CN110838580A - Titanium dioxide ultrathin carbon bubble confinement high-load red phosphorus composite electrode material and preparation method thereof - Google Patents
Titanium dioxide ultrathin carbon bubble confinement high-load red phosphorus composite electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a titanium dioxide ultrathin carbon bubble confinement high-load red phosphorus composite electrode material and a preparation method thereof, wherein the material consists of a core and a shell layer coated on the outer surface of the core: the core is a composite material consisting of high-load red phosphorus limited in ultrathin carbon bubbles; the shell is a titanium dioxide coating layer with controllable thickness. When the composite material is used as a cathode material of a lithium ion secondary battery, the titanium dioxide buffer layer can effectively maintain the structural integrity, and the ultrathin carbon bubbles used as host materials can form stable P-O-C bonds with red phosphorus while improving the conductivity, so that the red phosphorus is further effectively confined, the huge volume expansion of lithium phosphide in the charge-discharge process is relieved, and the cycle stability and the rate capability of the composite material are greatly improved.
Description
Technical Field
The invention relates to a lithium ion secondary battery cathode material, in particular to a titanium dioxide ultrathin carbon bubble confinement high-load red phosphorus composite electrode material, belonging to the technical field of lithium ion batteries.
Background
With the higher and higher performance requirements of the modern society on energy storage devices, lithium ion secondary batteries have been extensively and deeply studied due to their advantages of high energy density, high power density, and the like. Currently, carbon-based materials are not adaptable to emerging energy devices due to limitations on lower theoretical specific capacities and poor cycling stability. It is urgently required to develop a novel lithium ion secondary battery having a high specific capacity, a high power density and excellent cycle stability. Phosphorus can take up a large amount of lithium to form Li while retaining a small molar mass3P, therefore, the theoretical specific capacity can reach 2596mAh g-1. Compared with two allotropes of black phosphorus and white phosphorus, the red phosphorus is expected to become a high-performance lithium ion negative electrode material due to the advantages of easy preparation, high stability, low manufacturing cost and the like. However, its low conductivity and severe volume expansion during charge and discharge become difficult for application as a red phosphorus anode material. The active material is cracked due to the internal stress formed by the volume change, so that the red phosphorus is inevitably dropped from the current collector, the stable SEI film is damaged, the consumption of active lithium is increased, and other adverse effects are avoided, and the red phosphorus-based negative electrode material shows extremely poor electrochemical performance in the circulation process. Therefore, how to effectively improve the cycle stability and rate capability of the red phosphorus-based negative electrode material is an important subject in the field of electrode material development.
In order to alleviate the huge volume change of the red phosphorus-based negative electrode material during lithium intercalation and deintercalation in the charging and discharging process and improve the conductivity of the electrode material, researchers have adopted a plurality of strategies. Mainly comprises the following steps: (1) the construction of the red phosphorus-based nanostructure, for example, the preparation of the hollow red phosphorus nanosphere containing porous walls by a chemical wet separation method, when the nanosphere is used as the negative electrode of the lithium ion battery, the nanosphere effectively relieves the volume expansion due to the benefit of the hollow structure, and shows excellent electrochemical performance; (2) the effective limit of red phosphorus is in various porous carbon material nano frames, so that the conductivity is improved, and the volume expansion in the charging and discharging process can be relieved, such as red phosphorus-graphene, red phosphorus-carbon nano tubes, red phosphorus-carbon nano fibers, red phosphorus-porous carbon and other composite materials.
The existing synthetic method of the red phosphorus/carbon composite material usually adopts a high-energy ball milling method and a high-temperature pyrolysis carbon source, so that the energy consumption is large, the red phosphorus cannot be completely and effectively limited in a carbon frame, and the electrochemical performance of the material is not remarkably improved.
Disclosure of Invention
The invention aims to solve the problems of volume expansion, rapid capacity attenuation and poor stability of a red phosphorus base serving as a lithium ion secondary battery cathode material in the prior art, and provides a titanium dioxide/ultrathin carbon bubble limited domain high-load red phosphorus composite electrode material.
