CN110265637B - Synthesis method and application of tungsten selenide-collagen derived porous carbon composite sodium ion battery cathode material with excellent performance - Google Patents

Synthesis method and application of tungsten selenide-collagen derived porous carbon composite sodium ion battery cathode material with excellent performance Download PDF

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CN110265637B
CN110265637B CN201910415732.XA CN201910415732A CN110265637B CN 110265637 B CN110265637 B CN 110265637B CN 201910415732 A CN201910415732 A CN 201910415732A CN 110265637 B CN110265637 B CN 110265637B
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collagen
porous carbon
tungsten
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carbon composite
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陈庆华
康碧玉
曾令兴
钱庆荣
黄宝铨
肖荔人
罗奋强
方益兴
庄凌峰
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Fujian Normal University
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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
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    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
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    • H—ELECTRICITY
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    • 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
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    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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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 discloses a synthesis method and application of a tungsten selenide-collagen derived porous carbon composite sodium ion battery cathode material with excellent performance, wherein tungsten selenide particles in the material are confined in porous nanocarbon and have stable structure; the collagen derived porous carbon is co-doped with N and S heteroatoms, so that the conductivity can be improved by adjusting the internal electronic structure of the derived carbon, and tungsten selenide particles are effectively fixed, so that the structure is stable, and the sodium storage performance of the collagen derived porous carbon is improved. The technical scheme is as follows: firstly, extracting collagen powder from waste cow fur in tanning industry, compounding the collagen powder with a tungsten source after carbonization and activation, and finally selenizing to prepare the tungsten selenide-collagen derived porous carbon compound. The result shows that the sodium-ion battery negative electrode material has excellent electrochemical performance. The synthesis process is simple, the operability is strong, meanwhile, the wastes in the tanning industry are utilized in a green and high-valued manner, the requirements of the national resource circulation strategy are met, the cost is low, the large-scale production can be realized, and the environmental requirements are met.

Description

Synthesis method and application of tungsten selenide-collagen derived porous carbon composite sodium ion battery cathode material with excellent performance
Technical Field
The invention belongs to the field of sodium ion battery materials, and particularly relates to a synthetic method and application of a tungsten selenide-collagen derived porous carbon composite with excellent performance.
Background
Lithium Ion Batteries (LIBs) have advantages of high energy and high power density, and have been widely used in portable electronic devices, electric vehicles, and the like. However, lithium resources are scarce, the distribution is uneven, the cost is high, and the development of large-scale application is restricted to a great extent. Meanwhile, the safety problem of the lithium battery is always a big problem in the field of the lithium battery. Therefore, as an alternative energy source, the sodium ion battery of the energy storage device with the advantages of low cost, high performance, high safety and the like is produced. However, due to Na+Radius ratio Li+The large radius makes the development of sodium ion batteries challenging, such as large volume expansion, poor kinetic performance, and the like. Therefore, the design of the sodium ion battery cathode material with excellent performance has important significance.
In recent years two-dimensional layered transition metals such as MoS2、MoSe2The two-dimensional layered structure similar to graphene has larger interlayer spacing, thereby being beneficial to Na with larger radius+The conductive polymer has good conductivity and shows excellent electrochemical performance. Although WSe2Have the same physicochemical properties as them, but its density is relatively high and is comparable to MoS in terms of theoretical specific mass capacity2、MoSe2Low. However, WSe2Is low in overpotential, and WSe2Has higher density, higher specific volume capacity and volume spaceThe limited fields of power batteries, submarine batteries, aviation batteries and the like have good application prospects, and are potential next-generation sodium ion negative electrode materials.
The invention utilizes collagen powder extracted from waste cow fur in tanning industry as precursor carbon source to synthesize the tungsten selenide-collagen derived porous carbon compound. The difference from the general method is that: 1. the collagen derived porous nano carbon composite has the characteristics of high porosity, high specific surface area and the like, can provide a large number of sodium storage active sites, is beneficial to the transmission of sodium ions and electrons, and simultaneously promotes the electrolyte to permeate into active substances, thereby promoting the reaction kinetics; 2. the collagen is extracted from the waste cowhide hair, belongs to the green high-value utilization of wastes in the leather industry, changes waste into valuable, and is beneficial to reducing environmental pollution; 3. collagen in the waste cattle hide hair is a natural high molecular material, is composed of a plurality of amino acids, is rich in organic groups, a large amount of N and S elements in the collagen can be converted into N in situ in the calcining process, S heteroatom doping is carried out, the electronic structure in the derived carbon can be regulated and controlled, the conductivity of the compound is improved, the combination of the derived carbon and tungsten selenide can be effectively enhanced, the structure is more stable, and the electrochemical performance of the compound is further improved; 4. the porous nanocarbon derived from the collagen confines tungsten selenide particles in a porous structure, so that the structure is stable, and the volume change in the charge and discharge process can be buffered; 5. the porous carbon is derived through collagen activation and the material is synthesized through a one-step selenization method, so that the method is simple in process, strong in operability, capable of changing waste into valuable, high in conversion value, low in cost and promising in large-scale production. And the result shows that the sodium ion battery cathode material has excellent electrochemical performance and a certain application prospect.
