described in the present invention has a stable structure, good compatibility with the electrolyte, no oxygen precipitation during charging and discharging, and improves the safety of the battery.

(6) High density. Mo is larger than Mn, so Li2 _{- xMoyMzO3 -u has} higher tap density and higher volumetric energy density than _Li2MnO3 , the parent material _of Mn-based lithium-rich cathode materials.

(7) Easy to synthesize. The synthesis method of Li _2-x Mo _y M _z O _3-u is simple, the process is easy to control, and the synthesis temperature is not high (not higher than 800 ° C), avoiding the high cost caused by high-temperature calcination, high production efficiency, suitable for industrial chemical production.

Description of drawings

FIG. 1 is the XRD pattern of Li ₂ MoO ₃ in Example 1.

FIG. 2 is an SEM photo of Li ₂ MoO ₃ in Example 1.

Fig. 3 is the first cycle charge and discharge curve of Li ₂ MoO ₃ in Example 2.

Detailed ways

The technical solution of the present invention is further described in detail through specific examples below, and the following examples are further illustrations of the present invention, but do not limit the scope of the present invention.

The synthetic method of described Li _2-x Mo _y M _z O _3-u comprises sol-gel method, co-precipitation method, hydrothermal method, solid phase method, combustion method, chemical vapor deposition method, physical vapor deposition method, pulse Laser deposition method, molecular beam epitaxy method, etc., but not limited to these methods described.

The main components of the lithium-ion battery in the embodiment of the present invention include three parts: positive electrode sheet, negative electrode sheet and separator. A porous separator is inserted between the positive and negative electrodes and filled with electrolyte. One end of the positive pole and the negative pole are respectively welded with lead wires and connected to the two ends of the mutually insulated battery case or the electrode post. The battery can be made into various shapes and specifications such as button type (single layer), cylindrical shape (multi-layer winding), square (lamination, Z-folding or multi-layer winding) from the above basic structure.

Electrode sheet preparation: uniformly mix the positive electrode active material of the present invention with conductive carbon black and polyvinylidene fluoride (PVDF) N-methylpyrrolidone (NMP) solution at normal temperature and pressure (the weight ratio of the three after drying is 80:10:10), made into a slurry and evenly coated on the aluminum foil current collector to obtain a coating with a thickness of 2 to 50 microns to become a positive electrode sheet. After drying the positive electrode sheet at 50°C, press it under a pressure of 20Kg/cm ² , and then cut it into a square with an area of 0.8×0.8 cm ² as the working electrode of the simulated battery. Dry the cut square pole piece in a vacuum oven at 100°C for 12 hours to become a pole piece.

A lithium metal sheet was used as the counter electrode (excess lithium) of the simulated battery (Swaglock battery).

Battery assembly: The basic components other than the electrolyte, such as working electrodes, counter electrodes, separators, battery shells, etc., are fully dried and then assembled into simulated batteries according to conventional methods. The electrode sheet prepared above is used as the positive electrode, lithium metal is used as the negative electrode (excess negative electrode), PP/PE porous membrane (Celgard2300) is used as the separator, and the electrolyte is a mixed organic solvent EC:DMC=1:1 (v:v) , the electrolyte is 1mol/L LiPF ₆ , and a lithium-ion battery is assembled in a glove box filled with Ar gas. Both H ₂ O content and O ₂ content in the glove box are less than 0.1ppm.

Example 1-4

Li ₂ MoO ₃ was synthesized by solid phase method. Firstly, Li ₂ CO ₃ and MoO ₃ were mixed according to the ratio of 1.05:1, and heated at 600° C. for 10 h to obtain Li ₂ MoO ₄ . The obtained Li ₂ MoO ₄ was placed in a tube furnace, and Ar/H ₂ mixed gas was passed through, and heat-treated at 600° C. for 24 hours to obtain Li ₂ MoO ₃ powder. Typical XRD and SEM results of the obtained material are shown in Figures 1 and 2, respectively.

The obtained Li ₂ MoO ₃ powder was used as an electrode active material to prepare a positive electrode sheet and assemble a battery. The electrode sheet preparation, battery components and battery assembly processes are as described above. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The first cycle charge and discharge curve of Li ₂ MoO ₃ in Example 2 is shown in FIG. 3 . The charging and discharging conditions and cycle results are listed in Table 1.

Example 5

Li ₂ MoO ₃ was synthesized by sol-gel method. Mix Li ₂ CO ₃ and MoO ₃ powders evenly according to the ratio of 1.05:1, and add them into 1mol/L citric acid aqueous solution. Stir for 12h. Then the mixed solution was heated to 80° C., stirred and dried for 24 hours to obtain a dry gel, which was placed in a muffle furnace for calcination at 450° C. for 2 hours to obtain a precursor. Finally, the precursor was placed in a tube furnace, flowed with Ar/H ₂ mixed gas, and heat-treated at 600°C for 24 hours to obtain Li ₂ MoO ₃ powder.

The obtained Li ₂ MoO ₃ powder was used as an electrode active material to prepare a positive electrode sheet and assemble a battery. Electrode sheet preparation, battery components and battery assembly are the same as above. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 6

Li ₂ MoO ₃ was synthesized by co-precipitation method. Firstly, (NH ₄ ) ₆ Mo ₇ O ₂₄ ·4H ₂ O was dissolved in an appropriate amount of deionized water and stirred, then Li ₂ CO ₃ solution was added and its pH value was adjusted to about 8 with ammonia water. The obtained precipitate was filtered, washed with deionized water, dried at 80° C. for 12 hours, and then calcined at 500° C. for 5 hours in a muffle furnace. The calcined product was ground and mixed evenly with Li ₂ CO ₃ at a ratio of 7.35:1, placed in a tube furnace with Ar/H ₂ mixed gas, and heat-treated at 600°C for 24 hours to obtain Li ₂ MoO ₃ powder.

The obtained Li ₂ MoO ₃ powder was used as an electrode active material to prepare a positive electrode sheet and assemble a battery. Electrode sheet preparation, battery components and battery assembly are the same as above. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 7

Li _1.90 MoO _2.95 was synthesized by solid phase method. Li ₂ CO ₃ and MoO ₃ were mixed according to the ratio of 0.9975:1, and heated at 600° C. for 10 h to obtain Li _1.90 MoO _3.95 . Then Li _1.90 MoO _3.95 was placed in a tube furnace, flowed with Ar/H ₂ mixed gas, and heat-treated at 600°C for 24 hours to obtain Li _1.90 MoO _2.95 powder.

The obtained Li _1.90 MoO _2.95 powder was used as an electrode active material to prepare a positive electrode sheet and assemble a battery. Electrode sheet preparation, battery components and battery assembly are the same as above. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 8

Li _1.80 MoO _2.90 was synthesized by sol-gel method. Firstly, Li ₂ CO ₃ and MoO ₃ were mixed according to the ratio of 0.945:1, and then the uniformly mixed powder was added into 1 mol/L citric acid aqueous solution, and stirred for 12 hours to disperse the mixture evenly. Then the mixed solution was heated to 80° C. and stirred for 24 h to obtain a xerogel. The dry gel was calcined at 450° C. for 2 h in a muffle furnace to obtain a precursor. Finally, the precursor was placed in a tube furnace with Ar/H ₂ mixed gas and heat-treated at 600 °C for 24 h to obtain Li _1.80 MoO _2.90 powder.

