CN115986320A - Preparation method and application of oxygen-doped cobalt phosphide/carbon nanotube composite material - Google Patents
Preparation method and application of oxygen-doped cobalt phosphide/carbon nanotube composite material Download PDFInfo
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Abstract
The invention discloses a preparation method and application of an oxygen-doped cobalt phosphide/carbon nanotube (O-CoP/CNT) composite material. The catalyst is O-CoP/CNT nano material, and the method comprises the following steps: MWCNTs are added into a cobalt chloride aqueous solution and mixed evenly. Dropwise and slowly adding a small amount of ammonia water (25-28%) into the solution, reacting in an oil bath for 7-15 hours, and freeze-drying to obtain Co 3 O 4 a/CNT precursor; with NaH 2 PO 2 As a phosphorus source, the phosphorus source and a precursor are placed in a tubular furnace, and Co is subjected to low-temperature phosphating under protective gas atmosphere 3 O 4 the/CNT is converted into CoP/CNT; and continuously placing the product in an air atmosphere, and calcining at 100-400 ℃ for 30 minutes to obtain the O-CoP/CNT catalyst. The material of the invention is generated on the surface of the material by surface dopingThe trace cobalt metaphosphate enhances the adsorption effect on polysulfide, reduces the concentration of polysulfide in electrolyte, inhibits polysulfide shuttle effect, reduces the polarization of the battery, improves the diffusion rate of lithium ions, and thus obviously improves the electrochemical performance of the lithium-sulfur battery.
Description
Technical Field
The invention relates to a lithium-sulfur battery technology, in particular to a preparation method and application of an oxygen-doped cobalt phosphide/carbon nanotube composite material.
Background
With the development of new energy automobiles, the endurance mileage and the battery cost are receiving wide attention. The endurance mileage of the current mainstream new energy automobile is about 600km, and the cost of the battery is 6-8 ten thousand. The lithium-sulfur battery can enable the endurance mileage of the new energy automobile to reach over 1000km, and the battery cost is 10% of the cost of the mainstream lithium battery. Compared with the existing lithium ion battery, the lithium sulfur battery has better performance and less influence on the environment. Because of rich sulfur storage, low price, environmental protection and theoretical specific capacity (1675 mAh g) -1 ) High energy density (2500 Wh/kg) -1 Or 2800 Wh. L -1 ) Lithium sulfur batteries have become the focus of attention of researchers. However, the lithium sulfur battery has the problems of serious shuttle effect, lithium dendrite and the like, so that the lithium sulfur battery cannot be commercially produced. Currently, the main approach to the "shuttle effect" problem is to add a catalyst to the lithium sulfur battery.
Metal phosphide (CoP, ni) 2 P, feP, moP and Sn 4 P 3 Etc.) have outstanding metallic properties. When the metal phosphides act as sulfur hosts, they will greatly increase the conductivity of the electrode. In addition, these metal phosphides have strong polarity, so that the LipS can be adsorbed well to reduce the influence of the shuttle effect. Finally, their excellent catalytic effect can effectively catalyze most chemical reactions. Research progress shows that metal phosphide can promote the conversion of LiPS and increase the electrochemical reaction rate.
Due to these obvious advantages, functional metal phosphides are widely used in lithium sulfur batteries, greatly improving electrochemical performance. In addition, the O-CoP/CNT composite material is used as a catalyst of a lithium-sulfur battery and coated on a polypropylene diaphragm to prepare a functionalized diaphragm; and (2) carrying out anion doping on the CoP/CNT composite material by using O, so that the adsorption force of the CoP/CNT composite material on polysulfide is improved, and the shuttle effect is inhibited, thereby improving the electrochemical performance of the lithium-sulfur battery.
