CN113488651A - Titanium oxide @ C hollow composite framework embedded with noble metal silver, and preparation method and application thereof - Google Patents

Titanium oxide @ C hollow composite framework embedded with noble metal silver, and preparation method and application thereof Download PDF

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CN113488651A
CN113488651A CN202010901253.1A CN202010901253A CN113488651A CN 113488651 A CN113488651 A CN 113488651A CN 202010901253 A CN202010901253 A CN 202010901253A CN 113488651 A CN113488651 A CN 113488651A
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titanium oxide
hollow
noble metal
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sio
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CN113488651B (en
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洪波
赖延清
姜怀
杨杰伟
张治安
张凯
方静
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Central South University
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    • H01M4/02—Electrodes composed of, or comprising, active material
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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Abstract

The invention belongs to the field of lithium metal battery cathode materials, and particularly discloses a titanium oxide @ C hollow composite framework with noble metal silver embedded inside, and a preparation method and application thereof. The hollow composite framework comprises a titanium oxide hollow sphere with an independent closed cavity, noble metal silver nanoparticles embedded in the inner cavity of the titanium oxide hollow sphere, a carbon layer compounded on the surface of the titanium oxide and a nitrogen-containing functional group. Preparation of SiO uniformly loaded with silver nanoparticles by using silica template2The method comprises the following steps of (a) @ Ag composite template, adding a titanium source for hydrolysis, obtaining a titanium oxide precursor on the outer layer of the composite template, then carrying out in-situ polymerization to obtain a nitrogen-doped carbon-coated composite framework precursor, roasting at a certain temperature, and etching the silicon dioxide template by using strong base to obtain the titanium oxide @ C hollow composite framework internally embedded with noble metal silver. The composite hollow framework material has a closed cavity structure, good conductivity and excellent gradient lithium affinity, reduces nucleation overpotential of lithium deposition, selectively induces lithium metal to be deposited in the cavity structure, greatly avoids interface side reaction and volume effect, inhibits growth of lithium dendrite, creates favorable conditions for uniform lithium deposition/dissolution, and obviously improves the coulombic efficiency and the cycling stability of a lithium metal battery.

Description

Titanium oxide @ C hollow composite framework embedded with noble metal silver, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of electrode materials of lithium metal batteries, particularly relates to a current collector of a lithium metal battery, and particularly relates to a titanium oxide @ C hollow composite framework with noble metal silver embedded inside, and a preparation method and application thereof.
Background
The lithium metal has extremely high theoretical specific capacity of 3860mAhg-1The lowest electrochemical potential, 3.04V (relative to a standard hydrogen electrode), however uncontrolled lithium dendrite growth and severe interfacial side reactions lead to reduced cell coulombic efficiency and poor cycling performance, making lithium metal anodes difficult to commercialize.
It is currently considered to be an effective means to solve the volume effect and achieve uniform deposition of lithium by constructing a lithium-philic 3D current collector. The situation of uneven electron/ion distribution caused by overlarge local current density can be effectively reduced by introducing a 3D current collector or a skeleton structure. In addition, the 3D framework structure has abundant cavities that can carry lithium metal, mitigating volume changes due to repeated deposition/dissolution. For example, Huigang Zhang et al [ Jun P, J Li, K Zhang, et al, conductivity and lithium affinity gradients lithium depletion disorder [ J ]. Nature Communications,10(2019)1896 ] effectively reduce the density of the barrier current by constructing a gradient lithium affinity foam nickel skeleton, a longitudinal lithium affinity gradient is formed by a gold layer deviating from the strong lithium affinity of the diaphragm surface and a lithium affinity sparse aluminum oxide layer near the diaphragm surface, and lithium deposition is selectively induced to be far away from the diaphragm surface, so that the risk of penetrating the diaphragm by lithium dendrites is reduced, and the cycle life is greatly prolonged. Hao Zhang et al [ H Zhang, X Liao, Y Guan, et al, Lipophilic-lithiophobic gradient for a high grade stable lithium metal anode [ J ] Nature Communications,9(2018)3729 ] utilize carbon nanotubes with different zinc oxide loading as the interface layer of lithium metal, on one hand, the huge specific surface of the carbon nanotube can reduce the apparent current density and delay the growth of lithium dendrite; on the other hand, the lithium-philic gradient sandwich structure can be used for homogenizing the lithium ion concentration and inducing the lithium metal to be uniformly deposited. However, the open-structured lithium metal negative electrode has difficulty in blocking the occurrence of interfacial side reactions. Under practical current densities and capacities, repeated lithium deposition/dissolution is prone to the growth of large amounts of by-products, resulting in irreversible lithium loss and a significant reduction in coulombic efficiency. Based on the above situation, the structure of the lithium metal negative electrode needs to be further optimized to meet the practical application requirements.
