CN114975920B - Electrode material of core-shell structure graphite alkyne coated with metallic antimony, and preparation method and application thereof - Google Patents

Electrode material of core-shell structure graphite alkyne coated with metallic antimony, and preparation method and application thereof Download PDF

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CN114975920B
CN114975920B CN202210523428.9A CN202210523428A CN114975920B CN 114975920 B CN114975920 B CN 114975920B CN 202210523428 A CN202210523428 A CN 202210523428A CN 114975920 B CN114975920 B CN 114975920B
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graphite alkyne
cuprous oxide
stirring
antimony
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CN114975920A (en
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杨维清
卿月
白佳
唐琪
王勇彬
张明哲
蒲犇
刘妍
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Southwest Jiaotong University
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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
    • H01M4/62—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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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 graphite alkyne coated metal antimony electrode material with a core-shell structure, and a preparation method and application thereof, and the electrode material comprises the following steps: preparing cuprous oxide nano cubes, dispersing the cuprous oxide nano cubes in acetone, mixing the cuprous oxide nano cubes with hexaethynyl benzene-pyridine solution, stirring and reacting for 20-28 hours in a dark place, standing and reacting for 45-50 hours in a dark place, and washing and drying the mixture to obtain the cuprous oxide@graphite alkyne composite material; annealing the cuprous oxide@graphite alkyne composite material in a hydrogen-argon mixed gas atmosphere to obtain a copper nano cube@graphite alkyne composite material; mixing antimony trichloride with an organic solvent and tetrabutylammonium tetrafluoroborate, then mixing with copper nano cube @ graphite alkyne, stirring for reacting for 70-75 hours, and then washing and drying to obtain the copper nano cube @ graphite alkyne. The preparation method is quick, convenient and effective, the morphology of the prepared material is controllable, and the prepared sodium ion battery anode material has excellent rate performance and long-cycle performance and excellent electrochemical performance.

Description

Electrode material of core-shell structure graphite alkyne coated with metallic antimony, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a graphite alkyne coated metal antimony electrode material with a core-shell structure, and a preparation method and application thereof.
Background
The sodium ion battery has the advantages of rich raw material sodium resource reserves, compatibility with the existing lithium ion battery production process, capability of replacing copper foil with lower aluminum foil for current collector, capability of using low-concentration electrolyte, high safety and the like, and has great application prospect in the fields of large-scale energy storage, traffic, electrification and the like. If the battery breaks through in technology and realizes industrialization, the battery has revolutionary influence on the energy storage field. At present, the lack of a stable and efficient negative electrode material is one of important bottlenecks for limiting the technical development of sodium ion batteries, and the development of a novel sodium ion battery negative electrode material with high stability, high specific capacity and high rate performance is imperative. Among the negative electrode materials of sodium ion batteries, metal antimony (Sb) is a negative electrode material of sodium ion batteries with great potential, and has the advantages of high theoretical capacity (660 mAh/g), good conductivity, more suitable working voltage, rich resource reserves (China is the country with the most abundant antimony resource reserves in the world, and occupies 47% of the total global reserves) and the like.
The high-capacity antimony-based material has obvious volume expansion effect in the sodium storage process, so that the circulation stability is poor, and the practical application of the high-capacity antimony-based material on sodium ion batteries is severely restricted. Although carbon coating is one of the effective means to improve the stability of antimony-based materials, there are still: (1) The carbon shell has low sodium storage capacity, and the specific capacity of the composite material can be reduced after the carbon shell is compounded with the antimony-based material; (2) The rapid transmission of sodium ions is not facilitated, and the rate capability of the material is reduced; (3) High carbonization temperature leads to volatilization of low-melting-point metal antimony, and the problems of difficulty in guaranteeing high content of active material antimony and the like.
Disclosure of Invention
Aiming at the prior art, the invention provides a graphite alkyne coated metal antimony electrode material with a core-shell structure, and a preparation method and application thereof, so as to solve the problems of low sodium storage capacity, low specific capacity, low rate capability and the like of the existing carbon coated antimony-based material.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: the preparation method of the core-shell graphite alkyne coated metal antimony electrode material comprises the following steps:
(1) Preparing cuprous oxide nanometer cubes;
(2) Dispersing the cuprous oxide nano cubic block in acetone, mixing with hexaethynyl benzene-pyridine solution, stirring and reacting for 20-28 h in a dark place, standing and reacting for 45-50 h in a dark place, and washing and drying to obtain the cuprous oxide@graphite alkyne composite material;
(3) Annealing the cuprous oxide@graphite alkyne composite material in a hydrogen-argon mixed gas atmosphere to obtain a copper nano cube@graphite alkyne composite material;
(4) Mixing antimony trichloride with an organic solvent and tetrabutylammonium tetrafluoroborate, then mixing with copper nano cube @ graphite alkyne, stirring for reacting for 70-75 hours, and then washing and drying to obtain the copper nano cube @ graphite alkyne.
On the basis of the technical scheme, the invention can be improved as follows.
Further, the size of the cuprous oxide cubes is 100-500 nm.
