LU501904B1 - High-performance Sodium Ion Battery Anode Material And Its Preparation Method - Google Patents

High-performance Sodium Ion Battery Anode Material And Its Preparation Method Download PDF

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LU501904B1
LU501904B1 LU501904A LU501904A LU501904B1 LU 501904 B1 LU501904 B1 LU 501904B1 LU 501904 A LU501904 A LU 501904A LU 501904 A LU501904 A LU 501904A LU 501904 B1 LU501904 B1 LU 501904B1
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Luxembourg
Prior art keywords
anode material
ion battery
sodium ion
powders
preparation
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LU501904A
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French (fr)
Inventor
Shuo Tian
Pei Ding
Zhanjun Yu
Yinxiao Du
Haibo Huo
Mingyu Li
Yan Li
Li Shao
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Univ Zhengzhou Aeronautics
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525Selection 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/054Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M2004/026Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027Negative electrodes

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a high-performance sodium ion battery anode material and its preparation method, and it belongs to the technical field of electrochemistry. The present invention dissolves CoCl2·6H2O, NiCl2·6H2O and urotropine in deionized water, performs hydrothermal reaction under the nitrogen environment, and then performs the suction filtration, washing and drying treatment to obtain NiCo2(OH)6 powders; mixes the NiCo2(OH)6 powders with the sulfur powders, and then performs vulcanization reaction to obtain the NiCo2S4 nanometer hexagonal sheet, namely the high-performance sodium ion battery anode material; under the current density of 1000mA/g, the first reversible specific capacity of the anode material of high-performance sodium ion battery can reach 528mAh/g, the reversible specific capacity can reach 442mAh/g after 100 cycles and 402mAh/g after 500 cycles. The anode material has high specific capacity, good cycle performance and excellent electrochemical performance.