Disclosure of Invention
The invention aims to provide a tungsten selenide-collagen derived porous carbon composite with excellent performance, a synthesis method and application thereof, the tungsten selenide-collagen derived porous carbon composite is simple in process, strong in operability, low in cost, capable of realizing high-value utilization of wastes in the tanning industry, capable of realizing large-scale production and meeting the environmental requirements.
In order to achieve the purpose, the invention adopts the following technical scheme:
the tungsten selenide-collagen derived porous carbon compound is synthesized by adopting a simple and feasible activation and selenization method. The method comprises the following specific steps:
1) weighing a certain mass of waste cow fur (cow leather with hair), firstly carrying out ultrasonic pretreatment in ethanol, then shearing the mixture by using scissors, adding an enzyme preparation which accounts for 0.5-1% of the mass of the raw material for dissolution, carrying out salting-out on the enzyme preparation by using pepsin/papain/trypsin, and finally carrying out freeze-drying and grinding to obtain the collagen powder.
2) Collagen powder and zinc chloride are weighed into the polytetrafluoroethylene lining according to the mass ratio of 1 (0.2-2), a proper amount of water is added, the mixture is stirred for 4-8 hours, and the mixture is dried and then is added with N2Activating the mixture for 1 to 2 hours at the temperature rising rate of 5 to 10 ℃ per minute at the temperature of 500 ℃ to 900 ℃, washing and drying the mixture, and collecting a black solid sample;
3) weighing a certain mass of the sample obtained in the step (2) and a tungsten source, adding a certain amount of distilled water into a beaker, violently stirring for 6-12 h, centrifugally drying, and finally collecting a solid sample;
4) grinding the black sample obtained in the step 3) into powder, and respectively placing the powder and Se powder in a mass ratio of 1 (1.5-3) in two corundum boats at 10% vol H2Calcining for 2-5 hours at 800 ℃ under 500 ℃ in a 90 vol% Ar atmosphere tube furnace, and finally collecting a black powder sample to obtain the tungsten selenide-collagen derived porous carbon compound;
in the step 2), the collagen is extracted from waste cow fur in the leather industry, contains rich organic groups and amino acids, can be activated into N and S co-doped porous carbon, and confines tungsten selenide nanoparticles in a porous structure; the tungsten source can be a series of tungsten-containing salts, including but not limited to sodium tungstate, tungsten chloride, phosphotungstic acid; the mass ratio of the activated sample to the tungsten source is 1: 2-5, wherein the stirring time is 6-12 h, and the drying temperature is 80-100 ℃; in the step 4), the mass ratio of the black sample obtained in the step 3) to the selenium powder is 1: 1.5-3, the calcining temperature is 500-800 ℃, and the calcining time is 2-5 hours.
The composite carbon in the tungsten selenide-collagen derived porous carbon composite is nitrogen and sulfur co-doped porous nanocarbon, has high porosity and high specific surface area, and is favorable for sodium storage. The tungsten selenide-collagen derived porous carbon composite is applied to a sodium ion battery cathode, and is charged and discharged for 50 times when the voltage is 0.01-3.0V and the current density is 100 mA/g, the specific capacity is 368.2 mAh/g, the specific capacity is kept at 185.5 mAh/g after the charging and discharging are carried out for 500 times when the current density is 1A/g, the coulomb efficiency is high, and the multiplying power performance is excellent.