Further, the cuprous oxide nano-cube is prepared by the following steps: mixing 1.2-1.25M sodium hydroxide solution and 0.18-0.2M copper sulfate solution according to a volume ratio of 1:4, stirring for 4-6 min to obtain a mixed solution, mixing 0.03-0.05M ascorbic acid solution and the mixed solution according to a volume ratio of 1:2, stirring for 10-20 min, standing and aging for 0.8-1.2 h, and washing and drying precipitates in the solution to obtain the aqueous solution.
Further, hexaethynyl benzene-pyridine solution is prepared by the steps of: dissolving hexa (trimethylsilylethynyl) benzene in tetrahydrofuran solution, stirring for 10-20 min in ice bath, adding tetrabutylammonium fluoride, stirring for 10-20 min, extracting, steaming the extract, and dissolving the obtained solid powder in pyridine.
Further, the concentration of the cuprous oxide-acetone solution obtained in the step (2) is 5-20 mg/ml, and the molar ratio of the cuprous oxide nano-cube to hexaethynyl benzene in the step (2) is 5-50:1; the concentration of hexaethynyl benzene-pyridine solution in the step (2) is 5-20 mg/ml.
Further, H in the hydrogen-argon mixture gas 2 And Ar has a volume ratio of 92-96:4-8; the annealing treatment temperature is 200-450 ℃ and the annealing treatment time is 2-10 h.
Further, in the step (4), antimony trichloride (SbCl 3 ) And the molar ratio of copper in the copper nano cube @ graphite alkyne is 1:0.5-5; the organic solvent is twoMethyl sulfoxide, ethanol, isopropanol, toluene or n-hexane.
The invention also provides the electrode material of the core-shell structure graphite alkyne coated metal antimony prepared by the preparation method.
The invention also provides application of the graphite alkyne coated metal antimony electrode material with the core-shell structure in preparing sodium ion batteries.
Further, preparing electrode materials of core-shell graphite alkyne coated metal antimony, conductive carbon black and sodium carboxymethylcellulose into slurry according to a mass ratio of 7:2:1, coating the slurry on copper foil to obtain a negative electrode, assembling the negative electrode and a sodium metal sheet into a half cell, wherein a diaphragm is glass fiber, and an electrolyte is 1M NaClO 4 EC/DMC solution of (a).
The beneficial effects of the invention are as follows:
1. the preparation method is a rapid, convenient and effective preparation method for obtaining the metal antimony@graphite alkyne with the core-shell structure, the prepared material has controllable morphology, and the prepared negative electrode material of the sodium ion battery has excellent rate performance and long cycle performance and excellent electrochemical performance.
2. The graphite alkyne used in the invention has the advantages which are not possessed by other carbon materials: the graphite alkyne has large in-plane spacing and rich in-plane pore structure, and is beneficial to ion transmission; can grow at low temperature<100 ℃); the sodium storage sites are rich, and the specific capacity of the pure graphite alkyne is up to 760mAh g -1 . Compared with the traditional carbon-coated metal antimony, the metal antimony@graphite alkyne with the core-shell structure prepared by the preparation method is expected to realize long cycle life, high energy density and high power density of the sodium ion battery.
Drawings
FIG. 1 is a Scanning Electron Micrograph (SEM) of the cuprous oxide material prepared in example 1;
FIG. 2 is a Scanning Electron Micrograph (SEM) of cuprous oxide @ graphitized alkyne prepared in example 1;
FIG. 3 is a Transmission Electron Micrograph (TEM) of cuprous oxide @ graphite alkyne prepared in example 1;
FIG. 4 is a Raman spectrum (Raman) of cuprous oxide @ graphite alkyne prepared in example 1;
FIG. 5 is a Transmission Electron Micrograph (TEM) of copper @ graphite alkyne prepared in example 1;
FIG. 6 is a scanning electron micrograph (TEM) of antimony@graphite alkyne prepared in example 1;
FIG. 7 is an X-ray diffraction pattern (XRD) of the antimony @ graphite alkyne prepared in example 1;
FIG. 8 is a graph of 1000mA g of antimony @ graphite alkyne prepared in example 1 -1 Cycling performance plot at current density;
fig. 9 is a graph of the rate performance of antimony @ graphite alkyne prepared in example 1 at different current densities.
Detailed Description
The following describes the present invention in detail with reference to examples.
