CN113793919A - NC @ SnSb @ NC material and preparation method and application thereof - Google Patents

NC @ SnSb @ NC material and preparation method and application thereof Download PDF

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CN113793919A
CN113793919A CN202111085762.2A CN202111085762A CN113793919A CN 113793919 A CN113793919 A CN 113793919A CN 202111085762 A CN202111085762 A CN 202111085762A CN 113793919 A CN113793919 A CN 113793919A
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snsb
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程勇
石雪建
尹东明
刘万强
梁飞
王春丽
王立民
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Changchun Institute of Applied Chemistry of CAS
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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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • 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 provides an NC @ SnSb @ NC material, a preparation method and an application thereof, and relates to the field of alkali metal ion battery cathode materials. The material is prepared by preparing a polypyrrole supporting framework material by a sol-gel method, and treating the polypyrrole supporting framework material by a surfactant to obtain A-PPy; introducing an intermediate tin-antimony oxide to the A-PPy by using an ion exchange method to obtain the A-PPy @ Sn2Sb2O7(ii) a For the obtained A-PPy @ Sn2Sb2O7Carrying out in-situ carbon coating to obtain A-PPy @ Sn2Sb2O7@ PDA, and finally obtaining the NC @ SnSb @ NC material by a thermal reduction method. The composite material shows excellent electrochemistry property as a negative electrode of alkali metal ion batteries (LIBs, NIBs and KIBs)Can be used. In 1Ag‑1466, 386 and 236mAhg can be respectively released after 1500, 120 and 500 times of current circulation‑1The specific capacity of (A).

Description

NC @ SnSb @ NC material and preparation method and application thereof
Technical Field
The invention relates to the field of alkali metal ion battery cathode materials, in particular to an NC @ SnSb @ NC material and a preparation method and application thereof.
Background
At present, the development of electrochemical energy storage is very important due to the large-scale development and utilization of electronic products. Sustainable batteries, which are dominated by Lithium Ion Batteries (LIBs), have been widely studied for their high safety and long cycle life. However, graphite as a negative electrode of a lithium ion battery can provide only 372mAh g-1Which severely limits their development. Sodium and potassium ion batteries (NIBs/KIBs) are considered as products that can replace lithium ion batteries in view of their abundant availability and low cost. However, graphite anodes suitable for LIBs are not well utilized in NIBs/KIBs. For example, when graphite is used as the anode of SIBs, only 35mAh g can be maintained due to strong repulsive action of ion coordination-1The capacity of (c). In addition, the serious volume effect and poor cycle stability faced in the charging and discharging process make it imperative to find a universal negative electrode material with excellent electrochemical performance.
SnSb-based negative electrodes have recently been favored by many researchers because Sn and Sb undergo alloying reactions with alkali metal ions at different reaction potentials and have a high theoretical specific capacity (824 mAh g for LIBs)-1) May be a buffer matrix for each other. However, during storage of alkali metal ions, the electrode still has a severe volume effect, which causes active material agglomerates to break, resulting in separation of active material from the electrode during cycling and structural collapse. In this case, a large amount of active Li is consumed due to cracking and recombination of the SEI film+/Na+/K+Causing the capacity to decay rapidly. More importantly, Na+Radius of
Figure BDA0003265484340000011
And K+Radius of
Figure BDA0003265484340000013
Much greater than Li+Radius of
Figure BDA0003265484340000012
This often leads to problems with NIBs/KIBs battery systems that suffer from severe hysteresis in diffusion kinetics, large impedance and poor cycling performance. Therefore, it becomes increasingly difficult to select a suitable anode material. Currently, there are three approaches to improve the performance of SnSb-based electrodes. I) constructing SnSb-M alloy; m is Fe, Co, Ni, Zn, etc.; II) a carbon-based buffer material; carbon nanotubes, carbon fibers, graphene, and the like; III) reducing the particle size. For example, patent CN 104393268A discloses an aerogel modified SnSb/carbon nanotube composite electrode material having a high specific capacity when used in a negative electrode of a sodium ion battery, but having poor cycle stability, 0.1Ag-1At current density, the capacity had a tendency to decay significantly after 30 cycles. Patent CN 109728263A discloses a highly dispersed Sn-SnSb/carbon nanosheet composite material obtained by adopting rotary evaporation and high-temperature carbonization methods, which has good cycle stability but extremely poor rate capability when used as a negative electrode of a sodium ion battery, namely 2Ag-1The capacity is only maintained at 125mAh g under the current density-1. Therefore, it is very important to design SnSb-based negative electrode materials with high electron conductivity and high cycling stability. In addition, little research and little research are done on the general negative electrode materials of three battery systems (LIBs, NIBs, and KIBs), and the high capacity advantage of SnSb is not fully utilized. Therefore, the present invention is to solve the above problems and to prepare a high-performance negative electrode material for alkali metal ion batteries.
