Artificial Interphases for Highly Stable Lithium Metal Anode Rui Xu, Xin-Bing Cheng, Chong Yan, Xue-Qiang Zhang, Ye Xiao, Chen-Zi Zhao, Jia-Qi Huang, Qiang Zhang  Matter  Volume 1, Issue 2, Pages 317-344 (August 2019) DOI: 10.1016/j.matt.2019.05.016 Copyright © 2019 Elsevier Inc. Terms and Conditions

Matter 2019 1, 317-344DOI: (10.1016/j.matt.2019.05.016) Copyright © 2019 Elsevier Inc. Terms and Conditions

Figure 1 Schematic Illustrations of Electrode | Electrolyte Interfacial Protection Strategies with Artificial Films (A) Conceptual schematic illustrations of interfacial related science and engineering between Li | liquid electrolyte and Li | solid electrolyte. (B) A schematic illustration to describe an ideal artificial film at Li metal surface, which should be (1) chemically and electrochemically stable with electron insulation, (2) mechanically compliant and robust to withstand huge volume variations, and (3) possesses uniform and rapid ion pathways to facilitate a facile single Li-ion diffusion. Matter 2019 1, 317-344DOI: (10.1016/j.matt.2019.05.016) Copyright © 2019 Elsevier Inc. Terms and Conditions

Figure 2 Schematic Illustrations of Polymer Coating via Doctor-Blading Method to Protect Li Metal Anode (A) PI membrane with vertical nanoscale channels to regulate homogeneous Li+ flux distribution, and to render smooth, granular lithium deposition. Reproduced with permission from Liu et al.59 Copyright 2017, American Chemical Society. (B) High-polarity β-PVDF layer with strong coordination with Li+ to realize a dendrite-free Li deposition. Reproduced with permission from Luo et al.61 Copyright 2018, Wiley-VCH. (C) Adaptive solid-liquid coating layer with dynamic covalent bonds to provide a dynamic protection for Li metal anode. Reproduced with permission from Liu et al.62 Copyright 2017, American Chemical Society. Matter 2019 1, 317-344DOI: (10.1016/j.matt.2019.05.016) Copyright © 2019 Elsevier Inc. Terms and Conditions

Figure 3 Schematic Illustrations of Ex Situ Coating Layer via Doctor-Blading and Spin-Coating Methods (A) Transplantable LiF-rich layer through in situ reduction of NiF2. Reproduced with permission from Peng et al.65 Copyright 2017, Elsevier. (B) The fabrication process of the Cu3N + SBR composite artificial SEI. Reproduced with permission from Liu et al.66 Copyright 2017, Wiley-VCH. (C) Soft-rigid PVDF-HFP/LiF artificial protective layer to prevent dendrite propagation. Reproduced with permission from Xu et al.67 Copyright 2018, Wiley-VCH. (D) Spin-coated PDMS to stabilize Li metal anode. Reproduced with permission from Zhu et al.68 Copyright 2017, Wiley-VCH. Matter 2019 1, 317-344DOI: (10.1016/j.matt.2019.05.016) Copyright © 2019 Elsevier Inc. Terms and Conditions

Figure 4 Schematic Illustrations of Ex Situ Coating Layer via CVD Method (A) Thin and compact organic-inorganic hybrid silicate coatings with both hardness and flexibility. Reproduced with permission from Liu et al.85 Copyright 2017, Wiley-VCH. (B) The precisely designed double-layer nanodiamond interface with enhanced defect tolerance to enable uniform ion flux. Reproduced with permission from Liu et al.87 Copyright 2018, Elsevier. (C) ALD-coated Al2O3 to protect Li metal in corrosive Li-S battery system. Reproduced with permission from Kozen et al.88 Copyright 2015, American Chemical Society. (D) MLD-coated Alucone layer with considerable flexibility and robustness for stable Li metal anode. Reproduced with permission from Zhao et al.89 Copyright 2018, Wiley-VCH. Matter 2019 1, 317-344DOI: (10.1016/j.matt.2019.05.016) Copyright © 2019 Elsevier Inc. Terms and Conditions