Disclosure of Invention
Aiming at the problems of large volume effect, serious interface side reaction and low coulombic efficiency of the conventional lithium metal negative electrode under an actual charging and discharging system, the invention provides a titanium oxide @ C hollow composite framework material embedded with noble metal silver, aiming at improving the deposition behavior of lithium by a stable gradient lithium-philic structure, wherein the closed hollow structure can effectively weaken the interface side reaction and the volume effect; the nitrogen-doped conductive carbon layer is compounded, so that the reaction kinetics are improved, the cycling stability of lithium under large current is improved, and the electrochemical performance of the lithium metal cathode is improved.
Based on the above object, the present invention provides the following solutions:
a titanium oxide @ C hollow composite skeleton embedded with noble metal silver comprises a titanium oxide hollow ball with an independent closed cavity, noble metal silver nano particles embedded in the inner cavity of the titanium oxide hollow ball, a carbon layer compounded on the surface of titanium oxide and a nitrogen-containing functional group; the titanium oxide and the carbon layer are of a hollow framework structure of a closed chamber, and the carbon layer is compounded outside the titanium oxide hollow ball; the noble metal silver nano particles are uniformly embedded on the inner cavity wall of the titanium oxide hollow sphere; the nitrogen-containing functional group is in-situ doped on the carbon layer.
Preferably, the cavity structure is at least one of a sphere, a rugby ball, a disc, a persimmon cake and a red blood cell, and is preferably a sphere.
Preferably, the carbon in the carbon layer is at least one of graphitized carbon and amorphous carbon, and the thickness of the carbon layer is 4-150 nm.
Preferably, the thickness of the shell layer of the hollow framework structure is 10-2000 nm.
Preferably, the titanium oxide is TiO or TiO2And Ti2O3At least one of them, the thickness of the titanium oxide shell layer is 5-300 nm.
Preferably, the average diameter of the titanium oxide @ C hollow composite skeleton internally embedded with the noble metal silver is 30-3000 nm.
Preferably, the lithium-philic noble metal silver nanoparticles are silver simple substances, and the particle size of the silver simple substances is 0.5-100 nm; the content of the silver simple substance is 3-15 at.%.
Preferably, the nitrogen-containing functional groups uniformly distributed in the carbon layer have a nitrogen content of 0.5 to 12.5 at.%.
The research of the invention finds that the nitrogen-containing functional group has low affinity to lithium metal, and the further research finds that the hollow titanium oxide nanospheres can provide good support and stable structure for the hollow composite framework, have excellent lithium affinity and induce uniform lithium to be deposited into the cavity; meanwhile, the silver nanoparticles with more excellent lithium affinity can selectively induce lithium to be uniformly deposited in the hollow titanium oxide nanosphere cavity, so that the three-dimensional space of the hollow composite skeleton is effectively utilized, and the interface reaction and the volume effect are reduced. Further research shows that the hollow titanium oxide inner shell can always maintain contact with the carbon skeleton, and the stability of the titanium oxide @ C hollow composite skeleton embedded with noble metal silver in the repeated lithium deposition/dissolution process is ensured.
Based on the same inventive concept, the invention provides the titanium oxide @ C hollow composite internally embedded with the noble metal silverPreparation method of framework, namely preparing SiO uniformly loaded with silver nanoparticles by using silicon dioxide template2The method comprises the following steps of (@) adding a titanium source into an Ag composite template for hydrolysis, obtaining a titanium oxide precursor on the outer layer of the composite template, then carrying out in-situ polymerization to obtain a nitrogen-doped carbon-coated composite framework precursor, finally roasting at a certain temperature, and etching a silicon dioxide template by using strong base to obtain the titanium oxide @ C hollow composite framework internally embedded with noble metal silver.
Further, the preparation method of the titanium oxide @ C hollow composite framework material with the noble metal silver embedded therein comprises the following specific steps:
step (1), SiO2Preparation of a @ Ag composite template:
mixing SiO2The template is placed in a solution of a surfactant for surface activation, and the surface activated SiO is obtained by separation2A template; activating the surface of the SiO2Reaction of the template with a silver salt solution under the action of a reducing agent, SiO2Uniformly depositing silver nano particles on the template to obtain SiO2@ Ag template.
