CN105576231A - High-voltage lithium oil battery positive electrode material with spinel structure and preparation method of high-voltage lithium oil battery positive electrode material - Google Patents

Abstract

The invention relates to a high-voltage lithium-ion battery cathode material with a spinel structure and a preparation method thereof. The general chemical formula of the lithium-ion battery cathode material is Li[M1 _a Ni _b M2 _c Mn _1.5 ]O ₄ , where 0.025≤ a≤0.05, 0.4≤b≤0.45, 0.025≤c≤0.05, M1 and M2 are one or more of Mg, Zn, Fe, Li, Al, Cr, Co, first weigh the soluble Lithium source, nickel source, manganese source, M1 salt and M2 salt to prepare a gel, then heat and dry the gel, burn twice, and cool to room temperature to obtain a lithium ion battery positive electrode material. The preparation method of the present invention is simple, and the steps are easy to operate. The lithium-rich LiNi _0.5 Mn _1.5 O ₄ positive electrode material formed by doping Li and other metal elements is used. The prepared positive electrode material has uniform particles, a spinel structure, and high crystallinity. , The stability of the material is improved, the introduced doping elements can effectively improve the cycle and rate performance of the material, the nickel content is reduced, the production cost is reduced, and the pollution to the environment is also reduced.

Description

A high-voltage lithium-ion battery positive electrode material with spinel structure and preparation method thereof

technical field

The invention relates to a high-voltage lithium-ion battery cathode material with a spinel structure and a preparation method thereof, belonging to the technical field of lithium-ion batteries.

Background technique

Lithium-ion batteries have been widely used in various mobile electronic devices and high-energy devices, such as smartphones, notebooks, and electric vehicles, due to their advantages such as large specific energy, low self-discharge, long cycle life, and good safety performance.

Among many cathode materials, LiCoO ₂ has been successfully commercialized and widely used, while cobalt is a relatively poor and expensive resource, and it pollutes the environment. Compared with LiCoO ₂ , spinel LiMn ₂ O ₄ cathode material has the advantages of abundant resources, low cost, no environmental pollution, and good safety performance, and is considered to be the most promising cathode material to replace LiCoO ₂ . However, studies in recent years have shown that there is a Jahn-Teller effect in the LiMn ₂ O ₄ material during charge and discharge, resulting in poor cycle performance, specific capacity fading, and poor high temperature performance. In order to overcome these defects, SigalaC et al. proposed to use other metal elements to partially replace manganese to synthesize LiM _x Mn _2-x O ₄ (M=Co, Cr, Ni, Fe, Cu, etc.) to improve the performance of spinel LiMn ₂ O ₄ . Among them, the 5V high-voltage spinel LiNi _0.5 Mn _1.5 O ₄ has attracted much attention. The energy density of the battery is about the product of the discharge voltage and capacity of the battery. The high-voltage spinel LiNi _0.5 Mn _1.5 O ₄ has a discharge potential of about 4.7V and a theoretical capacity of about 147mAh/g, and its energy density reaches 686Wh/kg. High development potential.

Although the high-voltage spinel LiNi _0.5 Mn _1.5 O ₄ has extremely high discharge potential and energy density, the electrolyte of LiNi _0.5 Mn _1.5 O ₄ is easily oxidized at high voltage during the charging and discharging process. The formation of a solid electrolyte interface layer hinders the deintercalation of lithium ions, greatly reduces its capacity, and deteriorates its cycle performance, especially at high temperatures. In addition, in the synthesis and preparation of the material, when the calcination temperature is higher than 600 °C, it is easy to form impurities such as Li _x Ni _1-x O and NiO, which leads to the deterioration of its electrochemical performance.

Contents of the invention

The purpose of the present invention is to solve the problems of the existing high-voltage spinel LiNi _0.5 Mn _1.5 O ₄ cathode material for the first time with low Coulombic efficiency, poor cycle performance and rate performance, and provide a high-voltage spinel type with high performance and low cost Lithium-ion battery positive electrode material and preparation method thereof, and use Li doping to form lithium-rich LiNi _0.5 Mn _1.5 O ₄ positive electrode material, which improves chemical performance.