Example 1
The preparation method of the electrode material of the core-shell structure graphite alkyne coated metal antimony (antimony@graphite alkyne) comprises the following steps:
(1) Dissolving 1.5mmol of copper sulfate pentahydrate in 80ml of deionized water, taking 20ml of sodium hydroxide solution with the concentration of 1.25M, adding the sodium hydroxide solution into the copper sulfate pentahydrate solution under stirring, stirring for 5min, adding 50ml of ascorbic acid solution with the concentration of 0.05M into the solution under stirring, stirring for 15min, standing and aging for 1h, washing the precipitate in the solution with absolute ethyl alcohol, and drying in vacuum at 60 ℃ to obtain cuprous oxide nanometer cubes;
(2) Dissolving 195.8mg of a graphite alkyne precursor (hexakis (trimethylsilyl ethynyl) benzene) in a tetrahydrofuran solution, stirring for 15min under an ice bath, adding 1.610ml of tetrabutylammonium fluoride, stirring for 15min, pouring into a separating funnel, adding saturated saline water and ethyl acetate for extraction, performing rotary evaporation on the obtained organic solution after extraction is finished, and dissolving solid powder obtained by rotary evaporation in 39.1ml of pyridine solution to obtain a silicon-removed-base-protected graphite alkyne precursor (hexaethynyl benzene) -pyridine solution;
(3) Dispersing 1.5g of cuprous oxide nano cubes in 200ml of acetone, carrying out ultrasonic treatment for 30min to ensure that the solution is uniformly dispersed, adding hexaethynyl benzene-pyridine solution into the acetone, uniformly mixing, carrying out light-shielding stirring reaction for 24h, carrying out light-shielding standing reaction for 48h, washing the mixture by absolute ethyl alcohol, and carrying out vacuum drying at 60 ℃ to obtain the cuprous oxide@graphite alkyne composite material;
(4) Mixing cuprous oxide @ graphite alkyne composite material with hydrogen-argon mixed gas (H therein 2 And Ar with the volume ratio of 94:6) is annealed for 3 hours at 400 ℃ in the atmosphere to obtain the copper nano cube@graphite alkyne composite material;
(5) 228mg SbCl 3 And 3.29g of tetrabutylammonium Tetrafluoroborate (TBABF) 4 ) Dissolving in 200ml dimethyl sulfoxide (DMSO) solution to prepare SbCl 3 -TBABF 4 -DMSO solution, 64mg copper nano cube @ graphite alkyne was further dispersed in 20ml DMSO solution and sonicated for 30min, after which SbCl was added 3 -TBABF 4 Stirring and reacting for 72h in DMSO solution, washing with absolute ethanol, and vacuum drying at 60 ℃.
The preparation method of the negative electrode of the sodium ion battery uses the antimony@graphite alkyne material with the core-shell structure, and comprises the following steps:
the method comprises the steps of preparing slurry from antimony@graphite alkyne, conductive carbon black and sodium carboxymethylcellulose (CMC) according to a mass ratio of 7:2:1, coating the slurry on a copper foil, assembling the slurry with a sodium metal sheet to form a half cell, wherein a diaphragm is glass fiber, and an electrolyte is 1M NaClO 4 The electrochemical performance of the cell was examined at 1000mAg for EC/DMC (volume ratio 1:1) solution -1 At a current density, the capacity was 405.1mAh g -1 (as shown in figure eight).
Example 2
The preparation method of the core-shell structured graphite alkyne coated metallic antimony electrode material comprises the following steps:
(1) Dissolving 1.5mmol of copper sulfate pentahydrate in 80ml of deionized water, taking 20ml of sodium hydroxide solution with the concentration of 1.2M, adding the sodium hydroxide solution into the copper sulfate pentahydrate solution under stirring, stirring for 4min, adding 50ml of ascorbic acid solution with the concentration of 0.04M into the solution under stirring, stirring for 10min, standing and aging for 0.8h, washing the precipitate in the solution with absolute ethyl alcohol, and drying in vacuum at 60 ℃ to obtain cuprous oxide nano cubes;
(2) Dissolving 195.8mg of a graphite alkyne precursor (hexakis (trimethylsilyl ethynyl) benzene) in a tetrahydrofuran solution, stirring for 10min under an ice bath, adding 1.610ml of tetrabutylammonium fluoride, stirring for 15min, pouring into a separating funnel, adding saturated saline water and ethyl acetate for extraction, performing rotary evaporation on the obtained organic solution after extraction is finished, and dissolving solid powder obtained by rotary evaporation in 39.1ml of pyridine solution to obtain a silicon-removed-base-protected graphite alkyne precursor (hexaethynyl benzene) -pyridine solution;
(3) Dispersing 1.2g of cuprous oxide nano cubes in 150ml of acetone, carrying out ultrasonic treatment for 30min to ensure that the solution is uniformly dispersed, adding hexaethynyl benzene-pyridine solution into the acetone, uniformly mixing, carrying out light-shielding stirring reaction for 20h, carrying out light-shielding standing reaction for 45h, washing the mixture by absolute ethyl alcohol, and carrying out vacuum drying at 60 ℃ to obtain the cuprous oxide@graphite alkyne composite material;
(4) Mixing cuprous oxide @ graphite alkyne composite material with hydrogen-argon mixed gas (H therein 2 And Ar with the volume ratio of 92:8) is annealed for 4 hours at 400 ℃ in the atmosphere to obtain the copper nano cube@graphite alkyne composite material;
(5) 684mg SbCl was taken 3 And 9.87g of tetrabutylammonium Tetrafluoroborate (TBABF) 4 ) Dissolving in 200ml isopropanol solution to prepare SbCl 3 -TBABF 4 -isopropanol solution, 64mg copper nano-cubes @ graphite alkyne were dispersed in 20ml isopropanol solution and sonicated for 30min, after which SbCl was added 3 -TBABF 4 And (3) in isopropanol solution, stirring and reacting for 70 hours, washing by absolute ethyl alcohol, and drying in vacuum at 60 ℃ to obtain the finished product.
