CN110034283B - Tin phosphide composite material and preparation method and application thereof - Google Patents
Tin phosphide composite material and preparation method and application thereof Download PDFInfo
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- CN110034283B CN110034283B CN201811080354.6A CN201811080354A CN110034283B CN 110034283 B CN110034283 B CN 110034283B CN 201811080354 A CN201811080354 A CN 201811080354A CN 110034283 B CN110034283 B CN 110034283B
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/387—Tin or alloys based on tin
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- H—ELECTRICITY
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- 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
- H01M4/5805—Phosphides
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- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- 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 a tin phosphide composite material and a preparation method and application thereof. The preparation method comprises the following steps: carrying out hydrothermal reaction on a tin source material and a carbon source material under an alkaline condition to obtain a hollow tin dioxide ball with a carbon source attached to the surface; carrying out carbonization treatment on tin dioxide in an inert atmosphere to obtain a hollow tin dioxide ball with a surface coated with a carbon layer; and (3) heating the hollow tin dioxide ball coated with the carbon layer on the surface and a phosphorus source material in an inert atmosphere to react to obtain the composite material containing the tin phosphide, the hollow tin dioxide and carbon, wherein the carbon is the coating layer. The material obtained by the preparation method of the tin phosphide composite material comprises tin phosphide, hollow tin dioxide and carbon, and the carbon is a coating layer, so that the tin phosphide composite material has good conductivity, can effectively inhibit the volume expansion effect when being used as a battery cathode active material, and improves the electrochemical performance of a battery.
Description
Technical Field
The invention belongs to the technical field of tin phosphide materials, and particularly relates to a tin phosphide composite material and a preparation method and application thereof.
Background
With the rapid development of personal computers, video cameras, mobile phones and mobile devices and the rapid development of electric vehicles and hybrid electric vehicles, the demand of energy storage devices is also greatly increased. The secondary battery has the characteristic of being capable of circularly charging and discharging, so that the secondary battery is the mainstream direction of mobile energy storage equipment, the main secondary battery at present is the lithium ion battery, the materials of the positive electrode and the negative electrode in the lithium ion battery are core components of the battery, and the performance directly determines the electrochemical performance of the battery, so that the continuous research and development of the positive electrode material and the negative electrode material which have excellent performance and low price are the key points of the battery material, and the pattern of taking the binary material and the ternary material as the positive electrode material and taking the carbon-based material, the silicon-based material and the silicon-carbon composite material as the negative electrode material is formed so far, but the further research and development of the positive electrode material which can better meet the new potential.
Research shows that the capacity of tin in the sodium storage material is 847 mAh.g-1Phosphorus capacity of 2596mAh · g-1Tin phosphide (Sn) compound thereof4P3) Reacts with sodium to generate Na15Sn4And Na3P, therefore, when the tin phosphide is used as the sodium-based negative electrode material, the volume specific capacity is up to 6650mAh cm-3. In view of such a high specific volumetric capacity, tin phosphide is considered as a negative electrode active material for sodium ion batteries and lithium ion batteries. However, the current synthesis method of tin phosphide mostly adopts a high-energy ball milling method or a hydrothermal reaction method, for example, chinese patent publication No. CN105006551A discloses that metallic tin powder, phosphorus and grinding balls are added into a ball milling tank of a high-energy ball mill, and under the protection of inert gas or nitrogen, ball milling is carried out while chemical reaction occurs, so as to obtain nano tin phosphide particles. Also, for example, Chinese patent with publication No. CN106450306A discloses Sn4P3The preparation method of the sodium ion battery cathode material specifically comprises (1) carrying out ball milling treatment on red phosphorus; (2) dissolving a Sn salt in a solvent to prepare a dispersion liquid of the Sn salt; (3) mixing the Sn salt dispersion liquid with the red phosphorus subjected to ball milling to obtain a uniform mixed solution; (4) transferring the mixed solution into a reaction kettle, and reacting to obtain a suspension; (5) filtering the turbid liquid to obtain a precipitate, washing and drying the precipitate to obtain Sn4P3The negative electrode material of the sodium ion battery. In addition, it is reported in the literature that Sn can be prepared by reducing tin dioxide with sodium hypophosphite4P3. However, Sn prepared in these prior reports4P3Are all amorphous structures or solid nanometer spherical structures. Due to Sn4P3During battery cycling, there is a volume expansion effect with up to 400% volume change, and thus, solid structure Sn4P3The negative electrode material has a problem that structural pulverization is likely to occur during long-term cycling in a battery, and has a problem of poor conductivity.
