CN110970607A - Preparation method of cobalt-doped tungsten trioxide/CNTs sodium ion battery cathode material - Google Patents

Preparation method of cobalt-doped tungsten trioxide/CNTs sodium ion battery cathode material Download PDF

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CN110970607A
CN110970607A CN201911256170.5A CN201911256170A CN110970607A CN 110970607 A CN110970607 A CN 110970607A CN 201911256170 A CN201911256170 A CN 201911256170A CN 110970607 A CN110970607 A CN 110970607A
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China
Prior art keywords
cobalt
tungsten trioxide
sodium
doped tungsten
ion battery
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王新
王加义
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Zhaoqing South China Normal University Optoelectronics Industry Research Institute
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Zhaoqing South China Normal University Optoelectronics Industry Research Institute
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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
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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 relates to a preparation method of a cobalt-doped tungsten trioxide/CNTs sodium ion battery cathode material. The introduction of cobalt oxide and tungsten oxide in the invention effectively improves the discharge capacity and the cycling stability of the sodium-ion battery, and the existence of hydrogen in the preparation process improves the overall conductivity of the material.

Description

Preparation method of cobalt-doped tungsten trioxide/CNTs sodium ion battery cathode material
Technical Field
The invention relates to a preparation method of a cathode material for a sodium-ion battery, in particular to a preparation method of a cathode material for a sodium-ion battery, which comprises the steps of preparing cobalt-doped tungsten trioxide, and growing a carbon nano tube on the surface of the cobalt-doped tungsten trioxide by a vapor deposition method, and belongs to the field of material chemistry.
Background
The storage and conversion of energy has become an important issue that restricts the sustainable development of the world economy. Among the various technologies at present, the lithium ion battery technology has conquered the portable electronic market due to its advantages of high working voltage, high capacity, small self-discharge and long cycle life, and becomes the first choice of power source for electric vehicles and large-scale energy storage systems.
However, with the real arrival of the era of electric vehicles and smart grids, the global lithium resources cannot effectively meet the huge demand of power lithium ion batteries, so that the price of lithium-related materials is further increased, the battery cost is increased, and the development of new energy industry is finally hindered. Therefore, the need for developing other cheap phase energy storage technologies that can replace lithium ion batteries is urgent.
The storage amount of the sodium element in the earth is 4-5 orders of magnitude higher than that of the lithium element, so that the problem of resource shortage of lithium can be solved by replacing lithium with sodium. Because sodium resources are abundant and development cost is low, and sodium and lithium are elements in the same main group and have similar intercalation mechanisms, the application of similar compounds as electrode materials in the two systems becomes possible.
However, since the radius of sodium ions is larger than that of lithium, the migration of sodium ions in an electrode material is slow, and the deintercalation process is complicated, resulting in a decrease in reversible capacity and rate capability. At the same time, Na+The standard electrode potential of the/Na couple is-2.71V vs Li+the/Li is about 0.3V higher. Therefore, the energy density of sodium ion batteries is generally lower than that of corresponding lithium ion batteries compared with conventional cathode materials. However, since power and energy storage batteries have less stringent requirements for weight and volume, sodium ion batteries should still have a broad application prospect.
Disclosure of Invention
The invention aims to overcome the defects of low specific discharge capacity and poor cycling stability of the sodium-ion battery, and adopts the technical scheme for solving the technical problem that:
a preparation method of a sodium-ion battery negative electrode material comprises the following steps:
firstly, preparing a cobalt-doped tungsten trioxide material:
dissolving sodium tungstate and cobalt acetate in deionized water, adjusting the pH value to 2.5-3.0 by using a hydrochloric acid solution, uniformly stirring, transferring to a reaction kettle for reaction, centrifugally collecting a product, washing with deionized water and ethanol for three times respectively, and drying to obtain the cobalt-doped tungsten trioxide material.
Further, the mass-to-volume ratio of sodium tungstate to deionized water in the first step is 1: 10-50g/mL, and the mass-volume ratio of the cobalt acetate to the deionized water is 1: 100-500 g/mL.
Further, the reaction temperature in the reaction kettle in the first step is 150-.
Second step of preparing composite cathode material of sodium ion battery