The present invention adopts the following technical scheme: a high-voltage lithium-ion battery cathode material with a spinel structure, the general chemical formula of the cathode material is Li[M1 _a Ni _b M2 _c Mn _1.5 ]O ₄ , where 0.025≤a ≤0.05, 0.4≤b≤0.45, 0.025≤c≤0.05 and a+b+c=0.5, M1 and M2 are one or more of Mg, Zn, Fe, Li, Al, Cr, Co.

A preparation method of a high-voltage lithium-ion battery cathode material with a spinel structure, comprising the steps of:

(1) Lithium salt, manganese salt, nickel salt, M1 salt, M2 salt and citric acid are dissolved in deionized water under stirring conditions according to molar ratio, and then the pH of the solution is adjusted to neutral or slightly alkaline;

(2) Under the condition of 70-90°C, the mixed solution obtained in step (1) was evaporated at a constant temperature for 8-10 hours at a stirring speed of 200-500 rpm to obtain a sol;

(3) Put the sol in a blast drying oven and dry it at 80-120°C for 10-20 hours to remove water by evaporation to obtain a xerogel;

(4) Put the xerogel in a muffle furnace for calcination at a heating rate of 5°C/min, raise the temperature to 500°C, and calcine for 10 to 28 hours to obtain a precursor;

(5) After the precursor is cooled to room temperature, grind it in a mortar for 0.5 to 1 hour, compact the ground precursor and place it in a muffle furnace, and calcine it under oxygen-enriched conditions or in an air atmosphere. 3-8°C/min, heating up to 700-900°C, calcining for 12-28 hours, and cooling to room temperature to obtain the Li[M1 _a Ni _b M2 _c Mn _1.5 ]O ₄ anode material for lithium ion batteries.

Further, the molar ratio of lithium salt, manganese salt, nickel salt, M1 salt and M2 salt is 1.05:1.5:b:a:c, wherein 0.025≤a≤0.05, 0.4≤b≤0.45, 0.025≤c≤ 0.05 and a+b+c=0.5, wherein in order to prevent a small amount of volatilization of lithium under high temperature calcination, the amount of lithium substance is excessive 5%, M1 and M2 are magnesium salt, zinc salt, iron salt, lithium salt, aluminum salt, chromium One or more of salt and cobalt salt.

Further, the lithium salt is one or more of lithium carbonate, lithium nitrate, lithium acetate, and lithium hydroxide.

Further, the manganese salt is one or more of manganese carbonate, manganese nitrate and manganese acetate.

Further, the nickel salt is one or more of nickel carbonate, nickel nitrate, and nickel acetate.

Further, the magnesium salt is one or more of magnesium carbonate, magnesium nitrate and magnesium acetate; the zinc salt is one or more of zinc carbonate, zinc nitrate and zinc acetate; the iron salt is One or more of iron carbonate, iron nitrate and iron acetate; the cobalt salt is one or more of cobalt carbonate, cobalt nitrate and cobalt acetate, and the aluminum salt is aluminum carbonate, aluminum nitrate and aluminum acetate One or more of; the chromium salt is one or more of chromium carbonate, chromium nitrate and chromium acetate.

Further, the molar ratio of the total molar weight of nickel salt, manganese salt, M1 salt and M2 salt to citric acid is 1:1˜1:2.

Further, in the step (1), the pH of the solution is adjusted to 7-8 with ammonia water.

Further, in the step (5), the oxygen-enriched condition is that the oxygen concentration is 18-28%.

The preparation method of the present invention is simple, and the steps are easy to operate. The lithium-rich LiNi _0.5 Mn _1.5 O ₄ positive electrode material formed by doping Li and other metal elements is used. The prepared positive electrode material has uniform particles, a spinel structure, and high crystallinity. , the stability of the material is improved, and the nickel content is reduced, thereby reducing the production cost and reducing the pollution to the environment. The doping elements introduced in the invention can effectively improve the cycle and rate performance of the material.