Disclosure of Invention
Aiming at the problems of large volume expansion, poor conductivity and the like when the tin phosphide synthesized by the current tin phosphide synthesis method is used as a battery cathode material, the invention provides a tin phosphide composite material and a preparation method thereof.
Further, the invention also provides applications of the method in multiple fields.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of a tin phosphide composite material at least comprises the following steps:
mixing a tin source material and a carbon source material, and maintaining the mixture under an alkaline condition to perform a hydrothermal reaction to obtain hollow tin dioxide balls with carbon sources attached to the surfaces;
carbonizing the obtained hollow tin dioxide ball in an inert atmosphere to obtain a hollow tin dioxide ball with a surface coated with a carbon layer;
mixing the hollow tin dioxide ball coated with the carbon layer on the surface with a phosphorus source material, and heating the mixture in an inert atmosphere to react the hollow tin dioxide ball and the phosphorus source material to obtain a tin phosphide composite material;
the tin phosphide composite material at least contains tin phosphide, hollow tin dioxide and carbon, and the carbon is coated on the surfaces of the tin phosphide and the hollow tin dioxide.
Correspondingly, the tin phosphide composite material at least contains tin phosphide, hollow tin dioxide and carbon, and the carbon is coated on the surfaces of the tin phosphide and the hollow tin dioxide.
And the negative plate of the lithium ion battery or the sodium ion battery comprises a negative active material, wherein the negative active material is a tin phosphide composite material, the tin phosphide composite material at least contains tin phosphide, hollow tin dioxide and carbon, and the carbon is coated on the surfaces of the tin phosphide and the hollow tin dioxide.
And correspondingly, the lithium ion battery or the sodium ion battery comprises a negative plate, wherein the negative plate contains a tin phosphide composite material, the tin phosphide composite material at least contains tin phosphide, hollow tin dioxide and carbon, and the carbon is coated on the surfaces of the tin phosphide and the hollow tin dioxide.
The invention has the beneficial effects that:
compared with the prior art, the preparation method of the tin phosphide composite material has the advantages that the tin source material is combined with the carbon source material to prepare the hollow tin dioxide ball with the carbon source attached to the surface through hydrothermal reaction, then the carbon source is carbonized and reacts with the phosphorus source material to generate phosphine, the hollow tin dioxide is reduced by means of the phosphine to generate tin phosphide, and the structural framework of the original hollow tin dioxide is kept, so that the obtained tin phosphide composite material can effectively inhibit volume expansion when being used as a battery cathode material and has good conductivity; in addition, the preparation method has simple conditions and low requirements on equipment, and is suitable for large-scale production.
The tin phosphide composite material provided by the invention simultaneously comprises tin phosphide, hollow tin dioxide and carbon, and the carbon is coated on the surfaces of the tin phosphide and the hollow tin dioxide, so that the tin phosphide composite material has good conductivity, and when the tin phosphide composite material is used as a battery cathode active material, the volume expansion effect can be effectively inhibited, and the electrochemical performance of a battery is improved.
According to the lithium ion battery negative plate or the sodium ion battery negative plate provided by the invention, as the negative active material adopts the tin phosphide composite material containing tin phosphide, hollow tin dioxide and carbon, the negative plate has good conductivity and antibody volume expansion effect, and the problems of crushing, falling and the like of the negative plate in the battery charging and discharging circulation process can be solved.
According to the lithium ion battery or the sodium ion battery provided by the invention, the negative plate contains the tin phosphide composite material, the tin phosphide composite material contains tin phosphide, hollow tin dioxide and carbon, and the carbon is coated on the surfaces of the tin phosphide and the hollow tin dioxide, so that the lithium ion battery or the sodium ion battery has good conductivity, and the volume expansion in the charging and discharging process can be effectively inhibited, so that the lithium ion battery or the sodium ion battery has good electrochemical performance.