And (3) placing the cobalt-doped tungsten trioxide material prepared in the first step into a tubular furnace, heating to 500-700 ℃ in an argon atmosphere for high-temperature calcination, introducing acetylene and hydrogen simultaneously after the temperature is constant, closing the acetylene and the hydrogen after a certain time, and naturally cooling in the argon atmosphere to obtain the sodium-ion battery cathode material.
Furthermore, the dosage of the cobalt-doped tungsten trioxide material in the second step is 0.1-1 g, the flow rate of introduced hydrogen is 100-300mL/min, the flow rate of acetylene is 10-50mL/min, and the introduction time of acetylene and hydrogen is 10-30 min.
Further, the heating rate of the high-temperature calcination in the second step tubular furnace is 0.5-1 ℃/min;
the invention has the following beneficial effects:
in the preparation process, the cobalt oxide and the tungsten oxide are introduced, and have remarkable effects on improving the discharge specific capacity of the sodium ion battery and the cycling stability of the battery. The existence of hydrogen in the process of growing the carbon nano tube leads the tungsten oxide and the cobalt oxide to be in a mixed valence state, thus improving the whole conductivity, and then leading the grown carbon nano tube in the subsequent process, thus providing a guarantee for the conductivity of the cathode material.
Drawings
The invention is further illustrated with reference to the following figures and examples:
fig. 1 is a discharge specific capacity cycle diagram of the composite negative electrode material of the sodium-ion battery prepared in example 1.
Detailed Description
Example 1:
first step preparation of cobalt-doped tungsten trioxide material
Dissolving 5g of sodium tungstate and 0.5g of cobalt acetate in 80mL of deionized water, then adjusting the pH of the solution to 2.8 by using a hydrochloric acid solution, uniformly stirring the solution, transferring the solution to a reaction kettle for reaction at the reaction temperature of 180 ℃ for 24 hours, centrifugally collecting a product after the reaction is finished, washing the product with deionized water and ethanol for three times respectively, and drying the product to obtain the cobalt-doped tungsten trioxide material.
Second step of preparing composite cathode material of sodium ion battery
And (2) placing 0.3g of the cobalt-doped tungsten trioxide material prepared in the first step into a tubular furnace, heating to 600 ℃ at a heating rate of 0.5 ℃/min under an argon atmosphere, introducing mixed gas of acetylene and hydrogen simultaneously after the temperature is constant, wherein the hydrogen flow rate is 200mL/min, the acetylene flow rate is 30mL/min, continuously introducing for 20min, closing the hydrogen and the acetylene after the introduction, and naturally cooling under the argon atmosphere to obtain the sodium-ion battery cathode material.
Example 2:
firstly, preparing a cobalt-doped tungsten trioxide material:
taking 10g of sodium tungstate and 1g of cobalt acetate, dissolving in 100mL of deionized water, then adjusting the pH value to 3.0 by using a hydrochloric acid solution, uniformly stirring, transferring to a reaction kettle for reaction at the reaction temperature of 200 ℃ for 24h, centrifugally collecting a product after the reaction is finished, washing with deionized water and ethanol for three times respectively, and drying to obtain the cobalt-doped tungsten trioxide material.
The second step is to prepare the cathode material of the sodium-ion battery:
and (2) placing 0.3g of the cobalt-doped tungsten trioxide material prepared in the first step into a tubular furnace, heating to 700 ℃ at a heating rate of 1 ℃/min under argon atmosphere, introducing mixed gas of acetylene and hydrogen simultaneously after the temperature is constant, wherein the hydrogen flow rate is 300mL/min, the acetylene flow rate is 50mL/min, continuously introducing for 30min, closing the hydrogen and the acetylene after the introduction, and naturally cooling under argon atmosphere to obtain the sodium-ion battery cathode material.
Example 3:
firstly, preparing a cobalt-doped tungsten trioxide material:
1g of sodium tungstate and 0.1g of cobalt acetate are dissolved in 50mL of deionized water, then the pH value of the solution is adjusted to 2.5 by using a hydrochloric acid solution, the solution is uniformly stirred and then transferred to a reaction kettle for reaction, the reaction temperature is 150 ℃, the reaction time is 12 hours, after the reaction is finished, a product is centrifugally collected, and the product is washed by deionized water and ethanol for three times and then dried, so that the cobalt-doped tungsten trioxide material is obtained.
The second step is to prepare the cathode material of the sodium-ion battery:
and (2) placing 0.3g of the cobalt-doped tungsten trioxide material prepared in the first step into a tubular furnace, heating to 500 ℃ at a heating rate of 0.5 ℃/min under an argon atmosphere, introducing mixed gas of acetylene and hydrogen simultaneously after the temperature is constant, wherein the hydrogen flow rate is 100mL/min, the acetylene flow rate is 10mL/min, continuously introducing for 10min, closing hydrogen and acetylene after the introduction, and naturally cooling under the argon atmosphere to obtain the sodium-ion battery cathode material.

