Preparation of a porous nanostructured germanium from GeO<sub>2</sub>via a “reduction–alloying–dealloying” approach

Yin, Huayi; Xiao, Wei; Mao, Xuhui; Zhu, Hua

doi:10.1039/c4ta05244g

Cited by 25 publications

(25 citation statements)

References 34 publications

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“…In comparison, metallic Ge nanowires or nanoparticles (fig. S6, A to D) are obtained from electrolysis of solid GeO 2 in NaCl-CaCl 2 molten salts (33).…”

Section: Microstructure Of Cathodic Productmentioning

confidence: 99%

In situ electrochemical conversion of CO ₂ in molten salts to advanced energy materials with reduced carbon emissions

et al. 2020

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Fixation of CO2 on the occasion of its generation to produce advanced energy materials has been an ideal solution to relieve global warming. We herein report a delicately designed molten salt electrolyzer using molten NaCl-CaCl2-CaO as electrolyte, soluble GeO2 as Ge feedstock, conducting substrates as cathode, and carbon as anode. A cathode-anode synergy is verified for coelectrolysis of soluble GeO2 and in situ–generated CO2 at the carbon anode to cathodic Ge nanoparticles encapsulated in carbon nanotubes (Ge@CNTs), contributing to enhanced oxygen evolution at carbon anode and hence reduced CO2 emissions. When evaluated as anode materials for lithium-ion batteries, the Ge@CNTs hybrid shows high reversible capacity, long cycle life, and excellent high-rate capability. The process contributes to metallurgy with reduced carbon emissions, in operando CO2 fixation to advanced energy materials, and upgraded conversion of carbon bulks to CNTs.

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“…In comparison, metallic Ge nanowires or nanoparticles (fig. S6, A to D) are obtained from electrolysis of solid GeO 2 in NaCl-CaCl 2 molten salts (33).…”

Section: Microstructure Of Cathodic Productmentioning

confidence: 99%

In situ electrochemical conversion of CO ₂ in molten salts to advanced energy materials with reduced carbon emissions

et al. 2020

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“…Taking the preparation of SiGe alloy nanotubes as the example, the general protocol for the one‐pot electrolytic formation of SiGe hollow structures is schematically illustrated in Figure . According to the previous reports, direct electro‐reduction of individual solid SiO 2 and GeO 2 in molten chlorides can create metallic Si and Ge with well‐defined structures . When the mixture of SiO 2 and GeO 2 is involved, the de‐oxidation of GeO 2 is thermodynamically favorable according to the change in Gibbs free energy (Δ G ) and standard decomposition voltage ( V 0 ) for the reduction process of Ge and Si at 800 °C in the Equations (1) and :

GeO_{2} (normals) = Ge (normals) + O_{2} (normalg) Δ G = 373.5 kJ mol^{- 1} V^{0} = 0.97 V

SiO_{2} (normals) = Si (normals) + O_{2} (normalg) Δ G = 717.5 kJ mol^{- 1} V^{0} = 1.986 V

…”

Section: Figurementioning

confidence: 99%

Electrolytic Formation of Crystalline Silicon/Germanium Alloy Nanotubes and Hollow Particles with Enhanced Lithium‐Storage Properties

Xiao

Zhou

et al. 2016

Angewandte Chemie

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Crystalline silicon(Si)/germanium(Ge) alloy nanotubes and hollowp articles are synthesized for the first time through ao ne-pot electrolytic process.T he morphology of these alloy structures can be easily tailored from nanotubes to hollowp articles by varying the overpotential during the electro-reduction reaction. The continuous solid diffusion governed by the nanoscale Kirkendall effect results in the formation of inner void in the alloy particles.Benefitting from the compositional and structural advantages,t hese SiGe alloy nanotubes exhibit muche nhanced lithium-storage performance compared with the individual solid Si and Ge nanowires as the anode material for lithium-ion batteries.

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“…[23][24][25][26] Another advantage for the direct preparation of CaB 6 was that CaB 6 is more conductive than B; therefore, the IR drop during the solid-state reduction can be effectively reduced. As has been previously reported, Ca can be easily alloyed with Si and Ge at a slightly more negative potential that that of Si and Ge formation in the CaCl 2 -based melt.…”

Section: Resultsmentioning

confidence: 99%

Electrolytic calcium hexaboride for high capacity anode of aqueous primary batteries

et al. 2015

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The use of lightweight elements/compounds and the employment of multi-electron reaction (MER) chemistry are two approaches used to develope high energy density materials for batteries. In this work, nanoscaled calcium hexaboride (CaB 6 ) was prepared in one-step by the electro-reduction of solid calcium borate (CaB 2 O 4 ) in molten CaCl 2 -NaCl. CaB 2 O 4 was synthesized by a simple co-precipitation method. It was revealed that the electrolytic CaB 6 delivers a specific capacity of 2400 mA h g À1 in 30%KOH solution though a multi-electron reaction mechanism. Its practical gravimetric energy is three times that of Zn. Decrease of particle size substantially improves both the electrochemical activity and discharge capacity of CaB 6 . The electrolysis of CaB 2 O 4 in molten salt provides a straightforward and sustainable way to prepare high-capacity CaB 6 using low-cost and environmentally friendly boron and calcium resources, which can be recycled from the used CaB 6 primary batteries.

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Preparation of a porous nanostructured germanium from GeO₂via a “reduction–alloying–dealloying” approach

Cited by 25 publications

References 34 publications

In situ electrochemical conversion of CO ₂ in molten salts to advanced energy materials with reduced carbon emissions

In situ electrochemical conversion of CO ₂ in molten salts to advanced energy materials with reduced carbon emissions

Electrolytic Formation of Crystalline Silicon/Germanium Alloy Nanotubes and Hollow Particles with Enhanced Lithium‐Storage Properties

Electrolytic calcium hexaboride for high capacity anode of aqueous primary batteries

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Preparation of a porous nanostructured germanium from GeO2via a “reduction–alloying–dealloying” approach

Cited by 25 publications

References 34 publications

In situ electrochemical conversion of CO 2 in molten salts to advanced energy materials with reduced carbon emissions

In situ electrochemical conversion of CO 2 in molten salts to advanced energy materials with reduced carbon emissions

Electrolytic Formation of Crystalline Silicon/Germanium Alloy Nanotubes and Hollow Particles with Enhanced Lithium‐Storage Properties

Electrolytic calcium hexaboride for high capacity anode of aqueous primary batteries

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Preparation of a porous nanostructured germanium from GeO₂via a “reduction–alloying–dealloying” approach

In situ electrochemical conversion of CO ₂ in molten salts to advanced energy materials with reduced carbon emissions

In situ electrochemical conversion of CO ₂ in molten salts to advanced energy materials with reduced carbon emissions