CN116111119A - Honeycomb carbon anchored phosphorus doped cobalt selenide lithium carbon dioxide battery anode material and preparation method thereof - Google Patents
Honeycomb carbon anchored phosphorus doped cobalt selenide lithium carbon dioxide battery anode material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a honeycomb carbon anchored phosphorus doped cobalt selenide lithium carbon dioxide battery anode material and a preparation method thereof, wherein a matrix is of a honeycomb carbon structure, and the aperture of the honeycomb carbon is 0.5-2 mu m; the phosphorus doped nano cobalt selenide particles are uniformly distributed in the honeycomb carbon structure, and the particle size of the phosphorus doped nano cobalt selenide particles is 40-100nm. The electrode material has simple preparation process and unique appearance, the honeycomb structure is of micron order, the holes are beneficial to mass transfer process and storage of discharge products, and the wettability of electrolyte to the discharge products is enhanced; the cobalt selenide particles are nano-sized, can effectively increase the specific surface area and expose more catalytic active sites. These advantages help to improve the specific capacity and cycling stability of lithium carbon dioxide batteries.
Description
Technical Field
The invention belongs to the technical field of electrochemistry and new energy, and particularly relates to a honeycomb carbon anchored phosphorus doped cobalt lithium selenide carbon dioxide battery anode material and a preparation method thereof.
Background
The statements herein merely provide background information related to the present disclosure and may not necessarily constitute prior art.
Carbon dioxide is a major component of greenhouse gases and has caused serious environmental problems such as sea level elevation, global warming, ocean acidification, etc. With the increasing emission of carbon dioxide, in particular exhaust emissions from fuel automobiles, a series of uncontrollable factors and even disasters can result. Therefore, it is important to develop a technology for reducing carbon dioxide emissions and reasonably utilizing the same. Since lithium carbon dioxide cells have a relatively high discharge potential (-2.8V) and theoretical specific energy density (1876 Wh kg) -1 ) Has good application prospect in the fields of carbon dioxide fixation and energy storage. Research shows that the atmosphere on Mars is 95.32% of carbon dioxide, so that the lithium carbon dioxide battery has the unique advantage on Mars. However, lithium carbonate, which is a product generated in the charge and discharge processes of the battery system, is a poorly soluble substance and is difficult to decompose at low voltage, thereby affecting the coulombic efficiency and the cycle performance of the battery system. The high-efficiency positive electrode catalytic material can improve the reaction kinetics in the electrochemical process of the lithium carbon dioxide battery, and the reaction kinetics can be improved by adjusting the reaction conditions of gas and mediumThe adsorption energy of the intermediate products and other means are used for improving the overall performance of the battery. Thus, the method is applicable to a variety of applications. It is necessary to study the anode catalytic material of the high-efficiency lithium carbon dioxide battery.
In recent years, researchers have made many efforts to find high performance catalysts. Noble metal catalysts are widely studied in the catalytic field due to their excellent catalytic properties, however, such catalysts are expensive and greatly limit large-scale applications. The carbon material has low price, good conductivity and good catalytic performance, but the carbon material catalyst can not well play a role in a lithium carbon dioxide battery because lithium carbonate can not be effectively decomposed.
Disclosure of Invention
In view of the deficiencies of the prior art, the invention aims to provide a honeycomb carbon anchored phosphorus doped cobalt selenide (P-CoSe) 2 @C) positive electrode material of lithium carbon dioxide battery and preparation method thereof. The electrode material has simple preparation process and unique appearance, the honeycomb structure is of micron order, the holes are beneficial to mass transfer process and storage of discharge products, and the wettability of electrolyte to the discharge products is enhanced; the cobalt selenide particles are nano-sized, can effectively increase the specific surface area and expose more catalytic active sites. These advantages help to improve the specific capacity and cycling stability of lithium carbon dioxide batteries.