A sodium ion battery comprising a working electrode and a counter electrode, characterized in that: the weight ratio is as follows: the tungsten selenide-collagen derived porous carbon composite prepared by the synthesis method comprises the following steps: conductive agent acetylene black: the binder CMC 80: 10: 10 is mixed and ground, then is uniformly coated on a copper foil to be used as a working electrode, a metal sodium sheet is used as a counter electrode, 1 mol/L NaPF6Ethylene Carbonate (EC) and diethyl carbonate (DEC) are used as electrolyte to assemble a 2032 type button cell. The application of the tungsten selenide-collagen derived porous carbon composite is to apply the tungsten selenide-collagen derived porous carbon composite to the cathode of the sodium ion battery. Assembling the sodium-ion battery: according to the mass ratio, the porous carbon compound derived from tungsten selenide-collagen is as follows: conductive agent acetylene black: the binder CMC 80: 10: 10 is mixed and ground, and then is uniformly coated on a copper foil to be used as a working electrode, a metal sodium sheet is used as a counter electrode, and 1 mol/L NaPF6Ethylene Carbonate (EC) and diethyl carbonate (DEC) are used as electrolyte to assemble the button cell; all assembly was carried out in an inert atmosphere glove box.
The invention has the following remarkable advantages:
1) according to the invention, collagen powder extracted from waste cow fur in the leather industry is activated to derive nitrogen and sulfur co-doped porous nano carbon as a carrier, on one hand, the porous nano structure is favorable for transmission of sodium ions/electrons and permeation of electrolyte, and reaction kinetics are improved, on the other hand, nitrogen and sulfur co-doping can regulate the internal electronic structure of the derived carbon, and further conductivity of the compound is improved.
2) The collagen is extracted from the waste cow leather hair in the tanning industry, belongs to the high-value utilization of wastes in the tanning industry, changes wastes into valuables, is favorable for reducing environmental pollution, is used as a precursor carbon source, and has low cost.
3) The tungsten selenide nano particles are confined in a porous structure, can effectively inhibit the tungsten selenide from agglomerating, have stable structure and provide a certain buffer space for volume expansion in the charging and discharging process.
4) The tungsten selenide-collagen derived porous carbon composite is a brand new sodium ion battery cathode, the tungsten selenide-collagen derived porous carbon composite obtained in the embodiment 1 is applied to the sodium ion battery cathode, 50 times of charge-discharge cycles are carried out when the voltage is 0.01-3.0V and the current density is 100 mA/g, the specific capacity is 368.2 mAh/g, after 500 times of charge-discharge cycles are carried out when the current density is 1A/g, the specific capacity is still 185.5 mAh/g, the high coulombic efficiency is achieved, and meanwhile, the high rate capability is achieved.
5) The tungsten selenide-collagen derived porous carbon composite is an excellent sodium ion battery cathode material, the invention provides a method for synthesizing the tungsten selenide-collagen derived porous carbon composite for the first time, the preparation process is simple, the operability is strong, the wastes of the tanning industry are utilized with high value, the cost is low, the mass production can be realized, and the environmental requirements are met.
Drawings
Fig. 1 is an XRD pattern of the tungsten selenide-collagen-derived porous carbon composite obtained in example 1.
Fig. 2 is a graph of cycling performance at a current density of 100 mA/g of the tungsten selenide-collagen derived porous carbon composite obtained in example 1 as a sodium ion battery anode material.
Fig. 3 is a charge/discharge curve diagram at a current density of 100 mA/g when the tungsten selenide-collagen-derived porous carbon composite obtained in example 1 is used as a sodium ion battery anode material.
Fig. 4 is a long-life cycle performance graph and a coulombic efficiency graph at a current density of 1A/g when the tungsten selenide-collagen derived porous carbon composite obtained in example 1 is used as a sodium ion battery negative electrode material.
Fig. 5 is a graph of rate performance at different current densities of the tungsten selenide-collagen derived porous carbon composite obtained in example 1 as a sodium ion battery anode material.
Detailed Description
Example 1
1) Weighing waste cow fur (referring to waste cow leather with fur) with a certain mass, firstly carrying out ultrasonic pretreatment in ethanol, then shearing the mixture by using scissors, adding pepsin accounting for 0.5 percent of the mass of the raw materials for dissolving, then salting out, and finally carrying out freeze drying and grinding to obtain the collagen powder.
