CN109817899B - Preparation method and application of hetero-element-doped carbon nanotube-packaged metal sulfide composite negative electrode material - Google Patents
Preparation method and application of hetero-element-doped carbon nanotube-packaged metal sulfide composite negative electrode material Download PDFInfo
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Abstract
The invention discloses a preparation method and application of a hetero-element doped carbon nanotube packaged metal sulfide composite negative electrode material. The mixed element doped carbon nanotube encapsulated metal sulfide material is prepared by dispersing transition metal salt, fructose, cyanamide and the like in a solvent, uniformly mixing, performing rotary evaporation treatment on the mixture, fully drying the obtained powder, performing high-temperature sintering in an inert atmosphere, and performing thioacetamide hydrothermal vulcanization treatment on the heat-treated powder. The composite electrode prepared by using the heteroelement doped carbon nano tube to encapsulate the metal sulfide material is characterized in that a uniform carbon layer is encapsulated and coated outside the active substance according to the characteristics of the sodium ion battery cathode material in charge-discharge cycle, and the one-dimensional structure of the carbon nano tube is favorable for improving electron conduction, so that the electrochemical performance of the electrode material is effectively improved. The preparation method has the advantages of simple operation process, high yield, excellent charge and discharge performance of the material and convenience for industrial production.
Description
Technical Field
The invention relates to the technical field of cathode materials of sodium ion batteries, in particular to a preparation method and application of a mixed element doped carbon nanotube packaged metal sulfide composite cathode material.
Background
The working principle of the sodium ion battery is similar to that of the lithium ion battery, and the charge and discharge are realized by utilizing the insertion and separation process of sodium ions between a positive electrode and a negative electrode. Compared with lithium ion batteries, sodium ion batteries have the following advantages: (1) the sodium salt raw material has abundant reserves and low price, and compared with the ternary cathode material of the lithium ion battery, the adopted ferro-manganese nickel-based cathode material has half of the raw material cost; (2) due to the characteristics of sodium salt, the low-concentration electrolyte (the electrolyte with the same concentration and the sodium salt conductivity higher than that of the lithium electrolyte by about 20%) is allowed to be used, so that the cost is reduced; (3) sodium ions do not form an alloy with aluminum, and the negative electrode can adopt aluminum foil as a current collector, so that the cost can be further reduced by about 8 percent, and the weight can be reduced by about 10 percent; (4) the sodium ion battery is allowed to discharge to zero volts due to its no over-discharge characteristics. The energy density of the sodium ion battery is more than 100Wh/kg, and the sodium ion battery can be compared with a lithium iron phosphate battery, but the cost advantage is obvious, and the sodium ion battery is expected to replace the traditional lead-acid battery in large-scale energy storage.
So far, the research of the negative electrode material of the sodium ion battery is mainly based on the intercalation, alloying and conversion mechanism. Materials of intercalation mechanisms such as graphite and Na3V2(PO4)3Exhibit excellent cycling and rate performance, but their theoretical and actual capacities are low. Alloying mechanisms such as Sn and P or conversion mechanisms of metal oxides such as Fe2O3And CuO, which has a high theoretical sodium storage capacity, but their cycle life is poor due to their drawbacks such as large volume effect, large structural change, etc. The metal sulfide is a field which is more actively researched in recent years, and shows great potential due to higher specific capacity and better cycle performance in the direction of a sodium ion battery. In order to further improve the electrochemical performance of the metal sulfide, the metal sulfide is combined with a carbon material with good conductivity to prepare a composite negative electrode material, which is the mainstream research direction of the sodium battery at present.
Carbon nanotubes have the advantages of light weight, good conductivity, low lithium intercalation potential, small volume change in the de-intercalation process, low price and the like, and are widely applied to negative electrode composite materials. The transition metal sulfide is encapsulated in the carbon nano tube to form an embedded composite structure, so that the structure of the sulfide material is protected from being damaged in the process of sodium intercalation, the conductivity of the material can be further improved, and the polarization is reduced, thereby greatly improving and enhancing the cycle performance of the electrode material. However, up to now, the technology of encapsulating transition metal sulfide inside carbon nanotubes has been reported at home and abroad.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method and application of a hetero-element-doped carbon nanotube-packaged metal sulfide composite negative electrode material.
