CN113488651B - 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 PDFInfo
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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 embedded with noble metal silver, 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 template 2 The method comprises the following steps of adding a titanium source into a @ Ag composite template, carrying out 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 the silicon dioxide template by using strong base to obtain the titanium oxide @ C hollow composite framework 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
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 -1 The 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 cycle 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 highlyble 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 lithium metal anode of an open structure has difficulty in blocking the occurrence of interfacial side reactions. At 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 decrease 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 to 150nm.
Preferably, the shell layer of the hollow framework structure has a thickness of 10-2000 nm.
Preferably, the titanium oxide is TiO or TiO 2 And Ti 2 O 3 At 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 with noble metal silver embedded therein is 30 to 3000nm.
Preferably, the lithium-philic noble metal silver nano particles are silver simple substances, and the particle size of the silver simple substances is 0.5-100 nm; the content of 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 12.5at.%.
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 invention concept, the invention provides a preparation method of the titanium oxide @ C hollow composite framework internally embedded with the noble metal silver, and the SiO template is used for preparing SiO uniformly loaded with silver nano particles 2 The 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), siO 2 Preparation of a @ Ag composite template:
mixing SiO 2 The template is placed in a solution of a surfactant for surface activation, and the surface activated SiO is obtained by separation 2 A template; activating the surface of the SiO 2 Reaction of the template with a silver salt solution under the action of a reducing agent, siO 2 Uniformly depositing silver nano particles on the template to obtain SiO 2 @ Ag template.
Step (2), hydrolyzing a titanium source:
mixing SiO 2 Adding the @ Ag template, the surfactant and ammonia water into the organic solvent, stirring for 10min at normal temperature, adding the titanium source, stirring, filtering and cleaning to obtain SiO 2 @Ag@TiO 2 ；
Step (3), carbon coating:
mixing SiO 2 @Ag@TiO 2 Adding 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.
Step (4), roasting:
placing the hollow composite framework precursor in a tubular furnace of hydrogen-argon mixed gas flow for roasting to obtain the hollow titanium oxide composite carbon framework SiO containing the silicon template 2 @Ag@TiO 2 @C@N。
And (5) etching:
the roasted SiO 2 @Ag@TiO 2 @ C @ N in strong alkaline etchant solution to remove SiO 2 And drying the template to obtain the final titanium oxide @ C hollow composite framework with the noble metal silver embedded inside.
Further, in the step (1):
preferably, the SiO 2 The template is a uniform particle having a particle diameter of 150 to 600nm, more preferably 200 to 500nm.
Preferably, the surface active agent is sodium hydroxide, stannous chloride, pbCl 2 At least one of mercaptopropyl-trimethoxysilane; the concentration of the surfactant 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 is further preferably glucose;
the concentration of the reducing agent is preferably 0.005 to 0.5mol/L, and more preferably 0.01 to 0.3mol/L.
Further, in the step (2):
preferably, the titanium source is at least one of tetraisopropyl titanate, tetrabutyl titanate, isopropyl trititanate and diethylene titanate.
The concentration of the titanium source is preferably 100 to 1000g/L, more preferably 200 to 900g/L.
The stirring time is preferably 0.5 to 12 hours, more preferably 1 to 5 hours.
Further, in the 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.
Preferably, the concentration of the buffer solution is 0.005 to 1mol/L.
Preferably, the stirring time is 8 to 48 hours, and more preferably 10 to 24 hours.
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.
Preferably, the roasting temperature is 500-900 ℃, and more preferably 600-900 ℃;
preferably, the temperature rise rate of the tube 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 300min.
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 etching agent is 2-8 mol/L.
Preferably, the etching temperature of the template etching is 30-80 ℃, and more preferably 50-70 ℃;
the etching time is preferably 6 to 24 hours, and more preferably 6 to 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.
The thickness of the active layer is preferably 2 to 800. Mu.m, more preferably 10 to 100. Mu.m.
Preferably, the active layer is compounded on two planes of the metal current collector.