2) Respectively weighing 1g of collagen powder and 1g of zinc chloride into a polytetrafluoroethylene lining, adding a proper amount of water, stirring for 4 hours, drying, and adding N2Activating at 600 ℃ for 1 h in an atmosphere tube furnace at the temperature rise rate of 5 ℃/min, washing and drying, and collecting a black solid sample;
3) according to the mass ratio of 1: 2, weighing the sample obtained in the step 2) and phosphotungstic acid, adding a certain amount of distilled water into a beaker, violently stirring for 6 hours, centrifugally drying, and finally collecting a solid sample;
4) grinding the solid sample obtained in the step 3) into powder, and respectively placing the powder and Se powder in a mass ratio of 1: 1.5 into two corundum boats at 10% vol H2Calcining the mixture for 4 hours at 500 ℃ in a 90 vol% Ar atmosphere tubular furnace, and finally collecting a black powder sample to obtain a tungsten selenide-collagen derived porous carbon composite sodium ion battery cathode material with excellent performance, namely a tungsten selenide-collagen derived porous carbon composite;
the X-ray diffraction pattern of the tungsten selenide-collagen derived carbon composite shown in fig. 1 is obtained through an XRD experiment, and it can be known from the pattern that a diffraction peak with 2 theta of 26.0 degrees corresponds to the (002) crystal face of the collagen derived porous carbon, and wider diffraction peaks appearing at positions with 2 theta of 13.7 degrees, 31.4 degrees, 37.9 degrees, 56.0 degrees and 69.6 degrees respectively correspond to WSe2The (002), (100), (103), (110) and (203) crystal faces in (JCPDS:71-0600) show that the synthesized tungsten selenide is of a nano structure and has a small particle size. The tungsten selenide-collagen derived porous carbon composite synthesized by the present example: conductive agent acetylene black: the binder CMC is uniformly mixed and ground according to the mass percentage of 80: 10: 10Coating on copper foil as working electrode, metal sodium sheet as counter electrode, 1 mol/L NaPF6Ethylene Carbonate (EC) and diethyl carbonate (DEC) are used as electrolyte to assemble the button cell; all assembly was carried out in an inert atmosphere glove box. Under the current density of 100 mA/g, the test cycle performance is shown in figure 2, when the tungsten selenide-collagen derived porous carbon compound is used as the cathode material of the sodium ion battery, the specific capacity reaches 368.2 mAh/g after 50 times of charge and discharge cycles when the voltage is 0.01-3.0V and the current density is 100 mA/g. Fig. 3 is a charge and discharge curve of the material at a current density of 100 mA/g, and it can be seen from the graph that the charge and discharge curves of the electrode material are basically overlapped after the first cycle, which shows that the electrode material has higher electrochemical stability during charge and discharge. FIG. 4 is a graph of long-life cycle performance at a current density of 1A/g and a coulombic efficiency, and it can be seen that the electrode material maintains a specific capacity of 185.5 mAh/g even after 500 cycles of charge and discharge at a current density of 1A/g, indicating that the material has stable long-life cycle performance. In addition, as can be seen from the coulombic efficiency curve corresponding to the right ordinate axis in the figure, after 10 cycles of cycling, the coulombic efficiency is always stabilized at about 100%, and the discharge capacity of the electrode material is hardly attenuated, which indicates that the composite shows good coulombic efficiency and stable cycling performance. Fig. 5 is a graph of rate capability at different current densities at a voltage of 0.01-3.0V, and it can be seen that the specific capacities of the electrode at current densities of 0.05A/g, 0.1A/g, 0.2A/g, 0.5A/g, 1A/g and 2A/g are 392.9 mAh/g, 378.1 mAh/g, 330.8 mAh/g, 289.9 mAh/g, 253.7 mAh/g and 219.2 mAh/g, respectively, and the specific capacity is still maintained at 370 mAh/g after the current returns to 0.1A/g for 100 cycles, which indicates that the tungsten selenide-porous carbon collagen derivative composite maintains good morphology and structure during the cycling process, and the material does not collapse and pulverize, thus having excellent rate capability.
Therefore, the tungsten selenide-collagen derived porous carbon composite not only has high specific capacity under low current density and stable cycle performance under high current density, but also has excellent rate capability, is an environment-friendly high-performance sodium ion battery cathode material, and has good application prospect.
Example 2
1) Weighing waste cow fur (referring to waste cow leather with fur) with a certain mass, firstly carrying out ultrasonic pretreatment in ethanol, then shearing the mixture by using scissors, adding papain with the mass accounting for 0.8 percent of the mass of the raw materials for dissolving, then carrying out salting-out, and finally carrying out freeze drying and grinding to obtain the collagen powder.
