Dealloying technique in the synthesis of lithium-ion battery anode materials

Kunduraci, Muharrem

doi:10.1007/s10008-016-3226-3

Cited by 26 publications

(8 citation statements)

References 57 publications

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“…The in situ formed Sn nanostructured can then be cycled subsequently. The advantage of such a top-down nanosynthesis starting from bulk Mg 2 Sn is at least twofold: (i) Processing micrometer-sized Mg 2 Sn powder for large scale applications is more affordable than synthesizing nanostructured Sn using conventional bottom-up routes. − (ii) In a full battery configuration, Mg removed from Mg 2 Sn can be reversibly stored in the cathode, which means that the loss of material in the process can be avoided or minimized. Hence, starting from Mg 2 Sn could be more attractive than previous methodologies where sacrificial Sb is used to produce nanostructured Sn in situ from β-SnSb electrode materials. , In the following sections, we present the characterizations and electrochemical performances of Mg 2 Sn.…”

Section: Resultssupporting

confidence: 85%

In Situ Dealloying of Bulk Mg₂Sn in Mg-Ion Half Cell as an Effective Route to Nanostructured Sn for High Performance Mg-Ion Battery Anodes

Asl

Kumar

et al. 2018

Chem. Mater.

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Nanostructured Sn as negative electrode material in Mg-ion batteries suffers from very slow magnesiation kinetics when its nanoscale feature sizes are not in the sub-100 nm range. Herein, we use electrochemical experiments in combination finite element modeling (FEM) to demonstrate a cost-effective route to nanostructured Sn for high performance Mg-ion battery anodes. Using FEM we found that antagonistic stresses developed during dealloying of Mg 2 Sn induce pulverization of the dealloyed material and formation of nanostructured Sn with the characteristic feature size in the sub-100 nm range. These results were further confirmed through electrochemical experiments using a Mg halfcell consisting of bulk Mg 2 Sn particles with an average characteristic size larger than 10 μm as the working electrode, cycled versus Mg metal as counter and reference electrodes, and all-phenyl complex (APC) electrolyte. Ex situ electron microscopy and diffraction techniques were used to study the working electrode material in the pristine, demagnesiated, and remagnesiated forms. The results suggest that the starting micrometer-sized Mg 2 Sn particles are converted into nanostructured β-Sn with characteristic sizes ranging from 10 to 50 nm during the first demagnesiation. Electrochemical performance of the in situ formed nanostructured Sn was further investigated during subsequent (de)magnesiation cycles in combination with electrochemical impedance spectroscopy (EIS). EIS studies suggest the formation of passive films on the Mg 2 Sn electrode. A reversible capacity of 300 mAh/g was demonstrated over 150 cycles at the rate of C/5 after application of a combined sequence of regular galvanostatic cycling with an oxidative pulse to control the passive film formation. This work is expected to open new avenues for cost-effective routes to high performance alloytype Mg-ion battery anodes without complex nanosynthesis steps.

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Section: Resultssupporting

confidence: 85%

In Situ Dealloying of Bulk Mg₂Sn in Mg-Ion Half Cell as an Effective Route to Nanostructured Sn for High Performance Mg-Ion Battery Anodes

Asl

Kumar

et al. 2018

Chem. Mater.

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“…For obvious reasons gold, cannot be used because of its cost, but this work highlights a strategy to produce nanostructured tin electrodes with a good cycle life and fast kinetic properties. As a more practical solution, copper, nickel, and numerous bimetallic scaffolds can be formed using this dealloying method. , A potential drawback of these high-surface-area foams is their relatively high metal volume content, which can add inactive mass to the battery, thereby diminishing the returns of using a high-capacity active material. Furthermore, the first cycle Coulombic efficiency of these high-surface-area materials is low ( e.g.…”

