CN113336208A - Ultra-small nickel phosphide @ mesoporous carbon composite material and preparation method and application thereof - Google Patents
Ultra-small nickel phosphide @ mesoporous carbon composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an ultra-small nickel phosphide @ mesoporous carbon composite material and a preparation method and application thereof. The cathode material prepared by the method is made of ultra-small nickel phosphide (Ni)2P) nanoparticles and ordered mesoporous hollow carbon nanoarrays, in which ultra-small Ni2The P nano particles are uniformly distributed in the pore channels of the ordered mesoporous hollow carbon nano array. The invention effectively solves the problems of poor conductivity and easy generation of common metal phosphide when applied to electrochemical energy storageThe green agglomeration, the obvious volume effect and the like. When the material is used for a negative electrode material of a potassium ion battery, good electrochemical performance is shown. The invention provides a simple, effective, controllable, low-cost, safe and environment-friendly preparation method, and provides a feasible method for preparing other types of transition metal phosphide composite materials.
Description
Technical Field
The invention belongs to the technical field of nano composite materials, and particularly relates to an ultra-small nickel phosphide @ mesoporous carbon composite material as well as a preparation method and application thereof.
Background
Potassium ion batteries are considered alternatives to the next generation of rechargeable energy storage technologies due to their abundant natural abundance (K:2.09 wt% vs. li:0.0017 wt%) and similar electrochemical behavior. But due to K+ 
Radius greater than Li+ 
Resulting in poor rate performance and cycling stability of the potassium ion battery. In recent years, negative electrode materials for potassium ion batteries, such as alloys, metal oxides, metal sulfides, metal phosphides, carbonaceous materials, and the like, have been actively sought. Among them, the transition metal phosphide has the advantages of high theoretical specific capacity, good conductivity, abundant reserves and the like, and is widely used as a negative electrode material of a potassium ion battery. However, due to the intrinsic defects of the metal phosphide, the alkali metal ion battery cathode material which can be practically applied still cannot be obtained at present. The main reasons are as follows: (1) compared with a graphite cathode, the metal phosphide has poor conductivity, low ionic or electronic conductivity and poor reaction reversibility; (2) the active sites of the bulk metal phosphide are less exposed than the nanoparticles, so that the function of most active substances in the bulk metal phosphide cannot be well played; (3) during the intercalation and deintercalation of alkali metal ions, the volume of the negative electrode material may be expanded, and finally the electrode may be pulverized to lose contact with the current collector and fail. At present, the most common method for transition metal phosphide is gas-solid phase reaction, i.e. with P vapor, PH3Gas, NaH2PO2Or red phosphorus is used as a P source, and the metal or metal oxide precursor is converted into metal phosphide at the temperature of about 300 ℃. However, the formation of toxic gases severely limits the commercial production of metal phosphides. In addition, the lower temperature of the gas-solid phase reaction leads to lower crystallinity of the electrode material, so that the conductivity of the electrode material is poor, and the improvement of the electrochemical performance of the electrode material is limited. At a high temperature (>At 650 ℃ with H2Or CH4Reducing metal phosphates is another method of synthesizing transition metal phosphides. However, generalThe products obtained by this process are generally massive, with large crystal size and irregular morphology, greatly limiting their application in energy storage and conversion. In order to solve the problem, the method for preparing the metal phosphide cathode material with excellent electrical property is an effective method for compounding the carbon-based material and the metal phosphide or preparing the metal phosphide with a special morphology.
