A new ether-based electrolyte for dendrite-free lithium-metal based rechargeable batteries

Miao, Rongrong; Yang, Jun; Xu, Zhixin; Wang, Jiulin; Nuli, Yanna; Sun, Lu

doi:10.1038/srep21771

Cited by 169 publications

(154 citation statements)

References 39 publications

(51 reference statements)

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“…In addition to preventing dendrite induced short circuits, the last approach may impede unwanted parasitic reactions between the electrode and electrolyte that lead to formation of insulating products and loss of electrochemically active material, causing decay in the battery capacity with increasing charge-discharge cycles 12 . A common approach for the formation of artificial SEI on the metal involves use of special electrolyte additives such as vinylene carbonate 31, 32 , fluoroethylene carbonate 33 , dioxane 34 , sultones 30, 35 , or functional ionic liquids 7, which can electro-polymerize on the surface of electrode to form an elastic coating that protects the metal surface and accommodate volume changes in the electrode during charge and discharge. There are also recent reports of protecting the electrode interface by direct formation of a barrier layer by deliberate reaction between electrodes and reactive species in electrolytes 36–38 .…”

Section: Introductionmentioning

confidence: 99%

Designing solid-liquid interphases for sodium batteries

et al. 2017

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Secondary batteries based on earth-abundant sodium metal anodes are desirable for both stationary and portable electrical energy storage. Room-temperature sodium metal batteries are impractical today because morphological instability during recharge drives rough, dendritic electrodeposition. Chemical instability of liquid electrolytes also leads to premature cell failure as a result of parasitic reactions with the anode. Here we use joint density-functional theoretical analysis to show that the surface diffusion barrier for sodium ion transport is a sensitive function of the chemistry of solid–electrolyte interphase. In particular, we find that a sodium bromide interphase presents an exceptionally low energy barrier to ion transport, comparable to that of metallic magnesium. We evaluate this prediction by means of electrochemical measurements and direct visualization studies. These experiments reveal an approximately three-fold reduction in activation energy for ion transport at a sodium bromide interphase. Direct visualization of sodium electrodeposition confirms large improvements in stability of sodium deposition at sodium bromide-rich interphases.

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Section: Introductionmentioning

confidence: 99%

Designing solid-liquid interphases for sodium batteries

et al. 2017

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“…[18][19][20] Recently, diglyme (DEGDME) has been used for sodium-ion storage in graphite oxide and HC; good performance has been achieved owing to the intact nature of the SEI. Many intercalation/conversion/alloy-type electrode materials similar to those in LIBs have been explored.…”

Section: Introductionmentioning

confidence: 99%

Lithium‐Pretreated Hard Carbon as High‐Performance Sodium‐Ion Battery Anodes

Xiao

Soto

et al. 2018

Advanced Energy Materials

107

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large size of sodium-ions, there are also uniqueness in the development of SIB materials and the tuning of electrodeelectrolyte interphases, etc. [3] One of the most representative examples is that the intercalation of sodium-ion in graphite is thermodynamically inhibited by the interlayer distance, whereas the lithium-ion intercalation is favorable. [1,3] Hard carbon (HC) with expanded interlayer distance was investigated as the-state-of-the-art anode that allows sodium-ion storage via pore absorption, defect binding, and intercalation into the turbostratic graphenic nanodomains. [4][5][6][7] HC structure and the unique ion storage mechanism inevitably induce more reduction decomposition of the electrolyte, solid electrolyte interphase (SEI) formation, ion trapping, and hence lead to worse Coulombic efficiency than graphite. [8] Delicate control of the HC defects and surface area is therefore particularly required. [5,9] It is known that the electrochemical reversibility and the rate and life performance of LIBs and SIBs are to a great extent dictated by the SEI formation and its chemical/electrochemical reactivity and stability. [5,10,11] Concerning this, attempts also have been made to tune the SEI coverage, thickness, stability, and ionic conductivity, etc., by developing novel electrolytes or electrolyte additives that decompose preferentially to form SEI or tailoring the surface area and physiochemical properties of the carbon materials. [10][11][12][13] Ether-based electrolyte has been extensively used in lithium-air and lithiumsulfur batteries. [14,15] The solvent-in-salt electrolyte design also has expanded the application of ether electrolyte to LIBs with graphite anodes and high-voltage cathodes. [16,17] In SIBs, ether Hard carbon (HC) is the state-of-the-art anode material for sodium-ion batteries (SIBs). However, its performance has been plagued by the limited initialCoulombic efficiency (ICE) and mediocre rate performance. Here, experimental and theoretical studies are combined to demonstrate the application of lithium-pretreated HC (LPHC) as high-performance anode materials for SIBs by manipulating the solid electrolyte interphase in tetraglyme (TEGDME)-based electrolyte. The LPHC in TEGDME can 1) deliver > 92% ICE and ≈220 mAh g −1 specific capacity, twice of the capacity (≈100 mAh g −1 ) in carbonate electrolyte; 2) achieve > 85% capacity retention over 1000 cycles at 1000 mA g −1 current density (4 C rate, 1 C = 250 mA g −1 ) with a specific capacity of ≈150 mAh g −1 , ≈15 times of the capacity (10 mAh g −1 ) in carbonate. The full cell of Na 3 V 2 (PO 4 ) 3 -LPHC in TEGDME demonstrated close to theoretical specific capacity of ≈98 mAh g −1 based on Na 3 V 2 (PO 4 ) 3 cathode, ≈2.5 times of the value (≈40 mAh g −1 ) with nontreated HC. This work provides new perception on the anode development for SIBs.