Description of drawings

FIG. 1 is an XRD pattern of the cathode material Li[Li _0.025 Ni _0.45 Al _0.025 Mn _1.5 ]O ₄ prepared in Example 1 of the present invention. The abscissa is the scanning range 2θ (10-90°), and the ordinate is the intensity of the peak.

Fig. 2 is a SEM image of the cathode material Li[Li _0.05 Ni _0.4 Al _0.05 Mn _1.5 ]O ₄ prepared in Example 2 of the present invention. The magnification is 10000 times.

Fig. 3 is the first charge and discharge curve (3.0-5.1V, 0.2C, room temperature) of the positive electrode material Li[Li _0.025 Ni _0.45 Al _0.025 Mn _1.5 ]O ₄ prepared in Example 1 of the present invention. In the figure, the abscissa is the specific capacity, mAh/g, the ordinate is the voltage, the unit is V, curve A refers to the charging curve, and curve B refers to the discharging curve.

Fig. 4 is the first charge-discharge curve (3.0-5.1V, 0.1C, 55°C) of the positive electrode material Li[Li _0.05 Ni _0.4 Al _0.05 Mn _1.5 ]O ₄ prepared in Example 2 of the present invention. The abscissa is the specific capacity, mAh/g, and the ordinate is the voltage, the unit is V. Curve A in Fig. 4 refers to the charge curve, and curve B refers to the discharge curve.

Fig. 5 is the first discharge curves (3.0-5.1V, room temperature) of the cathode material Li[Li _0.025 Ni _0.45 Al _0.025 Mn _1.5 ]O ₄ prepared in Example 1 of the present invention at different rates. In the figure, the abscissa is the specific capacity, mAh/g, and the ordinate is the voltage, the unit is V.

detailed description

The present invention will be further described below in conjunction with specific embodiments.

Embodiment one: the preparation method of the positive electrode material of high-voltage lithium-ion battery with spinel structure, comprises the steps:

(1) Lithium nitrate, nickel acetate, manganese acetate and aluminum nitrate are 1.076:0.45:1.5:0.025 in molar ratio, fully dissolved with deionized water respectively, each solution after dissolving is mixed in a clean large beaker, Among them, in order to prevent a small amount of volatilization of lithium under high temperature environment, the excess of lithium nitrate is 5%, and finally mixed with citric acid and continuously stirred and added ammonia water to adjust the pH at 7-8, the molar ratio of the total amount of nickel acetate, manganese acetate and aluminum nitrate to citric acid 1:1;

(2) Under the condition of 80° C., the mixed solution obtained in step (1) was evaporated at a constant temperature for 10 hours at a stirring speed of 200 rpm to obtain a sol;

(3) Place the sol in an air blast drying oven and dry it at 80°C for 12 hours to remove water by evaporation to obtain a xerogel;

(4) Put the xerogel in a muffle furnace for calcination at a heating rate of 5°C/min, raise the temperature to 500°C, and calcine for 20 hours to obtain a precursor;

(5) After the precursor is cooled to room temperature, it is ground in a mortar for 0.5 hours, and the ground precursor is compacted and placed in a muffle furnace, and calcined under oxygen-enriched conditions or in an air atmosphere, and the heating rate is 3 °C/min, the temperature was raised to 800 °C, calcined for 15 hours, and cooled to room temperature to obtain the Li[Li _0.025 Ni _0.45 Al _0.025 Mn _1.5 ]O ₄ cathode material for lithium ion batteries.

It can be seen from Figure 1 that the positive electrode material Li[Li _0.025 Ni _0.45 Al _0.025 Mn _1.5 ]O ₄ prepared in Example 1 has characteristic peaks of spinel at 18°, 36° and 44° in the XRD spectrum, which is Crystal structure; the main peak is sharp, indicating that the positive electrode material Li[Li _0.025 Ni _0.45 Al _0.025 Mn _1.5 ]O ₄ crystal structure prepared in Example 1 is complete.

