Simultaneously in-situ fabrication of lithium fluoride and sulfide enriched artificial solid electrolyte interface facilitates high stable lithium metal anode

Yang, Jian; Hou, Junming; Fang, Zixuan; Khan, Kashif; Chen, Cheng; Li, Xinran; Zhou, Haiping; Zhang, Shu; Feng, Tingting; Xu, Ziqiang; Wu, Mengqiang

doi:10.1016/j.cej.2021.133193

Cited by 18 publications

(11 citation statements)

References 37 publications

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“…To achieve superior rate performance for primary cells, we purposed to develop multiple modified Li-B anodes for three reasons: (1) the original Li-B anodes possess 3D boride framework to reduce the local current density 7 ; (2) multiple modification of the Li-B surface with metal Ag, LiF and sulfide species can further facilitate both electrical conductivity and Li ion conductivity of the anode 17,18 ; (3) metal Ag is supposed to specifically show lithiophilic property to wettability of electrolyte and improve Li ion transfer, as reported previously. 19 Therefore, AgSCF 3 containing the three elements was chosen as the modification reagent.…”

Section: Resultsmentioning

confidence: 99%

“…10 On the other hand, surface modification methods of lithium anode with chemical, electrochemical, and doping have been intensively studied. 15,16 The resulting protection films or artificial solid electrolyte interfaces (SEIs) can prevent reactions between electrolyte and Li surface, and increase the Coulombic efficiency of Li electrochemical deposition/dissolution. Inspired by these approaches to achieve versatile functions for Li metal anodes, we sought to improve the rate performance of primary batteries using Li-B anodes by deliberated surface modification.…”

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confidence: 99%

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Multiple Modifications of Li-B Alloy Anodes for Primary Batteries

Tan¹,

Chen²,

Xiong³

et al. 2023

J. Electrochem. Soc.

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Lithium-boron (Li-B) alloys have long been applied in thermal batteries and have recently been used in secondary batteries due to their stable three-dimensional (3D) framework. To extend the application of Li-B anodes to primary cells, especially primary cells with high rate performance, we developed a new surface treatment method to modify Li-B. Using silver trifluoromethanethiolate (AgSCF3) as the single reagent to react with Li to produce metal Ag, LiF, and sulfide species at the surface of Li-B. For the symmetric cell, the resulting multiple modified Li-B shows two orders of magnitude smaller charge transfer impedance than the pristine Li-B (1.10 ohms vs. 205.40 ohms) and improved reaction kinetics in the first cycle. The modified Li-B/MnO2 primary cells show improved rate performance in the current density range of 0.5C-5C. Specifically, when discharging at 2C, the full cell using modified Li-B anode show specific capacity of 197 mAh/g and specific energy of 485 Wh/kg, 82% and 103% higher related to the cell using pristine Li-B anode, respectively. This study provides a new way to modify Li-B alloys that may have practical applications in high-power density primary batteries.

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Section: Resultsmentioning

confidence: 99%

mentioning

confidence: 99%

Multiple Modifications of Li-B Alloy Anodes for Primary Batteries

Tan¹,

Chen²,

Xiong³

et al. 2023

J. Electrochem. Soc.

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“…Figure 5i exhibits the Ragone plot of the NCM811|MS|PE|Ag 2 S|Li prototype in comparison with previously reported NCM811|Li cell models, all values were calculated based on the mass of electrode material. [21,[44][45][46][47][48][49][50] The NCM811|Li cell with MS|PE|Ag 2 S separator shows the highest power output of 2040 W kg −1 with the energy density of 408 Wh kg −1 at 5 C, which surpass the most values of the previously reported NCM811|Li metal batteries. Furthermore, the cycling stability of cell assembled with MS|PE|Ag 2 S separators is also superior to most previously reported metal batteries with other modified separators under lean electrolyte condition (Table S4, Supporting Information).…”

Section: Resultsmentioning

confidence: 99%

Boosting the Temperature Adaptability of Lithium Metal Batteries via a Moisture/Acid‐Purified, Ion‐Diffusion Accelerated Separator