Among various carbon-based materials, ordered mesoporous carbon has a large number of mesopores and a large pore volume, which facilitates transfer of electrons and ions during a circulation process, and the large pore volume provides a sufficient space to store an electrolyte, thereby increasing wettability of an active material. More importantly, a large number of mesoporous channels can be used as a nano reactor to limit the growth of the nano particles and prevent the aggregation of the nano particles. The high specific surface area and good structural stability can improve the conductivity and can effectively relieve the volume expansion in the charging and discharging processes. In the aspect of preparation method, Chinese patent CN106669794A discloses a nickel phosphide catalyst and a preparation method and application thereof, the preparation method comprises the steps of firstly dissolving nickel acetate and a phosphorus source in water to obtain a suspension, adding concentrated nitric acid to increase the solubility of the suspension, then adding an MCM-41 mesoporous molecular sieve to soak the suspension, drying and roasting the soaked solution to obtain a precursor; and (3) placing the precursor in a fixed bed reactor, raising the temperature in the fixed bed reactor to 350-600 ℃ in hydrogen flow, preserving the temperature for 1.5-2.5 h, then cooling to room temperature, and then carrying out passivation treatment to obtain the nickel phosphide catalyst. However, concentrated nitric acid in the reagents required for the preparation of the catalyst is highly corrosive, volatile and dangerous. CN108550821A discloses a core-shell structure nickel/carbon phosphide (Ni) based on Ni-MOF2The preparation method of the P/C) microsphere is to prepare a spherical nickel-based metal organic framework compound (Ni-MOF) precursor by utilizing an organic ligand and nickel salt, and obtain core-shell structure Ni through high-temperature carbonization and low-temperature phosphorization2P/C microspheres. However, the material prepared by the method is too large in size, so that the long-cycle test of the material is not facilitated, and meanwhile, the appearance of the material is greatly changed after phosphorization, and the microsphere structure of the material is not maintained.
Disclosure of Invention
In order to solve the technical problems, the invention provides an ultra-small nickel phosphide @ mesoporous carbon composite material and a preparation method and application thereof.
The invention provides an effective, controllable, low-cost and environment-friendly modification method, which can overcome the defects in the prior art. The prepared ultra-small nickel phosphide @ mesoporous carbon composite material has the advantages of high purity, small particles, regular and uniform appearance, high specific capacity of the assembled potassium ion battery, good circulation stability and good rate capability. The nano composite material which simultaneously has the characteristics of carbon composite, ordered mesopores, high specific surface area, large pore volume, ultra-small particles, uniform distribution and the like is prepared by a hard template method. Due to the existence of the graphitized ordered mesoporous carbon skeleton, the nickel phosphide can be prevented from being enlarged in particles in the preparation process, and the nickel phosphide is protected from reacting with HF or NaOH solution in the demolding process to cause the damage of the appearance; the conductivity of the negative electrode material can be enhanced, and the pulverization of the negative electrode material in the charging and discharging process can be effectively relieved, so that the performance of the metal phosphide in the aspects of electrochemical energy storage and conversion is improved.
The technical scheme provided by the invention is as follows:
in a first aspect, the invention provides a preparation method of an ultra-small nickel phosphide @ mesoporous carbon composite material, which comprises the following steps:
(1) adding tetraethyl orthosilicate (TEOS) into an acidic solution containing the amphiphilic block copolymer, stirring in a water bath, reacting, and filtering;
(2) filtering the filtrate obtained in the step (1) and keeping part of mother liquor for hydrothermal aging, and then filtering and drying;
(3) adding concentrated nitric acid and hydrogen peroxide into the product obtained in the step (2), stirring in a water bath to react completely, adding distilled water to dilute the mixed solution, performing suction filtration, and performing water washing, suction filtration and drying to obtain a silicon dioxide template;
(4) weighing Trimethylbenzene (TMB) and Furfuryl Alcohol (FA), and adding oxalic acid to prepare furfuryl alcohol solution;
(5) adding the silicon dioxide template into the furfuryl alcohol solution for full mixing, and keeping the temperature for full polymerization;
(6) calcining the product obtained in the step (5) in an inert atmosphere to obtain the ordered mesoporous carbon @ silicon dioxide template with the hollow structure;
(7) modifying the surface of the product obtained in the step (6) by using an ammonium persulfate solution to obtain an APS-ordered mesoporous carbon @ silicon dioxide template;
(8) dissolving a phosphorus source and a metal precursor in water, adding an APS-ordered mesoporous carbon @ silicon dioxide template, stirring at room temperature, and transferring the beaker to a forced air drying oven until the mixed solution is completely dried;
(9) putting the precursor obtained in the step 8) into a muffle furnace for calcining;
(10) transferring the intermediate product obtained in the step 9) to a tubular furnace, and calcining and reducing by hydrogen; when the temperature of the tube furnace is reduced to room temperature, taking out the product;
(11) removing the silicon dioxide template in the product obtained in the step (10) by using HF or NaOH solution, and then putting the product into a freeze dryer for freeze drying to obtain the final ultra-small nickel phosphide @ mesoporous carbon composite material named as Ni2P@OMC。
Further, the amphiphilic block copolymer contained in the step (1) comprises P123, F127 and F108.
Further, the water bath temperature in the step (1) is 35-38 ℃, and the stirring reaction time is 2-4 h.
