CN113460983A - Self-supporting transition metal phosphide/carbon composite material film, preparation method and application thereof, and battery - Google Patents
Self-supporting transition metal phosphide/carbon composite material film, preparation method and application thereof, and battery Download PDFInfo
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Abstract
The invention relates to a self-supporting transition metal phosphide/carbon composite material film, a preparation method and application thereof, and a battery, comprising the following steps: (1) dissolving a transition metal compound and carboxylate in polyol, stirring uniformly, heating and refluxing, and then cooling to obtain a transition metal alkoxide precursor; (2) cleaning the obtained transition metal alkoxide precursor by using an organic solvent, uniformly dispersing the transition metal alkoxide precursor in the organic solvent to form precursor dispersion liquid, then carrying out organic solvent evaporation treatment, and self-assembling in the organic solvent evaporation process to obtain a self-supporting transition metal alkoxide precursor film; (3) and respectively placing the precursor film and a phosphorus source into two containers, carrying out heating decomposition and simultaneous phosphorization under the atmosphere of protective gas, finally carrying out in-situ conversion to obtain the self-supporting transition metal phosphide/carbon composite material film, and directly applying the film as an electrode plate to a lithium ion battery or a sodium ion battery.
Description
Technical Field
The invention relates to the technical field of ion batteries, in particular to a self-supporting transition metal phosphide/carbon composite material film, a preparation method and application thereof, and a battery.
Background
In recent years, with the increasing demand for small-sized power supplies for precision devices such as electric vehicles, unmanned aerial vehicles, radio communication, medical instruments, portable electronic devices, and the like, people have made higher demands for energy density of lithium ion batteries. Among the components of a lithium ion battery, the capacity of the negative electrode plays an important role in the energy density of the lithium ion battery. However, a large amount of non-electrochemical active conductive agent and binder are required to be introduced in the process of preparing the cathode by using the traditional powder cathode material, so that the preparation process is complicated and time-consuming, the content of the active material in the cathode is reduced, the internal resistance is increased, and the actual capacity, rate capability and cycle life of the cathode are further obviously reduced. Numerous studies have shown that: the additive-free self-supporting negative electrode material is an effective way to avoid using a conductive agent and a binder, improve the energy density of a negative electrode, and simultaneously ensure good conductivity, lithium ion diffusion capacity and structural stability, and has the potential of meeting the market demand of small-size lithium ion batteries.
Because the theoretical capacity of the traditional commercial graphite negative active material is too low (only 372mAh g)-1) Transition metal phosphides (TMPs, M ═ Fe, Ni, Co, Cu, etc.) rely on their high theoretical capacity (500mAh · g)-1The above), high reactivity, low reaction potential, safety, low cost, etc. become one of the negative active materials with great attraction and development prospects. In addition, the electrochemical reaction products of TMPs have higher ionic conductivity (e.g., Li at room temperature) than reaction products of other conversion-type active materials such as oxides, sulfides3P：>10-4S cm-1，Li2O：5×10-8S cm-1，Li2S：10-13S cm-1) Thereby being beneficial to maintaining the high cycle reversibility of the cathode material.
The self-supporting TMPs/carbon composite negative electrode material constructed based on the high theoretical capacity TMPs can effectively improve the energy density of the lithium ion battery, but the practical application of the self-supporting TMPs/carbon composite negative electrode material still faces a bottleneck': low electron conductivity of TMPs and low rate performance and low cycle life due to large volume expansion (> 200%) during charge and discharge. Therefore, the self-supporting TMPs/carbon composite negative electrode material must have multiple functions such as effective electron transport network/ion diffusion channel and TMPs active material stable carrier to exert the advantage of high theoretical capacity of the TMPs active material. Unfortunately, the traditional construction scheme of the self-supporting TMPs/carbon composite negative electrode material still faces the problems of unreasonable composite mode, rough composite structure, complex preparation process, high cost, weak structure regulation capability and the like. Therefore, how to simply and effectively realize the densification and uniformity of the carbon self-supporting framework and the stable compounding and efficient utilization of the TMPs active materials are key problems for realizing the high-rate performance and high-cycle-life battery.
Disclosure of Invention
In order to solve the technical problems of how to simply and effectively realize the densification and uniformity of a carbon self-supporting framework and the stable compounding and efficient utilization of TMPs active materials, a self-supporting transition metal phosphide/carbon composite material film, a preparation method and application thereof and a battery are provided. The method can simultaneously realize the compactness and uniformity of the carbon self-supporting framework and the stable compounding and efficient utilization of TMPs active materials.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the preparation method of the self-supporting transition metal phosphide/carbon composite material film comprises the following steps:
(1) dissolving a transition metal compound and carboxylate in polyol, stirring uniformly, heating and refluxing, and then cooling to room temperature to obtain a transition metal alkoxide precursor;
(2) cleaning the obtained transition metal alkoxide precursor by using an organic solvent, uniformly dispersing the transition metal alkoxide precursor in the organic solvent to form precursor dispersion liquid, then carrying out organic solvent evaporation treatment, and self-assembling in the organic solvent evaporation process to obtain a self-supporting transition metal alkoxide precursor film;
(3) and respectively placing the precursor film and a phosphorus source into two containers, carrying out heating decomposition and simultaneous phosphorization under a protective gas atmosphere, and finally carrying out in-situ conversion to obtain the self-supporting transition metal phosphide/carbon composite material film.
