CN112201782A - Nickel phosphide/carbon/nickel phosphide composite material and preparation method and application thereof - Google Patents
Nickel phosphide/carbon/nickel phosphide composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a nickel phosphide/carbon/nickel phosphide composite material and a preparation method and application thereof, belonging to the technical field of materials. The material consists of hollow mesoporous carbon spheres and nickel phosphide nano-particles loaded on the inner surface and the outer surface of the hollow mesoporous carbon spheres, wherein the hollow structure in the hollow structure enables electrolyte to easily permeate into the inner area of an electrode, so that the internal resistance is reduced, and the rate capability is improved, and on the other hand, the nickel phosphide nano-particles can be simultaneously dispersed on the inner surface and the outer surface of the hollow mesoporous carbon spheres, so that the nickel phosphide is slowed downThe aggregation phenomenon among the nano particles leads the nano particles to have larger contact area with electrolyte, thereby being capable of providing more lithium ion de-intercalation and intercalation positions, more effectively improving the reversible lithium intercalation capacity of the material, being beneficial to relieving the volume expansion in the discharging/charging process, taking the composite material as the negative electrode material of the lithium ion battery, and leading the current density to be 100 mA.g‑1After circulating for 200 circles, the capacity is maintained at 465mAh g‑1. The preparation method of the composite material is simple, easy to operate, low in cost and suitable for expanded production.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a nickel phosphide/carbon/nickel phosphide composite material as well as a preparation method and application thereof.
Background
The demand of human beings is increasing, the traditional energy tends to be exhausted, and the supply and demand of human beings on the energy are not balanced. And the use of traditional energy can cause environmental pollution, so the development of green and sustainable new energy is urgently needed at the present stage. Experts have pointed out that the battery industry will gradually take a full position and occupy an important position in the energy industry, and lithium ion batteries will become one of the most ideal green power sources in the 21 st century. It is therefore self-evident that the development of lithium ion battery materials is of interest.
Lithium Ion Batteries (LIBs) are mainly used in various fields such as electric tools, electronic products, smart grid energy storage systems, mobile communication base stations, portable mobile power supplies and the like. Compared with the traditional nickel-hydrogen and nickel-cadmium batteries, the lithium ion battery has the advantages of small self-discharge, long cycle life, good safety performance and the like. Lithium ion batteries are widely used in various portable electronic devices, and although the performance of the batteries is close to the limit of the current electrode materials, the batteries still cannot meet the demand of people for high capacity. Therefore, development of high-performance lithium ion electrode materials is urgent. Since Nazar et al used metal phosphides as negative electrode materials for lithium ion batteries for the first time, researchers have prepared various high-capacity, low-polarization metal phosphides (FeP, Ni)3P、Ni2P、Co2P、CoP)。Ni2P belongs to metal-rich phosphide, has stronger metallicity and lower reaction potential, and is a lithium ion negative electrode material and a catalyst with great development prospect. When Ni is present2When P is used as a negative electrode material of a lithium ion battery, the lithium intercalation and lithium deintercalation mechanism is as follows:
in the cyclic process, metal-phosphorus (M-P)The bonds break and the volume expands causing a rapid decay in capacity. Furthermore, Ni2P has a low conductivity, which is unfavorable for Li+And the transport of electrons, resulting in a lower capacity thereof. However, by controlling the synthesis of nanomaterials with specific structures, on the one hand, Li can be shortened+A diffusion path increasing a contact area of the electrode material and the electrolyte; on the other hand, the special structure can relieve volume expansion, thereby improving the cycle performance of the electrode material. For example, Ni2Nanometer materials such as P nanometer particles and nanometer sheets have been prepared, but the performance of the nanometer materials still needs to be improved.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a nickel phosphide/carbon/nickel phosphide composite material; the second purpose is to provide a preparation method of the nickel phosphide/carbon/nickel phosphide composite material; the third purpose is to provide the application of the nickel phosphide/carbon/nickel phosphide composite material as the negative electrode material of the lithium ion battery.