The preparation method of the negative electrode of the sodium ion battery uses the antimony@graphite alkyne material with the core-shell structure, and comprises the following steps:
the method comprises the steps of preparing slurry from antimony@graphite alkyne, conductive carbon black and sodium carboxymethylcellulose (CMC) according to a mass ratio of 8:1:1, coating the slurry on a copper foil, assembling the slurry with a sodium metal sheet to form a half cell, wherein a diaphragm is glass fiber, and an electrolyte is 1M NaClO 4 The electrochemical performance of the cell was examined at 1000mAg for EC/DMC (volume ratio 1:1) solution -1 At current density, the capacity is 389.0mAh g -1 。
Example 3
The preparation method of the core-shell structured graphite alkyne coated metallic antimony electrode material comprises the following steps:
(1) Dissolving 1.5mmol of copper sulfate pentahydrate in 80ml of deionized water, taking 20ml of sodium hydroxide solution with the concentration of 1.25M, adding the sodium hydroxide solution into the copper sulfate pentahydrate solution under stirring, stirring for 6min, adding 50ml of ascorbic acid solution with the concentration of 0.03M into the solution under stirring, stirring for 20min, standing and aging for 1.2h, washing the precipitate in the solution with absolute ethyl alcohol, and drying in vacuum at 60 ℃ to obtain cuprous oxide nano cubes;
(2) Dissolving 195.8mg of a graphite alkyne precursor (hexakis (trimethylsilyl ethynyl) benzene) in a tetrahydrofuran solution, stirring for 20min under an ice bath, adding 1.610ml of tetrabutylammonium fluoride, stirring for 20min, pouring into a separating funnel, adding saturated saline water and ethyl acetate for extraction, performing rotary evaporation on the obtained organic solution after extraction is finished, and dissolving solid powder obtained by rotary evaporation in 39.1ml of pyridine solution to obtain a silicon-removed-base-protected graphite alkyne precursor (hexaethynyl benzene) -pyridine solution;
(3) Dispersing 1g of cuprous oxide nano cubes in 200ml of acetone, carrying out ultrasonic treatment for 30min to ensure that the solution is uniformly dispersed, adding hexaethynyl benzene-pyridine solution into the solution, uniformly mixing, carrying out light-shielding stirring reaction for 28h, carrying out light-shielding standing reaction for 50h, washing the reaction product by absolute ethyl alcohol, and carrying out vacuum drying at 60 ℃ to obtain the cuprous oxide@graphite alkyne composite material;
(4) Mixing cuprous oxide @ graphite alkyne composite material with hydrogen-argon mixed gas (H therein 2 And Ar with the volume ratio of 96:4) at 250 ℃ for 8 hours to obtain the copper nano cube@graphite alkyne composite material;
(5) 912mg SbCl is taken 3 And 13.16g of tetrabutylammonium Tetrafluoroborate (TBABF) 4 ) Dissolving in 200ml ethanol solution to prepare SbCl 3 -TBABF 4 -ethanol solution, dispersing 64mg copper nano-cube @ graphite alkyne in 20ml ethanol solution, and sonicating for 30min, followed by addition of SbCl 3 -TBABF 4 In ethanol solution, stirring again for 75h, followed by anhydrous reactionWashing with ethanol and vacuum drying at 60deg.C.
The preparation method of the negative electrode of the sodium ion battery uses the antimony@graphite alkyne material with the core-shell structure, and comprises the following steps:
the method comprises the steps of preparing slurry from antimony@graphite alkyne, conductive carbon black and sodium carboxymethylcellulose (CMC) according to a mass ratio of 7:2:1, coating the slurry on a copper foil, assembling the slurry with a sodium metal sheet to form a half cell, wherein a diaphragm is glass fiber, and an electrolyte is 1M NaClO 4 The electrochemical performance of the cell was examined at 1000mAg for EC/DMC (volume ratio 1:1) solution -1 At current density, the capacity is 411.6mAh g -1 。
Example 4
The preparation method of the core-shell structured graphite alkyne coated metallic antimony electrode material comprises the following steps:
(1) Dissolving 1.5mmol of copper sulfate pentahydrate in 80ml of deionized water, taking 20ml of sodium hydroxide solution with the concentration of 1.25M, adding the sodium hydroxide solution into the copper sulfate pentahydrate solution under stirring, stirring for 5min, adding 50ml of ascorbic acid solution with the concentration of 0.02M into the solution under stirring, stirring for 15min, standing and aging for 1h, washing the precipitate in the solution with absolute ethyl alcohol, and drying in vacuum at 60 ℃ to obtain cuprous oxide nano cubes;