Disclosure of Invention
The invention aims to provide a preparation method and application of an oxygen-doped cobalt phosphide/carbon nanotube composite material aiming at the defects of the prior art. The preparation method is simple, low in cost, environment-friendly and safe, and does not need to be completed under the sealed high-pressure reaction condition. The material prepared by the method provides more active sites for polysulfide adsorption, can accelerate the conversion of polysulfide, is coated on a diaphragm to prepare a functional diaphragm, can obviously improve the electrochemical performance of a lithium-sulfur battery, and effectively inhibits the shuttling of polysulfide.
The technical scheme for realizing the purpose of the invention is as follows:
a preparation method of an oxygen-doped cobalt phosphide/carbon nanotube composite material comprises the following steps:
1）Co 3 O 4 preparation of/CNT composite: dissolving cobalt chloride and carbon nano tube in water solution, dropwise adding 100 mul ammonia water, adjusting the temperature to 60-120 ℃, stirring at low speed for 7-15 hours to enable Co to grow on the surface of the carbon nano tube 3 O 4 Washing the particles with ethanol and deionized water after the reaction is finished, washing the mixture for 3 times, and freeze-drying the washed sample to obtain Co 3 O 4 the/CNT composite material, wherein the carbon nano tube is a multi-wall carbon nano tube, and the purpose of washing the product is mainly to remove reaction impurities and ensure that a pure product is obtained and is not influenced by the impurities;
2) Preparation of CoP/CNT composite: anhydrous sodium hypophosphite NaH 2 PO 2 Placing the Co prepared in the step 1) as a phosphorus source at the upstream of a tube furnace 3 O 4 Drying the/CNT material, placing the dried/CNT material at the downstream of a tubular furnace, heating to 350 ℃ in an inert protective gas atmosphere, keeping the temperature for 2 hours, wherein the heating rate is 5 ℃ per minute, the gas flow is 60 sccm, obtaining a CoP/CNT composite material,wherein the inert atmosphere is argon or nitrogen;
3) Preparation of O-CoP/CNT composite: and (3) placing the CoP/CNT prepared in the step 2) into a tubular furnace, heating to 100-400 ℃ in the air atmosphere, continuing for 30 minutes for oxygen doping, wherein the heating rate is 5 ℃ per minute, the gas flow is 60 sccm, and cooling to room temperature in the air atmosphere to obtain the O-CoP/CNT composite material, namely the oxygen-doped cobalt phosphide/carbon nanotube composite material.
The ammonia water in the step 1) is an aqueous solution containing 25% -28% of ammonia.
Co in step 2) 3 O 4 CNT and NaH 2 PO 2 The mass ratio of (1) to (10).
The oxygen-doped cobalt phosphide/carbon nanotube composite material prepared by the preparation method of the oxygen-doped cobalt phosphide/carbon nanotube composite material is used for preparing an O-CoP/CNT modified functionalized diaphragm, the diaphragm substrate of the functionalized diaphragm is Celgard 2500, and the O-CoP/CNT composite material is coated on the diaphragm substrate.
The preparation process of the functionalized diaphragm comprises the following steps: dispersing O-CoP/CNT, conductive carbon, a binder and a solvent to form uniform slurry, wherein the mass ratio of the O-CoP/CNT, the conductive carbon and the binder is 8; uniformly coating the obtained slurry on one side of a diaphragm base material by any one of a spraying mode, a scraper coating mode or a coating roller mode to form an O-CoP/CNT modified functional diaphragm, and drying the coated diaphragm in vacuum at 50-60 ℃ to obtain the O-CoP/CNT modified functional diaphragm, wherein conductive carbon is one or more of conductive carbon black, acetylene black, keqin carbon and active carbon, a binder is polyvinylidene fluoride (PVDF), and a solvent is N-methylpyrrolidone (NMP).
The oxygen-doped cobalt phosphide/carbon nanotube composite material prepared by the preparation method of the oxygen-doped cobalt phosphide/carbon nanotube composite material is applied to a lithium-sulfur battery.
