CN114927668A - Preparation method of nitrogen-doped antimony phosphate/carbon composite material for negative electrode of sodium ion battery - Google Patents

Preparation method of nitrogen-doped antimony phosphate/carbon composite material for negative electrode of sodium ion battery Download PDF

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CN114927668A
CN114927668A CN202210663126.1A CN202210663126A CN114927668A CN 114927668 A CN114927668 A CN 114927668A CN 202210663126 A CN202210663126 A CN 202210663126A CN 114927668 A CN114927668 A CN 114927668A
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composite material
round
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deionized water
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CN114927668B (en
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周卫民
牟远
张万涛
王璐瑶
李建科
徐桂英
王坤
李莉香
安百钢
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Haicheng Shenhe Tech Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • 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
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a preparation method of a nitrogen-doped antimony phosphate/carbon composite material for a cathode of a sodium ion battery, which comprises the following steps: 1) mixing nano Sb 2 O 3 Adding powder, graphene oxide and deionized water into a round-bottom flask for ultrasonic treatment; adding a phosphoric acid solution, heating in a water bath kettle, adding a hydrogen peroxide solution when the heating temperature is raised to 85-95 ℃, and refluxing for 2.0-2.5 hours at a constant temperature of 85-95 ℃; adding the suspension into deionized water, and performing ultrasonic treatment to obtain a suspension A; 2) adding deionized water into melamine and formaldehyde solution and ammonia water, and reacting in a water bath kettle to obtain solution B; 3) mixing the suspension A and the solution B, adding phosphoric acid, reacting at constant temperature, and centrifuging to obtain black powder;4) and heating the black powder in a tube furnace to obtain a finished product. The antimony phosphate/carbon composite material with uniform appearance is prepared by a simple water bath method and heat treatment.

Description

Preparation method of nitrogen-doped antimony phosphate/carbon composite material for negative electrode of sodium ion battery
Technical Field
The invention belongs to the field of negative electrode materials of sodium ion batteries, and particularly relates to a preparation method of a nitrogen-doped antimony phosphate/carbon composite material for a negative electrode of a sodium ion battery.
Background
With the increasing environmental problems and the depletion of fossil energy, electrochemical energy storage technology has been widely used in our lives. Lithium ion batteries have received much attention due to their advantages of high energy density, low self-discharge rate, light weight, good cycle performance, and the like. However, the application and development of lithium batteries are limited by the maldistribution and shortage of reserves of lithium, and sodium metal makes sodium ion batteries a potential substitute for lithium ion batteries due to the abundance of reserves and the similarity of lithium properties.
Among the negative electrode materials known at present, antimony-based negative electrode materials have attracted much attention because of their advantages of high specific capacity, suitable working voltage, easy synthesis, etc. Compared with antimony-based composite materials such as antimony oxide, antimony sulfide and the like, the phosphate has an open framework structure and unique physical and chemical properties, can effectively buffer volume change, avoids more side reactions and accordingly improves cycle stability. Meanwhile, in the antimony phosphate crystal, due to the existence of lone-pair electrons in antimony ions, the antimony phosphate crystal has good adsorption, doping, magnetism and conductivity. In addition, Na derived from phosphate 3 PO 4 Is an ion conductor, can reduce the diffusion energy barrier of sodium, promote reaction kinetics, and is generated in the sodium treatment process of antimony phosphateSb and Na x Sb can construct a three-dimensional path for electrons. However, pure antimony phosphate has problems such as poor cycle stability and poor conductivity when used as a negative electrode material for sodium ion batteries. For this reason, researchers often choose to compound antimony phosphate with carbon materials to solve the above problems.
Researches show that the structure and the morphology of the carbon material are one of important factors influencing the antimony phosphate/carbon composite material. Due to the unique structure, the graphene has high flexibility, and can effectively inhibit the huge volume change of antimony phosphate in the charging and discharging processes, so that the stability of the electrode is obviously enhanced. The melamine resin carbon source contains a large amount of melamine in the synthetic raw materials, so that the carbon material contains a plurality of nitrogen doping and defect sites, and the electrochemical performance of the composite material is improved. In addition, due to the existence of melamine, nitrogen atoms can be introduced into the graphene oxide, the conductivity of the graphene is improved, and a large number of active sites can be introduced into the surface of the graphene oxide, so that the ion adsorption capacity of the graphene oxide is enhanced.
