A Sodium–Antimony–Telluride Intermetallic Allows Sodium‐Metal Cycling at 100% Depth of Discharge and as an Anode‐Free Metal Battery (Adv. Mater. 1/2022)

Wang, Yixian; Dong, Hui; Katyal, Naman; Hao, Hongchang; Liu, Pengcheng; Celio, Hugo; Henkelman, Graeme; Watt, John; Mitlin, David

doi:10.1002/adma.202270001

Cited by 21 publications

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“…[ 25c ] The slight shift in the peak position might stem from instrumental effects caused by changes in sample conductivity. [ 7,25c,d ] The normalized concentration of each component was estimated by integrating the area of the individual peaks. The corresponding statistical histograms in Figure 4d,h show that the SEI of Al@G quickly stabilized during cycling.…”

Section: Resultsmentioning

confidence: 99%

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An Anode‐Free Potassium‐Metal Battery Enabled by a Directly Grown Graphene‐Modulated Aluminum Current Collector

Zhao

Liu

et al. 2022

Advanced Materials

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energy density. [3] Fortunately, the exploration of novel configurations of K-based energy storage systems is expected to provide key breakthroughs in overcoming performance bottlenecks. [4] An anode-free battery archi tecture tactfully eliminates active anode materials by pairing a fully preintercalated cathode with a bare anode current collector, thereby endowing the full-cell with increased energy density. [5] Pint et al. constructed an anode-free Na-metal battery using sodiated pyrite as the cathode and Al foils modified with a carbon nucleation layer as the anode current collector, achieving an energy density of ≈400 Wh kg −1 . [4a] Meanwhile, Luo et al. reported an anode-free porous Al||presodiated TiS 2 full-cell with increased energy density. [6] Recently, Mitlin et al. devised an innovative anode-free Na-metal battery comprising a Na 2 (Sb 2/6 Te 3/6 Vac 1/6 ) current collector and Na 3 V 2 (PO 4 ) 3 cathode, obtaining a capacity decay of only 0.23% per cycle. [7] Despite these achievements, anode-free K-metal batteries have rarely been explored.Besides possessing advantages over Cu in terms of cost and weight, Al foil can function as an anode current collector in anode-free K-metal batteries. [8] However, commercial Al current collectors are electrochemically potassiophobic and exhibit high nucleation resistance, inducing uneven electrochemical K deposition. [9] This results in poor reversibility during the plating/stripping process, which is reflected by a low Coulombic efficiency (CE). As anode-free K-metal batteries possess a finite K inventory in the cathode, the low CE might eventually result in capacity plunge and battery failure. [5,10] Therefore, it is of core significance to modulate the nucleation-growth behavior of K on an Al current collector through scalable and delicate surface modification. [11] Various conceptual models have been proposed to reveal the electrochemical growth behavior of metals that are complementary toward each other. [12] Recently, a film growth model was established to explain the growth of metals from a new perspective. [13] In this model, the electrochemical plating of K can be analogized as thin-film growth in vacuum and is governed by the surface energy of the substrate. [14] Based on this model, it is feasible to tune the surface energy of an Al current collector to ameliorate the nucleation-growth behavior Potassium (K)-metal batteries have emerged as a promising energy-storage device owing to abundant K resources. An anode-free architecture that bypasses the need for anode host materials can deliver an elevated energy density. However, the poor efficiency of K plating/stripping on potassiophobic anode current collectors results in rapid K inventory loss and a short cycle life. Herein, commercial Al foils are decorated with an ultrathin graphenemodified layer (Al@G) through roll-to-roll plasma-enhanced chemical vapor deposition. By harnessing strong adhesion (10.52 N m −1 ) and a high surface energy (66.6 mJ m −2 ), the designed Al@G structure ensures a highly...

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Section: Resultsmentioning

confidence: 99%

“…devised an innovative anode‐free Na‐metal battery comprising a Na 2 (Sb 2/6 Te 3/6 Vac 1/6 ) current collector and Na 3 V 2 (PO 4 ) 3 cathode, obtaining a capacity decay of only 0.23% per cycle. [ 7 ] Despite these achievements, anode‐free K‐metal batteries have rarely been explored.…”

Section: Introductionmentioning

confidence: 99%

An Anode‐Free Potassium‐Metal Battery Enabled by a Directly Grown Graphene‐Modulated Aluminum Current Collector

Zhao

Liu

et al. 2022

Advanced Materials

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“…These electrolytes are regarded as the commonly used choice for commercial LIBs, which possess many merits, including their low cost, better oxidation stability, and higher reduction potential that allows for high‐voltage cathode materials. [ 45 ] To the best of our knowledge, this is the very first and highly desired report on achieving stable and long‐term cycling stability under high current densities (i.e., ≥1000 h at 1 and 3 mA cm −2 , ≥700 h at 5 mA cm −2 ) of SMBs operated in carbonate electrolytes without any additives.…”

Section: Introductionmentioning

confidence: 99%

Stable Sodium‐Metal Batteries in Carbonate Electrolytes Achieved by Bifunctional, Sustainable Separators with Tailored Alignment