2) Respectively weighing 2 g of collagen powder and 4 g of zinc chloride into a polytetrafluoroethylene lining, adding a proper amount of water, stirring for 8 hours, drying, and adding N2Activating at 700 ℃ for 2 h at the heating rate of 10 ℃ per min in an atmosphere tube furnace, washing and drying, and collecting a black solid sample;
3) according to the mass ratio of 1: 3, weighing the sample obtained in the step 2) and sodium tungstate, adding a certain amount of distilled water into a beaker, violently stirring for 8 hours, centrifugally drying, and finally collecting a solid sample;
4) grinding the black sample obtained in the step 3) into powder, respectively placing the powder and Se powder in a mass ratio of 1: 2 in two corundum boats at 10% vol H2Calcining the mixture for 3 hours at 600 ℃ in a 90 vol% Ar atmosphere tubular furnace, and finally collecting a black powder sample to obtain a tungsten selenide-collagen derived porous carbon composite;
the tungsten selenide-collagen derived porous carbon composite synthesized by the present example: conductive agent acetylene black: mixing and grinding the binder CMC according to the mass percentage of 80: 10: 10, uniformly coating the mixture on a copper foil to form a working electrode, taking a metal sodium sheet as a counter electrode, and 1 mol/L NaPF6Ethylene Carbonate (EC) and diethyl carbonate (DEC) are used as electrolyte to assemble the button cell; all assembly was carried out in an inert atmosphere glove box.
Example 3
1) Weighing a certain mass of waste cow fur (cow leather with hair), firstly carrying out ultrasonic pretreatment in ethanol, then shearing the waste cow fur by using scissors, adding trypsin accounting for 0.7 percent of the mass of the raw materials for dissolving, then salting out, and finally carrying out freeze drying and grinding to obtain the collagen powder.
2) Respectively weighing 2 g of collagen powder and 0.5 g of zinc chloride into a polytetrafluoroethylene lining, adding a proper amount of water, stirring for 6 hours, drying, and adding N2Activating at 800 ℃ for 1 h at the temperature rise rate of 5 ℃/min in an atmosphere tube furnace, washing and drying, and collecting a black solid sample;
3) according to the mass ratio of 1: 4, weighing the sample obtained in the step 2) and tungsten chloride, adding a certain amount of distilled water into a beaker, violently stirring for 10 hours, centrifugally drying, and finally collecting a solid sample;
4) grinding the black sample obtained in the step 3) into powder, respectively placing the powder and Se powder in a mass ratio of 1: 3 in two corundum boats at 10% vol H2Calcining the mixture for 2 hours at 700 ℃ in a 90 vol% Ar atmosphere tubular furnace, and finally collecting a black powder sample to obtain a tungsten selenide-collagen derived porous carbon composite;
the tungsten selenide-collagen derived porous carbon composite synthesized by the present example: conductive agent acetylene black: the binder CMC is mixed and ground according to the mass percentage of 80: 10: 10 and then is evenly coated on a copper foil to be used as a working electrode, a metal sodium sheet is used as a counter electrode, and 1 mol/L NaPF6Ethylene Carbonate (EC) and diethyl carbonate (DEC) are used as electrolyte to assemble the button cell; all assembly was carried out in an inert atmosphere glove box.
Example 4
1) Weighing waste cow fur (cow leather with hair) with a certain mass, performing ultrasonic pretreatment in ethanol, shearing with scissors, adding pepsin accounting for 1% of the mass of the raw materials for dissolving, salting out, and finally freeze-drying and grinding to obtain collagen powder.
2) Respectively weighing 3 g of collagen powder and 2 g of zinc chloride into a polytetrafluoroethylene lining, adding a proper amount of water, stirring for 8 hours, drying, and adding N2Activating at 900 ℃ for 2 h at the temperature rise rate of 10 ℃ per min in an atmosphere tube furnace, washing and drying, and collecting a black solid sample;
3) according to the mass ratio of 1: 3, weighing the sample obtained in the step 2) and phosphotungstic acid, adding a certain amount of distilled water into a beaker, violently stirring for 12 hours, centrifugally drying, and finally collecting a solid sample;
4) grinding the black sample obtained in the step 3) into powder, respectively placing the powder and Se powder in a mass ratio of 1: 2 in two corundum boats at 10% vol H2Calcining the mixture for 5 hours at 800 ℃ in a 90 vol% Ar atmosphere tubular furnace, and finally collecting a black powder sample to obtain a tungsten selenide-collagen derived porous carbon composite;
the tungsten selenide-collagen derived porous carbon composite synthesized by the present example: : conductive agent acetylene black: the binder CMC is mixed and ground according to the mass percentage of 80: 10: 10 and then is evenly coated on a copper foil to be used as a working electrode, a metal sodium sheet is used as a counter electrode, and 1 mol/L NaPF6Ethylene Carbonate (EC) and diethyl carbonate (DEC) are used as electrolyte to assemble the button cell; all assembly was carried out in an inert atmosphere glove box.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.

