CN107946559B - Sb for solvothermal preparation of sodium ion battery cathode2Se3Method for preparing/C composite material - Google Patents

Sb for solvothermal preparation of sodium ion battery cathode2Se3Method for preparing/C composite material Download PDF

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CN107946559B
CN107946559B CN201711085746.7A CN201711085746A CN107946559B CN 107946559 B CN107946559 B CN 107946559B CN 201711085746 A CN201711085746 A CN 201711085746A CN 107946559 B CN107946559 B CN 107946559B
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曹丽云
郭玲
李嘉胤
黄剑锋
程娅伊
齐慧
席乔
何元元
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Shaanxi University of Science and Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection 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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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    • 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

Sb for solvothermal preparation of sodium ion battery cathode2Se3Method for preparing/C composite material, SbCl3Adding into absolute ethyl alcohol to obtain A1, adding carbon source into deionized water to obtain A2, and adding A2 into A1 to obtain solution A; adding Se powder into a sodium borohydride aqueous solution to obtain a solution B; dropwise adding the solution B into the solution A to obtain a mixed solution C; transferring the mixed solution C to a polytetrafluoroethylene lining, placing the polytetrafluoroethylene lining into a homogeneous phase reactor to react for 18-36 h at 150-200 ℃, cooling to room temperature along with a furnace, repeatedly washing with deionized water and absolute ethyl alcohol to separate precipitates, and freeze-drying to obtain Sb for the cathode of the sodium ion battery2Se3a/C composite material. The invention adopts a one-step solvothermal method without high-temperature calcination, which effectively avoids Sb in the calcination process2Se3The nano-crystal grows up to cause larger volume change, the preparation process is simple, and the period is short; the negative electrode of the sodium ion battery is 0.1A g‑1The capacity of 50 cycles can be kept at about 450mAh g‑1The circulation stability is obviously improved.

Description

Sb for solvothermal preparation of sodium ion battery cathode2Se3Method for preparing/C composite material
Technical Field
The invention belongs to the field of preparation of sodium ion battery cathode materials, and particularly relates to Sb for solvothermal preparation of a sodium ion battery cathode2Se3A method for preparing the/C composite material.
Background
Energy is the basis of human social developmentAnd the storage and conversion of energy have become important problems restricting the sustainable development of the world economy. According to the current research progress and technical development, the sodium ion battery energy storage technology has the advantages of rich raw material resources, low cost and wide distribution; the potential of the half cell is 0.3-0.4V (namely, electrolyte solvent and electrolyte salt with lower decomposition potential can be utilized, and the selection range of the electrolyte is wider); the advantages of relatively stable electrochemical performance, safer use and the like are paid attention by researchers, and the research and development of the sodium ion battery are considered to possibly develop a material with excellent performance, safety and stability to meet the energy requirement. The performance of sodium ion battery depends on anode and cathode materials to a great extent, and the metal compound in the cathode material has high specific energy, such as Sb of Sb-based selenide sodium ion battery cathode material Sb2Se3A V-VI compound with a layered structure as the cathode material of the sodium-ion battery, 1mol of Sb2Se3Can react with 12mol of Na+Reacting to obtain 678mAh g-1The theoretical capacity of (a). But the electrochemical reaction with a plurality of sodium ions brings high specific energy and simultaneously generates huge volume change. In the process of charging and discharging, along with the embedding and releasing of sodium ions, the high-specific-energy negative electrode repeatedly bears huge volume change, is easy to pulverize and strip, and causes the electrode structure to be seriously damaged, thereby causing the rapid reduction of the cyclic specific capacity of the electrode.