The positive electrode material obtained in Example 1 was assembled into a CR2032 button battery for charge and discharge cycle test. The electrode was prepared by the film coating method, and N-methyl-2-pyrrolidone (NMP) was used as the solvent, and the positive electrode material, acetylene black and polyvinylidene fluoride (PVDF) were weighed at a mass ratio of 80:12:8, and ground and mixed After uniformity, it is coated on a pretreated aluminum foil, and put into a vacuum drying oven to dry at 80° C. to obtain a positive electrode sheet. The pure metal lithium sheet is used as the negative electrode, the polypropylene microporous membrane Celgard2325 is used as the diaphragm, and the mixed solution of LB315 [m(DMC):m(EMC):m(EC)=1:1:1] is used as the electrolyte solution. A simulated battery was assembled in a glove box (H ₂ O content <1ppm). Use the LAND battery test system to carry out the constant current cycle charge and discharge test on the button battery; under the test voltage 3.0 ~ 5.1V, 0.2C charge and discharge conditions, the specific capacity of the first discharge at room temperature is 137.5mAh/g, the first coulombic efficiency is 93.0%, After 80 charge-discharge cycles, the capacity retention rate is 92.9%. Under the test voltage of 3.0-5.1V and 10C charge-discharge conditions, the specific capacity of the first discharge at room temperature is 103.1mAh/g.

It can be seen from Figure 3 that the first charge and discharge curve of the positive electrode material Li[Li _0.025 Ni _0.45 Al _0.025 Mn _1.5 ]O ₄ prepared in Example 1 has a good The charging platform is better and the discharging platform is also very good, and the discharge capacity is higher.

Figure 5 is the first discharge curves of the positive electrode material Li[Li _0.025 Ni _0.45 Al _0.025 Mn _1.5 ]O ₄ prepared in Example 1 at 0.1C, 0.2C, 1C, 5C, and 10C rates respectively, at 0.1C, 0.2C, It has a good discharge platform at a rate of 1C, and still has a high discharge capacity at a high rate of 10C.

Embodiment two: the preparation method of the positive electrode material of high-voltage lithium-ion battery with spinel structure, comprises the following steps:

(1) Lithium nitrate, nickel acetate, manganese acetate and aluminum nitrate are fully dissolved with deionized water respectively in a molar ratio of 1.10:0.4:1.5:0.05, each solution after dissolving is mixed in a clean large beaker, and Finally, citric acid is mixed in, wherein in order to prevent a small amount of volatilization of lithium under high temperature environment, lithium nitrate is excessively 5%, stirring continuously and adding ammonia water to adjust the pH at 7-8, the total amount of nickel acetate, manganese acetate and aluminum nitrate and the mole of citric acid The ratio is 1:1;

(2) Under the condition of 80°C, the mixed solution obtained in step (1) was evaporated at a constant temperature for 9 hours under the condition of a stirring speed of 300 rpm to obtain a sol;

(3) Put the sol in a blast drying oven and dry it at 90°C for 11 hours to drive off the water by evaporation to obtain a xerogel;

(4) Put the xerogel in a muffle furnace for calcination at a heating rate of 5°C/min, raise the temperature to 500°C, and calcine for 20 hours to obtain a precursor;

(5) After the precursor is cooled to room temperature, it is ground in a mortar for 0.5 hours, and the ground precursor is compacted and placed in a muffle furnace, and calcined under oxygen-enriched conditions or in an air atmosphere, and the heating rate is 3 °C/min, the temperature was raised to 800 °C, calcined for 16 hours, and cooled to room temperature to obtain the Li[Li _0.05 Ni _0.4 Al _0.05 Mn _1.5 ]O ₄ anode material for lithium ion batteries.

It can be seen from Fig. 2 that the positive electrode material Li[Li _0.05 Ni _0.4 Al _0.05 Mn _1.5 ]O ₄ prepared in Example 2 has uniform particle distribution and uniform crystal shape under SEM observation with a magnification of 10,000.

