An Artificial Solid Electrolyte Interphase with High Li‐Ion Conductivity, Mechanical Strength, and Flexibility for Stable Lithium Metal Anodes

Liu, Yayuan; Lin, Dingchang; Yuen, Pong Mo; Liu, Kai; Xie, Jin; Dauskardt, Reinhold H.; Cui, Yi

doi:10.1002/adma.201605531

Cited by 807 publications

(548 citation statements)

References 40 publications

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“…In contrast, chemically liquid or gas processing seems much simpler. 103 Li metals pretreated by polyphosphoric acid 104 and ystyrene-butadiene rubber (Cu 3 N + polymerized styrene butadiene rubber (SBR)) 105 indicate a superior stability against the liquid electrolytes in the subsequent cycles. Wen's group proposed several efficient agents to protect Li metal anode in Li−S batteries, such as Li 3 N layer through in-situ reaction between Li and N 2 , 106 (CH 3 ) 3 SiCl layer by exposing Li foils to tetrahydrofuran (THF) solvent, oxygen atmosphere, and (CH 3 ) 3 SiCl liquid in sequence.…”

Section: Metal Protection In Li−s Batteriesmentioning

confidence: 99%

Review—Li Metal Anode in Working Lithium-Sulfur Batteries

Cheng

Huang

Zhang

2017

J. Electrochem. Soc.

251

170

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Due to the high theoretical energy density of 2600 Wh kg −1 , lithium-sulfur batteries are strongly regarded as the promising nextgeneration energy storage devices. However, the practical applications of lithium-sulfur batteries are challenged by several obstacles, including the low sulfur utilization and poor lifespan, which are partly attributed to the shuttle of lithium polysulfides and lithium dendrite growth in working lithium-sulfur batteries. Suppressing lithium dendrite growth is a necessary step not only for a safe and efficient Li metal anode, but also for a high capacity cell with a high Coulombic efficiency. Herein we review the lithium metal anode protection in a polysulfide-rich environment, relative to most reviews on lithium metal anode without considering the effect of lithium polysulfides in lithium metal batteries. Firstly, the importance and dilemma of Li metal anode issues in lithium-sulfur batteries are underscored, aiming to arouse the attentions to Li metal anode protection. Specific attentions are paid to the surface chemistry of Li metal anode in a polysulfide-rich lithium-sulfur battery. Next, the proposed strategies to stabilize solid electrolyte interface and protect Li metal anode are included. Finally, a general conclusion and a perspective on the current limitations, as well as recommended future research directions of Li metal anode in lithium-sulfur batteries are presented. The ever-increasing requirement for efficient and economic energy storage technologies has triggered the continued research into advanced battery systems.1 Lithium ion batteries, based on the lithium intercalation chemistry, have dominated the battery market since their commercial application in the 1990s.2 However, conventional lithium ion batteries are very expensive and their energy densities (theoretically, 350 − 500 Wh kg −1 , practically, 100 − 250 Wh kg −1 ) seem insufficient for long-range electrical vehicles and high-end portable electronics. These emerging demands have energized the evolution of other alternative rechargeable batteries with higher energy density and longer lifespan.3 Lithium−sulfur (Li−S) battery, a 'beyond Li-ion' technology, has drawn extensive attentions due to its high specific capacity (1675 mAh g −1 ) and energy density (2600 Wh kg −1 ). 4-6The greater energy storage ability of Li−S batteries is realized through the phase-transformation electrochemistry based on elemental sulfur cathode and metallic lithium anode [S 8 + 16Li ↔ 8Li 2 S], 7,8 which is fundamentally different from current transition metal-based cathodes and graphite-based anodes in Li-ion batteries.The conversion chemistry in a Li−S cell offers not only significant advantages as mentioned above, but also some critical challenges, such as the low conductivity of sulfur and lithium sulfide, the huge volumetric change from sulfur (71 mol L −1 ) to lithium sulfide (36 mol L −1 ), and the shuttle of long-chain polysulfide intermediates during discharge/charge cycling.9-12 Therefore, a composite cathode with sulfur in ...

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Section: Metal Protection In Li−s Batteriesmentioning

confidence: 99%

Review—Li Metal Anode in Working Lithium-Sulfur Batteries

Cheng

Huang

Zhang

2017

J. Electrochem. Soc.

251

170

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“…[1,2] As the ideal anode material, Li metal possesses a high theoretical specific capacity (3860 mAh g −1 ), the lowest electrochemical potential for Li based electrochemistry (−3.040 V vs standard hydrogen electrode) and a very low density (0.534 g cm −3 ). [5][6][7] Various strategies have been adopted to improve the stability of the Li metal anode and deepen our understanding, including artificial SEI layer, [8][9][10] interface modification, [11][12][13][14][15] electrolyte additives, [16][17][18][19] and 3D host materials. Accompanying Li dendrite growth during cycling, due to high reactivity and large surface area, the formation of solid-electrolyte-interphase (SEI) leads to low Coulombic efficiency (CE) and poor cycling.…”

