CN114759177A - Phosphorus-based composite material, preparation method and application thereof - Google Patents

Phosphorus-based composite material, preparation method and application thereof Download PDF

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CN114759177A
CN114759177A CN202210426631.4A CN202210426631A CN114759177A CN 114759177 A CN114759177 A CN 114759177A CN 202210426631 A CN202210426631 A CN 202210426631A CN 114759177 A CN114759177 A CN 114759177A
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phosphorus
sulfur
doped
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季恒星
周恩
金洪昌
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University of Science and Technology of China USTC
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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
    • 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
    • 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
    • H01M4/38—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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals

Abstract

The invention provides a phosphorus-based composite material which comprises a sulfur-doped phosphorus nano material and a carbon material, wherein phosphorus atoms in the sulfur-doped phosphorus nano material are connected with the carbon material through covalent bonds. The application also provides a preparation method and application of the phosphorus-based composite material. The phosphorus-based composite material provided by the application can obviously improve the rate capability and the cycling stability of the phosphorus-based composite material as a negative electrode material by introducing sulfur atoms into a phosphorus lattice.

Description

Phosphorus-based composite material, preparation method and application thereof
Technical Field
The invention relates to the technical field of electrochemistry, in particular to a phosphorus-based composite material, a preparation method and application thereof.
Background
Currently, the industrial lithium ion battery is mainly limited by the fact that the theoretical capacity and rate performance of the widely used negative electrode material are too low, and therefore, a novel negative electrode material needs to be developed to prepare a commercial battery with high specific capacity and good quick charging capability.
The phosphorus cathode has extremely high theoretical specific capacity (2596mAh g)-1) Far higher than the graphite cathode (with the theoretical specific capacity of 372mAh g) which is commercialized at present-1) And the phosphorus-based nano material and different alkali metal ions have better reaction power And (5) learning. In addition, the phosphorus and the carbon material have good interface stability after being compounded, so that higher energy density and better rate performance can be realized. However, the phosphorus-based negative electrode undergoes large volume expansion during cycling, which results in the formation of a large amount of solid electrolyte film (SEI film) on the surface of the electrode, and the continuous volume change causes the breakage and continuous growth of the SEI film, resulting in excessive consumption of lithium ions, and thus in continuous capacity fade.
At present, the phosphorus and some carbon materials (such as graphite, Ketjen black and the like) are compounded to obtain better coulombic efficiency of the first ring (C: (C) (C))>80%) and a higher specific capacity, the problem of volume expansion in the process of cycling the phosphorus-based negative electrode is primarily solved. However, the phosphorus-based negative electrode undergoes a complex phase transition during the cycle of the alkali metal ion battery, which is accompanied by the fracture of the phosphorus-phosphorus chemical bond in the phosphorus-based material, and it is difficult to achieve a high reversible capacity and a good cycle stability at a high rate due to the high reaction resistance of the fracture of the phosphorus-phosphorus chemical bond during the reaction of the phosphorus-based negative electrode with the alkali metal ion. At present, the modification of phosphorus-based negative electrode materials mainly comprises designing different phosphorus-carbon-based composite materials or modified binders and electrolytes, and because the modification methods are difficult to promote the phase transformation of the phosphorus-based negative electrode fundamentally, the rapid charge advantage of the phosphorus-based negative electrode materials is difficult to exert (for example, in a lithium ion battery, 5.2A g -1Less than 200mAh g at a high current density-1Reversible capacity of).
In addition, the research on the current phosphorus-based materials in the potassium ion battery is rare, especially for the black phosphorus-based materials, mainly because the reaction impedance of the alloying reaction between the black phosphorus and the potassium ion battery is much higher than that of lithium ions and sodium ions, so that when the conventional black phosphorus-carbon-based composite material is used as a negative electrode material of the potassium ion battery, stable capacity and long service life are difficult to obtain.
Disclosure of Invention
The invention aims to provide a phosphorus-based composite material, and the phosphorus-based composite material provided by the application has better rate performance, reversible capacity and cycling stability as a negative electrode material.
In view of the above, the present application provides a phosphorus-based composite material, which is composed of a sulfur-doped phosphorus nanomaterial and a carbon material, wherein phosphorus atoms in the sulfur-doped phosphorus nanomaterial are covalently bonded to the carbon material.