The novel red phosphorus-based negative electrode material has high specific capacity, long cycle stability and high rate, overcomes the defects of poor conductivity, unsatisfactory rate performance and the like when the conventional red phosphorus is used as a negative electrode material, and improves the comprehensive performance of a lithium ion battery.
In order to achieve the above purpose, the invention provides the following technical scheme:
the titanium dioxide/ultrathin carbon bubble confinement high-load red phosphorus composite electrode material is characterized in that: the material consists of a core and a shell layer coated on the outer surface of the core, wherein the core is a composite material consisting of high-load red phosphorus limited in ultrathin carbon bubbles; the shell is a titanium dioxide coating layer with controllable thickness.
Further, the core comprises a uniformly dispersed red phosphorus nanoparticle inner core and host material ultrathin carbon bubbles. The red phosphorus is uniformly dispersed in the ultrathin carbon bubble nanospheres and forms P-O-C with the carbon spheres, and the ultrathin carbon bubbles have a three-dimensionally interconnected microsphere structure, so that the amorphous red phosphorus which is violently expanded due to phosphorization can be confined in the circulation process, and the efficient lithium storage of the red phosphorus and the electronic conductivity of the ultrathin carbon sphere three-dimensional interconnection structure can be well and synergistically exerted. The titanium dioxide coated on the shell layer of the ultrathin carbon bubble maintains the structural integrity of the ultrathin carbon bubble under the condition of ensuring high conductivity, and the overall stability of the material is improved. The composite electrode material has the advantages of red phosphorus, ultrathin carbon bubbles and titanium dioxide, and the composite electrode material realizes the optimal performance.
Further, the red phosphorus is amorphous, is dispersed in hollow ultrathin carbon spheres with the carbon wall of about 5nm, and is stably confined by introducing P-O-C in the ball milling process.
Further, the particle size range of the composite electrode material is 20-50 nm.
Further, the thickness of the shell layer is 5-15 nm. The titanium dioxide of the outer shell layer is controlled in the range, so that the high stability of the material is favorably exerted, and the cycle stability of the material is improved. According to different thicknesses of deposited titanium dioxide, the conductivity, stability, lithium ion conductivity and the like of the electrode material are different, and the optimized thickness of the titanium dioxide can make the best of the advantages and avoid the disadvantages, so that the performance optimization of the composite electrode material is realized. Meanwhile, the thickness of the titanium dioxide within the range is more beneficial to the charge and discharge performance of the electrode material to be in a better level range.
Furthermore, the composite electrode material is of a three-dimensional interconnected microsphere structure, red phosphorus is anchored in a core structure in the hollow carbon sphere in an amorphous state, and titanium dioxide is coated on the surface of the ultrathin carbon wall.
Meanwhile, the invention also provides a preparation method for preparing the titanium dioxide/ultrathin carbon bubble limited domain high-load red phosphorus composite electrode material, which comprises the following steps:
step (1): dissolving a certain amount of zinc nitrate hexahydrate and citric acid in deionized water by adopting a solvent combustion method to prepare a mixed solution, and stirring for 30 min;
step (2): placing the mixed solution in a resistance furnace with specific power and heating for a certain time to obtain yellowish porous foam gel;
and (3): heating the obtained porous foam gel in a muffle furnace to a certain temperature, preserving the temperature for a period of time to obtain a zinc oxide template, placing the zinc oxide template in a tube furnace, and placing the zinc oxide template in a N-shaped tube furnace2Introducing ethanol vapor under the atmosphere, heating to 500 ℃ under the condition of keeping 50sccm, keeping the temperature for 3 hours, and then carrying out Ar/H2Raising the temperature to a certain temperature under the atmosphere to obtain porous carbon bubbles;
and (4): mixing red phosphorus and deionized water, and ball-milling at the rotating speed of 350rmp for 3 hours to obtain red phosphorus nanoparticles;
and (5): mixing porous carbon bubbles and ball-milled red phosphorus nanoparticles according to a certain mass ratio, putting into a high-pressure reaction kettle, then placing into a muffle furnace, heating to 550 ℃ by an evaporation condensation method, keeping for 3 hours, and then cooling to 260 ℃ overnight; then cleaning, and drying in a forced air drying oven at 60 ℃ for 8 h;
and (6): and (5) carrying out low-temperature treatment on the titanium dioxide precursor with controllable thickness deposited on the surface of the sample obtained in the step (5) to obtain the titanium dioxide/ultrathin carbon bubble confinement high-load red phosphorus composite electrode material.