Further, the silica template in the step (3) comprises SBA-15-OH, KIT-6-OH, MCF-OH, FDU-12-OH, SBA-16-OH and P-SBA-15-OH. The silica template is prepared according to the method reported by the relevant literature: SBA-15-OH (J.Am.chem.Soc.1998,120,6024), MCF-OH (J.Am.chem.Soc.1999,121,254-255), KIT-6-OH (chem.Commun.2003,2136-2137), P-SBA-15-OH (chem.Mater.2004,16,4174-4180), FDU-12-OH (J.Am.chem.Soc.2005,127,10794-10795), SBA-16-OH (Mater.chem.,2006,16,1511-1519) and SBA-12-OH (J.Am.chem.Soc.1998,120, 6024-6036).
Further, in the step (3), the concentration of hydrogen peroxide is 40 wt%, the water bath reaction temperature is 80 ℃, and the reaction time is 3 hours.
Further, in the step (3), the usage ratio of the product in the step (2), the concentrated nitric acid and the hydrogen peroxide is as follows: 1.0g, 15mL, 5 mL; the water bath temperature is 80 ℃, and the reaction time is 3 h.
Further, the dosage ratio of trimethylbenzene, furfuryl alcohol and oxalic acid in the step (4) is as follows: 1.0mL:1.0mL:5.0mg, prepared as a 50% (v/v) furfuryl alcohol solution.
Further, in the step (5), the dosage ratio of the silicon dioxide template to the furfuryl alcohol solution is 1.0g: 0.674-4.422 mL.
Further, the furfuryl alcohol-filled silica template polymerization reaction method in the step (5) comprises the following steps: the temperature is first maintained at 50 ℃ for 1 day and then adjusted to 90 ℃ for 2 days.
Further, the surface modification in the step (7) is carried out in a water bath at 60 ℃; the concentration of the ammonium sulfate solution is 0.5-2.0 mol/L; the water bath time is 1-3 h.
Further, in the step (8), the phosphorus source is phosphoric acid, sodium dihydrogen phosphate, sodium hypophosphite or sodium hydrogen phosphate.
Further, the nickel salt is selected from nickel chloride, nickel acetate, nickel nitrate or nickel sulfate. Preferably, when the metal salt precursor is nickel nitrate, 85 wt% of phosphoric acid is used as a phosphorus source, and the metal salt precursor can be completely phosphated into Ni when the atomic ratio of Ni to P is 0.5-32P。
Further, in the step (9), when calcining is carried out in the air atmosphere, the temperature rising speed is 2-10 ℃/min, the temperature rises from room temperature to 300-450 ℃, and the temperature is kept for 3-7 h.
Further, in the step (10), during reduction in a hydrogen atmosphere, the hydrogen content is 20-100% (v/v), the temperature is raised from room temperature to 550-900 ℃ at a rate of 2-10 ℃/min, and then the temperature is maintained for 1-3 hours. And naturally cooling to room temperature to obtain the ultra-small nickel phosphide @ mesoporous carbon composite material.
Further, in the step (11), the final product is obtained by freeze drying for 12-48 hours at the temperature of-45 to-85 ℃.
In a second aspect, the present invention provides an ultra-small nickel phosphide @ mesoporous carbon composite prepared by the method of the first aspect.
In a third aspect, the invention provides an application of the ultra-small nickel phosphide @ mesoporous carbon composite material as an ion battery material.
The invention has the beneficial effects that:
1) the invention mainly utilizes ordered mesoporous carbon @ silicon dioxide with a hollow structure (such as: the pore channel in the OMC @ SBA-15) template is a micro-reactor, and a phosphorus source and a metal salt precursor are filled in the pore channel. Due to the confinement effect in the pore channels of the template, the in-situ hydrogen is reduced to form the ultra-small nickel phosphide @ mesoporous carbon composite material. And the pore size of the OMC @ SBA-15 template can be changed by changing the filling amount of furfuryl alcohol, so that the controllable preparation of the nickel phosphide nano-particles can be realized.
2) Before filling of a filling metal precursor, the OMC @ SBA-15 template is subjected to surface oxidation by an APS solution in advance, so that the hydrophilicity in a pore channel is increased.
3) The invention fills the metal salt precursor and the phosphoric acid in the pore channel of the template at the same time, thereby avoiding the additional use of H3P gas makes the preparation process more simple, safe and environment-friendly.