Step (2), hydrolyzing a titanium source:
mixing SiO2Adding the @ Ag template, the surfactant and ammonia water into an organic solvent, stirring for 10min at normal temperature, adding a titanium source, stirring, filtering and cleaning to obtain SiO2@Ag@TiO2；
Step (3), carbon coating:
mixing SiO2@Ag@TiO2Adding the nitrogen-containing polymer monomer solution, adding a buffering agent, adjusting the pH value to 8-10, stirring for a certain time, filtering and washing to obtain the hollow composite framework precursor.
And (4) roasting:
placing the hollow composite framework precursor into a tubular furnace of hydrogen-argon mixed gas flow for roasting to obtain the hollow titanium oxide composite carbon framework SiO containing the silicon template2@Ag@TiO2@C@N。
And (5) etching:
the roasted SiO2@Ag@TiO2@ C @ N is put in a strong alkali etchant solution to remove SiO2Drying the template to obtain the final noble metal embedded in the templateTitanium oxide @ C hollow composite framework of silver.
Further, in step (1):
preferably, the SiO2The template is uniform particles with the particle size of 150-600 nm, and the preferable particle size is 200-500 nm.
Preferably, the surface active agent is sodium hydroxide, stannous chloride, PbCl2At least one of mercaptopropyl-trimethoxysilane; the concentration of the surface active agent is 0.05-0.5 mol/L;
preferably, the concentration of the silver salt solution is 0.002-0.1 mol/L;
preferably, the reducing agent is at least one of formaldehyde, glucose, acetaldehyde and propionaldehyde, and more preferably glucose;
preferably, the concentration of the reducing agent is 0.005 to 0.5mol/L, and more preferably 0.01 to 0.3 mol/L.
Further, in the step (2):
preferably, the titanium source is at least one of tetraisopropyl titanate, tetrabutyl titanate, isopropyl trititanate and diethylene titanate.
Preferably, the concentration of the titanium source is 100 to 1000g/L, and more preferably 200 to 900 g/L.
Preferably, the stirring time is 0.5 to 12 hours, and more preferably 1 to 5 hours.
Further, in step (3):
preferably, the nitrogen-containing polymeric monomer is at least one of dopamine, polyaniline and acrylamide.
Preferably, the buffer is one or more of PVP, CTAB, SDS and tris (hydroxymethyl) -aminomethane.
Preferably, the buffer: the mass ratio of the nitrogen-containing polymeric monomer is 2: 1-3: 1.
Preferably, the concentration of the buffer solution is 0.005-1 mol/L.
Preferably, the stirring time is 8-48 h, and more preferably 10-24 h.
Further, in the step (4):
preferably, the volume ratio of the hydrogen to the argon in the hydrogen-argon mixed gas flow is 5-10: 90-95.
Preferably, the roasting temperature is 500-900 ℃, and more preferably 600-900 ℃;
preferably, the temperature rise rate of the tubular furnace is 0.5-20 ℃/min, and more preferably 1-10 ℃/min;
preferably, the baking time is 120 to 500min, and more preferably 150 to 300 min.
Further, in step (5):
preferably, the etching agent is at least one of potassium hydroxide, calcium hydroxide, sodium hydroxide, barium hydroxide and cesium hydroxide; the concentration of the etchant is 2-8 mol/L.
Preferably, the etching temperature of the template etching is 30-80 ℃, and further preferably 50-70 ℃;
preferably, the etching time is 6-24 hours, and more preferably 6-12 hours.
The invention also provides application of the titanium oxide @ C hollow composite framework internally embedded with the noble metal silver on a lithium battery metal anode.
The invention also provides a three-dimensional lithium metal anode prepared by the titanium oxide @ C hollow composite framework internally embedded with the noble metal silver.
The invention also provides a preparation method of the three-dimensional lithium metal anode, which comprises the following steps: mixing and slurrying a titanium oxide @ C hollow composite framework material internally embedded with noble metal silver and an adhesive to serve as an active layer, coating the active layer on a commercial copper current collector, and filling metal lithium into a cavity of the active layer after drying to obtain the high-stability three-dimensional lithium metal anode.
Preferably, the thickness of the active layer is 2 to 800 μm, and more preferably 10 to 100 μm.
Preferably, the active layers are compounded on two planes of the metal current collector.
Preferably, the method for filling the metallic lithium is electrodeposition and/or molten lithium filling, and more preferably electrodeposition.