mentioning

confidence: 99%

High‐Rate and Large‐Capacity Lithium Metal Anode Enabled by Volume Conformal and Self‐Healable Composite Polymer Electrolyte

et al. 2019

Self Cite

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The widespread implementation of lithium‐metal batteries (LMBs) with Li metal anodes of high energy density has long been prevented due to the safety concern of dendrite‐related failure. Here a solid–liquid hybrid electrolyte consisting of composite polymer electrolyte (CPE) soaked with liquid electrolyte is reported. The CPE membrane composes of self‐healing polymer and Li + ‐conducting nanoparticles. The electrodeposited lithium metal in a uniform, smooth, and dense behavior is achieved using a hybrid electrolyte, rather than dendritic and pulverized structure for a conventional separator. The Li foil symmetric cells can deliver remarkable cycling performance at ultrahigh current density up to 20 mA cm −2 with an extremely low voltage hysteresis over 1500 cycles. A large areal capacity of 10 mAh cm −2 at 10 mA cm −2 could also be obtained. Furthermore, the Li|Li 4 Ti 5 O 12 cells based on the hybrid electrolyte achieve a higher specific capacity and longer cycling life than those using conventional separators. The superior performances are mainly attributed to strong adhesion, volume conformity, and self‐healing functionality of CPE, providing a novel approach and a significant step toward cost‐effective and large‐scalable LMBs.

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“…Moreover, the fractures of dendrites during repeated Li deposition/stripping result in "dead" Li sections composed of isolated Li fragments surrounded by e −insulating SEI. [16][17][18][19] However, because of the volume change of Li metal, the structural integrity of the protective layers is hard to be maintained during prolonged running. [15] In order to inhibit Li dendrite growth and build stable SEI layers, considerable efforts have been made.…”

mentioning

confidence: 99%

“Top‐Down” Li Deposition Pathway Enabled by an Asymmetric Design for Li Composite Electrode

Yue

Bao

et al. 2019

Advanced Energy Materials

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safety issue due to dendrite growth during the repeated Li stripping/plating process. [7][8][9] On one hand, the surface defects of the bare Li serve as the active sites to increase the local current density, leading to uneven Li deposition. [10] On the other hand, the "hostless" feature of Li metal results in huge volume change during cycling, causing unstable solid electrolyte interphase (SEI). [11] As a result, the fresh Li exposure created by SEI fracturing consumes electrolyte continuously, leading to low coulombic efficiency. [12] As such, the Li dendrites develop in an uncontrolled fashion that can eventually pierce the separator and cause short circuit. Moreover, the fractures of dendrites during repeated Li deposition/stripping result in "dead" Li sections composed of isolated Li fragments surrounded by e −insulating SEI. [13,14] The "dead" Li with high impedance leads to poor kinetics and shortened lifespan of the battery. [15] In order to inhibit Li dendrite growth and build stable SEI layers, considerable efforts have been made. One approach is the coating of an artificial SEI with high mechanical strength onto the electrode surface. [16][17][18][19] However, because of the volume change of Li metal, the structural integrity of the protective layers is hard to be maintained during prolonged running. In order to remit the volume change, great efforts have been made to design porous frameworks to accommodate Li. [20][21][22][23][24][25][26] A series of host frameworks have been reported, such as 3D CoO/Ni foam skeleton, [27] coralloid carbon fiber scaffolds, [28] lithiophilic Cu-Ni core-shell nanowire network, [29] and 3D carbon fiber framework. [30] The host frameworks can not only accommodate the volume change of Li during cycling, but also reduce the local current density. [31][32][33][34] More importantly, the porous structure of these frameworks can suppress the dendrite formation by changing Li plating/ stripping behavior. [35][36][37] It should be noted that most of the reported composited electrodes possess symmetric structure for their two sides, especially for the electrodes fabricated by thermal infusion method. [38] However, as the anode for the battery, the two sides of the electrode are in different environments: one side contacts with the separator, while the other side faces the current collector. The requirements and functions for the two sides are thus quite different. [39] The side facing the separator should be facile for Li-ion transportation.Designing Li composite electrodes with host frameworks for accommodating Li metal has been considered to be an effective approach to suppress Li dendrites. Herein, an asymmetric design of a Mo net/Li metal film (MLF) composite electrode is developed by an inverted thermal infusion method. The asymmetric MLF electrode has a dense oxide passivated layer on the top side, a porous Mo net matrix on the back side, and active Li layer in between. The back side has a larger specific area and higher electric field than the top side, which contacts with ...

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An Artificial Solid Electrolyte Interphase with High Li‐Ion Conductivity, Mechanical Strength, and Flexibility for Stable Lithium Metal Anodes

Cited by 807 publications

References 40 publications

Review—Li Metal Anode in Working Lithium-Sulfur Batteries

Review—Li Metal Anode in Working Lithium-Sulfur Batteries

High‐Rate and Large‐Capacity Lithium Metal Anode Enabled by Volume Conformal and Self‐Healable Composite Polymer Electrolyte

“Top‐Down” Li Deposition Pathway Enabled by an Asymmetric Design for Li Composite Electrode

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