Further, the transition metal compound is at least one of an iron-containing compound, a nickel-containing compound, a copper-containing compound and a cobalt-containing compound; the carboxylate is at least one of potassium acetate, sodium propionate, sodium oleate and sodium caprate, preferably the carboxylate is potassium acetate; the polyalcohol is at least one of ethylene glycol, propylene glycol, diethylene glycol, glycerol and pentaerythritol, and preferably the polyalcohol is glycerol; the phosphorus source is at least one of phosphorus, sodium hypophosphite, phosphine, tri-n-octylphosphorus and triphenylphosphine.
Still further, the transition metal compound is an iron-containing compound and a nickel-containing compound, and is configured according to any proportion, preferably the molar ratio of the iron-containing compound to the nickel-containing compound is (0.1-0.5): (0.5-1); the iron-containing compound is at least one of ferric acetate, ferric chloride, ferric sulfate and ferric acetylacetonate, preferably the iron-containing compound is ferric acetate; the nickel-containing compound is at least one of nickel acetate, nickel chloride, nickel sulfate and nickel nitrate, preferably the nickel-containing compound is nickel acetate;
the transition metal compound, the carboxylate and the polyol are used in the proportion of (0.1-2) mol of (5-100) L, preferably in the proportion of (0.6-1.5) mol of (2-10) L; the stirring speed in the step (1) is 300-1000 rpm, the stirring time is 1-6 h, the preferred stirring speed is 400-700 rpm, the preferred stirring time is 1-3 h, the optimal stirring speed is 600rpm, and the optimal stirring time is 1 h;
in the step (1), heating and refluxing are carried out by heating to 160-220 ℃ at a heating rate of 0.1-10 ℃/min, preserving heat and refluxing, wherein the heating time is 5 min-2 h; preferably, the heating rate is 1-7 ℃/min, the preferred heat preservation temperature is 190-210 ℃, and the preferred heating time is 20 min-1 h; the optimal heating rate is 6 ℃/min, the optimal heat preservation temperature is 200 ℃, and the optimal heating time is 20 min.
Further, in the step (2), the organic solvent is at least one of methanol, ethanol, chloroform, acetone, ether, carbon tetrachloride and dichloromethane, and the cleaning process is to repeatedly carry out centrifugal cleaning for 1-5 times by adopting the organic solvent, wherein the centrifugal rotating speed is 1000-6000 rpm, and the centrifugal time is 2 min-1 h; the concentration of the precursor dispersion liquid is 2-50 g/L, and the concentration of the precursor dispersion liquid is optimally 5 g/L;
preferably, the organic solvent is at least one of methanol and ethanol, and preferably, the repeated centrifugal cleaning is carried out for 2-4 times, the centrifugal rotating speed is 2000-5000 rpm, and the centrifugal time is 20 min-1 h.
Further, the organic solvent evaporation treatment in the step (2) is carried out in a vacuum centrifugal concentrator for vacuum centrifugation-solvent evaporation for 0.5-4 h, namely, under the condition that the vacuum degree is 0.1mbar, the organic solvent is heated and evaporated under the centrifugal rotating speed of 500-2000rpm, and the temperature of the heating and evaporation is 20-80 ℃;
preferably, the centrifugal speed of the vacuum centrifugation-solvent evaporation is 1000rpm, the temperature of the heating evaporation is 40 ℃, and the time of the vacuum centrifugation-solvent evaporation is 1 h.
Further, the mass ratio of the precursor film to the phosphorus source in the step (3) is 1 (0.1-10); the protective gas is nitrogen or argon, the heating decomposition is carried out by heating to 300-1000 ℃ at a heating rate of 0.1-10 ℃/min and keeping the temperature for 30-8 h, preferably, the heating rate is 1-10 ℃/min, the keeping temperature is 300-600 ℃, and the keeping time is 30 min-2 h;
and (3) respectively placing the precursor film and the phosphorus source into two containers, then placing the containers into a tubular furnace, and placing the containers with the phosphorus source into an upper tuyere of the tubular furnace before carrying out heating decomposition and phosphorization.
In another aspect, the present invention provides a self-supporting transition metal phosphide/carbon composite material thin film prepared by the above preparation method, wherein the carbon material is a porous carbon nanosheet having a graphene-like layered structure into which the transition metal phosphide is attached.