In order to achieve the above object, the present invention is realized by the following technical scheme:
in a first aspect, the present invention provides a honeycomb carbon-anchored phosphorus-doped cobalt selenide (P-CoSe 2 @C) a lithium carbon dioxide battery anode material, wherein a matrix is of a honeycomb carbon structure, and the pore diameter of the honeycomb carbon is 0.5-2 mu m;
the phosphorus doped nano cobalt selenide particles are uniformly distributed in the honeycomb carbon structure, and the particle size of the phosphorus doped nano cobalt selenide particles is 40-100nm.
In some embodiments, the honeycomb carbon structure has a pore size of 1-1.5 μm.
In some embodiments, the phosphorus doped nano cobalt selenide particles have a particle size of 40-80nm; preferably 40-60nm.
Preferably, the wall thickness of the honeycomb carbon is 40-50nm.
In some embodiments, the honeycomb carbon-anchored phosphorus-doped cobalt selenide (P-CoSe 2 The specific surface area of the anode material of the @ C) lithium carbon dioxide battery is 12-66.87m 2 g -1 。
In a second aspect, the present invention provides a honeycomb carbon-anchored phosphorus-doped cobalt selenide (P-CoSe 2 The preparation method of the anode material of the@C) lithium carbon dioxide battery comprises the following steps:
dispersing polyvinylpyrrolidone and cobalt salt in deionized water, uniformly mixing, and then freeze-drying to obtain a Co-PVP precursor;
grinding the freeze-dried Co-PVP precursor, and calcining in an inert atmosphere to obtain a Co/C precursor;
grinding Co/C precursor, transferring into downstream porcelain boat, calcining sodium hypophosphite and selenium powder in inert atmosphere at 550-650deg.C for 1.5-2.5 hr to obtain P-CoSe 2 @C；
The mass ratio of the selenium powder to the sodium hypophosphite to the Co/C precursor is 3-5:1-3:1;
the mass ratio of polyvinylpyrrolidone to cobalt salt is 0.8-1.5:0.8-1.5.
In some embodiments, the mass ratio of polyvinylpyrrolidone, cobalt salt, and deionized water is 0.8-1.5:0.8-1.5:15-25.
Preferably, the cobalt salt is cobalt nitrate.
In some embodiments, the freeze-dried cold trap is below-50 ℃, the air pressure is below 10Pa, and the freeze-drying time is 20-30 hours. Because the component of the synthesized primary material is larger, the higher temperature and air pressure can lead to incomplete freeze-drying of the material and the appearance of transparent particles, which has influence on the post-treatment of the material.
In some embodiments, the Co-PVP precursor is calcined at a temperature of 750-850℃for a period of 1-2 hours. At the same time as calcining the carbon source to carbon, the material itself generates a small amount of gas at this temperature to form a micro-bulge-like structure which is beneficial for subsequent formation of the honeycomb-like final product.
In some embodiments, the polyvinylpyrrolidone is PVP (K30).
In some embodiments, the Co/C precursor is milled until a powder of uniform particle size is dispersed uniformly.
The freeze-dried material is in a block shape, and is difficult to fully mix with other raw materials for reaction when the freeze-dried material participates in the reaction again. The freeze-dried blocks are ground into powder, so that the freeze-dried blocks can be fully reacted with gas generated by selenium powder and sodium hypophosphite which are processed later.
Because the honeycomb structure is in a micron level, a honeycomb precursor structure is formed before selenization/phosphatization, and the material structure is damaged due to overlarge crushing degree, the grinding Co/C precursor should grasp the strength, and the freeze-dried block is uniformly ground.
The beneficial effects achieved by one or more embodiments of the present invention described above are as follows:
(1) The invention adopts a simple freeze drying method and a mode of simultaneously phosphating/selenizing under a protective atmosphere to construct the honeycomb carbon matrix anchored doped cobalt selenide catalyst, and the material has a three-dimensional pore structure and can be Li + And CO 2 The good conductivity of carbon also significantly promotes electron transport and accelerates slow reaction kinetics during charge and discharge. It is worth noting that the amount of doped phosphorus can be regulated and controlled by regulating the proportion of selenium powder and sodium hypophosphite, so that the catalytic activity of the material is regulated and controlled.