In order to achieve the purpose, the invention provides the following technical scheme:
1. the composite material consists of hollow mesoporous carbon spheres and nickel phosphide nanoparticles loaded on the inner and outer surfaces of the hollow mesoporous carbon spheres.
2. The preparation method of the nickel phosphide/carbon/nickel phosphide composite material comprises the following steps:
(1) mixing SiO2Dispersing the microspheres in water, adding formaldehyde and resorcinol, stirring and reacting to obtain SiO with a core-shell structure2/resorcinol formaldehyde oligomer complex, the SiO2Washing and drying the resorcinol formaldehyde oligomer compound, and then carbonizing to obtain SiO with a core-shell structure2a/C complex, finally removing the SiO2SiO in/C composite2To prepare hollow mesoporous carbon spheres;
(2) dissolving urea, nickel nitrate and polyvinylpyrrolidone in an ethanol solution, adding the hollow mesoporous carbon spheres prepared in the step (1), performing ultrasonic dispersion, moving the mixture to a reaction kettle for reaction, taking a solid phase after the reaction is finished, and mixing the solid phase with the reaction kettleThe solid phase is washed and dried to obtain Ni (OH)2/C/Ni(OH)2；
(3) Mixing the Ni (OH) prepared in the step (2)2/C/Ni(OH)2And NaH2PO2Mixing, grinding into powder, annealing, washing and drying to obtain the nickel phosphide/carbon/nickel phosphide composite material.
Preferably, in step (1), the SiO is2The mass mol ratio of the microspheres to the formaldehyde to the resorcinol is 300-350:0.0036-0.004:0.007-0.008, and the mass mol ratio of the microspheres to the formaldehyde to the resorcinol is mg: mol; the stirring reaction time is 20-24 h.
Preferably, in the step (1), the washing is specifically: washing with water and anhydrous ethanol alternately for 2-4 times.
Preferably, in the step (1), the carbonization treatment specifically includes: subjecting the SiO2The resorcinol formaldehyde oligomer compound is washed, dried and then placed in a tube furnace, and is roasted for 3-5h at the temperature of 700-800 ℃ under the protective atmosphere.
Preferably, the protective atmosphere is argon or helium.
Preferably, in the step (1), the SiO is removed2SiO in/C composite2The method comprises the following steps: subjecting the SiO2Adding the/C compound into a sodium hydroxide solution with the concentration of 2-5mol/L for soaking for 3-5 h.
Preferably, in the step (2), the mass-to-volume ratio of the urea, the nickel nitrate, the polyvinylpyrrolidone, the hollow mesoporous carbon spheres and the ethanol solution is 80-100:10-15:80-100:1-2:8-10, and mg: mg: mg: mg: mL; the volume ratio of ethanol to water in the ethanol solution is 7-10: 1; the reaction is carried out for 12-15h at the temperature of 120-140 ℃.
Preferably, in the step (2), the washing is specifically: washing with water and anhydrous ethanol alternately for 2-4 times.
Preferably, in step (3), the Ni (OH)2/C/Ni(OH)2With NaH2PO2The mass ratio of (A) to (B) is 1: 25-30.
Preferably, in the step (3), the annealing treatment specifically includes: under the protective atmosphere, the temperature is raised to 350 ℃ at the speed of 1-5 ℃/min, and then the temperature is preserved for 3-5 h.
Preferably, the protective atmosphere is argon or helium.
Preferably, in the step (3), the washing is specifically: washing with water to remove excess NaH2PO2。
Preferably, in the step (1), the step (2) and the step (3), the drying specifically comprises: drying at 70-100 deg.C to constant weight.
3. The nickel phosphide/carbon/nickel phosphide composite material is applied as a negative electrode material of a lithium ion battery.