In order to solve the problems of the prior art, the invention adopts the technical scheme that:
a preparation method of a mixed element doped carbon nanotube packaged metal sulfide composite negative electrode material comprises the steps of firstly preparing an ethanol-water mixed solution, sequentially adding cyanamide, transition metal salt and fructose into the mixed solution, continuously stirring until the mixture is completely dissolved during adding, then removing a solvent through rotary evaporation, and obtaining black powder through vacuum drying; secondly, sintering the black powder at high temperature in inert atmosphere; finally, carrying out thioacetamide hydrothermal vulcanization treatment on the heat-treated powder to obtain the mixed element doped carbon nanotube packaged metal sulfide composite negative electrode material; the transition metal salt is transition metal sulfate, transition metal chloride or transition metal nitrate; the transition metal is iron, cobalt or nickel.
The preparation method of the heteroelement-doped carbon nanotube-packaged metal sulfide composite negative electrode material comprises the following steps: step 1, preparing a mixed solution of absolute ethyl alcohol and water, wherein the volume ratio of the water to the ethyl alcohol is 9-19: 1; step 2, dispersing cyanamide in the mixed solution, adding a transition metal salt after complete ultrasonic dissolution, performing ultrasonic treatment for 20 minutes, then adding fructose for complete ultrasonic dissolution, removing the solvent by means of rotary evaporation, and performing vacuum drying to obtain precursor powder, wherein the mass ratio of the cyanamide to the fructose is 10-20:1, and the mass ratio of the transition metal salt to the fructose is 0.3-2: 1; step 3, transferring the precursor powder into a tubular furnace, heating to 600 ℃ at a constant speed in an inert atmosphere, keeping the temperature for 2 hours, continuing heating to 800 ℃, keeping the temperature for 2 hours, and then cooling to room temperature to obtain black powder; and 4, dispersing black powder in an ethanol solution of thioacetamide, carrying out ultrasonic stirring uniformly, transferring to a hydrothermal reaction kettle at the temperature of 150-220 ℃ for carrying out vulcanization treatment for 5-24h, stirring for 24h, carrying out suction filtration, cleaning filter residues, and drying to obtain the mixed element doped carbon nanotube packaged metal sulfide composite negative electrode material, wherein the mass ratio of the thioacetamide to the black powder is 3-5: 1.
the improvement is that the inert atmosphere in the step 3 is formed by Ar and Ar/H2Mixed gas or He.
As a modification, the constant temperature rise rate in step 4 is 2 ℃/min.
The application of the heteroelement doped carbon nanotube encapsulated metal sulfide composite negative electrode material in preparing a composite negative electrode.
The improvement is that the composite electrode is obtained by uniformly mixing the heteroelement doped carbon nanotube encapsulated metal sulfide composite negative electrode material, carbon black and carboxymethyl cellulose, and performing vacuum drying at 60 ℃ for 4 hours after film coating.
Advantageous effects
According to the characteristics of the sodium battery cathode material in charge-discharge circulation, the transition metal sulfide is packaged in the carbon nano tube to form an embedded composite structure, so that the structure of the sulfide material is protected from being damaged in the sodium-removing process, the conductivity of the material can be further improved, the polarization is reduced, and the circulation performance of the electrode material is greatly improved. The invention has the advantages of cheap preparation raw materials, simple operation process, high yield, excellent charge and discharge performance of the material and convenient industrial production. The invention obviously improves the cycle performance and rate performance of the active substance. In addition, one of the raw materials used in the invention is fructose, and the solvent is water, so that the method is environment-friendly, good in repeatability, low in cost, good in large-scale application potential and good in industrialization prospect.
Drawings
FIG. 1 is an SEM image of a composite cathode material of a heteroelement doped carbon nanotube encapsulated metal sulfide of the present invention, wherein (a) is a comparative example 1, (b) is an example 1, (c) is an example 3, and (d) is an example 5;
FIG. 2 is an XPS spectrum of a sample prepared in comparative example (without the addition of iron salt) of example 1;
FIG. 3 is an XRD spectrum of the heteroelement doped carbon nanotube encapsulated metal sulfide composite anode material of the present invention;
FIG. 4 shows that the electrode prepared from the composite negative electrode material of the metal sulfide encapsulated by the doped carbon nanotube of the hetero element in examples 1-5 is at 1 A.g-1The cycle performance test curve under the charge-discharge current density.