Preferably, the amount of the filled metal lithium is 0.4-150 mAh/cm2More preferably 2 to 100mAh/cm2More preferably 3 to 60mAh/cm2。
Preferably, the adhesive is at least one of polyvinyl alcohol, polytetrafluoroethylene, sodium carboxymethylcellulose, polyethylene, polypropylene, polyvinylidene fluoride, SBR rubber, fluorinated rubber and polyurethane;
preferably, the adhesive accounts for 1 to 40 wt.%, more preferably 5 to 20 wt.% of the active layer.
The invention also provides application of the high-stability three-dimensional lithium metal anode prepared from the titanium oxide @ C hollow composite framework internally embedded with the noble metal silver in a metal lithium battery. The metal lithium battery can be a lithium-sulfur battery, a lithium-iodine battery, a lithium-selenium battery, a lithium-tellurium battery, a lithium-oxygen battery or a lithium-carbon dioxide battery.
Compared with the prior art, the invention has the following technical effects:
1. the titanium oxide @ C hollow composite framework material with the noble metal silver embedded therein has a stable structure, and the titanium oxide layer with the noble metal silver embedded therein can be compounded with the conductive carbon layer for a long time, so that repeated lithium deposition/dissolution can be realized; the titanium oxide and silver with better lithium affinity selectively induce lithium to uniformly deposit in the inner cavity of the hollow composite framework.
2. The research of the invention innovatively discovers that the titanium oxide @ C hollow composite framework material embedded with the noble metal silver can remarkably induce the deposition behavior of lithium, obviously improve the volume effect, and the constructed lithium metal cathode can have excellent electrochemical performance, and the coulombic efficiency and the cycling stability are greatly improved.
3. The high-stability three-dimensional lithium metal anode is used for a lithium sulfur battery, can effectively adsorb polysulfide and convert while stabilizing lithium metal, and reduces the negative influence of the polysulfide on a lithium metal negative electrode interface.
Drawings
FIG. 1 is a schematic structural diagram of a titanium oxide @ C hollow composite framework material with noble metal silver embedded therein.
Detailed Description
The following is a detailed description of the preferred embodiments of the invention and is not intended to limit the invention in any way, i.e., the invention is not intended to be limited to the embodiments described below, and modifications and alternative compounds that are conventional in the art are intended to be included within the scope of the invention as defined in the claims.
Example 1:
SiO with an average diameter of 500nm2The spheres were prepared as a 10g/L sol using 0.05mol/L mercaptopropyl-trimethoxysilane solution, SiO2The volume ratio of the sol to the mercaptopropyl-trimethoxysilane solution is 1:2, normal-temperature activation treatment is carried out for 3 hours, suction filtration is carried out, deionized water is dispersed in 100ml of deionized water after being washed, 100ml of 0.01mol/L silver acetate solution is added, ammonia water solution is added dropwise to prepare silver ammonia solution, 125ml of 0.01mol/L propionaldehyde solution is added dropwise, water bath stirring is carried out at 50 ℃ for 2 hours, and SiO is prepared2@ Ag template. SiO 22Cleaning the @ Ag template, putting 0.5g of the cleaned @ Ag template into 35ml of ethanol solvent, adding 0.35g of hexadecylamine and 0.9ml of ammonia water, stirring for 10min, adding 0.3ml of biethylene titanate, reacting for 2h, filtering and cleaning to obtain SiO2@Ag@TiO2. Adding 150ml 0.01mol/L trihydroxymethyl-aminomethane, ultrasonic dispersing, adding 0.08g acrylamide, adjusting pH to 8.7, stirring for 12 hr, filtering, cleaning, and drying at 70 deg.C for 8 hr. Transferring into a tubular furnace under hydrogen-argon mixed gas flow, heating to 900 deg.C at a speed of 5 deg.C/min, calcining for 2h, and calcining at 5mol/L Ba (OH)2Stirring the solution for 12 hours at 70 ℃, filtering, washing and drying to obtain the TiO with the noble metal silver embedded inside2@ C hollow composite skeleton.
As can be seen from the experimental results, 0.01mol/L silver acetate solution produced SiO2The Ag template can be uniformly compounded with silver particles with the average particle size of 10nm, the Ag loading amounts are respectively 8 at.%, the N loading amount is 10 at.%, the carbon layer thickness is 15nm, and TiO is added2The thickness of the hollow shell layer is 30nm, the shell and the carbon layer are uniform, and the structure is complete.