The obtained Li _1.80 MoO _2.90 powder was used as an electrode active material to prepare a positive electrode sheet and assemble a battery. Electrode sheet preparation, battery components and battery assembly are the same as above. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 9

Li _1.70 MoO _2.85 was synthesized by co-precipitation method. Firstly (NH ₄ ) ₆ Mo ₇ O ₂₄ ·4H ₂ O was dissolved in an appropriate amount of water and stirred, then Li ₂ CO ₃ solution was added and its pH value was adjusted to about 8 with ammonia water. The obtained precipitate was filtered, washed with deionized water, dried at 80° C. for 12 hours, and then calcined at 500° C. for 5 hours in a muffle furnace. The calcined product was ground and mixed evenly with Li ₂ CO ₃ at a ratio of 6.2475:1, placed in a tube furnace with Ar/H ₂ mixed gas, and heat-treated at 600°C for 24 hours to obtain Li _1.70 MoO _2.85 powder.

The obtained Li _1.70 MoO _2.85 powder was used as an electrode active material to prepare a positive electrode sheet and assemble a battery. Electrode sheet preparation, battery components and battery assembly are the same as above. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 10

Li _1.60 MoO _2.80 was synthesized by solid phase method. Li ₂ CO ₃ and MoO ₃ were mixed according to the ratio of 0.84:1, and heated at 600° C. for 10 h to obtain Li _1.60 MoO _3.80 . Then, the obtained Li _1.60 MoO _3.80 was placed in a tube furnace, flowed with Ar/H ₂ mixed gas, and heat-treated at 600° C. for 24 hours to obtain Li _1.60 MoO _2.80 powder.

The obtained Li _1.60 MoO _2.80 powder was used as the electrode active material to prepare the positive electrode sheet and assemble the battery. Electrode sheet preparation, battery components and battery assembly are the same as above. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 11

Li _1.50 MoO _2.75 was synthesized by solid phase method. Li ₂ CO ₃ and MoO ₃ were mixed according to the ratio of 0.75:1, and heated at 600° C. for 10 h to obtain Li _1.50 MoO _2.75 . Then, the obtained Li _1.50 MoO _2.75 was placed in a tube furnace, flowed with Ar/H ₂ mixed gas, and heat-treated at 600° C. for 24 hours to obtain Li _1.50 MoO _2.75 powder.

The obtained Li _1.50 MoO _2.75 powder was used as an electrode active material to prepare a positive electrode sheet and assemble a battery. Electrode sheet preparation, battery components and battery assembly are the same as above. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 12

Li ₂ MoO _3.85 was synthesized by solid phase method. Li ₂ CO ₃ and MoO ₃ were mixed according to the ratio of 1.05:1, and heated at 600° C. for 10 h to obtain Li ₂ MoO ₄ . Then, the obtained Li ₂ MoO ₄ was placed in a tube furnace, and Ar/H ₂ mixed gas was passed through, and heat-treated at 500° C. for 5 hours to obtain Li ₂ MoO _3.85 powder.

The obtained Li ₂ MoO _3.85 powder was used as an electrode active material to prepare a positive electrode sheet and assemble a battery. Electrode sheet preparation, battery components and battery assembly are the same as above. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 13

Li ₂ MoO _3.75 was synthesized by solid phase method. Li ₂ CO ₃ and MoO ₃ were mixed according to the ratio of 1.05:1, and heated at 600° C. for 10 h to obtain Li ₂ MoO ₄ . Then put the obtained Li ₂ MoO ₄ into a tube furnace, flow Ar/H ₂ mixed gas, and heat-treat at 500° C. for 10 h to obtain Li ₂ MoO _3.75 powder.

The obtained Li ₂ MoO _3.75 powder was used as an electrode active material to prepare a positive electrode sheet and assemble a battery. Electrode sheet preparation, battery components and battery assembly are the same as above. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 14

Li ₂ MoO _3.55 was synthesized by sol-gel method. Firstly, Li ₂ CO ₃ and MoO ₃ were mixed according to the ratio of 1.05:1, and then the uniformly mixed powder was added to 1 mol/L citric acid aqueous solution, and stirred for 12 hours to disperse the mixture evenly. Then the mixed solution was heated to 80° C. and stirred for 24 h to obtain a xerogel. The dry gel was calcined at 450° C. for 2 h in a muffle furnace to obtain a precursor. Finally, put the precursor in a tube furnace, flow Ar/H ₂ mixed gas, and heat-treat at 500° C. for 24 hours to obtain Li ₂ MoO _3.55 powder.

The obtained Li ₂ MoO _3.55 powder was used as an electrode active material to prepare a positive electrode sheet and assemble a battery. Electrode sheet preparation, battery components and battery assembly are the same as above. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 15

Li ₂ MoO _3.20 was synthesized by solid phase method. Li ₂ CO ₃ and MoO ₃ were mixed according to the ratio of 1.05:1, and heated at 600° C. for 10 h to obtain Li ₂ MoO ₄ . Then put the obtained Li ₂ MoO ₄ into a tube furnace, flow Ar/H ₂ mixed gas, heat-treat at 600° C. for 10 h, and obtain Li ₂ MoO _3.20 powder.

The obtained Li ₂ MoO _3.20 powder was used as an electrode active material to prepare a positive electrode sheet and assemble a battery. Electrode sheet preparation, battery components and battery assembly are the same as above. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 16

Li ₂ MoO _3.15 was synthesized by solid phase method. Li ₂ CO ₃ and MoO ₃ were mixed according to the ratio of 1.05:1, and heated at 600° C. for 10 h to obtain Li ₂ MoO ₄ . Then, the obtained Li ₂ MoO ₄ was placed in a tube furnace, and Ar/H ₂ mixed gas was passed through, and heat treated at 700° C. for 10 h to obtain Li ₂ MoO _3.15 powder.

The obtained Li ₂ MoO _3.15 powder was used as an electrode active material to prepare a positive electrode sheet and assemble a battery. Electrode sheet preparation, battery components and battery assembly are the same as above. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 17

Li ₂ MoO _3.10 was synthesized by co-precipitation method. Firstly (NH ₄ ) ₆ Mo ₇ O ₂₄ ·4H ₂ O was dissolved in an appropriate amount of water and stirred, then Li ₂ CO ₃ solution was added and its pH value was adjusted to about 8 with ammonia water. The resulting precipitate was filtered, washed with deionized water, dried at 80° C. for 12 hours, and then calcined at 500° C. for 5 hours in a muffle furnace. The calcined product was ground and mixed evenly with Li ₂ CO ₃ at a ratio of 7.35:1, placed in a tube furnace with Ar/H ₂ mixed gas, and heat-treated at 500°C for 50 hours to obtain Li ₂ MoO _3.10 powder.

The obtained Li ₂ MoO _3.10 powder was used as an electrode active material to prepare a positive electrode sheet and assemble a battery. Electrode sheet preparation, battery components and battery assembly are the same as above. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 18

Li ₂ MoO _2.95 was synthesized by solid phase method. Li ₂ CO ₃ and MoO ₃ were mixed according to the ratio of 1.05:1, and heated at 600° C. for 10 h to obtain Li ₂ MoO ₄ . Then the obtained Li ₂ MoO ₄ was placed in a tube furnace, flowed with Ar/H ₂ mixed gas, and heat-treated at 700° C. for 24 hours to obtain Li ₂ MoO _2.95 powder.

The obtained Li ₂ MoO _2.95 powder was used as an electrode active material to prepare a positive electrode sheet and assemble a battery. Electrode sheet preparation, battery components and battery assembly are the same as above. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 19

Li ₂ MoO _2.90 was synthesized by solid phase method. Li ₂ CO ₃ and MoO ₃ were mixed according to the ratio of 1.05:1, and heated at 600° C. for 10 h to obtain Li ₂ MoO ₄ . Then, the obtained Li ₂ MoO ₄ was placed in a tube furnace, and Ar/H ₂ mixed gas was passed through, and heat treated at 700° C. for 50 h to obtain Li ₂ MoO _2.90 powder.