The method for preparing the titanium dioxide/ultrathin carbon bubble confinement high-load red phosphorus composite electrode material mainly comprises the steps of recombining zinc oxide foam obtained by a simple solvent combustion method with ethanol steam to generate ZnO-C foam with a core-shell structure, and volatilizing the zinc oxide steam at high temperature to obtain graphene-based ultrathin three-dimensional interconnected hollow carbon bubbles. Subsequently, red phosphorus was diffused into the pores of the carbon bubbles by a steam condensation method. And finally, coating a layer of uniform titanium dioxide on the surface of the carbon bubble by adopting a low-temperature atomic layer deposition technology. The obtained titanium dioxide/ultrathin carbon bubble confinement high-load red phosphorus composite electrode material can perfectly place amorphous confinement in hollow ultrathin carbon bubbles through an O-P-O bond, and simultaneously compact TiO uniformly deposited on the surface2Effectively inhibits the volume expansion of the whole electrode and improves the cycle stability and high rate performance of the composite electrode material.
The preparation method comprises the steps of firstly obtaining zinc oxide foam through a solvent combustion method, then introducing ethanol at a certain temperature, decomposing the ethanol under the catalytic action of the zinc oxide to deposit a carbon layer on the surface of the ethanol, and volatilizing the zinc oxide at a high temperature in a steam mode to generate a large number of nano-scale holes by utilizing the characteristic of low boiling point of the zinc oxide foam. The obtained carbon bubbles and red phosphorus are mixed according to a certain proportion, the red phosphorus is dispersed in the hollow carbon bubbles by an evaporation and condensation method, and the stability of the structure is improved by introducing P-O-C bonds in the material composition. Finally, the titanium dioxide precursor material of the compact layer is uniformly deposited on the surface of the hollow carbon bubble, and a uniformly coated titanium dioxide shell layer is obtained through a pyrolysis process, so that the cycle life and the charge rate performance of the electrode material are effectively improved.
Specifically, in the preparation method, red phosphorus is diffused to the hollow carbon bubble core through a hole formed by volatilization of nano zinc oxide by using an evaporation condensation method, and forms a P-O-C chemical bond with a carbon-carbon framework, so that the red phosphorus active material is well confined.
Meanwhile, a small amount of red phosphorus is inevitably anchored on the surface of the hollow carbon bubble, and red phosphorus nanoparticles are easily agglomerated on the surface of the carbon framework in the circulation process. When the titanium dioxide precursor is coated, a new protective layer is formed on red phosphorus, the red phosphorus is converted into a titanium dioxide outer shell layer protective structure after sintering and forming, the integrity of the ultrathin carbon bubbles is kept, the structural stability of the material is improved, excellent electrochemical stability is shown, and the problems that the red phosphorus is easy to agglomerate and is dissolved in electrolyte to cause rapid capacity attenuation when the red phosphorus is not coated are solved.
The preparation method has the advantages of easily obtained raw materials, simple operation process and avoidance of complicated treatment steps such as hydrothermal treatment, sol-gel treatment and the like. When the prepared composite material is used as a cathode of a lithium ion secondary battery, the titanium dioxide can protect red phosphorus nanoparticles attached to the surface of the ultrathin carbon bubble to be dissolved in electrolyte, so that the agglomeration of the red phosphorus nanoparticles is prevented, and the structural integrity of the hollow carbon bubble is maintained. In addition, the P-O-C bond between the ultrathin carbon bubbles and the red phosphorus can better confine the red phosphorus, the hollow structure can relieve the volume expansion of the red phosphorus in the charging and discharging processes, the stability and the long cycle performance of the material structure are improved, and meanwhile, the rate capability of the composite material is improved due to the introduction of the high-conductivity titanium dioxide shell.