Example 2:
SiO with an average diameter of 200nm2The spheres were prepared as a 10g/L sol using 0.05mol/L lead chloride solution, SiO2Sol and PbCl2The volume ratio of the solution is 1:2, the activation treatment is carried out for 3h at normal temperature, the filtration is carried out, the deionized water is dispersed in 100ml of deionized water after being washed, 100ml of 0.005mol/L silver chlorate solution is added, ammonia water solution is added dropwise to prepare silver ammonia solution, 125ml of 0.01mol/L formaldehyde solution is added dropwise, the mixture is stirred for 2h in water bath at 50 ℃ to prepare SiO2@ Ag template. Mixing SiO2Cleaning the @ Ag template, putting 0.5g of the cleaned @ Ag template into 35ml of ethanol solvent, adding 0.35g of hexadecylamine and 0.9ml of ammonia water, stirring for 10min, adding 0.3ml of tetrabutyl titanate, reacting for 2h, filtering and cleaning to obtain SiO2@Ag@TiO2. Adding 150ml of 0.01mol/L trihydroxymethyl-aminomethane, performing ultrasonic dispersion, adding 0.1g of dopamine, adjusting pH to 8.5, stirring for 12h, filtering, cleaning, and drying at 70 deg.C for 8 h. Transferring into a tubular furnace, heating to 900 deg.C at 5 deg.C/min under hydrogen-argon mixed gas flow for 2h, and calcining at 5mol/L Ca (OH)2Stirring the solution in water bath at 70 ℃ for 12h, filtering, washing and drying to obtain the TiO with the noble metal silver embedded inside2@ C hollow composite skeleton. As can be seen from the experimental results, SiO is prepared from 0.01mol/L silver chlorate solution2The Ag template can be uniformly compounded with silver particles with the average particle size of 8nm, the Ag loading amounts are respectively 6 at.%, the N loading amount is 15at.%, the carbon layer thickness is 25nm, and TiO2The thickness of the hollow shell layer is 30nm, the shell and the carbon layer are uniform, and the structure is complete.
Example 3:
SiO with an average diameter of 800nm2The spheres were prepared as a 10g/L sol using 0.05mol/L sodium hydroxide solution, SiO2The volume ratio of the sol to the sodium hydroxide solution is 1:2, normal temperature activation treatment is carried out for 3 hours, suction filtration is carried out, deionized water is dispersed in 100ml of deionized water after being washed, 100ml of 0.1mol/L silver fluoride solution is added, ammonia water solution is dropwise added to prepare silver-ammonia solution, 125ml of 0.1mol/L acetaldehyde solution is dropwise added, water bath stirring is carried out at 50 ℃ for 2 hours, and SiO is prepared2@ Ag template. SiO 22Cleaning the @ Ag template, adding 0.5g of the cleaned @ Ag template into 35ml of propanol solvent, and adding 0.35g of hexadecaneStirring amine and 0.9ml ammonia water for 10min, adding 0.5ml isopropyl trititanate, reacting for 2h, filtering and cleaning to obtain SiO2@Ag@TiO2. Adding 150ml of 0.01mol/L trihydroxymethyl-aminomethane, performing ultrasonic dispersion, continuously adding 0.2g of polyaniline, adjusting pH to 9, stirring for 12h, filtering, cleaning, and drying at 70 deg.C for 8 h. Transferring into a tubular furnace under hydrogen-argon mixed gas flow at 5 ℃/min, heating to 900 ℃, roasting for 2h, finally stirring in 5mol/L KOH solution in water bath at 70 ℃ for 12h, filtering, washing and drying to obtain TiO internally embedded with noble metal silver2@ C hollow composite skeleton. As can be seen from the experimental results, 0.1mol/L silver fluoride solution produced SiO2The Ag template can be uniformly compounded with silver particles with the average particle size of 100nm, the Ag loading amounts are respectively 15at.%, the N loading amount is 11 at.%, the carbon layer thickness is 18nm, and TiO2The thickness of the hollow shell layer is 50nm, the shell and the carbon layer are uniform, and the structure is complete.
