Highly Fluorinated Interphases Enable High-Voltage Li-Metal Batteries

Fan, Xiulin; Chen, Long; Ji, Xiao; Deng, Tao; Hou, Singyuk; Chen, Ji; Zheng, Jing; Wang, Fei; Jian-jun, Jiang; Xu, Kang; Wang, Chunsheng

doi:10.1016/j.chempr.2017.10.017

Cited by 793 publications

(680 citation statements)

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“…Although graphite carbon holds the main market of anodic materials in commercial LIBs due to its cycling stability, the low theoretical capacity (372 mAh g −1 , LiC 6 ) hinders its further development and applications in high‐energy LIBs . Lithium metal (LM) is a promising anode material because of the high theoretical specific capacity (3860 mAh g −1 ), however, the safety issue and the uncontrollable Li dendrites growth are still difficult to overcome . Comparing with lithium metal, the intercalation‐type silicon (Si) anode affords an even higher theoretical specific capacity (4200 mAh g −1 , Li 4.4 Si) with accommodating over 4 Li + per Si .…”

Section: Introductionmentioning

confidence: 99%

A Quadruple‐Hydrogen‐Bonded Supramolecular Binder for High‐Performance Silicon Anodes in Lithium‐Ion Batteries

Zhang

Yang

Chen

et al. 2018

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With extremely high specific capacity, silicon has attracted enormous interest as a promising anode material for next-generation lithium-ion batteries. However, silicon suffers from a large volume variation during charge/discharge cycles, which leads to the pulverization of the silicon and subsequent separation from the conductive additives, eventually resulting in rapid capacity fading and poor cycle life. Here, it is shown that the utilization of a self-healable supramolecular polymer, which is facilely synthesized by copolymerization of tert-butyl acrylate and an ureido-pyrimidinone monomer followed by hydrolysis, can greatly reduce the side effects caused by the volume variation of silicon particles. The obtained polymer is demonstrated to have an excellent self-healing ability due to its quadruple-hydrogen-bonding dynamic interaction. An electrode using this self-healing supramolecular polymer as binder exhibits an initial discharge capacity as high as 4194 mAh g and a Coulombic efficiency of 86.4%, and maintains a high capacity of 2638 mAh g after 110 cycles, revealing significant improvement of the electrochemical performance in comparison with that of Si anodes using conventional binders. The supramolecular binder can be further applicable for silicon/carbon anodes and therefore this supramolecular strategy may increase the choice of amendable binders to improve the cycle life and energy density of high-capacity Li-ion batteries.

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Section: Introductionmentioning

confidence: 99%

A Quadruple‐Hydrogen‐Bonded Supramolecular Binder for High‐Performance Silicon Anodes in Lithium‐Ion Batteries

Zhang

Yang

Chen

et al. 2018

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201

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“…[1] In spite of these advantages, a substantial gap remains before practical application due to vulnerable dendritic growth during repeated Li deposition and stripping. [10][11][12][13] In the case of artificial SEI layers, while their effect is noticeable in the early cycling period, inevitable Lithium metal has been hailed as a key enabler of upcoming rechargeable batteries with high energy densities. One is the "space charge" model.…”

mentioning

confidence: 99%

“…[12] Qian et al [13] first demonstrated that ether-based HCEs indeed significantly suppress dendritic growth and achieve high Coulombic efficiencies (CEs; >97%). Moreover, high Li ion concentrations in HCEs delay the onset point of ion depletion to a higher current density and could thus alleviate dendrite growth markedly.…”

mentioning

confidence: 99%

“…[12] Qian et al [13] first demonstrated that ether-based HCEs indeed significantly suppress dendritic growth and achieve high Coulombic efficiencies (CEs; >97%). [12] However, such high concentrations, in turn, bring critical drawbacks in fabricating cells due to the low wettability and high viscosity of electrolytes. For this reason, it is widely accepted [15] that ether-based electrolytes exhibit superior cycling performance for Li metal anodes compared with carbonate-based ones.…”

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confidence: 99%

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Tuning the Electron Density of Aromatic Solvent for Stable Solid‐Electrolyte‐Interphase Layer in Carbonate‐Based Lithium Metal Batteries