The positive electrode material obtained in Example 2 was assembled into a CR2032 button battery for charge and discharge cycle test. The electrode was prepared by the film coating method, and N-methyl-2-pyrrolidone (NMP) was used as the solvent, and the positive electrode material, acetylene black, and polyvinylidene fluoride (PVDF) were weighed at a mass ratio of 80:12:8, and ground and mixed. After uniformity, it is coated on a pretreated aluminum foil, and put into a vacuum drying oven to dry at 80° C. to obtain a positive electrode sheet. The pure metal lithium sheet is used as the negative electrode, the polypropylene microporous membrane Celgard2325 is used as the diaphragm, and the mixed solution of LB315 [m(DMC):m(EMC):m(EC)=1:1:1] is used as the electrolyte solution. A simulated battery was assembled in a glove box (H ₂ O content <1ppm). Use the LAND battery test system to conduct a constant current cycle charge and discharge test on the button battery; under the test voltage of 3.0-5.1V, 0.2C charge and discharge conditions, the specific capacity of the first discharge at room temperature is 132.2mAh/g, and the first Coulombic efficiency is 95.3%. , after 80 charge-discharge cycles, the capacity retention rate can be higher than 91.3%; under the test voltage of 3.0-5.1V, 0.1C charge-discharge conditions, the specific capacity of the first discharge at 55°C is 131.1mAh/g, and the first Coulombic efficiency is 92.1%. .

Figure 4 is the first charge and discharge curve of the positive electrode material Li[Li _0.05 Ni _0.4 Al _0.05 Mn _1.5 ]O ₄ prepared in Example 2. Under the conditions of 3.0-5.1V, 0.1C, and 55°C, the positive electrode material has a better charging platform , The discharge platform is also very good, and the discharge capacity is high.

Embodiment three: the preparation method of the positive electrode material of high-voltage lithium-ion battery with spinel structure, comprises the following steps:

(1) The molar ratio of lithium nitrate, nickel acetate, manganese acetate and chromium nitrate is 1.10:0.4:1.5:0.05 (wherein in order to prevent a small amount of volatilization of lithium under high temperature environment, lithium nitrate is excessive 5%), respectively with deionized water Dissolve fully, mix each solution after dissolving in a clean large beaker, and finally mix in citric acid, stir constantly and add ammonia water to adjust pH at 7～8, the total amount of described nickel acetate, manganese acetate and chromium nitrate and The molar ratio of citric acid is 1:1;

(2) Under the condition of 80°C, the mixed solution obtained in step (1) was evaporated at a constant temperature for 9 hours under the condition of a stirring speed of 400 rpm to obtain a sol;

(3) Put the sol in a blast drying oven and dry it at 90°C for 11 hours to drive off the water by evaporation to obtain a xerogel;

(4) Put the xerogel in a muffle furnace for calcination at a heating rate of 5°C/min, raise the temperature to 500°C, and calcine for 20 hours to obtain a precursor;

(5) After the precursor is cooled to room temperature, it is ground in a mortar for 0.5 hours. The ground precursor is compacted and placed in a muffle furnace for calcination in an oxygen-enriched condition or an air atmosphere. The heating rate is 3°C /min, heated up to 800°C, calcined for 18 hours, and cooled to room temperature to obtain Li[Li _0.05 Ni _0.4 Cr0.05Mn _1.5 ]O ₄ anode material for lithium ion batteries.

The positive electrode material obtained in Example 3 was assembled into a CR2032 button battery for charge and discharge cycle test. The electrode was prepared by the film coating method, and N-methyl-2-pyrrolidone (NMP) was used as the solvent, and the positive electrode material, acetylene black, and polyvinylidene fluoride (PVDF) were weighed at a mass ratio of 80:12:8, and ground and mixed. After uniformity, it is coated on a pretreated aluminum foil, and put into a vacuum drying oven to dry at 80° C. to obtain a positive electrode sheet. The pure metal lithium sheet is used as the negative electrode, the polypropylene microporous membrane Celgard2325 is used as the diaphragm, and the mixed solution of LB315 [m(DMC):m(EMC):m(EC)=1:1:1] is used as the electrolyte solution. A simulated battery was assembled in a glove box (H ₂ O content <1ppm). Use the LAND battery test system to carry out the constant current cycle charge and discharge test on the button battery; under the test voltage of 3.0 ~ 5.1V, 0.2C charge and discharge conditions, the specific capacity of the first discharge at room temperature is 134.8mAh/g, and the first Coulombic efficiency is 90.7%. After 80 charge-discharge cycles, the capacity retention rate can be higher than 90.2%.