Detailed Description
Embodiments of the invention are further described below with reference to the accompanying drawings: the following examples are carried out on the premise of the technical scheme of the invention, and detailed embodiments and specific operation processes are given, but the scope of the invention is not limited to the following examples.
Example 1
A preparation method of a hetero-element doped carbon nanotube packaged metal sulfide composite negative electrode material comprises the following steps:
1) preparing 100mL of a mixed solution of absolute ethyl alcohol and water, wherein the volume ratio of the water to the ethyl alcohol is 9: 1;
2) dispersing 3g of cyanamide in the mixed solution, adding 0.3g of ferric sulfate after complete ultrasonic dissolution, adding 0.3g of fructose after ultrasonic dissolution for 20 minutes, completely ultrasonic dissolution, removing the solvent by a rotary evaporation mode, and performing vacuum drying to obtain precursor powder;
3) transferring the precursor powder into a tubular furnace, heating to 600 ℃ at the heating rate of 2 ℃/min under argon, preserving the temperature for two hours, heating to 800 ℃ at the heating rate of 2 ℃/min, preserving the temperature for two hours, and then cooling to room temperature to obtain black powder, namely the carbon nano tube packaging iron nano particle composite material;
4) dispersing 0.1g of the carbon nano tube packaged iron nano particle composite material into an ethanol solution of thioacetamide (containing 0.3g of thioacetamide), after uniformly stirring by ultrasonic waves, transferring the mixture into a hydrothermal reaction kettle for 12 hours of vulcanization reaction at 180 ℃, carrying out suction filtration after the reaction is finished, and drying after cleaning to obtain a composite, namely the mixed element doped carbon nano tube packaged metal sulfide composite negative electrode material;
5) fully grinding the mixed element doped carbon nanotube packaged metal sulfide composite negative electrode material, uniformly mixing the ground mixed element doped carbon nanotube packaged metal sulfide composite negative electrode material with carbon black and carboxymethyl cellulose according to the weight ratio of 70: 15, coating, and performing vacuum drying at 60 ℃ for 4 hours to prepare the composite electrode. Placing the composite electrode in a 2025 battery case, using sodium sheet as counter electrode, polyethylene film as separator, and 1M NaClO4The constant current charge and discharge test was carried out on an assembled battery using EC: EMC: DMC (1/1/1 vol.) + 5% FEC as an electrolyte.
Example 2
A preparation method of a hetero-element doped carbon nanotube packaged metal sulfide composite negative electrode material comprises the following steps:
1) preparing 200mL of a mixed solution of absolute ethyl alcohol and water, wherein the ratio of the water to the ethyl alcohol is 19: 1;
2) dispersing 3g of cyanamide in the mixed solution, adding 0.6g of ferric sulfate after complete ultrasonic dissolution, adding 0.3g of fructose after ultrasonic dissolution for 20 minutes, removing the solvent by a rotary evaporation mode, and performing vacuum drying to obtain precursor powder;
3) putting the precursor powder into a tube furnace, heating to 600 ℃ at the heating rate of 2 ℃/min under argon, preserving the heat for two hours, heating to 800 ℃ at the heating rate of 2 ℃/min, preserving the heat for two hours, and then cooling to room temperature to obtain black powder, namely the carbon nano tube packaged iron nano particle composite material;
4) dispersing 0.1g of the carbon nano tube packaged iron nano particle composite material into an ethanol solution of thioacetamide (containing 0.5g of thioacetamide), after uniformly stirring by ultrasonic waves, transferring the mixture into a hydrothermal reaction kettle for 6 hours of vulcanization reaction at 200 ℃, filtering after the reaction is finished, cleaning, and drying to obtain a composite, namely the mixed element doped carbon nano tube packaged metal sulfide composite negative electrode material;
6) fully packaging the metal sulfide composite cathode material by the carbon nano tube doped with the mixed elementGrinding, uniformly mixing with carbon black and carboxymethyl cellulose according to the weight ratio of 70: 15, coating, and vacuum drying at 60 ℃ for 4h to prepare the composite electrode. Placing the composite electrode in a 2025 battery case, using sodium sheet as counter electrode, polyethylene film as separator, and 1M NaClO4The constant current charge and discharge test was carried out on an assembled battery using EC: EMC: DMC (1/1/1 vol.) + 5% FEC as an electrolyte.