4) The invention is also suitable for different types of mesoporous silica templates, such as SBA-15-OH, KIT-6-OH, MCF-OH, FDU-12-OH, SBA-16-OH and P-SBA-15-OH.
5) The material prepared by the invention shows excellent cycling stability and higher specific capacity in the aspect of electrochemical performance.
6) The material prepared by the invention has a high specific surface, large pore volume and uniform pore channel structure, wherein the size of the generated nickel phosphide nano-particles can change along with the change of the pore channel size due to the limitation of the pore channel, and the nano-particles have uniform size and uniform distribution.
7) The invention has the advantages of environmental protection, low cost, high safety, high yield and the like in the preparation process.
Drawings
Fig. 1 is a TEM image of an ultra small nickel phosphide @ mesoporous carbon composite.
FIG. 2 is an XRD pattern of the ultra-small nickel phosphide @ mesoporous carbon composite material.
Fig. 3 is a graph of rate performance of the ultra-small nickel phosphide @ mesoporous carbon composite material at different current densities when the ultra-small nickel phosphide @ mesoporous carbon composite material is applied to a potassium ion battery.
FIG. 4 shows that when the ultra-small nickel phosphide @ mesoporous carbon composite material is applied to a potassium ion battery, the composite material is subjected to treatment by adding 6.0Ag-1Current density of (a).
Detailed Description
The following further describes the specific implementation steps of the present invention with reference to the drawings, and the present invention is not limited thereto at all.
Taking OMC @ SBA-15 template as an example, the main steps are as follows:
1. preparation of APS-OMC @ SBA-15 template:
1) 20.0g of the block copolymer P123 was added to a mixed solution containing 650mL of distilled water and 100mL of 37 wt% hydrochloric acid, and stirred in a water bath at 35 to 38 ℃ for 2 hours. After P123 had dissolved sufficiently, 41.6g of tetraethyl orthosilicate (TEOS) were added to the solution and stirring was continued for 24h, with a speed of 500 rpm. And after stirring, carrying out suction filtration on the solution, transferring the solution into a 500mL polytetrafluoroethylene hydrothermal kettle, and carrying out hydrothermal treatment for 24-48 h at the temperature of 90-130 ℃ in a blast drying oven. And (3) cooling the hydrothermal kettle to room temperature, carrying out suction filtration on the aged SBA-15 template by using a Buchner funnel, drying in a forced air drying oven at 50-80 ℃, and then keeping for later use.
2) And (2) taking 8.0g of the product dried in the step 2), putting the product into a 1L round-bottom flask, adding 120mL of concentrated nitric acid and 40mL of 40 wt% hydrogen peroxide, stirring in a water bath at 80 ℃ for 3 hours, adding distilled water, diluting, performing suction filtration, continuously washing with water, performing suction filtration, drying at 50-80 ℃ to obtain an SBA-15 template (named as SBA-15-OH) with a surface rich in-OH, and then reserving for later use.
3) 5.0mL of Trimethylbenzene (TMB) and 5.0mL of Furfuryl Alcohol (FA) were pipetted using a pipette and 25.0mg of oxalic acid was added to make a 50% (v/v) furfuryl alcohol solution.
4) Putting 0.5g of SBA-15-OH dried in the step 3) into a 20mL glass bottle by using an electronic balance scale, then adding 0.337-2.211 mL of 50% (v/v) furfuryl alcohol solution into the bottle, manually stirring for 10-20 min until the solution and the SBA-15-OH template are fully mixed, sealing the glass bottle, putting the glass bottle into a forced air drying oven, preserving the heat at 50 ℃ for 1 day, and then regulating the temperature to 90 ℃ for 2 days.
5) And (3) after the furfuryl alcohol is completely polymerized in the step 5), transferring the product into a tubular furnace, and calcining for 4 hours at 850 ℃ under an inert atmosphere to obtain OMC @ SBA-15.
6) And (3) modifying the surface of the OMC @ SBA-15 prepared in the step 6) by using a 1mol/L Ammonium Persulfate Solution (APS) to make the surface more hydrophilic, so as to obtain an APS-OMC @ SBA-15 template.
2. Preparation of the ultra-small nickel phosphide @ mesoporous carbon composite material: and simultaneously filling a phosphorus source and a metal salt precursor into an APS-OMC @ SBA-15 template, and filling the precursor into pore channels of the template through a solvent volatilization process. And then the nickel phosphide @ mesoporous carbon composite material is obtained by air roasting and high-temperature hydrogen reduction.
