CN110104623B - Preparation method of phosphorus-rich transition metal phosphide cobalt tetraphosphate with different morphologies - Google Patents
Preparation method of phosphorus-rich transition metal phosphide cobalt tetraphosphate with different morphologies Download PDFInfo
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Abstract
The invention discloses a preparation method of phosphorus-rich transition metal phosphide cobalt tetraphosphite with different morphologies. The method comprises the steps of mixing cobalt-based precursors (cobaltosic oxide, cobalt hydroxide, cobalt-based organic and inorganic precursors and the like) with different shapes and phosphorus sources according to the atomic ratio of cobalt to phosphorus of 1: 4.5-1: 5.5, packaging the mixture in a quartz tube in high vacuum at the temperature of 1100-1200K and the vacuum degree of 5 x 10‑5~5×10‑4The reaction is carried out for 6-10 h under the condition of Pa at high temperature and high pressure, the chemical potential which can not be achieved by cobalt tetraphosphate synthesis under the common condition is overcome, and CS is used2The obtained gray black sample is treated to remove redundant phosphorus, so that cobalt tetraphosphate with high purity and high crystallinity and different shapes can be obtained, the raw materials are cheap, the synthesis is simple, the operation is convenient, the shape is controllable, and the method is suitable for large-scale preparation and application.
Description
Technical Field
The invention belongs to the field of inorganic phosphorus materials, and particularly relates to a preparation method of phosphorus-rich transition metal phosphide cobalt tetraphosphorate with different shapes.
Background
The cobalt tetraphosphoride material belongs to a cubic crystal system structure, each cobalt atom is surrounded by eight phosphorus atoms, and the peripheral phosphorus atoms form an octahedral structure. The cobalt tetraphosphorate formed by the structure has a very small band gap, forms special electricity and thermal transport characteristics, and becomes potential electrocatalytic decomposition water, a battery cathode material and a thermoelectric material. Under the common conditions of low temperature and low pressure, only a cobalt phosphide material can be synthesized, and a cobalt tetraphosphoride material is difficult to synthesize and the shape of the cobalt tetraphosphoride material cannot be regulated. Because the synthesis of cobalt tetraphosphate needs to overcome the chemical potential which cannot be achieved by synthesis under common conditions, relevant documents for cobalt tetraphosphate synthesis are very few. In 1967, the method for sintering transition metal simple substance cobalt and red phosphorus is adopted for the first time by Ronald A, Munson and the like4（Inorg. Chem.,1968, volume seven, page 390-391), which was hardly reported thereafter. The size of the cobalt tetraphosphoride synthesized by the method is more than micron level, the cobalt low-phosphide is easy to appear, the shape regulation is not facilitated, in addition, the expensive price of the transition metal simple substance cobalt is not beneficial to large-scale preparation, and therefore, the cheap method for synthesizing the high-purity cobalt tetraphosphoride and regulating the shape of the cobalt tetraphosphoride has important significance.
Disclosure of Invention
The invention aims to provide a preparation method of phosphorus-rich transition metal phosphide cobalt tetraphosphate, which is simple to operate, easy to synthesize, low in cost and controllable in shape.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
a preparation method of phosphorus-rich transition metal phosphide cobalt tetraphosphide with different morphologies comprises the following steps: mixing cobalt-based precursors with different morphologies and a phosphorus source according to the atomic ratio of cobalt to phosphorus of 1: 4.5-1: 5.5, packaging the mixture in a quartz tube in high vacuum at the temperature of 1100-1200K and the vacuum degree of 5 multiplied by 10-5～5×10-4The reaction is carried out for 6-10 h under the condition of Pa at high temperature and high pressure, the chemical potential which can not be achieved by cobalt tetraphosphate synthesis under the common condition is overcome, and CS is used2Treating the obtained sample to remove excessive phosphorus to obtain the product.