Further, in the present invention,in the step (1), the molar ratio of the zinc nitrate to the citric acid is 2:3-3:2, and the concentration of the zinc nitrate in the water is 0.5mol L-1-1.0mol L-1Preferably, stirring is carried out at room temperature (15-25 ℃);
further, in the step (2), the power is 500W; preferably, the heating time is 8-15min, and the solution system can expand and foam rapidly;
further, in the step (3), the heating temperature is 400 adding; preferably, the heat preservation time is 2 hours;
further, in the step (4), the mass ratio of the porous carbon bubbles to the red phosphorus nanoparticles is 2:7-4: 7; preferably the entire process is carried out under vacuum conditions; preferably, the heating rate is kept at the whole time of 1 selection;
preferably, in step (4), excess CS is used2Cleaning black phosphorus generated at high temperature and attached to the surface of the carbon bubble;
further, in the step (6), the TiO2The precursor is obtained by the reaction of titanium hydroxide or titanium tetrachloride and water; preferably, titanium dioxide/ultra-thin carbon bubble confinement high-load red phosphorus and ethanol solution are uniformly mixed, then the mixture is coated on a substrate and placed in an atomic layer deposition system instrument, titanium tetrachloride and water are used as reaction sources, the reaction temperature is 60-100B, and atomic deposition is carried out for a plurality of 200-500 circles.
Further, the titanium dioxide precursor is titanium hydroxide. Preferably, the titanium dioxide precursor is coated on the surface of the product of the step 5, namely, the titanium dioxide precursor is coated on the surface of the ultrathin carbon bubble confinement high-load red phosphorus composite electrode material.
Compared with the prior art, the invention has the beneficial effects that:
1. the preparation method of the titanium dioxide/ultrathin carbon bubble confinement high-load red phosphorus composite electrode material with the core-shell structure has the advantages of simple process, readily available raw materials and simple operation process, and avoids complicated treatment steps such as hydrothermal treatment, sol-gel treatment and the like. The ultra-thin carbon bubble confinement high-load red phosphorus composite electrode material is obtained by a simple combustion explosion and evaporation condensation method, and then the titanium dioxide/ultra-thin carbon bubble confinement high-load red phosphorus composite electrode material with the core-shell structure can be prepared by an atomic deposition technology and heat treatment.
2. According to the titanium dioxide/ultrathin carbon bubble confinement high-load red phosphorus composite electrode material with the core-shell structure, amorphous red phosphorus is stably distributed in the hollow ultrathin carbon bubbles through P-O-C bonds, and severe volume change of the red phosphorus in the charging and discharging processes is effectively relieved. At the same time, the surface is uniformly deposited with dense TiO2Effectively inhibits the volume expansion of the whole electrode and improves the cycle stability and rate capability of the composite material.
3. The titanium dioxide/ultrathin carbon bubble confinement high-load red phosphorus composite electrode material with the core-shell structure, prepared by the invention, solves the problems of low conductivity, rapid capacity attenuation caused by volume expansion and the like of other red phosphorus negative electrode materials in application, and shows excellent cycle and rate performance. At 100mA g-1The first discharge specific capacity reaches 1150mAh g under the current density-1After 200 cycles, 890mAh g-1 is obtained, and the blood pressure is 100, 200,400, 600, 800, 1000 and 2000mA g-1The specific discharge capacities of the lead-acid batteries are 841, 715, 657, 608, 553, 518 and 460mAh g respectively-1。
Drawings
FIG. 1 is a Fourier infrared spectrum of an ultrathin carbon bubble confinement high-load red phosphorus composite material and a titanium dioxide/ultrathin carbon bubble confinement high-load red phosphorus composite electrode material.
FIG. 2 is an X-ray photoelectron spectrum of a titanium dioxide/ultrathin carbon bubble confinement high-loading red phosphorus composite electrode material.
FIG. 3 is a Fourier SEM image of a titanium dioxide/ultrathin carbon bubble confinement high-load red phosphorus composite electrode material.
FIG. 4 shows that the titanium dioxide/ultrathin carbon bubble confinement high-load red phosphorus composite electrode material is 100mA g-1Current charge-discharge cycle diagram.