The invention has the beneficial effects that: the invention provides a nickel phosphide/carbon/nickel phosphide composite material and a preparation method and application thereof, the material is composed of hollow mesoporous carbon spheres and nickel phosphide nano-particles loaded on the inner surface and the outer surface of the hollow mesoporous carbon spheres, on one hand, the hollow structure in the material enables electrolyte to easily permeate into the inner area of an electrode, thereby reducing internal resistance and improving multiplying power performance, on the other hand, the nickel phosphide nano-particles can be simultaneously dispersed on the inner surface and the outer surface of the nickel phosphide nano-particles, thereby slowing down the agglomeration phenomenon among the nickel phosphide nano-particles, leading the nickel phosphide nano-particles to have larger contact area with the electrolyte, further providing more positions for lithium ion de-intercalation and intercalation, more effectively improving the reversible lithium intercalation capacity of the material, being beneficial to relieving volume expansion in the discharging/charging process, and controlling the loading capacity of the nickel phosphide nano-particles on the inner surface and the outer surface of the hollow mesoporous carbon spheres by controlling the preparation process conditions, thereby further improving the electrochemical performance of the composite material. The composite material is used as a lithium ion battery cathode material and has a current density of 100 mA-g-1After circulating for 200 circles, the capacity is maintained at 465mAh g-1. The preparation method of the composite material is simple, easy to operate, low in cost and suitable for expanded production.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objectives and other advantages of the invention may be realized and attained by the means of the instrumentalities and combinations particularly pointed out hereinafter.
Drawings
For the purposes of promoting a better understanding of the objects, aspects and advantages of the invention, reference will now be made to the following detailed description taken in conjunction with the accompanying drawings in which:
FIG. 1 shows Ni (OH) prepared in example 12/C/Ni(OH)2And Ni2P/C/Ni2XRD pattern of P (a, b are sequentially Ni (OH))2/C/Ni(OH)2And Ni2P/C/Ni2XRD pattern of P);
FIG. 2 shows Ni (OH) prepared in example 12/C/Ni(OH)2And Ni2P/C/Ni2A Raman spectrum of P;
FIG. 3 is SiO prepared in example 12/C composite, hollow mesoporous carbon sphere, Ni (OH)2/C/Ni(OH)2And Ni2P/C/Ni2SEM image of P (a, b, c, d are SiO in order2/C composite, hollow mesoporous carbon sphere, Ni (OH)2/C/Ni(OH)2And Ni2P/C/Ni2SEM image of P);
FIG. 4 shows Ni prepared in example 12P/C/Ni2TEM image of P at different magnifications;
FIG. 5 shows Ni prepared in example 12P/C/Ni2The voltage of the lithium ion battery with P as the cathode material is 0.005-3.0V, and the scanning rate is 0.5mV-1CV curves measured under the conditions;
FIG. 6 shows Ni prepared in example 12P/C/Ni2The voltage of the lithium ion battery with P as the cathode material is 0.005-3.0V, and the current density is 100 mA-g-1A charge-discharge voltage curve chart measured under the condition;
FIG. 7 shows Ni prepared in example 12P/C/Ni2The voltage of the lithium ion battery with P as the cathode material is 0.005-3.0V, and the current density is 100 mA-g-1A measured cycle performance profile under the conditions;
FIG. 8 shows Ni prepared in example 12P/C/Ni2The voltage of the lithium ion battery with P as the cathode material is 0.005-3.0V, and different currentsA multiplying power performance curve chart measured under the condition of density;
FIG. 9 shows Ni prepared in example 12P/C/Ni2P is an electrochemical impedance spectrum test result graph of the lithium ion battery with the cathode material;
fig. 10 is an equivalent analog circuit diagram.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Example 1
Preparation of nickel phosphide/carbon/nickel phosphide composite material