Preferably, the ratio of sulfur atoms to phosphorus atoms in the sulfur-doped phosphorus nanomaterial is greater than zero and less than 1.
Preferably, the carbon material is selected from one or more of graphite, C60, C70, carbon nano tubes, a product obtained by high-temperature carbonization of a high molecular polymer, a product obtained by high-temperature carbonization of a metal organic framework material and a product obtained by high-temperature carbonization of a biomass material.
The application also provides a preparation method of the phosphorus-based composite material, which comprises the following steps:
mixing phosphorus source powder with a sulfur source, heating and ball-milling to obtain a sulfur-doped phosphorus nano material;
and carrying out ball milling on the sulfur-doped phosphorus nano material and a carbon material to obtain the phosphorus-based composite material.
Preferably, the phosphorus source is selected from red phosphorus, black phosphorus, purple phosphorus, yellow phosphorus, orange phosphorus, green phosphorus or blue phosphorus; the sulfur source is selected from sublimed sulfur, precipitated sulfur or refined sulfur.
Preferably, in the step of obtaining the sulfur-doped phosphorus nanomaterial, the heating is performed under an inert gas atmosphere.
Preferably, in the step of obtaining the sulfur-doped phosphorus nano material, the rotation speed of the ball mill is 500-1000 rpm, and the time is 5-24 h.
Preferably, the heating temperature is 100-200 ℃, and the time is 6-12 h.
The application also provides an alkali metal secondary battery which comprises a positive electrode and a negative electrode, wherein the negative electrode is made of the phosphorus-based composite material or the phosphorus-based composite material prepared by the preparation method.
Preferably, the alkali metal secondary battery is a lithium ion secondary battery, a sodium ion secondary battery, or a potassium ion secondary battery.
The application provides a phosphorus-based composite material which is prepared by doping a phosphorus nano material and a carbon material with sulfur And the phosphorus atoms in the sulfur-doped phosphorus nano material are connected with the carbon material through covalent bonds. The application also provides a preparation method of the phosphorus-based composite material. In the method, sulfur atoms are introduced into phosphorus crystal lattices, and in the circulating process, the introduction of the sulfur-phosphorus chemical bond has an obvious promotion effect on the fracture of the phosphorus-phosphorus chemical bond, so that the reaction impedance of the phosphorus-phosphorus chemical bond as a negative electrode material is obviously reduced, and the rate capability of the battery is obviously improved; further, sulfur doping in phosphorus-based composites can form sulfides, such as Li, during formation2PS3The sulfides have good ionic conductivity and chemical stability, and the stability of the electrode material in the circulating process is remarkably improved. In addition, sulfur atoms are introduced into the crystal lattice of the phosphorus nano material, so that the ion diffusion coefficient of the material can be obviously improved.
Drawings
FIG. 1 is a scanning electron microscope image of a sample of black phosphorus powder prepared in example 1;
FIG. 2 is a scanning electron microscope image of the sulfur-doped black phosphorus-graphite composite material prepared in example 5;
FIG. 3 shows the element characterization results of example 5 under a transmission electron microscope;
FIG. 4 is a graph of specific discharge capacity as a function of cycle number for lithium ion batteries of composite materials of black phosphorus (10% sulfur-doped black phosphorus) and carbon materials 1:1 in examples 2 and 5 at different charge and discharge rates;
FIG. 5 shows that the black phosphorus (10% sulfur doped black phosphorus) and carbon material 1:1 composite of example 2 and example 5, when used in a lithium ion battery, was at 2.6A g-1The discharge specific capacity is along with the change curve chart of cycle turns under the current density;
FIG. 6 is a graph of the black phosphorus (10% sulfur doped black phosphorus) and carbon material 1:1 composite of example 2 and example 5 for a sodium ion battery at 0.26A g-1The discharge specific capacity is along with the change curve chart of cycle turns under the current density;
FIG. 7 shows that the black phosphorus (10% sulfur-doped black phosphorus) and carbon material 1:1 composite material of example 2 and example 5, when used in a potassium ion battery, was at 0.26A g-1The discharge specific capacity is plotted along with the change of cycle turns.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
Aiming at the main factors influencing the rate performance of the phosphorus-based negative electrode material, particularly higher reaction impedance in the phase transition process, the application provides the sulfur-doped phosphorus-based composite material, sulfur atoms are introduced into the crystal structure of the phosphorus nano material, and the sulfur-phosphorus chemical bonds are formed in the negative electrode material, so that the fracture of the phosphorus-phosphorus chemical bonds in the phosphorus negative electrode is facilitated, the rate performance and the reversible capacity of the phosphorus negative electrode are obviously improved, and sulfides are formed in the phosphorus negative electrode due to the introduction of the sulfur atoms, so that the sulfur-doped phosphorus-based composite material is a fast ion conductor with good stability, and the improvement of the cycle stability of the phosphorus negative electrode is facilitated. Specifically, the embodiment of the invention discloses a phosphorus-based composite material which comprises a sulfur-doped phosphorus nano material and a carbon material, wherein phosphorus atoms in the sulfur-doped phosphorus nano material are connected with the carbon material through covalent bonds.