The obtained Li ₂ MoO _2.90 powder was used as an electrode active material to prepare a positive electrode sheet and assemble a battery. Electrode sheet preparation, battery components and battery assembly are the same as above. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 20

Li _1.80 MoO ₃ was synthesized by solid phase method. Li ₂ CO ₃ and MoO ₃ were mixed according to the ratio of 0.945:1, and heated at 600° C. for 10 h to obtain Li _1.8 MoO ₄ . Then the obtained Li _1.8 MoO ₄ was placed in a tube furnace, and Ar/H ₂ mixed gas was passed through, and heat-treated at 650° C. for 48 hours to obtain Li _1.80 MoO ₃ powder.

The obtained Li _1.80 MoO ₃ powder was used as the electrode active material to prepare the positive electrode sheet and assemble the battery. Electrode sheet preparation, battery components and battery assembly are the same as above. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 21

Li _1.60 MoO ₃ was synthesized by solid phase method. Li ₂ CO ₃ and MoO ₃ were mixed according to the ratio of 1.05:1, and heated at 600° C. for 10 h to obtain Li ₂ MoO ₄ . Then the obtained Li ₂ MoO ₄ was placed in a tube furnace, and Ar/H ₂ mixed gas was passed through, and heat treated at 650° C. for 48 hours to obtain Li ₂ MoO ₃ powder. Finally, an appropriate amount of Li ₂ MoO ₃ powder was placed in 0.1 mol/L Br ₂ /CHCl ₃ solution, shielded from light and stirred for 24 hours to obtain Li _1.60 MoO ₃ powder.

The obtained Li _1.60 MoO ₃ powder was used as the electrode active material to prepare the positive electrode sheet and assemble the battery. Electrode sheet preparation, battery components and battery assembly are the same as above. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 22

Li _1.40 MoO ₃ was synthesized by solid phase method. Li ₂ CO ₃ and MoO ₃ were mixed according to the ratio of 1.05:1, and heated at 600° C. for 10 h to obtain Li ₂ MoO ₄ . Then the obtained Li ₂ MoO ₄ was placed in a tube furnace, and Ar/H ₂ mixed gas was passed through, and heat treated at 650° C. for 48 hours to obtain Li ₂ MoO ₃ powder. Finally, an appropriate amount of Li ₂ MoO ₃ powder was placed in 0.1 mol/L Br ₂ /CHCl ₃ solution, shielded from light and stirred for 36 hours to obtain Li _1.40 MoO ₃ powder.

The obtained Li _1.40 MoO ₃ powder was used as the electrode active material to prepare the positive electrode sheet and assemble the battery. Electrode sheet preparation, battery components and battery assembly are the same as above. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 23

Li _1.20 MoO ₃ was synthesized by solid phase method. Li ₂ CO ₃ and MoO ₃ were mixed according to the ratio of 1.05:1, and heated at 600° C. for 10 h to obtain Li ₂ MoO ₄ . Then the obtained Li ₂ MoO ₄ was placed in a tube furnace, and Ar/H ₂ mixed gas was passed through, and heat treated at 650° C. for 48 hours to obtain Li ₂ MoO ₃ powder. Finally, an appropriate amount of Li ₂ MoO ₃ powder was placed in 0.1 mol/L Br ₂ /CHCl ₃ solution, shielded from light and stirred for 48 hours to obtain Li _1.20 MoO ₃ powder.

The obtained Li _1.20 MoO ₃ powder was used as the electrode active material to prepare the positive electrode sheet and assemble the battery. Electrode sheet preparation, battery components and battery assembly are the same as above. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 24

Li _1.10 MoO ₃ was synthesized by solid phase method. Li ₂ CO ₃ and MoO ₃ were mixed according to the ratio of 1.05:1, and heated at 600° C. for 10 h to obtain Li ₂ MoO ₄ . Then the obtained Li ₂ MoO ₄ was placed in a tube furnace, and Ar/H ₂ mixed gas was passed through, and heat treated at 650° C. for 48 hours to obtain Li ₂ MoO ₃ powder. Finally, an appropriate amount of Li ₂ MoO ₃ powder was placed in 0.1 mol/L Br ₂ /CHCl ₃ solution, shielded from light and stirred for 55 h to obtain Li _1.10 MoO ₃ powder.

The obtained Li _1.10 MoO ₃ powder was used as the electrode active material to prepare the positive electrode sheet and assemble the battery. Electrode sheet preparation, battery components and battery assembly are the same as above. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 25

LiMoO ₃ was synthesized by solid phase method. Li ₂ CO ₃ and MoO ₃ were mixed according to the ratio of 1.05:1, and heated at 600° C. for 10 h to obtain Li ₂ MoO ₄ . Then the obtained Li ₂ MoO ₄ was placed in a tube furnace, and Ar/H ₂ mixed gas was passed through, and heat treated at 650° C. for 48 hours to obtain Li ₂ MoO ₃ powder. Finally, an appropriate amount of Li ₂ MoO ₃ powder was placed in 0.1 mol/L Br ₂ /CHCl ₃ solution, shielded from light and stirred for 60 h to obtain LiMoO ₃ powder.

The obtained LiMoO ₃ powder was used as the electrode active material to prepare the positive electrode sheet and assemble the battery. Electrode sheet preparation, battery components and battery assembly are the same as above. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 26

LiOH, MoO ₂ and MnO ₂ were weighed and mixed uniformly according to the molar ratio of 2.1:0.85:0.15, and then heat-treated in a tube furnace at 700°C for 24 hours in an argon atmosphere to obtain Li ₂ Mo _0.85 Mn _0.15 O ₃ powder. The pole piece was prepared with Li ₂ Mo _0.85 Mn _0.15 O ₃ and the battery was assembled. Electrode sheet preparation, battery components and battery assembly are the same as above. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 27

Weigh Li ₂ MoO ₂ and C ₂ NiO ₄ ·4H ₂ O according to the molar ratio of 0.9:0.1 and dissolve them in deionized water respectively, then add the two solutions into 1mol/L citric acid aqueous solution, stir and dry at 80°C for 12h Afterwards, dry at 80°C for 24 hours to obtain a xerogel. The dry gel was calcined at 450° C. for 2 h in a muffle furnace to obtain a precursor. Finally, put the precursor in a tube furnace, flow Ar/H ₂ mixed gas, and heat-treat at 600° C. for 24 hours to obtain Li ₂ Mo _0.9 Ni _0.1 O _2.9 powder. The resulting powder was used to prepare pole pieces and assemble batteries. Electrode sheet preparation, battery components and battery assembly are the same as above. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 28

Weigh Li ₂ CO ₃ , MoO ₃ , and Co(CH ₃ COO) ₂ ·4H ₂ O according to the molar ratio of 1.05:0.9:0.1 and dissolve in deionized water, add excess oxalic acid solution and place in a hydrothermal reaction kettle , kept at 180°C for 12 hours and then cooled naturally. Heat and stir the reaction product until the solvent is completely volatilized, then heat-treat the solid product at 450°C for 5h, then place it in a tube furnace with Ar/H ₂ mixed gas, and heat-treat at 700°C for 24h to obtain Li ₂ Mo _0.9 Co _0.1 O _2.95 powder. The prepared materials were used to prepare pole pieces and assemble batteries. Electrode sheet preparation, battery components and battery assembly are the same as above. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 29