Description

Description LU501904 High-performance Sodium Ion Battery Anode Material And Its Preparation Method
TECHNICAL FIELD The invention relates to the technical field of electrochemistry, and in particular to a high-performance sodium ion battery anode material and a preparation method thereof.
BACKGROUND The lithium ion battery system has been widely used owing to the advantages of the high discharge voltage, the large energy density, the low self-discharge, the long cycle life, and the environmental protection. However, due to the shortage of lithium resources, it is urgent to develop the next generation energy storage battery system with excellent comprehensive performance. However, the difficulties in the study of sodium ion batteries lie in the fact that the larger radius of the sodium ion makes the ion deintercalation more difficult in the electrochemical reaction process and the structure of the electrode material more unstable, which makes the overall electrochemical performance of sodium ion batteries worse than that of lithium ion batteries. Therefore, how to prepare the anode material for sodium ion battery with high specific capacity and good cycle performance is an urgent technical problem to be solved.
SUMMARY The main purpose of the present invention is to provide a high-performance sodium ion battery anode material and its preparation method, so as to solve the problems of the unstable electrode material structure and the poor electrochemical performance of sodium ion battery in the prior art. Under the current density of 1000mA/g, the first reversible specific capacity of the anode material of high-performance sodium ion battery can reach 528mAh/g, the reversible specific capacity can reach 442mAh/g after 100 cycles and 402mAh/g after 500 cycles. The anode material has high specific capacity, good cycle performance and excellent electrochemical performance.
In order to achieve the above purpose, the invention provides the following scheme: One of the purposes of the present invention is to provide a preparation method of the high-performance sodium ion battery anode material, comprising the following steps: Dissolving CoCl2-6H20, NiCl;'6H2O and urotropine in the deionized water, performing hydrothermal reaction under the nitrogen environment, and then performing the suction filtration, washing and, 501904 drying treatment to obtain NiCo2(OH)s powders; mixing the NiCo,(OH)s powders with the sulfur powders, and then performing the vulcanization reaction to obtain the NiCo,S4 nanometer hexagonal sheets, namely the high-performance sodium ion battery anode material; The molar ratio of the CoClz 6H>0, the NiCl»-6H:0 and urotropine is (1-2):(3-5): (15-18); The mass ratio of the NiCo2(OH)s powders to the sulfur powders is (3-4):(2-3).
Further, the molar volume ratio of CoCl,-6H,O to the deionized water is Immol:400mL.
Further, the hydrothermal reaction is performed under the magnetic stirring at 120°C, for 6 hours.
Further, the washing means washing twice with deionized water and then twice with the ethanol; the drying means drying in an oven at 80°C for 8 hours.
Further, the vulcanization reaction is carried out in a mixture of hydrogen and argon at 280°C for 2 hours.
Further, the volume ratio of hydrogen to argon in the hydrogen-argon mixed gas is 10:90.
The second object of the invention is to provide a preparation method of high-performance sodium ion battery anode material.
The third object of the invention is to provide an application of the high-performance sodium ion battery anode material in the preparation of the sodium ion battery.
The invention discloses the following technical effects: Under the current density of 1000mA/g, the first reversible specific capacity of the high-performance sodium ion battery anode material in the invention can reach 528mAh/g, the reversible specific capacity can reach 442mAh/g after 100 cycles and 402mAh/g after 500 cycles. The anode material has high specific capacity, good cycle performance and excellent electrochemical performance;
DESCRIPTION OF THE INVENTION Various exemplary embodiments of the present invention will now be described in detail, which should not be regarded as a limitation of the present invention, but rather as a more detailed description of certain aspects, characteristics and embodiments of the present invention.
It should be understood that the terms described in the present invention are only for describing specific embodiments, and are not intended to limit the present invention. In addition, the numerical range in the present invention should be understood as every intermediate value between the upper limit and the lower limit of the range is also specifically disclosed 50 1904 Intermediate values within any stated value or stated range and every smaller range between any other stated value or intermediate values within the stated range are also included in the present invention. The upper and lower limits of these smaller ranges can be independently included in or excluded from the range.
Without departing from the scope or spirit of the invention, it is obvious to those skilled in this field that many modifications and changes can be made to the specific embodiments of the specification of the invention. Other embodiments derived from the description of the present invention will be apparent to the skilled person. The specification and examples of this application are only exemplary.
As used herein, the terms "including", "comprising", "having", "containing", etc. are all open terms, which means including but not limited to.
Embodiment 1 CoCly-6H,0, NiCly-6H,0 and urotropine are dissolved in deionized water. The molar ratio of CoCl,:6H,0, NiCl,:6H,O and urotropine is 1.5:3:17, and the molar volume ratio of CoCly-6H,0 to deionized water is Immol:400mL, the hydrothermal reaction is carried out under nitrogen and magnetic stirring conditions. The temperature of the hydrothermal reaction is 120°C and the time is 6 hours; then, the precipitate is obtained by extraction and filtration; the precipitate is washed twice with deionized water and twice with ethanol, and dried for 8 hours in an oven at 80°C to obtain NiCo2(OH)s powders; and then mixed it with the sulfur powders, the mass ratio of NiCox(OH)s powders to sulfur powders is 3.5:3; and the mixed powder is vulcanized for 2 hours at 280°C in a mixture of hydrogen and argon (the volume ratio of hydrogen to argon is 10:90), to obtain the high-performance sodium ion battery anode material.