Disclosure of Invention
The invention aims to provide an NC @ SnSb @ NC material, a preparation method and application thereof, wherein the composite material is used as a negative electrode of alkali metal ion batteries (LIBs, NIBs and KIBs) to show excellent electrochemical performance.
The invention firstly provides a preparation method of an NC @ SnSb @ NC material, which comprises the following steps:
the method comprises the following steps: preparing a polypyrrole support framework material by using a sol-gel method, and treating the polypyrrole support framework material by using a surfactant to obtain A-PPy;
step two: introducing an intermediate tin-antimony oxide to the A-PPy by an ion exchange method to obtain the A-PPy @ Sn2Sb2O7；
Step three: for the A-PPy @ Sn obtained in the step two2Sb2O7Carrying out in-situ carbon coating to obtain A-PPy @ Sn2Sb2O7@PDA；
Step four: for the A-PPy @ Sn obtained in the step three2Sb2O7And carrying out reduction heat treatment on @ PDA to obtain the NC @ SnSb @ NC material.
Preferably, the first step is specifically:
1) FeCl is added3And pyrrole was added dropwise to C14H14N3SO3Stirring in Na aqueous solution to obtain polypyrrole PPy;
2) the polypyrrole PPy obtained in the step 1) is put in C12H25SO3And ultrasonically dispersing in Na solution to obtain the A-PPy.
Preferably, the step 1) FeCl3Mass g of (2): c14H14N3SO3Mass g of Na: volume μ L of pyrrole is 0.972: 0.194: 420.
preferably, the second step is specifically:
1) sb2O3Ultrasonic dispersion of the powder into H2O2Refluxing and stirring the solution to obtain a product Sb2O5·4H2O；
2) SnCl2·2H2Dissolving O in an acidic aqueous solution containing A-PPy to obtain A-PPy @ Sn2+An intermediate medium, then the product Sb obtained in step 1)2O5·4H2Adding O into the solution, and carrying out reflux reaction to obtain a product A-PPy @ Sn2Sb2O7。
Preferably, theStep 2) of Sb2O3Powder, SnCl2·2H2The mass ratio of O to A-PPy is 5:2.27: 0.5.
Preferably, the third step is specifically:
1) dissolving Tris in deionized water, and adding an acid solution to adjust the pH value to obtain a Tris solution;
2) adding A-PPy @ Sn into the Tris solution obtained in the step 1)2Sb2O7Stirring evenly, adding dopamine hydrochloride and stirring to obtain the product A-PPy @ Sn2Sb2O7@PDA。
Preferably, A-PPy @ Sn in the step 2)2Sb2O7The mass ratio of the dopamine hydrochloride to the dopamine hydrochloride is 1: 1-3.
Preferably, the temperature of the reduction heat treatment in the fourth step is 450-600 ℃, and the time is 2-4 h.
The invention also provides the NC @ SnSb @ NC-based material prepared by the preparation method.
The invention also provides application of the NC @ SnSb @ NC material as a negative electrode in an alkali metal ion battery.
