Structure and ionic conductivity of the solid electrolyte interphase layer on tin anodes in Na-ion batteries

Kuo, Liang-Yin; Moradabadi, Ashkan; Huang, Hsin‐Fu; Hwang, Bing‐Joe; Kaghazchi, Payam

doi:10.1016/j.jpowsour.2016.11.077

Cited by 33 publications

(22 citation statements)

References 31 publications

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“…Some of the associated concentration profiles and the results have been presented in Figs. 4b and 25 Na-diffusivities in some of the components of the SEI layer formed on Sn electrode in Na 'half cells' (again, coin cells containing NaClO 4 in EC/DEC as ) estimated with our a-Si film electrodes. Nevertheless, it is still acknowledged that such simple estimation, as reported here, may not yield a very correct value for the diffusivity of Na in a-Si material per se, primarily since it does not take into account whether any surface film (such as SEI; though expected to be very thin in the first cycle) or stress buildup might also partly contribute toward limiting the overall transport.…”

Section: Resultsmentioning

confidence: 91%

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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Section: Resultsmentioning

confidence: 91%

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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“…Since organic SEI components usually showed inferior ion‐conductivity to their inorganic counterparts, electrolyte with EC/PC solvents and VC/FEC additives, which preferred to form inorganic salts at their decomposition, might be more favorable to construct SEI with better ionic transfer properties. Recently, the Na + conductivities in main SEI components have been calculated for NaF, Na 2 CO 3, and Na 2 O providing instructive guidance for future design of the SEI inorganic component. With increasing realization about the importance of tuning the SEI for more efficient Na + transport, we expect that work on the Na electrolyte additives would intensify.…”

Section: The Effect Of Sei On Na‐ion Transfermentioning

confidence: 99%

Interphases in Sodium‐Ion Batteries

Song

Xiao

Lin

et al. 2018

Advanced Energy Materials

274

212

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search for alternative high energy batteries using abundant and low cost materials is imperative. [2] Sodium ion batteries (SIBs), which as LIBs' close analogy was first explored in the 1980s, have regained substantial spotlights for their great potential as beyond/ post lithium battery chemistry in lowcost electrical energy storage (EES) systems. [3] Being in the same alkaline group with Li, Na chemistry/electrochemistry bears many similarities to Li, hence the SIB development naturally follows the track of success left by LIBs. A variety of cathode/anode pairs and electrolyte have been explored within a short period of time and some of them have been proven to be potentially practical for SIBs. [4] With the understanding deepened, however, it becomes clear that the choice of electrode materials in SIBs and LIBs and their corresponding performance have much less in common than expected, and in many cases even contradictory to each other despite the similarity of the intercalation chemistry between Na-ions and Li-ions.Among the implications ensuing from such differences, the uniqueness of electrode/electrolyte interphases in SIBs profoundly affects the SIBs performances and has not been thoroughly investigated. Such interphases, also known as SEI on anode surface or cathode electrolyte interphase (CEI) on cathode surface, are to a great extent dictated by the chemistry and electrochemistry of Na salts dissolved in aprotic solvent molecules. After the solid electrolyte interphase (SEI)/CEI formation in the initial cycles of SIBs, their chemical/electrochemical reactivity/stability will determine the reversibility and rate of the cell reactions for the rest of the cell life. Solid Electrolyte InterphaseIn battery systems of high voltages such as LIBs, the electrodes operate at potentials outside of the thermodynamic stability limits of the electrolyte. In some cases (but not all), an interphase forms at the interface between electrode (cathode/anode) and electrolyte at the decomposition of the latter, which prevents parasitic reactions and kinetically stabilizes the system. Figure 1A shows a simplified schematic illustration of the anode/cathode surface in LIBs/SIBs with SEI/CEI configuration. The Li/Na ions transport in the bulk electrolyte in the form of solvated ions, and must go through a desolvation process to pass these SEI/CEI into the electrode. Early notions of an ideal SEI layer must possess the general attributes such as: (1) an Sodium-ion batteries (SIBs) as economical, high energy alternatives to lithiumion batteries (LIBs) have received significant attention for large-scale energy storage in the last few years. While the efforts of developing SIBs have benefited from the knowledge learned in LIBs, thanks to the apparent proximity between Na-ions and Li-ions, the unique physical and chemical properties of Na-ions also distinctly differ themselves from Li-ions. It is expected that SIBs have drastically different electrode material structure, solvation-desolvation behavior, electrode-electrolyte interp...

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“…Last Kaghazchi and co‐workers analyzed the content and ionic conductivity values of the SEI layer on a Sn anode stemming from a EC:DEC electrolyte solution using Raman spectroscopy and DFT simulations. Their work concluded that the SEI layer was composed primarily of Na 2 O and Na 2 CO 3 , with the Na 2 O displaying much better ionic conductivity …”

Section: Seimentioning

confidence: 99%

“…Their work concluded that the SEI layer was composed primarily of Na 2 O and Na 2 CO 3 , with the Na 2 O displaying much better ionic conductivity. [83]…”

Section: Characterization and Comparisons With-li-based Seimentioning

confidence: 99%

Electrolytes, SEI Formation, and Binders: A Review of Nonelectrode Factors for Sodium‐Ion Battery Anodes

Bommier

2018

Small

267

181

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Through intense effort in recent years, knowledge of Na-ion batteries has been advanced significantly, pertaining to electrodes. Often, such progress has been accompanied by using a convenient choice of electrolyte or binder. Nevertheless, it has been witnessed that "external" factors to electrodes, such as electrolytes, solid electrolyte interphase, and binders, affect the functions of electrodes profoundly. And generally, certain types of electrodes favor some electrolytes or binders. With a rapidly increasing number of publications in the area, trends in terms of electrolytes and binders are possibly exploitable. Unfortunately, the field has yet to see a review article that devotes itself to these nonelectrode aspects of Na-ion batteries. Here, the gap is filled by conducting a comprehensive review of these nonelectrode external factors, especially by looking into their correlation with electrochemical properties, such as cycle life, and first cycle coulombic efficiency. Not only are the representative reports reviewed, but also quantitative analyses on the database that are constructed are provided. With such analyses, some new data-driven perspectives are postulated, which are of great value to the community.

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Structure and ionic conductivity of the solid electrolyte interphase layer on tin anodes in Na-ion batteries

Cited by 33 publications

References 31 publications

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

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

Interphases in Sodium‐Ion Batteries

Electrolytes, SEI Formation, and Binders: A Review of Nonelectrode Factors for Sodium‐Ion Battery Anodes

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