The process of preparing the lithium-sulfur battery by the functionalized diaphragm comprises the following steps:
the method comprises the steps of taking a sulfur/graphene composite material as a positive electrode, taking a metal lithium sheet as a negative electrode, and assembling an O-CoP/CNT composite material modified functional diaphragm and ether electrolyte into a lithium-sulfur battery, wherein the O-CoP/CNT composite material modified functional diaphragm and the ether electrolyte are used for assembling the lithium-sulfur batteryAnd one side of the O-CoP/CNT composite material covered on the diaphragm substrate is opposite to the positive plate, and the other side of the O-CoP/CNT composite material is opposite to the negative plate, and a 2032 type button cell is prepared in a glove box with the water oxygen content lower than 0.01 ppm, wherein: the sulfur/graphene composite material is formed by uniformly grinding sulfur and graphene in a mass ratio of 9; the positive pole piece is formed by mixing sulfur/graphene, conductive carbon black SP and polyvinylidene fluoride according to the mass ratio of 8; the ether electrolyte is 1M lithium bistrifluoromethanesulfonylimide LiTFSI, dioxolane DOL and glycol dimethyl ether DME and 1 wt% lithium nitrate LiNO 3 The mixed solution of (1).
Compared with the prior art, the technical scheme has the following beneficial effects:
according to the technical scheme, air is introduced by calcining in a tube furnace, oxygen doping is carried out on CoP, cobalt metaphosphate is generated on the surface of the oxygen-doped cobalt phosphide/carbon nano tube composite material, more active sites can be provided for absorbing polysulfide, the conversion of polysulfide is accelerated, the oxygen-doped cobalt phosphide/carbon nano tube composite material is coated on the membrane to prepare the functional membrane, the electrochemical performance of the lithium-sulfur battery can be remarkably improved, and the shuttle of polysulfide is effectively inhibited.
2. The O-CoP/CNT composite material prepared by the technical scheme is applied to the lithium-sulfur battery, and the 526.4 mAh.g of the lithium-sulfur battery is realized at the current density of 5C -1 The specific capacity of the resin composition is kept at 961.7 mAh g after 0.2C circulation for 500 circles -1 The specific capacity of (a).
The preparation method is simple, low in cost, environment-friendly and safe, and does not need to be completed under the sealed high-pressure reaction condition. The material prepared by the method provides more active sites for polysulfide adsorption, can accelerate the conversion of polysulfide, is coated on a diaphragm to prepare a functional diaphragm, can obviously improve the electrochemical performance of a lithium-sulfur battery, and effectively inhibits the shuttling of polysulfide.
Drawings
FIG. 1 shows Co in example 3 O 4 X-ray diffraction pattern of/CNT;
FIG. 2 shows Co in example 3 O 4 Raman spectrum of/CNT;
FIG. 3 is a Raman spectrum of the CoP/CNT composite and the O-CoP/CNT composite of the examples;
FIG. 4 is a TEM image of the O-CoP/CNT composite material in the example;
FIG. 5 is a drawing of the polysulfide adsorption of the CoP/CNT composite and O-CoP/CNT composite of the examples;
FIG. 6 is a graph of electrochemical performance of lithium sulfur cells assembled with different separators in the examples;
FIG. 7 is a graph of rate performance of lithium sulfur batteries assembled with different separators in the examples;
fig. 8 is a graph of cycle performance of lithium sulfur batteries assembled with different separators in the examples.
Detailed description of the preferred embodiments
The invention will be further illustrated by the following figures and examples, but is not limited thereto.
