AlF3-modified anode-electrolyte interface for effective Na dendrites restriction in NASICON-based solid-state electrolyte

Miao, Xianguang; Di, Haoxiang; Ge, Xiaoli; Zhao, Danyang; Wang, Peng; Wang, Rutao; Wang, Cheng-Xiang; Yin, Longwei

doi:10.1016/j.ensm.2020.05.011

Cited by 103 publications

(82 citation statements)

References 58 publications

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“…Moreover, the total resistance starts to decrease until cycling at 1.0 mA cm −2 (Figure 3f and Figure S11c, Supporting Information) and ultimately shows a high CCD of 1.4 mA cm −2 , which to our best knowledge is the top‐level among reported NASICON‐based SSEs in published literatures up to now (Figure 3g). [ 37–41 ] It also shows excellent long‐term galvanostatic cycling stability at RT. As shown in Figure 3h, the Na/SPAN‐NASICON/Na cell delivers a stable cycling performance for up to 500 h at 0.1 and 0.25 mA cm −2 , further confirming the effective suppression of dendrites growth and highly improved cycling stability among anode–electrolyte interface.…”

Section: Resultsmentioning

confidence: 99%

Isotropous Sulfurized Polyacrylonitrile Interlayer with Homogeneous Na⁺ Flux Dynamics for Solid‐State Na Metal Batteries

Miao

Wang

Sun

et al. 2021

Advanced Energy Materials

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Inorganic solid‐state electrolyte (SSE) based Na‐metal batteries have received extensive attention in next‐generation lithium‐free energy storage systems with both high‐security and superior electrochemical performance. Herein, in contrast to the conventionally used polymer/ceramic/polymer sandwich electrolyte, an efficient green and scalable powder‐polishing synthetic method is developed to fabricate a pyrolyzed‐polyacrylonitrile modified Na super ionic conductor (NASICON) electrolyte to relieve polarization of integrated composite SSE and ameliorate interfacial contact between the electrolyte and the Na anode. Furthermore, introducing S in the preferable isotropous sulfurized polyacrylonitrile (SPAN) interlayer can trigger dehydrogenation and cyclization of polyacrylonitrile with chemically‐bonded short‐chain SS segments, which can bond with Na+ to redistribute the interfacial electric field and homogenize transported Na+ flux, leading to transition of Na deposition behavior from dendrite growth mode to lateral flat‐shape growth tendency. The conjugated polymer backbones possess delocalized radicals that can activate formed short‐chain sulfides to reconnect to the backbones, thus maintaining superior structural stability. Benefiting from the rational interfacial design, a record‐high value of 1.4 mA cm−2 for critical current density of Na/SPAN‐NASICON/Na cells is obtained. Moreover, SPAN is used as a cathode to assemble solid‐state Na/SPAN‐NASICON/SPAN Na‐organosulfur batteries, demonstrating superior capacity and cycling‐stability. The rational SPAN‐based structural design strategy may provide an avenue for potential application of solid‐state alkali metal batteries.

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Section: Resultsmentioning

confidence: 99%

Isotropous Sulfurized Polyacrylonitrile Interlayer with Homogeneous Na⁺ Flux Dynamics for Solid‐State Na Metal Batteries

Miao

Wang

Sun

et al. 2021

Advanced Energy Materials

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“…[ 10a,29 ] The ontological impedance ( R s ) also increases with increasing cycles, which may be due to the loss of salt in electrolyte during the process of repairing SEI layer, leading to the decrease of solute and the increase of solution resistance. [ 30 ] In contrast, R s and R ct of symmetric cell with Na‐O‐CCF electrode become smaller with increasing cycles (Figure 6f). Additional proof, that the charge‐transfer kinetic is much faster in Na‐O‐CCF electrode, can be seen from the exchange current densities ( I 0 ; Figure 6h).…”

Section: Resultsmentioning

confidence: 99%

Superior Sodium Metal Anodes Enabled by Sodiophilic Carbonized Coconut Framework with 3D Tubular Structure

Sun

Gao

et al. 2020

Advanced Energy Materials

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Although extensive efforts have been made to stabilize metal sodium anodes and prevent dendrite formation, it is still difficult to achieve long‐term stability at large area capacity and high current density due to a series of complex failure modes, including uneven Na nucleation and subsequent dendrite formation. Herein, an oxygen‐containing carbonized coconut framework (O‐CCF) with a 3D tubular structure is designed to inhibit dendrite growth. The 3D tubular structure can regulate the uniform distribution of electric field, making Na+ diffuse evenly on the electrode surface. The oxygen functional groups with sodiophilicity contribute to the adsorption of Na+ and reduce the Na nucleation energy on the surface of O‐CCF. The interaction of 3D tubular structure and oxygen functional groups enable Na stripping/plating over 10 000 cycles at 50 mA cm−2, as well as cycling stably for 1000 cycles with coulombic efficiency of 99.6% at 5 mA cm−2 and high areal capacity of 10 mAh cm−2. As a proof of concept, full cells of O‐CCF//Na‐Na3V2(PO4)3 (NVP) and Na‐O‐CCF//Fe7S8 are assembled and exhibit outstanding electrochemical performance. This work presents a promising strategy for fabrication of safe Na metal anodes.