Figure 5 Schematic Illustrations of Ex Situ Layer via PVD and Other Methods (A) Magnetic sputtered MoS2 protective layer to improve the stability of Li metal. Reproduced with permission from Cha et al.94 Copyright 2018, Nature publishing group. (B) Interconnected hollow carbon sphere to form stable SEI and physically suppress dendrite. Reproduced with permission from Zheng et al.98 Copyright 2014, Nature publishing group. (C) Glass fiber interlayer to uniformize Li+ flux and eliminate tip effect. Reproduced with permission from Cheng et al.99 Copyright 2016, Wiley-VCH. (D) Mixed ionic and electronic conductor film formed by in situ reaction between LLTO and Li metal. Glass fiber interlayer to uniformize Li+ flux and eliminate tip effect. Reproduced with permission from Yang et al.100 Copyright 2018, Wiley-VCH. Matter 2019 1, 317-344DOI: (10.1016/j.matt.2019.05.016) Copyright © 2019 Elsevier Inc. Terms and Conditions

Figure 6 Schematic Illustrations of In Situ Formed Protective Layers via Chemical Pretreatment (A) Skin-grafting strategy to form a uniform SEI with improved density and flexibility. Reproduced with permission from Gao et al.106 Copyright 2017, American Chemical Society. (B) Pretreating Li metal surface to form uniform and stable Li3PO4 SEI film. Reproduced with permission from Li et al.108 Copyright 2016, Wiley-VCH. (C) LiF-rich SEI by in situ hydrolysis of LiPF6 on Cu current collector to render columnar Li deposition behavior. Reproduced with permission from Zhang et al.109 Copyright 2017, Wiley-VCH. (D) Alloy interface formed by direct reduction of the metal chlorides by Li to deliver fast Li+ transport. Reproduced with permission from Liang et al.110 Copyright 2017, Nature publishing group. (E) Stable dual-layered interphase formed by soaking Li anode in FEC solvent. Reproduced with permission from Yan et al.111 Copyright 2018, Wiley-VCH. Matter 2019 1, 317-344DOI: (10.1016/j.matt.2019.05.016) Copyright © 2019 Elsevier Inc. Terms and Conditions

Figure 7 Schematic Illustrations of In Situ Formed Protective Layers via Electrochemical Pretreatment (A) Artificial SEI formed by precycling Li in FEC electrolyte. Reproduced with permission from Liu et al.128 Copyright 2015, Wiley-VCH. (B) Dual-layered artificial SEI composed of elastic bottom layer formed by pre-cycling in DOL-containing electrolyte and LiPON top layer via ALD. Reproduced with permission from Chen et al.92 Copyright 2017, American Chemical Society. (C) Implantable SEI formed by electrochemical pre-cycling, which shows excellent performance in both carbonate and ether electrolyte systems. Reproduced with permission from Cheng et al.129 Copyright 2017, Elsevier. (D) Ultrasmooth ultrathin multilayered SEI formed by multistep electrochemical polishing processes. Reproduced with permission from Gu et al.130 Copyright 2018, Nature publishing group. Matter 2019 1, 317-344DOI: (10.1016/j.matt.2019.05.016) Copyright © 2019 Elsevier Inc. Terms and Conditions

Figure 8 Schematic Illustrations of Strategies to Decrease Interfacial Resistance in Solid-State Batteries (A) ALD Al2O3 coating to negate interfacial resistance. Reproduced with permission from Han et al.144 Copyright 2017, Nature publishing group. (B) Graphite-based soft interface drew with pencil with good lithiophilicity. Reproduced with permission from Shao et al.151 Copyright 2018, American Chemical Society. (C) Polymer/ceramic/polymer sandwiched electrolyte to improve the performance of solid-state Li metal batteries. Reproduced with permission from Zhou et al.152 Copyright 2016, American Chemical Society. (D) Anion-immobilized electrolyte to prevent Li dendrite formation. Reproduced with permission from Zhao et al.153 Copyright 2017, National Academy of Sciences. (E) Solvate ionic liquid LiG3 with decreased reactivity not only displays negligible nucleophilic attack toward sulfide electrolytes, but also paves additional ion pathways in the solid-state batteries. Reproduced with permission from Oh et al.154 Copyright 2015, Wiley-VCH. Matter 2019 1, 317-344DOI: (10.1016/j.matt.2019.05.016) Copyright © 2019 Elsevier Inc. Terms and Conditions

Figure 9 The Development Milestones in Constructing Stable Interfacial Films at the Li/Solid-Electrolyte and Li/Liquid-Electrolyte Interfaces Matter 2019 1, 317-344DOI: (10.1016/j.matt.2019.05.016) Copyright © 2019 Elsevier Inc. Terms and Conditions