FIG. 5 shows that the titanium dioxide/ultrathin carbon bubble confinement high-load red phosphorus composite electrode material is 1000mA g-1Current charge-discharge cycle diagram.
FIG. 6 is a graph of different current density multiplying power of a red phosphorus, titanium dioxide/ultra-thin carbon bubble limited domain high-load red phosphorus composite electrode material and a titanium dioxide/ultra-thin carbon bubble limited domain high-load red phosphorus composite electrode material.
Detailed Description
The present invention will be described in further detail with reference to test examples and specific embodiments. It should not be understood that the scope of the above-described subject matter of the present invention is limited to the following examples, and any techniques realized based on the present disclosure are within the scope of the present invention.
< example 1>
The titanium dioxide/ultrathin carbon bubble confinement high-load red phosphorus composite electrode material consists of a core and a shell layer coated on the outer surface of the core; the core is a composite material consisting of ultrathin nanometer carbon bubbles and red phosphorus dispersed in the hollow carbon bubbles; the outer shell layer is titanium dioxide.
The red phosphorus limited domain forms a three-dimensional interconnected microsphere structure in the hollow ultrathin carbon bubble, the structure comprises an inner core which is amorphous red phosphorus and a hollow carbon bubble with a carbon wall within 5nm, a titanium dioxide outer shell layer with the thickness of 5-10nm is atomically deposited on the surface of the hollow carbon bubble, and the particle size of each carbon bubble microsphere is within the range of 20-50 nm. The amorphous red phosphorus of the composite electrode material is stably distributed in the hollow ultrathin carbon bubbles through P-O-C bonds, so that the severe volume change of the red phosphorus in the charging and discharging processes is effectively relieved. At the same time, the surface is uniformly deposited with dense TiO2Effectively inhibits the volume expansion of the whole electrode, improves the cycle stability and the rate capability of the composite material, and has important significance for the performance upgrade of the lithium ion battery.
< example 2>
Step (1): dissolving zinc nitrate hexahydrate and citric acid in a molar ratio of 2:3 in 50ml of deionized water by adopting a solvent combustion method to prepare a mixed solution, and stirring for 30 min.
Step (2): and (3) putting the mixed solution into a resistance furnace with the power of 500W to heat for 10min to obtain yellowish porous foam gel.
And (3): and heating the obtained porous foam gel to 400 ℃ in a muffle furnace, and preserving the temperature for 2h to obtain the zinc oxide template. And placed in a tube furnace in N2Introducing ethanol vapor under the atmosphere, heating to 500 ℃ under the condition of keeping 50sccm, keeping the temperature for 3 hours, and then carrying out Ar/H2Raising the temperature to 800 ℃ in the atmosphere, and preserving the heat for 4 hours to obtain the porous carbon foam.
And (4): mixing red phosphorus and deionized water, and ball-milling at the rotating speed of 350rmp for 3h to obtain the red phosphorus nanoparticles.
And (5): mixing the porous carbon bubbles and the ball-milled red phosphorus nanoparticles according to a mass ratio of 3:7, putting the mixture into a high-pressure reaction kettle, then placing the high-pressure reaction kettle into a muffle furnace, heating the mixture to 550 ℃ by an evaporation condensation method, keeping the mixture for 3 hours, and then cooling the mixture to 260 ℃ overnight. Then using CS2Cleaning, and drying in a forced air drying oven at 60 deg.C for 8 hr.
And (6): and (3) mixing the sample obtained in the step (5) with ethanol, coating the mixture on a substrate, placing the substrate in an atomic layer deposition system, and obtaining the titanium dioxide/ultrathin carbon bubble limited-area high-load red phosphorus composite material by taking titanium tetrachloride and water as reaction sources, wherein the reaction temperature is 60 ℃ and the atomic layer deposition period is 200 circles.