3. Removing the silicon dioxide template by taking a certain amount of 5-10 wt% of HF or 0.2-1.0 mol/L NaOH solution, and then putting the silicon dioxide template into a freeze dryer for freeze drying to obtain the final ultra-small nickel phosphide @ mesoporous carbon composite material.
4. And carrying out electrochemical performance test on the prepared composite material.
Example 1
1) Preparation of APS-OMC @ SBA-15 template: putting 0.5g of the dried SBA-15-OH template into a 20mL glass bottle by using an electronic balance scale, then adding 0.337mL of 50% (v/v) furfuryl alcohol solution into the bottle, manually stirring for 10min until the solution and the SBA-15-OH template are fully mixed, sealing the glass bottle, putting the glass bottle into a forced air drying oven, preserving the temperature at 50 ℃ for 1 day, and then adjusting the temperature to 90 ℃ for 2 days. After the furfuryl alcohol is completely polymerized, transferring the product to a tubular furnace, and calcining at 850 ℃ in an inert atmosphere to obtain OMC @ SBA-15, wherein the temperature rise procedure is from room temperature to 150 ℃,1 ℃/min and 4 hours; 150-300 ℃ at 1 ℃/min; 300-850 ℃, 5 ℃/min and 4 h. And cooling to room temperature, adding the product into 60mL of 1mol/L Ammonium Persulfate Solution (APS), stirring in a water bath at 60 ℃ for 2h, and modifying the surface of the OMC @ SBA-15 to make the surface more hydrophilic to obtain an APS-OMC @ SBA-15 template.
2) Preparation of the ultra-small nickel phosphide @ mesoporous carbon composite material: 0.4556g of nickel nitrate and 0.338mL of 85 wt% phosphoric acid were added to a beaker (50mL) containing 10mL of water, mechanically stirred at room temperature, after sufficient dissolution and dispersion, 1.0g of APS-OMC @ SBA-15 was added, stirred for 2h, and the mixture was transferred to a 90 ℃ forced air drying cabinet and stirred until all the water was evaporated. And putting the obtained powder precursor into a muffle furnace to calcine for 5 hours at the temperature of 300 ℃ and at the speed of 2 ℃/min. After the temperature is reduced to room temperature, the mixture is transferred to a tube furnace and calcined for 2 hours at the temperature of 600 ℃ and at the speed of 2 ℃/min under the atmosphere of 40 percent (v/v) hydrogen. And (3) removing the silicon dioxide template by taking 40mL of 5 wt% HF, and then putting the silicon dioxide template into a freeze dryer at the temperature of-85 ℃ for freeze drying for 24 hours to obtain the final ultra-small nickel phosphide @ mesoporous carbon composite material. As shown in fig. 1 and fig. 2, the obtained ultra-small nickel phosphide nanoparticles are uniformly distributed on the mesoporous carbon.
Example 2
0.6556g of nickel chloride and 0.538mL of 85 wt% phosphoric acid were added to a beaker (50mL) containing 20mL of water, and mechanically stirred at room temperature to dissolve and disperse the solution sufficiently, and then 1.0g of the APS-OMC @ SBA-15 template prepared in step (1) of example 1 was added and stirred for 2 hours, and the mixture was transferred to a 90 ℃ forced air drying cabinet and stirred until all the water was evaporated. And putting the obtained powder precursor into a muffle furnace to calcine for 5 hours at the temperature of 300 ℃ and at the speed of 2 ℃/min. After the temperature is reduced to room temperature, the mixture is transferred to a tube furnace and calcined for 2 hours at the temperature of 600 ℃ and at the speed of 2 ℃/min under the atmosphere of 60 percent (v/v) hydrogen. And (3) removing the silicon dioxide template by taking 80mL of 0.5mol/L NaOH solution, and then putting the silicon dioxide template into a freeze dryer at the temperature of-85 ℃ for freeze drying for 24 hours to obtain the final ultra-small nickel phosphide @ mesoporous carbon composite material.
Example 3
MCF-OH is used as a template to prepare the ultra-small nickel phosphide @ mesoporous carbon composite material.