Preferably, the method for filling the metallic lithium is electrodeposition and/or melting lithium filling, and more preferably electrodeposition.
Preferably, the amount of the metal lithium to be filled is 0.4 to 150mAh/cm 2 More preferably 2 to 100mAh/cm 2 More preferably 3 to 60mAh/cm 2 。
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 40wt.%, more preferably 5 to 20wt.% 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 500nm 2 The spheres were prepared as a 10g/L sol using 0.05mol/L mercaptopropyl-trimethoxysilane solution, siO 2 The volume ratio of the sol to the mercaptopropyl-trimethoxysilane solution is 1 2 @ Ag template. SiO 2 2 Cleaning 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 SiO 2 @Ag@TiO 2 . 150ml 0.01mol/L trihydroxymethyl-aminomethane is added and dispersed by ultrasonic, 0.08g acrylamide is added continuously, pH is adjusted to 8.7, stirring is carried out for 12h, filtering and cleaning are carried out, and drying is carried out for 8h at 70 ℃. 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) 2 Stirring the solution for 12 hours at 70 ℃, filtering, washing and drying to obtain the TiO with the noble metal silver embedded inside 2 @ C hollow composite skeleton.
As can be seen from the experimental results, 0.01mol/L silver acetate solution produced SiO 2 The Ag template can be uniformly compounded with silver particles with the average particle size of 10nm, the Ag loading amounts are respectively 8at.%, the N loading amount is 10at.%, the carbon layer thickness is 15nm, tiO 2 The 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 200nm 2 The spheres were prepared as a 10g/L sol using 0.05mol/L lead chloride solution, siO 2 Sol and PbCl 2 The volume ratio of the solution is 1 2 @ Ag template. Mixing SiO 2 Cleaning 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 SiO 2 @Ag@TiO 2 . 150ml 0.01mol/L trihydroxymethyl-aminomethane is added and dispersed by ultrasonic, 0.1g dopamine is added continuously, pH is adjusted to 8.5, stirring is carried out for 12h, filtering and cleaning are carried out, and drying is carried out for 8h at 70 ℃. 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) 2 Water in solutionStirring for 12h at 70 ℃, filtering, washing and drying to obtain TiO internally embedded with noble metal silver 2 @ C hollow composite skeleton. As can be seen from the experimental results, siO is prepared from 0.01mol/L silver chlorate solution 2 The Ag template can be uniformly compounded with silver particles with the average particle size of 8nm, the Ag loading amounts are respectively 6at.%, the N loading amount is 15at.%, the carbon layer thickness is 25nm, and TiO is added 2 The 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 800nm 2 The spheres were prepared as a 10g/L sol using 0.05mol/L sodium hydroxide solution, siO 2 Carrying out normal-temperature activation treatment for 3h with the volume ratio of the sol to the sodium hydroxide solution being 1 2 @ Ag template. SiO 2 2 Cleaning the @ Ag template, taking 0.5g of the template, putting the template into 35ml of propanol solvent, adding 0.35g of hexadecylamine and 0.9ml of ammonia water, stirring for 10min, adding 0.5ml of isopropyl trititanate, reacting for 2h, filtering and cleaning to obtain SiO 2 @Ag@TiO 2 . Adding 150ml of 0.01mol/L trihydroxymethyl-aminomethane, performing ultrasonic dispersion, adding 0.2g of polyaniline, adjusting pH to 9, stirring for 12h, filtering, cleaning, and drying at 70 deg.C for 8h. 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 silver 2 @ C hollow composite frameworks. As can be seen from the experimental results, 0.1mol/L silver fluoride solution produced SiO 2 The @ 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 11at.