According to literature reports, most researches adopt methods such as nanocrystallization, compounding with an inert phase, compounding with a carbon material and the like to reduce the volume change of a high-specific-energy negative electrode in the charging and discharging processes and improve the cycle stability. Wenxi Zhao et al adopts a 'one-pot' method to compound Sb2Se3 and nitrogen-doped graphene oxide, under the current density of 0.1A g-1, the first discharge capacity is 1000mA h g-1, and the capacity can still be kept at 560mA h g-1 after 50 cycles (ZHao W, Li C M. Mesh-structured N-doped graphene @ Sb2Se3hybrid as an for large capacity batteries-ion batteries. [ J ]. Journal of Colloid & Interface Science,2016,488: 356: 364). Xing Qu et al, which compounds Sb2Se3 with reduced graphene, can maintain the capacity at 471mA h g-1(Ou X, Yang C, Xiong X, et al. A New rGO-Overcoated Sb2Se3 nanoeyes for Na + Battery: In Situ X-Ray Diffraction Study on active software/demodulation Process [ J ]. Advanced Functional Materials,2017.) after 500 cycles at a current density of 1.0A g-1. The reports all show that the cycling stability of the Sb2Se3 sodium ion battery cathode material can be obviously improved by compounding with a carbon material, but most of carbon sources used in the current research are graphene which is a material with high price and long preparation period, so that the finding of a carbon source which is low in price, green and environment-friendly and can improve the cycling stability and a preparation method suitable for large-scale production is significant.
Disclosure of Invention
The invention aims to provide Sb for solvothermal preparation of sodium ion battery negative electrode2Se3A method for preparing the/C composite material. Prepared Sb2Se3the/C composite material is used as a negative electrode material of a sodium-ion battery and shows excellent cycling stability.
In order to achieve the purpose, the invention adopts the technical scheme that:
1) according to the following steps: (1-10) taking SbCl in a mass ratio3And a carbon source, then mixing SbCl3Adding into absolute ethyl alcohol and stirring until the mixture is completely dissolved to obtain SbCl3Adding a carbon source into deionized water and stirring until the carbon source is completely dissolved to obtain a transparent carbon source solution A2 with the carbon source concentration of 0.0023 g/mL-0.3422 g/mL, adding A1 into A2 and stirring until the carbon source is completely dispersed and marked as A, wherein the concentration of the transparent carbon source solution A1 is 0.002 moL/L-0.1 moL/L;
2) according to SbCl3: se: sodium borohydride is (0.1-1.5): (0.15-2.25): (0.225-3.375) preparing sodium borohydride into 0.015-0.675 moL/L sodium borohydride aqueous solution, adding Se powder into the sodium borohydride aqueous solution, and stirring to obtain a transparent solution B; rapidly dropwise adding the solution B into the solution A under stirring, and uniformly stirring and dispersing to obtain a black mixed solution C;
3) transferring the black mixed solution C to a polytetrafluoroethylene lining, placing the polytetrafluoroethylene lining into a homogeneous phase reactor to react for 18-36 h at 150-200 ℃, cooling to room temperature along with a furnace, repeatedly washing with deionized water and absolute ethyl alcohol to separate precipitates, and freeze-drying to obtain the sodium ion batterySb for negative electrode2Se3a/C composite material.
The carbon source in the step 1) adopts glucose, sucrose, raffinose or β -cyclodextrin.
And 2) stirring in the step 1) and the step 2) by using a magnetic stirrer, wherein the stirring speed is 500-1000 r/min.
The filling ratio of the mixed solution C transferred to the polytetrafluoroethylene lining in the step 3) is 30-80%.
The freeze drying temperature in the step 3) is-40 ℃, and the pressure is 60 Pa.
Sb for sodium ion battery cathode prepared by the preparation method of the invention2Se3the/C composite material is carbon-coated nanorod-shaped Sb2Se3Structure, rod-like Sb2Se3The diameter is about 100nm, the thickness of the carbon layer is 5-20 nm, and the coating is uniform.
