Experimental Study on Sodiation of Amorphous Silicon for Use as Sodium-Ion Battery Anode

Lim, Chek Hai; Huang, Tzu‐Yang; Shao, Pei-Sian; Chien, Jen-Hao; Weng, Yu‐Ting; Huang, Hsin‐Fu; Hwang, Bing‐Joe; Wu, Nae‐Lih

doi:10.1016/j.electacta.2016.06.031

Cited by 74 publications

(70 citation statements)

References 26 publications

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“…More importantly, a number of insertion sites had E b < 0 for Na, implying that a-Si should be electrochemically active for Na (while c-Si is not). In 2016, exactly this was confirmed in an experimental study of Lim et al [38]. This is an example of theory leading the experiment in the design of new electrode materials for post-Li batteries.…”

Section: Interactions Of LI Na K and Mg With Monoelemental Group Isupporting

confidence: 61%

“…The defect formation energies of Na, and Mg defects (vs. vacuum reference states) in a-Si and a-C are comparable with the respective metal cohesive energies, meaning that insertion of Na and Mg atoms could be feasible. Sodiation of a-Si has now been confirmed experimentally [38]. This is in contrast to c-Si and graphite, where the storage of Na and Mg atoms is limited due to high energy cost of Na and Mg insertion into c-Si.…”

Section: Discussionmentioning

confidence: 60%

“…Some of these studies considered for the first time phononic effects on lithiation, sodiation, and magnesiation, and effects on voltage of doping. While most of these studies helped explain the mechanism and parameters of performance which had already been observed experimentally, some of them predicted electrochemical activity before it was confirmed experimentally, for example, the recently confirmed sodiation of amorphous silicon [20,38] or voltages achieved with magnesiated TiO 2 [22,39]. Some of the calculations we performed and review below still await experimental confirmation such as our prediction of significantly enhanced insertion energetics by p-doping.…”

Section: This Reviewmentioning

confidence: 95%

See 2 more Smart Citations

Insertion of Mono- vs. Bi- vs. Trivalent Atoms in Prospective Active Electrode Materials for Electrochemical Batteries: An ab Initio Perspective

2017

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Rational design of active electrode materials is important for the development of advanced lithium and post-lithium batteries. Ab initio modeling can provide mechanistic understanding of the performance of prospective materials and guide design. We review our recent comparative ab initio studies of lithium, sodium, potassium, magnesium, and aluminum interactions with different phases of several actively experimentally studied electrode materials, including monoelemental materials carbon, silicon, tin, and germanium, oxides TiO 2 and V x O y as well as sulphur-based spinels MS 2 (M = transition metal). These studies are unique in that they provided reliable comparisons, i.e., at the same level of theory and using the same computational parameters, among different materials and among Li, Na, K, Mg, and Al. Specifically, insertion energetics (related to the electrode voltage) and diffusion barriers (related to rate capability), as well as phononic effects, are compared. These studies facilitate identification of phases most suitable as anode or cathode for different types of batteries. We highlight the possibility of increasing the voltage, or enabling electrochemical activity, by amorphization and p-doping, of rational choice of phases of oxides to maximize the insertion potential of Li, Na, K, Mg, Al, as well as of rational choice of the optimum sulfur-based spinel for Mg and Al insertion, based on ab initio calculations. Some methodological issues are also addressed, including construction of effective localized basis sets, applications of Hubbard correction, generation of amorphous structures, and the use of a posteriori dispersion corrections.

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Section: Interactions Of LI Na K and Mg With Monoelemental Group Isupporting

confidence: 61%

Section: Discussionmentioning

confidence: 60%

Section: This Reviewmentioning

confidence: 95%

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Insertion of Mono- vs. Bi- vs. Trivalent Atoms in Prospective Active Electrode Materials for Electrochemical Batteries: An ab Initio Perspective

2017

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“…By contrast, less than an year back, Xu et al 17 reported that reversible uptake of Na in c-Si nanoparticles is possible (with reversible capacity of ∼250 mAh g −1 ), albeit at much reduced particle sizes of ∼20 nm; which would throw significant processing/handling challenges (in addition to lower tap densities). In another very recent work by Lim et al, 12 coating of a-Si by Sn led to net Na-capacities of ∼230 mAh g −1 , even though bare Si hardly showed any Na-capacity. With respect to Si-based composite electrodes, Zhao et al 18 reported Na-capacity of ∼280 mAh g −1…”

mentioning

confidence: 99%

“…11 Such predicted Na-capacity, even though significantly lesser compared to the Li-capacity, would still be considerably superior to those of most other potential anode materials. [3][4][5][6]15,16 Furthermore, lower Na-intake in Si would result in lower volume expansion compared to the case of Li-intake (viz., ∼114% for Na vs. ∼400% for Li), 11 which might just lead to lesser problems related to stress induced degradation and capacity fade in the case of Na.Due to the earlier belief concerning electrochemical Na-insertion being difficult in Si, [6][7][8][9][10]13 only very recently few experimental works 12,17,18 have explored the possibilities of electrochemical sodiation/de-sodiation in crystalline (c-Si) 6,17 and amorphous Si (a-Si) 12,18 in the form of nanoparticles. Indeed, both Ellis et al 7 and Komaba et al, 6 in their studies with Si particle sizes of 325 mesh * Electrochemical Society Student Member.…”