Embodiment four: the preparation method of the positive electrode material of high-voltage lithium-ion battery with spinel structure, comprises the following steps:

(1) The molar ratio of lithium nitrate, nickel acetate, manganese acetate and cobalt nitrate is 1.10:0.4:1.5:0.05 (wherein in order to prevent a small amount of volatilization of lithium under high temperature environment, lithium nitrate is excessive 5%), use deionized water respectively fully dissolve, each solution after dissolving is mixed in a clean large beaker, and citric acid is finally mixed in, constantly stirring and adding ammonia water to adjust pH at 7～8, the total amount of described nickel acetate, manganese acetate and cobalt nitrate and The molar ratio of citric acid is 1:1;

(2) Under the condition of 80° C., the mixed solution obtained in step (1) was evaporated at a constant temperature for 8 hours at a stirring speed of 500 rpm to obtain a sol;

(3) Place the sol in an air blast drying oven and dry it at 120°C for 10 hours to remove water by evaporation to obtain a xerogel;

(4) Put the xerogel in a muffle furnace for calcination at a heating rate of 5°C/min, raise the temperature to 500°C, and calcine for 20 hours to obtain a precursor;

(5) After the precursor is cooled to room temperature, it is ground in a mortar for 0.5 hours, and the ground precursor is compacted and placed in a muffle furnace, and calcined under oxygen-enriched conditions or in an air atmosphere, and the heating rate is 3 °C/min, the temperature was raised to 800 °C, calcined for 20 hours, and cooled to room temperature to obtain the Li[Li _0.05 Ni _0.4 Co _0.05 Mn _1.5 ]O ₄ anode material for lithium ion batteries.

The positive electrode material obtained in Example 4 was assembled into a CR2032 button battery for charge and discharge cycle test. The electrode was prepared by the film coating method, and N-methyl-2-pyrrolidone (NMP) was used as the solvent, and the positive electrode material, acetylene black, and polyvinylidene fluoride (PVDF) were weighed at a mass ratio of 80:12:8, and ground and mixed. After uniformity, it is coated on a pretreated aluminum foil, and put into a vacuum drying oven to dry at 80° C. to obtain a positive electrode sheet. The pure metal lithium sheet is used as the negative electrode, the polypropylene microporous membrane Celgard2325 is used as the diaphragm, and the mixed solution of LB315 [m(DMC):m(EMC):m(EC)=1:1:1] is used as the electrolyte solution. A simulated battery was assembled in a glove box (H ₂ O content <1ppm). Use the LAND battery test system to carry out the constant current cycle charge and discharge test on the button battery; under the test voltage 3.0 ~ 5.1V, 0.2C charge and discharge conditions, the specific capacity of the first discharge at room temperature is 126.2mAh/g, and the first coulombic efficiency is 95.7%. After 80 charge-discharge cycles, the capacity retention rate can be higher than 94.3%.

Claims (10)

1. there is a high-voltage lithium ion battery cathode material for spinel structure, it is characterized in that: the chemical general formula of described positive electrode is Li [M1 _ani _bm2 _cmn _1.5] O ₄, wherein 0.025≤a≤0.05,0.4≤b≤0.45,0.025≤c≤0.05 and a+b+c=0.5, M1 and M2 are one or more in Mg, Zn, Fe, Li, Al, Cr, Co.