Claims (5)

1. A method for synthesizing a tungsten selenide-collagen derived porous carbon composite sodium ion battery cathode material with excellent performance comprises the following steps:
1) weighing waste cow fur with a certain mass, performing ultrasonic pretreatment by using ethanol, shearing by using scissors, adding an enzyme preparation accounting for 0.5-1% of the mass of the waste cow fur for dissolving, performing salting-out by using pepsin, papain or trypsin, and finally performing freeze drying and grinding to obtain collagen powder;
2) collagen powder and zinc chloride are weighed into the polytetrafluoroethylene lining according to the mass ratio of 1 (0.2-2), a proper amount of water is added, the mixture is stirred for 4-8 hours, and the mixture is dried and then is added with N2Activating at the temperature of 500-900 ℃ for 1-2 h at the temperature of 5-10 ℃/min in an atmosphere tube furnace, washing and drying, and collecting a black solid sample;
3) weighing the black solid sample obtained in the step 2) and a tungsten source, adding a certain amount of distilled water into a beaker, violently stirring for 6-12 h, centrifugally drying, and finally collecting the solid sample;
4) grinding the solid sample obtained in the step 3) into powder, and respectively placing the powder and Se powder in a mass ratio of 1 (1.5-3) in two corundum boats at 10% vol H2Calcining at 800 ℃ of 500 DEG and 90 vol% in a tubular furnace with Ar atmosphere for 2-5 hoursFinally, collecting a black powder sample to obtain the tungsten selenide-collagen derived porous carbon composite;
in the step 1), the waste cattle hide hair is derived from wastes of leather-making industry, collagen extracted from the waste cattle hide hair is rich in organic groups, contains a large amount of hetero elements, contains nitrogen and sulfur, and can be converted into N and S hetero atoms in situ for doping; in the step 3), the tungsten source is a series of tungsten-containing salts, including sodium tungstate, tungsten chloride or phosphotungstic acid; the mass ratio of the collagen to the tungsten source is 1: 2-5, and the drying temperature is 80-100 ℃.
2. The tungsten selenide-collagen derived porous carbon composite sodium ion battery cathode material with excellent performance prepared by the synthesis method of claim 1.
3. The excellent performance tungsten selenide-collagen derived porous carbon composite sodium ion battery anode material according to claim 2, wherein: the collagen derived porous nano carbon composite has the characteristics of high porosity and high specific surface area, can provide a large amount of sodium storage active sites and promotes the electrolyte to permeate into the active substances; meanwhile, tungsten selenide particles are confined in the porous nano carbon, so that the structure is stable, and the volume change in the circulating process can be buffered; the N and S elements in the collagen can be converted into N and S heteroatoms in situ in the calcining process, so that the electronic structure in the derived carbon can be regulated and controlled, and the conductivity of the compound is improved.
4. The use of the excellent performance tungsten selenide-collagen derived porous carbon composite sodium ion battery negative electrode material as claimed in any one of claims 2 to 3, wherein: the tungsten selenide-collagen derived porous carbon composite is applied to a sodium ion battery cathode, 50 times of charge-discharge circulation are carried out when the voltage is 0.01-3.0V and the current density is 100 mA/g, the specific capacity is 368.2 mAh/g, after 500 times of charge-discharge circulation is carried out when the current density is 1A/g, the specific capacity is still 185.5 mAh/g, the coulomb efficiency is high, and the multiplying power performance is excellent.
5. A sodium ion battery comprising a working electrode and a counter electrode, characterized in that: the weight ratio is as follows: the excellent performance tungsten selenide-collagen derived porous carbon composite sodium ion battery anode material as claimed in any one of claims 2 to 3: conductive agent acetylene black: the binder CMC 80: 10: 10 is mixed and ground and then evenly coated on a copper foil to be used as a working electrode, a metal sodium sheet is used as a counter electrode, 1 mol/L NaPF6Ethylene Carbonate (EC) and diethyl carbonate (DEC) are used as electrolyte to assemble a 2032 type button cell.
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