Further, the self-supporting transition metal phosphide/carbon composite material film is a Fe-Ni-P transition metal phosphide/carbon composite material film. The preparation method provided by the invention is also applicable to other transition metals except Fe and Ni.
The third aspect of the invention provides an application of the self-supporting transition metal phosphide/carbon composite material film prepared by the preparation method in a battery, wherein the self-supporting transition metal phosphide/carbon composite material film is directly used as an electrode plate of the battery.
The battery comprises the self-supporting transition metal phosphide/carbon composite material film prepared by the preparation method as an electrode plate, and the battery comprises a lithium ion battery and a sodium ion battery.
The self-supporting transition metal phosphide/carbon composite material film is prepared by the method, the transition metal is iron and nickel as an example, the prepared composite material film is the Fe-Ni-P transition metal phosphide/carbon composite material film, wherein the carbon material is a porous carbon nanosheet with a graphene-like layered structure, fine Fe-Ni-P nanoparticles are densely embedded in the layered structure of the nanosheet, the size of the Fe-Ni-P nanoparticles is 1-900 nm, and the thickness of the porous carbon nanosheet is 5 nm-1 mu m. The invention adopts the unique space confinement effect of the carbon substrate generated in situ to ensure that Fe-Ni-P nano particles are stably embedded in the densely stacked carbon nano sheets. The preparation method comprises the steps of synthesizing an ultrathin Fe-Ni composite alkoxide nanosheet precursor with a graphene-like structure by using carboxylic acid to regulate and control the complexation of polyhydric alcohol on transition metal ions under a high-temperature condition, then realizing the self-assembly of graphene-like Fe-Ni composite alkoxide nanosheets on a liquid-vacuum interface by using a vacuum centrifugation-solvent evaporation process to obtain a Fe-Ni composite alkoxide film, and finally carrying out condition-controlled thermal decomposition and phosphorization in-situ conversion on the self-supporting Fe-Ni composite alkoxide film to obtain the self-supporting Fe-Ni-P/carbon composite material film. The porous carbon nanosheets with graphene-like structures provide reliable electron transmission networks and volume expansion buffer layers for Fe-Ni-P nanoparticles with uniform and fine internal sizes. The composite material film can be directly used as an electrode plate to be applied to lithium ion batteries or sodium ion batteries and the like.
Compared with the prior art, the invention has the following beneficial technical effects:
(1) because the metal alkoxide has a complex structure and different growth properties from those of a common crystal, the microstructure of the metal alkoxide at present is mostly in the shapes of flowers, spheres, polyhedrons and the like, which have smaller specific surface area and are not beneficial to compact and stable assembly. The Fe-Ni composite alkoxide with a layered structure in the invention is Fe3+And Ni2+The ions are exposed in the c-axis direction, and anions on the carboxylate and the exposed transition metal ions are chelated and attached to the (001) surface of the Fe-Ni composite alkoxide, so that the growth and agglomeration of the Fe-Ni composite alkoxide in the c-axis direction can be effectively inhibited, and the ultrathin Fe-Ni composite alkoxide nanosheet with the graphene-like layered structure can be obtained simply in one step. Namely, the carboxylate added in the method plays a role in regulating and controlling the precursor transition metal composite alkoxide to form a nanosheet with a graphene-like structure, and finally the composite material film with the graphene-like structure is obtained.
(2) Most of the traditional nano TMPs/carbon composite materials are powder materials, and the low tap density characteristic of the powder materials causes that a large amount of non-electrochemical active conductive agents (such as conductive carbon black, acetylene and the like) and binders (such as PVDF and the like) need to be added in the practical application of the lithium ion battery. However, the invention firstly carries out vacuum centrifugation-solvent evaporation on the prepared Fe-Ni composite alkoxide nano-sheet with a graphene-like structure to generate induction and enable the nano-sheet to be self-assembled, and then the nano-sheet is converted into a porous carbon nano-sheet densely embedded with fine transition metal phosphide in situ through thermal decomposition and a phosphorization process, thereby constructing the self-supporting thin film electrode material. In the process of vacuum centrifugation-solvent evaporation, the solvent is quickly evaporated to generate huge surface tension, the combination of the surface tension and the centrifugal force promotes the compact and stable assembly of the product, and if only vacuum centrifugation or solvent evaporation is adopted, the product is loosely assembled, the structure is unstable, and even the assembly cannot be successful. The self-supporting transition metal phosphide/carbon composite material film can effectively improve the capacity, the rate capability and the cycle life of the battery because the film can be directly used for a lithium ion battery as a negative pole piece without adding other conductive agents or binders.