At present, the research on the antimony phosphate/carbon composite material for the cathode of the sodium ion battery has defects, and the composite material is synthesized by basically adopting a hydrothermal method, an electrostatic spinning method and other methods. The hydrothermal method has the problems of variable synthesis process, difficult control of size and shape, high production cost and the like in the electrostatic spinning method.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a preparation method of a nitrogen-doped antimony phosphate/carbon composite material for a sodium ion battery cathode.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the preparation method of the nitrogen-doped antimony phosphate/carbon composite material for the cathode of the sodium ion battery comprises the following steps:
1) 0.6-0.8 g of nano Sb 2 O 3 Adding the powder, 0.1-0.3 g of graphene oxide and 8-15 ml of deionized water into a 50ml round-bottom flask, and carrying out ultrasonic treatment for 20-40 min;
2) adding 0.2-0.5 g of phosphoric acid solution with the mass concentration of 85% into a round-bottom flask, and heating the round-bottom flask in a water bath kettle at the stirring speed of 10-30 r/min;
3) when the heating temperature is increased to 85-95 ℃, adding 5-10 mL of 30% hydrogen peroxide solution into the round-bottom flask, and refluxing for 2.0-2.5 h at the constant temperature of 85-95 ℃; after the reaction is finished, centrifuging for 2-3 times by using deionized water, adding the deionized water into 20-60 ml of deionized water, and performing ultrasonic treatment for 25-35 min to obtain a suspension A;
4) weighing melamine and formaldehyde solution according to the mass ratio of 1: 3-1: 4, wherein the mass of the melamine is 0.2-0.8 g; sequentially injecting the melamine prepolymer into a 25mL flask, dripping 0.5-1 mL of ammonia water, adding deionized water to adjust the pH value to 8-9, reacting for 20-40 min in a water bath kettle at the reaction temperature of 65-75 ℃ to obtain a melamine prepolymer solution, and marking as a solution B;
5) adding the suspension A into a 250mL round-bottom flask, controlling the temperature to be 65-75 ℃, adding the solution B, dropwise adding phosphoric acid with the mass concentration of 85% after the suspension A and the solution B are fully mixed to adjust the pH value of a system to be 5-6, reacting at constant temperature for 2-4 h, centrifuging the obtained feed liquid after the reaction is finished, and drying to obtain black powder;
6) and (3) placing the black powder in the step 5) into a tubular furnace, heating to 650-750 ℃ at the heating rate of 3-6 ℃/min, and preserving heat for 1-3h to obtain the antimony phosphate/carbon composite material.
The ammonia water in the step 4) is analytically pure ammonia water.
Compared with the prior art, the invention has the beneficial effects that:
the antimony phosphate/carbon composite material with uniform appearance is prepared by a simple water bath method and heat treatment, the scheme is simple and efficient, the production cost is low, the phosphorus source and the antimony source are rich, the repeatability is high, the defects that the process is variable and the size and the appearance are difficult to control in the hydrothermal reaction are effectively overcome, and meanwhile, the experimental facility is simple and cheap. In addition, the graphene oxide has high flexibility, and the special morphology and structure of the composite material are formed by abundant nitrogen sources in the melamine resin, so that the antimony phosphate/carbon composite material has excellent electrochemical performance. In addition, the hydrosolvent reaction system adopted by the invention effectively avoids the safety hazard and the influence on the sample purity caused by the thermal evaporation of the organic solvent in the organic solvent reaction system, and has strong feasibility.
Drawings
FIG. 1 is a flow chart of preparation of nitrogen-doped antimony phosphate/carbon composite material for sodium ion battery negative electrode.
FIG. 2 is an XRD spectrum of a sample prepared in examples 1-4.