The invention has the advantages of
The invention provides an NC @ SnSb @ NC material and a preparation method and application thereof, wherein the material is prepared by preparing a polypyrrole framework supporting material by a sol-gel method and treating the polypyrrole framework supporting material with a surfactant to obtain A-PPy; introducing an intermediate tin-antimony oxide to the A-PPy by using an ion exchange method to obtain the A-PPy @ Sn2Sb2O7(ii) a For the obtained A-PPy @ Sn2Sb2O7Carrying out in-situ carbon coating to obtain A-PPy @ Sn2Sb2O7@ PDA, and finally obtaining the NC @ SnSb @ NC material by a thermal reduction method. The NC @ SnSb @ NC material prepared by the method is similar to a corn structure, wherein the SnSb alloy successfully disperses the surface of the PPy framework, the nano-confinement growth of highly dispersed SnSb particles is realized under the double protection of the inner carbon layer and the outer carbon layer, and the average diameter of the active SnSb particles is 50-100 nm. This material has the following advantages:
(1) sn and Sb may be mixed with alkali metal ions (Li)+/Na+/K+) Alloying is carried out at different potentials, and the generated synergistic effect can inhibit the crushing of materials and can be used as a buffer matrix.
(2) The large specific surface area of the three-dimensional NC @ SnSb @ NC composite material prepared by the invention can increase the adsorption active sites of alkali metal ions, and the large pore size is beneficial to the transmission of the alkali metal ions and the permeation of electrolyte. Pyridine N and pyrrole N doping can generate a large amount of external impurity defects and active sites, and accelerate Li+/Na+/K+To be transmitted.
(3) Abundant sufficient space provided by the porous internal and external carbon networks can effectively relieve volume change, has higher mechanical flexibility and keeps the integrity of the whole electrode.
(4) The composite material shows excellent electrochemical performance as a negative electrode of alkali metal ion batteries (LIBs, NIBs, and KIBs). In 1Ag-1466, 386 and 236mAh g can be respectively released after 1500, 120 and 500 times of circulation under current-1The specific capacity of (A).
Drawings
FIG. 1 is an SEM image of NC @ SnSb @ NC obtained in example 1 of the present invention (panel a), SnSb obtained in comparative example 1 (panel b) and NC @ SnSb @ NC obtained in example 2 (panel c).
FIG. 2 is an XRD pattern of NC @ SnSb @ NC obtained in example 1 of the present invention and an XRD pattern of SnSb composite obtained in comparative example 1.
FIG. 3 shows that the current density of the NC @ SnSb @ NC composite material obtained in example 1 of the invention is 1Ag-1The cycle performance of the anode of the alkali metal ion battery is shown.
FIG. 4 shows the current density of SnSb obtained in comparative example 1 at 1Ag-1The cycle performance of the anode of the alkali metal ion battery is shown.
Detailed Description
The invention firstly provides a preparation method of an NC @ SnSb @ NC material, which comprises the following steps:
the method comprises the following steps: preparing a polypyrrole support framework material by using a sol-gel method, and treating the polypyrrole support framework material by using a surfactant to obtain A-PPy; the PPy can play a role of a supporting framework after being subjected to activation treatment of a surfactant, so that the nano-confinement growth of highly dispersed SnSb particles is realized;
specifically, it is preferable that: 1) c is to be14H14N3SO3Na is dissolved in deionized water to form C14H14N3SO3Aqueous solution of Na, FeCl3Is added dropwise to C14H14N3SO3Uniformly stirring in the Na aqueous solution, then dropwise adding pyrrole and stirring, wherein the stirring time is preferably 12-36h, sequentially washing the product with hot pure water and ethanol, and centrifuging to obtain a black product polypyrrole PPy; the FeCl3Mass g of (2): c14H14N3SO3Mass g of Na: the volume μ L of pyrrole is preferably 0.972: 0.194: 420.
2) the polypyrrole PPy obtained in the step 1) is put in C12H25SO3Ultrasonic dispersing in Na solution for 2-4 hr to activate surface with anionic surfactant, centrifuging to wash and eliminate excessive C12H25SO3Na, drying to obtain A-PPy. Said C12H25SO3The concentration of the Na solution is preferably 0.3 wt%.