In the phosphorus-based composite material provided by the application, sulfur atoms are connected with phosphorus atoms in a phosphorus nano material through chemical bonds to realize the doping of sulfur, and phosphorus is connected with a carbon material at the edge position of the carbon material through covalent bonds.
In the phosphorus-based composite material, the ratio of sulfur atoms to phosphorus atoms in the sulfur-doped phosphorus nanomaterial is greater than zero and less than 1, and in a specific embodiment, the sulfur doping amount in the sulfur-doped phosphorus nanomaterial is 10%. In the present application, the mass ratio of the sulfur-doped phosphorus nanomaterial to the carbon material may be arbitrarily selected according to needs, and in specific embodiments, the mass ratio of the sulfur-doped phosphorus nanomaterial to the carbon material is 1:1, 3:2, or 7: 3.
The application also provides a preparation method of the phosphorus-based composite material, which comprises the following steps:
mixing phosphorus source powder with a sulfur source, heating and ball-milling to obtain a sulfur-doped phosphorus nano material;
and carrying out ball milling on the sulfur-doped phosphorus nano material and a carbon material to obtain the phosphorus-based composite material.
In the application, in the preparation process of the sulfur-doped phosphorus nano material, phosphorus nano powder is prepared firstly, namely, large blocks of phosphorus materials are ground into small particles and then are dispersed in a solvent for ultrasonic treatment, so that the nano-scale phosphorus powder is obtained. In the present application, the phosphorus material is selected from the group of allotropes of phosphorus, in particular from red phosphorus, black phosphorus, purple phosphorus, yellow phosphorus, orange phosphorus, green phosphorus or blue phosphorus. After the nano-scale phosphorus powder is obtained, the nano-scale phosphorus powder is mixed with a sulfur source, the mixture is heated in the argon atmosphere to be uniformly mixed, and then the cooled material is ball-milled in the inert gas atmosphere, such as the argon atmosphere, so that the sulfur-doped nano-phosphorus is obtained. The sulfur source is selected from sublimed sulfur, precipitated sulfur or refined sulfur. The rotation speed of the ball mill is 500-1000 rpm, and the time is 5-24 h; more specifically, the rotation speed of the ball mill is 600-800 rpm, and the time is 12-18 h; the heating temperature is 100-200 ℃, and the time is 6-12 h; more specifically, the heating temperature is 120-180 ℃, and the time is 8-10 h.
Carrying out ball milling on the obtained sulfur-doped phosphorus nano material and a carbon material to obtain a phosphorus-based composite material; the carbon material includes fully graphitized carbon material and its derivatives, e.g. graphite, C60、C70Carbon nanotubes, etc., and also include partially graphitized, amorphous conductive carbon blacks and some hard carbon materials and their derivatives, such as high molecular polymers, metal organic frameworks, and products of biomass materials after high temperature carbonization. The rotation speed of the ball mill is 500-1200 rpm, and the time is 5-24 h; in a specific embodiment, the rotation speed of the ball mill is 600-1000 rpm, and the time is 12-18 h.
The application also provides an alkali metal secondary battery, which comprises a positive electrode and a negative electrode, wherein the negative electrode is made of the phosphorus-based composite material. The alkali metal secondary battery described herein may be a lithium ion secondary battery, may be a sodium ion secondary battery, and may also be a potassium ion secondary battery.