(1) Mixing SiO2Dispersing the microspheres in water, adding formaldehyde and resorcinol, stirring and reacting for 24h to obtain SiO with a core-shell structure2/Resorcinol Formaldehyde oligomer Complex in which SiO2The mass mol ratio of the microspheres to the formaldehyde to the resorcinol is 300:0.0036:0.007, and the mass mol ratio of the microspheres to the formaldehyde to the resorcinol is mg: mol, mixing SiO2Washing resorcinol formaldehyde oligomer compound with distilled water and anhydrous ethanol for 4 times alternately, drying at 70 deg.C to constant weight, and calcining in a tube furnace at 700 deg.C under argon atmosphere for 5 hr to obtain SiO with core-shell structure2a/C complex, finally SiO2Adding 2mol/L sodium hydroxide solution into the/C compound to soak for 5 hours to remove SiO2SiO in/C composite2To prepare hollow mesoporous carbon spheres;
(2) dissolving urea, nickel nitrate and polyvinylpyrrolidone in an ethanol solution (the volume ratio of ethanol to water is 7:1), adding the hollow mesoporous carbon spheres prepared in the step (1), wherein the mass volume ratio of the urea, the nickel nitrate, the polyvinylpyrrolidone, the hollow mesoporous carbon spheres to the ethanol solution is 100:10:100:1:8, mg: mg: mg: mL, ultrasonically dispersing for 1h, transferring the mixture into a reaction kettle, reacting for 12h at 120 ℃, centrifuging after the reaction is finished, and taking out a solidPhase, washing the solid phase with distilled water and anhydrous ethanol alternately for 3 times, drying at 70 deg.C to constant weight to obtain Ni (OH)2/C/Ni(OH)2；
(3) Mixing the Ni (OH) prepared in the step (2)2/C/Ni(OH)2And NaH2PO2Mixing according to the mass ratio of 1:30, grinding into powder, heating to 300 ℃ at the speed of 1 ℃/min in the argon atmosphere, preserving heat for 3h, and finally washing with distilled water until redundant NaH is removed2PO2Then, the mixture is dried to constant weight at 70 ℃ to prepare the nickel phosphide/carbon/nickel phosphide composite material (Ni)2P/C/Ni2P)。
In FIG. 1, a and b are Ni (OH) prepared in example 1 in this order2/C/Ni(OH)2And Ni2P/C/Ni2XRD pattern of P, diffraction peak in a in figure 1 belongs to Ni (OH)2(ii) a The diffraction peak in b in FIG. 1 belongs to Ni2P。
FIG. 2 shows Ni (OH) prepared in example 12/C/Ni(OH)2And Ni2P/C/Ni2Raman spectrum of P, as shown in FIG. 2, Ni (OH)2/C/Ni(OH)2And Ni2P/C/Ni2P is each about 1361cm in wave number-1And 1583cm-1There are two peaks, corresponding to the carbon D and G peaks, respectively. I isD/IGThe value of (the ratio of the intensity of the D peak to the intensity of the G peak) may reflect the degree of crystallinity of the carbon, since the D peak value is significantly less than the G peak value in the figures, indicating that the degree of crystallinity of the carbon is higher in both products.
In FIG. 3, a, b, c and d are SiO prepared in the example 12/C composite, hollow mesoporous carbon sphere, Ni (OH)2/C/Ni(OH)2And Ni2P/C/Ni2SEM image of P, from FIG. 3, SiO2the/C composite has a regular spherical shape, the average size of the hollow mesoporous carbon spheres is between 200 and 400nm, Ni (OH)2/C/Ni(OH)2In (Ni (OH))2The nano-sheet grows on the surface of the carbon sphere uniformly, Ni2P/C/Ni2The surface of the P medium carbon sphere is loaded with a large amount of Ni2P nanoparticles with little cracked Ni2P/C/Ni2P shows that the inner cavity of the tube is also loaded with Ni2P nanoparticles.
In FIG. 4, a and b are Ni prepared in example 12P/C/Ni2TEM image of P at different magnifications, Ni is shown in FIG. 42P/C/Ni2Ni in P2The P nano particles are distributed on the surface and the inner cavity of the hollow mesoporous carbon sphere, the distribution mode can shorten the transmission distance of Li ions, slow down the agglomeration phenomenon among nano particles, has larger contact area with an electrolyte, can provide more positions for lithium ion de-intercalation and intercalation, more effectively improves the reversible lithium intercalation capacity of the material, and is favorable for relieving the volume expansion in the discharging/charging process.