(3) The invention adopts the controllable preparation-effective assembly-in-situ conversion strategy of Fe-Ni composite alkoxide with a graphene-like structure to realize the preparation of the self-supporting Fe-Ni-P/carbon composite material film with high rate performance and long cycle life, and the prepared material is directly used as the electrode plate of the battery. The invention improves the rate capability and the cycle life of the traditional transition metal phosphide by the following structural design. Firstly, a self-supporting film is constructed by layer-by-layer stacking and assembling of ultrathin Fe-Ni-P/carbon composite nanosheets with graphene-like structures to serve as a negative electrode so as to improve the rate capacity of the battery; the porous carbon nanosheet structure with the developed pore structure has a large specific surface area, so that the blockage of an ion diffusion channel possibly caused by close packing is avoided, the fine Fe-Ni-P transition metal phosphide nanoparticles uniformly embedded in the porous carbon nanosheets further enhance the transmission/diffusion capability of electrons/ions in the self-supporting material, and the graphene-like structural unit with the large specific surface area increases the electrochemical reaction active site of the battery and the contact area of a negative electrode and an electrolyte, so that the structural characteristics of the material are favorable for improving the multiplying power performance of the battery; the volume expansion in the charging and discharging process is relieved through the compounding of the Fe-Ni double transition metal phosphide, and a reliable volume expansion buffer layer is provided by the uniform coating of the porous carbon layer on the fine Fe-Ni-P nano particles, so that the structural stability is improved to obtain a high cycle life; the prepared self-supporting Fe-Ni-P/carbon composite material film has excellent cycle stability and high rate performance in the electrochemical cycle process as the cathode material of the lithium ion battery.
(4) The invention has the advantages of low cost of raw materials and equipment, simple and controllable operation condition and easy amplification.
Drawings
FIG. 1 is a schematic diagram showing the formation of a self-supporting Fe-Ni-P/carbon composite thin film material obtained in example-3.
Fig. 2 is an FESEM view of the prepared ultrathin Fe-Ni composite alkoxide precursor nanosheet obtained in step (1) of example 1.
FIG. 3 is a FESEM image of a self-supporting Fe-Ni-P/carbon composite film finally obtained in example 1.
FIG. 4 is a TEM image of the Fe-Ni-P/carbon composite nanosheet structural units in the self-supporting Fe-Ni-P/carbon composite thin film finally prepared in example 1.
FIG. 5 shows the temperature of 4A g of the lithium ion battery prepared by using the self-supporting Fe-Ni-P/carbon composite film finally prepared in example 1 as the negative electrode-1Cycling performance under current density conditions.
FIG. 6 is an FESEM (A) diagram of Fe-Ni composite alkoxide precursor nanosheets prepared in step (1) of example 2, and a TEM (B) diagram of Fe-Ni-P/carbon composite nanosheet structural units in the Fe-Ni-P/carbon composite thin film.
FIG. 7 shows the temperature of 4A g of the lithium ion battery prepared by using the self-supporting Fe-Ni-P/carbon composite film finally prepared in example 3 as the negative electrode-1FESEM images of the films after 500 cycles under current density conditions.
Fig. 8 is a FESEM view of the structural morphology of the alkoxide assembled product obtained in comparative example 1 through step (2) self-assembly-solvent evaporation.
FIG. 9 is a FESEM image of the structural morphology of the alkoxide product obtained in comparative example 2 through step (1).
FIG. 10 is a FESEM image of the structural morphology of the alkoxide product of comparative example 3 obtained through step (1).
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention and the accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless specifically stated otherwise, the numerical values set forth in these examples do not limit the scope of the invention. Techniques, methods known to those of ordinary skill in the relevant art may not be discussed in detail, but are intended to be part of the specification where appropriate. In all examples shown and discussed herein, any particular value should be construed as merely illustrative, and not limiting. Thus, other examples of the exemplary embodiments may have different values.
The experimental methods of the following examples, which are not specified under specific conditions, are generally determined according to national standards; if no corresponding national standard exists, the method is carried out according to the universal international standard or the standard requirement proposed by related enterprises. Unless otherwise indicated, all parts are parts by weight and all percentages are percentages by weight.