LiOH, MoO ₂ and FeC ₂ O ₄ ·2H ₂ O were weighed and mixed uniformly according to the molar ratio of 2.1:0.9:0.1, and heat treated in a tube furnace at 700°C for 24 hours in an argon atmosphere to obtain Li ₂ Mo _0.9 Fe _0.1 O _2.9 powder. The synthesized Li ₂ Mo _0.9 Fe _0.1 O _2.9 was used to prepare pole pieces and assemble batteries. Electrode sheet preparation, battery components and battery assembly are the same as above. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 30

LiOH, MoO ₂ and Al ₂ (SO ₄ ) ₃ were weighed and mixed uniformly at a molar ratio of 2.1:0.9:0.05, and then heat-treated in a tube furnace at 800°C for 24 hours in an argon atmosphere to obtain Li ₂ Mo _0.9 Al _0.1 O _2.95 powder. The as-synthesized Li ₂ Mo _0.9 Al _0.1 O _2.95 was used to prepare pole pieces and assemble batteries. Electrode sheet preparation, battery components and battery assembly are the same as above. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 31

LiOH, MoO ₂ and ZrO ₂ were weighed and mixed uniformly at a molar ratio of 2.1:0.9:0.1, and then heat-treated in a tube furnace at 700°C for 24 hours in an argon atmosphere to obtain Li ₂ Mo _0.9 Zr _0.1 O ₃ powder. The prepared Li ₂ Mo _0.9 Zr _0.1 O ₃ was used to prepare pole pieces and assemble batteries. The as-synthesized Li ₂ Mo _0.9 Zr _0.1 O ₃ was used to prepare pole pieces and assemble batteries. Electrode sheet preparation, battery components and battery assembly are the same as above. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 32

Li ₂ CO ₃ , MoO ₃ , and Ti(OC ₄ H ₉ ) ₄ were weighed according to the molar ratio of 1.05:0.9:0.1 and dissolved in deionized water. After adding excess oxalic acid solution, they were placed in a hydrothermal reaction kettle. After 12 hours of heat preservation at 180°C, it was naturally cooled. The reaction product was heated and stirred until the solvent was completely volatilized, and the solid product was heat-treated at 450°C for 5h, then placed in a tube furnace with Ar/H ₂ mixed gas, and heat-treated at 700°C for 24h to obtain Li ₂ Mo _0.9 Ti _0.1 O ₃ powder. The prepared Li ₂ Mo _0.9 Ti _0.1 O ₃ was used to prepare pole pieces and assemble batteries. Electrode sheet preparation, battery components and battery assembly are the same as above. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 33

LiOH, MoO ₂ and SnO ₂ were weighed and mixed uniformly at a molar ratio of 2.1:0.8:0.2, and then heat-treated in a tube furnace at 800°C for 24 hours in an argon atmosphere to obtain Li ₂ Mo _0.8 Sn _0.2 O ₃ powder. The as-synthesized Li ₂ Mo _0.8 Sn _0.2 O ₃ was used to prepare pole pieces and assemble batteries. Electrode sheet preparation, battery components and battery assembly are the same as above. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 34

LiOH, MoO ₂ and RuO ₂ were weighed and mixed uniformly according to the molar ratio of 2.1:0.8:0.2, and then heat-treated in a tube furnace at 800°C for 24 hours in an argon atmosphere to obtain Li ₂ Mo _0.8 Ru _0.2 O ₃ powder. The as-synthesized Li ₂ Mo _0.8 Ru _0.2 O ₃ was used to prepare pole pieces and assemble batteries. Electrode sheet preparation, battery components and battery assembly are the same as above. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 35

LiOH, MoO ₂ and V ₂ O ₅ were weighed and mixed uniformly according to the molar ratio of 2.1:0.8:0.1, and then heat-treated in a tube furnace at 800°C for 24 hours in an argon-hydrogen atmosphere to obtain Li ₂ Mo _0.8 V _0.2 O ₃ powder. The as-synthesized Li ₂ Mo _0.8 V _0.2 O ₃ was used to prepare pole pieces and assemble batteries. Electrode sheet preparation, battery components and battery assembly are the same as above. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 36

LiOH, MoO ₂ and Ta ₂ O ₅ were weighed and mixed uniformly according to the molar ratio of 2.1:0.8:0.1, and then heat-treated in a tube furnace at 800°C for 24 hours in an argon atmosphere to obtain Li ₂ Mo _0.8 Ta _0.2 O _3.1 powder. The as-synthesized Li ₂ Mo _0.8 Ta _0.2 O _3.1 was used to prepare pole pieces and assemble batteries. Electrode sheet preparation, battery components and battery assembly are the same as above. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 37

LiOH, MoO ₂ and CaCO ₃ were weighed and mixed uniformly at a molar ratio of 2.1:0.8:0.2, and then heat-treated in a tube furnace at 800°C for 24 hours in an argon atmosphere to obtain Li ₂ Mo _0.8 Ca _0.2 O _2.8 powder. The as-synthesized Li ₂ Mo _0.8 Ca _0.2 O _2.8 was used to prepare pole pieces and assemble batteries. Electrode sheet preparation, battery components and battery assembly are the same as above. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 38

LiOH, MoO ₂ and Nb ₂ O ₅ were weighed and mixed uniformly at a molar ratio of 2.1:0.85:0.075, and then heat-treated in a tube furnace at 800°C for 24 hours in an argon atmosphere to obtain Li ₂ Mo _0.85 Nb _0.15 O _3.075 powder. The as-synthesized Li ₂ Mo _0.85 Nb _0.15 O _3.075 was used to prepare pole pieces and assemble batteries. Electrode sheet preparation, battery components and battery assembly are the same as above. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 39

LiOH, MoO ₂ and Cr ₂ O ₃ were weighed and mixed uniformly at a molar ratio of 2.1:0.9:0.05, and then heat-treated in a tube furnace at 800°C for 24 hours in an argon atmosphere to obtain Li ₂ Mo _0.9 Cr _0.1 O _2.95 powder. The as-synthesized Li ₂ Mo _0.9 Cr _0.1 O _2.95 was used to prepare pole pieces and assemble batteries. Electrode sheet preparation, battery components and battery assembly are the same as above. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 40

Li ₂ Mo _0.70 Mn _0.15 Co _0.10 Ni _0.15 O ₃ was synthesized by co-precipitation method. First, (NH ₄ ) ₆ Mo ₇ O ₂₄ ·4H ₂ O, Mn(CH ₃ COO) ₂ ·4H ₂ O, Co(CH ₃ COO) ₂ ·4H ₂ O and Ni(CH ₃ COO) ₂ ·4H ₂ O was dissolved in an appropriate amount of water at a molar ratio of 0.1:0.15:0.1:0.15 and stirred, then Li ₂ CO ₃ solution was added and its pH value was adjusted to about 8 with ammonia water. The resulting precipitate was filtered, washed with deionized water, dried at 80° C. for 12 hours, and then calcined at 500° C. for 5 hours in a muffle furnace. Grind the calcined product and mix it evenly with Li ₂ CO ₃ at a ratio of 7.35:1, place it in a tube furnace, pass Ar/H ₂ mixed gas, and heat-treat at 500°C for 50 hours to obtain Li ₂ Mo _0.70 Mn _0.15 Co _0.10 Ni _0.15 O ₃ powder. The as-synthesized Li ₂ Mo _0.70 Mn _0.15 Co _0.10 Ni _0.15 O ₃ was used to prepare pole pieces and assemble batteries. Electrode sheet preparation, battery components and battery assembly are the same as above. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 41