Step two: introducing an intermediate tin-antimony oxide to the A-PPy by an ion exchange method to obtain the A-PPy @ Sn2Sb2O7；
The second step is specifically as follows: 1) sb2O3Ultrasonic dispersion of the powder into H2O2Refluxing and stirring the solution at the preferred stirring temperature of 60-80 ℃ for 24-48h, washing and drying to obtain a product Sb2O5·4H2O；H2O2The concentration of the solution is preferably 30 wt%;
2) SnCl2·2H2Dissolving O in an acidic aqueous solution containing A-PPy to obtain A-PPy @ Sn2+An intermediate medium, then the product Sb obtained in step 1)2O5·4H2Adding O into the solution, performing reflux reaction at 50-70 deg.C for 10-14 hr, washing, and dryingThen obtaining the product A-PPy @ Sn2Sb2O7. The acidic aqueous solution is preferably HCl solution, and the Sb is2O3Powder, SnCl2·2H2The mass ratio of O to A-PPy is 5:2.27: 0.5; the SnCl of the invention2·2H2O needs to be present in an acidic environment to inhibit its hydrolysis. On the contrary, the particle size of the obtained granular product is not uniform.
Step three: for the A-PPy @ Sn obtained in the step two2Sb2O7Carrying out in-situ carbon coating to obtain A-PPy @ Sn2Sb2O7@PDA；
The third step is specifically as follows: 1) dissolving Tris in deionized water, and adding an acid solution to adjust the pH value to obtain a Tris solution; the acid solution is preferably HCl solution, the concentration is preferably 1M, and the pH value is 8.5; 2) adding A-PPy @ Sn into the Tris solution obtained in the step 1)2Sb2O7Uniformly stirring, adding dopamine hydrochloride, and stirring for 12-36h to obtain the product A-PPy @ Sn2Sb2O7@PDA；A-PPy@Sn2Sb2O7The mass ratio of the dopamine hydrochloride to the dopamine hydrochloride is preferably 1:1-3, more preferably 1: 1; the content of in-situ coated carbon is controlled by controlling the addition of dopamine hydrochloride.
Step four: the product A-PPy @ Sn obtained in the third step2Sb2O7@ PDA at Ar/H2Then, carrying out reduction heat treatment at the temperature of preferably 450-600 ℃, more preferably 500 ℃ for 2-4h, more preferably 2h to obtain the product NC @ SnSb @ NC. The invention controls the shape and size of the material by adjusting the temperature and time of the reduction heat treatment.
The invention also provides the NC @ SnSb @ NC material prepared by the preparation method.
The invention also provides application of the NC @ SnSb @ NC material as a negative electrode in an alkali metal ion battery.
According to the invention, the method for preparing the negative electrode by using the NC @ SnSb @ NC material specifically comprises the following steps: preparing slurry from an active material (NC @ SnSb @ NC composite material), acetylene black (Super-P) and a sodium carboxymethylcellulose solution (CMC.1.5%) according to the proportion of 70 wt% to 20 wt% to 10 wt%, coating the slurry on a copper foil, and performing vacuum drying at 60 ℃ overnight to obtain the cathode material.
The following will further describe specific contents and embodiments of the present invention with reference to examples, which are only examples for implementing the present invention and should not be construed as limiting the technical scope of the present invention.
Example 1
a. Preparing a polypyrrole framework supporting material, and treating with a surfactant (A-PPy):
1) first, 0.194g C is added14H14N3SO3Na was dissolved in 120mL of deionized water to form a clear orange solution. Then 0.972g FeCl3The solution is added dropwise and stirred to be uniform, and then 420 mu L of pyrrole is added dropwise and stirred for 24 hours. And finally, sequentially washing the product with hot pure water and ethanol, and centrifuging to obtain a black product polypyrrole PPy.
2) PPy at C12H25SO3Continuous ultrasonic dispersion in Na solution (0.3 wt%, 300ml) for 3h to better activate the surface with anionic surfactant, and centrifugal washing of the product while removing excess C12H25SO3And (4) Na. Drying to obtain the A-PPy.
b. Introduction of intermediate tin antimony oxide (A-PPy @ Sn) by ion exchange method2Sb2O7)：
1) Sb2O3Powder (5g) ultrasonic Dispersion 100mL H2O2Solution (H)2O230wt percent) at 70 ℃ for 36h, washing and drying to obtain the product Sb2O5·4H2O。
2) SnCl2·2H2O (0.01mol,2.27g) was completely dissolved in an acidic aqueous solution (1g concentrated HCl, 100ml water) containing A-PPy (500mg) to give A-PPy @ Sn2+An intermediate medium. Prepared Sb2O5·4H2Ultrasonic dispersion of O (4.15g) powder A-PPy @ Sn2+Refluxing the solution for 12h at the temperature of 60 ℃, washing and drying to obtain a product A-PPy @ Sn2Sb2O7。
c. In-situ carbon coating (A-PPy @ Sn) is carried out on the intermediate at normal temperature2Sb2O7@PDA)：
1) Tris (1.21g) was first dissolved in deionized water (100mL) and 1M HCl solution was added to a pH of 8.5.