FIG. 3 shows XPS survey and N1s fine spectra of samples prepared in example 2.
FIG. 4 is a scanning electron micrograph of a sample prepared according to example 2.
FIG. 5 is a graph of rate performance of samples prepared in examples 1-4 applied to a sodium ion battery.
FIG. 6 is a graph showing the cycle performance of the samples prepared in examples 1 to 4 when applied to a sodium ion battery at a current density of 100 mA/g.
FIG. 7 is a graph of the cycling performance of samples prepared in example 2 applied to a sodium ion battery at a current density of 1000 mA/g.
Detailed Description
The present invention is described in detail below, but it should be noted that the practice of the present invention is not limited to the following embodiments.
Example 1
MFC@SbPO 4 -0.3 preparation of composite material, the specific preparation process is as follows, see fig. 1:
1) 0.7g of nano Sb 2 O 3 The powder, 0.2g Graphene Oxide (GO) and 10ml deionized water were added to a 50ml round bottom flask and sonicated for 30 min.
2) And adding 0.4g of 85% phosphoric acid solution into a 50ml round-bottom flask, putting the flask into a water bath, and starting heating at a stirring speed of 10-30 revolutions per minute.
3) When the temperature of the reaction system rises to 90 ℃, 5mL of 30% hydrogen peroxide solution by mass is added to the round-bottom flask and refluxed at a constant temperature of 90 ℃ for 2 hours. And after the reaction is finished, centrifuging for 2-3 times by using deionized water, adding the deionized water into 50ml of deionized water, and performing ultrasonic treatment for 30min to obtain a suspension A.
4) Weighing melamine and formaldehyde solution (wherein the mass of the melamine is 0.3g) in a mass ratio of 1:3, sequentially injecting the melamine and formaldehyde solution into a 25mL flask, dripping 0.5mL ammonia water (analytically pure, national medicine group), adding a proper amount of water to adjust the pH value to 8-9, reacting in a water bath kettle for 30min (the reaction temperature is 70 ℃) to obtain melamine prepolymer solution, and marking the solution as solution B;
5) adding the suspension A into a 250mL round-bottom flask, controlling the temperature to be 70 ℃, then adding the solution B into the round-bottom flask, dropwise adding a proper amount of phosphoric acid to adjust the pH value of the system to 5-6 after the two are fully mixed, reacting for 3 hours at constant temperature, centrifuging the obtained feed liquid after the reaction is finished, and drying to obtain black powder, wherein the black powder is a graphene oxide/melamine resin/antimony phosphate compound.
6) Finally, placing the graphene oxide/melamine resin/antimony phosphate compound into a tube furnace, heating to 700 ℃ at a heating rate of 5 ℃/min, and preserving heat for 2 hours to obtain a final product, namely the antimony phosphate/carbon composite material, and naming the final product as MFC @ SbPO 4 0.3, 0.3 represents the mass of melamine added in the experiment.
Example 2
MFC@SbPO 4 -0.5 preparation of composite material, the specific preparation process is as follows, see fig. 1:
1) 0.7g of nano Sb 2 O 3 The powder, 0.2g Graphene Oxide (GO) and 10ml deionized water were added to a 50ml round bottom flask and sonicated for 30 min.
2) And adding 0.4g of 85% phosphoric acid solution into the round-bottom flask, and putting the round-bottom flask into a water bath kettle to start heating, wherein the stirring speed is 10-30 r/min.
3) When the temperature of the reaction system was raised to 90 ℃, 5mL of a 30% hydrogen peroxide solution by mass was added to the round-bottom flask and refluxed at a constant temperature of 90 ℃ for 2 hours. And after the reaction is finished, centrifuging for 2-3 times by using deionized water, adding the deionized water into 50ml of deionized water, and performing ultrasonic treatment for 30min to obtain a suspension A.