Further, the cobalt-based precursor can be a commercially available commodity, and can also be prepared by hydrothermal, solvothermal, gel sol and other methods, specifically a cobalt-based precursor hollow nanosphere sheet, cobaltosic oxide powder, a cobalt-based precursor nanowire, a cobalt-based precursor nanosheet or a cobalt-based precursor nanosphere.
The synthesis temperature is 1100-1200K, and the heating rate is 2-4K/min.
Further, the specific preparation process of the cobalt-based precursor hollow nanosphere sheet is as follows:
(1) pouring 25mL of isopropanol and 7mL of glycerol into a 50mL beaker, uniformly stirring, adding 0.582g of cobalt nitrate hexahydrate, and stirring for dissolving;
(2) pouring the solution obtained in the step (1) into a 50mL inner container of a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction at 180 ℃ for 6h, naturally cooling to room temperature, centrifuging, washing and drying the precipitate;
(3) and (3) dispersing the powder obtained in the step (2) into 32mL of ultrapure water, carrying out hydrothermal reaction at 180 ℃ for 6h, naturally cooling to room temperature, centrifuging the precipitate, washing with water, and drying to obtain the nano-composite material.
Further, the specific preparation process of the cobaltosic oxide powder is as follows:
(1) pouring 6mL of 0.26mol/L cobalt nitrate solution into 40mL of 1.18mol/L dimethyl imidazole, stirring at normal temperature for 12h, collecting precipitate, and drying at 80 ℃ to obtain a cobalt-based precursor;
(2) and annealing the cobalt-based precursor in air at 300 ℃ for 5 hours to obtain black cobaltosic oxide powder.
The specific preparation process of the cobalt-based precursor nanowire comprises the following steps:
(1) firstly, soaking the carbon cloth in dilute nitric acid with the mass fraction of 20% for 2 hours, taking out the carbon cloth, washing and drying for later use;
(2) dissolving 0.582g of cobalt nitrate hexahydrate, 0.186g of ammonium fluoride and 0.6g of urea in water in sequence, and stirring at normal temperature for 30 minutes to obtain a solution;
(3) transferring the solution into a 50mL polytetrafluoroethylene reaction kettle liner, vertically putting the washed dry carbon cloth into the reaction kettle liner, sealing the reaction kettle, carrying out hydrothermal reaction at 120 ℃ for 6 hours, taking out the carbon cloth, cleaning, and drying at normal temperature to obtain the carbon cloth.
The specific preparation process of the cobalt-based precursor nanosheet is as follows:
(1) firstly, soaking the carbon cloth in dilute nitric acid with the mass fraction of 20% for 2 hours, taking out the carbon cloth, washing and drying for later use;
(2) dissolving 2.328g of cobalt nitrate hexahydrate, 0.106g of ammonium fluoride and 1.2g of urea in 40mL of water in sequence, and stirring at normal temperature for 60 minutes to obtain a uniform solution;
(3) and transferring the uniform solution into a 50mL polytetrafluoroethylene reaction kettle liner, vertically putting the washed dry carbon cloth into the reaction kettle liner, sealing the reaction kettle, carrying out hydrothermal reaction at 120 ℃ for 22h, taking out the carbon cloth, cleaning, and drying at normal temperature to obtain the finished product.
The specific preparation process of the cobalt-based precursor nanosphere is as follows:
(1) firstly, soaking the carbon cloth in dilute nitric acid with the mass fraction of 20% for 2 hours, taking out the carbon cloth, washing and drying for later use;
(2) dissolving 1.455g of cobalt nitrate hexahydrate and 0.2g of ammonium nitrate in 40mL of ultrapure water in sequence, stirring at normal temperature for 60 minutes to obtain a uniform solution, adding 5mL of ammonia water with the mass fraction of 25wt% into the solution, and stirring for thirty minutes to obtain the uniform solution;
(3) and transferring the uniform solution into a 25mL polytetrafluoroethylene reaction kettle liner, vertically putting the washed dry carbon cloth into the reaction kettle liner, sealing the reaction kettle, carrying out hydrothermal reaction at 90 ℃ for 14h, taking out the carbon cloth, cleaning, and drying at normal temperature to obtain the finished product.