2. there is the preparation method of the high-voltage lithium ion battery cathode material of spinel structure as claimed in claim 1, it is characterized in that: comprise the steps:

(1) in molar ratio lithium salts, manganese salt, nickel salt, M1 salt, M2 salt and citric acid are dissolved in deionized water under agitation, then regulate pH value of solution to neutral or alkalescent;

(2) under the condition of 70 ~ 90 DEG C, carry out evaporation at constant temperature 8 ~ 10 hours under the condition of the mixed solution low whipping speed 200 ~ 500 revs/min that step (1) obtains, obtain colloidal sol;

(3) colloidal sol is placed in air dry oven under 80 ~ 120 DEG C of conditions dry 10 ~ 20 hours, to evaporate expeling moisture, obtains xerogel;

(4) xerogel is placed in Muffle furnace to calcine, programming rate is 5 DEG C/min, is warming up to 500 DEG C, calcines 10 ~ 28 hours, obtains presoma;

(5) presoma grinds 0.5 ~ 1 hour after being cooled to room temperature in mortar machine, presoma compacting after grinding is placed in Muffle furnace, in excess oxygen or air atmosphere under calcine, programming rate is 3 ~ 8 DEG C/min, be warming up to 700 ~ 900 DEG C, calcine 12 ~ 28 hours, after being cooled to room temperature, namely obtain described anode material for lithium-ion batteries Li [M1 _ani _bm2 _cmn _1.5] O ₄.

3. there is the preparation method of the high-voltage lithium ion battery cathode material of spinel structure as claimed in claim 2, it is characterized in that: the mol ratio of described lithium salts, manganese salt, nickel salt, M1 salt and M2 salt is 1.05:1.5:b:a:c, wherein 0.025≤a≤0.05,0.4≤b≤0.45,0.025≤c≤0.05 and a+b+c=0.5, wherein in order to prevent a small amount of volatilization of lithium under high-temperature calcination, the amount of substance excessive 5%, M1 of lithium and M2 are one or more in magnesium salts, zinc salt, molysite, lithium salts, aluminium salt, chromic salts, cobalt salt.

4. there is the preparation method of the high-voltage lithium ion battery cathode material of spinel structure as claimed in claim 2, it is characterized in that: described lithium salts is one or more in lithium carbonate, lithium nitrate, lithium acetate, lithium hydroxide.

5. there is the preparation method of the high-voltage lithium ion battery cathode material of spinel structure as claimed in claim 2, it is characterized in that: described manganese salt is one or more in manganese carbonate, manganese nitrate, manganese acetate.

6. there is the preparation method of the high-voltage lithium ion battery cathode material of spinel structure as claimed in claim 2, it is characterized in that: described nickel salt is one or more in nickelous carbonate, nickel nitrate, nickel acetate.

7. there is the preparation method of the high-voltage lithium ion battery cathode material of spinel structure as claimed in claim 2, it is characterized in that: described magnesium salts is one or more in magnesium carbonate, magnesium nitrate and magnesium acetate; Described zinc salt is one or more in zinc carbonate, zinc nitrate and zinc acetate; Described molysite is one or more in ferric carbonate, ferric nitrate and ferric acetate; Described cobalt salt is one or more in cobalt carbonate, cobalt nitrate, cobalt acetate, and described aluminium salt is one or more in aluminium carbonate, aluminum nitrate and aluminium acetate; Described chromic salts is one or more in chromium carbonate, chromic nitrate and chromium acetate.

8. there is the preparation method of the high-voltage lithium ion battery cathode material of spinel structure as claimed in claim 2, it is characterized in that: the integral molar quantity of described nickel salt, manganese salt, M1 salt and M2 salt and the mol ratio of citric acid are 1:1 ~ 1:2.

9. there is the preparation method of the high-voltage lithium ion battery cathode material of spinel structure as claimed in claim 2, it is characterized in that: pH value of solution is adjusted to 7 ~ 8 with ammoniacal liquor in (1) by step.

10. have the preparation method of the high-voltage lithium ion battery cathode material of spinel structure as claimed in claim 2, it is characterized in that: in step (5), described excess oxygen is oxygen concentration is 18 ~ 28%.