%, the carbon layer thickness is 18nm, and TiO 2 The 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 400nm 2 The spheres were prepared as a 10g/L sol using 0.05mol/L chlorinationStannous solution, siO 2 The volume ratio of the sol to the stannous chloride solution is 1 3 Dropwise adding ammonia water solution to obtain silver ammonia solution, dropwise adding 125ml 0.025mol/L glucose solution, stirring at 50 deg.C in water bath for 2h to obtain SiO 2 @ Ag template. SiO 2 2 Cleaning the @ Ag template, putting 0.5g of the 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 SiO 2 @Ag@TiO 2 . 150ml of 0.01mol/L trihydroxymethyl-aminomethane is added into the mixture and is subjected to ultrasonic dispersion, 0.1g of dopamine is continuously added, the pH value is adjusted to 8.5, the mixture is stirred for 12 hours, filtered and cleaned, and the mixture is dried for 8 hours at 70 ℃. 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 silver 2 @ C hollow composite frameworks. As can be seen from the experimental results, 0.025mol/LAgNO 3 Solution prepared SiO 2 The Ag template can be uniformly compounded with silver particles with the average particle size of 40nm, the Ag loading amounts are respectively 11at.%, the N loading amount is 11.2at.%, the carbon layer thickness is 1691m, and TiO 2 The 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 400nm 2 Preparing 10g/L sol from the spheres, and using stannous chloride solution with the concentration of 0.05mol/L and SiO 2 And (3) carrying out normal-temperature activation treatment for 3h, carrying out suction filtration, washing with deionized water, dispersing in 100ml of deionized water, and adding 100ml of 0.025mol/L AgNO 3 Dropwise adding ammonia water solution to prepare silver ammonia solution, dropwise adding 125ml 0.025mol/L glucose solution, stirring for 2h in water bath at 50 ℃ to obtain SiO 2 @ Ag template. SiO 2 2 Cleaning @ Ag template, adding 0.5g of template into 35ml of ethanol solvent, and adding 0.35g of hexadecylamine and0.9ml ammonia water, stirring for 10min, adding 0.4ml tetraisopropyl titanate, reacting for 2h, filtering and cleaning to obtain SiO 2 @Ag@TiO 2 . 150ml 0.01mol/L formaldehyde is added and dispersed by ultrasonic, 0.1g resorcinol is added continuously, stirring is carried out for 12h, filtering and cleaning are carried out, and drying is carried out for 8h at 70 ℃. 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 silver 2 @ C hollow composite skeleton. As can be seen from the experimental results, 0.025mol/LAgNO 3 Solution produced SiO 2 The Ag template can be uniformly compounded with silver particles with the average particle size of 40nm, the Ag loading amounts are respectively 11at.%, the N loading amount is 0at.%, the carbon layer thickness is 1691m 2 The thickness of the hollow shell layer is 45nm, the shell and the carbon layer are uniform, and the structure is complete.
Comparative examples 4 to 2:
in comparison with example 4, the difference is only that no TiO is present 2 The method specifically comprises the following steps:
SiO with an average diameter of 400nm 2 The ball is prepared into 10g/L sol, stannous chloride solution with the concentration of 0.05mol/L and SiO are used 2 And (3) carrying out normal-temperature activation treatment for 3h, carrying out suction filtration, washing with deionized water, dispersing in 100ml of deionized water, and adding 100ml of 0.025mol/L AgNO 3 Dropwise adding ammonia water solution to prepare silver ammonia solution, dropwise adding 125ml 0.025mol/L glucose solution, stirring for 2h in water bath at 50 ℃ to obtain SiO 2 @ Ag template. SiO 2 2 Cleaning the @ Ag template, adding 150ml of 0.01mol/L trihydroxymethyl-aminomethane into 0.5g of the template, 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 8h. 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/LAgNO 3 Solution prepared SiO 2 @ Ag template with Ag particles of 40nm average size, 11 at% Ag and 11.2 at% NThe carbon layer has a thickness of 16nm, is uniform and has a complete structure.