The prepared composite electrode material is subjected to Fourier infrared test, and the blue curve of the composite electrode material is shown in figure 1 and is 1008cm-1The absorption peak is the characteristic peak of P-O-C, and further shows that red phosphorus is stably dispersed in the hollow ultrathin carbon bubbles through P-O-C bonds and is at 1220cm-1And 1080cm-1The bonds P ═ O and P — O in the reaction mixture are due to oxidation by air. The prepared composite electrode material was subjected to XPS testing, and the characteristic peak at 287.3, as shown in fig. 2, further confirms the presence of P-O-C bonds. The prepared composite electrode material is subjected to SEM test, and as shown in FIG. 3, the material is a three-dimensional interconnected network structure formed by hollow ultrathin carbon bubbles.
The prepared composite electrode material is assembled into a button battery with the CR2032 specification, and the charge and discharge performance of the button battery is tested by a blue spot battery testing system CT 2001A.
First, at 100mA g-1The current density of the composite electrode material is charged and discharged, as shown in figure 4, the composite electrode material still keeps 795mAh g after being cycled for 200 times-1(ii) a As in fig. 5, at 1000mA g-1The current density is charged and discharged, and the current density is still maintained at 446.5mAh g after 500 times of circulation-1The coulomb efficiency is as high as 100%; as shown in FIG. 6, at 100, 200,400, 600, 800, 1000, 2000mA g-1The specific discharge capacity of the electrode reaches 841, 715, 657, 608, 553, 518 and 460mAh g-1。
< example 3>
Step (1): dissolving zinc nitrate hexahydrate and citric acid in a molar ratio of 3:2 in 50ml of deionized water by adopting a solvent combustion method to prepare a mixed solution, and stirring for 30 min.
Step (2): and (3) putting the mixed solution into a resistance furnace with the power of 500W to heat for 10min to obtain yellowish porous foam gel.
And (3): and heating the obtained porous foam gel to 400 ℃ in a muffle furnace, and preserving the temperature for 2h to obtain the zinc oxide template. And placed in a tube furnace in N2Introducing ethanol vapor under the atmosphere, heating to 500 ℃ under the condition of keeping 50sccm, keeping the temperature for 3 hours, and then carrying out Ar/H2Raising the temperature to 800 ℃ in the atmosphere, and preserving the heat for 4 hours to obtain the porous carbon foam.
And (4): mixing red phosphorus and deionized water, and ball-milling at the rotating speed of 350rmp for 3h to obtain the red phosphorus nanoparticles.
And (5): mixing the porous carbon bubbles and the ball-milled red phosphorus nanoparticles according to a mass ratio of 3:7, putting the mixture into a high-pressure reaction kettle, then placing the high-pressure reaction kettle into a muffle furnace, heating the mixture to 550 ℃ by an evaporation condensation method, keeping the mixture for 3 hours, and then cooling the mixture to 260 ℃ overnight. Then using CS2Cleaning, and drying in a forced air drying oven at 60 deg.C for 8 hr.
And (6): and (3) mixing the sample obtained in the step (5) with ethanol, coating the mixture on a substrate, placing the substrate in an atomic layer deposition system, and obtaining the titanium dioxide/ultrathin carbon bubble limited-area high-load red phosphorus composite material by taking titanium tetrachloride and water as reaction sources, wherein the reaction temperature is 60 ℃ and the atomic layer deposition period is 200 circles.
< example 4>
Step (1): dissolving zinc nitrate hexahydrate and citric acid in a molar ratio of 3:2 in 50ml of deionized water by adopting a solvent combustion method to prepare a mixed solution, and stirring for 30 min.
Step (2): and (3) putting the mixed solution into a resistance furnace with the power of 500W to heat for 10min to obtain yellowish porous foam gel.
And (3):and heating the obtained porous foam gel to 400 ℃ in a muffle furnace, and preserving the temperature for 2h to obtain the zinc oxide template. And placed in a tube furnace in N2Introducing ethanol vapor under the atmosphere, heating to 500 ℃ under the condition of keeping 50sccm, keeping the temperature for 3 hours, and then carrying out Ar/H2Raising the temperature to 800 ℃ in the atmosphere, and preserving the heat for 4 hours to obtain the porous carbon foam.