Zhang

Liu

Gan

et al. 2022

Advanced Energy Materials

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solutions, explorative studies of the electro-redox couples, with the concurrent high retrievable capacity, enlarged nominal voltage gap, and rapid reaction kinetics, hold the key to promote the energy-dense battery construction at the extreme power output. [1] For the lithium ion batteries, the energy densities of traditional formats (LiCoO 2 /LiFePO 4 cathodes and graphite anodes) have approached their theoretical limits. [2] Alternatively, the unit cell prototyping of the high-capacity Li metal anode with the nickel-rich cathode can achieve the enhanced level of energy densities at the device level. [3,4] When soaking this electrode couples in the conventional carbonate-based electrolytes, however, the Fermi-energy incompatibility at the multiscale interface would cause the uncontrollable dendrite growth on the metallic foil and cathode structure collapse upon the high-voltage cycling. [5] Therefore, the reliable operation of the energy-dense battery necessitates the harmony balance of the enlarged voltage gap and the interfacial stability at multiple scales, yet still remains challenging.As the most attractive cathode type of the practical relevance, nickel-rich (Ni content >0.8) layered oxides exhibit the merits of the large specific capacity (>200 mAh g −1 ), environmental benignity and relative lower cost as compared to the LiCoO 2 cathode. Despite of the dominant nickel occupancy in the layered oxides for elevating the Li storage sites, the increased nickel ratio adversely deteriorates the cycle performance. The transition metal (TM) layer of the oxide structure at the highvoltage charged states would oxidize the carbonate solvents in the presence of moisture, leading to serious self-discharge rates upon the high-temperature storage. [6] Additionally, the hydrofluoric acid (HF) formed by the decomposition of the lithium hexafluorophosphate (LiPF 6 ) salt aggravates the TM ions (Co 2+ , Ni 2+ , and Mn 2+ ) dissolution and structural collapse of the layered cathode, meanwhile the TM species would deposit on the anode surface and degrade the solid electrolyte interface (SEI). [7] So far, a plethora of mitigation strategies were implemented to insulate the direct contact of the oxide particles with the electrolyte, for instance the exquisite coatings with The reliable operation of Li metal batteries suffers from cathode collapse due to high-voltage cycling, interfacial reactivity of the Li deposits, self-discharge at the elevated temperatures, as well as the power output deterioration in low-temperature scenarios. In contrast to the individual electrode optimization, herein, a hetero-layered separator with an asymmetric functional coating on polyethylene is proposed in response to the aforementioned issues: On the face-to-cathode side, the hybrid layer of the molecular sieve and sulfonated melamine formaldehyde can scavenge the hydrofluoric acid and moisture residues from the carbonate electrolyte, maintaining the cathode robustness in both the high-voltage cycling or high-temperature storage scenarios; while...

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Section: Remaining LI Anode Stablementioning

confidence: 99%

“…Other composite artificial SEIs: Composite artificial SEI structures are gaining attention, including Li 3 Sb/LiF SEI, 176 Li 2 S/Li 2 Se (LSSe) SEI, 177 LiI/LiF, 178 Li polyoxymethylene/LiF, 179 and LiF/sulfide. 180 To further control the composition and thickness of the SEI film, a sophisticated multilayer SEI design, leveraging both atomic layer deposition (ALD) and molecular layer deposition (MLD) techniques, is considered an ideal improved approach for Li metal anodes. Zhao et al 166 utilized these two techniques to design a dual protective SEI layer with different sequences of an inorganic Al 2 O 3 layer and an organic MLD alucone layer on the anode surfaces (Figure 7G).…”

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confidence: 99%

An examination and prospect of stabilizing Li metal anode in lithium–sulfur batteries: A review of latest progress

Song,

Su,

Liu

et al. 2023

Electron

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The Li metal anode emerges as a formidable competitor among anode materials for lithium–sulfur (Li‐S) batteries; nevertheless, safety issues pose a significant hurdle in its path toward commercial viability. This review enumerates three historical challenges inherent to the Li metal anode: unavoidable volume expansion, multifunctional solid electrolyte interface formation, and uncontrollable lithium dendrite growth. In particular, when paired with a sulfur cathode, the Li anode presents an additional unique hurdle: the shuttle effect. To address these issues, this article offers a thorough examination of the latest innovations aimed at stabilizing the Li metal anode within Li‐S batteries. We categorize these approaches into five classifications: liquid electrolyte optimization, enhancement of non‐liquid‐state electrolytes, Li metal surface modification, Li anode architecture design, and Li alloy improvement. For several noteworthy results within these categories, we have compiled their electrochemical performance into tables, facilitating direct comparison. This detailed analysis illuminates feasible strategies and suggests directions warranting further exploration for optimizing the capability and safety of Li metal anodes in Li‐S batteries.

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Simultaneously in-situ fabrication of lithium fluoride and sulfide enriched artificial solid electrolyte interface facilitates high stable lithium metal anode

Cited by 18 publications

References 37 publications

Multiple Modifications of Li-B Alloy Anodes for Primary Batteries

Multiple Modifications of Li-B Alloy Anodes for Primary Batteries

Boosting the Temperature Adaptability of Lithium Metal Batteries via a Moisture/Acid‐Purified, Ion‐Diffusion Accelerated Separator

An examination and prospect of stabilizing Li metal anode in lithium–sulfur batteries: A review of latest progress

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