Example 4:
SiO with an average diameter of 400nm2The ball is prepared into 10g/L sol, stannous chloride solution with the concentration of 0.05mol/L and SiO are used2The volume ratio of the sol to the stannous chloride solution is 1:2, normal temperature activation treatment is carried out for 3 hours, suction filtration is carried out, deionized water is dispersed in 100ml of deionized water after being washed, 100ml of 0.025mol/L AgNO is added3Adding ammonia water solution dropwise to obtain silver ammonia solution, adding 125ml 0.025mol/L glucose solution dropwise, stirring at 50 deg.C for 2 hr to obtain SiO2@ Ag template. SiO 22Cleaning the @ Ag template, putting 0.5g of the cleaned @ Ag template into 35ml of ethanol solvent, adding 0.35g of hexadecylamine and 0.9ml of ammonia water, stirring for 10min, adding 0.4ml of tetraisopropyl titanate, reacting for 2h, filtering and cleaning to obtain SiO2@Ag@TiO2. Adding 150ml of 0.01mol/L trihydroxymethyl-aminomethane, performing ultrasonic dispersion, adding 0.1g of dopamine, adjusting pH to 8.5, stirring for 12h, filtering, cleaning, and drying at 70 deg.C for 8 h. Transferring into a tubular furnace under hydrogen-argon mixed gas flow at 5 ℃/min, heating to 900 ℃, roasting for 2h, finally stirring in 5mol/L NaOH solution in water bath at 70 ℃ for 12h, filtering, washing and drying to obtain TiO internally embedded with noble metal silver2@ C hollow composite skeleton. As can be seen from the experimental results, 0.025mol/LAgNO3Preparation of the solutionSiO of (2)2The Ag template can be uniformly compounded with silver particles with the average particle size of 40nm, the Ag loading amounts are respectively 11 at.%, the N loading amount is 11.2 at.%, the carbon layer thickness is 16nm, and TiO2The thickness of the hollow shell layer is 45nm, the shell and the carbon layer are uniform, and the structure is complete.
Comparative example 4-1:
compared with example 4, the difference is only that no nitrogen is doped, specifically:
SiO with an average diameter of 400nm2The ball is prepared into 10g/L sol, stannous chloride solution with the concentration of 0.05mol/L and SiO are used2The volume ratio of the sol to the stannous chloride solution is 1:2, normal temperature activation treatment is carried out for 3 hours, suction filtration is carried out, deionized water is dispersed in 100ml of deionized water after being washed, 100ml of 0.025mol/L AgNO is added3Adding ammonia water solution dropwise to obtain silver ammonia solution, adding 125ml 0.025mol/L glucose solution dropwise, stirring at 50 deg.C for 2 hr to obtain SiO2@ Ag template. SiO 22Cleaning the @ Ag template, putting 0.5g of the cleaned @ Ag template into 35ml of ethanol solvent, adding 0.35g of hexadecylamine and 0.9ml of ammonia water, stirring for 10min, adding 0.4ml of tetraisopropyl titanate, reacting for 2h, filtering and cleaning to obtain SiO2@Ag@TiO2. Adding 150ml of 0.01mol/L formaldehyde, performing ultrasonic dispersion, adding 0.1g of resorcinol continuously, stirring for 12h, filtering, cleaning, and drying at 70 ℃ for 8 h. Transferring into a tubular furnace under hydrogen-argon mixed gas flow at 5 ℃/min, heating to 900 ℃, roasting for 2h, finally stirring in 5mol/L NaOH solution in water bath at 70 ℃ for 12h, filtering, washing and drying to obtain TiO internally embedded with noble metal silver2@ C hollow composite skeleton. As can be seen from the experimental results, 0.025mol/LAgNO3Solution prepared SiO2The Ag template can be uniformly compounded with silver particles with the average particle size of 40nm, the Ag loading amounts are respectively 11 at.%, the N loading amount is 0 at.%, the carbon layer thickness is 16nm, and TiO2The thickness of the hollow shell layer is 45nm, the shell and the carbon layer are uniform, and the structure is complete.
Comparative example 4-2:
in comparison with example 4, the difference is only that no TiO is present2The method specifically comprises the following steps:
SiO with an average diameter of 400nm2The spheres were configured as a 10g/L sol,using stannous chloride solution of 0.05mol/L, SiO2The volume ratio of the sol to the stannous chloride solution is 1:2, normal temperature activation treatment is carried out for 3 hours, suction filtration is carried out, deionized water is dispersed in 100ml of deionized water after being washed, 100ml of 0.025mol/L AgNO is added3Adding ammonia water solution dropwise to obtain silver ammonia solution, adding 125ml 0.025mol/L glucose solution dropwise, stirring at 50 deg.C for 2 hr to obtain SiO2@ Ag template. SiO 22Cleaning the @ Ag template, adding 0.5g of 150ml of 0.01mol/L trihydroxymethyl-aminomethane, performing ultrasonic dispersion, continuously adding 0.1g of dopamine, adjusting the pH value to 8.5, stirring for 12h, filtering, cleaning, and drying at 70 ℃ for 8 h. And (3) transferring the mixture to a tubular furnace, heating to 900 ℃ at a speed of 5 ℃/min under a hydrogen-argon mixed gas flow, roasting for 2h, finally stirring for 12h in a 5mol/L NaOH solution in a water bath at a temperature of 70 ℃, filtering, washing and drying to obtain the hollow composite framework internally embedded with the noble metal silver. As can be seen from the experimental results, 0.025mol/LAgNO3Solution prepared SiO2The template @ Ag can be uniformly compounded with silver particles with the average particle size of 40nm, the Ag loading amounts are respectively 11 at.%, the N loading amount is 11.2 at.%, the carbon layer thickness is 16nm, the carbon layer is uniform, and the structure is complete.