(2) Since the skeleton of the material is a carbon matrix, P-CoSe 2 The @ C material has lighter volume density, larger specific surface area and more catalytic active sites, and the catalytic activity can be greatly improved. The three-dimensional hole space provided by the carbon matrix is beneficial to the storage of discharge products, the accumulation of the discharge products on the surface of the electrode is prevented, and the reasonable accumulation is also beneficial to the decomposition of the discharge products.
The honeycomb carbon structure is constructed, the phosphorus doped cobalt selenide particles are anchored on the honeycomb carbon, the overall conductivity of the material is improved, and meanwhile, more discharge products can be accommodated in the material. The preparation method of the invention not only can obtain the carbon matrix supported orthogonal phase doped cobalt selenide particles, but also can obtain the catalytic material with good morphology through freeze drying, and the subsequent stepsThe sintering step of the catalyst can be multiplied to prepare the lithium carbon dioxide battery P-CoSe with high performance 2 The catalyst material @ C lays a foundation for mass production of the catalyst material and plays a role in promoting and assisting commercialization of lithium carbon dioxide batteries.
(3) The shape and electrochemical performance of the anode catalytic material prepared by the invention have good repeatability and higher cycling stability. In a specific embodiment, the electrode material is described as being at 100mAg -1 Has a current density of 1000mAh g and a cut-off capacity of -1 At this time, 214 turns may be cycled steadily. At 1000mAg -1 Has a current density of 500mAh g and a cut-off capacity of -1 When the device is in use, the device can stably circulate for 150 circles.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 is an SEM image of a Co-PVP precursor synthesized by the method of the present invention;
FIG. 2 is a cellular P-CoSe synthesized by the method of the present invention 2 SEM image of @ C;
FIG. 3 is a cellular P-CoSe synthesized by the method of the present invention 2 XRD pattern of @ C;
FIG. 4 shows a cellular P-CoSe synthesized by the method of the present invention 2 BET profile at @ C;
FIG. 5 shows a cellular P-CoSe synthesized by the method of the present invention 2 EDS-Mapping profile of @ C, wherein (a) is P-CoSe 2 SEM image of @ C, (b) is P-CoSe 2 Summarizing the EDS-Mapping diagram of each element @ C, (C) Mapping diagram of the P element, (d) Mapping diagram of the Co element, (e) Mapping diagram of the Se element, and (f) Mapping diagram of the C element;
FIG. 6 is a cellular P-CoSe synthesized by the method of the present invention 2 The cycle performance chart for lithium carbon dioxide battery test at current density of 100mA g -1 Cut-off capacity of 1000mAh g -1 ；
FIG. 7 is a cellular P-CoSe synthesized by the method of the present invention 2 @C for lithiumCarbon dioxide cell test cycle performance chart with current density of 1000mAg -1 Cut-off capacity of 500mAh g -1 ；
FIG. 8 is a cellular P-CoSe synthesized by the method of the present invention 2 Initial performance graph of @ C for lithium carbon dioxide battery test with current density of 500mAg -1 ；
FIG. 9 is a cellular P-CoSe synthesized by the method of the present invention 2 Ratio performance graph of @ C for lithium carbon dioxide battery test with current density of 200mAg -1 、400mAg -1 、600mAg -1 、800mAg -1 、200mAg -1 。
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The invention is further illustrated below with reference to examples.
Example 1
Cellular P-CoSe 2 @c, prepared by the steps of:
(1) 6g of cobalt nitrate hexahydrate and 6g of polyvinylpyrrolidone were added to 120mL of deionized water and magnetically stirred for 10 minutes to obtain a homogeneous solution. Liquid nitrogen was then poured around the solution and container to obtain a uniform frozen liquid sample, which was transferred to a freeze-drying oven at-50 ℃ and a gas pressure below 10Pa for 24h of lyophilization.
(2) Transferring the purple freeze-dried block obtained in the step (1) into a mortar to be ground into powder, transferring into a porcelain boat, and heating in an argon atmosphere at a temperature rising rate of 5 ℃ for min -1 Heating to 800 ℃, preserving heat for 1.5h, and naturally cooling to room temperature to obtain the Co/C precursor.
