Versatile Asymmetric Separator with Dendrite‐Free Alloy Anode Enables High‐Performance Li–S Batteries

Lithium–sulfur batteries (LSBs) with extremely‐high theoretical energy density (2600 Wh kg−1) are deemed to be the most likely energy storage system to be commercialized. However, the polysulfides shuttling and lithium (Li) metal anode failure in LSBs limit its further commercialization. Herein, a versatile asymmetric separator and a Li‐rich lithium–magnesium (Li–Mg) alloy anode are applied in LSBs. The asymmetric separator is consisted of lithiated‐sulfonated porous organic polymer (SPOP‐Li) and Li6.75La3Zr1.75Nb0.25O12 (LLZNO) layers toward the cathode and anode, respectively. SPOP‐Li serves as a polysulfides barrier and Li‐ion conductor, while the LLZNO functions as an “ion redistributor”. Combining with a stable Li–Mg alloy anode, the symmetric cell achieves 5300 h of Li stripping/plating and the modified LSBs exhibit a long lifespan with an ultralow fading rate of 0.03% per cycle for over 1000 cycles at 5 C. Impressively, even under a high‐sulfur‐loading (6.1 mg cm−2), an area capacity of 4.34 mAh cm−2 after 100 cycles can still be maintained, demonstrating high potential for practical application.

[1]  L. Fu,et al.  Li4Ti5O12 Coating on Copper Foil as Ion Redistributor Layer for Stable Lithium Metal Anode , 2022, Advanced Energy Materials.

[2]  L. Fu,et al.  Boosting Polysulfide Catalytic Conversion and Facilitating Li+ Transportation by Ion-Selective COFs Composite Nanowire for LiS Batteries. , 2022, Small.

[3]  Jiaqi Huang,et al.  Anode Material Options Toward 500 Wh kg−1 Lithium–Sulfur Batteries , 2021, Advanced science.

[4]  Nan Wang,et al.  Towards High Performance Li–S Batteries via Sulfonate‐Rich COF‐Modified Separator , 2021, Advanced materials.

[5]  De‐Yin Wu,et al.  Defects Engineering of Lightweight Metal-Organic Frameworks-Based Electrocatalytic Membrane for High-Loading Lithium-Sulfur Batteries. , 2021, ACS nano.

[6]  I. Manke,et al.  A Highly Conductive COF@CNT Electrocatalyst Boosting Polysulfide Conversion for Li–S Chemistry , 2021, ACS Energy Letters.

[7]  Wei Lv,et al.  Rich Heterointerfaces Enabling Rapid Polysulfides Conversion and Regulated Li2S Deposition for High-Performance Lithium-Sulfur Batteries. , 2021, ACS nano.

[8]  L. Mai,et al.  Metal-organic frameworks enable broad strategies for lithium-sulfur batteries , 2021, National science review.

[9]  Qiang Zhang,et al.  A Robust Ternary Heterostructured Electrocatalyst with Conformal Graphene Chainmail for Expediting Bi‐Directional Sulfur Redox in Li–S Batteries , 2021, Advanced Functional Materials.

[10]  Li Cao,et al.  Ion Selective Covalent Organic Framework Enabling Enhanced Electrochemical Performance of Lithium-Sulfur Batteries. , 2021, Nano letters.

[11]  Zaichun Liu,et al.  Nonporous Gel Electrolytes Enable Long Cycling at High Current Density for Lithium-Metal Anodes. , 2021, ACS applied materials & interfaces.

[12]  Zhonglin Li,et al.  The Electrostatic Attraction and Catalytic Effect Enabled by Ionic–Covalent Organic Nanosheets on MXene for Separator Modification of Lithium–Sulfur Batteries , 2021, Advanced materials.

[13]  Xiaofei Yang,et al.  Recent progress of functional separators with catalytic effects for high-performance lithium-sulfur batteries , 2021 .

[14]  Xuejun Liu,et al.  Dual-engineered separator for highly robust, all-climate lithium-sulfur batteries , 2020 .

[15]  Shanqing Zhang,et al.  Ni/SiO2/Graphene-modified separator as a multifunctional polysulfide barrier for advanced lithium-sulfur batteries , 2020 .

[16]  Zhanxu Yang,et al.  Lithiation of covalent organic framework nanosheets facilitating lithium-ion transport in lithium-sulfur batteries , 2020 .

[17]  Tongchao Liu,et al.  Activating Li2S as the Lithium-Containing Cathode in Lithium–Sulfur Batteries , 2020 .

[18]  Yi Zhang,et al.  Methods to Improve Lithium Metal Anode for Li-S Batteries , 2019, Front. Chem..

[19]  Liumin Suo,et al.  Intercalation-conversion hybrid cathodes enabling Li–S full-cell architectures with jointly superior gravimetric and volumetric energy densities , 2019, Nature Energy.

[20]  Sang‐young Lee,et al.  Solvent-Free, Single Lithium-Ion Conducting Covalent Organic Frameworks. , 2019, Journal of the American Chemical Society.

[21]  Xueping Gao,et al.  Lithium–Magnesium Alloy as a Stable Anode for Lithium–Sulfur Battery , 2019, Advanced Functional Materials.

[22]  Deyu Wang,et al.  Tailoring Lithium Deposition via an SEI‐Functionalized Membrane Derived from LiF Decorated Layered Carbon Structure , 2019, Advanced Energy Materials.

[23]  Rui Zhang,et al.  An ion redistributor for dendrite-free lithium metal anodes , 2018, Science Advances.

[24]  Chongwu Zhou,et al.  Functional interlayer of PVDF-HFP and carbon nanofiber for long-life lithium-sulfur batteries , 2018, Nano Research.

[25]  Jianming Zheng,et al.  Accurate Determination of Coulombic Efficiency for Lithium Metal Anodes and Lithium Metal Batteries , 2018 .

[26]  Hongwei Wang,et al.  Gel polymer electrolytes for lithium ion batteries: Fabrication, characterization and performance , 2017 .

[27]  Lain‐Jong Li,et al.  Metal-Organic Framework-Based Separators for Enhancing Li-S Battery Stability: Mechanism of Mitigating Polysulfide Diffusion , 2017 .

[28]  Tingzheng Hou,et al.  Lithium Bond Chemistry in Lithium-Sulfur Batteries. , 2017, Angewandte Chemie.

[29]  Jianming Zheng,et al.  Electrolyte additive enabled fast charging and stable cycling lithium metal batteries , 2017, Nature Energy.

[30]  Zhengyuan Tu,et al.  Highly Conductive, Sulfonated, UV-Cross-Linked Separators for Li–S Batteries , 2016 .

[31]  Haoshen Zhou,et al.  Metal–organic framework-based separator for lithium–sulfur batteries , 2016, Nature Energy.

[32]  R. Banerjee,et al.  Interplaying Intrinsic and Extrinsic Proton Conductivities in Covalent Organic Frameworks , 2016 .

[33]  R. Katiyar,et al.  Kinetic analysis of the Li+ ion intercalation behavior of solution derived nano-crystalline lithium manganate thin films , 2005 .

[34]  R. Service.  Lithium-sulfur batteries poised for leap. , 2018, Science.