Drawings
To more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is an SEM image of a tin phosphide composite material prepared in example 1 of the present invention;
FIG. 2 is an XRD pattern of a tin phosphide composite material prepared in example 1 of the present invention;
FIG. 3 is a cyclic voltammetry curve of a lithium ion negative electrode sheet made of the tin phosphide composite material prepared in example 1 of the present invention and assembled into a half-cell;
FIG. 4 is an AC impedance curve of a half-cell assembled by a lithium ion battery negative electrode sheet made of the tin phosphide composite material prepared in example 1 of the present invention;
FIG. 5 is a cycle curve of half-cells assembled by lithium ion battery negative electrode sheets made of the tin phosphide composite material prepared in example 1 of the invention under different multiplying powers;
FIG. 6 is a cycle curve of a half-cell assembled by a lithium ion battery negative electrode sheet made of the tin phosphide composite material prepared in example 1 of the invention;
FIG. 7 is an XRD pattern of a tin phosphide composite material prepared in example 2 of the present invention;
FIG. 8 is an SEM image of a tin phosphide composite material prepared in example 2 of the present invention;
FIG. 9 is an EDS map of elements within the box area of FIG. 7 in example 2 of the present invention;
FIG. 10 is a cycle curve of a half-cell assembled by a lithium ion battery negative electrode sheet made of the tin phosphide composite material prepared in example 2 of the invention;
fig. 11 is a circulation curve of half-cells assembled by lithium ion battery negative electrode sheets made of the tin phosphide composite material prepared in example 2 of the invention under different multiplying powers.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. It should be noted that, in the present invention, the hollow sphere or hollow sphere structure represents the physical property of the tin dioxide material, and the expression means the same meaning.
The embodiment of the invention provides a preparation method of a tin phosphide composite material.
Specifically, the preparation method of the tin phosphide composite material at least comprises the following steps:
mixing a tin source material and a carbon source material, and maintaining the mixture under an alkaline condition to perform a hydrothermal reaction to obtain hollow tin dioxide balls with carbon sources attached to the surfaces;
carbonizing the obtained hollow tin dioxide ball in an inert atmosphere to obtain a hollow tin dioxide ball with a surface coated with a carbon layer;
mixing the hollow tin dioxide ball coated with the carbon layer on the surface with a phosphorus source material, and heating the mixture in an inert atmosphere to react the hollow tin dioxide ball and the phosphorus source material to obtain a tin phosphide composite material;
the tin phosphide composite material at least contains tin phosphide, hollow tin dioxide and carbon, and the carbon is coated on the surfaces of the tin phosphide and the hollow tin dioxide.
The following is a detailed explanation of the preparation method of the tin phosphide composite material.
The tin source material, which is one of the synthetic raw materials of the tin phosphide composite material, may be potassium stannate (K)2SnO3·3H2O) and sodium stannate. The two tin source materials can generate tin dioxide with hollow sphere shape under the hydrothermal reaction condition.
The carbon source material is used as a carbon source to be attached to the surface of the generated hollow spherical tin dioxide in the reaction, and lays a carbon source foundation for further carbonization into amorphous carbon coated on the surface of the hollow spherical tin dioxide.
Preferably, the carbon source material is polyvinyl alcohol, the polyvinyl alcohol is used as the carbon source material, a thin carbon source layer is formed on the surface of the hollow spherical tin dioxide in the hydrothermal reaction process, and the carbon source layer is carbonized to form an amorphous carbon coating layer with an amorphous thin layer, and further preferably, the concentration of the polyvinyl alcohol in the reaction process is 2-10 g/L.
In the mixing process of the tin source material and the carbon source material, absolute ethyl alcohol can be used as a solvent, deionized water can be used as a solvent, or a mixed solution of the deionized water and the ethyl alcohol can be used as the solvent.
Preferably, urea or the like may be added as an acid-base modifier to a mixed solution obtained by mixing the tin source material and the carbon source material, so that the pH of the mixed solution becomes alkaline, thereby facilitating the production of hollow spherical tin dioxide.