Examples
Example 1: the preparation method of the O-CoP/CNT composite material comprises the following steps:
1）Co 3 O 4 preparation of/CNT composite: dissolving 11.897 g of cobalt chloride hexahydrate in 50 ml of deionized water to form a uniform solution; adding 100 mg of hydroxylated carbon nano tube into the solution, stirring and ultrasonically mixing the suspension uniformly; dripping 100 mul of ammonia water solution into the suspension, and continuously stirring uniformly; putting the solution in an oil bath pan, adjusting the temperature to 80 ℃, stirring at low speed for 12 hours until precipitation occurs, namely growing Co on the surface of the carbon nano tube 3 O 4 Particles; carrying out suction filtration on the obtained solution, and washing the product for 3 times by using ethanol and deionized water respectively; drying the product obtained by suction filtration for 24 hours in a freezing way; taking out the dried sample to obtain powder Co 3 O 4 a/CNT composite;
2) Preparation of CoP/CNT composite: anhydrous sodium hypophosphite is used as a phosphorus source, the phosphorus source is arranged at the upstream of a tube furnace, and the dried Co is put into the tube furnace 3 O 4 the/CNT composite is placed downstream of a tube furnace, where Co 3 O 4 The mass ratio of the/CNT composite material to the anhydrous sodium hypophosphite is 1Heating to 350 ℃ under the atmosphere, preserving heat for 2 hours, carrying out phosphorization at the heating rate of 5 ℃ for minutes and the gas flow of 60 sccm, and cooling to room temperature to obtain a CoP/CNT composite material;
3) Preparation of O-CoP/CNT composite: and (3) continuously placing the CoP/CNT composite material prepared in the step 2) into a tubular furnace, heating to 300 ℃ in an air atmosphere, preserving the temperature for 30 minutes, and carrying out oxygen doping, wherein the heating rate is 5 ℃ per minute, and the gas flow is 60 sccm, so as to obtain the O-CoP/CNT composite material.
The X-ray diffraction pattern of the above-prepared material was measured, as shown in FIG. 1, co 3 O 4 Co removal is not observed in XRD diffraction peaks of/CNT composite material 3 O 4 And other hetero-phase peaks of CNT, indicating that pure Co is prepared 3 O 4 the/CNT composite material has good crystallinity, and the XRD pattern of the CoP/CNT composite material shows that Co is in a high-temperature environment 3 O 4 After phosphorization of the/CNT composite material, co 3 O 4 The diffraction peak of (2) completely disappeared, and only the diffraction peaks of CoP and CNT were observed, indicating that Co was present 3 O 4 Is successfully phosphated into cobalt phosphide, and in addition, other impurities are not detected, and the diffraction peaks of the O-CoP/CNT composite material and the CoP/CNT composite material are matched with each other along with further heat treatment in an air atmosphere, so that oxygen doping has no obvious influence on the structure of a CoP bulk phase.
Raman characterization is carried out on the composite material before and after oxygen doping, and as shown in figure 3, the thickness of the CoP/CNT composite material is 187.4cm -1 And 269.5cm -1 Two peaks are located, corresponding to active mode F2g generated by natural oxidation in oxidation crystal lattice and characteristic Eg active mode in CoP crystal lattice respectively, after annealing in air, the Raman spectrum of the O-CoP/CNT composite material is in-682 cm -1 And 1153cm -1 Two peaks appear at the position, which respectively correspond to the active modes A1g and v in the oxide lattice 3 (PO 3 ) Antisymmetric stretching vibration, and the results show that the CoP surface structure exists in an oxygen-doped form;
TEM representation is carried out on the prepared material, as shown in figure 4, nano particles of the O-CoP/CNT composite material are distributed around the carbon nano tube to form a three-dimensional network structure, which is beneficial to accelerating charge transfer in the electrochemical process, and a plurality of obvious holes can be found due to O doping;
equal mass of CNT, coP/CNT and O-CoP/CNT were added to 4 ml of 2mM Li, respectively 2 S 6 Polysulfide adsorption experiments were performed in solution, with O-CoP/CNT-added Li, as shown in FIG. 5 2 S 6 The solution faded significantly after standing for 10min, while Li of CNT was added 2 S 6 The solution remained yellow, li of CoP/CNT 2 S 6 The solution showed only slight discoloration.