Further, the phosphorus source is one or a mixture of more than two of sodium hypophosphite, potassium hypophosphite, hypophosphorous acid, white phosphorus and red phosphorus in any proportion.
The invention has the advantages that:
the cobalt tetraphosphorylation of different morphologies is synthesized by taking cobalt-based precursors (cobalt oxide, cobalt hydroxide, cobalt-based organic and inorganic precursors and the like) of different morphologies and a phosphorus source as raw materials, and the method has the advantages of cheap raw materials, simple synthesis, convenient operation and controllable morphology, and is suitable for large-scale preparation and application. The prepared phosphorus-rich cobalt tetraphosphate has good application prospects in the aspects of desulfurization and hydrogenation of petroleum and coal, electrocatalytic decomposition of water, battery cathode materials, thermoelectric materials and the like.
Drawings
FIG. 1 is CoP prepared in example 14XRD and SEM images of hollow nanospheres;
FIG. 2 is CoP prepared in example 24XRD and SEM images of nano-polyhedra;
FIG. 3 is CoP prepared on carbon cloth in example 34XRD and SEM images of nanowire arrays;
FIG. 4 shows CoP prepared on carbon cloth in example 44XRD and SEM images of the nanoplate array;
FIG. 5 is a drawing showingCoP prepared on carbon cloth in example 54XRD and SEM images of nanosphere arrays;
FIG. 6 is CoP prepared in comparative example 14XRD and SEM pictures of the particles;
fig. 7 is an XRD pattern of CoP prepared in comparative example 2.
Detailed Description
The synthesis of cobalt tetraphosphates of different morphologies according to the present invention will be further illustrated with reference to the following specific examples, which should not be construed as limiting the invention in any way.
The flexible carbon cloth used in the paper is purchased from Shanghai Hesen electric appliances Co., Ltd, and the model is as follows: HCP330N (hydrophilic type).
Example 1
The preparation method of the phosphorus-rich cobalt tetraphosphorate hollow nanosphere sheet in the embodiment comprises the following steps:
the first step is as follows: 25mL of isopropanol and 7mL of glycerol were poured into a 50mL beaker and stirred well, and then 0.582g of cobalt nitrate hexahydrate was dissolved in the above mixed solution to form a purple transparent solution.
The second step is that: and pouring the purple transparent solution obtained in the last step into a 50mL inner container of a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction for 6h at 180 ℃, naturally cooling to room temperature, centrifuging the precipitate, washing with absolute ethyl alcohol for three times, and drying at normal temperature to obtain powder.
The third step: and dispersing the powder obtained in the last step into 32mL of ultrapure water, carrying out hydrothermal reaction at 180 ℃ for 6h, naturally cooling to room temperature, centrifuging and washing the precipitate for three times, and drying at room temperature to obtain the cobalt-based precursor hollow nanosphere.
The fourth step: mixing the cobalt-based precursor hollow nanospheres 100mg obtained in the previous step with red phosphorus 200mg, and vacuum-pressing at 5 × 10-5Sealing in a quartz tube under Pa, performing high-temperature conformal phosphorization at 1150K for 8 hr, taking out, and immersing in pure CS2The surface of the cobalt tetraphosphoric hollow nanosphere is removed to be pure black after the treatment for 30min, and the SEM photograph and XRD pattern of the cobalt tetraphosphoric hollow nanosphere are shown in figure 1, and as can be seen from the SEM and XRD (figure 1) of the cobalt tetraphosphoric hollow nanosphere, the high-purity and high-crystallinity cobalt tetraphosphoric hollow nanosphere is successfully synthesized in example 1Further analysis shows that the synthesized cobalt tetraphosphoride hollow nanosphere sheet is 800nm sphere formed by stacking sheets with the thickness of several nanometers, the size of the synthesized cobalt tetraphosphoride hollow nanosphere sheet is very small, the unique hollow nanostructure of the cobalt tetraphosphoride hollow nanosphere sheet has very large specific surface area, more active sites can be exposed in electrocatalytic decomposition of water for hydrogen evolution and desulfurization and hydrogenation of petroleum and coal, and the cobalt tetraphosphoride hollow nanosphere sheet has very wide application prospect.