4) Weighing melamine and formaldehyde solution (the mass of the melamine is 0.5g) in a mass ratio of 1:3, then sequentially injecting the melamine and formaldehyde solution into a 25mL flask, dripping 0.5mL ammonia water (analytically pure, national medicine group), adding a proper amount of water to adjust the pH value to 8-9, then reacting in a water bath kettle for 30min (the reaction temperature is 70 ℃) to obtain melamine prepolymer solution, and marking the melamine prepolymer solution as solution B;
5) adding the suspension A into a 250mL round-bottom flask, controlling the temperature to be 70 ℃, then adding the solution B into the round-bottom flask, dropwise adding phosphoric acid to adjust the pH value of the system to 5-6 after the suspension A and the solution B are fully mixed, reacting at constant temperature for 3 hours, centrifuging the obtained feed liquid after the reaction is finished, and drying to obtain black powder, wherein the black powder is a graphene oxide/melamine resin/antimony phosphate compound.
6) Finally, placing the graphene oxide/melamine resin/antimony phosphate compound into a tube furnace, heating to 700 ℃ at a heating rate of 5 ℃/min, and preserving heat for 2 hours to obtain a final product, namely the antimony phosphate/carbon composite material, and naming the final product as MFC @ SbPO 4 -0.5, 0.5 represents the mass of melamine added in the experiment.
Example 3
MFC@SbPO 4 -0.7 preparation of composite material, the specific preparation process is as follows, see fig. 1:
1) 0.7g of nano Sb 2 O 3 The powder, 0.2g Graphene Oxide (GO) and 10ml deionized water were added to a 50ml round bottom flask and sonicated for 30 min.
2) Then, 0.4g of 85% phosphoric acid solution by mass concentration is added into the round-bottom flask, and the round-bottom flask is placed into a water bath to start heating (the stirring speed is 10-30 r/min).
3) When the temperature of the reaction system was raised to 90 ℃, 5mL of a 30% hydrogen peroxide solution by mass was added to the round-bottom flask and refluxed at a constant temperature of 90 ℃ for 2 hours. And after the reaction is finished, centrifuging for 2-3 times by using deionized water, adding the deionized water into 50ml of deionized water, and performing ultrasonic treatment for 30min to obtain a suspension A.
4) Weighing melamine and formaldehyde solution (wherein the mass of the melamine is 0.7g) in a mass ratio of 1:3, sequentially injecting the melamine and formaldehyde solution into a 25mL flask, dripping 0.5mL ammonia water (analytically pure, national medicine group), adding a proper amount of water to adjust the pH value to 8-9, reacting in a water bath kettle for 30min (the reaction temperature is 70 ℃) to obtain melamine prepolymer solution, and marking the solution as solution B;
5) adding the suspension A into a 250mL round-bottom flask, controlling the temperature to be 70 ℃, then adding the solution B into the round-bottom flask, dropwise adding a proper amount of phosphoric acid to adjust the pH value of the system to 5-6 after the suspension A and the solution B are fully mixed, reacting for 3 hours at a constant temperature, centrifuging the obtained feed liquid after the reaction is finished, and drying to obtain black powder, wherein the black powder is a graphene oxide/melamine resin/antimony phosphate compound.
6) Finally, placing the graphene oxide/melamine resin/antimony phosphate compound into a tube furnace, heating to 700 ℃ at a heating rate of 5 ℃/min, and preserving heat for 2 hours to obtain a final product, namely the antimony phosphate/carbon composite material, and naming the final product as MFC @ SbPO 4 0.7, 0.7 representing the mass of melamine added in the experiment.
Example 4
The preparation of the MFC electrode material comprises the following specific preparation flow:
1) 0.2g of Graphene Oxide (GO) and 10ml of deionized water were added to a 50ml round bottom flask and sonicated for 30 min.
2) And adding 0.4g of 85% phosphoric acid solution into the round-bottom flask, putting the round-bottom flask into a water bath, and heating at a stirring speed of 10-30 r/min.
3) When the temperature of the reaction system was raised to 90 ℃, 5mL of a 30% hydrogen peroxide solution by mass was added to the round-bottom flask and refluxed at a constant temperature of 90 ℃ for 2 hours. And after the reaction is finished, centrifuging for 2-3 times by using deionized water, adding the deionized water into 50ml of deionized water, and performing ultrasonic treatment for 30min to obtain a suspension A.