Comparative examples 4 to 3:
compared with example 4, the difference is that there is no silver nanoparticle, specifically:
SiO with an average diameter of 400nm 2 Adding 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 SiO 2 @TiO 2 . 150ml 0.01mol/L trihydroxymethyl-aminomethane is added and dispersed by ultrasonic, 0.1g dopamine is added continuously, pH is adjusted to 8.5, stirring is carried out for 12h, filtering and cleaning are carried out, and drying is carried out for 8h at 70 ℃. Transferring into tubular furnace, heating to 900 deg.C at 5 deg.C/min under hydrogen-argon mixed gas flow, calcining for 2h, stirring in 5mol/L NaOH solution in water bath at 70 deg.C for 12h, filtering, washing, and drying to obtain TiO 2 @ C hollow composite skeleton. As can be seen from the experimental results, the N loading was 11.2at.%, the carbon layer thickness was 1691m 2 The thickness of the hollow shell layer is 45nm, the shell body and the carbon layer are uniform, and the structure is complete.
The materials prepared in example 4 and comparative examples 4-1, 4-2 and 4-3 were used as working electrodes, a metallic lithium sheet was used as a counter electrode, and a 1M LiTFSI/DOL: DME (volume ratio = 1) 3 And (4) carrying out button cell assembly and charge-discharge cycle test on the electrolyte. At 2mA/cm 2 The 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
The results show that the TiO embedded with the noble metal silver 2 The 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 plate was used as a counter electrode,1% wt LiNO 3 Assembling the button half cell for the electrolyte, and depositing 3mAh/cm 2 And (4) disassembling the battery, cleaning 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
The results show that the TiO with the high flexibility of the lithium-philic gradient and the inner inlaid noble metal silver 2 The @ 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; tiO with noble metal silver inlaid in another side 2 The @ 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 (2)
1. A preparation method of a titanium oxide @ C hollow composite framework with noble metal silver embedded therein is characterized by comprising the following specific steps:
step (1), siO 2 Preparation of a @ Ag composite template:
mixing SiO 2 The template is placed in a solution of a surfactant for surface activation, and the surface activated SiO is obtained by separation 2 A template; the surface active agent isSodium hydroxide, stannous chloride, pbCl 2 At least one of mercaptopropyl-trimethoxysilane; the concentration of the surface active agent is 0.05 to 0.5mol/L;
activating the surface of the SiO 2 Depositing uniform silver nano particles by the template and silver salt solution under the action of reducing agent to obtain SiO 2 @ Ag; the concentration of the silver salt solution is 0.002 to 0.1mol/L; the reducing agent is at least one of formaldehyde, glucose, acetaldehyde and propionaldehyde; the concentration of the reducing agent is 0.005 to 0.5mol/L;
step (2), hydrolyzing a titanium source:
mixing SiO 2 Adding 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 SiO 2 @Ag@TiO 2 ；
Step (3), carbon coating:
mixing SiO 2 @Ag@TiO 2 Adding the mixture into a nitrogenous polymerization monomer solution, adding a buffering agent, adjusting the pH to 8 to 10, stirring for a certain time, filtering and washing to obtain a hollow composite framework precursor;
step (4), roasting:
placing the hollow composite framework precursor in a tubular furnace of hydrogen-argon mixed gas flow for roasting to obtain the hollow titanium oxide composite carbon framework SiO containing the silicon template 2 @Ag@TiO 2 @ C @ N; the roasting temperature is 500 to 900 ℃; the roasting time is 120 to 500 min;
and (5) etching:
the roasted SiO 2 @Ag@TiO 2 Putting @ C @ N in strong alkaline etchant solution to remove SiO 2 Drying 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 to 8mol/L.
2. The method for preparing the titanium oxide @ C hollow composite skeleton with noble metal silver embedded therein according to claim 1, wherein in the step (1), the surfactant, siO 2 The weight ratio of the template to the silver salt to the reducing agent is 0.1 to 17 to 50, 2 to 30; in the step (2), the mass ratio of the buffering agent to the nitrogen-containing polymeric monomer is 2 to 1, and the concentration of the buffering agent is 0.005 to 1mol/L.
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