And (4): mixing red phosphorus and deionized water, and ball-milling at the rotating speed of 350rmp for 3h to obtain the red phosphorus nanoparticles.
And (5): mixing the porous carbon bubbles and the ball-milled red phosphorus nanoparticles according to a mass ratio of 2:7, putting the mixture into a high-pressure reaction kettle, then placing the reaction kettle into a muffle furnace, heating the mixture to 550 ℃ by an evaporation condensation method, keeping the mixture for 3 hours, and then cooling the mixture to 260 ℃ overnight. Then using CS2Cleaning, and drying in a forced air drying oven at 60 deg.C for 8 hr.
And (6): and (3) mixing the sample obtained in the step (5) with ethanol, coating the mixture on a substrate, placing the substrate in an atomic layer deposition system, and obtaining the titanium dioxide/ultrathin carbon bubble limited-area high-load red phosphorus composite material by taking titanium tetrachloride and water as reaction sources, wherein the reaction temperature is 60 ℃ and the atomic layer deposition period is 200 circles.
< comparative example 1>
Comparing the influence of the thickness of the titanium dioxide coating layer on the composite electrode material in the preparation process
This comparative example refers to the preparation process of example 1 with raw materials taken and the parameter conditions in the control process, except that different number of cycles of 5 atomic layer deposition was designed, and the number of cycles was controlled to be 0, 100, 200 and 300 cycles, respectively. The samples prepared were analyzed and the results showed that the materials were at 100, 200,400, 600, 800, 1000, 2000mA g/g in 0-turn (see FIG. 6)-1The specific discharge capacity of the electrode reaches 1180, 835, 702, 575, 468, 410 and 310mAh g-1Although the specific discharge capacity of the first ring can be improved in a short time, the capacity is quickly attenuated due to the collapse of a carbon frame and the irreversible loss of an active material caused by the loss of the protection of a titanium dioxide outer shell layer in the long-cycle process; when the number of deposition turns was 300, although the material exhibited excellent cycle stability during the cycle, the specific volume wasThe amount is generally lower because too thick a titanium dioxide coating reduces the overall specific capacity of the material.
< comparative example 2>
Comparing the effect of temperature on the performance of the composite electrode material during the preparation process
This comparative example refers to the preparation of example 2 taking the raw materials and controlling the parameters conditions in the process, for step 3 the material was placed in a tube furnace in N2Introducing ethanol vapor under the atmosphere, and heating to 400, 500 and 600 ℃ respectively under the condition of keeping 50sccm for 3 hours. The prepared sample is analyzed, and the result shows that when the temperature is 400 ℃, ethanol cannot be fully cracked to deposit a carbon layer on the surface of the zinc oxide nanosphere due to too low temperature, so that the carbon bubble structure is incomplete, and the circulation stability in the circulation process is not ideal; and when the temperature is 600 ℃, a large amount of carbon is deposited on the surface of the zinc oxide nanospheres, and the carbon wall is too thick, so that red phosphorus is prevented from diffusing to the inner core of the hollow ultrathin carbon nanospheres, and the integral specific capacity is reduced.
< comparative example 3>
Comparing the influence of evaporation and condensation time on the performance of the composite electrode material in the preparation process
This comparative example refers to the preparation of example 4 taking the starting materials and controlling the parameters in the process, for step 4 heating to 550 ℃ by evaporative condensation for 2, 3 and 4h respectively followed by cooling to 260 ℃ overnight. The prepared sample is analyzed, and the result shows that the sample kept for 2 hours has short evaporation time, so that red phosphorus can not fully enter the hollow carbon bubbles due to gasification at 550 ℃, and the loss of active mass is caused; the active mass of the samples fed in 3h and 4h is not greatly different, and obviously the feeding in 3h is the optimal condition in view of the problem of energy consumption.
The above-listed examples are merely illustrative of specific operations of the present invention and are not intended to limit the scope of the claims of the present invention. All experimental conclusions about the procedures, structures and principles of the invention described in the claims should be included in the scope of the claims.