2) Then 0.1g of A-PPy @ Sn was added to the solution2Sb2O7Stirring until the mixture is uniformly dispersed, then adding 0.1g of dopamine hydrochloride, stirring for 24 hours, washing and drying to obtain a product A-PPy @ Sn2Sb2O7@PDA。
d. Obtaining a target product (NC @ SnSb @ NC) by thermal reduction treatment
For the above-mentioned A-PPy @ Sn2Sb2O7The product of @ PDA was passed over Ar/H2And (4) carrying out reduction heat treatment (500 ℃, 2h) to obtain a target product NC @ SnSb @ NC.
And the SnSb-nitrogen doped carbon three-dimensional composite material is used as the electrochemical representation of the cathode of the alkali metal ion battery.
The steps are as follows: preparing slurry from an active material (NC @ SnSb @ NC composite material), acetylene black (Super-P) and a sodium carboxymethylcellulose solution (CMC.1.5%) according to the proportion of 70 wt% to 20 wt% to 10 wt%, coating the slurry on a copper foil, and performing vacuum drying at 60 ℃ overnight to obtain the cathode material.
Example 2
a. Preparing a polypyrrole framework supporting material, and treating with a surfactant (A-PPy):
1) first, 0.194g C is added14H14N3SO3Na was dissolved in 120mL of deionized water to form a clear orange solution. Then 0.972g FeCl was added3Dropwise adding the mixture into the solution, and stirring the mixture until the mixture is uniform. 420 μ L of pyrrole were added dropwise and stirred for 24 h. And finally, sequentially washing the product with hot pure water and ethanol, and centrifuging to obtain a black product polypyrrole PPy.
2) PPy at C12H25SO3Continuous ultrasonic dispersion in Na solution (0.3 wt%, 300ml) for 3h to better activate the surface with anionic surfactant, and centrifugal washing of the product while removing excess C12H25SO3Na, drying to obtain A-PPy。
b. Introduction of intermediate tin antimony oxide (A-PPy @ Sn) by ion exchange method2Sb2O7)：
1) First, Sb is added2O3Powder (5g) ultrasonic Dispersion 100mL H2O2Solution (H)2O230wt percent) at 70 ℃ for 36h, washing and drying to obtain the product Sb2O5·4H2O。
2) SnCl2·2H2O (0.01mol,2.27g) was completely dissolved in an acidic aqueous solution (1g concentrated HCl, 100ml water) containing A-PPy (500mg) to give A-PPy @ Sn2+An intermediate medium. Prepared Sb2O5·4H2Ultrasonic dispersion of O (4.15g) powder A-PPy @ Sn2+Refluxing the solution at 60 ℃ for 12h, washing and drying to obtain a product A-PPy @ Sn2Sb2O7。
c. In-situ carbon coating (A-PPy @ Sn) is carried out on the intermediate at normal temperature2Sb2O7@PDA)：
1) Tris (1.21g) was first dissolved in deionized water (100mL) and 1M HCl solution was added to a pH of 8.5.
2) Then 0.1g of A-PPy @ Sn was added to the solution2Sb2O7Stirring until the dispersion is uniform. 0.1g dopamine hydrochloride is added and stirred for 24 h. Washing and drying to obtain the product A-PPy @ Sn2Sb2O7@PDA。
d. Obtaining a target product (NC @ SnSb @ NC) by thermal reduction treatment
For the above-mentioned A-PPy @ Sn2Sb2O7The product of @ PDA was passed over Ar/H2And (4) carrying out reduction heat treatment (600 ℃, 2h) to obtain a target product NC @ SnSb @ NC.
And the SnSb-nitrogen doped carbon three-dimensional composite material is used as the electrochemical representation of the cathode of the alkali metal ion battery.