Compared with the prior art, the invention has the following beneficial effects:
1) glucose, sucrose, raffinose and β -cyclodextrin are used as carbon sources, so that the cost is reduced, and the preparation method is green and environment-friendly;
2) the adoption of the one-step solvothermal method does not need high-temperature calcination, which effectively avoids Sb in the calcination process2Se3The nano-crystal grows up to cause larger volume change, the preparation process is simple, and the period is short;
3) sb with different carbon layer thicknesses can be prepared by controlling the adding amount of the carbon source2Se3The coating is uniform and the repeatability is good;
4) sb prepared by adopting the method2Se3the/C composite material is used as a negative electrode of a sodium ion battery and is 0.1A g-1The capacity of 50 cycles can be kept at about 450mAh g-1The circulation stability is obviously improved.
The method can meet the requirement of large-scale production in terms of preparation method, and the cathode of the sodium-ion battery has excellent electrochemical performance in terms of performance.
Drawings
FIG. 1 shows Sb prepared in example 12Se3An X-ray diffraction (XRD) pattern of the electrode material;
FIG. 2 shows Sb prepared in example 12Se3Scanning Electron Microscope (SEM) photographs of the electrode material;
FIG. 3 shows Sb prepared in example 12Se3Transmission Electron Microscope (TEM) photographs of the electrode material;
FIG. 4 shows Sb prepared in example 12Se3A cycle performance profile of the electrode material; wherein, Cycle number: the number of cycles; capacity: capacity;
FIG. 5 shows Sb prepared in example 62Se3Scanning Electron Microscope (SEM) photographs of the electrode material;
FIG. 6 shows Sb prepared in example 62Se3Transmission Electron Microscope (TEM) photographs of the electrode material;
FIG. 7 shows Sb prepared in example 62Se3A rate performance graph of the electrode material; wherein, Cycle number: the number of cycles; capacity: capacity.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
Example 1:
1) take 0.1mmoLSbCl3Adding the mixture into absolute ethyl alcohol, and stirring the mixture by magnetic force at 500r/min until the mixture is completely dissolved to obtain SbCl3Clear solution A1 at a concentration of 0.002moL/L as SbCl3And the carbon source is 1:1, adding glucose as a carbon source into deionized water, stirring by magnetic force of 500r/min until the glucose is completely dissolved to obtain a transparent carbon source solution A2 with the carbon source concentration of 0.0023g/mL, adding A2 into A1, and stirring until the glucose is completely dispersed to be marked as A;
2) preparing 0.015moL/L sodium borohydride aqueous solution from 0.225mmoL of sodium borohydride, adding 0.15mmoL of Se powder into the sodium borohydride aqueous solution, and magnetically stirring at 500r/min to obtain a transparent solution B; rapidly dropwise adding the solution B into the solution A under stirring, and uniformly stirring and dispersing to obtain a black mixed solution C;
3) transferring the black mixed solution C to a polytetrafluoroethylene lining according to the filling ratio of 70 percent, putting the polytetrafluoroethylene lining into a homogeneous reactor to react for 36 hours at the temperature of 150 ℃, cooling the mixture to room temperature along with a furnace, and using the mixtureRepeatedly washing deionized water and absolute ethyl alcohol to separate precipitates, freezing to (-40 ℃, 60Pa) and drying to obtain Sb for the cathode of the sodium ion battery2Se3a/C composite material.
Analysis of the samples (Sb) with a Japanese science D/max2000 PCX-ray diffractometer2Se3/C composite powder), and Sb of an orthorhombic system with JCPDS serial numbers of 15-0861 was found in the sample2Se3The structure is consistent and no other miscellaneous peak appears (figure 1); when the sample was observed with a Field Emission Scanning Electron Microscope (FESEM) of S-4800 type, FEI corporation, USA, it was found that the prepared pure phase Sb was2Se3The nanocrystalline is a rod-shaped structure, the diameter of the nanocrystalline is about 100nm, and the surface of the nanocrystalline is provided with a coating. (FIG. 2). When the sample was observed with a field emission transmission electron microscope of Tecnaig2F20S-TWIN type, FEI Inc., USA, it was found that rod-like Sb was formed2Se3The surface is coated with carbon, and the thickness of the carbon layer is about 3nm (figure 3).