Example 2
The preparation method of the phosphorus-rich cobalt tetraphosphorate nano-polyhedron in the embodiment comprises the following steps
The first step is as follows: and pouring 6mL of 0.26mol/L cobalt nitrate solution into 40mL of 1.18mol/L dimethyl imidazole, continuously stirring for 12h at normal temperature, collecting the obtained purple precipitate, and drying for 8-10 h at 80 ℃ to obtain the cobalt-based precursor.
The second step is that: and annealing the cobalt-based precursor in air at 300 ℃ for five hours to obtain black cobaltosic oxide powder.
The third step: mixing 100mg of black cobaltosic oxide powder and 200mg of red phosphorus, and vacuum-compressing to 5X 10-5Sealing in a quartz tube under Pa, performing high-temperature conformal phosphorization at 1150K for 8 hr, taking out, and immersing in pure CS2The redundant phosphorus is removed after the treatment is carried out for 30min, the surface of the cobalt tetraphosphoric nano polyhedron is changed into pure black, the phosphorus-rich cobalt tetraphosphoric nano polyhedron can be obtained, the SEM and XRD figures of the cobalt tetraphosphoric nano polyhedron are shown in figure 2 in detail, the cobalt tetraphosphoric nano polyhedron with high purity and crystallinity is successfully synthesized in the embodiment 2, and further analysis shows that the size of the synthesized cobalt tetraphosphoric nano polyhedron is about 300-600 nm, in addition, the precursor is an organic matter, and carbon load can be naturally formed in the annealing and phosphorization process, so that the conductivity can be further improved, and the cobalt tetraphosphoric nano polyhedron has important application in lithium and sodium ion batteries.
Example 3
The preparation method for the self-supporting growth of the cobalt tetraphosphorylation nanowire on the carbon cloth in the embodiment comprises the following steps
The first step is as follows: the flexible carbon cloth is firstly soaked in dilute nitric acid with the mass fraction of 20% for two hours, protonation is carried out on the flexible carbon cloth, and then the flexible carbon cloth is taken out and washed by water and absolute ethyl alcohol for three times in sequence and dried for standby.
The second step is that: 0.582g of cobalt nitrate hexahydrate, 0.186g of ammonium fluoride and 0.6g of urea were dissolved in 40mL of ultrapure water in this order, and stirred at normal temperature for 30 minutes to obtain a uniform solution.
The third step: and transferring the uniform solution into a 50mL polytetrafluoroethylene reaction kettle liner, vertically putting the washed and dried flexible carbon cloth for later use into the reaction kettle liner, sealing the reaction kettle, carrying out hydrothermal reaction at 120 ℃ for 6h, taking out the carbon cloth, cleaning the surface with water and absolute ethyl alcohol, and drying at normal temperature to obtain the cobalt-based precursor nanowire growing on the carbon cloth for later use.
The fourth step: mixing the dried carbon cloth with 70mg of red phosphorus under vacuum pressure of 5X 10-5Sealing in a quartz tube under Pa, performing high-temperature conformal phosphorization at 1100K for 6 hr, taking out, and immersing in pure CS2And (3) performing intermediate treatment for 30min to remove redundant phosphorus, and changing the surface to be pure black to obtain the cobalt tetraphosphorate nanowire array which grows on the carbon cloth in a self-supporting mode, wherein the SEM and XRD patterns are shown in detail in figure 3. As can be seen from SEM and XRD (fig. 3) of the cobalt tetraphosphoride nanowire array, the cobalt tetraphosphoride nanowire array with high purity and crystallinity has been successfully synthesized in this embodiment, and further analysis shows that the synthesized cobalt tetraphosphoride nanowires uniformly grow on the carbon cloth, each nanowire is about 20nm thick and 1 μm long, and the self-supporting flexible electrode can be directly used as a negative electrode material and an electrocatalytic material of a battery, thereby avoiding the complexity of using a powder material as an electrode.