The steps are as follows: preparing slurry from an active material (NC @ SnSb @ NC composite material), acetylene black (Super-P) and a sodium carboxymethylcellulose solution (CMC.1.5%) according to the proportion of 70 wt% to 20 wt% to 10 wt%, coating the slurry on a copper foil, and performing vacuum drying at 60 ℃ overnight to obtain the cathode material.
Comparative example 1
a. Preparation of intermediate tin antimony oxide (Sn) by ion exchange2Sb2O7)：
(1) First, Sb is added2O3Powder (5g) ultrasonic Dispersion 100mL H2O2Solution (H)2O230wt percent) at 70 ℃ for 36h, washing and drying to obtain the product Sb2O5·4H2O。
(2) SnCl2·2H2O (0.01mol,2.27g) completely dissolved in the acidic aqueous solution (1g concentrated HCl, 100ml water). Prepared Sb2O5·4H2O (4.15g) powder SnCl dispersed by ultrasonic2Refluxing in acid solution at 60 deg.C for 12 hr, washing and drying to obtain Sn product2Sb2O7。
b. Obtaining a target product (SnSb) by reduction heat treatment:
subjecting the above product to Ar/H2And (4) carrying out reduction heat treatment (500 ℃, 2h) to obtain a target product SnSb.
SEM and XRD analyses of the samples obtained in examples 1 and 2 and comparative example 1 are shown in FIGS. 1 and 2, and the SEM analysis result shows that NC @ SnSb @ NC has a corn-like structure and the particles of the sample obtained in example 1 are uniformly dispersed. Namely at Ar/H2The material can maintain structural integrity when heated at 500 ℃ for 2h, compared with the condition of heating at 600 ℃ for 2h under the atmosphere. The good structure can greatly release the potential of high specific capacity of the material. XRD analysis results also confirm that the SnSb phase exists in the NC @ SnSb @ NC composite material, and electrochemical performance data also confirm the analysis.
Electrochemical performance analysis was performed on the sample composite materials obtained in example 1(NC @ SnSb @ NC) and comparative example 1(SnSb), and a button-type half cell (CR2025) was assembled with NC @ SnSb @ NC and SnSb as the negative electrode materials of the alkali metal ion battery, respectively, and lithium, sodium and potassium foils as the counter electrodes to measure the electrochemical performance. The button cells were assembled in an argon-filled glove box with oxygen and moisture levels less than 0.1 ppm. The voltage test interval of the alkali metal ion battery is 0.01-2V (LIBs, NIBs and KIBs), 1M LiPF is adopted as electrolyte respectively6DEC DMC (volume ratio 1:1:1, FEC 10 wt%), 1M NaClO4/PC and 5M KFSI/DME. Button cells were tested at room temperature using the LAND CT2001A multichannel. As a result, as shown in fig. 3 and 4, in sharp contrast to the SnSb negative electrode, the NC @ SnSb @ NC composite exhibited excellent electrochemical performance as the negative electrodes of alkali metal ion batteries (LIBs, NIBs, and KIBs). In 1Ag-1466, 386 and 236mAh g can be respectively released after 1500, 120 and 500 times of circulation under current-1The specific capacity of (A).
The above description is intended to describe in detail the preferred embodiments of the present invention, but the embodiments are not intended to limit the scope of the claims of the present invention, and all equivalent changes and modifications made within the technical spirit of the present invention should fall within the scope of the claims of the present invention.

Claims (10)

1. A preparation method of an NC @ SnSb @ NC material is characterized by comprising the following steps:
the method comprises the following steps: preparing a polypyrrole support framework material by using a sol-gel method, and treating the polypyrrole support framework material by using a surfactant to obtain A-PPy;
step two: introducing an intermediate tin-antimony oxide to the A-PPy by an ion exchange method to obtain the A-PPy @ Sn2Sb2O7；
Step three: for the A-PPy @ Sn obtained in the step two2Sb2O7Carrying out in-situ carbon coating to obtain A-PPy @ Sn2Sb2O7@PDA；
Step four: for the A-PPy @ Sn obtained in the step three2Sb2O7And carrying out reduction heat treatment on @ PDA to obtain the NC @ SnSb @ NC material.