Claims (10)
1. The titanium dioxide ultrathin carbon bubble confinement high-load red phosphorus composite electrode material is characterized in that: the material consists of a core and a shell layer coated on the outer surface of the core, wherein the core is a composite material consisting of high-load red phosphorus limited in ultrathin carbon bubbles; the shell is a titanium dioxide coating layer with controllable thickness.
2. The composite electrode material of claim 1, wherein the core comprises a uniformly dispersed core of red phosphorus nanoparticles and ultrathin carbon bubbles of host material.
3. The composite electrode material according to claim 1, wherein the graphitized carbon wall thickness of the carbon bubbles is less than 5 nm.
4. The composite electrode material of claim 1, wherein the composite electrode material has a particle size of 20nm and an unsupported phosphorus carbon bubble surface area of up to 1404.4m2g-1Pore volume up to 6.2cm2g-1The specific surface area of the film is about 160.4m after evaporation and condensation and low-temperature atomic layer deposition2g-1Pore volume 0.8cm2g-1Preferably, the thickness of the outer shell layer is 5 nm.
5. The preparation method of the titanium dioxide/ultrathin carbon bubble confinement high-load red phosphorus composite electrode material as claimed in claim 1, characterized by comprising the following steps: the preparation method comprises the following steps:
step (1): dissolving a certain amount of zinc nitrate hexahydrate and citric acid in deionized water by adopting a solvent combustion method to prepare a mixed solution, and stirring for 30 min;
step (2): placing the mixed solution in a resistance furnace with specific power and heating for a certain time to obtain yellowish porous foam gel;
and (3): heating the obtained porous foam gel in a muffle furnace to a certain temperature, preserving the temperature for a period of time to obtain a zinc oxide template, placing the zinc oxide template in a tubular furnace, and placing the zinc oxide template in an N-type tubular furnace2Introducing B under the atmosphereHeating to 500 deg.C with alcohol vapor and maintaining 50sccm constant temperature for 3H, and then Ar/H2Raising the temperature to a certain temperature under the atmosphere to obtain porous carbon bubbles;
and (4): mixing red phosphorus and deionized water, and ball-milling at the rotating speed of 350rmp for 3 hours to obtain red phosphorus nanoparticles;
and (5): mixing porous carbon bubbles and ball-milled red phosphorus nanoparticles according to a certain mass ratio, putting into a high-pressure reaction kettle, then placing into a muffle furnace, heating to 550 ℃ by an evaporation condensation method, keeping for 3 hours, and then cooling to 260 ℃ overnight; then cleaning, and drying in a forced air drying oven at 60 ℃ for 8 h;
and (6): and (5) carrying out low-temperature treatment on the titanium dioxide precursor with controllable thickness deposited on the surface of the sample obtained in the step (5) to obtain the titanium dioxide/ultrathin carbon bubble confinement high-load red phosphorus composite electrode material.
6. The method for preparing a composite material according to claim 5, wherein in the step (1), the molar ratio of the zinc nitrate to the citric acid is 2:3 to 3:2, and the concentration of the zinc nitrate in water is 0.5mol L-1-1.0mol L-1。
7. The method for preparing a composite material according to claim 5, wherein in the step (2), the power is 500W; preferably, the heating time is 8-15 min.
8. The method for preparing a composite material according to claim 5, wherein, in the step (3), the heating temperature is 400 ℃; preferably, the incubation time is 2 h.
9. The method for preparing a composite material according to claim 5, wherein in the step (4), the mass ratio of the porous carbon bubbles to the red phosphorus nanoparticles is 2:7-4: 7; preferably the entire process is carried out under vacuum conditions; preferably, the temperature increase rate is maintained at 1 deg.C/min.
10. The method for producing a composite material according to claim 5, wherein in the step (6), the titanium oxide precursor is titanium hydroxide or titanium tetrachloride obtained by reacting titanium hydroxide with water; preferably, titanium dioxide/ultra-thin carbon bubble confinement high-load red phosphorus and ethanol solution are uniformly mixed, then the mixture is coated on a substrate and placed in an atomic layer deposition system instrument, titanium tetrachloride and water are used as reaction sources, the reaction temperature is 60-100 ℃, and atomic deposition is carried out for a plurality of 200-500 circles.
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