Example 4:
the preparation method for the self-supporting growth of the cobalt tetraphosphorylation nanosheet on the carbon cloth in the embodiment comprises the following steps
The first step is as follows: the flexible carbon cloth is firstly soaked in dilute nitric acid with the mass fraction of 20% for two hours, protonation is carried out on the flexible carbon cloth, and then the flexible carbon cloth is taken out and washed by water and absolute ethyl alcohol for three times in sequence and dried for standby.
The second step is that: 2.328g of cobalt nitrate hexahydrate, 0.106g of ammonium fluoride and 1.2g of urea were dissolved in 40mL of water in this order, and stirred at normal temperature for 60 minutes to obtain a uniform solution.
The third step: and transferring the uniform solution into a 50mL polytetrafluoroethylene reaction kettle liner, vertically putting the washed and dried standby flexible carbon cloth into the reaction kettle liner, sealing the reaction kettle, carrying out hydrothermal reaction at 120 ℃ for 22h, taking out the carbon cloth, cleaning the surface with water and ethanol, and drying at normal temperature to obtain cobalt-based precursor nanosheets growing on the carbon cloth for later use.
The fourth step: mixing the dried carbon cloth and 70mg of red phosphorus in the last step, and vacuum-compressing to 5X 10-5Sealing in a quartz tube under Pa, performing high-temperature conformal phosphorization at 1100K for 7 hr, taking out, and immersing in pure CS2And (3) removing excessive phosphorus by intermediate treatment for 30min, and obtaining the cobalt tetraphosphoride nanosheet array growing on the carbon cloth in a self-supporting manner by changing the surface to be pure black, wherein the SEM and XRD patterns are shown in detail in figure 4. As can be seen from SEM and XRD (fig. 4) of the cobalt tetraphosphorate nanosheet array, the cobalt tetraphosphorate nanosheet array with high purity and crystallinity has been successfully synthesized in this embodiment, and further analysis finds that the synthesized cobalt tetraphosphorate nanosheets uniformly grow on carbon cloth, each nanosheet is about 10nm thick, and the self-supporting flexible electrode can be directly used as a negative electrode material and an electrocatalytic material of a battery, thereby avoiding the complexity of using a powder material as an electrode.
Example 5:
the preparation method of the cobalt tetraphosphorylation nanospheres growing on the carbon cloth in the embodiment by self-supporting comprises the following steps:
the first step is as follows: the flexible carbon cloth is firstly soaked in dilute nitric acid with the mass fraction of 20% for two hours, is protonated, and then is taken out, washed with water and ethanol sequentially for three times and dried for standby.
The second step is that: 1.455g of cobalt nitrate hexahydrate and 0.2g of ammonium nitrate are sequentially dissolved in 15mL of ultrapure water, the mixture is stirred at normal temperature for 60 minutes to obtain a uniform solution, and 5mL of ammonia water with the mass fraction of 25wt% is added into the solution and stirred for thirty minutes to obtain the uniform solution.
The third step: and transferring the uniform solution in the last step into a 25mL polytetrafluoroethylene reaction kettle inner container, vertically putting the washed and dried flexible carbon cloth for later use into the reaction kettle inner container, sealing the reaction kettle, carrying out hydrothermal reaction at 90 ℃ for 14h, taking out the carbon cloth, washing the surface with water and absolute ethyl alcohol, and drying at normal temperature to obtain the cobalt-based precursor nanosphere growing on the carbon cloth for later use.