Preparation of O-CoP/CNT composite modified functionalized membrane: dispersing the prepared O-CoP/CNT composite material, conductive carbon, a binder and a solvent to form uniform slurry, wherein the mass ratio of the O-CoP/CNT composite material to the conductive carbon to the binder is 8; uniformly coating the obtained slurry on one side of a diaphragm base material by using a scraper to form a functional diaphragm modified by an O-CoP/CNT composite material; and (3) drying the coated diaphragm in vacuum at 50 ℃, and cooling to room temperature to obtain the O-CoP/CNT modified functionalized diaphragm.
Assembling the O-CoP/CNT composite material modified functional diaphragm lithium-sulfur battery: a sulfur/graphene composite material is used as a positive electrode, a metal lithium sheet is used as a negative electrode, and an O-CoP/CNT modified functionalized diaphragm (polypropylene Celgard 2500) and DOL/DME (V: V = 1.
FIG. 6 is a graph of electrochemical performance of lithium sulfur batteries assembled by coating different materials on a separator, showing typical two-step discharge and one-step charge behavior of a sulfur positive electrode, from which two cathode peaks at 2.3V and 2.0V, attributed to polysulfide intermediates and products, are known from the O-CoP/CNT curveSubstance Li 2 And (3) forming S, wherein the anode peak at the position of 2.1V corresponds to the oxidation process, and the comparison shows that the O-CoP/CNT coated diaphragm battery has higher redox current, narrower current peak and relatively smaller polarization, thereby proving that the O-CoP/CNT has higher electrochemical conversion speed.
FIG. 7 shows the rate capability of lithium-sulfur battery assembled by coating different materials on the separator, and it can be seen from FIG. 7 that the specific capacity of the first discharge of O-CoP/CNT at corresponding rate is higher than that of the CoP/CNT composite material, and the O-CoP/CNT composite material can reach 526.4 mAh g at 5C rate -1 The method has good rate performance, the performance improvement is probably due to the fact that the anchoring effect of O-doped CoP on polysulfide is further improved, and the formed Co-O bond can promote the redox conversion rate of polysulfide, accelerate the redox reaction kinetics of lithium polysulfide in a lithium sulfur battery and play a role in inhibiting the shuttle effect.
FIG. 8 shows the cycle performance of a lithium-sulfur battery assembled by coating different materials on a separator, and it can be seen from FIG. 8 that the specific first discharge capacity of O-CoP/CNT at 0.2C is 1280.8 mAh g -1 The capacity remained at 961.7 mAh g even after 500 cycles -1 As can be seen from the figure, the O-CoP/CNT composite material has the best cycle performance, and the specific discharge capacity is obviously improved.
Example 2: the preparation method of the O-CoP/CNT composite material comprises the following steps:
1）Co 3 O 4 preparation of/CNT composite:
dissolving 11.897 g of cobalt chloride hexahydrate in 50 ml of deionized water to form a uniform solution; adding 100 mg of hydroxylated carbon nano tubes into the solution, stirring and ultrasonically mixing the suspension uniformly; dripping 100 mul of ammonia water solution into the suspension, and continuously stirring uniformly; placing the solution in an oil bath pan, adjusting the temperature to 60 ℃, stirring at low speed for 16 hours until precipitation occurs, namely growing Co on the surface of the carbon nano tube 3 O 4 Particles; carrying out suction filtration on the obtained solution, and washing the product for 3 times by using ethanol and deionized water respectively; the product obtained by suction filtration is usedDrying for 24 hours in a freezing mode; taking out the dried sample to obtain powder Co 3 O 4 a/CNT composite;
2) Preparation of CoP/CNT composite: anhydrous sodium hypophosphite is used as a phosphorus source, the phosphorus source is arranged at the upstream of a tube furnace, and the dried Co is put into the tube furnace 3 O 4 the/CNT composite is placed downstream of a tube furnace, where Co 3 O 4 Heating the CNT composite material to 350 ℃ in an inert protective gas atmosphere, keeping the temperature for 2 hours for phosphorization, wherein the mass ratio of the CNT composite material to anhydrous sodium hypophosphite is 1;
3) Preparation of O-CoP/CNT composite: and (3) continuously placing the CoP/CNT composite material prepared in the step 2) in a tubular furnace, heating to 100 ℃ in an air atmosphere, and keeping the temperature for 30 minutes for oxygen doping, wherein the heating rate is 5 ℃ per minute, and the air flow is 60 sccm, so as to obtain the O-CoP/CNT composite material.