MoO ₃ and urea were weighed at a molar ratio of 1:0.1 and added to deionized water, stirred evenly, placed in a hydrothermal reaction kettle, kept at 180°C for 12 hours, and then cooled naturally. The reaction product was heated and stirred until the solvent was completely volatilized, and the solid product was mixed with Li ₂ CO ₃ at a molar ratio of 1.05:1, placed in a tube furnace with Ar/H ₂ mixed gas, and heat-treated at 700°C for 24 hours to obtain N Doped _{Li2MoO3 powder} . The as-prepared N-doped Li ₂ MoO ₃ was used to prepare pole pieces and assemble batteries. Electrode sheet preparation, battery components and battery assembly are the same as above. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 42

Li ₂ MoO ₃ prepared in Example 1 was uniformly mixed with an appropriate amount of NH ₄ F , placed in a tube furnace, passed through Ar/H ₂ mixed gas, and heat-treated at 450° C. for 5 hours to obtain Li ₂ MoO _2.9 F _0.2 . Li ₂ MoO _2.9 F _0.2 was used to prepare pole pieces and assemble batteries. Electrode sheet preparation, battery components and battery assembly are the same as above. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 43

Li ₂ CO ₃ , MoO ₂ and Li ₃ PO ₄ ·1/2H ₂ O were mixed uniformly according to the molar ratio of 0.9:1:0.1, and then heat-treated in a tube furnace at 700°C for 24 hours in an argon atmosphere to obtain Li ₂ MoO _2.85 ( PO ₄ ) _0.1 Powder. Li ₂ MoO _2.85 (PO ₄ ) _0.1 powder was used to prepare pole pieces and assemble batteries. Electrode sheet preparation, battery components and battery assembly are the same as above. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 44

LiOH, NiO and MoO ₂ were weighed and mixed uniformly at a molar ratio of 1.8:0.1:1, and then heat-treated in a tube furnace at 700°C for 24 hours in an argon atmosphere to obtain Li _1.8 Ni _0.1 MoO ₃ powder. The as-prepared Li _1.8 Ni _0.1 MoO ₃ was used to prepare pole pieces and assemble batteries. Electrode sheet preparation, battery components and battery assembly are the same as above. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 45

LiOH, Co(CH ₃ COO) ₂ 4H ₂ O and MoO ₂ were weighed and mixed uniformly at a molar ratio of 1.7:0.1:1, and then heat-treated in a tube furnace at 700°C for 24 hours in an argon atmosphere to obtain Li _1.7 Co _{0.1 MoO3} powder. The as-prepared Li _1.7 Co _0.1 MoO ₃ was used to prepare pole pieces and assemble batteries. Electrode sheet preparation, battery components and battery assembly are the same as above. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 46

LiOH, ZnCO ₃ and MoO ₂ were weighed and mixed uniformly at a molar ratio of 1.9:0.05:1, and then heat-treated in a tube furnace at 700°C for 24 hours in an argon atmosphere to obtain Li _1.9 Zn _0.05 MoO ₃ powder. The as-prepared Li _1.9 Zn _0.05 MoO ₃ was used to prepare pole pieces and assemble batteries. Electrode sheet preparation, battery components and battery assembly are the same as above. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 47

LiOH, NaOH and MoO ₂ were weighed and mixed uniformly at a molar ratio of 1.8:0.2:1, and then heat-treated in a tube furnace at 700°C for 24 hours in an argon atmosphere to obtain Li _1.8 Na _0.2 MoO ₃ powder. The as-prepared Li _1.8 Na _0.2 MoO ₃ was used to prepare pole pieces and assemble batteries. Electrode sheet preparation, battery components and battery assembly are the same as above. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 48

NaOH and MoO ₂ were weighed and mixed uniformly at a molar ratio of 2:1, and then heat-treated in a tube furnace at 700°C for 24 hours in an argon atmosphere to obtain Na ₂ MoO ₃ powder. The prepared Na ₂ MoO ₃ powder was used to prepare pole pieces and assemble batteries. Electrode sheet preparation and battery components are the same as above. The battery assembly process is: the basic components other than the electrolyte, such as the working electrode, counter electrode, separator, battery case, etc., are fully dried and then assembled into a simulated battery according to the conventional method. The prepared electrode sheet is used as the positive electrode, the metal Na is used as the negative electrode (the negative electrode is excessive), the PP/PE porous membrane (Celgard2300) is used as the separator, and the electrolyte is a mixed organic solvent EC:DMC=1:1(v:v) , the electrolyte is 1mol/L NaPF ₆ , and a sodium-ion battery is assembled in a glove box filled with Ar gas. Both H ₂ O content and O ₂ content in the glove box are less than 0.1ppm. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 49

NaOH, LiOH and MoO ₂ were weighed and mixed uniformly at a molar ratio of 1.8:0.2:1, and then heat-treated in a tube furnace at 700°C for 24 hours in an argon atmosphere to obtain Na _1.8 Li _0.2 MoO ₃ powder. The as-prepared Na _1.8 Li _0.2 MoO ₃ was used to prepare pole pieces and assemble batteries. The electrode sheet preparation, battery components and battery assembly are the same as those described in Example 48. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 50

NaOH, MoO ₂ and MnO ₂ were weighed and mixed uniformly at a molar ratio of 2:0.9:0.1, and then heat-treated in a tube furnace at 700°C for 24 hours in an argon atmosphere to obtain Na ₂ Mo _0.9 Mn _0.1 O ₃ powder. The prepared Na ₂ Mo _0.9 Mn _0.1 O ₃ was used to prepare pole pieces and assemble batteries. The electrode sheet preparation, battery components and battery assembly are the same as those described in Example 48. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 51

After weighing NaOH and MoO ₂ according to the molar ratio of 2:1 and mixing them uniformly, heat treatment in a tube furnace at 700°C for 24 hours in an argon atmosphere to obtain Na ₂ MoO ₃ powder, and then mix it with an appropriate amount of NH ₄ F and place In a tube furnace, pass an argon-hydrogen mixture, and heat-treat at 450°C for 5 hours to obtain Na ₂ MoO _2.9 F _0.2 . The prepared Na ₂ MoO _2.9 F _0.2 was used to prepare pole pieces and assemble batteries. The electrode sheet preparation, battery components and battery assembly are the same as those described in Example 48. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 52

After weighing MgO and MoO ₂ according to a molar ratio of 1:1 and mixing them uniformly, heat treatment at 700°C for 24 hours in a tube furnace in an argon atmosphere to obtain MgMoO ₃ powder. The as-prepared _MgMoO3 was used to prepare pole pieces and assemble batteries. Electrode sheet preparation and battery components are the same as above. The battery assembly process is: the basic components other than the electrolyte, such as the working electrode, counter electrode, separator, battery case, etc., are fully dried and then assembled into a simulated battery according to the conventional method. The prepared electrode sheet is used as the positive electrode, the metal Mg is used as the negative electrode (the negative electrode is excessive), the PP/PE porous membrane (Celgard2300) is used as the separator, the electrolyte is Mg(AlCl ₂ BuEt) ₂ /THF, and the electrode is filled with Ar gas. Magnesium-ion batteries were assembled in the glove box. Both H ₂ O content and O ₂ content in the glove box are less than 0.1ppm. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 53

MgO, ZnCO ₃ and MoO ₂ were weighed and mixed uniformly at a molar ratio of 0.9:0.1:1, and then heat-treated in a tube furnace at 700°C for 24 hours in an argon atmosphere to obtain Mg _0.9 Zn _0.1 MoO ₃ powder. The as-prepared Mg _0.9 Zn _0.1 MoO ₃ was used to prepare pole pieces and assemble batteries. The electrode sheet preparation, battery components and battery assembly are the same as those described in Example 52. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 54

MgO, MoO ₂ and MnO ₂ were weighed and mixed uniformly at a molar ratio of 1:0.9:0.1, and then heat-treated in a tube furnace at 700°C for 24 hours in an argon atmosphere to obtain MgMo _0.9 Mn _0.1 O ₃ powder. The as-prepared MgMo _0.9 Mn _0.1 O ₃ was used to prepare pole pieces and assemble batteries. The electrode sheet preparation, battery components and battery assembly are the same as those described in Example 52. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 55

MgO, LiF, and MoO ₂ were weighed and mixed uniformly at a molar ratio of 0.8:0.2:1, and then heat-treated in a tube furnace at 700°C for 24 hours in an argon atmosphere to obtain Mg _0.8 Li _0.2 MoO _2.8 F _0.2 powder. The prepared Mg _0.8 Li _0.2 MoO _2.8 F _0.2 powder was used to prepare pole pieces and assemble batteries. The electrode sheet preparation, battery components and battery assembly are the same as those described in Example 52. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 1.