Yoo

Yang

Yun

et al. 2018

Advanced Energy Materials

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green electric transportation due to its low redox potential (−3.04 V vs standard hydrogen electrode) and unprecedented theoretical capacity (3860 mAh g −1 or 2060 mAh mL −1 ). [1] In spite of these advantages, a substantial gap remains before practical application due to vulnerable dendritic growth during repeated Li deposition and stripping. Dendrite growth causes indiscriminate electrolyte decomposition and dead Li, resulting in inferior charge-discharge reversibility and ultimately severe capacity fading.Li dendrite growth has been described by two models. One is the "space charge" model. This model focuses on ion depletion at the electrode-electrolyte interface; as current density increases, an ion depletion layer on the electrode surface is formed and thickens. [2] In this interfacial evolution, Sand's time, an onset point where an ion depletion layer begins to form, serves as a useful descriptor. Above this point, due to Li ion depletion, Li ions tend to lose their homogeneous distribution in the bulk electrolyte and are rather concentrated toward local spots (so-called surface "tips") with higher electron densities. While this model well explains the behaviors of dendrite growth at different current densities, those at low current densities below Sand's time are described limitedly.The other model focuses on the "uniformity" of the solidelectrolyte-interphase (SEI) layer with respect to morphology and composition, without taking current density into consideration. [3] This model relies on a viewpoint that in the nonuniform SEI layer, Li ion transport becomes uneven over the electrode area, which accelerates dendrite growth and consequently destroys the SEI layer. Therefore, from this model's perspective, success in suppressing dendrite growth depends largely on the uniformity and durability of the SEI layer.Based on the consensus regarding the importance of a uniform SEI layer, numerous approaches have been introduced, including artificial SEI layers, [4] LiNO 3 additives, [5] vinylene carbonate additives, [6,7] fluoroethylene carbonate additives, [8] polymer electrolytes, [9] and high-concentration electrolytes (HCEs). [10][11][12][13] In the case of artificial SEI layers, while their effect is noticeable in the early cycling period, inevitable Lithium metal has been hailed as a key enabler of upcoming rechargeable batteries with high energy densities. Nonetheless, uncontrolled dendritic growth and resulting formation of a nonuniform solid-electrolyte-interphase (SEI) layer constitute an ever-challenging obstacle in long-term cyclability and safety. So far, these drawbacks have been addressed mainly by using noncarbonate electrolytes based on their relatively mild decomposition under reductive environments. Here, toluene as a co-solvent of carbonate-based electrolytes for lithium metal anodes is reported. The electron-donating nature of the methyl group of toluene shifts the reduction of toluene prior to that of commonly used carbonate solvents, resulting in a more uniform and rigid SEI layer. Moreove...

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“…Moreover, chemistry of SEI layer also depends on the concentration of lithium salt by modulating the reductive stability of salt anions and solvents. Wang's group obtained a fluorinated interphase in concentrated carbonate electrolyte with about 10 M LiFSI salt . This F‐rich layer contributed to dendrite‐free surface and desirable efficiency over 99 %.…”

Section: Liquid Electrolytesmentioning

confidence: 99%

Recent Progress of Electrolyte Design for Lithium Metal Batteries

Wang

et al. 2020

Batteries & Supercaps

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Lithium metal batteries (LMBs) bring a bright future for the industrialization with higher voltage and energy density than conventional lithium ion batteries (LIBs) as lithium metal offers an ultra‐high specific capacity and the lowest electrochemical potential. However, they tend to confront unstable interface with electrolytes, uncontrollable dendrite growth and notorious safety concerns, seriously blocking the practical application of lithium metal anodes. Electrolyte is always considered as the most critical factor, directly affecting the overall battery behavior. In this case, the rearrangement of active components or designing novel electrolytes become indispensable approaches and tremendous efforts are required to seek for positive solutions. Herein, we provide recent advancements in prevailing liquid, solid and gel electrolytes from the perspective of their potential application in LMBs. The key scientific issues related to enhanced performance have also been highlighted.

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Highly Fluorinated Interphases Enable High-Voltage Li-Metal Batteries

Cited by 793 publications

References 55 publications

A Quadruple‐Hydrogen‐Bonded Supramolecular Binder for High‐Performance Silicon Anodes in Lithium‐Ion Batteries

A Quadruple‐Hydrogen‐Bonded Supramolecular Binder for High‐Performance Silicon Anodes in Lithium‐Ion Batteries

Tuning the Electron Density of Aromatic Solvent for Stable Solid‐Electrolyte‐Interphase Layer in Carbonate‐Based Lithium Metal Batteries

Recent Progress of Electrolyte Design for Lithium Metal Batteries

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