Example 1
The self-supporting transition metal phosphide/carbon composite material film of the embodiment is a self-supporting Fe-Ni-P/carbon composite film, and the preparation method comprises the following steps:
(1) weighing 0.5mmol of iron acetate, 1mmol of nickel acetate and 5mmol of potassium acetate, dissolving in 50mL of glycerol, stirring at the stirring speed of 700rpm for 2h to obtain a mixed solution, transferring the mixed solution to a 100mL round-bottom flask, heating to 200 ℃ at the heating rate of 6 ℃/min, heating at the temperature and refluxing for 20min, and naturally cooling to room temperature to obtain a Fe-Ni composite alkoxide precursor;
alcohol Heat Generation in step 1The thermal reaction of alcohol can generate hydrogen ion as by-product to corrode alkoxide product, but the invention generates OH by hydrolyzing strong alkali and weak acid salt—Neutralize H+A byproduct, thereby protecting the alkoxide product; on the other hand, the carboxyl of the carboxylate is adsorbed on the surface of the alkoxide product, so that the appearance is regulated and controlled;
(2) repeatedly centrifuging and cleaning the obtained Fe-Ni composite alkoxide precursor with ethanol for 4 times, wherein the centrifugation speed is 5000rpm and the centrifugation time is 20min each time; uniformly dispersing the cleaned Fe-Ni composite alkoxide precursor in methanol (ultrasonic dispersion can be adopted) to obtain 30mL (the concentration is 5mg/mL) of Fe-Ni composite alkoxide dispersion liquid; then transferring the dispersion liquid into a vacuum centrifugal concentrator for vacuum centrifugation-solvent evaporation treatment, wherein the vacuum degree of a vacuum chamber of the vacuum centrifugal concentrator is 0.1mbar, the temperature is set to be 40 ℃, the centrifugal rotating speed is 1000rpm, the vacuum centrifugation-solvent evaporation is carried out for 1h under the condition, and a precursor is subjected to self-assembly in the process of organic solvent methanol evaporation to finally obtain a self-supporting Fe-Ni composite alkoxide precursor film;
(3) taking out the self-supporting Fe-Ni composite alkoxide precursor film, separately placing the precursor film and sodium hypophosphite in two corundum boats according to the mass ratio of 1:2 of the self-supporting Fe-Ni composite alkoxide precursor film to the sodium hypophosphite, transferring the corundum boats together into a tubular furnace, wherein the corundum boats of the sodium hypophosphite are positioned at an upper air inlet of the tubular furnace, heating and decomposing the corundum boats from room temperature to 500 ℃ at the heating rate of 2 ℃/min under the condition of nitrogen atmosphere and simultaneously carrying out phosphorization, and carrying out thermal decomposition-phosphorization for 2h and then carrying out in-situ conversion to obtain the self-supporting Fe-Ni-P/carbon composite film.
The reason why the precursor film and the phosphorus source are respectively placed in the two containers in the step 3 is that: if the two are mixed directly, the final product may be contaminated with a phosphorus source that is not completely consumed, resulting in impurities in the final product. In addition, the phosphorus source is arranged in the upper tuyere because the phosphorus steam can reach the precursor film along with the air flow, and if the phosphorus source is arranged in the lower tuyere, the phosphorus steam is directly taken away by the air flow and does not participate in the phosphating reaction.
Observing the shape of the Fe-Ni composite alkoxide precursor obtained in the step (1), wherein a Field Emission Scanning Electron Microscope (FESEM) picture is shown in figure 2, and as can be seen from figure 2, the Fe-Ni composite alkoxide is in a nanosheet structure, the width of the nanosheet is less than 10 microns, and the average thickness is about 10 nm.
Observing the shape of the self-supporting Fe-Ni-P/carbon composite film finally obtained in the step (3), wherein a Field Emission Scanning Electron Microscope (FESEM) picture is shown in fig. 3, as can be seen from fig. 3, the film is a porous carbon nanosheet with a layered structure similar to graphene, and is formed by closely laminating a plurality of nanosheets, Fe-Ni-P nanoparticles are attached between nanosheets, the thickness of the porous carbon nanosheet is 5 nm-1 mu m, and the size of the Fe-Ni-P nanoparticles is 1-900 nm.
Observing the structural unit of the Fe-Ni-P/carbon composite nanosheet in the self-supporting Fe-Ni-P/carbon composite film finally obtained in the step (3) by using a Transmission Electron Microscope (TEM), and as can be seen from a figure 4, the structural unit of the Fe-Ni-P/carbon composite nanosheet in the film has an obvious porous structure which is carbon formed by thermal decomposition, and Fe-Ni-P nanoparticles with the average particle size of 4nm are uniformly and densely distributed in the porous carbon nanosheet.
The application comprises the following steps: the self-supporting Fe-Ni-P/carbon composite film prepared in the example was cut into small disks with a diameter of 13mm at room temperature to prepare electrode plates for batteries. And (3) assembling the lithium ion battery CR2032 button battery in a glove box filled with argon: the self-supporting Fe-Ni-P/carbon composite film prepared in the embodiment is directly used as a negative pole piece, a metal lithium piece is used as a counter electrode, a diaphragm is celgard 2400, and an electrolyte contains 1mol/LLIPF6A mixed solution of diethyl carbonate and ethylene carbonate (volume ratio of diethyl carbonate to ethylene carbonate is 1: 1). A battery test system (BTS-5V50mA type, New Weil) is adopted to carry out electrochemical performance test at 25 ℃, and the charge-discharge range is 0.01-3.0V.
The self-supporting Fe-Ni-P/carbon composite film of the present embodiment is applied to a lithium ion battery as a negative electrode, and the cycle performance of the battery after 500 cycles under the condition of 4A/g current density is shown in FIG. 4, and it can be known from FIG. 4 that after 500 cycles, the battery using the self-supporting Fe-Ni-P/carbon composite film of the present embodiment as the negative electrode can still obtain the discharge capacity as high as 702.7 mAh/g.