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“…Electrochemical tests indicated that the resistance of symmetric batteries with interface modified NASICON electrolytes was much lower than that of symmetric batteries with normal NZSICON electrolytes (400 Ω cm 2 vs. 4000 Ω cm 2 ), which could be attributed to the better wetting and attachment across the Na/NASICON interface. Miao et al [64] initially employed AlF 3 as the Na/SSE interface layer in solid-state sodium batteries to hinder the growth of Na dendrites. As demonstrated in Figure 8a, compared with the bare NASICON Na 3 Zr 2 Si 2 PO 12 , the AlF 3 layer could not only efficiently ameliorate the interfacial contact between SSEs and Na metal anodes, but also induced a Na + conducting buffer layer.…”

Section: Anode/sse Interfacementioning

confidence: 99%

“…4000 Ω cm 2 ), which could be attributed to the better wetting and attachment across the Na/NASICON interface. Miao et al [64] . initially employed AlF 3 as the Na/SSE interface layer in solid‐state sodium batteries to hinder the growth of Na dendrites.…”

Section: Interface Engineeringmentioning

confidence: 99%

NASICON‐Type Na₃Zr₂Si₂PO₁₂ Solid‐State Electrolytes for Sodium Batteries**

et al. 2021

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Owing to their low cost, high energy density, and reliable safety, all-solid-state sodium batteries have been regarded as one of the most promising candidates beyond lithium-ion batteries. Sodium super ionic conductor (NASICON)-structured solid-state electrolytes (SSEs), with good electrochemical stability and environmental friendliness, are potential candidates for SSEs. In this Minireview, we summarize the basic properties of Na 3 Zr 2 Si 2 PO 12 SSEs, including structural characteristics, preparation methods, ionic conductivity, and the strategies, substituting proper elements, optimizing preparation approaches, increasing packing density, and so forth, to improve the bulk and grain boundary conductivity. Additionally, we also analyze the challenges and approaches for interfacial modification between electrodes and SSEs in all-solid-state sodium batteries. Finally, future research directions for facilitating the development of allsolid-state sodium batteries are proposed.

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AlF3-modified anode-electrolyte interface for effective Na dendrites restriction in NASICON-based solid-state electrolyte

Cited by 103 publications

References 58 publications

Isotropous Sulfurized Polyacrylonitrile Interlayer with Homogeneous Na⁺ Flux Dynamics for Solid‐State Na Metal Batteries

Isotropous Sulfurized Polyacrylonitrile Interlayer with Homogeneous Na⁺ Flux Dynamics for Solid‐State Na Metal Batteries

Superior Sodium Metal Anodes Enabled by Sodiophilic Carbonized Coconut Framework with 3D Tubular Structure

NASICON‐Type Na₃Zr₂Si₂PO₁₂ Solid‐State Electrolytes for Sodium Batteries**

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AlF3-modified anode-electrolyte interface for effective Na dendrites restriction in NASICON-based solid-state electrolyte

Cited by 103 publications

References 58 publications

Isotropous Sulfurized Polyacrylonitrile Interlayer with Homogeneous Na+ Flux Dynamics for Solid‐State Na Metal Batteries

Isotropous Sulfurized Polyacrylonitrile Interlayer with Homogeneous Na+ Flux Dynamics for Solid‐State Na Metal Batteries

Superior Sodium Metal Anodes Enabled by Sodiophilic Carbonized Coconut Framework with 3D Tubular Structure

NASICON‐Type Na3Zr2Si2PO12 Solid‐State Electrolytes for Sodium Batteries**

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Isotropous Sulfurized Polyacrylonitrile Interlayer with Homogeneous Na⁺ Flux Dynamics for Solid‐State Na Metal Batteries

Isotropous Sulfurized Polyacrylonitrile Interlayer with Homogeneous Na⁺ Flux Dynamics for Solid‐State Na Metal Batteries

NASICON‐Type Na₃Zr₂Si₂PO₁₂ Solid‐State Electrolytes for Sodium Batteries**