The feeding ratio of the tin source material to the carbon source material is determined by the thin-layer coating formed on the surface of the formed hollow spherical tin dioxide by the carbon source material, namely, the concentration of the carbon source (polyvinyl alcohol) in the reaction is 2-10 g/L.
Preferably, the hydrothermal reaction temperature is 120-200 ℃, the reaction time is 10-24 hours, and hollow spherical tin dioxide precipitates with relatively uniform particle sizes are obtained at the hydrothermal reaction temperature.
And centrifuging, washing and drying the hollow spherical tin dioxide precipitate to obtain the hollow spherical tin dioxide with the carbon source attached to the surface.
In the case of carbonizing the hollow spherical tin dioxide, the inert atmosphere may be argon gas, helium gas, or the like, but may be nitrogen gas. Preferably, the carbonization treatment temperature is 350-450 ℃, the carbonization treatment time is 4-10 h, and the carbon source material is completely converted into amorphous carbon through carbonization and is coated on the surface of the hollow spherical tin dioxide to form a thin coating layer.
The phosphorus source material of the invention should be capable of decomposing to generate phosphine under the heating condition, the phosphine gas and the hollow spherical tin dioxide undergo reduction reaction to generate metallic tin, and the generated metallic tin further reacts with the phosphine to generate tin phosphide (Sn)4P3). When the amount of the phosphorus source material is sufficient, the metallic tin generated by the tin dioxide is completely converted into tin phosphide, and if the amount of the phosphorus source material is insufficient or the heating time is insufficient, the product can also contain a small amount of metallic tin, and in this case, the tin phosphide composite material comprises tin phosphide, hollow spherical tin dioxide, metallic tin, carbon and the like.
Preference is given toThe phosphorus source material is sodium hypophosphite (NaH)2PO2). The sodium hypophosphite can be decomposed to generate phosphine at a lower heating temperature, so that the preparation process is simpler. Further preferably, the molar ratio of tin dioxide: the phosphorus source material is 1: 1-8.
When sodium hypophosphite is used as a phosphorus source material, the heating temperature is preferably 250-300 ℃, and the reaction time is 10 min-2 h.
According to the preparation method of the tin phosphide composite material, a tin source material is combined with a carbon source material to prepare a hollow tin dioxide ball with a carbon source attached to the surface through a hydrothermal reaction, then the carbon source is carbonized and reacts with a phosphorus source material to generate phosphine, the hollow tin dioxide is reduced by means of the phosphine to generate tin phosphide, and the structural framework of the original hollow tin dioxide is maintained, so that the obtained tin phosphide composite material can effectively inhibit volume expansion when being used as a battery cathode material and has good conductivity; in addition, the preparation method has simple conditions and low requirements on equipment, and is suitable for large-scale production.
According to the mass percentage content of the tin phosphide composite material, the tin phosphide composite material contains 5-98% of tin phosphide and 2-90% of hollow tin dioxide. In addition, the carbon content in the tin phosphide composite material is the coating amount of the thin layer, and generally does not exceed 15% of the total mass of the tin phosphide composite material. Furthermore, the tin phosphide composite material obtained by the invention can also contain a small amount of metallic tin.
The hollow spherical structure is beneficial to slowing down the capacity loss caused by material crushing of the tin phosphide composite material serving as the negative electrode of the lithium ion battery or the sodium ion battery in the charging and discharging processes, so that the cycle life of the battery is prolonged, and the tin phosphide has the effect of improving the first coulombic efficiency of the material.
Therefore, the invention further provides a lithium ion battery negative plate or a sodium ion battery negative plate, the lithium ion battery negative plate or the sodium ion battery negative plate contains a negative active material, and the negative active material is the tin phosphide composite material prepared by the preparation method of the tin phosphide composite material. Specifically, the negative electrode active material of the lithium ion battery negative electrode sheet or the negative electrode active material of the sodium ion battery negative electrode sheet at least contains tin phosphide, hollow tin dioxide and carbon, and the carbon is coated on the surfaces of the tin phosphide and the hollow tin dioxide.
Preferably, the tin phosphide composite material contains 5-98% of tin phosphide, 2-90% of hollow tin dioxide and 1-15% of carbon.