Compared with the phosphorus-carbon material composite material without sulfur doping, in the circulating process, the introduction of the sulfur-phosphorus chemical bond has obvious promotion effect on the fracture of the phosphorus-phosphorus chemical bond, so that the reaction impedance of the cathode material is obviously reduced, and the rate capability of the battery is obviously improved. Taking a black phosphorus-based negative electrode material as an example, a sulfur-doped black phosphorus/graphite composite negative electrode doped with 10% of sulfur atoms (the mass ratio of the two is 1:1) is arranged in a lithium ion battery at 0.26A g -1Can provide 1400mAh g at the current density of-1And at 5.2A g-1Still can provide 1000mAh g under the large current density-1The reversible capacity of (a); in sodium ion batteries, at 0.26A g-1Can still provide 1100mAh g at the current density of-1Reversible capacity of (a); in potassium ion batteries, at 0.26A g-1Can provide 700mAh g at a current density of-1The reversible capacity of (a).
Sulfur-doped phosphorus-based composites may form some sulfides (e.g., Li) during cycling2PS3) These sulfides can significantly improve the stability of the electrode material during cycling due to their good ionic conductivity and chemical stability. In addition, sulfur atoms are introduced into the crystal lattices of the phosphorus nano-material, so that the ion diffusion coefficient of the material can be obviously improved. Taking the black phosphorus cathode as an example, the synthesized sulfur-doped black phosphorus-based nanomaterial doped with 10% of sulfur atoms (the mass ratio of the sulfur-doped black phosphorus to the graphite is 1:1) is 2.6A g in a lithium ion battery-1After 500 cycles at the current density of (a), the capacity retention rate is still 75% relative to the second cycle; in sodium ion batteries, at 0.26A g-1After 100 cycles at the current density of (a), the capacity retention rate is still 92% relative to the second cycle; in potassium ion batteries, at 0.26A g -1After 100 cycles at the current density of (a), the capacity retention rate relative to the second cycle is still 95%.
In order to further understand the present invention, the following examples are given to illustrate the phosphorus-based composite material, the preparation method and the application thereof in detail, and the scope of the present invention is not limited by the following examples.
Example 1
The black phosphorus bulk was ground into powder and ultrasonically dispersed in N-methylpyrrolidone (NMP), and after being ultrasonically treated in a 500W pin ultrasonic machine for 24 hours, vacuum filtration was performed, followed by washing and drying to obtain black phosphorus powder (BP).
The black phosphorus powder sample prepared in example 1 of the present invention was characterized by Scanning Electron Microscopy (SEM), and the characterization results are shown in fig. 1.
Example 2
The black phosphorus powder sample obtained in example 1 and commercial graphite powder are ball milled for 12 hours at the rotating speed of 600rpm under the protection of argon atmosphere in the mass ratio of 1:1, 6:4 and 7:3 to obtain the black phosphorus-graphite composite material.
Example 3
The black phosphorus powder obtained in example 1 and sublimed sulfur (S) were uniformly milled in an agate bowl at the mass ratios of 99:1, 90:10, and 80:20, and then heated at 155 ℃ for 10 hours under an argon atmosphere to obtain a physically mixed sample (S @ BP) of black phosphorus and sublimed sulfur.
Example 4
And (3) ball-milling the S @ BP obtained in example 3 at the rotation speed of 600rpm for 12 hours in an argon filled atmosphere to obtain a sulfur-doped black phosphorus sample.
Example 5
The sulfur-doped black phosphorus sample obtained in example 4 of the invention and commercial graphite powder are ball-milled for 12 hours at a rotation speed of 600rpm under the protection of argon atmosphere according to the mass ratio of 1:1, 6:4 and 7:3 to obtain the sulfur-doped black phosphorus-graphite composite material.
Scanning Electron Microscope (SEM) characterization is performed on the sulfur-doped black phosphorus-graphite composite material prepared in the embodiments of the present invention, and the characterization result is shown in fig. 2.
Example 6
The composite material sample of 10% sulfur-doped black phosphorus and carbon material 1:1 obtained in example 5 of the present invention was characterized by Transmission Electron Microscopy (TEM) elemental mapping, and the characterization results are shown in fig. 3.
Example 7
The powder samples obtained in the embodiments 2 and 5 of the invention are respectively uniformly ground with conductive carbon black (Ketjen black) and polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, then N-methyl pyrrolidone (NMP) is added as a solvent, and the mixture is uniformly mixed into black paste slurry to be uniformly coated on a copper foil, and the black paste slurry is dried in vacuum at 60 ℃ for 12 hours to obtain the electrode plate of the negative electrode material.