2. The preparation method of the NC @ SnSb @ NC material as claimed in claim 1, wherein the first step is specifically as follows:
1) FeCl is added3And pyrrole was added dropwise to C14H14N3SO3Stirring in Na aqueous solution to obtain polypyrrole PPy;
2) the polypyrrole PPy obtained in the step 1) is put in C12H25SO3And ultrasonically dispersing in Na solution to obtain the A-PPy.
3. The preparation method of NC @ SnSb @ NC material according to claim 2, characterized in that the step 1) FeCl3Mass g of (2): c14H14N3SO3Mass g of Na: volume μ L of pyrrole is 0.972: 0.194: 420.
4. the preparation method of the NC @ SnSb @ NC material as claimed in claim 1, wherein the second step is specifically as follows:
1) sb2O3Ultrasonic dispersion of the powder into H2O2Refluxing and stirring the solution to obtain a product Sb2O5·4H2O；
2) SnCl2·2H2Dissolving O in an acidic aqueous solution containing A-PPy to obtain A-PPy @ Sn2+An intermediate medium, then the product Sb obtained in step 1)2O5·4H2Adding O into the solution, and carrying out reflux reaction to obtain a product A-PPy @ Sn2Sb2O7。
5. The preparation method of NC @ SnSb @ NC material according to claim 4, characterized in that Sb in the step 2) is Sb2O3Powder, SnCl2·2H2The mass ratio of O to A-PPy is 5:2.27: 0.5.
6. The preparation method of the NC @ SnSb @ NC material as claimed in claim 1, wherein the third step is specifically as follows:
1) dissolving Tris in deionized water, and adding an acid solution to adjust the pH value to obtain a Tris solution;
2) adding A-PPy @ Sn into the Tris solution obtained in the step 1)2Sb2O7Stirring evenly, adding dopamine hydrochloride and stirring to obtain the product A-PPy @ Sn2Sb2O7@PDA。
7. The preparation method of NC @ SnSb @ NC material as claimed in claim 6, wherein A-PPy @ Sn in the step 2) is2Sb2O7The mass ratio of the dopamine hydrochloride to the dopamine hydrochloride is 1: 1-3.
8. The method for preparing NC @ SnSb @ NC material as claimed in claim 1, wherein the temperature of the reduction heat treatment in the fourth step is 450-600 ℃ and the time is 2-4 h.
9. NC @ SnSb @ NC material obtained by the preparation method of claim 1.
10. Use of the NC @ SnSb @ NC material of claim 9 as a negative electrode in an alkali metal ion battery.
CN202111085762.2A 2021-09-16 2021-09-16 NC @ SnSb @ NC material and preparation method and application thereof Pending CN113793919A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1688044A (en) * 2005-05-08 2005-10-26 北京科技大学 Method of preparing Sn-Sb alloy material for negative electrode of lithium ion cell
CN102544462A (en) * 2012-02-21 2012-07-04 武汉大学 Anode material of lithium-ion battery
CN103861550A (en) * 2014-04-02 2014-06-18 清华大学 Preparation method of adsorbent containing SnO2/Sb2O5, product and application of adsorbent
CN109728263A (en) * 2018-12-06 2019-05-07 盐城工学院 A kind of preparation method and application of Sn-SnSb/ carbon nanosheet composite material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1688044A (en) * 2005-05-08 2005-10-26 北京科技大学 Method of preparing Sn-Sb alloy material for negative electrode of lithium ion cell
CN102544462A (en) * 2012-02-21 2012-07-04 武汉大学 Anode material of lithium-ion battery
CN103861550A (en) * 2014-04-02 2014-06-18 清华大学 Preparation method of adsorbent containing SnO2/Sb2O5, product and application of adsorbent
CN109728263A (en) * 2018-12-06 2019-05-07 盐城工学院 A kind of preparation method and application of Sn-SnSb/ carbon nanosheet composite material

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
BOYANG RUAN ET AL.: "Carbon-Encapsulated Sn@N-Doped Carbon Nanotubes as AnodeMaterials for Application in SIBs", 《ACS APPL. MATER. INTERFACES》 *
JINWEN SHI ET AL.: "A Novel Sn2Sb2O7 Nanophotocatalyst for Visible-Light-Driven H2 Evolution", 《NANO RES.》 *

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