In addition, the anode active material may also contain a small amount of metallic tin.
The invention further provides a lithium ion battery or a sodium ion battery, which comprises a negative plate, wherein the negative plate contains a tin phosphide composite material, the tin phosphide composite material at least contains tin phosphide, hollow tin dioxide and carbon, and the carbon is coated on the surfaces of the tin phosphide and the hollow tin dioxide.
Preferably, the tin phosphide composite material on the lithium ion battery or sodium ion battery negative plate contains 5-98% of tin phosphide, 2-90% of hollow tin dioxide and 1-15% of carbon.
In order to more effectively explain the technical solution of the present invention, a plurality of specific examples are described below.
Example 1
A preparation method of a tin phosphide composite material specifically comprises the following steps:
(1) 1.5g of K are weighed2SnO3·3H2O (potassium stannate), 1.2g of urea and 1.2g of polyvinyl alcohol (the alcoholysis degree is 87%), and simultaneously preparing 180m L of deionized water and 120m L of absolute ethyl alcohol;
(2) and (2) uniformly mixing the potassium stannate, polyvinyl alcohol, urea, deionized water and absolute ethyl alcohol to obtain a first mixed material, then placing the first mixed material into a reaction kettle with a polytetrafluoroethylene inner container, reacting for 15 hours at 150 ℃, centrifuging, cleaning with ethanol and deionized water, and drying for 12 hours in vacuum at 60 ℃.
(3) And (3) placing the dried sample in a tubular furnace, introducing argon, reacting for 4 hours at 400 ℃, and cooling to obtain the hollow spherical tin dioxide material with the surface coated with the amorphous carbon.
(4) And (3) mixing 1.5g of the hollow spherical tin dioxide material obtained in the step (3) with 5g of sodium hypophosphite, uniformly mixing, placing in a tubular furnace, introducing argon, heating to 280 ℃, preserving heat for 10min, naturally cooling, washing with deionized water, and drying to obtain the composite material.
The composite material obtained in example 1 was subjected to corresponding performance tests, including Scanning Electron Microscope (SEM) testing, XRD testing, and testing of assembled batteries.
Wherein, SEM scanning is as shown in fig. 1, as can be seen from fig. 1, most of the composite material is spherical and hollow, the surface of the spherical composite material is coated with a small amount of other components, and there is no obvious agglomeration phenomenon between particles;
FIG. 2 is an XRD pattern of the composite material of example 1, and it can be seen from FIG. 2 that the resulting composite material contains tin phosphide, tin and tin dioxide.
The composite material obtained is determined to be a tin phosphide composite material, 0.14g of the determined tin phosphide composite material, 0.02g of conductive carbon microspheres and 0.4g of sodium carboxymethylcellulose (the solid content is 5 wt%) are uniformly mixed, then the mixture is coated on a copper foil with the thickness of 7 microns, the copper foil is dried in a vacuum oven at the temperature of 80 ℃ for 12 hours, the dried pole piece is cut into a 12mm raw piece, a counter electrode is a metal lithium piece, and a button cell is assembled, wherein the electrolyte of the button cell is prepared from ethylene carbonate, diethyl carbonate and fluoroethylene carbonate in a volume ratio of 1: 1: 0.05, the solute is lithium hexafluorophosphate, the concentration of the lithium hexafluorophosphate is 1 mol/L, and after standing, cyclic voltammetry, alternating current impedance test, cyclic curve test with different multiplying powers, and cyclic current density of 400mA/g and room temperature are carried out, wherein fig. 3 is a cyclic voltammetry curve, fig. 4 is an alternating current impedance curve, fig. 5 is a cyclic voltammetry curve with different multiplying powers, and fig. 6 is a cyclic voltammetry curve of the button cell at room temperature with the current density of 400 mA/g.
As can be seen from fig. 3, the potential of the material for insertion/extraction of lithium ions is stable under charge-discharge conditions;
as can be seen from fig. 4, the impedance of the battery pole piece is small;
as can be seen from FIG. 5, the material has good rate capability;
as can be seen from FIG. 6, the material is shown to have good recycling properties.
