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

A technology of titanium oxide and noble metals, applied in the direction of active material electrodes, structural parts, electrical components, etc., can solve problems such as large volume effect, low Coulombic efficiency, and interface side reactions, so as to reduce negative effects, improve volume effect, and stabilize the structure Effect

Active Publication Date: 2021-10-08
CENT SOUTH UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] Aiming at the problems of large volume effect, serious interfacial side reactions and low coulombic efficiency of the existing lithium metal negative electrode under the actual charge-discharge system, the present invention provides a titanium oxide@C hollow composite framework material embedded with precious metal silver, aiming at The deposition behavior of lithium is improved through a stable gradient lithium-friendly structure, and the closed hollow structure can effectively weaken the interface side reaction and volume effect; the composite nitrogen-doped conductive carbon layer improves the reaction kinetics and improves the cycle stability of lithium under high current enhance the electrochemical performance of lithium metal anode

Method used

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  • Titanium oxide@C hollow composite framework embedded with precious metal silver, and preparation method and application thereof
  • Titanium oxide@C hollow composite framework embedded with precious metal silver, and preparation method and application thereof
  • Titanium oxide@C hollow composite framework embedded with precious metal silver, and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0069] SiO with an average diameter of 500 nm 2 The ball is configured into a 10g / L sol, using a mercaptopropyl-trimethoxysilane solution with a concentration of 0.05mol / L, SiO 2 The volume ratio of the sol to the mercaptopropyl-trimethoxysilane solution is 1:2, and it is activated at room temperature for 3 hours, filtered with suction, rinsed with deionized water, dispersed in 100ml of deionized water, and added with 100ml of 0.01mol / L silver acetate solution. Add ammonia solution dropwise to prepare silver ammonia solution, then add 125ml 0.01mol / L propionaldehyde solution dropwise and stir in water bath at 50°C for 2h to prepare SiO 2 @Ag template. SiO 2 After the @Ag template is cleaned, take 0.5g into 35ml of ethanol solvent, add 0.35g of hexadecylamine and 0.9ml of ammonia water, stir for 10min, then add 0.3ml of diethylene titanate, react for 2h, filter and wash to obtain SiO 2 @Ag@TiO 2 . Add 150ml of 0.01mol / L trismethylol-aminomethane and ultrasonically disperse...

Embodiment 2

[0072] SiO with an average diameter of 200 nm 2 The ball is configured into a 10g / L sol, using a lead chloride solution with a concentration of 0.05mol / L, SiO 2 Sol and PbCl 2 The volume ratio of the solution is 1:2, carry out activation treatment at room temperature for 3 hours, suction filter, rinse with deionized water, disperse in 100ml deionized water, add 100ml 0.005mol / L silver chlorate solution, add ammonia solution dropwise to prepare silver ammonia solution, and then add 125ml 0.01mol / L formaldehyde solution dropwise at 50°C for 2h in a water bath to prepare SiO 2 @Ag template. SiO 2 After the @Ag template is cleaned, take 0.5g in 35ml ethanol solvent, add 0.35g hexadecylamine and 0.9ml ammonia water, stir for 10min, then add 0.3ml tetrabutyl titanate, react for 2h, filter and wash to get SiO 2 @Ag@TiO 2 . Add 150 ml of 0.01 mol / L tris-aminomethane and ultrasonically disperse, continue to add 0.1 g of dopamine, adjust the pH to 8.5, stir for 12 hours, filter an...

Embodiment 3

[0074] SiO with an average diameter of 800 nm 2 The ball is configured into a 10g / L sol, using a sodium hydroxide solution with a concentration of 0.05mol / L, SiO 2 The volume ratio of the sol to the sodium hydroxide solution is 1:2, activate at room temperature for 3 hours, filter with suction, rinse with deionized water and disperse in 100ml of deionized water, add 100ml of 0.1mol / L silver fluoride solution, and add ammonia dropwise The aqueous solution was prepared as a silver ammonia solution, and then 125ml of 0.1mol / L acetaldehyde solution was added dropwise and stirred in a water bath at 50°C for 2 hours to obtain SiO 2 @Ag template. SiO 2 After the @Ag template is cleaned, take 0.5g in 35ml of propanol solvent, add 0.35g of hexadecylamine and 0.9ml of ammonia water, stir for 10min, then add 0.5ml of isopropyl trititanate, react for 2h, filter and wash to get SiO 2 @Ag@TiO 2 . Add 150ml of 0.01mol / L trismethylol-aminomethane and ultrasonically disperse, continue to...

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Abstract

The invention belongs to the field of lithium metal battery negative electrode materials, and particularly discloses a titanium oxide@C hollow composite framework embedded with precious metal silver, and a preparation method and application thereof. The hollow composite framework comprises a titanium oxide hollow ball with an independent closed cavity, precious metal silver nanoparticles embedded in an 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 preparation method comprises the following steps: preparing a SiO2@Ag composite template uniformly loaded with silver nanoparticles by using a silicon dioxide template, adding a titanium source, hydrolyzing, 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 skeleton precursor, roasting at a certain temperature, and etching the silicon dioxide template with a strong alkali 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, the nucleation overpotential of lithium deposition is reduced, lithium metal is selectively induced to be deposited into the cavity structure, the interface side reaction and the volume effect are greatly avoided, the growth of lithium dendrites is inhibited, favorable conditions are created for uniform lithium deposition / dissolution, and the coulombic efficiency and the cycling stability of the lithium metal battery are remarkably improved.

Description

technical field [0001] The invention belongs to the technical field of electrode materials for lithium metal batteries, and in particular relates to a current collector for lithium metal batteries, in particular to a titanium oxide@C hollow composite skeleton embedded with noble metal silver and its preparation method and application. Background technique [0002] Lithium metal has a very high theoretical specific capacity of 3860mAhg -1 , the lowest electrochemical potential -3.04V (relative to the standard hydrogen electrode), however, the uncontrollable lithium dendrite growth and severe interfacial side reactions lead to a decrease in the coulombic efficiency of the battery and a deterioration in cycle performance, making it difficult for commercial applications of lithium metal anodes . [0003] At present, the construction of lithium-philic 3D current collectors is considered to be an effective means to solve the volume effect and achieve uniform lithium deposition. ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M4/62H01M4/134H01M10/052
CPCH01M4/625H01M4/628H01M4/134H01M10/052H01M2004/021H01M2004/027Y02E60/10
Inventor 洪波赖延清姜怀杨杰伟张治安张凯方静
Owner CENT SOUTH UNIV
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