Sb for negative electrode of sodium ion battery2Se3The active material, a conductive agent (Super-p and conductive graphite) and a binder (hydroxymethyl cellulose CMC and polyacrylic acid PAA) are dissolved in deionized water according to the mass ratio of 7 (1:1) to (0.5:0.5) to be ground, coated with slurry, dried, sliced and taken as a negative electrode to be assembled into a button sodium ion battery in a glove box filled with argon, and after the battery is placed aside for 48 hours, an electrochemical performance test is carried out by adopting a blue electric tester. At 0.1A g-1The capacity of 50 cycles can be kept at about 400mAh g-1The cycling stability was significantly improved (fig. 4).
Example 2:
1) take 0.3mmoLSbCl3Adding the mixture into absolute ethyl alcohol, and stirring the mixture by magnetic force at 600r/min until the mixture is completely dissolved to obtain SbCl3Clear solution A1 at a concentration of 0.005moL/L as SbCl3And the carbon source is 1: 3, adding sucrose as a carbon source into deionized water, stirring by magnetic force of 600r/min until the sucrose is completely dissolved to obtain a transparent carbon source solution A2 with the carbon source concentration of 0.01g/mL, adding A2 into A1, and stirring until the sucrose is completely dispersed to be marked as A;
2) preparing 0.052moL/L sodium borohydride aqueous solution from 0.80mmoL L sodium borohydride, adding 0.45mmoL Se powder into the sodium borohydride aqueous solution, and magnetically stirring at 600r/min to obtain a transparent solution B; rapidly dropwise adding the solution B into the solution A under stirring, and uniformly stirring and dispersing to obtain a black mixed solution C;
3) transferring the black mixed solution C to a polytetrafluoroethylene lining according to the filling ratio of 80%, placing the polytetrafluoroethylene lining into a homogeneous phase reactor to react for 30h at 160 ℃, cooling the polytetrafluoroethylene lining to room temperature along with a furnace, repeatedly washing the cooled mixed solution C with deionized water and absolute ethyl alcohol to separate precipitates, freezing the precipitates at (-40 ℃, 60Pa) and drying the precipitates to obtain Sb for the cathode of the sodium ion battery2Se3a/C composite material.
Example 3:
1) take 0.7mmoLSbCl3Adding the mixture into absolute ethyl alcohol, and stirring the mixture by magnetic force at 500r/min until the mixture is completely dissolved to obtain SbCl3Clear solution A1 at a concentration of 0.02moL/L as SbCl3And the carbon source is 1: 5, adding carbon source raffinose into deionized water, stirring by magnetic force of 500r/min until the raffinose is completely dissolved to obtain a transparent carbon source solution A2 with the carbon source concentration of 0.05g/mL, adding A2 into A1, and stirring until the raffinose is completely dispersed and marked as A;
2) preparing 0.143moL/L sodium borohydride solution from 0.225mmoL sodium borohydride, adding 1.5mmoL Se powder into the sodium borohydride solution, and magnetically stirring at 700r/min to obtain a transparent solution B; rapidly dropwise adding the solution B into the solution A under stirring, and uniformly stirring and dispersing to obtain a black mixed solution C;
3) transferring the black mixed solution C to a polytetrafluoroethylene lining according to the filling ratio of 60%, placing the polytetrafluoroethylene lining into a homogeneous reactor to react for 24 hours at 170 ℃, cooling the polytetrafluoroethylene lining to room temperature along with the furnace, repeatedly washing the cooled mixed solution C with deionized water and absolute ethyl alcohol to separate precipitates, freezing the precipitates at (-40 ℃, 60Pa) and drying the precipitates to obtain Sb for the cathode of the sodium ion battery2Se3a/C composite material.
