<b>Preparation of hydroxide ion conductive KOH–layered double hydroxide electrolytes for an all-solid-state iron–air secondary battery</b>

Tsuneishi, Taku; Sakamoto, Hisatoshi; Hayashi, Kazushi; Kawamura, Go; Muto, Hiroyuki; Matsuda, Atsunori

doi:10.1016/j.jascer.2014.03.003

Cited by 17 publications

(7 citation statements)

References 20 publications

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“…However, in addition to the increase in local order, the reduction in fwhm may also be attributed to an increase in Li + ion mobility. The mobility of Li + ions 50−53 implies that OH − ions are simultaneously mobile, as was found in OH − based LDH electrolytes 54 and molecular dynamics simulations of jump diffusion in LDH materials. 55 All spectra are well fit by a single Gaussian line shape with no evidence of a superimposed broad signal.…”

Section: Resultsmentioning

confidence: 85%

Unraveling Gibbsite Transformation Pathways into LiAl-LDH in Concentrated Lithium Hydroxide

Graham

Zhang

et al. 2019

Inorg. Chem.

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Gibbsite (α-Al(OH) 3 ) transformation into layered double hydroxides, such as lithium aluminum hydroxide dihydrate (LiAl-LDH), is generally thought to occur by solidstate intercalation of Li + , in part because of the intrinsic structural similarities in the quasi-2D octahedral Al 3+ frameworks of these two materials. However, in caustic environments where gibbsite solubility is high relative to LiAl-LDH, a dissolutionreprecipitation pathway is conceptually enabled, proceeding via precipitation of tetrahedral (T d ) aluminate anions (Al(OH) 4 − ) at concentrations held below 150 mM by rapid LiAl-LDH nucleation and growth. In this case, the relative importance of solid-state versus solution pathways is unknown because it requires in situ techniques that can distinguish Al 3+ in solution and in the solid phase (gibbsite and LiAl-LDH), simultaneously. Here, we examine this transformation in partially deuterated LiOH solutions, using multinuclear, magic angle spinning, and high field nuclear magnetic resonance spectroscopy ( 27 Al and 6 Li MAS NMR), with supporting X-ray diffraction and scanning electron microscopy. In situ 27 Al MAS NMR captured the emergence and decline of metastable aluminate ions, consistent with dissolution of gibbsite and formation of LiAl-LDH by precipitation. High field, ex situ 6 Li NMR of the the progressively reacted solids resolved an O h Li + resonance that narrowed during the transformation. This is likely due to increasing local order in LiAl-LDH, correlating well with observations in high field, ex situ 27 Al MAS NMR spectra, where a comparatively narrow LiAl-LDH O h 27 Al resonance emerges upfield of gibbsite resonances. No intermediate pentahedral Al 3+ is resolvable. Quantification of aluminate ion concentrations suggests a prominent role for the solution pathway in this system, a finding that could help improve strategies for manipulating Al 3+ concentrations in complex caustic waste streams, such as those being proposed to treat the high-level nuclear waste stored at the U.S. Department of Energy's Hanford Nuclear Reservation in Washington State, USA.

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Section: Resultsmentioning

confidence: 85%

Unraveling Gibbsite Transformation Pathways into LiAl-LDH in Concentrated Lithium Hydroxide

Graham

Zhang

et al. 2019

Inorg. Chem.

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“…11 Tsuneishi and co-workers reported a solid oxide iron-air secondary battery using KOH-LDH (Mg-Al layered double hydroxide) as a solid electrolyte and Fe 3 O 4 particlesupported carbon as an anode material, but only about a stable 30% charge-discharge efficiency is achieved at room temperature. 12 Xu and co-workers reported a new solid oxide iron-air battery with the combination of a solid oxide fuel cell (SOFC) using a Y 2 O 3 stabilized ZrO 2 electrolyte for the redox of H 2 /H 2 Omediated FeO/Fe, as a means of storing electrical-chemical energy in situ via the H 2 /H 2 O-mediated FeO/Fe reversible electrochemical-chemical looping reactions at 800 C. 13 Inoishi and co-workers also proposed an Fe-air rechargeable battery using an LaGaO 3 based oxide ion conductor as an electrolyte at 600 C. 14 However, the redox cycle stability, which is due to reoxidation and aggregation of the anode, is a common issue that needs to be overcome. 15 We introduced a new class of rechargeable batteries, the molten (electrolyte) air batteries, which exhibit amongst the highest reversible electrical energy storage capabilities of any battery.…”

Section: Introductionmentioning

confidence: 99%

Critical advances for the iron molten air battery: a new lowest temperature, rechargeable, ternary electrolyte domain

Liu

Cui

et al. 2015

J. Mater. Chem. A

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“…This feature makes it suitable for application as electrode in the Zn-air battery. 63 In these devices, the LDH works as a hydroxide-ion conductor. The publication reports the hydroxide-ion conductivities of solid electrolytes based on MgAl LDH with the addition of KOH.…”

Section: Metal-air Batterymentioning

confidence: 99%

Layered double hydroxide: a new promising nanomaterial in energy application

Coluccini

Sporer

Leuteritz

et al. 2014

Nanomaterials and Energy

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Recent synthetic approaches allowed to obtain layered double hydroxides (LDHs) with different functions. Due to the controlled structure of the LDH the high potential in the energy application have been found as electrode, dielectric, and even semiconductor. It is a promising new-generation nanomaterial for the energy application. This report has been reviewing the synthetic approaches for these LDHs and their utilisations in the field of energy application. Layered double hydroxide: a new promising nanomaterial in energy application Coluccini, Sporer, Leuteritz, Kuehnert and Wang ICE Publishing: All rights reserved Keywords: energy/functional nanomaterials/nanocomposites/ nanostructures/property 1 2 3 4 5

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Preparation of hydroxide ion conductive KOH–layered double hydroxide electrolytes for an all-solid-state iron–air secondary battery

Abstract: (2014) Preparation of hydroxide ion conductive KOH-layered double hydroxide electrolytes for an all-solid-state iron-air secondary battery,

Cited by 17 publications

References 20 publications

Unraveling Gibbsite Transformation Pathways into LiAl-LDH in Concentrated Lithium Hydroxide

Unraveling Gibbsite Transformation Pathways into LiAl-LDH in Concentrated Lithium Hydroxide

Critical advances for the iron molten air battery: a new lowest temperature, rechargeable, ternary electrolyte domain

Layered double hydroxide: a new promising nanomaterial in energy application

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