Example 56-66

Prepare Li ₂ MoO ₃ according to the method in Example 1, and combine it with LiCoO ₂ , LiNiO ₂ , LiFePO ₄ , LiNi _0.8 Co _0.2 O ₂ , LiMn ₂ O ₄ , LiNi _1/3 Co _1/3 Mn _1/3 O ₂ , LiNi _0.4 Co _0.2 Mn _0.4 O ₂ , LiNi _0.85 Co _0.15 O ₂ , Li ₂ MnO ₃ , 0.5Li ₂ MnO ₃ 0.5LiNi _1/3 Co _1/3 Mn _1/3 O ₂ , LiNi _0.5 Mn _1.5 O ₄ was mixed according to the mass ratio of 1:9 and used as the positive electrode active material to prepare the pole piece and assemble the battery. The electrode sheet preparation, battery components and battery assembly are the same as those described in Example 1. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 2.

Examples 67-77

Prepare Li ₂ Mo _0.85 Mn _0.15 O ₃ according to the method in Example 26, and combine it with LiCoO ₂ , LiNiO ₂ , LiFePO ₄ , LiNi _0.8 Co _0.2 O ₂ , LiMn ₂ O ₄ , LiNi _1/3 Co _1/3 Mn _1/3 O ₂ , LiNi _0.4 Co _0.2 Mn _0.4 O ₂ , LiNi _0.85 Co _0.15 O ₂ , Li ₂ MnO ₃ , 0.5Li ₂ MnO ₃ 0.5LiNi _1/3 Co _1/3 Mn _1/3 O ₂ , LiNi _0.5 Mn _1.5 O ₂ was mixed according to the mass ratio of 3:7 and used as the positive electrode active material to prepare the pole piece and assemble the battery. The electrode sheet preparation, battery components and battery assembly are the same as those described in Example 1. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 2.

Examples 78-88

Prepare Li _1.90 MoO _2.95 according to the method in Example 07, and combine it with LiCoO ₂ , LiNiO ₂ , LiFePO ₄ , LiNi _0.8 Co _0.2 O ₂ , LiMn ₂ O ₄ , LiNi _1/3 Co _1/3 Mn _1/3 O ₂ , LiNi _0.4 Co _0.2 Mn _0.4 O ₂ , LiNi _0.85 Co _0.15 O ₂ , Li ₂ MnO ₃ , 0.5Li ₂ MnO ₃ 0.5LiNi _1/3 Co _1/3 Mn _1/3 O ₂ , LiNi _0.5 Mn _1.5 O ₂ was mixed according to the mass ratio of 5:5 and used as the positive electrode active material to prepare the pole piece and assemble the battery. The electrode sheet preparation, battery components and battery assembly are the same as those described in Example 1. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 2.

Examples 89-99

Prepare Li ₂ Mo _0.70 Mn _0.15 Co _0.10 Ni _0.15 O ₃ according to the method in Example 40, and combine it with LiCoO ₂ , LiNiO ₂ , LiFePO ₄ , LiNi _0.8 Co _0.2 O ₂ , LiMn ₂ O ₄ , LiNi _1/3 Co _1/3 Mn _1/3 O ₂ , LiNi _0.4 Co _0.2 Mn _0.4 O ₂ , LiNi _0.85 Co _0.15 O ₂ , Li ₂ MnO ₃ , 0.5Li ₂ MnO ₃ 0.5LiNi _1/3 Co _1/3 Mn _{1/ 3} O ₂ , LiNi _0.5 Mn _1.5 O ₂ were mixed according to a mass ratio of 7:3 and then used as positive active materials to prepare pole pieces and assemble batteries. The electrode sheet preparation, battery components and battery assembly are the same as those described in Example 1. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 2.

Examples 100-110

Prepare Li _1.8 Ni _0.1 MoO ₃ according to the method in Example 44, and combine it with LiCoO ₂ , LiNiO ₂ , LiFePO ₄ , LiNi _0.8 Co _0.2 O ₂ , LiMn ₂ O ₄ , LiNi _1/3 Co _1/3 Mn _{1 /3} O ₂ , LiNi _0.4 Co _0.2 Mn _0.4 O ₂ , LiNi _0.85 Co _0.15 O ₂ , Li ₂ MnO ₃ , 0.5Li ₂ MnO ₃ 0.5LiNi _1/3 Co _1/3 Mn _1/3 O ₂ , LiNi _0.5 Mn _1.5 O ₂ was mixed according to the mass ratio of 9:1 and used as the positive electrode active material to prepare the pole piece and assemble the battery. The electrode sheet preparation, battery components and battery assembly are the same as those described in Example 1. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 2.

Example 111

Li ₂ CO ₃ and MoO ₃ were mixed according to the ratio of 1.05:1, and heated at 600° C. for 10 h to obtain Li ₂ MoO ₄ . Mix it with 5wt% graphene evenly, put it in a tube furnace, blow it with argon, and heat it at 600°C for 24h to obtain C-coated Li ₂ MoO ₃ powder. The coated material is used to prepare pole pieces and assemble the battery. The electrode sheet preparation, battery components and battery assembly are the same as those described in Example 1. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 2.

Example 112

Li ₂ MoO ₃ was prepared according to the method in Example 1, and coated with Al ₂ O ₃ . Appropriate amounts of Al ₂ (SO ₄ ) ₃ and NaOH were dissolved in deionized water, respectively. Disperse Li ₂ MoO ₃ in an aqueous solution of Al ₂ (SO ₄ ) ₃ , and then drop NaOH solution into it. The mixed solution was stirred at 80°C for 5h, cleaned with deionized water, dried in an oven at 80°C for 12h, placed in a tube furnace with argon, and heat-treated at 600°C for 2h to obtain Al ₂ O ₃ coated Li ₂ MoO ₃ . The coated material is used to prepare pole pieces and assemble the battery. The electrode sheet preparation, battery components and battery assembly are the same as those described in Example 1. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 2.

Example 113

Li ₂ MoO ₃ was prepared according to the method in Example 1 and coated with MgO. Appropriate amounts of _MgCl2 and NaOH were dissolved in deionized water, respectively. _{Disperse Li2MoO3} in an aqueous solution of _MgCl2 , and then drop NaOH solution into it. The mixed solution was stirred at 80°C for 5h, cleaned with deionized water, dried in an oven at 80°C for 12h, then placed in a tube furnace with argon, and heat-treated at 600°C for 2h to obtain MgO-coated Li ₂ MoO ₃ . The coated material is used to prepare pole pieces and assemble the battery. The electrode sheet preparation, battery components and battery assembly are the same as those described in Example 1. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 2.