Example 3
A preparation method of a hetero-element doped carbon nanotube packaged metal sulfide composite negative electrode material comprises the following steps:
1) 200mL of a mixed solution of absolute ethyl alcohol and water is prepared, and the ratio of the water to the ethyl alcohol is 15: 1.
2) Dispersing 3g of cyanamide in the mixed solution, adding 0.1g of ferric sulfate after complete ultrasonic dissolution, adding 0.3g of fructose after ultrasonic dissolution for 20 minutes, removing the solvent by a rotary evaporation mode, and performing vacuum drying to obtain precursor powder;
3) putting the precursor powder into a tube furnace, heating to 600 ℃ at the heating rate of 2 ℃/min under argon, preserving the heat for two hours, heating to 800 ℃ at the heating rate of 2 ℃/min, preserving the heat for two hours, and then cooling to room temperature to obtain black powder, namely the carbon nano tube packaged iron nano particle composite material;
4) dispersing 0.1g of the powder material obtained in the step 3) in an ethanol solution of thioacetamide (containing 0.4g of thioacetamide), ultrasonically stirring uniformly, transferring the powder material to a hydrothermal reaction kettle for vulcanization reaction at 220 ℃ for 3 hours, carrying out suction filtration after the reaction is finished, cleaning, and drying to obtain a compound, namely the mixed element doped carbon nanotube packaged metal sulfide composite negative electrode material.
6) Fully grinding the mixed element doped carbon nanotube packaged metal sulfide composite negative electrode material, uniformly mixing the ground mixed element doped carbon nanotube packaged metal sulfide composite negative electrode material with carbon black and carboxymethyl cellulose according to the weight ratio of 70: 15, coating, and performing vacuum drying at 60 ℃ for 4 hours to prepare the composite electrode. Placing the composite electrode in a 2025 battery case, using sodium sheet as counter electrode, polyethylene film as separator, and 1M NaClO4In EC: EMC: DMC (1/1/1 vol.) + 5% FEC as electrolyte componentAnd (5) carrying out constant current charge and discharge test on the battery.
Example 4
A preparation method of a hetero-element doped carbon nanotube packaged metal sulfide composite negative electrode material comprises the following steps:
1) 200mL of a mixed solution of absolute ethyl alcohol and water is prepared, and the ratio of the water to the ethyl alcohol is 10: 1.
2) Dispersing 6g of cyanamide in the mixed solution, adding 0.5g of cobalt chloride after complete ultrasonic dissolution, adding 0.3g of fructose after ultrasonic dissolution for 20 minutes, removing the solvent by a rotary evaporation mode, and performing vacuum drying to obtain precursor powder;
3) putting the precursor powder into a tube furnace, and performing Ar/H reaction on the precursor powder2Heating to 600 ℃ at the heating rate of 2 ℃/min, preserving heat for two hours, heating to 800 ℃ at the heating rate of 2 ℃/min, preserving heat for two hours, and then cooling to room temperature to obtain black powder, namely the carbon nano tube packaging cobalt nano particle composite material;
4) dispersing 0.1g of the carbon nano tube packaged cobalt nano particle composite material into an ethanol solution of thioacetamide (containing 0.35g of thioacetamide), after uniformly stirring by ultrasonic, transferring the mixture into a hydrothermal reaction kettle for 24h of vulcanization reaction at 150 ℃, filtering after the reaction is finished, cleaning, and drying to obtain a composite, namely the mixed element doped carbon nano tube packaged metal sulfide composite negative electrode material.
6) Fully grinding the sintered material, uniformly mixing the material with carbon black and carboxymethyl cellulose according to the weight ratio of 70: 15, coating, and performing vacuum drying at 60 ℃ for 4 hours to prepare the composite electrode. Placing the electrode in 2025 battery case, using sodium sheet as counter composite electrode, using polyethylene film as separator, and using 1M NaClO4The constant current charge and discharge test was carried out on an assembled battery using EC: EMC: DMC (1/1/1 vol.) + 5% FEC as an electrolyte.
