Electrolyte design for LiF-rich solid–electrolyte interfaces to enable high-performance microsized alloy anodes for batteries

Chen, Ji; Fan, Xiulin; Li, Qin; Yang, Hongbin; Khoshi, M. Reza; Xu, Yaobin; Hwang, Sooyeon; Chen, Long; Ji, Xiao; Yang, Changping; He, Huixin; Wang, Chongmin; Garfunkel, Eric; Su, Dong; Borodin, Oleg; Chun-sheng, Wang

doi:10.1038/s41560-020-0601-1

Cited by 750 publications

(629 citation statements)

References 63 publications

Supporting

Mentioning

573

Contrasting

Order By: Relevance

“…In the previous research, a dense NaF layer possessed a high modulus to restrain the volume change but suffered from a low ionic conductivity. [ 45,46 ] Considering the decomposition of FEC, the thick NaF may not be dense in the EC/DEC‐derived SEI due to the F‐containing organic component was generated simultaneously, [ 47 ] which could not prevent the continuous decomposition of the electrolyte, as the evidence by low CE and poorcyclic stability. The cycle performance of Bi/C in EC/DEC‐based electrolyte without FEC additive was conducted to clarify the role of FEC.…”

Section: Resultsmentioning

confidence: 99%

Ionic‐Conducting and Robust Multilayered Solid Electrolyte Interphases for Greatly Improved Rate and Cycling Capabilities of Sodium Ion Full Cells

Yuan

Wei

et al. 2020

Advanced Energy Materials

View full text Add to dashboard Cite

and similar electrochemistry to lithiumion batteries (LIBs) for energy storage applications. Despite these advantages of SIBs, their energy density is still much lower than that of LIBs. [1-5] Accordingly, high-capacity alloy-type materials are being considered as potential anodes to achieve high-energy SIBs. However, the huge volume change and sluggish chargestorage kinetics of the alloying anodes limit their practical and industrial applications. The repeated volume changes can destroy the preformed solid electrolyte interface (SEI), resulting in the continuous decomposition of the electrolyte. Consequently, the subsequent accumulation of thick SEI films will greatly impede the transfer of ions/electrons and deplete the active mass of the battery. [6,7] Among the various alloy-type anode materials under consideration for SIBs, bismuth is attractive because of its high reversible capacity (385 mAh g −1) and low operating voltage (≈0.6 V). Additionally, the large lattice fringe along the c-axis (d (003) = 3.95 Å) allows bismuth to insert/extract large-sized ions in a reversible manner during the charging and discharging cycles. However, bismuth is limited by low cyclic and rate performances arising from the large volume expansion and sluggish electrode kinetics, which are commonly observed in alloy-type anodes. For the past few years, tremendous efforts have been devoted to improving the cyclic stability by modifying alloying materials through carbon coating, porous architectures, and nanostructural designs. [8-11] The nanostructure of the bismuth anode was capable of achieving less or even zero strain for SEI formation, as well as providing a fast electron/ion transfer pathway for enhanced rate capabilities. For example, the Bi@ graphene nanocomposite and bismuth nanodots confined in the metal-organic framework derived carbon arrays exhibited dramatic improvement, in terms of their specific capacity. [12] However, the capacity decreased at high rates and after longterm cyclic tests. Thus, the sodium storage performance of the nanostructured bismuth-based anodes was not yet satisfactory. Another approach was to develop a new electrolyte and to modify the associated interface. Recently, it was reported that The energy storage performance of sodium-ion batteries has been greatly improved by pairing ether-based electrolytes with high-capacity alloy-type anodes. However, the origin of this performance improvement by a unique electrode/electrolyte interface has yet to be explored. To understand such results, herein, the deterministic and distinct interfacial chemistries and solid electrolyte interphase (SEI) layers in both the ether-and ester-based electrolytes are described, as verified by post mortem, in-depth X-ray photoelectron spectroscopy, and electron energy loss spectroscopy analyses, employing a hierarchical Bi/C composite anode as the model system. In the ether-based electrolyte, fast sodium-ion storage kinetics and structural integrity are achieved due to the highly ionic-conducting and robust multi-layered...

show abstract

Section: Resultsmentioning

confidence: 99%

Ionic‐Conducting and Robust Multilayered Solid Electrolyte Interphases for Greatly Improved Rate and Cycling Capabilities of Sodium Ion Full Cells

Yuan

Wei

et al. 2020

Advanced Energy Materials

View full text Add to dashboard Cite

show abstract

“…Tremendous efforts have been made to regulate electrolytes by altering the salts, solvents, additives, and/or concentrations. [ 9,10 ] In the case of the salt for PIBs, the most attractive one is potassium bis(fluorosulfonyl)imide (KFSI), as it could lead to a more stable SEI than is possible with other salts, such as KPF 6 and potassium bis(trifluoromethanesulfonyl)imide. [ 11–14 ] Also, it has been demonstrated that the stability of graphite can be enhanced by simply increasing the salt concentration in conventional carbonate or ether‐based electrolytes.…”