(2) Dissolving 195.8mg of a graphite alkyne precursor (hexakis (trimethylsilyl ethynyl) benzene) in a tetrahydrofuran solution, stirring for 15min under an ice bath, adding 1.610ml of tetrabutylammonium fluoride, stirring for 15min, pouring into a separating funnel, adding saturated saline water and ethyl acetate for extraction, performing rotary evaporation on the obtained organic solution after extraction is finished, and dissolving solid powder obtained by rotary evaporation in 39.1ml of pyridine solution to obtain a silicon-removed-base-protected graphite alkyne precursor (hexaethynyl benzene) -pyridine solution;
(3) Dispersing 2g of cuprous oxide nano cubes in 200ml of acetone, carrying out ultrasonic treatment for 30min to ensure that the solution is uniformly dispersed, adding hexaethynyl benzene-pyridine solution into the solution, uniformly mixing, carrying out light-shielding stirring reaction for 24 hours, carrying out light-shielding standing reaction for 48 hours, washing the mixture by absolute ethyl alcohol, and carrying out vacuum drying at 60 ℃ to obtain the cuprous oxide@graphite alkyne composite material;
(4) Mixing cuprous oxide @ graphite alkyne composite material with hydrogen-argon mixed gas (H therein 2 And Ar with the volume ratio of 94:6) is annealed for 6 hours at 400 ℃ in the atmosphere to obtain the copper nano cube@graphite alkyne composite material;
(5) 570mg SbCl 3 And 8.225g of tetrabutylammonium Tetrafluoroborate (TBABF) 4 ) Dissolving in 200ml isopropanol solution to prepare SbCl 3 -TBABF 4 -isopropanol solution, 64mg copper nano-cubes @ graphite alkyne were dispersed in 20ml isopropanol solution and sonicated for 30min, after which SbCl was added 3 -TBABF 4 And (3) in isopropanol solution, stirring and reacting for 72 hours, washing by absolute ethyl alcohol, and drying in vacuum at 60 ℃ to obtain the finished product.
The preparation method of the negative electrode of the sodium ion battery uses the antimony@graphite alkyne material with the core-shell structure, and comprises the following steps:
the method comprises the steps of preparing slurry from antimony@graphite alkyne, conductive carbon black and sodium carboxymethylcellulose (CMC) according to a mass ratio of 8:1:1, coating the slurry on a copper foil, assembling the slurry with a sodium metal sheet to form a half cell, wherein a diaphragm is glass fiber, and an electrolyte is 1M NaClO 4 The electrochemical performance of the cell was examined at 1000mAg for EC/DMC (volume ratio 1:1) solution -1 At current density, the capacity is 374.3mAh g -1 。
Example 5
The preparation method of the core-shell structured graphite alkyne coated metallic antimony electrode material comprises the following steps:
(1) Dissolving 1.5mmol of copper sulfate pentahydrate in 80ml of deionized water, taking 20ml of sodium hydroxide solution with the concentration of 1.25M, adding the sodium hydroxide solution into the copper sulfate pentahydrate solution under stirring, stirring for 5min, adding 50ml of ascorbic acid solution with the concentration of 0.02M into the solution under stirring, stirring for 15min, standing and aging for 1h, washing the precipitate in the solution with absolute ethyl alcohol, and drying in vacuum at 60 ℃ to obtain cuprous oxide nano cubes;
(2) Dissolving 195.8mg of a graphite alkyne precursor (hexakis (trimethylsilyl ethynyl) benzene) in a tetrahydrofuran solution, stirring for 15min under an ice bath, adding 1.610ml of tetrabutylammonium fluoride, stirring for 15min, pouring into a separating funnel, adding saturated saline water and ethyl acetate for extraction, performing rotary evaporation on the obtained organic solution after extraction is finished, and dissolving solid powder obtained by rotary evaporation in 39.1ml of pyridine solution to obtain a silicon-removed-base-protected graphite alkyne precursor (hexaethynyl benzene) -pyridine solution;
(3) Dispersing 1g of cuprous oxide nano cubes in 50ml of acetone, carrying out ultrasonic treatment for 30min to ensure that the solution is uniformly dispersed, adding hexaethynyl benzene-pyridine solution into the acetone, uniformly mixing, carrying out light-shielding stirring reaction for 24 hours, carrying out light-shielding standing reaction for 48 hours, washing the mixture by absolute ethyl alcohol, and carrying out vacuum drying at 60 ℃ to obtain the cuprous oxide@graphite alkyne composite material;
(4) Mixing cuprous oxide @ graphite alkyne composite material with hydrogen-argon mixed gas (H therein 2 And Ar with the volume ratio of 94:6) is annealed for 6 hours at 300 ℃ in the atmosphere to obtain the copper nano cube@graphite alkyne composite material;
(5) 684mg SbCl was taken 3 And 9.87g of tetrabutylammonium Tetrafluoroborate (TBABF) 4 ) Dissolving in 200ml toluene solution to prepare SbCl 3 -TBABF 4 -toluene solution, 64mg copper nano-cubes @ graphite alkyne were dispersed in 20ml toluene solution and sonicated for 30min, after which SbCl was added 3 -TBABF 4 And (3) in toluene solution, stirring and reacting for 72 hours, washing by absolute ethyl alcohol and drying in vacuum at 60 ℃ to obtain the catalyst.
