NaF-rich protective layer on PTFE coating microcrystalline graphite for highly stable Na metal anodes

Xie, Yangyang; Liu, Congyin; Zheng, Jinyun; Zhang, Liuyun; Zhang, Zhian

doi:10.1007/s12274-022-4985-z

Cited by 12 publications

(5 citation statements)

References 39 publications

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“…To further explore the composition of the SEI, XPS analysis is conducted on the surface of cycled Na foil. From the Na 1s spectra (Figure h), the signals attributed to NaF/Na 2 O appear at 1071.2 eV and the weak Na 2 CO 3 signal likely results from the air contact with Na 2 O or degradation of IWA. ,, The presence of Na 2 O and NaF species with a protective effect and Na-ion permeation is further confirmed by the Na–O bond at 531.1 eV in O 1s spectra (Figure i) and the Na–F bond at 684.6 eV in F 1s spectra (Figure j). , The concentrations of these species do not undergo change before and after etching, indicating the uniformity of SEI. The C–F bond is observed at 688.6 eV in F 1s spectra, originating from the outer elastic layer formed by the interaction between Na 3 GaF 6 and solidified IWA.…”

Section: Resultsmentioning

confidence: 76%

“…From the Na 1s spectra (Figure 5h), the signals attributed to NaF/Na 2 O appear at 1071.2 eV and the weak Na 2 CO 3 signal likely results from the air contact with Na 2 O or degradation of IWA. 40,47,48 The presence of Na 2 O and NaF species with a protective effect and Na-ion permeation is further confirmed by the Na−O bond at 531.1 eV in O 1s spectra (Figure 5i) and the Na−F bond at 684.6 eV in F 1s spectra (Figure 5j). 42,47 The concentrations of these species do not undergo change before and after etching, indicating the uniformity of SEI.…”

Section: Two-mentioning

confidence: 73%

“…40,47,48 The presence of Na 2 O and NaF species with a protective effect and Na-ion permeation is further confirmed by the Na−O bond at 531.1 eV in O 1s spectra (Figure 5i) and the Na−F bond at 684.6 eV in F 1s spectra (Figure 5j). 42,47 The concentrations of these species do not undergo change before and after etching, indicating the uniformity of SEI. The C−F bond is observed at 688.6 eV in F 1s spectra, 49 originating from the outer elastic layer formed by the interaction between Na 3 GaF 6 and solidified IWA.…”

Section: Two-mentioning

confidence: 73%

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Liquid Metal Mediated Heterostructure Fluoride Solid Electrolytes of High Conductivity and Air Stability for Sustainable Na Metal Batteries

Yu,

Hu,

Nie

et al. 2024

ACS Nano

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Fluoride-based solid electrolytes (SEs) have emerged as a promising component for high-energy-density rechargeable solid-state batteries (SSBs) in view of their wide electrochemical window, high air stability, and interface compatibility, but they still face the challenge of low ion conductivity and the lack of a desired structure for sodium metal SSBs. Here, we report a sodium-rich heterostructure fluoride SE, Na 3 GaF 6 − Ga 2 O 3 −NaCl (NGFOC-G), synthesized via in situ oxidation of liquid metal gallium and in situ chlorination using low-melting GaCl 3 . The distinctive features of NGFOC-G include single-crystal Na 3 GaF 6 domains within an open-framework structure, composite interface decoration of Ga 2 O 3 and NaCl with a concentration gradient, exceptional air stability, and high electrochemical oxidation stability. By leveraging the penetration of gallium at NaF grain boundaries and the in situ self-oxidation to form Ga 2 O 3 nanodomains, the solid-phase reaction kinetics of NaF and GaF 3 is activated for facilitating the synthesis of main component Na 3 GaF 6 . The introduction of a small amount of a chlorine source during synthesis further softens and modifies the boundaries of Na 3 GaF 6 along with Ga 2 O 3 . Benefiting from the enhanced interface ion transport, the optimized NGFOC-G exhibits an ionic conductivity up to 10 −4 S/cm at 40 °C, which is the highest level reported among fluoride-based sodium-ion SEs. This SE demonstrates a "self-protection" mechanism, where the formation of a high Young's modulus transition layer rich in NaF and Na 2 O under electrochemical driving prevents the dendrite growth of sodium metal. The corresponding Na/Na symmetric cells show minimal voltage hysteresis and stable cycling performance for at least 1000 h. The Na/NGFOC-G/ Na 3 V 2 (PO 4 ) 3 cell demonstrates stable capacity release around 100 mAh/g at room temperature. The Na/NGFOC-G/FeF 3 cell delivers a high capacity of 461 mAh/g with an excellent stability of conversion reaction cycling.