Section: Figurementioning

confidence: 99%

Manipulating the Solvation Structure of Nonflammable Electrolyte and Interface to Enable Unprecedented Stability of Graphite Anodes beyond 2 Years for Safe Potassium‐Ion Batteries

et al. 2020

View full text Add to dashboard Cite

redox potential of K + is close to that of Li + but lower than for Na +. [1-4] Another important motivation for PIB research is that K + cations can be reversibly intercalated into the commercial graphite anode used for LIBs with a high theoretical capacity of 279 mAh g −1 based, on the generated compound KC 8 , which offers the encouraging prospect of PIBs suitable for high manufacturability, by using the commercial production lines for LIBs. [5-7] For the large-scale applications of PIBs, long-term calendar life and high safety are the most two critical factors. The graphite anode in PIBs, however, suffers from poor stability due to the continual decomposition of the electrolyte and insufficient solid electrolyte interphase (SEI) protection. [8] The electrolyte plays a vital role in determining the performance of electrode materials and regulating the SEI to eliminate interfacial side reactions and ensure long-term cyclability and high safety. Tremendous efforts have been made to regulate electrolytes by altering the salts, solvents, additives, and/ or concentrations. [9,10] In the case of the salt for PIBs, the most attractive one is potassium bis(fluorosulfonyl)imide (KFSI), as it could lead to a more stable SEI than is possible with other salts, such as KPF 6 and potassium bis(trifluoromethanesulfonyl) imide. [11-14] Also, it has been demonstrated that the stability of graphite can be enhanced by simply increasing the salt concentration in conventional carbonate or ether-based electrolytes. An electrolyte consisting of KFSI and ethyl methyl carbonate (EMC) at the high molar ratio of 1:2.5 made the graphite anode work for 17 months. Benefiting from the robust inorganic-rich SEI layer generated by the concentrated KFSI with EMC, this long cycle-life performance of graphite is the best that has ever been achieved in reported electrolytes. [15] The carbonate or ether-based electrolytes are highly combustible and volatile, however, which poses a great potential hazard for accidents involving explosion and fire. Although the volatility and flammability can be reduced in highly concentrated electrolytes, safety still remains an issue, especially for large-scale implementation. [16,17] It is well known that the flammability of the electrolyte is mainly determined by the property of solvents, and thus, there are also efforts toward developing nonflammable electrolytes Potassium-ion batteries (PIBs) are attractive for low-cost and large-scale energy storage applications, in which graphite is one of the most promising anodes. However, the large size and the high activity of K + ions and the highly catalytic surface of graphite largely prevent the development of safe and compatible electrolytes. Here, a nonflammable, moderate-concentration electrolyte is reported that is highly compatible with graphite anodes and that consists of fire-retardant trimethyl phosphate (TMP) and potassium bis(fluorosulfonyl)imide (KFSI) in a salt/solvent molar ratio of 3:8. It shows unprecedented stability, as evidenced by its 74% capacity r...

show abstract

“…[ 36,38‐41 ] Furthermore, the choice of the binder and electrolyte additives can influence the structure of the SEI significantly. [ 34,35,40,42‐50 ] The effort of fluoroethylene carbonate on stabilizing the SEI layer for both anodes and cathodes has been widely studied. [ 51‐55 ]…”

Section: Introductionmentioning

confidence: 99%

β‐cyclodextrin as Lithium‐ion Diffusion Channel with Enhanced Kinetics for Stable Silicon Anode

Chen

Zhang

et al. 2020

Energy & Environ Materials

View full text Add to dashboard Cite

Silicon (Si) is regarded as a promising anode material for next‐generation lithium‐ion batteries due to its ultrahigh theoretical capacity. However, the drastic volume change and the continuous solid electrolyte interphase (SEI) formation during the lithiation/delithiation process seriously hinder its practical application as commercial anodes. Herein, macrocyclic beta‐cyclodextrin (β‐CD) has been designed as the diffusion channel for lithium ions at the molecular scale. The diameter of molecular channel is approximately comparable with the solvated lithium ions, which enables the transport of lithium ions and prevents the penetration of solvent molecules. Moreover, the addition of β‐CD changes the formation behavior of SEI layer and stabilizes the Si nanoparticles. The enhanced electrochemical performances in terms of fast kinetics and improved stability have been achieved. The Si anode with the particularly selected lithium‐ion diffusion channel and stabilized SEI layer exhibits a high reversible capability of 2 562 mAh g−1 after 50 cycles at the current density of 500 mA g−1, 1 944 mAh g−1 after 200 cycles at the current density of 1 A g−1, and high rate performance. The novel strategy of molecular channel for lithium‐ion diffusion offers new insights into the design of alloy‐typed anode electrodes with high capacity for lithium‐ion batteries.

show abstract

Electrolyte design for LiF-rich solid–electrolyte interfaces to enable high-performance microsized alloy anodes for batteries

Cited by 750 publications

References 63 publications

Ionic‐Conducting and Robust Multilayered Solid Electrolyte Interphases for Greatly Improved Rate and Cycling Capabilities of Sodium Ion Full Cells

Ionic‐Conducting and Robust Multilayered Solid Electrolyte Interphases for Greatly Improved Rate and Cycling Capabilities of Sodium Ion Full Cells

Manipulating the Solvation Structure of Nonflammable Electrolyte and Interface to Enable Unprecedented Stability of Graphite Anodes beyond 2 Years for Safe Potassium‐Ion Batteries

β‐cyclodextrin as Lithium‐ion Diffusion Channel with Enhanced Kinetics for Stable Silicon Anode

Contact Info

Product

Resources

About