Ni prepared in example 12P/C/Ni2And mixing the P, the carbon black and a carboxymethyl cellulose adhesive (CMC) according to a mass ratio of 7:2:1, adding the mixture into distilled water to obtain slurry, coating the slurry on a copper foil, and drying to obtain the working electrode. The reference electrode (metal lithium), the diaphragm and the prepared working electrode are moved into a glove box filled with argon gas to assemble the lithium ion button cell, the model of the used button cell is CR2032, the model of the diaphragm is porous Celgard 2300, and the electrolyte of the lithium ion cell is 1mol/L LiPF6(the solvent was Ethylene Carbonate (EC) and diethyl carbonate (DEC) mixed in a volume ratio of 1: 1), and after assembly, the cell was removed from the glove box.
Using cyclic voltammetry at a voltage of 0.005-3.0V and a scan rate of 0.5mV · s-1The CV curve of the above cell was measured under the conditions shown in FIG. 5, and it was found that a peak was generated at 0.71V during the first discharge, which was caused by two reactions, one of which was Ni2P/C/Ni2Li in P+The corresponding reaction is: ni2P+3Li++3e-→Li3P +2Ni, another is associated with some irreversible reactions, such as decomposition of the electrolyte and formation of a solid electrolyte interface (SEI film); after the first discharge, the reduction peak of the second turn was shifted to 1.43V, and the reduction peaks of the third to fifth turns were shifted to 1.57V, which was caused by the SEI film effect. During charging, its oxidation peak is always at 1.25V, its formation is associated with Li+From Li3P in de-intercalationIn this regard, the corresponding reactions are: li3P+2Ni→Ni2P+3Li++3e-。
Using cyclic voltammetry at a voltage of 0.005-3.0V and a current density of 100 mA-g-1The charging and discharging voltage curve of the battery was measured under the conditions, as shown in fig. 6, it can be seen that the voltage plateau was at 1.35V during the first discharging, there was no significant voltage plateau thereafter, and there was no significant voltage plateau during the charging. In the first charge-discharge cycle, Ni2P/C/Ni2P has a specific discharge capacity of 696 mAh.g-1The charging specific capacity is 470mAh g-1. In this process, the capacity reduction results from irreversible processes such as SEI film formation and decomposition of an electrolyte. The charge-discharge capacity at the 200 th cycle was higher than that at the 50 th and 100 th cycles, because the electrode material was activated during the cycles and the decomposition of the electrolyte produced a polymer/gel film.
At a voltage of 0.005-3.0V and a current density of 100mA g-1The cycle performance curve of the above-mentioned battery was measured under the conditions shown in FIG. 7, and it was found that Ni2P/C/Ni2The specific discharge capacity of P is still maintained at 465mAh g after 200 times of circulation-1And there is no tendency to decay because of the material Ni2P nano-particles are distributed on the surface and the inner cavity of the hollow mesoporous carbon sphere, so that Ni is slowed down2The aggregation phenomenon among the P nano particles has larger contact area with the electrolyte, so that more positions for lithium ion de-intercalation and intercalation can be provided, and the reversible lithium intercalation capacity of the material can be more effectively improved.
The rate performance curve of the battery was measured under the conditions of voltage of 0.005-3.0V and different current density, and as shown in FIG. 8, it can be seen that when the current density was from 100mA g-1、200mA·g-1、300mA·g-1、500mA·g-1Change to 1000mA g-1When the discharge capacity is 385mAh g-1、294mAh·g-1、264mAh·g-1、218mAh·g-1And 185 mAh. g-1The final current density is recovered to 100mAh g-1The capacity is 375mAh g-1. Thus, Ni2P/C/Ni2P has good rate capability.
The Electrochemical Impedance Spectroscopy (EIS) test was performed on the above-mentioned battery at a frequency ranging from 0.1 to 10000Hz, and the results are shown in FIG. 9, FIG. 10 is an equivalent simulation circuit diagram, and the curve in FIG. 9 is composed of a semicircle of a high frequency region and a diagonal line of a low frequency region, wherein the diameter of the semicircle and the lithium ion charge transfer resistance (R) arect) And Li+Transmission resistance (R) on SEI filmf) The slope of the slope is related to the diffusion rate (Z) of lithium ions in the solidw) Regarding, Ni is known from the equivalent analog circuit diagram2P/C/Ni2The Rct value of P is 160.9 Ω, which has good conductivity.