Comparative examples 4 to 3:
compared with example 4, the difference is that no nano silver particles are present, specifically:
SiO with an average diameter of 400nm2Adding 0.5g of ball into 35ml of ethanol solvent, adding 0.35g of hexadecylamine and 0.9ml of ammonia water, stirring for 10min, adding 0.4ml of tetraisopropyl titanate, reacting for 2h, filtering and cleaning to obtain SiO2@TiO2. Adding 150ml of 0.01mol/L trihydroxymethyl-aminomethane, performing ultrasonic dispersion, adding 0.1g of dopamine, adjusting pH to 8.5, stirring for 12h, filtering, cleaning, and drying at 70 deg.C for 8 h. Transferring into tubular furnace hydrogen-argon mixed gas flow at 5 deg.C/min, heating to 900 deg.C, calcining for 2h, stirring in 5mol/L NaOH solution in water bath at 70 deg.C for 12h, filtering, washing, and drying to obtain TiO2@ C hollow composite skeleton. From the experimental results it can be seen that the N loading is 11.2 at.%, the carbon layer thickness is 16nm, the TiO is2The thickness of the hollow shell layer is 45nm, the shell and the carbon layer are uniform, and the structure is complete.
Example 4 withComparative examples 4-1, 4-2 and 4-3 prepared materials as working electrodes, metallic lithium sheets as counter electrodes, and 1M LiTFSI/DOL: DME (volume ratio of 1:1) containing 2 wt.% LiNO3And (4) carrying out button cell assembly and charge-discharge cycle test on the electrolyte. At 2mA/cm2The current density of the current sensor was selected for charge-discharge cycle testing, and the test results are shown in table 1 below:
table 1 charge-discharge cycle test results
Figure BDA0002658588740000111
The results show that the TiO embedded with the noble metal silver2The electrochemical performance of the @ C hollow composite skeleton electrode is optimal, the gradient lithium-philic structure has positive influence on the uniform deposition/dissolution of lithium, and the improvement of the coulombic efficiency of the battery and the improvement of the cycling stability of the battery are facilitated.
The materials prepared in example 4 and comparative examples 4-1 and 4-3 were used as working electrodes, a metallic lithium sheet was used as a counter electrode, and 1M LiTFSI/DOL DME (volume ratio: 1) containing 1 wt% LiNO3Assembling the button half cell for the electrolyte, and depositing 3mAh/cm2And (4) disassembling the battery, washing the battery by using DME, and reassembling the lithium-sulfur full battery. The charge-discharge cycle test was performed at 1C, and the test results are shown in table 2 below:
TABLE 2 Charge-discharge cycling test results
Figure BDA0002658588740000112
Figure BDA0002658588740000121
The results show that the TiO with the high flexibility of the lithium-philic gradient and the inner inlaid noble metal silver2The @ C hollow composite framework material has the optimal electrode electrochemical performance. On one hand, the titanium oxide thin layer with the silver nanoparticle structure induces lithium metal to be uniformly deposited in the inner cavity of the hollow composite framework, so that interface side reaction and volume effect are inhibited; the other partyTiO with noble metal silver inlaid in surface2The @ C hollow composite framework can play a role in catalytic conversion on polysulfide, and inhibits the shuttle effect of lithium polysulfide, so that the stability and the promotion of the cycle performance of the lithium-sulfur full battery are facilitated.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A titanium oxide @ C hollow composite skeleton embedded with noble metal silver is characterized by comprising a titanium oxide hollow ball with an independent closed cavity, noble metal silver nano particles embedded in the inner cavity of the titanium oxide hollow ball, a carbon layer compounded on the surface of the titanium oxide and a nitrogen-containing functional group; the titanium oxide and the carbon layer are of a hollow framework structure of a closed chamber, and the carbon layer is compounded outside the titanium oxide hollow ball; the noble metal silver nano particles are uniformly embedded on the inner cavity wall of the titanium oxide hollow sphere; the nitrogen-containing functional group is in-situ doped on the carbon layer.
