CN107706407B - Pure-phase lithium ion battery negative electrode material Mo4O11Method of synthesis of - Google Patents

Pure-phase lithium ion battery negative electrode material Mo4O11Method of synthesis of Download PDF

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CN107706407B
CN107706407B CN201710990344.5A CN201710990344A CN107706407B CN 107706407 B CN107706407 B CN 107706407B CN 201710990344 A CN201710990344 A CN 201710990344A CN 107706407 B CN107706407 B CN 107706407B
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lithium ion
ion battery
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product
reaction
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CN107706407A (en
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曹丽云
贺菊菊
李嘉胤
黄剑锋
张宁
齐樱
仵婉晨
李倩颖
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Shaanxi University of Science and Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a pure-phase lithium ion battery cathode material Mo4O11The synthesis method comprises the following steps: 1) dissolving a molybdenum source into a sufficient amount of ethanol-water mixed solvent according to the formula amount, fully stirring, and then adjusting the pH value to 1-5 by using oxidizing oxyacid; 2) carrying out solvothermal reaction on the product at the reaction temperature of 90-180 ℃ for 3-30 h; 3) after the reaction is finished, cooling the product, washing and drying; 4) placing the product in an inert atmosphere at 350-700 ℃ for heat treatment for 1-3 h to obtain a target product Mo4O11. The invention also discloses a pure-phase lithium ion battery cathode material Mo4O11Mo prepared by the invention4O11Uniform chemical composition, high purity and uniform appearance.