Claims (5)

1. A preparation method of a cobalt-doped tungsten trioxide/CNTs sodium ion battery cathode material comprises the following steps:
firstly, preparing a cobalt-doped tungsten trioxide material:
taking a proper amount of sodium tungstate, dissolving cobalt acetate in deionized water, adjusting the pH value to 2.5-3.0 by using a hydrochloric acid solution, uniformly stirring, transferring to a reaction kettle for reaction, centrifugally collecting a product, washing with deionized water and ethanol for three times respectively, and drying to obtain a cobalt-doped tungsten trioxide material;
the second step is to prepare the composite cathode material of the sodium-ion battery:
and (3) placing the cobalt-doped tungsten trioxide material prepared in the first step into a tubular furnace, heating to 500-700 ℃ in an argon atmosphere for high-temperature calcination, introducing acetylene and hydrogen simultaneously after the temperature is constant, closing the acetylene and the hydrogen after a certain time, and naturally cooling in the argon atmosphere to obtain the sodium-ion battery cathode material.
2. The preparation method according to claim 1, wherein the mass-to-volume ratio of sodium tungstate to deionized water in the first step is 1: 10-50g/mL, and the mass-volume ratio of the cobalt acetate to the deionized water is 1: 100-500 g/mL.
3. The method according to claim 1, wherein the reaction temperature in the reaction kettle in the first step is 150 ℃ to 200 ℃, and the reaction time is 12 to 24 hours.
4. The method as set forth in claim 1, wherein the amount of the cobalt-doped tungsten trioxide material used in the second step is 0.1-1 g, the flow rate of the introduced hydrogen is 100-300mL/min, the flow rate of the acetylene is 10-50mL/min, and the time of the introduction of the acetylene and the hydrogen is 10-30 min.
5. The method according to claim 1, wherein the temperature rise rate of the high-temperature calcination in the second step tube furnace is 0.5 to 1 ℃/min.
CN201911256170.5A 2019-12-10 2019-12-10 Preparation method of cobalt-doped tungsten trioxide/CNTs sodium ion battery cathode material Pending CN110970607A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115020704A (en) * 2022-06-15 2022-09-06 李致朋 Self-supporting negative electrode material, preparation method thereof and sodium ion battery

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US20120028124A1 (en) * 2008-12-30 2012-02-02 University Of Louisville Research Foundation, Inc. Anode materials for lithium-ion batteries
CN104934584A (en) * 2015-05-13 2015-09-23 陕西科技大学 Porous hollow WO3/WS2 nanometer material and preparation method thereof
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115020704A (en) * 2022-06-15 2022-09-06 李致朋 Self-supporting negative electrode material, preparation method thereof and sodium ion battery

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