Section: Electrode Architecturementioning

confidence: 99%

Deterministic Design of Chemistry and Mesostructure in Li-Ion Battery Electrodes

Cook

2018

ACS Nano

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All battery electrodes have complex internal three-dimensional architectures that have traditionally been formed through the random packing of the electrode components. What is now emerging is a new concept in battery electrode design, where the important electronic and ionic pathways, as well as the chemical interactions between the components of the electrode, are deterministically designed. Deterministic design enables far better properties than are possible through random packing, including dramatic improvements in both power and energy. Such a design approach is particularly attractive for emerging high-energy-density materials, which require available free volume as they swell during cycling. In addition to controlled structure, another important facet of the design of such systems is the stable chemical linkages between the active material and the conductive network that survive the lithiation and delithiation processes. In this Perspective, we discuss and provide our views on deterministically designed battery electrodes.

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“…Wang et al discovered the ease with which Mg alloy precursors can be dealloyed, which facilitated the current study . Research on dealloying less noble materials − such as Si − has been studied to a much lesser extent, in spite of its potential use in energy storage applications …”

Section: Introductionmentioning

confidence: 97%

The Fabrication and Characterization of Bimodal Nanoporous Si with Retained Mg through Dealloying

Balk

2017

Adv Eng Mater

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The fabrication and characterization of bimodal nanoporous silicon films with retained magnesium, achieved through a novel approach utilizing free corrosion dealloying of precursor Si-Mg films in distilled water, is studied. Investigation of film structure and chemical composition using various techniques reveals important characteristics potentially relevant to lithium-ion battery applications. Dealloying of precursor films results in a hierarchal structure, where larger ligaments have an average width of 83 nm and smaller ligaments an average width of 19 nm. A thin, porous surface layer is present on most dealloyed films and is largely composed of magnesium and silicon oxides, as verified by XPS surface analysis. TEM studies reveal that as-dealloyed films are amorphous, but nanocrystalline silicon grains form after vacuum annealing at 500 C. EDS mapping and XPS reveal three distinct chemical composition regions through the film thickness, where residual magnesium generally increases as a function of film thickness, with the highest amount of retained magnesium at the surface. The ligament size, composition, and structure, combined with the simple, non-hazardous nature of the dealloying method, make this an attractive material and processing technique for efficient and scalable production of lithium-ion battery anode material.

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Dealloying technique in the synthesis of lithium-ion battery anode materials

Cited by 26 publications

References 57 publications

In Situ Dealloying of Bulk Mg₂Sn in Mg-Ion Half Cell as an Effective Route to Nanostructured Sn for High Performance Mg-Ion Battery Anodes

In Situ Dealloying of Bulk Mg₂Sn in Mg-Ion Half Cell as an Effective Route to Nanostructured Sn for High Performance Mg-Ion Battery Anodes

Deterministic Design of Chemistry and Mesostructure in Li-Ion Battery Electrodes

The Fabrication and Characterization of Bimodal Nanoporous Si with Retained Mg through Dealloying

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Dealloying technique in the synthesis of lithium-ion battery anode materials

Cited by 26 publications

References 57 publications

In Situ Dealloying of Bulk Mg2Sn in Mg-Ion Half Cell as an Effective Route to Nanostructured Sn for High Performance Mg-Ion Battery Anodes

In Situ Dealloying of Bulk Mg2Sn in Mg-Ion Half Cell as an Effective Route to Nanostructured Sn for High Performance Mg-Ion Battery Anodes

Deterministic Design of Chemistry and Mesostructure in Li-Ion Battery Electrodes

The Fabrication and Characterization of Bimodal Nanoporous Si with Retained Mg through Dealloying

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In Situ Dealloying of Bulk Mg₂Sn in Mg-Ion Half Cell as an Effective Route to Nanostructured Sn for High Performance Mg-Ion Battery Anodes

In Situ Dealloying of Bulk Mg₂Sn in Mg-Ion Half Cell as an Effective Route to Nanostructured Sn for High Performance Mg-Ion Battery Anodes