1) Preparation of APS-OMC @ MCF template: putting 0.5g of the dried MCF-OH template into a 20mL glass bottle by using an electronic balance, then adding 0.674mL of 50% (v/v) furfuryl alcohol solution into the bottle, manually stirring for 15min until the solution and the MCF-OH template are fully mixed, sealing the glass bottle, putting the glass bottle into a forced air drying oven, preserving the temperature at 50 ℃ for 1 day, and then regulating the temperature to 90 ℃ for 2 days. After the furfuryl alcohol is completely polymerized, transferring the product to a tubular furnace, and calcining at 850 ℃ in an inert atmosphere to obtain OMC @ MCF, wherein the temperature rise procedure is from room temperature to 150 ℃,1 ℃/min and 4 hours; 150-300 ℃ at 1 ℃/min; 300-850 ℃, 5 ℃/min and 4 h. And (3) cooling to room temperature, adding the product into 60mL of 1mol/L Ammonium Persulfate Solution (APS), stirring in a water bath at 60 ℃ for 2h, and modifying the surface of the OMC @ MCF to make the OMC @ MCF more hydrophilic to obtain an APS-OMC @ MCF template.
2) Preparation of the ultra-small nickel phosphide @ mesoporous carbon composite material: 0.4556g of nickel nitrate and 0.338mL of 85 wt% phosphoric acid were added to a beaker (50mL) containing 15mL of water, mechanically stirred at room temperature, after sufficient dissolution and dispersion, 1.0g of APS-OMC @ MCF was added, stirred for 2h, and the mixture was transferred to a 90 ℃ forced air drying cabinet and stirred until all the water was evaporated. And putting the obtained powder precursor into a muffle furnace to calcine for 5 hours at the temperature of 300 ℃ and at the speed of 2 ℃/min. After the temperature is reduced to room temperature, the mixture is transferred to a tubular furnace and calcined for 2 hours at the temperature of 600 ℃ and at the speed of 2 ℃/min under the atmosphere of hydrogen. And (3) removing the silicon dioxide template by taking 40mL of 5 wt% HF, and then putting the silicon dioxide template into a freeze dryer at the temperature of-85 ℃ for freeze drying for 24 hours to obtain the final ultra-small nickel phosphide @ mesoporous carbon composite material.
Application example 1
The prepared ultra-small nickel phosphide @ mesoporous carbon composite material is prepared into a CR2025 button type potassium ion battery, electrochemical performance tests are carried out, such as testing the cycle life, the coulombic efficiency, the alternating current impedance and the like of the battery under different current densities, and the reason for the excellent electrochemical performance is analyzed. The preparation method comprises the following steps:
1) uniformly mixing an active substance, acetylene black and 5% by mass of polytetrafluoroethylene aqueous dispersion emulsion together to obtain a mixture; dropwise adding N-methyl pyrrolidone into the mixture to obtain a mixture for coating;
the active substance in the step 1) is the ultra-small nickel phosphide @ mesoporous carbon composite material prepared in the example 1;
the mass fraction of active substances in the mixture in the step 1) is 70%, the mass fraction of acetylene black is 20%, and the mass fraction of polytetrafluoroethylene is 10%;
the mass ratio of the volume of the N-methylpyrrolidone to the active substance in the step 1) is (1-2 mL): (5-10 mg);
2) uniformly coating the mixture for coating obtained in the step 1) on a copper foil with the diameter of 14mm, and then carrying out vacuum drying at the temperature of 80 ℃ for 12h to obtain a pole piece with the surface containing active substances; obtaining the mass of the active substance on the pole piece by using a difference method;
3) and transferring the pole piece with the surface containing the active substances into a vacuum glove box to complete the assembly of the button cell, wherein a glass fiber diaphragm (GD/Whatman) is a cell diaphragm, a potassium sheet is a counter electrode, the pole piece with the surface containing the active substances is a working electrode, assembling the working electrode, the diaphragm, the counter electrode, a gasket and a cell shell into the CR2025 button cell in the glove box, sealing the button cell by using a sealing machine, and finally standing the prepared button cell at normal temperature for 12h to activate the cell, thus completing the preparation of the CR2025 button potassium ion cell.