Example 3: the preparation method of the O-CoP/CNT composite material comprises the following steps:
1） Co 3 O 4 preparation of/CNT composite: dissolving 11.897 g of cobalt chloride hexahydrate in 50 ml of deionized water to form a uniform solution; adding 100 mg of hydroxylated carbon nano tube into the solution, stirring and ultrasonically mixing the suspension uniformly; dripping 100 mul of ammonia water solution into the suspension, and continuously stirring uniformly; putting the solution in an oil bath pan, adjusting the temperature to 100 ℃, stirring at low speed for 10 hours until precipitation occurs, namely growing Co on the surface of the carbon nano tube 3 O 4 Particles; carrying out suction filtration on the obtained solution, and washing the product for 3 times by using ethanol and deionized water respectively; drying the product obtained by suction filtration for 24 hours in a freezing way; taking out the dried sample to obtain powder Co 3 O 4 a/CNT composite;
2) Preparation of CoP/CNT composite: anhydrous sodium hypophosphite is used as a phosphorus source, the phosphorus source is arranged at the upstream of a tube furnace, and the dried Co is put into the tube furnace 3 O 4 the/CNT composite is placed downstream of a tube furnace, where Co 3 O 4 The mass ratio of the/CNT composite material to the anhydrous sodium hypophosphite is 1Heating to 350 ℃ under the atmosphere of inert protective gas, preserving heat for 2 hours, carrying out phosphorization, wherein the heating rate is 5 ℃ per minute, the gas flow is 60 sccm, and cooling to room temperature to obtain a CoP/CNT composite material;
3) Preparation of O-CoP/CNT composite: and (3) continuously placing the CoP/CNT composite material prepared in the step 2) into a tubular furnace, heating to 200 ℃ in an air atmosphere, preserving the temperature for 30 minutes, and carrying out oxygen doping, wherein the heating rate is 5 ℃ per minute, and the gas flow is 60 sccm, so as to obtain the O-CoP/CNT composite material.
Example 4: the preparation method of the O-CoP/CNT composite material comprises the following steps:
1） Co 3 O 4 preparation of/CNT composite: dissolving 11.897 g of cobalt chloride hexahydrate in 50 ml of deionized water to form a uniform solution; adding 100 mg of hydroxylated carbon nano tube into the solution, stirring and ultrasonically mixing the suspension uniformly; dripping 100 mul of ammonia water solution into the suspension, and continuously stirring uniformly; placing the solution in an oil bath pan, adjusting the temperature to 120 ℃, stirring at low speed for 7 hours until precipitation occurs, namely growing Co on the surface of the carbon nano tube 3 O 4 A particle; carrying out suction filtration on the obtained solution, and washing the product for 3 times by using ethanol and deionized water respectively; drying the product obtained by suction filtration for 24 hours in a freezing way; taking out the dried sample to obtain powder Co 3 O 4 a/CNT composite;
2) Preparation of CoP/CNT composite: anhydrous sodium hypophosphite is used as a phosphorus source, the phosphorus source is arranged at the upstream of a tube furnace, and the dried Co is put into the tube furnace 3 O 4 the/CNT composite is placed downstream of a tube furnace, where Co 3 O 4 Heating the CNT composite material to 350 ℃ in an inert protective gas atmosphere, keeping the temperature for 2 hours for phosphorization, wherein the mass ratio of the CNT composite material to anhydrous sodium hypophosphite is 1;
3) Preparation of O-CoP/CNT composite: and (3) continuously placing the CoP/CNT composite material prepared in the step 2) in a tubular furnace, heating to 400 ℃ in air atmosphere, and keeping the temperature for 30 minutes for oxygen doping, wherein the heating rate is 5 ℃ per minute, and the air flow is 60 sccm, so as to obtain the O-CoP/CNT composite material.