Example 5
A preparation method of a hetero-element doped carbon nanotube packaged metal sulfide composite negative electrode material comprises the following steps:
1) 200mL of a mixed solution of absolute ethyl alcohol and water is prepared, and the ratio of the water to the ethyl alcohol is 10: 1.
2) Dispersing 6g of cyanamide in the mixed solution, adding 0.1g of nickel nitrate after complete ultrasonic dissolution, adding 0.3g of fructose after ultrasonic dissolution for 20 minutes, removing the solvent by a rotary evaporation mode, and performing vacuum drying to obtain precursor powder;
3) putting the precursor powder into a tube furnace, heating to 600 ℃ at the heating rate of 2 ℃/min under He gas, preserving heat for two hours, heating to 800 ℃ at the heating rate of 2 ℃/min, preserving heat for two hours, and then cooling to room temperature to obtain black powder, namely the carbon nano tube packaged nickel nano particle composite material;
4) dispersing 0.1g of the carbon nano tube packaged nickel nano particle composite material into an ethanol solution of thioacetamide (containing 0.35g of thioacetamide), after uniformly stirring by ultrasonic waves, transferring the mixture into a hydrothermal reaction kettle for 15h of vulcanization reaction at 180 ℃, filtering after the reaction is finished, cleaning, and drying to obtain a composite, namely the mixed element doped carbon nano tube packaged metal sulfide composite negative electrode material.
6) Fully grinding the mixed element doped carbon nanotube packaged metal sulfide composite negative electrode material, uniformly mixing the ground mixed element doped carbon nanotube packaged metal sulfide composite negative electrode material with carbon black and carboxymethyl cellulose according to the weight ratio of 70: 15, coating, and performing vacuum drying at 60 ℃ for 4 hours to prepare the composite electrode. Placing the composite electrode in a 2025 battery case, using sodium sheet as counter electrode, polyethylene film as separator, and 1M NaClO4The constant current charge and discharge test was carried out on an assembled battery using EC: EMC: DMC (1/1/1 vol.) + 5% FEC as an electrolyte.
The structural morphology of the composite material and the electrochemical performance of the composite material prepared by the invention are tested and characterized by specific characterization.
1. SEM analysis
FIG. 1 is a TEM photograph of samples prepared in examples 1, 3 and 5 and related samples according to the present invention. FIG. 1(a) is a scheme one comparative example without the addition of iron salt. It can be seen that the prepared material has a lamellar structure without the addition of iron salt, and has no nanotube structure morphology. Fig. 1(b), fig. 1(c) and fig. 1(d) are SEM images corresponding to examples 1, 3 and 5, and it can be seen from the images that the heteroelement-doped carbon nanotube-encapsulated metal sulfide composite anode material has a carbon nanotube-shaped structure. In addition, the presence of the nanoparticle structure is clearly visible in the middle of the nanotube. The walls of the carbon nanotubes are very thin. This is a structure that ordinary carbon nanotubes cannot assume.
2. XPS and XRD analysis
FIG. 2 XPS spectra of samples prepared from the comparative example of example 1 (without the addition of iron salt). As can be seen from the figure, the sample mainly contains C, N, O three elements, wherein carbon accounts for 80 atomic%, nitrogen accounts for 17 atomic%, and oxygen accounts for 3 atomic%. The doping of the nitrogen element can improve the conductivity of the composite material to a higher degree, so that the polarization of the electrode material under a large multiplying power is reduced. FIG. 3 is an XRD (X-ray diffraction) diagram of the mixed-element-doped carbon nanotube-encapsulated metal sulfide composite anode material prepared in embodiments 1-3 of the invention, and it can be seen from the XRD diagram that the mixed-element-doped carbon nanotube-encapsulated metal sulfide composite anode material shows FeS2The crystal phase structure, and the steamed bread peak appearing at about 25 degrees is the characteristic peak of the amorphous carbon material.