The preparation method of the negative electrode of the sodium ion battery uses the antimony@graphite alkyne material with the core-shell structure, and comprises the following steps:
the method comprises the steps of preparing slurry from antimony@graphite alkyne, conductive carbon black and sodium carboxymethylcellulose (CMC) according to a mass ratio of 7:2:1, coating the slurry on a copper foil, assembling the slurry with a sodium metal sheet to form a half cell, wherein a diaphragm is glass fiber, and an electrolyte is 1M NaClO 4 The electrochemical performance of the cells was examined at 1000mA g for EC/DMC (volume ratio 1:1) solution -1 At current density, the capacity is 385.7mAh g -1 。
Example 6
The preparation method of the core-shell structured graphite alkyne coated metallic antimony electrode material comprises the following steps:
(1) Dissolving 1.5mmol of copper sulfate pentahydrate in 80ml of deionized water, taking 20ml of sodium hydroxide solution with the concentration of 1.25M, adding the sodium hydroxide solution into the copper sulfate pentahydrate solution under stirring, stirring for 5min, adding 50ml of ascorbic acid solution with the concentration of 0.04M into the solution under stirring, stirring for 15min, standing and aging for 1h, washing the precipitate in the solution with absolute ethyl alcohol, and drying in vacuum at 60 ℃ to obtain cuprous oxide nanometer cubes;
(2) Dissolving 195.8mg of a graphite alkyne precursor (hexakis (trimethylsilyl ethynyl) benzene) in a tetrahydrofuran solution, stirring for 15min under an ice bath, adding 1.610ml of tetrabutylammonium fluoride, stirring for 15min, pouring into a separating funnel, adding saturated saline water and ethyl acetate for extraction, performing rotary evaporation on the obtained organic solution after extraction is finished, and dissolving solid powder obtained by rotary evaporation in 39.1ml of pyridine solution to obtain a silicon-removed-base-protected graphite alkyne precursor (hexaethynyl benzene) -pyridine solution;
(3) Dispersing 2g of cuprous oxide nano cubes in 100ml of acetone, carrying out ultrasonic treatment for 30min to ensure that the solution is uniformly dispersed, adding hexaethynyl benzene-pyridine solution into the acetone, uniformly mixing, carrying out light-shielding stirring reaction for 24 hours, carrying out light-shielding standing reaction for 48 hours, washing the mixture by absolute ethyl alcohol, and carrying out vacuum drying at 60 ℃ to obtain the cuprous oxide@graphite alkyne composite material;
(4) Mixing cuprous oxide @ graphite alkyne composite material with hydrogen-argon mixed gas (H therein 2 And Ar with the volume ratio of 94:6) is annealed for 8 hours at 200 ℃ in the atmosphere to obtain the copper nano cube@graphite alkyne composite material;
(5) 1140mg SbCl 3 And 16.45g of tetrabutylammonium Tetrafluoroborate (TBABF) 4 ) Dissolving in 200ml toluene solution to prepare SbCl 3 -TBABF 4 -toluene solution, 64mg copper nano-cubes @ graphite alkyne were dispersed in 20ml toluene solution and sonicated for 30min, after which SbCl was added 3 -TBABF 4 And (3) in toluene solution, stirring and reacting for 72 hours, washing by absolute ethyl alcohol and drying in vacuum at 60 ℃ to obtain the catalyst.
The preparation method of the negative electrode of the sodium ion battery uses the antimony@graphite alkyne material with the core-shell structure, and comprises the following steps:
the method comprises the steps of preparing slurry from antimony@graphite alkyne, conductive carbon black and sodium carboxymethylcellulose (CMC) according to a mass ratio of 8:1:1, coating the slurry on a copper foil, assembling the slurry with a sodium metal sheet to form a half cell, wherein a diaphragm is glass fiber, and an electrolyte is 1M NaClO 4 The electrochemical performance of the cell was examined at 1000mAg for EC/DMC (volume ratio 1:1) solution -1 At current density, the capacity is 427.9mAh g -1 。
Example 7
The preparation method of the core-shell structured graphite alkyne coated metallic antimony electrode material comprises the following steps:
(1) Dissolving 1.5mmol of copper sulfate pentahydrate in 80ml of deionized water, taking 20ml of sodium hydroxide solution with the concentration of 1.25M, adding the sodium hydroxide solution into the copper sulfate pentahydrate solution under stirring, stirring for 5min, adding 50ml of ascorbic acid solution with the concentration of 0.05M into the solution under stirring, stirring for 15min, standing and aging for 1h, washing the precipitate in the solution with absolute ethyl alcohol, and drying in vacuum at 60 ℃ to obtain cuprous oxide nanometer cubes;
(2) Dissolving 195.8mg of a graphite alkyne precursor (hexakis (trimethylsilyl ethynyl) benzene) in a tetrahydrofuran solution, stirring for 15min under an ice bath, adding 1.610ml of tetrabutylammonium fluoride, stirring for 15min, pouring into a separating funnel, adding saturated saline water and ethyl acetate for extraction, performing rotary evaporation on the obtained organic solution after extraction is finished, and dissolving solid powder obtained by rotary evaporation in 39.1ml of pyridine solution to obtain a silicon-removed-base-protected graphite alkyne precursor (hexaethynyl benzene) -pyridine solution;
(3) Dispersing 2g of cuprous oxide nano cubes in 150ml of acetone, carrying out ultrasonic treatment for 30min to ensure that the solution is uniformly dispersed, adding hexaethynyl benzene-pyridine solution into the acetone, uniformly mixing, carrying out light-shielding stirring reaction for 24 hours, carrying out light-shielding standing reaction for 48 hours, washing the mixture by absolute ethyl alcohol, and carrying out vacuum drying at 60 ℃ to obtain the cuprous oxide@graphite alkyne composite material;
(4) Mixing cuprous oxide @ graphite alkyne composite material with hydrogen-argon mixed gas (H therein 2 And Ar with the volume ratio of 94:6) is annealed for 8 hours at 250 ℃ in the atmosphere to obtain the copper nano cube @ stoneAn ink alkyne composite material;
(5) 342mg SbCl is taken 3 And 4.935g of tetrabutylammonium Tetrafluoroborate (TBABF) 4 ) Dissolving in 200ml ethanol solution to prepare SbCl 3 -TBABF 4 -ethanol solution, dispersing 64mg copper nano-cube @ graphite alkyne in 20ml ethanol solution, and sonicating for 30min, followed by addition of SbCl 3 -TBABF 4 And (3) in ethanol solution, stirring and reacting for 72 hours, washing by absolute ethanol and drying in vacuum at 60 ℃ to obtain the catalyst.