4) Weighing melamine and formaldehyde solution (wherein the mass of the melamine is 0.5g) in a mass ratio of 1:3, then sequentially injecting the melamine and formaldehyde solution into a 25mL flask, dripping 0.5mL ammonia water (analytically pure, national medicine group), adding a proper amount of water to adjust the pH value to 8-9, then reacting in a water bath kettle for 30min (the reaction temperature is 70 ℃) to obtain melamine prepolymer solution, and marking the solution as solution B.
5) Adding the suspension A into a 250mL round-bottom flask, controlling the temperature to be 70 ℃, then adding the solution B into the round-bottom flask, dropwise adding a proper amount of phosphoric acid to adjust the pH value of the system to 5-6 after the two are fully mixed, reacting for 3 hours at constant temperature, centrifuging the obtained feed liquid after the reaction is finished, and drying to obtain black powder, wherein the black powder is a graphene oxide/melamine resin compound.
6) And finally, placing the graphene oxide/melamine resin compound into a tubular furnace, heating to 700 ℃ at a heating rate of 5 ℃/min, and preserving heat for 2 hours to obtain a final product, namely a pure carbon reference sample, and naming the final product as MFC.
Example 5
MFC@SbPO 4 -0.6 preparation of composite material, the specific preparation process is as follows, see fig. 1:
1) 0.7g of nano Sb 2 O 3 The powder, 0.15g Graphene Oxide (GO) and 10ml deionized water were added to a 50ml round bottom flask and sonicated for 30 min.
2) And adding 0.5g of 85% phosphoric acid solution into the round-bottom flask, putting the round-bottom flask into a water bath, and heating at a stirring speed of 10-30 r/min.
3) When the temperature of the reaction system was raised to 90 ℃, 5mL of a 30% hydrogen peroxide solution by mass was added to the round-bottom flask and refluxed at a constant temperature of 90 ℃ for 2 hours. And after the reaction is finished, centrifuging for 2-3 times by using deionized water, adding the deionized water into 50ml of deionized water, and performing ultrasonic treatment for 30min to obtain a suspension A.
4) Weighing melamine and formaldehyde solution (the mass of the melamine is 0.6g) in a mass ratio of 1:3, then sequentially injecting the melamine and formaldehyde solution into a 25mL flask, dripping 0.5mL ammonia water (analytically pure, national medicine group), adding a proper amount of water to adjust the pH value to 8-9, then reacting in a water bath kettle for 30min (the reaction temperature is 70 ℃) to obtain melamine prepolymer solution, and marking the melamine prepolymer solution as solution B;
5) adding the suspension A into a 250mL round-bottom flask, controlling the temperature to be 70 ℃, then adding the solution B into the round-bottom flask, dropwise adding phosphoric acid to adjust the pH value of the system to 5-6 after the suspension A and the solution B are fully mixed, reacting for 3 hours at constant temperature, centrifuging the obtained feed liquid after the reaction is finished, and drying to obtain black powder, wherein the black powder is a graphene oxide/melamine resin/antimony phosphate compound.
6) Finally, placing the graphene oxide/melamine resin/antimony phosphate compound into a tube furnace, heating to 700 ℃ at a heating rate of 5 ℃/min, and preserving heat for 2 hours to obtain a final product, namely the antimony phosphate/carbon composite material, and naming the final product as MFC @ SbPO 4 -0.6, 0.6 representing the mass of melamine added in the experiment.
Example 6
MFC@SbPO 4 -0.4 preparation of composite material, the specific preparation process is as follows, see fig. 1:
1) 0.6g of nano Sb 2 O 3 The powder, 0.2g Graphene Oxide (GO) and 10ml deionized water were added to a 50ml round bottom flask and sonicated for 30 min.
2) And adding 0.5g of 85% phosphoric acid solution into the round-bottom flask, and putting the round-bottom flask into a water bath kettle to start heating, wherein the stirring speed is 10-30 r/min.