(3) Transferring the Co/C precursor collected in the step (2) into a downstream porcelain boat in a tube furnace, wherein the mass ratio of the upstream porcelain boat is 2:1 sodium hypophosphite and selenium powder, the Co/C precursor amount is 1/2 of that of the selenium powder, and then the temperature rising rate is 3 ℃ for min in argon atmosphere -1 Heating to 600 ℃, and preserving heat for 2 hours. CoolingAfter reaching room temperature, the honeycomb P-CoSe is obtained 2 Sample @ C.
FIG. 1 is an SEM image of a Co-PVP precursor material synthesized according to the present invention, showing that the precursor has a foamed structure; FIG. 2 is a diagram of a synthesized cellular P-CoSe of the present invention 2 Material @ C, due to the pH generated during sintering of sodium hypophosphite 3 Gas leaving pores to form a honeycomb structure; FIG. 3 is a cellular P-CoSe 2 XRD pattern of @ C sample, diffraction data and CoSe 2 (PDF # 53-0449); FIG. 4 shows a honeycomb-shaped P-CoSe synthesized according to the invention 2 BET plot of @ C material, measured as a sample specific surface area of 66.87m 2 g -1 . FIG. 5 is a schematic diagram of a synthetic honeycomb P-CoSe of the present invention 2 EDS-Mapping pattern of @ C material, it was observed that the elements were uniformly distributed on the material.
The cellular P-CoSe obtained in example 1 2 The electrode was prepared as follows:
respectively weighing cellular P-CoSe according to the mass ratio of 7:2:1 2 Sample @ C, super P and PTFE, which were sonicated in an appropriate amount of isopropanol to obtain an electrode material slurry. The slurry was then uniformly sprayed on a round carbon paper having a diameter of 19mm, and vacuum-dried at 120 ℃ for 12 hours to obtain a positive electrode sheet. 2032 button battery with hole in positive electrode shell for electrochemical test of lithium carbon dioxide battery, metal lithium sheet is used as negative electrode, and electrolyte is 1mol L -1 LiNO 3 and/DMSO, whatman GF/D glass fiber is used as the membrane. The battery is assembled in a glove box filled with argon, and is subjected to charge and discharge test in pure carbon dioxide atmosphere at room temperature, and the test equipment is a LAND CT 2001A multichannel battery tester.
FIGS. 6 and 7 show the honeycomb P-CoSe obtained in this example 2 The cycle performance diagram of the@C electrode material for testing the lithium carbon dioxide battery is 100mAg and 1000mAg respectively -1 Current density of 1000, 500mAh g -1 Can reach 214 and 150 cycles of cycle life, respectively.
FIG. 8 shows a honeycomb-like P-CoSe obtained by the method of the present invention 2 First-circle performance chart of@C electrode material for lithium carbon dioxide battery test, and test conditions500mA g -1 Has a specific charge/discharge capacity of 10320/13300mAh g -1 。
FIG. 9 shows a honeycomb-like P-CoSe obtained by the method of the present invention 2 The @ C electrode is used for a rate performance graph of a lithium carbon dioxide battery test, and the result shows that the change of the charge-discharge terminal voltage along with the increase of the current density is smaller, so that the catalytic material has good rate performance.
Example 2
Cellular P-CoSe 2 @c, prepared by the steps of:
(1) 6g of cobalt nitrate hexahydrate and 3g of polyvinylpyrrolidone were added to 120mL of deionized water and magnetically stirred for 10 minutes to obtain a homogeneous solution. Liquid nitrogen was then poured around the solution and container to obtain a frozen liquid sample that was frozen uniformly, and transferred to a freeze-drying oven at-50 ℃ and a gas pressure below 10Pa for 24h of lyophilization.
(2) Transferring the purple freeze-dried block obtained in the step (1) into a mortar to be ground into powder, then transferring into a porcelain boat, and heating at a temperature rising rate of 5 ℃ for min under an argon atmosphere -1 Heating to 800 ℃ in a tube furnace under the condition, preserving heat for 1.5h, and naturally cooling to room temperature to obtain the Co/C precursor.