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Section: Resultsmentioning

confidence: 76%

Section: Two-mentioning

confidence: 73%

Section: Two-mentioning

confidence: 73%

See 1 more Smart Citation

Liquid Metal Mediated Heterostructure Fluoride Solid Electrolytes of High Conductivity and Air Stability for Sustainable Na Metal Batteries

Yu,

Hu,

Nie

et al. 2024

ACS Nano

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“…Due to the low mechanical strength and inferior flexibility of the electrolyte-derived SEI for B-Li, irregular Li + diffusion channels are created, leading to interface cracks and the subsequent exposure to fresh Li metal following Li plating. 50,51 Following that, the fracture regions create preferential deposition sites for Li + , creating problems with dendrite growth and continuous electrolyte consumption after several plating/stripping cycles. On the contrary, the 3D structure of FSHL may successfully lower the current density and volume change locally during Li plating/stripping, retaining the overall electrode's structural integrity (Figure 1B).…”

Section: Resultsmentioning

confidence: 99%

Electrolytic construction of nanosphere‐assembled protective layer toward stable lithium metal anode

Lu,

Li,

Yue

et al. 2023

Battery Energy

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The uncontrolled dendrite growth and electrolyte consumption in lithium metal batteries result from a heterogeneous and unstable solid electrolyte interphase (SEI). Here, a high‐voltage forced electrolysis strategy is proposed to stabilize the lithium metal via electrodepositing a spherical protective layer. This peculiar SEI is composed of a nanosized Li sphere that is encased with adjustable composition, as proved by cryo‐transmission electron microscopy and multiple surface‐sensitive spectroscopies. Such a three‐dimensional nanosphere‐assembled protective layer has homogeneous components, mechanical strength, and rapid Li‐ion conductivity, enabling it to alleviate the volume expansion and prevent dendrite growth during Li deposition. The symmetric cell can be stably operated for ultralong‐term cycling time of 2000 and 800 h even at high current densities of 1 and 10 mA cm−2, respectively. Using this interface permits stable cycling of full cells paired with LiFePO4 and LiNi0.8Co0.1Mn0.1O2 cathodes with low negative/positive capacity ratio, high current density, and limited Li excess. This tactic also fosters a novel insight into interface design in the battery community and encourages the practical implementation of lithium metal batteries.

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“…Inspired by the PVDF/NaF layer, Yu et al further treated Na with PTFE via in-suit rolling with the formation of NaF/organic carbon species, which function with C=C and C-F groups [117]. They experimentally verified the high mechanical strength, fast ionic kinetics and good sodiophilicity of this protective layer [117][118][119][120]. As reported by Tao et al, the PTFE-derived NaF/carbon layer can be rapidly induced by pressure and a diglyme-induced defluorination reaction, as shown in in Figure 7a.…”

Section: Hybrid Interphasementioning

confidence: 99%

Progress on Designing Artificial Solid Electrolyte Interphases for Dendrite-Free Sodium Metal Anodes

Shi

Cheng

et al. 2023

Batteries

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Nature-abundant sodium metal is regarded as ideal anode material for advanced batteries due to its high specific capacity of 1166 mAh g−1 and low redox potential of −2.71 V. However, the uncontrollable dendritic Na formation and low coulombic efficiency remain major obstacles to its application. Notably, the unstable and inhomogeneous solid electrolyte interphase (SEI) is recognized to be the root cause. As the SEI layer plays a critical role in regulating uniform Na deposition and improving cycling stability, SEI modification, especially artificial SEI modification, has been extensively investigated recently. In this regard, we discuss the advances in artificial interface engineering from the aspects of inorganic, organic and hybrid inorganic/organic protective layers. We also highlight key prospects for further investigations.

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NaF-rich protective layer on PTFE coating microcrystalline graphite for highly stable Na metal anodes

Cited by 12 publications

References 39 publications

Liquid Metal Mediated Heterostructure Fluoride Solid Electrolytes of High Conductivity and Air Stability for Sustainable Na Metal Batteries

Liquid Metal Mediated Heterostructure Fluoride Solid Electrolytes of High Conductivity and Air Stability for Sustainable Na Metal Batteries

Electrolytic construction of nanosphere‐assembled protective layer toward stable lithium metal anode

Progress on Designing Artificial Solid Electrolyte Interphases for Dendrite-Free Sodium Metal Anodes

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