3) When the temperature of the reaction system was raised to 90 ℃, 5mL of a 30% hydrogen peroxide solution by mass was added to the round-bottom flask and refluxed at a constant temperature of 90 ℃ for 2 hours. And after the reaction is finished, centrifuging for 2-3 times by using deionized water, adding the deionized water into 50ml of deionized water, and performing ultrasonic treatment for 30min to obtain a suspension A.
4) Weighing melamine and formaldehyde solution (the mass of the melamine is 0.4g) in a mass ratio of 1:3, then sequentially injecting the melamine and formaldehyde solution into a 25mL flask, dripping 0.5mL ammonia water (analytically pure, national medicine group), adding a proper amount of water to adjust the pH value to 8-9, then reacting in a water bath kettle for 30min (the reaction temperature is 70 ℃) to obtain melamine prepolymer solution, and marking the melamine prepolymer solution as solution B;
5) adding the suspension A into a 250mL round-bottom flask, controlling the temperature to be 70 ℃, then adding the solution B into the round-bottom flask, dropwise adding phosphoric acid to adjust the pH value of the system to 5-6 after the suspension A and the solution B are fully mixed, reacting for 3 hours at constant temperature, centrifuging the obtained feed liquid after the reaction is finished, and drying to obtain black powder, wherein the black powder is a graphene oxide/melamine resin/antimony phosphate compound.
6) Finally, placing the graphene oxide/melamine resin/antimony phosphate compound into a tubular furnace, heating to 700 ℃ at a heating rate of 5 ℃/min, and preserving heat for 2 hours to obtain a final product, namely the antimony phosphate/carbon composite material, and naming the final product as MFC @ SbPO 4 -0.4, 0.4 represents the mass of melamine added in the experiment.
The assembling process of the sodium-ion battery comprises the preparation of electrode plates and the process of assembling the sodium-ion battery, and specifically comprises the following steps:
the preparation method comprises the steps of weighing an antimony phosphate/carbon composite material, a conductive agent (acetylene black) and a binder (polyvinylidene fluoride, PVDF) according to a mass ratio of 70:15:15, grinding and mixing uniformly, adding 4-8 ml of N-methylpyrrolidone (NMP) to prepare viscous slurry, and then uniformly coating the slurry on the surface of a current collector (copper foil) by using a film coating device.
And (3) putting the copper foil coated with the slurry into a vacuum oven at 120 ℃ for baking for 12h, and removing the NMP solvent. And finally, cutting the copper foil into circular electrode plates with the diameter of 11mm for later use. The sequence of packaging the batteries is as follows: negative electrode shell, sodium piece, diaphragm, negative electrode piece, gasket, spring leaf, positive electrode shell. The sodium sheet served as the counter and reference electrodes throughout the test element. The whole process of packaging the sodium ion battery is carried out in a glove box filled with argon, and the water and oxygen contents are less than 0.1 ppm.
From FIG. 2, it can be seen that MFC @ SbPO 4 -0.3、MFC@SbPO 4 -0.5、MFC@SbPO 4 All the obvious diffraction peaks in the spectrum of the-0.7 composite material can be well corresponded to the diffraction peaks in the standard color chart of antimony phosphate (ICOD 00-035- 4 -0.3、MFC@SbPO 4 -0.5、MFC@SbPO 4 All three samples-0.7 were successfully prepared. The diffraction peaks at 25.7 ° and 42.5 ° for the MFC sample correspond to the (002) and (100) peaks, respectively, of the carbon material.
From the full spectrum (a) of FIG. 3, it is known that MFC @ SbPO 4 The-0.5 sample mainly contains five elements of C, N, O, Sb and PBiotin, also from the fine spectrum of N1s (FIG. 3 (b)), MFC @ SbPO 4 The nitrogen doping in the 0.5 sample occurs in three main forms, corresponding to the curves pyridine nitrogen at 397.8eV (relative peak area 32.9%), pyrrole nitrogen at 398.8eV (relative peak area 35.5%) and quaternary nitrogen at 400.9eV (relative peak area 31.6%), respectively.