(3) Transferring the Co/C precursor collected in the step (2) into a downstream porcelain boat in a tube furnace, wherein the mass ratio of the upstream porcelain boat is 2:1 sodium hypophosphite and selenium powder, the Co/C precursor amount is 1/2 of that of the selenium powder, and then the temperature rising rate is 3 ℃ for min in argon atmosphere -1 Is heated to 600 ℃ and is kept for 2 hours. Cooling to room temperature to obtain honeycomb P-CoSe 2 Sample @ C.
Example 3
Cellular P-CoSe 2 @c, prepared by the steps of:
(1) 6g of cobalt nitrate hexahydrate and 6g of polyvinylpyrrolidone were added to 200mL of deionized water and magnetically stirred for 10min to obtain a homogeneous solution. Liquid nitrogen was then poured around the solution and container to obtain a frozen liquid sample that was frozen uniformly, and transferred to a freeze-drying oven at-50 ℃ and a gas pressure of less than 10Pa for lyophilization for 48h.
(2) Transferring the purple freeze-dried block obtained in the step (1) into a mortar to be ground into powder, then transferring into a porcelain boat,in argon atmosphere, the temperature rising rate is 5 ℃ for min -1 Heating to 800 ℃ in a tube furnace under the condition, preserving heat for 1.5h, and naturally cooling to room temperature to obtain the Co/C precursor.
(3) Transferring the Co/C precursor collected in the step (2) into a downstream porcelain boat in a tube furnace, wherein the mass ratio of the upstream porcelain boat is 2:1 sodium hypophosphite and selenium powder, the Co/C precursor amount is 1/2 of that of the selenium powder, and then the temperature rising rate is 3 ℃ for min in argon atmosphere -1 Is heated to 600 ℃ and is kept for 2 hours. Cooling to room temperature to obtain honeycomb P-CoSe 2 Sample @ C.
Example 4
Cellular P-CoSe 2 @c, prepared by the steps of:
(1) 6g of cobalt nitrate hexahydrate and 6g of polyvinylpyrrolidone were added to 120mL of deionized water and magnetically stirred for 10 minutes to obtain a homogeneous solution. Liquid nitrogen was then poured around the solution and container to obtain a frozen liquid sample that was frozen uniformly, and transferred to a freeze-drying oven at-50 ℃ and a gas pressure below 10Pa for 24h of lyophilization.
(2) Transferring the purple freeze-dried block obtained in the step (1) into a mortar to be ground into powder, then transferring into a porcelain boat, and heating at a temperature rising rate of 5 ℃ for min under an argon atmosphere -1 Heating to 800 ℃ in a tube furnace under the condition, preserving heat for 1.5h, and naturally cooling to room temperature to obtain the Co/C precursor.
(3) Transferring the Co/C precursor collected in the step (2) into a downstream porcelain boat in a tube furnace, wherein the mass ratio of the upstream porcelain boat is 3:1 sodium hypophosphite and selenium powder, the Co/C precursor amount is 1/2 of that of the selenium powder, and then the temperature rising rate is 3 ℃ for min in argon atmosphere -1 Is heated to 600 ℃ and is kept for 2 hours. Cooling to room temperature to obtain honeycomb P-CoSe 2 Sample @ C.
Example 5
Cellular P-CoSe 2 @c, prepared by the steps of:
(1) 6g of cobalt nitrate hexahydrate and 6g of polyvinylpyrrolidone were added to 120mL of deionized water and magnetically stirred for 10 minutes to obtain a homogeneous solution. Liquid nitrogen was then poured around the solution and container to obtain a frozen liquid sample that was frozen uniformly, and transferred to a freeze-drying oven at-50 ℃ and a gas pressure below 10Pa for 24h of lyophilization.
(2) Transferring the purple freeze-dried block obtained in the step (1) into a mortar to be ground into powder, then transferring into a porcelain boat, and heating at a temperature rising rate of 5 ℃ for min under an argon atmosphere -1 Heating to 800 ℃ in a lower tube furnace, preserving heat for 1.5h, and naturally cooling to room temperature to obtain the Co/C precursor.