Example 114

Li ₂ MoO ₃ was prepared according to the method in Example 1, and it was coated with TiO ₂ . Li ₂ MoO ₃ was dispersed in N-methylpyrrolidone (NMP), and then Ti(OC ₄ H ₉ ) ₄ was dropped into NMP. After the mixed solution was stirred at 60° C. for 24 h, it was placed in a tube furnace and argon was blown, and it was heat-treated at 450° C. for 5 h to obtain Li ₂ MoO ₃ coated with TiO ₂ . The coated material is used to prepare pole pieces and assemble the battery. The electrode sheet preparation, battery components and battery assembly are the same as those described in Example 1. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 2.

Example 115

Li ₂ MoO ₃ was prepared according to the method in Example 1, and it was coated with ZrO ₂ . A layer of ZrO ₂ is deposited on the surface of Li ₂ MoO ₃ powder under the condition of 120° C. by ALD to obtain Li ₂ MoO _{3 coated with ZrO 2 .} The coated material is used to prepare pole pieces and assemble the battery. The electrode sheet preparation, battery components and battery assembly are the same as those described in Example 1. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 2.

Example 116

Li ₂ MoO ₃ was prepared according to the method in Example 1, and coated with Al(OH) ₃ . Dissolve an appropriate amount of Al(C ₃ H ₇ O) ₃ in ethanol, then disperse Li ₂ MoO ₃ in the ethanol solution of Al(C ₃ H ₇ O) ₃ , stir at 80°C for 5 h, remove excess Ionized water was added to the solution, and the reaction product was dried at 110° C. for 24 hours to obtain Al(OH) ₃ coated Li ₂ MoO ₃ . The coated material is used to prepare pole pieces and assemble the battery. The electrode sheet preparation, battery components and battery assembly are the same as those described in Example 1. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 2.

Example 117

Li ₂ MoO ₃ was prepared according to the method in Example 1, and coated with AlPO ₄ . Appropriate amounts of (NH ₄ ) ₂ HPO ₄ and Al(NO ₃ ) ₃ were dissolved in deionized water, respectively. Disperse Li ₂ MoO ₃ in an aqueous solution of Al(NO ₃ ) ₃ , and then drop in (NH ₄ ) ₂ HPO ₄ solution. After the mixed solution was stirred at 80° C. for 5 h, it was washed with deionized water. After being dried in an oven at 80°C for 12 hours, placed in a tube furnace with argon, and heat-treated at 700°C for 5 hours to obtain Li ₂ MoO ₃ coated with AlPO ₄ . The coated material is used to prepare pole pieces and assemble the battery. The electrode sheet preparation, battery components and battery assembly are the same as those described in Example 1. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 2.

Example 118

Li ₂ MoO ₃ was prepared according to the method in Example 1, and coated with Co ₃ (PO ₄ ) ₂ . Appropriate amounts of (NH ₄ ) ₂ HPO ₄ and Co(NO ₃ ) ₂ ·6H ₂ O were dissolved in deionized water, respectively. Disperse Li ₂ MoO ₃ in an aqueous solution of Co(NO ₃ ) ₂ ·6H ₂ O, and then drop in (NH ₄ ) ₂ HPO ₄ solution. After the mixed solution was stirred at 80° C. for 5 h, it was washed with deionized water. After being dried in an oven at 80°C for 12 hours, it was placed in a tube furnace with argon gas and heat-treated at 700°C for 5 hours to obtain Li ₂ MoO ₃ coated with Co ₃ (PO ₄ ) ₂ . The coated material is used to prepare pole pieces and assemble the battery. The electrode sheet preparation, battery components and battery assembly are the same as those described in Example 1. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 2.

Example 119

Li ₂ MoO ₃ was prepared according to the method in Example 1, and coated with AlF ₃ . Appropriate amounts of NH ₄ F and Al(NO ₃ ) ₃ were dissolved in deionized water, respectively. Disperse Li ₂ MoO ₃ in an aqueous solution of Al(NO ₃ ) ₃ , and then drop in NH ₄ F solution. After the mixed solution was stirred at 80° C. for 5 h, it was washed with deionized water. After drying in an oven at 80°C for 12 hours, place it in a tube furnace with argon, and heat-treat at 400°C for 5 hours to obtain Li ₂ MoO ₃ coated with AlF ₃ . The coated material is used to prepare pole pieces and assemble the battery. The electrode sheet preparation, battery components and battery assembly are the same as those described in Example 1. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 2.

Example 120

Li ₂ MoO ₃ was prepared according to the method in Example 5, and it was coated with YF ₃ . Appropriate amounts of NH ₄ F and Y(NO ₃ ) ₃ were dissolved in deionized water, respectively. Disperse Li ₂ MoO ₃ in an aqueous solution of Y(NO ₃ ) ₃ , and then drop in NH ₄ F solution. After the mixed solution was stirred at 80° C. for 5 h, it was washed with deionized water. After being dried in an oven at 80°C for 12 hours, it was placed in a tube furnace with argon, and heat-treated at 400°C for 5 hours to obtain Li ₂ MoO ₃ coated with YF ₃ . The coated material is used to prepare pole pieces and assemble the battery. The electrode sheet preparation, battery components and battery assembly are the same as those described in Example 1. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 2.

Example 121

Li ₂ MoO ₃ was prepared according to the method in Example 9, and coated with PPy. Ultrasound the prepared Li ₂ MoO ₃ in deionized water for 0.5h, add an appropriate amount of sodium p-benzoate and pyrrole monomer solution into the ultrasonic solution, and then drop the FeCl ₃ solution (Py:Fe=1:1) into the mixing The solution was stirred in an ice bath for 8 hours, washed with deionized water and ethanol, and dried in an oven at 80° C. for 12 hours to obtain PPy-coated Li ₂ MoO ₃ . The coated material is used to prepare pole pieces and assemble the battery. The electrode sheet preparation, battery components and battery assembly are the same as those described in Example 1. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 2.

Example 122

Mix the material prepared in Example 61 with an appropriate amount of glucose solution, pour it into a hydrothermal reaction kettle, and conduct a hydrothermal reaction at 160°C for 4 hours, centrifuge the obtained product and wash it three times with deionized water, dry it at 60°C and place it in a tubular Furnace with argon gas, heat treatment at 500°C for 6h to obtain C-coated Li ₂ MoO ₃ /LiNi _1/3 Co _1/3 Mn _1/3 O ₂ powder. The coated material is used to prepare pole pieces and assemble the battery. The electrode sheet preparation, battery components and battery assembly are the same as those described in Example 1. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 2.

Examples 123-126

The materials in Example 61 were respectively coated with Al ₂ O ₃ , MgO, TiO ₂ , and ZrO ₂ according to the method of Examples 112-115. The coated material is prepared into a pole piece and assembled into a battery. The electrode sheet preparation, battery components and battery assembly are the same as those described in Example 1. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 2.

Examples 127-132

Li _1.8 Ni _0.1 MoO ₃ /Li ₂ MnO ₃ was synthesized by the method in Example 108, and then Al(OH) ₃ , AlPO ₄ , Co ₃ (PO ₄ ) ₂ , AlF ₃ , YF ₃ , PPy coating. The coated material is prepared into a pole piece and assembled into a battery. The electrode sheet preparation, battery components and battery assembly are the same as those described in Example 1. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 2.