The fourth step: mixing the dried carbon cloth and 70mg of red phosphorus in the last step, and vacuum-compressing to 5X 10-5Sealing in a quartz tube under Pa, performing high-temperature conformal phosphorization at 1200K for 10 hr, taking out, and immersing in pure CS2And (3) removing excessive phosphorus by middle treatment for 30min, and obtaining the cobalt tetraphosphate nanosphere array which grows on the carbon cloth in a self-supporting mode by changing the surface to be pure black, wherein the SEM and XRD patterns are shown in detail in figure 5. As can be seen from SEM and XRD (fig. 5) of the cobalt tetraphosphoride nanosphere array, the cobalt tetraphosphoride nanosphere array with high purity and crystallinity has been successfully synthesized in this embodiment, and further analysis shows that the synthesized cobalt tetraphosphoride nanospheres uniformly grow on the carbon cloth, each nanosphere has a diameter of about 400nm, and the self-supporting flexible electrode can be directly used as a negative electrode material and an electrocatalytic material of a battery, thereby avoiding the complexity of using a powder material as an electrode.
Comparative example 1
The preparation method of cobalt tetraphosphoride in this comparative example was:
according to the synthesis method of Ronald A. Munson and the like in 1967, the purchased metal cobalt powder and red phosphorus are sintered for 10 hours at a high temperature of 750 ℃ to obtain the cobalt tetraphosphorate, the SEM and XRD figures of the cobalt tetraphosphorate are shown in figure 6 in detail, as can be seen from figure 6, the cobalt tetraphosphorate synthesized by the method has irregular shapes, micron-sized sizes and small specific surface areas, and the cobalt powder is not favorable for expensive industrial preparation and application.
Comparative example 2
The cobalt-based precursor synthesized in example 3 and 70mg of red phosphorus were directly sealed in a quartz tube under normal pressure, and directly phosphated at a high temperature of 350 ℃ in a tube furnace, and even when the temperature was raised to 950 ℃ for phosphatization for 20 hours, the synthesized material was found to be cobalt monophosphates, and XRD is shown in fig. 7, from which it can be seen that the synthesis of cobalt tetraphosphate could be synthesized only by overcoming the chemical potential that synthesis under normal conditions could not achieve, and could not be synthesized under normal conditions.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A preparation method of phosphorus-rich transition metal phosphide cobalt tetraphosphite with different morphologies is characterized by comprising the following steps of: mixing cobalt-based precursors with different shapes and a phosphorus source according to the atomic ratio of cobalt to phosphorus of 1: 4.5-1: 5.5 at the temperature of 1100-1200K and the vacuum degree of 5 multiplied by 10-5~5×10-4The reaction is carried out for 6 to 10 hours under the sealed condition of Pa, and the reaction product is taken out and then used with CS2And (4) treating the obtained sample to remove redundant phosphorus to obtain the phosphorus-free phosphorus-containing material.
2. The method for preparing phosphorus-rich transition metal phosphide cobalt tetraphosphate in different morphologies as claimed in claim 1, wherein the cobalt-based precursor in different morphologies is specifically a cobalt-based precursor hollow nanosphere sheet, cobaltosic oxide powder, a cobalt-based precursor nanowire, a cobalt-based precursor nanosheet or a cobalt-based precursor nanosphere.
3. The method for preparing the phosphorus-rich transition metal phosphide cobalt tetraphosphate of different morphologies as claimed in claim 2, wherein the specific preparation process of the cobalt-based precursor hollow nanospheres is as follows:
(1) pouring 25mL of isopropanol and 7mL of glycerol into a 50mL beaker, uniformly stirring, adding 0.582g of cobalt nitrate hexahydrate, and stirring for dissolving;
(2) pouring the solution obtained in the step (1) into a 50mL inner container of a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction at 180 ℃ for 6h, naturally cooling to room temperature, centrifuging, washing and drying the precipitate;
(3) and (3) dispersing the powder obtained in the step (2) into 32mL of ultrapure water, carrying out hydrothermal reaction at 180 ℃ for 6h, naturally cooling to room temperature, centrifuging the precipitate, washing with water, and drying to obtain the nano-composite material.