Example 2
The self-supporting transition metal phosphide/carbon composite material film of the embodiment is a self-supporting Fe-Ni-P/carbon composite film, and the preparation method comprises the following steps:
(1) weighing 0.2mmol of ferric chloride, 0.6mmol of nickel nitrate, 10mmol of sodium propionate and 80mL of propylene glycol, stirring for 1h at a stirring speed of 500rpm to obtain a mixed solution, then transferring the mixed solution to a 100mL round-bottom flask, heating to 180 ℃ at a heating rate of 3 ℃/min, heating and refluxing for 50min at the temperature, and naturally cooling to room temperature to obtain a Fe-Ni composite alkoxide precursor;
(2) repeatedly centrifuging and cleaning the obtained Fe-Ni composite alkoxide precursor with ethanol for 3 times, wherein the centrifugation speed is 4000rpm and the centrifugation time is 10min each time; uniformly dispersing the cleaned Fe-Ni composite alkoxide precursor in ethanol (ultrasonic dispersion can be adopted) to obtain 40mL (the concentration is 20mg/mL) of Fe-Ni composite alkoxide dispersion liquid; then transferring the dispersion liquid into a vacuum centrifugal concentrator for vacuum centrifugation-solvent evaporation treatment, wherein the vacuum degree of a vacuum chamber of the vacuum centrifugal concentrator is 0.1mbar, the temperature is set to be 50 ℃, the centrifugal rotating speed is 1500rpm, the vacuum centrifugation-solvent evaporation is carried out for 2h under the condition, and a precursor is subjected to self-assembly in the process of organic solvent methanol evaporation to finally obtain a self-supporting Fe-Ni composite alkoxide precursor film;
(3) taking out the self-supporting Fe-Ni composite alkoxide precursor film, separately placing the precursor film and sodium hypophosphite in two corundum boats according to the mass ratio of 1:3 of the self-supporting Fe-Ni composite alkoxide precursor film to the sodium hypophosphite, transferring the corundum boats together into a tubular furnace, wherein the corundum boats of the sodium hypophosphite are positioned at an upper air inlet of the tubular furnace, heating and decomposing the corundum boats from room temperature to 600 ℃ at the heating rate of 5 ℃/min under the argon atmosphere condition, simultaneously carrying out phosphorization, carrying out thermal decomposition-phosphorization for 1h, and then carrying out in-situ conversion to obtain the self-supporting Fe-Ni-P/carbon composite film.
Observing the Fe-Ni composite alkoxide precursor obtained in the step (1) in the embodiment with a field emission scanning electron microscope, and observing the unit structure of the Fe-Ni-P/carbon composite nanosheet in the self-supporting Fe-Ni-P/carbon composite thin film prepared in the embodiment with a projection electron microscope, wherein as can be seen from the FESEM (A) diagram and the TEM (B) diagram in FIG. 6, the Fe-Ni composite alkoxide prepared in the embodiment is also in a nanosheet structure, the width of the Fe-Ni composite alkoxide prepared in the embodiment is less than 20 μm, and the thickness of the Fe-Ni composite alkoxide prepared in the embodiment is less than 110 nm; the Fe-Ni-P nanoparticles having an average particle size of about 8nm are uniformly and densely distributed in the porous carbon matrix. The product structure of this example is the same as that of example 1.
The application comprises the following steps: the self-supporting Fe-Ni-P/carbon composite film prepared in the example was cut into small disks with a diameter of 13mm at room temperature to prepare electrode plates for batteries. And (3) assembling the lithium ion battery CR2032 button battery in a glove box filled with argon: the self-supporting Fe-Ni-P/carbon composite film prepared in the embodiment is directly used as a negative pole piece, a metal lithium piece is used as a counter electrode, a diaphragm is celgard 2400, and an electrolyte contains 1mol/LLIPF6A mixed solution of diethyl carbonate and ethylene carbonate (volume ratio of diethyl carbonate to ethylene carbonate is 1: 1). A battery test system (BTS-5V50mA type, New Weil) is adopted to carry out electrochemical performance test at 25 ℃, and the charge-discharge range is 0.01-3.0V.
The self-supporting Fe-Ni-P/carbon composite film of the embodiment is used as a negative electrode to be applied to a lithium ion battery, and the battery can still obtain the discharge capacity of 691.5mAh/g after 500 cycles under the condition of 4A/g current density.