Embodiment 2 CoCly-6H,0, NiCly-6H,0 and urotropine are dissolved in deionized water. The molar ratio of CoCl,:6H:0, NiCl,-6H,O and urotropine is 1:3:15, and the molar volume ratio of CoCly-6H,0 to deionized water is Immol:400mL, the hydrothermal reaction is carried out under nitrogen and magnetic stirring conditions. The temperature of the hydrothermal reaction is 120°C and the time is 6 hours; then, the precipitate is obtained by extraction and filtration; the precipitate is washed twice with deionized water and twice with ethanol, and dried for 8 hours in an oven at 80°C to obtain NiCoz(OH)s powders, and then mixed it with the sulfur powders, the mass ratio of NiCo,(OH)s powders to sulfur powders is 3:2; and the mixed powder is vulcanized, 501904 for 2 hours at 280°C in a mixture of hydrogen and argon (the volume ratio of hydrogen to argon is 10:90), to obtain the high-performance sodium ion battery anode material.
Embodiment 3 CoCly-6H,0, NiCly-6H,0 and urotropine are dissolved in deionized water. The molar ratio of CoCl,:6H:0, NiCl,-6H,O and urotropine is 2:5:18, and the molar volume ratio of CoCl»6H20 to deionized water is Immol:400mL, the hydrothermal reaction is carried out under nitrogen and magnetic stirring conditions. The temperature of the hydrothermal reaction is 120°C and the time is 6 hours; then, the precipitate is obtained by extraction and filtration; the precipitate is washed twice with deionized water and twice with ethanol, and dried for 8 hours in an oven at 80°C to obtain NiCo2(OH)s powders, and then mixed it with the sulfur powders, the mass ratio of NiCo,(OH)s powders to sulfur powders is 4:3; and the mixed powder is vulcanized for 2 hours at 280°C in a mixture of hydrogen and argon (the volume ratio of hydrogen to argon is 10:90), to obtain the high-performance sodium ion battery anode material.
Comparative example 1 CoCly-6H,0, NiCly-6H,0 and urotropine are dissolved in deionized water. The molar ratio of CoCl,:6H,0, NiCl,:6H,O and urotropine is 1.5:3:17, and the molar volume ratio of CoCly-6H,0 to deionized water is Immol:400mL, the hydrothermal reaction is carried out under nitrogen and magnetic stirring conditions. The temperature of the hydrothermal reaction is 120°C and the time is 6 hours; then, the precipitate is obtained by extraction and filtration; the precipitate is washed twice with deionized water and twice with ethanol, and dried for 8 hours in an oven at 80°C to obtain NiCo,(OH)e powders; the sodium ion battery anode material is obtained without vulcanization reaction.
Comparative example 2 CoCly-6H,0, NiCly-6H,0 and urotropine are dissolved in deionized water. The molar ratio of CoCl,:6H:0, NiCl,-6H,O and urotropine is 2:1:18, and the molar volume ratio of CoCl»6H20 to deionized water is Immol:400mL, the hydrothermal reaction is carried out under nitrogen and magnetic stirring conditions. The temperature of the hydrothermal reaction is 120°C and the time is 6 hours; then, the precipitate is obtained by extraction and filtration; the precipitate is washed twice with deionized water and twice with ethanol, and dried for 8 hours in an oven at 80°C to obtain NiCoz(OH)s powders, and then mixed it with the sulfur powders, the mass ratio of NiCox(OH)s powders to sulfur powders is 3.5:3; and the mixed powder (550 1904 vulcanized for 2 hours at 280°C in a mixture of hydrogen and argon (the volume ratio of hydrogen to argon is 10:90), to obtain the high-performance sodium ion battery anode material.
Comparative example 3 CoCly-6H,0, NiCly-6H,0 and urotropine are dissolved in deionized water. The molar ratio of CoCl,:6H,0, NiCl,:6H,O and urotropine is 1.5:3:17, and the molar volume ratio of CoCly-6H,0 to deionized water is Immol:400mL, the hydrothermal reaction is carried out under nitrogen and magnetic stirring conditions. The temperature of the hydrothermal reaction is 120°C and the time is 6 hours; then, the precipitate is obtained by extraction and filtration; the precipitate is washed twice with deionized water and twice with ethanol, and dried for 8 hours in an oven at 80°C to obtain NiCoz(OH)s powders, and then mixed it with the sulfur powders, the mass ratio of NiCox(OH)s powders to sulfur powders is 1:1.2; and the mixed powder is vulcanized for 2 hours at 280°C in a mixture of hydrogen and argon (the volume ratio of hydrogen to argon is 10:90), to obtain the high-performance sodium ion battery anode material.
Effect verification example The 2032 type button cell is assembled by using the materials prepared in each example and comparative example as the anodes, the graphene as a conductive additive, the polyvinylidene fluoride as a binder ( The mass ratio of anode material, graphene and polyvinylidene fluoride is 70:15:15), sodium metal as a counter electrode, polypropylene microporous membrane as a separator, and 1mol/L of NaSO;CF3/ diethylene glycol dimethyl ether as an electrolyte. The whole battery assembly process is completed in the glove box with water/oxygen content below
0.15mg/m°. The constant current charge-discharge test of the battery is performed at room temperature by the LANDCT2001A battery test system with a test voltage range of 0.01-2.80V and a current density of 1000 mA/g. The cyclic voltametric test is carried out on CHI 660e electrochemical work station, and the specific results are shown in table 1.
Table 1 LU501904 The first reversible | The reversible specific | The reversible specific Projects specific capacity | capacity of 100 cycles | capacity of 500 cycles (mAh/g) (mAh/g) (mAh/g) Comparative 436 364 348 example 1 Comparative 482 385 326 example 2 Comparative 475 364 339 example 3 As shown in table 1, under the current density of 1000mA/g, the first reversible specific capacity of the high-performance sodium ion battery anode material can reach 528mAh/g, the reversible specific capacity can reach 442mAh/g after 100 cycles, and 402mAh/g after 500 cycles, which indicates that the anode material has high specific capacity, good cycle performance and excellent electrochemical performance.
The above-mentioned embodiments only describe the preferred mode of the present invention, and do not limit the scope of the present invention. Without departing from the design spirit of the present invention, variations and improvements made by general technicians in this field should fall within the protection scope determined by the claims of the present invention.