Claims (6)
1. The preparation method of the oxygen-doped cobalt phosphide/carbon nanotube composite material is characterized by comprising the following steps of:
1）Co 3 O 4 preparation of/CNT composite: dissolving cobalt chloride and carbon nano tube in water solution, dropwise adding 100 mu l of ammonia water, adjusting the temperature to 60-120 ℃, stirring at low speed for 7-15 hours to enable Co to grow on the surface of the carbon nano tube 3 O 4 Washing the particles with ethanol and deionized water after the reaction is finished, washing the mixture for 3 times, and freeze-drying the washed sample to obtain Co 3 O 4 a/CNT composite wherein the carbon nanotubes are multi-walled carbon nanotubes;
2) Preparation of CoP/CNT composite: anhydrous sodium hypophosphite NaH 2 PO 2 Placing the Co prepared in the step 1) as a phosphorus source at the upstream of a tube furnace 3 O 4 Drying the/CNT material, then placing the dried/CNT material at the downstream of a tubular furnace, heating to 350 ℃ in an inert protective gas atmosphere, and keeping the temperature for 2 hours, wherein the heating rate is 5 ℃ per minute, the gas flow is 60 sccm, so as to obtain the CoP/CNT composite material, wherein the inert atmosphere is argon or nitrogen;
3) Preparation of O-CoP/CNT composite: and (3) placing the CoP/CNT prepared in the step 2) into a tubular furnace, heating to 100-400 ℃ in the air atmosphere, continuing for 30 minutes for oxygen doping, wherein the heating rate is 5 ℃ per minute, the gas flow is 60 sccm, and cooling to room temperature in the air atmosphere to obtain the O-CoP/CNT composite material, namely the oxygen-doped cobalt phosphide/carbon nanotube composite material.
2. The method for preparing the oxygen-doped cobalt phosphide/carbon nanotube composite material according to claim 1, wherein the ammonia water in the step 1) is an aqueous solution containing 25% -28% of ammonia.
3. The method for preparing the oxygen-doped cobalt phosphide/carbon nanotube composite material according to claim 1, wherein the Co in the step 2) is 3 O 4 CNT and NaH 2 PO 2 The mass ratio of (1) to (10).
4. The O-CoP/CNT modified functionalized membrane prepared from the oxygen-doped cobalt phosphide/carbon nanotube composite material prepared by the method for preparing the oxygen-doped cobalt phosphide/carbon nanotube composite material as set forth in claim 1, 2 or 3, wherein the membrane substrate of the functionalized membrane is Celgard 2500, and the O-CoP/CNT composite material is coated on one side of the membrane substrate.
5. The O-CoP/CNT modified functionalized membrane of claim 4, wherein the functionalized membrane is prepared by the following steps: dispersing O-CoP/CNT, conductive carbon, a binder and a solvent to form uniform slurry, wherein the mass ratio of the O-CoP/CNT, the conductive carbon and the binder is 8; uniformly coating the obtained slurry on one side of a diaphragm base material by any one of a spraying mode, a scraper coating mode or a coating roller mode to form an O-CoP/CNT modified functional diaphragm, and drying the coated diaphragm in vacuum at 50-60 ℃ to obtain the O-CoP/CNT modified functional diaphragm, wherein conductive carbon is one or more of conductive carbon black, acetylene black, keqin carbon and active carbon, a binder is polyvinylidene fluoride (PVDF), and a solvent is N-methylpyrrolidone (NMP).
6. Use of the oxygen-doped cobalt phosphide/carbon nanotube composite prepared by the method for preparing oxygen-doped cobalt phosphide/carbon nanotube composite according to claim 1, 2 or 3 in a lithium-sulfur battery.
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