FIG. 3 and FIG. 4 are a graph of the rate performance of the potassium ion battery prepared in example 4 at different current densities and at 6.0Ag-1Long cycle life test plots at current density. As shown in FIG. 3, when the ultra-small nickel phosphide @ mesoporous carbon composite material is applied to the negative electrode of the potassium ion battery, the composite material shows higher reversible specific capacity under lower current density, and when the current density is increased to 6.0Ag-1While still keeping close to 100mAh g-1When the current density is again reduced to 0.05Ag-1And the reversible specific capacity returns to the original value, and the result shows that the ultra-small nickel phosphide @ mesoporous carbon composite material has good structural stability, so that the ultra-small nickel phosphide @ mesoporous carbon composite material has good rate performance. When the current density is 6.0Ag-1When the material is circulated for 3500 circles, the reversible specific capacity is still kept at 160mAh g-1And (figure 4) shows high reversible specific capacity and excellent rate capability and cycling stability.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any modification, equivalent replacement, and improvement made by those skilled in the art within the technical scope of the present invention should be included in the scope of the present invention.
Claims (10)
1. A preparation method of an ultra-small nickel phosphide @ mesoporous carbon composite material is characterized by comprising the following steps:
(1) adding tetraethyl orthosilicate (TEOS) into an acidic solution containing the amphiphilic block copolymer, stirring in a water bath, reacting, and filtering;
(2) filtering the filtrate obtained in the step (1) and keeping part of mother liquor for hydrothermal aging, and then filtering and drying;
(3) adding concentrated nitric acid and hydrogen peroxide into the product obtained in the step (2), stirring in a water bath to react completely, adding distilled water to dilute the mixed solution, performing suction filtration, and performing water washing, suction filtration and drying to obtain a silicon dioxide template;
(4) weighing Trimethylbenzene (TMB) and Furfuryl Alcohol (FA), and adding oxalic acid to prepare furfuryl alcohol solution;
(5) adding furfuryl alcohol solution into a silicon dioxide template, fully mixing, and keeping the temperature to fully polymerize;
(6) calcining the product obtained in the step (5) in an inert atmosphere to obtain the ordered mesoporous carbon @ silicon dioxide template with the hollow structure;
(7) modifying the surface of the product obtained in the step (6) by using an ammonium persulfate solution to obtain an APS-ordered mesoporous carbon @ silicon dioxide template;
(8) dissolving a phosphorus source and a metal precursor in water, adding an APS-ordered mesoporous carbon @ silicon dioxide template, stirring at room temperature, and transferring the beaker to a forced air drying oven until the mixed solution is completely dried;
(9) putting the precursor obtained in the step (8) into a muffle furnace for calcining;
(10) transferring the intermediate product obtained in the step (9) to a tubular furnace, and calcining and reducing by hydrogen; when the temperature of the tube furnace is reduced to room temperature, taking out the product;
(11) and (3) removing the silicon dioxide template in the product obtained in the step (10) by using HF or NaOH solution, and then putting the product into a freeze dryer for freeze drying to obtain the final ultra-small nickel phosphide @ mesoporous carbon composite material.
2. The method of claim 1, wherein: the amphiphilic block copolymer contained in the step (1) comprises P123, F127 and F108.
3. The method of claim 1, wherein: the silicon dioxide template in the step (3) comprises SBA-15-OH, KIT-6-OH, MCF-OH, P-SBA-15-OH, FDU-12-OH and SBA-16-OH.
4. The method of claim 1, wherein: the concentration of the hydrogen peroxide in the step (3) is 40 wt%, the water bath reaction temperature is 80 ℃, and the reaction time is 3 hours.
5. The method of claim 1, wherein: the dosage ratio of trimethylbenzene, furfuryl alcohol and oxalic acid in the step (4) is as follows: 1.0mL, 5.0 mg.
6. The method of claim 1, wherein: the polymerization method of the furfuryl alcohol-filled silicon dioxide template in the step (5) comprises the following steps: the temperature is first maintained at 50 ℃ for 1 day and then adjusted to 90 ℃ for 2 days.
7. The method of claim 1, wherein: the surface modification in the step (7) is carried out in a water bath at the temperature of 50-70 ℃; the concentration of the ammonium sulfate solution is 0.5-2.0 mol/L; the water bath time is 1-3 h.
8. The method of claim 1, wherein: in the step (8), the phosphorus source is phosphoric acid, sodium dihydrogen phosphate, sodium hypophosphite or sodium hydrogen phosphate, and the metal salt precursor is nickel nitrate, nickel chloride, nickel sulfate or nickel acetate.
9. An ultra-small nickel phosphide @ mesoporous carbon composite material is characterized in that: prepared by the process of any one of claims 1 to 8.
10. Use of the ultra-small nickel phosphide @ mesoporous carbon composite material as defined in claim 9 as an alkali metal ion battery material.
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