Example 2
Preparation of nickel phosphide/carbon/nickel phosphide composite material
(1) Mixing SiO2Dispersing the microspheres in water, adding formaldehyde and resorcinol, stirring and reacting for 20h to obtain SiO with a core-shell structure2/Resorcinol Formaldehyde oligomer Complex in which SiO2The mass mol ratio of the microspheres to the formaldehyde to the resorcinol is 350:0.0038:0.008, mg: mol, mixing SiO2The resorcinol formaldehyde oligomer compound is alternately washed by distilled water and absolute ethyl alcohol for 3 times, dried to constant weight at 85 ℃, and then roasted for 3 hours in a tubular furnace at 800 ℃ under helium atmosphere to prepare SiO with a core-shell structure2a/C complex, finally SiO2Adding 3mol/L sodium hydroxide solution into the/C compound to soak for 4 hours to remove SiO2SiO in/C composite2To prepare hollow mesoporous carbon spheres;
(2) dissolving urea, nickel nitrate and polyvinylpyrrolidone in an ethanol solution (the volume ratio of ethanol to water is 8:1), adding the hollow mesoporous carbon spheres prepared in the step (1), wherein the mass volume ratio of the urea, the nickel nitrate, the polyvinylpyrrolidone, the hollow mesoporous carbon spheres to the ethanol solution is 80:12:90:1:9, mg: mg: mg: mL, ultrasonically dispersing for 1h, transferring the mixture into a reaction kettle to react for 15h at 130 ℃, centrifuging after the reaction is finished, taking a solid phase, alternately washing the solid phase for 2 times by using distilled water and absolute ethanol, and drying at 85 ℃ to constant weight to obtain Ni (OH)2/C/Ni(OH)2；
(3) Mixing the Ni (OH) prepared in the step (2)2/C/Ni(OH)2And NaH2PO2Mixing according to the mass ratio of 1:25, grinding into powder, heating to 320 ℃ at the speed of 3 ℃/min in the atmosphere of helium, preserving heat for 5 hours, and finally washing with distilled water until redundant NaH is removed2PO2Then, the mixture is dried to constant weight at 85 ℃ to prepare the nickel phosphide/carbon/nickel phosphide composite material (Ni)2P/C/Ni2P)。
Example 3
Preparation of nickel phosphide/carbon/nickel phosphide composite material
(1) Mixing SiO2Dispersing the microspheres in water, adding formaldehyde and resorcinol, stirring and reacting for 22h to obtain SiO with a core-shell structure2/Resorcinol Formaldehyde oligomer Complex in which SiO2The mass mol ratio of the microspheres to the formaldehyde to the resorcinol is 320:0.004:0.007, and the mass mol ratio of the microspheres to the formaldehyde to the resorcinol is mg: mol2Washing resorcinol formaldehyde oligomer compound with distilled water and anhydrous ethanol for 2 times alternately, drying at 100 deg.C to constant weight, and calcining in a tube furnace at 750 deg.C under argon atmosphere for 4 hr to obtain SiO with core-shell structure2a/C complex, finally SiO2Adding 5mol/L sodium hydroxide solution into the/C compound to soak for 3 hours to remove SiO2SiO in/C composite2To prepare hollow mesoporous carbon spheres;
(2) dissolving urea, nickel nitrate and polyvinylpyrrolidone in an ethanol solution (the volume ratio of ethanol to water is 10:1), adding the hollow mesoporous carbon spheres prepared in the step (1), wherein the mass volume ratio of the urea, the nickel nitrate, the polyvinylpyrrolidone, the hollow mesoporous carbon spheres to the ethanol solution is 90:15:80:2:10, mg: mg: mg: mL, ultrasonically dispersing for 1h, transferring the mixture into a reaction kettle, reacting for 13h at 140 ℃, centrifuging after the reaction is finished, taking a solid phase, alternately washing the solid phase for 4 times by using distilled water and absolute ethanol, and drying at 100 ℃ to constant weight to obtain Ni (OH)2/C/Ni(OH)2；
(3) Mixing the Ni (OH) prepared in the step (2)2/C/Ni(OH)2And NaH2PO2Mixing and grinding according to the mass ratio of 1:30Grinding into powder, heating to 350 deg.C at a rate of 5 deg.C/min under argon atmosphere, maintaining the temperature for 4h, and washing with distilled water to remove excessive NaH2PO2Then, the mixture is dried to constant weight at 100 ℃ to prepare the nickel phosphide/carbon/nickel phosphide composite material (Ni)2P/C/Ni2P)。
Finally, the above embodiments are only intended to illustrate the technical solutions of the present invention and not to limit the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all of them should be covered by the claims of the present invention.