Example 3
The self-supporting transition metal phosphide/carbon composite material film of the embodiment is a self-supporting Fe-Ni-P/carbon composite film, and the preparation method comprises the following steps:
(1) weighing 0.5mmol of ferric acetylacetonate, 0.5mmol of nickel sulfate and 12mmol of sodium oleate, dissolving in 30mL of pentaerythritol, stirring at a stirring speed of 800rpm for 3 hours to obtain a mixed solution, transferring the mixed solution to a 100mL round-bottom flask, heating to 220 ℃ at a heating rate of 6 ℃/min, heating at the temperature and refluxing for 30 minutes, and naturally cooling to room temperature to obtain a Fe-Ni composite alkoxide precursor;
(2) repeatedly centrifuging and cleaning the obtained Fe-Ni composite alkoxide precursor with ethanol for 5 times, wherein the centrifugation speed is 6000rpm each time, and the centrifugation time is 12 min; uniformly dispersing the cleaned Fe-Ni composite alkoxide precursor in acetone (ultrasonic dispersion can be adopted) to obtain 10mL (with the concentration of 30mg/mL) of Fe-Ni composite alkoxide dispersion liquid; then transferring the dispersion liquid into a vacuum centrifugal concentrator for vacuum centrifugation-solvent evaporation treatment, wherein the vacuum degree of a vacuum chamber of the vacuum centrifugal concentrator is 0.1mbar, the temperature is set to be 60 ℃, the centrifugal rotating speed is 2000rpm, the vacuum centrifugation-solvent evaporation is carried out for 3h under the condition, and a precursor is subjected to self-assembly in the process of organic solvent methanol evaporation to finally obtain a self-supporting Fe-Ni composite alkoxide precursor film;
(3) taking out the self-supporting Fe-Ni composite alkoxide precursor film, separately placing the precursor film and sodium hypophosphite in two corundum boats according to the mass ratio of 1:5 of the self-supporting Fe-Ni composite alkoxide precursor film to the sodium hypophosphite, transferring the corundum boats together into a tubular furnace, wherein the corundum boats of the sodium hypophosphite are positioned at an upper air inlet of the tubular furnace, heating and decomposing the corundum boats from room temperature to 500 ℃ at the heating rate of 10 ℃/min under the argon atmosphere condition, simultaneously carrying out phosphorization, carrying out thermal decomposition-phosphorization for 3h, and then carrying out in-situ conversion to obtain the self-supporting Fe-Ni-P/carbon composite film.
The product structure of the present embodiment is the same as the product structure of example 1, and is found by performing field emission scanning electron microscope observation on the Fe-Ni composite alkoxide precursor obtained in step (1) of the present embodiment and performing projection electron microscope observation on the unit structure of the Fe-Ni-P/carbon composite nanosheet in the self-supporting Fe-Ni-P/carbon composite thin film prepared in the present embodiment, and both porous carbon having a graphene-like structure and Fe-Ni-P nanoparticles attached to the layered structure.
The application comprises the following steps: the self-supporting Fe-Ni-P/carbon composite film prepared in the example was cut into small disks with a diameter of 13mm at room temperature to prepare electrode plates for batteries. And (3) assembling the lithium ion battery CR2032 button battery in a glove box filled with argon: the self-supporting Fe-Ni-P/carbon composite film prepared in the embodiment is directly used as a negative pole piece, a metal lithium piece is used as a counter electrode, a diaphragm is celgard 2400, and an electrolyte contains 1mol/LLIPF6A mixed solution of diethyl carbonate and ethylene carbonate (volume ratio of diethyl carbonate to ethylene carbonate is 1: 1). A battery test system (BTS-5V50mA type, New Weil) is adopted to carry out electrochemical performance test at 25 ℃, and the charge-discharge range is 0.01-3.0V.
The self-supporting Fe-Ni-P/carbon composite film of the embodiment is used as a negative electrode to be applied to a lithium ion battery, and the battery can still obtain the discharge capacity of 649.8mAh/g after 500 cycles under the condition of 4A/g current density; FESEM observation of the self-supporting Fe-Ni-P/carbon composite film cathode after being cycled 500 times under the condition of 4A/g current density is carried out, and the result is shown in FIG. 7. As can be seen from FIG. 7, the self-supporting Fe-Ni-P/carbon composite film of the embodiment still maintains better structural stability after being cycled for a long time under high current.
Comparative example 1
This comparative example is the same as the preparation method of example 1 except that the step (2) is not subjected to vacuum centrifugation but only conventional solvent evaporation is used, the temperature is set to 40 ℃, and solvent evaporation is performed under the conditions for 1 hour. The structural morphology of the alkoxide assembly product obtained by self-assembly-solvent evaporation in the step (2) is shown in fig. 8, and as can be seen from fig. 8, the nanosheets are stacked in a disordered manner, and a dense and stable nanosheet self-assembled film cannot be formed.
Comparative example 2
The comparative example is the same as the preparation method of example 1, except that the carboxylic acid salt potassium acetate is replaced by urea in the step (1), the structural morphology of the alkoxide product prepared in the step (1) is shown in a 9-dimensional graph, and as can be seen from fig. 9, the morphology of the alkoxide product prepared in the step (1) is irregular and has different sizes.