2. The titanium oxide @ C hollow composite skeleton with noble metal silver embedded therein according to claim 1, wherein the thickness of the hollow skeleton structure is 10-2000 nm; the titanium oxide is TiO or TiO2And Ti2O3At least one of the titanium oxide hollow spheres, wherein the shell layer thickness of the titanium oxide hollow sphere is 5-300 nm; the carbon in the carbon layer is at least one of graphitized carbon and amorphous carbon, and the thickness of the carbon layer is 4-150 nm.
3. The titanium oxide with embedded noble metal silver @ C hollow composite skeleton of claim 1, wherein the average diameter of the titanium oxide with embedded noble metal silver @ C hollow composite skeleton is 30-3000 nm.
4. The titanium oxide @ C hollow composite skeleton with embedded noble metal silver as claimed in claim 1, wherein the lithium-philic noble metal silver nanoparticles are silver simple substance, the particle size of the silver simple substance is 0.5-100 nm, and the content of the silver simple substance is 3-15 at.%.
5. The titanium oxide with embedded noble metal silver @ C hollow composite skeleton of claim 1, wherein the nitrogen-containing functional group has a nitrogen content of 0.5 to 12.5 at.%.
6. A method for preparing the titanium oxide embedded with noble metal silver @ C hollow composite skeleton as claimed in any one of claims 1 to 5, wherein SiO uniformly loaded with silver nanoparticles is prepared by using a silica template2The @ Ag composite template is hydrolyzed by adding a titanium source into SiO2Obtaining a titanium oxide precursor on the outer layer of the @ Ag composite template, then carrying out in-situ polymerization to obtain a nitrogen-doped carbon-coated composite framework precursor, roasting the composite framework precursor, and etching the silicon dioxide template by using strong base to obtain the titanium oxide @ C hollow composite framework internally embedded with the noble metal silver.
7. The method for inlaying the titanium oxide @ C hollow composite skeleton of noble metal silver in the claim 6 is characterized by comprising the following specific steps:
step (1), SiO2Preparation of a @ Ag composite template:
mixing SiO2The template is placed in a solution of a surfactant for surface activation, and the surface activated SiO is obtained by separation2A template; the surface active agent is sodium hydroxide, stannous chloride and PbCl2At least one of mercaptopropyl-trimethoxysilane; the concentration of the surface active agent is 0.05-0.5 mol/L;
activating the surface of the SiO2Depositing uniform silver nano particles by the template and silver salt solution under the action of reducing agent to obtain SiO2@ Ag; the concentration of the silver salt solution is 0.002-0.1 mol/L; the reducing agent is at least one of formaldehyde, glucose, acetaldehyde and propionaldehyde; the concentration of the reducing agent is 0.005-0.5 mol/L;
step (2), hydrolyzing a titanium source:
mixing SiO2Adding the @ Ag template, the surfactant and ammonia water into an organic solvent, stirring for 10min at normal temperature, adding a titanium source, stirring, filtering and cleaning to obtain SiO2@Ag@TiO2；
Step (3), carbon coating:
mixing SiO2@Ag@TiO2Adding the mixture into a nitrogenous polymerization monomer solution, adding a buffering agent, adjusting the pH value to 8-10, stirring for a certain time, filtering and washing to obtain a hollow composite framework precursor;
and (4) roasting:
placing the hollow composite framework precursor into a tubular furnace of hydrogen-argon mixed gas flow for roasting to obtain the hollow titanium oxide composite carbon framework SiO containing the silicon template2@Ag@TiO2@ C @ N; the roasting temperature is 500-900 ℃; the roasting time is 120-500 min;
and (5) etching:
the roasted SiO2@Ag@TiO2@ C @ N is put in a strong alkali etchant solution to remove SiO2Drying the template to obtain a final titanium oxide @ C hollow composite framework with noble metal silver embedded inside;
the concentration of the strong alkali etchant is 2-8 mol/L.
8. The method of inlaying the noble metal silver-embedded titanium oxide @ C hollow composite skeleton of claim 1, wherein in the step (1), the surfactant, SiO2The weight ratio of the template to the silver salt to the reducing agent is 0.1-1: 7-50: 2-30: 1-20; in the step (2), the mass ratio of the buffering agent to the nitrogenous polymerized monomer is 2: 1-3: 1, and the concentration of the buffering agent is 0.005-1 mol/L.
9. A three-dimensional lithium metal anode, characterized in that it is prepared from the titanium oxide with embedded noble metal silver @ C hollow composite skeleton as described in any one of claims 1 to 5 or prepared by the method as described in any one of claims 7 to 8.
10. Use of the three-dimensional lithium metal anode of claim 9 in a lithium metal battery.
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