Example 4:
1) take 1mmoLSbCl3Adding into absolute ethyl alcohol and stirring by magnetic force of 700r/min until the SbCl is completely dissolved to obtain SbCl3Clear solution A1 at a concentration of 0.04moL/L, as SbCl3And the carbon source is 1: 7 the mass ratio of the carbon source raffinose to deionized water is added, the magnetic stirring is carried out at 700r/min until the raffinose is completely dissolved to obtain a transparent carbon source solution A2 with the carbon source concentration of 0.1g/mL, A2 is added into A1, and the solution is stirred until the raffinose is completely dispersedIs A;
2) preparing 0.25moL/L sodium borohydride aqueous solution from 2mmoL of sodium borohydride, adding 1.5mmoL of Se powder into the sodium borohydride aqueous solution, and magnetically stirring at 700r/min to obtain a transparent solution B; rapidly dropwise adding the solution B into the solution A under stirring, and uniformly stirring and dispersing to obtain a black mixed solution C;
3) transferring the black mixed solution C to a polytetrafluoroethylene lining according to the filling ratio of 50%, placing the polytetrafluoroethylene lining into a homogeneous phase reactor to react for 20 hours at 180 ℃, cooling the polytetrafluoroethylene lining to room temperature along with the furnace, repeatedly washing the cooled mixed solution C with deionized water and absolute ethyl alcohol to separate precipitates, freezing the precipitates at (-40 ℃, 60Pa) and drying the precipitates to obtain Sb for the cathode of the sodium ion battery2Se3a/C composite material.
Example 5:
1) 1.2mmoLSbCl is taken3Adding the mixture into absolute ethyl alcohol, and stirring the mixture by magnetic force at 600r/min until the mixture is completely dissolved to obtain SbCl3Clear solution A1 at a concentration of 0.08moL/L as SbCl3And the carbon source is 1: 8, adding glucose as a carbon source into deionized water, stirring by magnetic force at 600r/min until the glucose is completely dissolved to obtain a transparent carbon source solution A2 with the carbon source concentration of 0.2g/mL, adding A2 into A1, and stirring until the glucose is completely dispersed to obtain A;
2) preparing 0.386moL/L sodium borohydride aqueous solution from 2.6mmoL sodium borohydride, adding 1.8mmoL Se powder into the sodium borohydride aqueous solution, and magnetically stirring at 600r/min to obtain a transparent solution B; rapidly dropwise adding the solution B into the solution A under stirring, and uniformly stirring and dispersing to obtain a black mixed solution C;
3) transferring the black mixed solution C to a polytetrafluoroethylene lining according to the filling ratio of 40%, placing the polytetrafluoroethylene lining into a homogeneous reactor to react for 24 hours at the temperature of 150 ℃, cooling the polytetrafluoroethylene lining to room temperature along with a furnace, repeatedly washing the cooled mixed solution C with deionized water and absolute ethyl alcohol to separate precipitates, freezing the precipitates at the temperature of minus 40 ℃ and 60Pa, and drying the precipitates to obtain Sb for the cathode of the sodium ion battery2Se3a/C composite material.
Example 6:
1) 1.5mmoLSbCl is taken3Adding the mixture into absolute ethyl alcohol, and stirring the mixture by magnetic force at 500r/min until the mixture is completely dissolved to obtain SbCl3Clear solution A1 at a concentration of 0.1moL/L as SbCl3Adding β -cyclodextrin as carbon source in a mass ratio of 1: 10 to the carbon sourceStirring ionized water by magnetic force of 500r/min until the ionized water is completely dissolved to obtain a transparent carbon source solution A2 with the carbon source concentration of 0.3422g/mL, adding A2 into A1, and stirring until the carbon source solution is completely dispersed and marked as A;
2) preparing 0.675moL/L sodium borohydride aqueous solution from 3.375mmoL of sodium borohydride, adding 2.25mmoL of Se powder into the sodium borohydride aqueous solution, and magnetically stirring at 600r/min to obtain a transparent solution B; rapidly dropwise adding the solution B into the solution A under stirring, and uniformly stirring and dispersing to obtain a black mixed solution C;
3) transferring the black mixed solution C to a polytetrafluoroethylene lining according to the filling ratio of 30%, putting the polytetrafluoroethylene lining into a homogeneous phase reactor, reacting for 18h at 180 ℃, cooling to room temperature along with the furnace, repeatedly washing with deionized water and absolute ethyl alcohol to separate precipitates, freezing to the temperature of minus 40 ℃, and drying to obtain Sb for the cathode of the sodium ion battery2Se3a/C composite material.