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“…LiTFSI 和 VC 一起添加到 LiPF 6 电解液中, 可减少产气, 提高高温存储性能 [75] . 另外, LiFSI 离子电导率较高, 可抑制电池在高倍率下循环时 Li 枝晶的形成 [76] . [79] .…”

Section: Figureunclassified

Review of Electrolyte Additives for Ternary Cathode Lithium-ion Battery

Deng¹,

Sun²,

Wan³

et al. 2018

Acta Chim. Sinica

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, M＝Mn, NMC; M＝Al, NCA)} are one of the most promising cathode materials of lithium-ion batteries (LIBs). However, in the traditional electrolyte system, they will undergo dramatic structural changes and interface side reactions at high potential and high temperature, which will bring great challenges to their practical application, especially for their cycle life and safety. Developing appropriate electrolyte additive is one of the most economical and effective methods to improve the electrochemical performance of LIBs. Based on the intrinsic structure of material, electrolyte additives used for NMC and NCA ternary cathode and their reaction mechanism in the past 5 years are reviewed in this paper, which include vinylene carbonate (VC), fluoro-compounds, new lithium salts, P-based, B-based, S-based, nitrile, others and combinative additives. Among them, VC becomes a kind of universal additive, which can improve the efficiency and cycle life at low voltage and normal temperature. Fluoro-compounds have been developed from mono substituted such as Fluorinated ethylene carbonate (FEC) to multi-fluorine substituted, which can improve the stability of electrode/electrolyte interface under high voltage. New lithium salt additives are mainly used to improve the film forming performance under high voltage and high temperature, such as Lithium bis(fluorosulfonyl)imide (LiFSI), Lithium difluorophosphate (LiDFP). P-contained additives [such as Tris(trimethylsilyl)phosphite (TMSPi)] are mainly to improve the stability of anode-electrolyte interface, and it has obvious synergistic effect when they combined with additives such as VC. B-contained additives are mainly used to improve the dissociation degree and stability of lithium salt, such as Tris(trimethylsilyl)borate (TMSB). S-contained additives are mainly used to improve the ionic conductivity and stability of anode SEI film, such as Prop-1-ene-1,3-sultone (PES). Nitriles are benefited from the strong electron withdrawing effect of -CN, which can improve the stability of the electrode/electrolyte interface at high voltage. Other types of additives are some heterocyclic compounds having film forming ability and various silanes which can eliminate HF and H 2 O. Combinative additives are developed from VC based composite to PES and PBF (pyridine boron trifluoride) system, which can endure even harsher conditions.

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A new ether-based electrolyte for dendrite-free lithium-metal based rechargeable batteries

Cited by 169 publications

References 39 publications

Designing solid-liquid interphases for sodium batteries

Designing solid-liquid interphases for sodium batteries

Lithium‐Pretreated Hard Carbon as High‐Performance Sodium‐Ion Battery Anodes

Review of Electrolyte Additives for Ternary Cathode Lithium-ion Battery

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