The two electrode sheets obtained were used as working electrodes, metal lithium as a counter electrode, and 1mol/L lithium hexafluorophosphate (LiPF) 6) The standard button cell CR2032 is assembled by using a solution dissolved in ethylene carbonate/diethyl carbonate (EC: DEC: 1 volume ratio) as an electrolyte and polypropylene as a diaphragm, and the charging and discharging voltage range is 0.001-2.5V. Respectively at 0.26, 0.52, 1.3, 2.6, 5.2, 0.26A g-1The current density of the carbon black/phosphorus composite material was determined by cycling for 10 cycles, and the specific discharge capacity of the carbon black/phosphorus composite material (graphite/BP) and the carbon black/phosphorus composite material (graphite/S-BP) were determined to vary with the number of cycles as shown in FIG. 4 at 2.6A g-1The specific discharge capacity of these two materials as a function of the number of cycles is shown in fig. 5. The data relating to the composite materials of different black phosphorus (sulfur doped black phosphorus) and graphite in different proportions are shown in table 1;
TABLE 1 electrochemical Performance data sheet for composites with different proportions of sulfur doping and graphite
Figure BDA0003609889420000071
Figure BDA0003609889420000081
As can be seen in fig. 4, the sulfur-doped black phosphorus-graphite composite electrode is at 5.2A g-1Still 1000mAh g at a current density of-1The specific discharge capacity of the electrode is only 20mAh g, and the black phosphorus-graphite composite electrode has the specific discharge capacity of the electrode-1The specific discharge capacity of the sulfur-doped black phosphorus-based composite material shows that the sulfur-doped black phosphorus-based composite material has much better rate performance compared with the black phosphorus-based composite material, which is mainly attributed to the fact that the introduction of sulfur atoms can obviously reduce the reaction impedance of black phosphorus and lithium ion batteries.
As can be seen in FIG. 5, at 2.6A g-1The sulfur-doped black phosphorus-graphite composite material still has a capacity retention rate of 73% relative to the second cycle after 500 cycles, while the black phosphorus-graphite composite material has almost no reversible capacity after about 150 cycles, and in addition, it can be seen from table 1: under the condition that the proportion of black phosphorus and graphite is the same, the capacity retention rate of the sulfur-doped black phosphorus-based composite negative electrode is also obviously higher than that of the black phosphorus-based composite negative electrode. These results demonstrate that sulfur-doped black phosphorus-based composites have significantly superior cycling stability relative to black phosphorus-based composites due, on the one hand, to a significant reduction in reaction impedance and, on the other hand, to the rapid ion conductor with some sulfide formation in the electrode material due to the introduction of sulfur atoms (e.g., Li)2PS3) The materials have good ionic conductivity and extremely high chemical stability, and are very helpful for improving the cycling stability of the electrode.
The result of example 7 shows that the phosphorus-based composite material provided by the invention can realize good cycle stability under high rate and large current in a lithium ion battery.
Example 8
The powder samples obtained in the embodiments 2 and 5 of the invention are respectively uniformly ground with conductive carbon black (Ketjen black) and polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, then N-methyl pyrrolidone (NMP) is added as a solvent, and the mixture is uniformly mixed into black paste slurry to be uniformly coated on a copper foil, and the black paste slurry is dried in vacuum at 60 ℃ for 12 hours to obtain the electrode plate of the negative electrode material. Meanwhile, the two materials, namely the composite material (graphite/BP) with the mass ratio of black phosphorus to the carbon material of 1:1 and the composite material (graphite/S-BP) with the mass ratio of 10% sulfur-doped black phosphorus to the carbon material of 1:1 are used for key analysis, and the obtained two electrode plates take a metal sodium sheet as a counter electrode and 1mol/L sodium hexafluorophosphate (NaPF) 6) Dissolved in ethylene carbonate/diethyl carbonate (EC: D)EC is 1:1 volume ratio) as an electrolyte, and glass fiber is used as a diaphragm, and a standard button cell CR2032 is assembled, wherein the charging and discharging voltage range is 0.001-2.0V. At 0.26A g-1The specific discharge capacity of the two materials as a function of the number of cycles is shown in fig. 6. The obtained two electrode plates use metal potassium sheets as counter electrodes and 0.8mol/L sodium hexafluorophosphate (KPF)6) The standard button cell CR2032 is assembled by using a solution dissolved in ethylene carbonate/diethyl carbonate (EC: DEC: 1 volume ratio) as an electrolyte and glass fiber as a diaphragm, and the charging and discharging voltage range is 0.001-2.0V. At 0.26A g-1The specific discharge capacity of the two materials as a function of the number of cycles is shown in fig. 7.