Comparative example 3
The comparative example is the same as the preparation method of example 1, except that in step (1), the carboxylate potassium acetate is replaced by sodium carbonate and polyvinylpyrrolidone (mass ratio is 1:1), the structural morphology of the alkoxide product prepared in step (1) is shown in fig. 10, and as can be seen from fig. 10, the alkoxide product prepared in step (1) has irregular morphology and different sizes.
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 person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. The preparation method of the self-supporting transition metal phosphide/carbon composite material film is characterized by comprising the following steps:
(1) dissolving a transition metal compound and carboxylate in polyol, stirring uniformly, heating and refluxing, and then cooling to room temperature to obtain a transition metal alkoxide precursor;
(2) cleaning the obtained transition metal alkoxide precursor by using an organic solvent, uniformly dispersing the transition metal alkoxide precursor in the organic solvent to form precursor dispersion liquid, then carrying out organic solvent evaporation treatment, and self-assembling in the organic solvent evaporation process to obtain a self-supporting transition metal alkoxide precursor film;
(3) and respectively placing the precursor film and a phosphorus source into two containers, carrying out heating decomposition and simultaneous phosphorization under a protective gas atmosphere, and finally carrying out in-situ conversion to obtain the self-supporting transition metal phosphide/carbon composite material film.
2. The method of claim 1, wherein the transition metal compound is at least one of an iron-containing compound, a nickel-containing compound, a copper-containing compound, and a cobalt-containing compound; the carboxylate is at least one of potassium acetate, sodium propionate, sodium oleate and sodium caprate; the polyhydric alcohol is at least one of ethylene glycol, propylene glycol, diethylene glycol, glycerol and pentaerythritol; the phosphorus source is at least one of phosphorus, sodium hypophosphite, phosphine, tri-n-octylphosphorus and triphenylphosphine.
3. The method of claim 2, wherein the transition metal compound is an iron-containing compound and a nickel-containing compound in any ratio; the iron-containing compound is at least one of ferric acetate, ferric chloride, ferric sulfate and ferric acetylacetonate; the nickel-containing compound is at least one of nickel acetate, nickel chloride, nickel sulfate and nickel nitrate;
the dosage proportion of the transition metal compound, the carboxylate and the polyol is (0.1-2) mol, (1-20) mol, (5-100) L; the stirring speed in the step (1) is 300-1000 rpm, and the stirring time is 1-6 h;
in the step (1), heating and refluxing are carried out by heating to 160-220 ℃ at a heating rate of 0.1-10 ℃/min, preserving heat and refluxing, and the heating time is 5 min-2 h.
4. The method for preparing the self-supporting transition metal phosphide/carbon composite material film according to any one of claims 1 to 3, wherein the organic solvent in the step (2) is at least one of methanol, ethanol, chloroform, acetone, diethyl ether, carbon tetrachloride and dichloromethane, and the cleaning process comprises repeatedly carrying out centrifugal cleaning for 1 to 5 times by using the organic solvent, wherein the centrifugal rotation speed is 1000 to 6000rpm, and the centrifugal time is 2min to 1 h; the concentration of the precursor dispersion liquid is 2-50 g/L.
5. The method as claimed in any one of claims 1 to 3, wherein the organic solvent evaporation treatment in step (2) is performed by vacuum centrifugation-solvent evaporation for 0.5 to 4 hours in a vacuum centrifugal concentrator, wherein the temperature of the heating evaporation is 20 to 80 ℃ and the evaporation is performed while the organic solvent is centrifuged at a centrifugal speed of 500-2000rpm under a vacuum degree of 0.1 mbar.
6. The method for preparing a self-supporting transition metal phosphide/carbon composite material film according to any one of claims 1 to 3, wherein the mass ratio of the precursor film to the phosphorus source in the step (3) is 1 (0.1 to 10); the protective gas is nitrogen or argon, and the heating decomposition is carried out by heating to 300-1000 ℃ at a heating rate of 0.1-10 ℃/min and keeping the temperature for 30 min-8 h;
and (3) respectively placing the precursor film and the phosphorus source into two containers, then placing the containers into a tubular furnace, and placing the containers with the phosphorus source into an upper tuyere of the tubular furnace before carrying out heating decomposition and phosphorization.
7. The self-supporting transition metal phosphide/carbon composite film prepared by the preparation method according to any one of claims 1 to 6, wherein the carbon material in the composite film is a porous carbon nanosheet having a graphene-like layered structure into which transition metal phosphide is attached.
8. The self-supporting transition metal phosphide/carbon composite film according to claim 7, wherein the composite film is a Fe-Ni-P transition metal phosphide/carbon composite film.
9. Use of a self-supporting transition metal phosphide/carbon composite film according to claim 8 in a battery, wherein said composite film is used directly as an electrode sheet of the battery.
10. A battery having a structure including a self-supporting transition metal phosphide/carbon composite thin film produced by the production method according to any one of claims 1 to 6 as an electrode sheet, wherein the battery includes a lithium ion battery or a sodium ion battery.
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