Example 2
A preparation method of a tin phosphide composite material specifically comprises the following steps:
(1) 1.5g of K are weighed2SnO3·3H2O (potassium stannate), 1.2g of urea, 1.2g of polyvinyl alcohol (degree of alcoholysis: 87%), while deionized water 300m L was prepared;
(2) and (2) uniformly mixing the potassium stannate, polyvinyl alcohol, urea and deionized water to obtain a first mixed material, then placing the first mixed material into a reaction kettle with a polytetrafluoroethylene inner container, reacting for 15 hours at 150 ℃, centrifuging, washing with ethanol and deionized water, and vacuum-drying for 12 hours at 60 ℃.
(3) And (3) placing the dried sample in a tubular furnace, introducing argon, reacting for 4 hours at 400 ℃, and cooling to obtain the hollow spherical tin dioxide material with the surface coated with the amorphous carbon.
(4) And (3) mixing 1.5g of the hollow spherical tin dioxide material obtained in the step (3) with 8g of sodium hypophosphite, uniformly mixing, placing in a tubular furnace, introducing argon, heating to 280 ℃, keeping the temperature for 15min, naturally cooling, washing with deionized water, and drying to obtain the composite material.
The composite material obtained in example 2 was subjected to corresponding performance tests, including Scanning Electron Microscope (SEM) testing, XRD testing, and testing of assembled batteries.
Fig. 7 shows XRD measurement, and it can be seen from fig. 7 that the composite material contains tin phosphide and tin dioxide.
Fig. 8 is an SEM scan, and it can be seen from fig. 8 that the composite material is mostly spherical and hollow, the surface of the spherical composite material is coated with a small amount of other components, and there is no obvious agglomeration phenomenon between particles.
Fig. 9 is an EDS spectrum of the elements in the box of fig. 8, and as can be seen from fig. 9, the region contains Sn, P, C and O, and the result is consistent with the XRD test result of fig. 7, indicating that the composite material obtained in this example 2 is indeed a tin phosphide composite material.
The obtained composite material is determined to be a tin phosphide composite material, 0.14g of the determined tin phosphide composite material, 0.02g of conductive carbon microspheres and 0.4g of PVDF0 (solid content is 5 wt%), the tin phosphide composite material, the conductive carbon microspheres and the PVDF0.4g are uniformly mixed, coated on a copper foil with the thickness of 7 microns, dried in a vacuum oven at the temperature of 80 ℃ for 12 hours, the dried pole piece is cut into a 12mm raw piece, a metal lithium piece is taken as a counter electrode, and a button battery is assembled, wherein the electrolyte of the button battery is prepared from ethylene carbonate, diethyl carbonate and fluoroethylene carbonate in a volume ratio of 1: 1: 0.05, the solute is lithium hexafluorophosphate, the concentration of the lithium hexafluorophosphate is 1 mol/L, and corresponding performance tests are carried out after standing, wherein a room-temperature cycle curve of the button battery under the current density of 400mA/g is shown in a figure 10, and a rate performance of the battery is.
As can be seen from FIG. 10, the battery still has good cycle performance at a current density of 400 mA/g;
as can be seen from fig. 11, the battery has a higher capacity at different current densities.
From the results of example 1 and example 2, it is known that the tin phosphide composite material prepared by the preparation method of the tin phosphide composite material of the present invention does contain tin phosphide and tin dioxide, and tin dioxide is in a hollow spherical structure, and the surfaces of tin phosphide and tin dioxide are coated with carbon layers.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The preparation method of the tin phosphide composite material is characterized by at least comprising the following steps:
mixing a tin source material and a carbon source material, and maintaining the mixture under an alkaline condition to perform a hydrothermal reaction to obtain hollow tin dioxide balls with carbon sources attached to the surfaces;
carbonizing the obtained hollow tin dioxide ball in an inert atmosphere to obtain a hollow tin dioxide ball with a surface coated with a carbon layer;
mixing the hollow tin dioxide ball coated with the carbon layer on the surface with a phosphorus source material, and heating the mixture in an inert atmosphere to react the hollow tin dioxide ball and the phosphorus source material to obtain a tin phosphide composite material;
the tin phosphide composite material at least contains tin phosphide, hollow tin dioxide and carbon, and the carbon is coated on the surfaces of the tin phosphide and the hollow tin dioxide.