As can be seen in fig. 6 and 7, in the sodium ion battery system, the sulfur-doped black phosphorus-graphite composite electrode is at 0.26A g-1The capacity retention rate of 92% relative to the second circle is still maintained after the current density of the black phosphorus-graphite composite electrode is cycled for 100 circles, and the capacity retention rate of the black phosphorus-graphite composite electrode is only 8%. In a potassium ion battery system, at 0.26A g-1At the current density of (a), the black phosphorus-graphite composite electrode hardly has reversible capacity after 50 cycles, while the sulfur-doped black phosphorus-graphite composite electrode still has 95% capacity retention rate relative to the second cycle after 100 cycles.
In addition, it can be seen from table 2 (table 2 is the data table of the cycle capacity retention of the composite material formed by the black phosphorus doped with phosphorus or sulfur and the carbon material in examples 2 and 5 under different current densities): under the condition that the proportions of black phosphorus, sulfur-doped black phosphorus and graphite are the same, the capacity retention rate of the sulfur-doped black phosphorus-based composite negative electrode is also obviously higher than that of the black phosphorus-based composite negative electrode. This is mainly due to the extremely high reaction impedance of the alloying reaction between black phosphorus and sodium/potassium ions, whereas the incorporation of sulfur atoms into the black phosphorus lattice significantly reduces the reaction impedance.
TABLE 2 data table of the cycle capacity retention of composites of carbon material and black phosphorus doped with different phosphorus or sulfur in examples 2 and 5 at different current densities
Figure BDA0003609889420000101
The results of example 8 show that the phosphorus-based composite material provided by the invention can realize high reversible capacity and better cycle stability in sodium ion batteries and potassium ion batteries.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, it is possible to make various improvements and modifications to the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. A phosphorus-based composite material comprises a sulfur-doped phosphorus nano material and a carbon material, wherein phosphorus atoms in the sulfur-doped phosphorus nano material are connected with the carbon material through covalent bonds.
2. The phosphorus-based composite material of claim 1, wherein the sulfur-doped phosphorus nanomaterial has a ratio of sulfur atoms to phosphorus atoms greater than zero and less than 1.
3. The phosphorus-based composite material of claim 1, wherein the carbon material is selected from one or more of graphite, C60, C70, carbon nanotubes, a high temperature carbonized product of a high molecular polymer, a high temperature carbonized product of a metal-organic framework material, and a high temperature carbonized product of a biomass material.
4. A method of preparing the phosphorus-based composite material of claim 1, comprising the steps of:
mixing phosphorus source powder with a sulfur source, heating and ball-milling to obtain a sulfur-doped phosphorus nano material;
and ball-milling the sulfur-doped phosphorus nano material and a carbon material to obtain the phosphorus-based composite material.
5. The method of claim 4, wherein the phosphorus source is selected from red phosphorus, black phosphorus, purple phosphorus, yellow phosphorus, orange phosphorus, green phosphorus, or blue phosphorus; the sulfur source is selected from sublimed sulfur, precipitated sulfur or refined sulfur.
6. The method according to claim 4, wherein in the step of obtaining the sulfur-doped phosphorus nanomaterial, the heating is performed under an inert gas atmosphere.
7. The preparation method of claim 4, wherein in the step of obtaining the sulfur-doped phosphorus nanomaterial, the rotation speed of the ball mill is 500-1000 rpm, and the time is 5-24 hours.
8. The method according to claim 4, wherein the heating is carried out at a temperature of 100 to 200 ℃ for 6 to 12 hours.
9. An alkali metal secondary battery comprising a positive electrode and a negative electrode, wherein the material of the negative electrode is the phosphorus-based composite material according to any one of claims 1 to 3 or the phosphorus-based composite material prepared by the preparation method according to any one of claims 4 to 8.
10. The alkali metal secondary battery according to claim 9, wherein the alkali metal secondary battery is a lithium ion secondary battery, a sodium ion secondary battery, or a potassium ion secondary battery.
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