Lithium whisker growth and stress generation in an in situ atomic force microscope–environmental transmission electron microscope set-up

With advantages such as high theoretical capacity, low cost, and nontoxicity, Zn metal has been widely investigated as an anode for aqueous batteries. However, the problems of dendrite formation and sustained corrosion originating from severe interfacial side reactions and uncontrolled Zn electrodeposition in aqueous electrolytes significantly slows down the practical application of Zn metal anodes. To address these issues, herein, an anti‐corrosion elastic constraint (AEC) is introduced that is built with nanosized TiO2 and polyvinylidene fluoride (PVDF) matrix to Zn anode, where the PVDF layer serves as an elastic H2O/O2‐blocking layer and the decorated TiO2 nanoparticles assist uniform Zn electrodeposition. With this corrosion‐inhibition and electrodeposition‐redirection coating, the electrodeposition consistency and thermodynamic stability of the Zn anode are significantly improved, enabling a long‐term stable plating/stripping performance for 2000 h with an ultralow overpotential (<50 mV) and a high average Coulombic efficiency (>99.4%) for 1000 cycles without obvious dendrite formation. Even at a high current density of 8.85 mA cm−2 with limited Zn supply (DODZn = 60%), stable Zn deposition is achieved over 250 h. When coupled with a MnO2 cathode, the AEC‐Zn anode shows a remarkably enhanced full‐cell cycling stability, indicative of high reliability of aqueous Zn batteries for practical application.

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“…[ 19 ] Here, the elasticity of the AEC layer is expected to be strong enough to accommodate the volumetric change of Zn electrodeposition. [ 20 ]…”

Section: Resultsmentioning

confidence: 99%

Redirected Zn Electrodeposition by an Anti‐Corrosion Elastic Constraint for Highly Reversible Zn Anodes

Zhao

Yang

Liu

et al. 2020

Adv Funct Materials

253

210

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“…Our work demonstrates that single crystal NCM811 with good mechanical integrity breaks the electrochemical performance limit of conventional polycrystalline NCM811 in ASSBs. It should be noted that the detailed working mechanism of the outstanding performance of S‐NCM in ASSBs remains to be further investigated, such as quantitative chemical heterogeneity and stress evolution at the particle level, and long‐/short‐ range evolution differences between the ASSBs and LIBs, which will get help from some utilization of advanced characterization techniques, such as multispectral Xray camera, [ 28 ] atomic force microscope, [ 29 ] and high resolution ssNMR. [ 8f ]…”

Section: Resultsmentioning

confidence: 99%

Electrochemo‐Mechanical Effects on Structural Integrity of Ni‐Rich Cathodes with Different Microstructures in All Solid‐State Batteries

Liu

Zheng

Zhao

et al. 2021

Advanced Energy Materials

Self Cite

137

121

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The electrochemo‐mechanical effects on the structural integrity of electrode materials during cycling is a non‐negligible factor that affects the cyclability and rate performance of all solid‐state batteries (ASSBs). Herein, combined with in situ electrochemical impedance spectroscopy (EIS), focused ion beam (FIB)–scanning electron microscope (SEM), and solid state nuclear magnetic resonance (ssNMR) techniques, the electrochemical performance and electrochemo‐mechanical behavior are compared of conventional polycrystalline NCM811 (LiNi0.8Co0.1Mn0.1O2), small‐size polycrystalline NCM811 and single‐crystal (S‐) NCM811 in Li10SnP2S12 based ASSBs during long charge–discharge cycles. The results show that the deteriorating performance of both large and small polycrystalline NCM811 originates from their inherent structural instability at >4.15 V, induced by the visible voids between the randomly oriented grains and microcracks due to the electrode pressing process and severe anisotropic volume change during cycling, rather than lithium ion transport in the primary particle. In contrast, S‐NCM811 with good microstructural integrity show remarkably high capacity (187 mAh g−1, 18 mA g−1), stable cyclability (100 cycles, retention of 64.5%), and exceptional rate capability (102 mAh g−1 at 180 mA g−1) in ASSBs even without surface modification. Moreover, 1 wt% LiNbO3@S‐NCM811 further demonstrates excellent initial discharge capacity and capacity retention. This work highlights the critical role of electrochemo‐mechanical integrity and offers an promising path towards mechanically‐reliable cathode materials for ASSBs.

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“…Li@CA-LiNO 3 exhibits an average Young's modulus of 6.61 GPa, which is three times higher than that of Li metal (2.11 GPa). It is reported that the surface layer with a Young's modulus greater than twice of Li is able to inhibit Li dendrite formation 49,50 . Therefore, this stiff surface of Li@CA-LiNO 3 , which may be related to fine-grain strengthening effect of nanosized Li, is capable of inhibiting dendrite growth.…”

Section: Resultsmentioning

confidence: 99%

Constructing multifunctional solid electrolyte interface via in-situ polymerization for dendrite-free and low N/P ratio lithium metal batteries

et al. 2021

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Stable solid electrolyte interface (SEI) is highly sought after for lithium metal batteries (LMB) owing to its efficient electrolyte consumption suppression and Li dendrite growth inhibition. However, current design strategies can hardly endow a multifunctional SEI formation due to the non-uniform, low flexible film formation and limited capability to alter Li nucleation/growth orientation, which results in unconstrained dendrite growth and short cycling stability. Herein, we present a novel strategy to employ electrolyte additives containing catechol and acrylic groups to construct a stable multifunctional SEI by in-situ anionic polymerization. This self-smoothing and robust SEI offers multiple sites for Li adsorption and steric repulsion to constrain nucleation/growth process, leading to homogenized Li nanosphere formation. This isotropic nanosphere offers non-preferred Li growth orientation, rendering uniform Li deposition to achieve a dendrite-free anode. Attributed to these superiorities, a remarkable cycling performance can be obtained, i.e., high current density up to 10 mA cm−2, ultra-long cycle life over 8500 hrs operation, high cumulative capacity over 4.25 Ah cm−2 and stable cycling under 60 °C. A prolonged lifespan can also be achieved in Li-S and Li-LiFePO4 cells under lean electrolyte content, low N/P ratio or high temperature conditions. This facile strategy also promotes the practical application of LMB and enlightens the SEI design in related fields.

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Lithium whisker growth and stress generation in an in situ atomic force microscope–environmental transmission electron microscope set-up

Cited by 251 publications

References 30 publications

Redirected Zn Electrodeposition by an Anti‐Corrosion Elastic Constraint for Highly Reversible Zn Anodes

Redirected Zn Electrodeposition by an Anti‐Corrosion Elastic Constraint for Highly Reversible Zn Anodes

Electrochemo‐Mechanical Effects on Structural Integrity of Ni‐Rich Cathodes with Different Microstructures in All Solid‐State Batteries

Constructing multifunctional solid electrolyte interface via in-situ polymerization for dendrite-free and low N/P ratio lithium metal batteries

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