Wang

Zhang

et al. 2022

Advanced Materials

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Sodium (Na) is the most appealing alternative to lithium as an anode material for cost‐effective, high‐energy‐density energy‐storage systems by virtue of its high theoretical capacity and abundance as a resource. However, the uncontrolled growth of Na dendrites and the limited cell cycle life impede the large‐scale practical implementation of Na‐metal batteries (SMBs) in commonly used and low‐cost carbonate electrolytes. Herein, the employment of a novel bifunctional electrospun nanofibrous separator comprising well‐ordered, uniaxially aligned arrays, and abundant sodiophilic functional groups is presented for SMBs. By tailoring the alignment degree, this unique separator integrates with the merits of serving as highly aligned ion‐redistributors to self‐orientate/homogenize the flux of Na‐ions from a chemical molecule level and physically suppressing Na dendrite puncture at a mechanical structure level. Remarkably, unprecedented long‐term cycling performances at high current densities (≥1000 h at 1 and 3 mA cm−2, ≥700 h at 5 mA cm−2) of symmetric cells are achieved in additive‐free carbonate electrolytes. Moreover, the corresponding sodium–organic battery demonstrates a high energy density and prolonged cyclability over 1000 cycles. This work opens up a new and facile avenue for the development of stable, low‐cost, and safe‐credible SMBs, which could be readily extended to other alkali‐metal batteries.

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“…In this respect, “anode‐less” (or “anode‐free”) cells promise high safety and low‐cost high‐energy density sodium metal batteries (SMBs). [ 18 ] However, given the limited sodium inventory supplied by the cathode, [ 19 ] enabling a highly efficient Na deposition/dissolution on the anode current collector is essential to achieve high performance cells.…”

Section: Introductionmentioning

confidence: 99%

Sodiophilic Current Collectors Based on MOF‐Derived Nanocomposites for Anode‐Less Na‐Metal Batteries

Zhang

et al. 2022

Advanced Energy Materials

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for the practical application of SIBs. On the anode side, metallic sodium is the ideal candidate. In fact, with its high theoretical capacity (1166 mA h g −1 ) and low redox potential (−2.71 V vs standard hydrogen electrode), sodium could enable high energy batteries. Indeed, multiple battery chemistries based on sodium metal anodes (SMAs) have been proposed, such as sodium-sulfur (commercial), [4] sodium-air, [5] sodiumseawater, [6] and sodium-carbon dioxide batteries. [7] However, similar to the Li-metal anode, metallic Na suffers from a few crucial problems, i.e., side reactions with the electrolyte and formation of Na dendrites, which may cause both cell failure and safety concerns. [8] The commonly used ester-based electrolytes are particularly affected by side reactions with sodium. [9] Comparatively, ether-based electrolytes feature improved stability, making them more suitable for reactive metal anodes. [10] Besides the side reactions, the growth of dendritic Na upon repeated plating/stripping process is another phenomenon leading to both performance deterioration and safety issues. On one side, Na dendrites, with their large surface area, are more reactive to the electrolyte causing more severe side reactions. [11] Additionally, the cumulative growth of Na-metal dendrites, originating from the non-uniform charge distribution at the electrode-electrolyte interface, might penetrate the separator and lead to a short-circuit of the cell. [8a] Finally, the uneven Na deposition results in the solid electrolyte interphase (SEI) of SMAs to repeatedly break "Anode-less" sodium metal batteries (SMBs) with high energy may become the next-generation batteries due to the abundant resources. However, their cycling performance is still insufficient for practical uses. Herein, a metal organic frameworks (MOF)-derived copper-carbon (Cu@C) composite is developed as a sodiophilic layer to improve the Coulombic efficiency (CE) and cycle life. The Cu particles can provide abundant nucleation sites to spatially guide Na deposition and the carbon framework offer void volume to avoid volume changes during the plating/stripping process. As a result, Cu@C-coated copper and aluminum foils (denoted as Cu-Cu@C and Al-Cu@C foil) can be used as efficient current collectors for sodium plating/stripping, achieving, nearly 1600 and 240 h operation upon cycling at 0.5 mA cm −2 and 1 mA h cm −2 , respectively. In situ dilatometry measurements demonstrate that Cu@C promotes the formation of dense Na deposits, thereby inhibiting side reactions, dendrite growth, and accumulation of dead Na. Such current collectors are employed in Na metal cells using carbon-coated Na 3 V 2 (PO 4 ) 3 (NVP/C) and copper selenides (Cu 2−x Se@C) cathodes, achieving outstanding rate capability and improved cycling performance. Most noticeably, "anode-less" Na batteries using Al-Cu@C as anode and NVP/C as cathode demonstrate promising CE as high as 99.5%, and long-term cycling life.

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A Sodium–Antimony–Telluride Intermetallic Allows Sodium‐Metal Cycling at 100% Depth of Discharge and as an Anode‐Free Metal Battery (Adv. Mater. 1/2022)

Cited by 21 publications

References 0 publications

An Anode‐Free Potassium‐Metal Battery Enabled by a Directly Grown Graphene‐Modulated Aluminum Current Collector

An Anode‐Free Potassium‐Metal Battery Enabled by a Directly Grown Graphene‐Modulated Aluminum Current Collector

Stable Sodium‐Metal Batteries in Carbonate Electrolytes Achieved by Bifunctional, Sustainable Separators with Tailored Alignment

Sodiophilic Current Collectors Based on MOF‐Derived Nanocomposites for Anode‐Less Na‐Metal Batteries

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