The preparation method of the negative electrode of the sodium ion battery uses the antimony@graphite alkyne material with the core-shell structure, and comprises the following steps:
the method comprises the steps of preparing slurry from antimony@graphite alkyne, conductive carbon black and sodium carboxymethylcellulose (CMC) according to a mass ratio of 8:1:1, coating the slurry on a copper foil, assembling the slurry with a sodium metal sheet to form a half cell, wherein a diaphragm is glass fiber, and an electrolyte is 1M NaClO 4 The electrochemical performance of the cell was examined at 1000mAg for EC/DMC (volume ratio 1:1) solution -1 At current density, the capacity is 414.2mAh g -1 。
Example 8
The preparation method of the core-shell structured graphite alkyne coated metallic antimony electrode material comprises the following steps:
(1) Dissolving 1.5mmol of copper sulfate pentahydrate in 80ml of deionized water, taking 20ml of sodium hydroxide solution with the concentration of 1.25M, adding the sodium hydroxide solution into the copper sulfate pentahydrate solution under stirring, stirring for 5min, adding 50ml of ascorbic acid solution with the concentration of 0.03M into the solution under stirring, stirring for 15min, standing and aging for 1h, washing the precipitate in the solution with absolute ethyl alcohol, and drying in vacuum at 60 ℃ to obtain cuprous oxide nano cubes;
(2) Dissolving 195.8mg of a graphite alkyne precursor (hexakis (trimethylsilyl ethynyl) benzene) in a tetrahydrofuran solution, stirring for 15min under an ice bath, adding 1.610ml of tetrabutylammonium fluoride, stirring for 15min, pouring into a separating funnel, adding saturated saline water and ethyl acetate for extraction, performing rotary evaporation on the obtained organic solution after extraction is finished, and dissolving solid powder obtained by rotary evaporation in 39.1ml of pyridine solution to obtain a silicon-removed-base-protected graphite alkyne precursor (hexaethynyl benzene) -pyridine solution;
(3) Dispersing 1g of cuprous oxide nano cubes in 150ml of acetone, carrying out ultrasonic treatment for 30min to ensure that the solution is uniformly dispersed, adding hexaethynyl benzene-pyridine solution into the solution, uniformly mixing, carrying out light-shielding stirring reaction for 24 hours, carrying out light-shielding standing reaction for 48 hours, washing the mixture by absolute ethyl alcohol, and carrying out vacuum drying at 60 ℃ to obtain the cuprous oxide@graphite alkyne composite material;
(4) Mixing cuprous oxide @ graphite alkyne composite material with hydrogen-argon mixed gas (H therein 2 And Ar with the volume ratio of 94:6) is annealed for 6 hours at 350 ℃ in the atmosphere to obtain the copper nano cube@graphite alkyne composite material;
(5) 798mg SbCl was taken 3 And 11.52g of tetrabutylammonium Tetrafluoroborate (TBABF) 4 ) Dissolving in 200ml toluene solution to prepare SbCl 3 -TBABF 4 -toluene solution, 64mg copper nano-cubes @ graphite alkyne were dispersed in 20ml toluene solution and sonicated for 30min, after which SbCl was added 3 -TBABF 4 And (3) in toluene solution, stirring and reacting for 72 hours, washing by absolute ethyl alcohol and drying in vacuum at 60 ℃ to obtain the catalyst.