(3) Transferring the Co/C precursor collected in the step (2) into a downstream porcelain boat in a tube furnace, wherein the mass ratio of the upstream porcelain boat is 4:1 sodium hypophosphite and selenium powder, the Co/C precursor amount is 1/2 of that of the selenium powder, and then the temperature rising rate is 3 ℃ for min in argon atmosphere -1 Is heated to 600 ℃ and is kept for 2 hours. Cooling to room temperature to obtain honeycomb P-CoSe 2 Sample @ C.
Example 6
Cellular P-CoSe 2 @c, prepared by the steps of:
(1) 6g of cobalt nitrate hexahydrate and 6g of polyvinylpyrrolidone were added to 120mL of deionized water and magnetically stirred for 10 minutes to obtain a homogeneous solution. Liquid nitrogen was then poured around the solution and container to obtain a frozen liquid sample that was frozen uniformly, and transferred to a freeze-drying oven at-50 ℃ and a gas pressure below 10Pa for 24h of lyophilization.
(2) Transferring the purple freeze-dried block obtained in the step (1) into a mortar to be ground into powder, then transferring into a porcelain boat, and heating at a temperature rising rate of 5 ℃ for min under an argon atmosphere -1 Heating to 800 ℃ in a tube furnace under the condition, preserving heat for 1.5h, and naturally cooling to room temperature to obtain the Co/C precursor.
(3) Transferring the Co/C precursor collected in the step (2) into a downstream porcelain boat in a tube furnace, wherein the mass ratio of the upstream porcelain boat is 2:1 sodium hypophosphite and selenium powder, the Co/C precursor amount is 1/2 of that of the selenium powder, and then the temperature rising rate is 3 ℃ for min in argon atmosphere -1 Is heated to 700 ℃ and is kept for 2 hours. Cooling to room temperature to obtain honeycomb P-CoSe 2 Sample @ C.
Example 7
Cellular P-CoSe 2 @c, prepared by the steps of:
(1) 6g of cobalt nitrate hexahydrate and 6g of polyvinylpyrrolidone were added to 120mL of deionized water and magnetically stirred for 10 minutes to obtain a homogeneous solution. Liquid nitrogen was then poured around the solution and container to obtain a frozen liquid sample that was frozen uniformly, and transferred to a freeze-drying oven at-50 ℃ and a gas pressure below 10Pa for 24h of lyophilization.
(2) Transferring the purple freeze-dried block obtained in the step (1) into a mortar to be ground into powder, then transferring into a porcelain boat, and heating at a temperature rising rate of 5 ℃ for min under an argon atmosphere -1 Heating to 800 ℃ in a tube furnace under the condition, preserving heat for 1.5h, and naturally cooling to room temperature to obtain the Co/C precursor.
(3) Transferring the Co/C precursor collected in the step (2) into a downstream porcelain boat in a tube furnace, wherein the mass ratio of the upstream porcelain boat is 2:1 sodium hypophosphite and selenium powder, the Co/C precursor amount is 1/1 of that of the selenium powder, and then the temperature rising rate is 3 ℃ for min in argon atmosphere -1 Is heated to 600 ℃ and is kept for 2 hours. Cooling to room temperature to obtain honeycomb P-CoSe 2 Sample @ C.
Example 8
Cellular P-CoSe 2 @c, prepared by the steps of:
(1) 6g of cobalt nitrate hexahydrate and 6g of polyvinylpyrrolidone were added to 120mL of deionized water and magnetically stirred for 10 minutes to obtain a homogeneous solution. Liquid nitrogen was then poured around the solution and container to obtain a frozen liquid sample that was frozen uniformly, and transferred to a freeze-drying oven at-50 ℃ and a gas pressure below 10Pa for 24h of lyophilization.
(2) Transferring the purple freeze-dried block obtained in the step (1) into a mortar to be ground into powder, then transferring into a porcelain boat, and heating at a temperature rising rate of 5 ℃ for min under an argon atmosphere -1 Heating to 800 ℃ in a tube furnace under the condition, preserving heat for 1.5h, and naturally cooling to room temperature to obtain the Co/C precursor.