Example 133

Li ₂ MoO ₃ was synthesized by the method in Example 1. Li ₂ MoO ₃ coated with LiCoO ₂ was prepared by co-precipitation method. Add Li ₂ MoO ₃ powder into the solution in which Co(NO ₃ ) ₂ ·6H ₂ O is dissolved, stir evenly, then add Li ₂ CO ₃ solution and adjust the pH value of the solution to about 8 with ammonia water. The resulting precipitate was filtered and cleaned with deionized water. After drying at 80°C for 12 h, the product was ground and mixed with Li ₂ CO ₃ (Li:Co=2:1), placed in a sealed quartz tube, and then The quartz tube was placed in a muffle furnace for heat treatment at 800° C. for 12 hours to obtain LiCoO ₂ coated Li ₂ MoO ₃ powder. The coated material is prepared into a pole piece and assembled into a battery. The electrode sheet preparation, battery components and battery assembly are the same as those described in Example 1. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 2.

Example 134

Li ₂ MoO ₃ was synthesized by the method in Example 1. Li ₂ MoO ₃ coated with LiNiO ₂ was prepared by co-precipitation method. Add Li ₂ MoO ₃ powder into the solution dissolved in Ni(NO ₃ ) ₂ ·6H ₂ O, stir evenly, add Li ₂ CO ₃ solution and adjust the pH value of the solution to about 8 with ammonia water. The resulting precipitate was filtered and cleaned with deionized water. After drying at 80°C for 12 h, the product was ground and mixed with Li ₂ CO ₃ (Li:Ni=2:1), placed in a sealed quartz tube, and then The quartz tube was placed in a muffle furnace for heat treatment at 700° C. for 12 hours to obtain LiNiO ₂ coated Li ₂ MoO ₃ powder. The coated material is prepared into a pole piece and assembled into a battery. The electrode sheet preparation, battery components and battery assembly are the same as those described in Example 1. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 2.

Example 135

Li ₂ MoO ₃ was synthesized by the method in Example 1. Li ₂ MoO ₃ coated with LiFePO ₄ was prepared by sol-gel method. Add Li ₂ MoO ₃ powder into the solution dissolved in LiNO ₃ , Fe(NO ₃ ) ₃ 9H ₂ O, NH ₄ H ₂ PO ₄ , C ₆ H ₈ O ₇ (Li:Fe:P=1:1: 1), and adjust the pH value of the solution to about 6 with dilute nitric acid. The solution was heated and stirred until a xerogel was obtained, and then the product was calcined in a muffle furnace at 800° C. for 6 hours to obtain the final coated product. The coated material is prepared into a pole piece and assembled into a battery. The electrode sheet preparation, battery components and battery assembly are the same as those described in Example 1. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 2.

Example 136

Li ₂ MoO ₃ was synthesized by the method in Example 1. Li ₂ MoO ₃ coated with LiNi _0.8 Co _0.2 O ₂ was prepared by coprecipitation method. Add Li ₂ MoO ₃ powder into the solution dissolved in Ni(NO ₃ ) ₂ 6H ₂ O and Co(NO ₃ ) ₂ 6H ₂ O, stir evenly, add Li ₂ CO ₃ solution and adjust the pH of the solution with ammonia water value to around 8. The resulting precipitate was filtered and cleaned with deionized water. After drying at 80°C for 12 hours, the product was ground and mixed with Li ₂ CO ₃ (Li:Ni:Co=2:0.8:0.2), and placed in a sealed Then put the quartz tube in a muffle furnace for heat treatment at 800° C. for 12 hours to obtain LiNi _0.8 Co _0.2 O ₂ coated Li ₂ MoO ₃ powder. The coated material is prepared into a pole piece and assembled into a battery. The electrode sheet preparation, battery components and battery assembly are the same as those described in Example 1. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 2.

Example 137

Li ₂ MoO ₃ was synthesized by the method in Example 1. Li ₂ MoO ₃ coated with LiMn ₂ O ₄ was prepared by Rongming gel method. Add Li ₂ MoO ₃ powder into the solution of LiNO ₃ , Mn(NO ₃ ) ₂ and C ₆ H ₈ O ₇ (Li:Mn=1:2), heat and stir at 140°C until dry gel is obtained, then The product was calcined at 800° C. for 6 h in a muffle furnace to obtain the final coated product. The coated material is prepared into a pole piece and assembled into a battery. The electrode sheet preparation, battery components and battery assembly are the same as those described in Example 1. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 2.

Examples 138-143

LiNi _1/3 Co _1/3 Mn _1/3 O ₂ , LiNi _0.4 Co _0.2 Mn _0.4 O ₂ , LiNi _0.85 Co _0.15 O ₂ , Li ₂ MnO ₃ , 0.5Li ₂ MnO ₃ 0.5LiNi _1/3 Co _{1 /3} Mn _1/3 O ₂ and LiNi _0.5 Mn _1.5 O ₂ were respectively coated with Li ₂ MoO ₃ . Dissolve (NH ₄ ) ₆ Mo ₇ O ₂₄ ·4H ₂ O in an appropriate amount of water and stir, then add LiNi _1/3 Co _1/3 Mn _1/3 O ₂ , LiNi _0.4 Co _0.2 Mn _0.4 O ₂ , LiNi _0.85 Co _0.15 O ₂ , Li ₂ MnO ₃ , 0.5Li ₂ MnO ₃ 0.5LiNi _1/3 Co _1/3 Mn _1/3 O ₂ , LiNi _0.5 Mn _1.5 O ₂ , after stirring for 2 hours, add the Li ₂ CO ₃ solution And adjust its pH value to about 8 with ammonia water. The obtained precipitates were filtered separately, washed with deionized water, dried at 80° C. for 12 hours, and then calcined in a muffle furnace at 500° C. for 5 hours. The calcined product was ground and mixed evenly with Li ₂ CO ₃ at a ratio of 7.35:1, placed in a tube furnace, blown with argon, and heat-treated at 500°C for 50 hours to obtain the final coated product. The coated material is prepared into a pole piece and assembled into a battery. The electrode sheet preparation, battery components and battery assembly are the same as those described in Example 1. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 2.

Examples 144-150

The materials in Examples 144-150 were prepared using the solid phase method. Li ₂ CO ₃ , MoO ₃ , MnCO ₃ , Co(CH ₃ CO) ₂ 4H ₂ O and Ni(CH ₃ COO) ₂ 4H ₂ O, ZrO ₂ are dosed according to the stoichiometric ratio, wherein the molar amount of Li Excessive 1%-10%. After mixing the raw materials evenly, place them in a muffle furnace for heat treatment at 800°C for 24h. The obtained reaction product is prepared into a pole piece and assembled into a battery. The electrode sheet preparation, battery components and battery assembly are the same as those described in Example 1. After the battery was left to stand for 4 hours, the battery was charged and discharged with a constant current (10mA/g) using a LAND tester. The charging and discharging conditions and cycle results are listed in Table 2.

Table 1. The electrochemical cycle performance of Li _2-x Mo _y M _z O _3-u in each embodiment

Table 2. Electrochemical cycle performance of Li ₂ MoO ₃ combined with other electrode materials in each embodiment

Claims (2)

1. Secondary battery electrode material lithium molybdate, its chemical formula is Li _2-x Mo _y M _z O _3-u , where, -2≤x≤2, 0<y≤5, 0≤z≤9, -9 ≤u≤3, M contains selected from C, N, F, Na, Mg, Al, Si, P, S, Cl, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu , Zn, Ga, Ge, As, Se, Br, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Cd, In, Sn, Sb, Te, I, Cs, Ba, Ta , W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, Po, At, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb , one of Lu or a combination of them. 2. the electrode material as claimed in claim 1, described Li _2-x Mo _y M _z O _3-u can be used for secondary lithium battery, lithium ion battery, secondary sodium battery, sodium ion as the positive electrode material of secondary battery batteries, magnesium-ion batteries, and lithium-sulfur batteries.