2. The method of preparing the tin phosphide composite material as set forth in claim 1, wherein the tin source material is at least one of potassium stannate and sodium stannate;
and/or the carbon source material is polyvinyl alcohol;
and/or the phosphorus source material is sodium hypophosphite.
3. The method for preparing the tin phosphide composite material as claimed in claim 1, wherein the hydrothermal reaction temperature is 120 to 200 ℃ and the reaction time is 10 to 24 hours.
4. The preparation method of the tin phosphide composite material as claimed in claim 1, wherein the temperature of the heating reaction is 250 to 300 ℃ and the reaction time is 10min to 2 h.
5. The method for preparing the tin phosphide composite material as claimed in claim 1 or 2, wherein the concentration of the carbon source in the reaction is 2 to 10 g/L.
6. The method of preparing a tin phosphide composite material as set forth in claim 1, wherein the molar ratio of tin dioxide: the phosphorus source material is 1: 1-8.
7. The tin phosphide composite material is characterized by being prepared by the preparation method of the tin phosphide composite material as claimed in any one of claims 1 to 6, at least comprising tin phosphide, hollow tin dioxide and carbon, wherein the carbon is coated on the surfaces of the tin phosphide and the hollow tin dioxide.
8. The tin phosphide composite material as set forth in claim 7, wherein the tin phosphide composite material contains 5 to 98% of tin phosphide and 2 to 90% of hollow tin dioxide by mass%.
9. A lithium ion battery or sodium ion battery negative plate comprises a negative active material, and is characterized in that the negative active material is a tin phosphide composite material prepared by the method of any one of claims 1 to 6, the tin phosphide composite material at least contains tin phosphide, hollow tin dioxide and carbon, and the carbon is coated on the surfaces of the tin phosphide and the hollow tin dioxide.
10. A lithium ion battery or a sodium ion battery comprises a negative plate, and is characterized in that the negative plate comprises the tin phosphide composite material prepared by the method of any one of claims 1 to 6, the tin phosphide composite material at least comprises tin phosphide, hollow tin dioxide and carbon, and the carbon is coated on the surfaces of the tin phosphide and the hollow tin dioxide.
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| CN108493425B (en) * | 2018-04-12 | 2020-05-05 | 合肥工业大学 | Preparation method of Sn4P3 nanoparticle sodium ion battery cathode material coated by mesoporous carbon nanotube |
| CN110993913B (en) * | 2019-12-06 | 2021-01-01 | 湘潭大学 | Tin phosphide/expanded graphite cathode composite material of sodium ion battery and preparation method thereof |
| CN111082034B (en) * | 2019-12-16 | 2023-02-28 | 上海交通大学 | Preparation of tin/tin phosphide/carbon composite material of alkali metal ion battery cathode |
| CN111682184B (en) * | 2020-06-23 | 2023-07-14 | 欣旺达电动汽车电池有限公司 | Tin-based composite material, preparation method thereof, negative plate and lithium ion battery |
| CN112072084B (en) * | 2020-07-31 | 2022-06-14 | 华南理工大学 | Composite electrode material and preparation method and application thereof |
| CN114122386B (en) * | 2020-08-31 | 2024-03-19 | 中南大学 | Tin phosphide@carbon composite anode active precursor material, anode active material and anode of lithium sulfur battery and preparation of anode |
| CN112201782B (en) * | 2020-10-16 | 2022-09-30 | 西南大学 | Nickel phosphide/carbon/nickel phosphide composite material and preparation method and application thereof |
| CN113161535B (en) * | 2021-03-30 | 2022-10-25 | 华南理工大学 | Method and material for improving discharge specific capacity and cycling stability of lithium-rich cathode material through gas-phase surface phosphating treatment |
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| CN101289176B (en) * | 2008-05-22 | 2011-05-04 | 复旦大学 | Sn4P3 cathode material for lithium ion battery and method for preparing same |
| CN105006551B (en) * | 2015-06-03 | 2017-06-06 | 中南大学 | A kind of sodium-ion battery phosphorization tin/Graphene anode material and preparation method thereof |
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