Claims (8)

CLAIMS LU501904
1. A preparation method of a high-performance sodium ion battery anode material, which is characterized by comprising the following steps: dissolving CoCl»6H:0, NiCl»:6H:0 and urotropine in deionized water, performing hydrothermal reaction under the nitrogen environment, and then performing the suction filtration, washing and drying treatment to obtain NiCo2(OH)s powders; mixing the NiCo,(OH)s powders with sulfur powders, and then performing the vulcanization reaction to obtain the high-performance sodium ion battery anode material; the molar ratio of the CoCl,:6H:0, the NiCl,6H:0 and the urotropine is (1-2):(3-5):(15-18); the mass ratio of the NiCo,(OH)s powders to the sulfur powders is (3-4):(2-3).
2. According to the preparation method of claim 1, which is characterized in that the molar volume ratio of CoCl,:6H:0 to deionized water is Immol:400mL.
3. According to the preparation method of claim 1, which is characterized in that the hydrothermal reaction is carried out with the magnetic stirring, the temperature of the hydrothermal reaction is 120°C, and the duration is 6 hours.
4. According to the preparation method of claim 1, which is characterized in washing twice with deionized water and twice with ethanol and drying in an oven at 80°C for 8 hours.
5. According to the preparation method of claim 1, which is characterized in that the vulcanization reaction is carried out in a mixture of hydrogen and argon at 280°C for 2 hours.
6. According to the preparation method of claim 5, which is characterized in that the volume ratio of hydrogen to argon in the hydrogen-argon mixed gas is 10:90.
7. A high-performance sodium ion battery anode material is prepared by the preparation method of any one of claims 1 to 6.
8. An application of the high-performance sodium ion battery anode material according to claim 7 is included in the preparation of the sodium ion battery.
LU501904A 2022-04-22 2022-04-22 High-performance Sodium Ion Battery Anode Material And Its Preparation Method LU501904B1 (en)

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