(3) Transferring the Co/C precursor collected in the step (2) into a downstream porcelain boat in a tube furnace, wherein the mass ratio of the upstream porcelain boat is 1:1 sodium hypophosphite and selenium powder, the Co/C precursor amount is 1/1 of that of the selenium powder, and then the temperature rising rate is 3 ℃ for min in argon atmosphere -1 Is heated to 600 ℃ and is kept for 2 hours. Cooling to room temperature to obtain honeycomb P-CoSe 2 Sample @ C.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A honeycomb carbon anchoring phosphorus doped cobalt selenide lithium carbon dioxide battery anode material is characterized in that: the matrix is of a honeycomb carbon structure, and the pore diameter of the honeycomb carbon is 0.5-2 mu m;
the phosphorus doped nano cobalt selenide particles are uniformly distributed in the honeycomb carbon structure, and the particle size of the phosphorus doped nano cobalt selenide particles is 40-100nm.
2. The honeycomb carbon-anchored phosphorus-doped cobalt-lithium selenide carbon dioxide battery cathode material of claim 1, wherein the cathode material is characterized by: the pore size of the honeycomb carbon structure is 1-1.5 μm.
3. The honeycomb carbon-anchored phosphorus-doped cobalt-lithium selenide carbon dioxide battery cathode material of claim 1, wherein the cathode material is characterized by: the particle size of the phosphorus doped nano cobalt selenide particles is 40-80nm; preferably 40-60nm.
4. The honeycomb carbon-anchored phosphorus-doped cobalt-lithium selenide carbon dioxide battery cathode material of claim 1, wherein the cathode material is characterized by: the wall thickness of the honeycomb carbon is 40-50nm.
5. The honeycomb carbon-anchored phosphorus-doped cobalt-lithium selenide carbon dioxide battery cathode material of claim 1, wherein the cathode material is characterized by: the specific surface area of the honeycomb carbon anchored phosphorus doped cobalt-lithium selenide carbon dioxide battery anode material is 12-66.87m 2 g -1 。
6. A preparation method of a honeycomb carbon anchored phosphorus doped cobalt selenide lithium carbon dioxide battery anode material is characterized by comprising the following steps: the method comprises the following steps:
dispersing polyvinylpyrrolidone and cobalt salt in deionized water, uniformly mixing, and then freeze-drying to obtain a Co-PVP precursor;
grinding the freeze-dried Co-PVP precursor, and calcining in an inert atmosphere to obtain a Co/C precursor;
grinding Co/C precursor, transferring into downstream porcelain boat, calcining sodium hypophosphite and selenium powder in inert atmosphere at 550-650deg.C for 1.5-2.5 hr to obtain P-CoSe 2 @C；
The mass ratio of the selenium powder to the sodium hypophosphite to the Co/C precursor is 3-5:1-3:1;
the mass ratio of polyvinylpyrrolidone to cobalt salt is 0.8-1.5:0.8-1.5.
7. The method for preparing the honeycomb carbon-anchored phosphorus-doped cobalt-lithium selenide carbon dioxide battery anode material, which is characterized in that: the mass ratio of polyvinylpyrrolidone, cobalt salt and deionized water is 0.8-1.5:0.8-1.5:15-25;
preferably, the cobalt salt is cobalt nitrate.
8. The method for preparing the honeycomb carbon-anchored phosphorus-doped cobalt-lithium selenide carbon dioxide battery anode material, which is characterized in that: the freeze-drying cold trap is below-50 ℃, the air pressure is below 10Pa, and the freeze-drying time is 20-30h.
9. The method for preparing the honeycomb carbon-anchored phosphorus-doped cobalt-lithium selenide carbon dioxide battery anode material, which is characterized in that: the Co-PVP precursor is calcined at 750-850 ℃ for 1-2h.
10. The method for preparing the honeycomb carbon-anchored phosphorus-doped cobalt-lithium selenide carbon dioxide battery anode material, which is characterized in that: when the Co/C precursor is grinded, the Co/C precursor is grinded into powder with uniform particle size.
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