When the sample was observed with a Field Emission Scanning Electron Microscope (FESEM) of S-4800 type, FEI corporation, USA, it was found that the prepared pure phase Sb was2Se3The nanocrystals have rod-like structure with diameter of about 100nm and surface coating (FIG. 5). When the sample was observed with a field emission transmission electron microscope of Tecnaig2F20S-TWIN type, FEI Inc., USA, it was found that rod-like Sb was formed2Se3The surface is coated with carbon, the thickness of the carbon layer is about 50nm, and the coating is uniform (figure 6).
Sb for negative electrode of sodium ion battery2Se3The active material, a conductive agent (Super-p and conductive graphite) and a binder (hydroxymethyl cellulose CMC and polyacrylic acid PAA) are dissolved in deionized water according to the mass ratio of 7 (1:1) to (0.5:0.5) to be ground, coated with slurry, dried, sliced and taken as a negative electrode to be assembled into a button sodium ion battery in a glove box filled with argon, and after the battery is placed aside for 48 hours, an electrochemical performance test is carried out by adopting a blue electric tester. At 0.1A g-1The capacity of 50 cycles can be kept at about 450mAh g-1The cycling stability was significantly improved (fig. 7).

Claims (4)

1. Sb for solvothermal preparation of sodium ion battery cathode2Se3A method of producing a/C composite material, characterized by:
1) according to the following steps: (1-10) taking SbCl in a mass ratio3And a carbon source, then mixing SbCl3Adding into absolute ethyl alcohol and stirring until the mixture is completely dissolved to obtain SbCl3Adding a carbon source into deionized water and stirring until the carbon source is completely dissolved to obtain a transparent carbon source solution A2 with the carbon source concentration of 0.0023 g/mL-0.3422 g/mL, adding A1 into the A2 and stirring until the carbon source is completely dispersed and marked as A, wherein the concentration of the transparent carbon source solution A1 is 0.002 moL/L-0.1 moL/L;
2) according to SbCl3: se: sodium borohydride is (0.1-1.5): (0.15-2.25): (0.225-3.375) preparing sodium borohydride into 0.015-0.675 moL/L sodium borohydride aqueous solution, adding Se powder into the sodium borohydride aqueous solution, and stirring to obtain a transparent solution B; rapidly dropwise adding the solution B into the solution A under stirring, and uniformly stirring and dispersing to obtain a black mixed solution C;
3) transferring the black mixed solution C to a polytetrafluoroethylene lining, placing the polytetrafluoroethylene lining into a homogeneous phase reactor to react for 18-36 h at 150-200 ℃, cooling to room temperature along with a furnace, repeatedly washing with deionized water and absolute ethyl alcohol to separate precipitates, and freeze-drying to obtain Sb for the cathode of the sodium ion battery2Se3a/C composite material;
the carbon source in the step 1) adopts glucose, sucrose, raffinose or β -cyclodextrin.
2. Sb for solvothermally preparing sodium-ion battery negative electrode according to claim 12Se3A method of producing a/C composite material, characterized by: and 2) stirring in the step 1) and the step 2) by using a magnetic stirrer, wherein the stirring speed is 500-1000 r/min.
3. Sb for solvothermally preparing sodium-ion battery negative electrode according to claim 12Se3A method of producing a/C composite material, characterized by: the filling ratio of the mixed solution C transferred to the polytetrafluoroethylene lining in the step 3) is 30-80%.
4. Solvothermal preparation of Sb for sodium-ion battery negative electrode according to claim 12Se3C complexThe material combination method is characterized by comprising the following steps: the freeze drying temperature in the step 3) is-40 ℃, and the pressure is 60 Pa.
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