Claims (10)
1. The nickel phosphide/carbon/nickel phosphide composite material is characterized by comprising hollow mesoporous carbon spheres and nickel phosphide nanoparticles loaded on the inner surfaces and the outer surfaces of the hollow mesoporous carbon spheres.
2. A method for preparing a nickel phosphide/carbon/nickel phosphide composite material as defined in claim 1, which comprises the steps of:
(1) mixing SiO2Dispersing the microspheres in water, adding formaldehyde and resorcinol, stirring and reacting to obtain SiO with a core-shell structure2/resorcinol formaldehyde oligomer complex, the SiO2Washing and drying the resorcinol formaldehyde oligomer compound, and then carbonizing to obtain SiO with a core-shell structure2a/C complex, finally removing the SiO2SiO in/C composite2To prepare hollow mesoporous carbon spheres;
(2) dissolving urea, nickel nitrate and polyvinylpyrrolidone in an ethanol solution, adding the hollow mesoporous carbon spheres prepared in the step (1), performing ultrasonic dispersion, moving the mixture to a reaction kettle for reaction, taking a solid phase after the reaction is finished, washing and drying the solid phase to obtain Ni (OH)2/C/Ni(OH)2；
(3) Mixing the Ni (OH) prepared in the step (2)2/C/Ni(OH)2And NaH2PO2Mixing, grinding into powder, annealing, washing and drying to obtain the nickel phosphide/carbon/nickel phosphide composite material.
3. The method of claim 2, wherein in step (1), the SiO is2The mass mol ratio of the microspheres to the formaldehyde to the resorcinol is 300-350:0.0036-0.004:0.007-0.008, and the mass mol ratio of the microspheres to the formaldehyde to the resorcinol is mg: mol; the stirring reaction time is 20-24 h.
4. The method according to claim 2, wherein in the step (1), the carbonization treatment is specifically: subjecting the SiO2The resorcinol formaldehyde oligomer compound is washed, dried and then placed in a tube furnace, and is roasted for 3-5h at the temperature of 700-800 ℃ under the protective atmosphere.
5. The method of claim 2, wherein in step (1), the SiO is removed2SiO in/C composite2The method comprises the following steps: subjecting the SiO2Adding the/C compound into a sodium hydroxide solution with the concentration of 2-5mol/L for soaking for 3-5 h.
6. The method of claim 2, wherein in step (2), the mass-to-volume ratio of the urea, the nickel nitrate, the polyvinylpyrrolidone, the hollow mesoporous carbon spheres and the ethanol solution is 80-100:10-15:80-100:1-2:8-10, mg: mg: mg: mg: mL; the volume ratio of ethanol to water in the ethanol solution is 7-10: 1; the reaction is carried out for 12-15h at the temperature of 120-140 ℃.
7. The method according to claim 2, wherein in the step (3), the Ni (OH)2/C/Ni(OH)2With NaH2PO2The mass ratio of (A) to (B) is 1: 25-30.
8. The method according to claim 2, wherein in the step (3), the annealing treatment is specifically: under the protective atmosphere, the temperature is raised to 350 ℃ at the speed of 1-5 ℃/min, and then the temperature is preserved for 3-5 h.
9. The method according to claim 2, wherein in the step (1), the step (2) and the step (3), the drying is specifically: drying at 70-100 deg.C to constant weight.
10. The use of a nickel phosphide/carbon/nickel phosphide composite material as described in claim 1 as a negative electrode material for a lithium ion battery.
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