Description

Pure-phase lithium ion battery negative electrode material Mo4O11Method of synthesis of
Technical Field
The invention belongs to the technical field of synthesizing intermediate valence transition metal oxide electrode materials, and particularly relates to an intermediate valence transition metal oxide Mo applied to a lithium ion battery electrode material4O11The method of (1). The method is simple to operate, and the prepared Mo4O11The purity is high.
Background
As a major breakthrough in the field of energy conversion and storage devices, lithium ion battery technology has been rapidly developed in recent years, and has been rapidly popularized in the fields of electronic tools, backup power supplies, power supply systems for vehicles, and the like. Designing and preparing electrode materials with high capacity, high rate performance, long service life and low cost becomes one of the most important research directions in the field of the current lithium ion batteries. Graphite materials meet most of the requirements as ideal anode materials and are currently widely commercialized anode materials. However, the relatively low energy density and power density of the graphite negative electrode material cannot meet the requirements of the next generation of high-performance lithium ion battery, and the development of the high-performance lithium ion battery negative electrode material becomes a very urgent task at present.
Many important transition metal oxides are involved in the switching reaction mechanism during the electrode reaction, and therefore such materials tend to have high reversible specific capacities and energy densities. At present, the research of taking transition metal oxide as the negative electrode material of the lithium ion battery has made great progress.
Molybdenum-based oxide materials are an important class of oxide materials. Due to the variable molybdenum valence and various phase structures, molybdenum-based oxide materials with unique appearance and different components can be designed under different synthesis conditions, so that the molybdenum-based oxide has very large application potential as a lithium ion battery cathode material.
Molybdenum oxide of intermediate valence state (Mo)4O11) As a lithium ion battery cathode material, the material has high conductivity and high theoretical specific capacity up to 1050 mAh.g-1In particular, the metal-like conductivity-greatly overcomes the disadvantage of poor conductivity common to metal oxides. The reason is that the introduced oxygen vacancy is taken as a shallow donor energy level, so that the concentration of current carriers is improved, and the electronic conductivity is improved; on the other hand, the introduction of oxygen vacancy provides more active sites for conversion reaction, and the charge transfer kinetics is improved.
At present, the synthesis of pure phase Mo is concerned4O11Methods for making negative electrode materials for lithium ion batteries have not been reported. The patent adopts high-efficiency and simple solvent heat combination heat treatment method to prepare pure-phase Mo4O11. Effectively overcomes the defect that the common binary molybdenum oxide is used as the cathode material of the lithium ion battery.
Disclosure of Invention
The invention aims to provide a transition metal oxide molybdenum oxide Mo with an intermediate valence state4O11And is applied to the synthesis method of the lithium ion battery cathode material. The molybdenum oxide Mo4O11Having a density of up to 1050mAh g-1The material has the advantages of high theoretical specific capacity and metalloid conductivity, and is greatly advantageous for being applied to electrode materials of lithium ion batteries. The method is simple to operate, and the prepared Mo4O11The product has high purity.
The specific technical scheme is as follows: pure-phase lithium ion battery negative electrode material Mo4O11The synthesis method comprises the following steps:
(1) selecting a molybdenum source, weighing a certain mass, dissolving the molybdenum source in a mixed solvent (water: absolute ethyl alcohol) with the volume of 70 ml, stirring for 5-30 min, and then stirring while using HNO with different concentrations3Adjusting the pH value to obtain a uniform solution A;
(2) pouring the stirred solution A into a hydrothermal kettle with a polytetrafluoroethylene lining, sealing, and then placing into a homogeneous reactor for solvothermal reaction;
(3) after the reaction is finished, cooling the reaction kettle at room temperature, alternately washing the product with deionized water and an organic solvent for a plurality of times, and drying in vacuum to obtain a product B;
(4) weighing a certain amount of product B after vacuum drying, placing the product B in a porcelain boat, and carrying out heat treatment in an inert atmosphere at the temperature of 350-700 ℃ for 1-3 h to obtain a target product Mo4O11；
The molybdenum source in the step (1) is ammonium molybdate tetrahydrate ((NH)4)6Mo7O24·4H2O) and sodium molybdate dihydrate (Na)2MoO4·2H2O) or both.
The certain mass in the step (1) is 1-5 g.
The volume ratio of the mixed solvent (water: absolute ethyl alcohol) with different volume ratios in the step (1) is (0.75-69): 1.
HNO with different concentrations in the step (1)3The range is 4mol/L to 16 mol/L.
The pH range in the step (1) is 1-5.
The solvothermal reaction temperature in the step (2) is 90-180 ℃, and the reaction time is 3-30 h.
The organic solvent in the step (3) is one or two of absolute ethyl alcohol and acetone.
And (3) vacuum drying at 40-60 ℃ for 4-12 h.
Weighing 0.1-3 g of a certain amount of vacuum-dried product B in the step (4)
The inert atmosphere in the step (4) is N2Or Ar.
And a pure-phase lithium ion battery negative electrode material Mo4O11Prepared by the method.
Compared with the prior art, the invention can obtain the following beneficial effects:
(1) the method adopts the solvent thermal combination inert gas heat treatment method to synthesize the final product, overcomes the defect that the reducing atmosphere adopted by the traditional calcination is used for synthesizing the molybdenum oxide with the intermediate valence state, does not need large-scale equipment and harsh reaction conditions, has cheap and easily obtained raw materials, low cost, high yield, no need of post treatment, environmental friendliness and high safety, and can be suitable for large-scale production.
(2) The product Mo prepared by the method4O11Uniform chemical composition, high purity and uniform appearance.