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confidence: 99%

Feasibility of Reversible Electrochemical Na-Storage and Cyclic Stability of Amorphous Silicon and Silicon-Graphene Film Electrodes

Jangid

Vemulapally

Sonia

et al. 2017

J. Electrochem. Soc.

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The feasibility of reversible electrochemical Na-alloying in amorphous silicon (a-Si), along with influences of transport limitations of Na, dimensional aspects of a-Si and usage of few layers graphene (FLG) as interlayer (between a-Si and current collector) on Na-capacities and cyclic stabilities, have been demonstrated here with the use of continuous film electrodes (sans binder/additive). Systematic variations of a-Si film thicknesses have indicated that electrochemical Na-alloying, even though feasible, is 'transport limited', especially for a-Si dimensions beyond ∼100 nm. Nevertheless, decent performances, such as initial reversible Na-capacities of ∼340 mAh g −1 , with ∼120 mAh g −1 retained after 100 cycles, could be achieved upon reduction of film thickness to 50 nm. Analytical computation studies indicate that overall diffusivity of Na in such a-Si electrodes may be of the order of ∼10 −19 m 2 s −1 . In the presence of FLG interlayer (∼7 well-ordered continuous graphene layers), 'transport limitation' related issues got suppressed even for 250 nm thick a-Si film; viz., leading to considerably enhanced Na-capacities and improved cyclic stabilities. Accordingly, reversible Na-capacities recorded with the 250 and 50 nm a-Si films at the end of 100 cycles were ∼120 and ∼240 mAh g −1 ; which are possibly the best reported to-date for Si-based electrode materials. Due to limited lithium reserves in the world as compared to the more widespread and abundant reserves of sodium, there has been recent surge of interests toward the development of Na-ion batteries (SIBs), possibly in lieu of the Li-ion technology.1,2 However, one of the major issues associated with the Na-ion system is that graphitic carbon, the commonly used anode material for Li-ion batteries (LIBs), possesses reversible Na-capacity of just ∼35 mAh g −1 .1, [3][4][5][6][7][8][9] This is an order of magnitude lower compared to the corresponding Li-capacity; 3,10-12 and is caused by the larger size of the Na-ion. Accordingly, metallic anode materials, such as Ge, Sb and Sn, have been investigated for SIBs, but without much success in terms of cyclic stabilities due to dimensional changes (and detrimental stress developments) upon Na-alloying/dealloying. [3][4][5][6] It is a bit surprising that silicon, which possesses possibly the highest theoretical capacity for Li and extensively investigated for LIBs, was hitherto believed to be 'inactive' toward sodiation via electrochemical routes.6-10,13 Kulish et al., 8 via first principles, showed that sodiation of bulk Si is unfavorable, with Na binding energies being 0.6 eV, along with larger diffusion barrier of 1.06 eV. By contrast, the available Na-Si phase diagram 14 indicates that Na-alloying in Si is possible (up to Na 1 Si phase); with more recent calculations predicting that one Si atom can host at most 0.76 Na (i.e., up to Na 0.76 Si; corresponding to specific capacity of ∼725 mAh g −1 ). 11 Such predicted Na-capacity, even though significantly lesser compared to the Li-capacity, would still be co...

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Design of Phosphide Anodes Harvesting Superior Sodium Storage: Progress, Challenges, and Perspectives

Hao

Shao²,

Yuan

et al. 2023

Adv Funct Materials

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Sodium (Na) ion batteries (SIBs) are promising in stationary energy storage applications. Research is also afoot to seek suitable electroactive materials for use in SIBs. Recently, phosphides to be used in the anode for Na storage are particularly appealing due to their high specific capacities and low working potentials. The following matters are to deal with their inherent drawbacks of large volume variation and inferior interfacial stability upon Na insertion/ extraction, which is believed to be largely responsible for capacity and cycling decay. Despite striking progress in addressing the above drawbacks, current studies on phosphides remain preliminary. In this review, an in-depth understanding of phosphides regarding Na storage mechanism, capacity assessment, phase change, and reaction types is provided. The effective strategies and the sound designs of phosphides for Na storage are also discussed. Their correlations between electrochemical behavior and chemical/structural characteristics are analyzed, in a bid to sort out the basic ideas for the design of high-performance phosphides that enable high-energy and durable SIBs. Doubtless, the experience and knowledge gained from the research on phosphides are shared, and the strategies are expected to extend the scope beyond phosphides.

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Experimental Study on Sodiation of Amorphous Silicon for Use as Sodium-Ion Battery Anode

Cited by 74 publications

References 26 publications

Insertion of Mono- vs. Bi- vs. Trivalent Atoms in Prospective Active Electrode Materials for Electrochemical Batteries: An ab Initio Perspective

Insertion of Mono- vs. Bi- vs. Trivalent Atoms in Prospective Active Electrode Materials for Electrochemical Batteries: An ab Initio Perspective

Feasibility of Reversible Electrochemical Na-Storage and Cyclic Stability of Amorphous Silicon and Silicon-Graphene Film Electrodes

Design of Phosphide Anodes Harvesting Superior Sodium Storage: Progress, Challenges, and Perspectives

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