As can be seen in FIG. 4, MFC @ SbPO 4 The-0.5 composite material is a blocky structure with different sizes from several micrometers to dozens of micrometers, and meanwhile, as can be seen from a scanning electron microscope image with a larger multiple, a plurality of flaky structures are uniformly distributed on the composite material, and the special structure brings excellent electrochemical performance to the composite material.
As can be seen from fig. 5, the rate performance of the antimony phosphate/carbon composite materials prepared in examples 1, 2 and 3 is greatly improved compared to the MFC sample without antimony phosphate prepared in example 4, which is mainly due to the introduction of antimony phosphate in the composite material. Wherein MFC @ SbPO 4 The 0.5 composite material shows the most excellent rate capability, has high specific discharge capacity of 480, 419.6, 384, 354.3, 326.1, 301.9, 260.2mAh/g at current density of 50mA/g, 100mA/g, 200mA/g, 500mA/g, 1000mA/g, 2000mA/g, 5000mA/g, respectively, and still can have 415.7mAh/g when the current density returns to 100A/g from 5000mA/g, corresponding to capacity retention rate of 99.07%.
As can be seen from FIGS. 6 and 7, MFC @ SbPO 4 -0.5 composite material having specific discharge capacity of 387mAh/g after cycling 100 cycles at a current density of 100 mA/g. In addition thereto MFC @ SbPO 4 The-0.5 composite material still has a specific discharge capacity of 271mAh/g after being cycled for 300 cycles under a high current density of 1000 mA/g.
The electrochemical experiment results show that the antimony phosphate/carbon composite material prepared by the simple water bath method has better electrochemical properties, a new method is added for storing energy of the antimony-based composite material, and a new thought is provided for carbon coating of other phosphates and the like.

Claims (2)

1. The preparation method of the nitrogen-doped antimony phosphate/carbon composite material for the cathode of the sodium ion battery is characterized by comprising the following steps of:
1) 0.6-0.8 g of nano Sb 2 O 3 Adding the powder, 0.1-0.3 g of graphene oxide and 8-15 ml of deionized water into a 50ml round-bottom flask, and carrying out ultrasonic treatment for 20-40 min;
2) adding 0.2-0.5 g of phosphoric acid solution with the mass concentration of 85% into a round-bottom flask, and heating the round-bottom flask in a water bath kettle at the stirring speed of 10-30 r/min;
3) when the heating temperature is increased to 85-95 ℃, adding 5-10 mL of hydrogen peroxide solution with the mass concentration of 30% into the round-bottom flask, and refluxing for 2.0-2.5 h at the constant temperature of 85-95 ℃; after the reaction is finished, centrifuging for 2-3 times by using deionized water, adding the deionized water into 20-60 ml of deionized water, and performing ultrasonic treatment for 25-35 min to obtain a suspension A;
4) weighing melamine and formaldehyde solution according to the mass ratio of 1:3 to 1:4, wherein the mass of the melamine is 0.2-0.8 g; sequentially injecting the melamine prepolymer into a 25mL flask, dripping 0.5-1 mL of ammonia water, adding deionized water to adjust the pH value to 8-9, reacting for 20-40 min in a water bath kettle at the reaction temperature of 65-75 ℃ to obtain a melamine prepolymer solution, and marking as a solution B;
5) adding the suspension A into a 250mL round-bottom flask, controlling the temperature to be 65-75 ℃, adding the solution B, dropwise adding phosphoric acid with the mass concentration of 85% after the suspension A and the solution B are fully mixed to adjust the pH value of a system to be 5-6, reacting at constant temperature for 2-4 h, centrifuging the obtained feed liquid after the reaction is finished, and drying to obtain black powder;
6) and (3) placing the black powder in the step 5) into a tubular furnace, heating to 650-750 ℃ at the heating rate of 3-6 ℃/min, and preserving heat for 1-3h to obtain the antimony phosphate/carbon composite material.
2. The method for preparing the nitrogen-doped antimony phosphate/carbon composite material for the negative electrode of the sodium-ion battery as claimed in claim 1, wherein the ammonia water in the step 4) is analytically pure ammonia water.
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