(3) The product prepared by the method can show excellent electrochemical performance as a lithium ion battery cathode material, and the electrochemical performance is 100 mA.g-1Has a capacity of 897mAh g-1And the capacity retention rate is 82% after 100 cycles of charge and discharge.
Drawings
FIG. 1 is an X-ray diffraction analysis of the product of example 1.
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
(1) 1g of ammonium molybdate tetrahydrate ((NH) was weighed4)6Mo7O24·4H2O), dissolvingDissolving in 70 ml mixed solvent (water: absolute ethyl alcohol =11: 1), stirring for 20 min, and adding 4mol/L HNO while stirring3Adjusting pH =1 to obtain homogeneous solution a;
(2) pouring the stirred solution A into a hydrothermal kettle with a polytetrafluoroethylene lining, sealing, and then placing into a homogeneous reactor for solvothermal reaction at 150 ℃ for 15 hours;
(3) after the reaction is finished, cooling the reaction kettle at room temperature, alternately washing the product for 6 times by using deionized water and organic solvent absolute ethyl alcohol, and drying in vacuum to obtain a product B;
(4) weighing 0.5g of vacuum-dried product B, placing the product B in a porcelain boat, and carrying out heat treatment in Ar at the heat treatment temperature of 600 ℃ for 2h to obtain a target product Mo4O11。
The sample prepared in this example was subjected to XRD measurement, and the measurement results are shown in fig. 1. FIG. 1 shows that the product prepared in this example is Mo4O11The chemical composition is uniform and the purity is high.
The sample of the embodiment is subjected to an electrochemical cycle performance test, and the test result shows that the product prepared by the invention is 100 mA.g-1At a current density of (D), the capacity is up to 897mA g-1And the capacity retention rate is 82% after 100 cycles of charge and discharge. The above results show that Mo prepared by the present invention4O11The battery negative electrode material has excellent electrochemical performance.
Example 2
(1) 1g of sodium molybdate dihydrate (Na) was weighed2MoO4·2H2O), dissolved in a mixed solvent (water: absolute ethanol =3: 1), stirring for 20 min, and then using 4mol/L HNO while stirring3Adjusting pH =1 to obtain homogeneous solution a;
(2) pouring the stirred solution A into a hydrothermal kettle with a polytetrafluoroethylene lining, sealing, and then placing into a homogeneous reactor for solvothermal reaction at 120 ℃ for 15 hours;
(3) after the reaction is finished, cooling the reaction kettle at room temperature, alternately washing the product for 6 times by using deionized water and organic solvent acetone, and drying in vacuum to obtain a product B;
(4) weighing 0.5g of vacuum-dried product B, placing the product B in a porcelain boat, and carrying out heat treatment in Ar at the heat treatment temperature of 500 ℃ for 2h to obtain a target product Mo4O11。
Example 3
(1) 1g of ammonium molybdate tetrahydrate ((NH) was weighed4)6Mo7O24·4H2O), dissolved in a mixed solvent (water: absolute ethanol =6: 1), stirring for 20 min, and then using 16mol/L HNO while stirring3Adjusting pH =1 to obtain homogeneous solution a;
(2) pouring the stirred solution A into a hydrothermal kettle with a polytetrafluoroethylene lining, sealing, and then placing into a homogeneous reactor for solvothermal reaction at 180 ℃ for 6 hours;
(3) after the reaction is finished, cooling the reaction kettle at room temperature, alternately washing the product for 6 times by using deionized water and organic solvent absolute ethyl alcohol, and drying in vacuum to obtain a product B;
(4) weighing 1g of vacuum dried product B, placing the product B in a porcelain boat, and carrying out heat treatment in Ar at the heat treatment temperature of 600 ℃ for 1h to obtain a target product Mo4O11。
Example 4
(1) 1g of ammonium molybdate tetrahydrate ((NH) was weighed4)6Mo7O24·4H2O), dissolved in a mixed solvent (water: absolute ethanol =6: 1), stirring for 20 min, and then using 16mol/L HNO while stirring3Adjusting pH =1 to obtain homogeneous solution a;
(2) pouring the stirred solution A into a hydrothermal kettle with a polytetrafluoroethylene lining, sealing, and then placing into a homogeneous reactor for solvothermal reaction at 120 ℃ for 12 hours;
(3) after the reaction is finished, cooling the reaction kettle at room temperature, alternately washing the product for 6 times by using deionized water and organic solvent absolute ethyl alcohol, and drying in vacuum to obtain a product B;
(4) weighing 1g of vacuum dried product B, placing the product B in a porcelain boat, and carrying out heat treatment in Ar at the heat treatment temperature of 600 ℃ for 2h to obtain a target product Mo4O11。
Example 5
(1) 1g of sodium molybdate dihydrate (Na) was weighed2MoO4·2H2O), dissolved in a mixed solvent (water: absolute ethanol =3: 1), stirring for 20 min, and then using 4mol/L HNO while stirring3Adjusting pH =5 to obtain homogeneous solution a;
(2) pouring the stirred solution A into a hydrothermal kettle with a polytetrafluoroethylene lining, sealing, and then placing into a homogeneous reactor for solvothermal reaction at 90 ℃ for 30 hours;
(3) after the reaction is finished, cooling the reaction kettle at room temperature, alternately washing the product for 6 times by using deionized water and organic solvent acetone, and drying in vacuum to obtain a product B;
(4) 0.5g of the product B after vacuum drying are weighed and placed in a porcelain boat under N2Heat treatment is carried out at 700 ℃ for 1h to obtain the target product Mo4O11。
Example 6
(1) 1g of sodium molybdate dihydrate (Na) was weighed2MoO4·2H2O), dissolved in a mixed solvent (water: absolute ethyl alcohol =3: 1), stirring for 20 min, and then using 8mol/L HNO while stirring3Adjusting pH =1 to obtain homogeneous solution a;
(2) pouring the stirred solution A into a hydrothermal kettle with a polytetrafluoroethylene lining, sealing, and then placing into a homogeneous reactor for solvothermal reaction at 180 ℃ for 3 hours;
(3) after the reaction is finished, cooling the reaction kettle at room temperature, alternately washing the product for 6 times by using deionized water and organic solvent acetone, and drying in vacuum to obtain a product B;
(4) 0.5g of the product B after vacuum drying are weighed and placed in a porcelain boat under N2In the middle of heat treatmentThe heat treatment temperature is 350 ℃, the time is 3h, and the target product Mo is obtained4O11。