3. Cycle performance test
FIG. 4 shows that the composite electrode prepared by the composite negative electrode material of the hetero-element-doped carbon nanotube encapsulated metal sulfide prepared in examples 1-5 is at 1 A.g-1The cycle performance test curve under the charge-discharge current density. It can be seen from the figure that all the electrodes prepared in the examples can maintain high reversible specific capacity even under high charge-discharge current density, and basically have no attenuation after being cycled for about 100 times.
In conclusion, according to the heteroelement-doped carbon nanotube-encapsulated metal sulfide composite negative electrode material prepared by the invention, the sulfide nanoparticles are successfully coated in the carbon nanotubes, and the hollow carbon nanotube structure enables the active material particles to effectively inhibit the extremely large volume expansion in the charging and discharging processes, so that the cycle performance of the material is greatly improved. In addition, the doping of the hetero element N can sufficiently improve the electronic conductivity of the composite electrode material. The wall of the carbon nano tube prepared by the special preparation method is very thin. The characteristics are combined, so that the prepared sulfide composite negative electrode can efficiently and stably operate in a sodium ion battery.
Claims (5)
1. A preparation method of a mixed element doped carbon nanotube packaged metal sulfide composite negative electrode material is characterized by comprising the steps of firstly preparing an ethanol-water mixed solution, sequentially adding cyanamide, transition metal salt and fructose into the mixed solution, continuously stirring until the cyanamide, the transition metal salt and the fructose are completely dissolved during adding, removing a solvent through rotary evaporation, and drying in vacuum to obtain black powder; secondly, sintering the black powder at high temperature in inert atmosphere; finally, carrying out thioacetamide hydrothermal vulcanization treatment on the powder after high-temperature sintering to obtain the mixed element doped carbon nanotube packaged metal sulfide composite negative electrode material; the transition metal salt is transition metal sulfate, transition metal chloride or transition metal nitrate; the transition metal is iron; the method specifically comprises the following steps: step 1, preparing a mixed solution of absolute ethyl alcohol and water, wherein the volume ratio of the water to the ethyl alcohol is 9-19: 1; step 2, dispersing cyanamide in the mixed solution, adding a transition metal salt after complete ultrasonic dissolution, performing ultrasonic treatment for 20 minutes, then adding fructose for complete ultrasonic dissolution, removing the solvent by means of rotary evaporation, and performing vacuum drying to obtain precursor powder, wherein the mass ratio of the cyanamide to the fructose is 10-20:1, and the mass ratio of the transition metal salt to the fructose is 0.3-2: 1; step 3, transferring the precursor powder into a tubular furnace, heating to 600 ℃ at a heating rate of 2 ℃/min in an inert atmosphere, preserving heat for two hours, then heating to 800 ℃ at a heating rate of 2 ℃/min in an inert atmosphere, preserving heat for two hours, and then cooling to room temperature to obtain black powder, namely the carbon nano tube encapsulated iron nano particle composite material; step 4, dispersing the black powder in an ethanol solution of thioacetamide, carrying out ultrasonic stirring uniformly, transferring to a hydrothermal reaction kettle for vulcanization treatment at the temperature of 150 ℃ and 220 ℃ for 5-24h, stirring for 24h, carrying out suction filtration, cleaning filter residues and drying to obtain the mixed element doped carbon nanotube packaged metal sulfide composite negative electrode material, wherein the metal sulfide is FeS2The mass ratio of thioacetamide to black powder is 3-5: 1.
2. the method for preparing the heteroelement-doped carbon nanotube-encapsulated metal sulfide composite anode material according to claim 1, wherein the inert atmosphere in the step 3 is Ar or Ar/H2Mixed gas or He.
3. The method for preparing the heteroelement-doped carbon nanotube-encapsulated metal sulfide composite anode material according to claim 1, wherein the constant temperature rise rate in the step 4 is 2 ℃/min.
4. The use of the heteroelement-doped carbon nanotube-encapsulated metal sulfide composite negative electrode material prepared according to claim 1 for preparing a composite negative electrode.
5. The application of the composite electrode as claimed in claim 4, wherein the composite electrode is obtained by uniformly mixing the doped carbon nanotube containing impurity element encapsulated metal sulfide composite negative electrode material, carbon black and carboxymethyl cellulose, and performing vacuum drying at 60 ℃ for 4 hours after film coating.
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