4. The method for preparing the phosphorus-rich transition metal phosphide cobalt tetraphosphate of different morphologies as claimed in claim 2, wherein the specific preparation process of the cobaltosic oxide powder is as follows:
(1) pouring 6mL of 0.26mol/L cobalt nitrate solution into 40mL of 1.18mol/L dimethyl imidazole, stirring at normal temperature for 12h, collecting precipitate, and drying at 80 ℃ to obtain a cobalt-based precursor;
(2) and annealing the cobalt-based precursor in air at 300 ℃ for 5 hours to obtain black cobaltosic oxide powder.
5. The method for preparing the phosphorus-rich transition metal phosphide cobalt tetraphosphate with different morphologies as claimed in claim 2, wherein the specific preparation process of the cobalt-based precursor nanowire is as follows:
(1) firstly, soaking the carbon cloth in dilute nitric acid with the mass fraction of 20% for 2 hours, taking out the carbon cloth, washing and drying for later use;
(2) dissolving 0.582g of cobalt nitrate hexahydrate, 0.186g of ammonium fluoride and 0.6g of urea in 40mL of ultrapure water in sequence, and stirring at normal temperature for 30 minutes to obtain a solution;
(3) transferring the solution into a 50mL polytetrafluoroethylene reaction kettle liner, vertically putting the washed dry carbon cloth into the reaction kettle liner, sealing the reaction kettle, carrying out hydrothermal reaction at 120 ℃ for 6 hours, taking out the carbon cloth, cleaning, and drying at normal temperature to obtain the carbon cloth.
6. The method for preparing the phosphorus-rich transition metal phosphide cobalt tetraphosphate with different morphologies as claimed in claim 2, wherein the specific preparation process of the cobalt-based precursor nanosheet is as follows:
(1) firstly, soaking the carbon cloth in dilute nitric acid with the mass fraction of 20% for 2 hours, taking out the carbon cloth, washing and drying for later use;
(2) dissolving 2.328g of cobalt nitrate hexahydrate, 0.106g of ammonium fluoride and 1.2g of urea in 40mL of water in sequence, and stirring at normal temperature for 60 minutes to obtain a uniform solution;
(3) and transferring the uniform solution into a 50mL polytetrafluoroethylene reaction kettle liner, vertically putting the washed dry carbon cloth into the reaction kettle liner, sealing the reaction kettle, carrying out hydrothermal reaction at 120 ℃ for 22h, taking out the carbon cloth, cleaning, and drying at normal temperature to obtain the finished product.
7. The method for preparing the phosphorus-rich transition metal phosphide cobalt tetraphosphate with different morphologies as claimed in claim 2, wherein the specific preparation process of the cobalt-based precursor nanosphere is as follows:
(1) firstly, soaking the carbon cloth in dilute nitric acid with the mass fraction of 20% for 2 hours, taking out the carbon cloth, washing and drying for later use;
(2) sequentially dissolving 1.455g of cobalt nitrate hexahydrate and 0.2g of ammonium nitrate in water, stirring at normal temperature for 60 minutes to obtain a uniform solution, adding 5mL of 25wt% ammonia water into the solution, and stirring for thirty minutes to obtain a uniform solution;
(3) and transferring the uniform solution into a 25mL polytetrafluoroethylene reaction kettle liner, vertically putting the washed dry carbon cloth into the reaction kettle liner, sealing the reaction kettle, carrying out hydrothermal reaction at 90 ℃ for 14h, taking out the carbon cloth, cleaning, and drying at normal temperature to obtain the finished product.
8. The method for preparing the phosphorus-rich transition metal phosphide cobalt tetraphosphate with different morphologies as claimed in claim 1, wherein the phosphorus source is one or a mixture of two or more of sodium hypophosphite, potassium hypophosphite, hypophosphorous acid, white phosphorus and red phosphorus in any proportion.
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