Claims (6)

1. Pure-phase lithium ion battery negative electrode material Mo4O11The synthesis method is characterized by comprising the following steps:
1) dissolving a molybdenum source into a sufficient amount of ethanol-water mixed solvent according to the formula amount, fully stirring, and then adjusting the pH value to 1-5 by using oxidizing oxyacid;
2) carrying out solvothermal reaction on the product obtained in the step 1), wherein the reaction temperature is 90-180 ℃, and the reaction time is 3-30 h;
3) after the reaction is finished, cooling the product in the step 2), washing and drying;
4) placing the product obtained in the step 3) in an inert atmosphere at 350-700 ℃ for heat treatment for 1-3 h to obtain a target product Mo4O11；
The molybdenum source is ammonium molybdate tetrahydrate or sodium molybdate dihydrate;
in the ethanol-water mixed solvent, the ratio of water: the volume ratio of the absolute ethyl alcohol is (0.75-69): 1;
the oxidizing oxoacid is HNO3An aqueous solution of (a).
2. The pure-phase lithium ion battery anode material Mo of claim 14O11The synthesis method is characterized in that the solvothermal reaction in the step 2) is carried out in a homogeneous reactor by adopting a hydrothermal kettle with a polytetrafluoroethylene lining.
3. The pure-phase lithium ion battery anode material Mo of claim 14O11The synthesis method of (3) is characterized in that the washing in the step 3) adopts deionized water and an organic solvent to alternately wash, and the organic solvent is absolute ethyl alcohol, acetone or a mixture of the absolute ethyl alcohol and the acetone.
4. The pure-phase lithium ion battery anode material Mo of claim 14O11The synthesis method is characterized in that the drying in the step 3) is carried out for 4-12 hours at 40-60 ℃ in vacuum.
5. The pure-phase lithium ion battery anode material Mo of claim 14O11Characterized in that the inert atmosphere is N2、Ar。
6. The pure-phase lithium ion battery anode material Mo of claim 14O11The synthesis method is characterized in that the step 4) specifically comprises the steps of placing the product obtained in the step 3) in a ceramic carrier, carrying out heat treatment under the protection of inert atmosphere, and carrying out heat treatment at 350-700 ℃ for 1-3 h to obtain a target product Mo4O11。
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CN109301211B (en) * 2018-09-29 2021-09-17 陕西科技大学 Self-assembled flower spherical nitrogen-doped Mo4O11Lithium ion battery cathode material and preparation method thereof
CN115259228A (en) * 2022-07-06 2022-11-01 北京化工大学常州先进材料研究院 Method for preparing molybdenum-tungsten composite oxide material by solvothermal method

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