The preparation method of the negative electrode of the sodium ion battery uses the antimony@graphite alkyne material with the core-shell structure, and comprises the following steps:
the method comprises the steps of preparing slurry from antimony@graphite alkyne, conductive carbon black and sodium carboxymethylcellulose (CMC) according to a mass ratio of 8:1:1, coating the slurry on a copper foil, assembling the slurry with a sodium metal sheet to form a half cell, wherein a diaphragm is glass fiber, and an electrolyte is 1M NaClO 4 The electrochemical performance of the cells was examined at 1000mA g for EC/DMC (volume ratio 1:1) solution -1 At current density, the capacity is 377.5mAh g -1 。
FIG. 8 shows that the antimony@graphite alkyne electrode material is at 1000mAh g -1 Cycle characteristics at current density. At 1000mAh g -1 The discharge specific capacity of the antimony@graphite alkyne electrode material is up to 583.7mAh g in the first circle (the second circle of total circulation) under the current density -1 . After 1000 circles, the material still keeps 405.1mAh g -1 Is high in reversible specific capacity, capacity retention is 70%, and average coulombic efficiency is 997 percent of antimony@graphite alkyne electrode material has excellent long-cycle performance.
Fig. 9 shows the rate capability of the antimony @ graphite alkyne electrode at different current densities. When the current density is from 1A g -1 Sequentially increasing to 2A g -1 、5A g -1 And 10A g -1 When the discharge capacity of the first ring of the antimony@graphite alkyne electrode is from 369.7mAh g -1 Reduced to 311.9, 230.6, and 160mAh g -1 When the current density is restored to 1A g -1 When the reversible capacity is recovered to 334.4mAh g -1 The antimony@graphite alkyne electrode material has excellent rate capability.
While specific embodiments of the invention have been described in detail in connection with the examples, it should not be construed as limiting the scope of protection of the patent. Various modifications and variations which may be made by those skilled in the art without the creative effort are within the scope of the patent described in the claims.

Claims (10)

1. The preparation method of the core-shell structured graphite alkyne coated metallic antimony electrode material is characterized by comprising the following steps of:
(1) Preparing cuprous oxide nanometer cubes;
(2) Dispersing the cuprous oxide nano cubic block in acetone, mixing with hexaethynyl benzene-pyridine solution, stirring and reacting for 20-28 h in a dark place, standing and reacting for 45-50 h in a dark place, and washing and drying to obtain the cuprous oxide@graphite alkyne composite material;
(3) Annealing the cuprous oxide@graphite alkyne composite material in a hydrogen-argon mixed gas atmosphere to obtain a copper nano cube@graphite alkyne composite material;
(4) Mixing antimony trichloride with an organic solvent and tetrabutylammonium tetrafluoroborate, then mixing with copper nano cube @ graphite alkyne, stirring for reacting for 70-75 hours, and then washing and drying to obtain the copper nano cube @ graphite alkyne.
2. The method of manufacturing according to claim 1, characterized in that: the size of the cuprous oxide cube is 100-500 nm.
3. The preparation method according to claim 1 or 2, wherein the cuprous oxide nano-cubes are prepared by the steps of: mixing 1.2-1.25M sodium hydroxide solution and 0.18-0.2M copper sulfate solution according to a volume ratio of 1:4, stirring for 4-6 min to obtain a mixed solution, mixing 0.03-0.05M ascorbic acid solution and the mixed solution according to a volume ratio of 1:2, stirring for 10-20 min, standing and aging for 0.8-1.2 h, and washing and drying precipitates in the solution to obtain the aqueous solution.
4. The preparation method according to claim 1, wherein the hexaethynyl benzene-pyridine solution is prepared by the steps of: dissolving hexa (trimethylsilylethynyl) benzene in tetrahydrofuran solution, stirring for 10-20 min in ice bath, adding tetrabutylammonium fluoride, stirring for 10-20 min, extracting, steaming the extract, and dissolving the obtained solid powder in pyridine.
5. The method of manufacturing according to claim 1, characterized in that: the concentration of the cuprous oxide-acetone solution obtained in the step (2) is 5-20 mg/ml, and the molar ratio of the cuprous oxide nano-cube to hexaethynyl benzene in the step (2) is 5-50:1; the concentration of hexaethynyl benzene-pyridine solution in the step (2) is 5-20 mg/ml.
6. The method of manufacturing according to claim 1, characterized in that: h in the hydrogen-argon mixture gas 2 And Ar has a volume ratio of 92-96:4-8; the annealing treatment temperature is 200-450 ℃ and the annealing treatment time is 2-10 h.
7. The method of manufacturing according to claim 1, characterized in that: in the step (4), the molar ratio of the antimony trichloride to the copper in the copper nano cube @ graphite alkyne is 1:0.5-5; the organic solvent is dimethyl sulfoxide, ethanol, isopropanol, toluene or n-hexane.
8. The electrode material of core-shell structure graphite alkyne coated metallic antimony prepared by the preparation method according to any one of claims 1 to 7.
9. The use of the core-shell structured graphite alkyne coated metallic antimony electrode material according to claim 8 in the preparation of sodium ion batteries.
10. The use according to claim 9, characterized in that: preparing electrode material of core-shell structure graphite alkyne coated metal antimony, conductive carbon black and sodium carboxymethylcellulose into slurry according to a mass ratio of 7:2:1, coating the slurry on copper foil to obtain a negative electrode, assembling the negative electrode and a sodium metal sheet into a half cell, wherein a diaphragm is glass fiber, and an electrolyte is 1M NaClO 4 EC/DMC solution of (a).
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