Mo-Pre-Intercalated MnO2 Cathode with Highly Stable Layered Structure and Expanded Interlayer Spacing for Aqueous Zn-Ion Batteries.

Although manganese-based oxides possess high voltage and low cost, the sluggish reaction kinetics and poor structural stability hinder their applications in aqueous rechargeable Zn-ion batteries (ZIBs). Herein, a molybdenum (Mo) pre-intercalation strategy is proposed to solve the above issues of δ-MnO2. The pre-intercalated Mo dopants, acting as the interlayer pillars, can not only expand the interlayer spacing but also reinforce the layered structure of δ-MnO2, finally achieving enhanced reaction kinetics and superb cycling stability during carrier (de)intercalation. Moreover, oxygen defects, introduced due to Mo-pre-intercalation, play a critical role in the fast reaction kinetics and capacity improvement of the Mo-pre-intercalated δ-MnO2 (Mo-MnO2) cathode. Therefore, the Mo-MnO2 cathode displays a high energy density of 451 Wh kg-1 (based on cathode mass), excellent rate capability, and admirable long-term cycling performance with a high capacity of 159 mAhg-1 at 1.0 A g-1 after 1000 cycles. In addition, the energy storage mechanism of Zn2+/H+ stepwise reversible (de)intercalation is also revealed by ex situ experiments. This work provides an insightful guide for boosting the electrochemical performance of Mn-based oxide cathodes for ZIBs.

[1]  Xiao-Ling Sun,et al.  Defect Engineering via Copper Doping on Oxygen‐Deficient Manganese Oxide for Durable Aqueous Zinc‐Ion Battery , 2022, Energy Technology.

[2]  Ling Ni,et al.  Layered MnO2 nanodots as high-rate and stable cathode materials for aqueous zinc-ion storage , 2022, Energy Storage Materials.

[3]  Youyuan Huang,et al.  Molecular Tailoring of MnO2 by Bismuth doping to Achieve Aqueous Zinc-Ion Battery with Capacitor-Level Durability , 2022, Energy Storage Materials.

[4]  J. Xue,et al.  Boosting Aqueous Zn/MnO2 Batteries via a Synergy of Edge/Defect-Rich Cathode and Dendrite-Free Anode. , 2022, ACS applied materials & interfaces.

[5]  Gongzheng Yang,et al.  Bi Doping-Enhanced Reversible-Phase Transition of α-MnO2 Raising the Cycle Capability of Aqueous Zn-Mn Batteries. , 2021, ACS applied materials & interfaces.

[6]  Hao Yang,et al.  Manipulating intercalation-extraction mechanisms in structurally modulated δ-MnO2 nanowires for high-performance aqueous zinc-ion batteries , 2021, Chemical Engineering Journal.

[7]  Chun Yang,et al.  Unveiling performance evolution mechanisms of MnO2 polymorphs for durable aqueous zinc-ion batteries , 2021, Energy Storage Materials.

[8]  Feng Zhang,et al.  Oxygen-vacancy and phosphate coordination triggered strain engineering of vanadium oxide for high-performance aqueous zinc ion storage , 2021 .

[9]  Liping Zhao,et al.  Al-Intercalated MnO2 cathode with reversible phase transition for aqueous Zn-Ion batteries , 2021 .

[10]  Lei Liu,et al.  High-performance Cu0.95V2O5 nanoflowers as cathode materials for aqueous zinc-ion batteries , 2021, Rare Metals.

[11]  Yirong Zhu,et al.  Recent Developments and Future Prospects for Zinc‐Ion Hybrid Capacitors: a Review , 2021, Advanced Energy Materials.

[12]  Yunhui Huang,et al.  Inhibition of Manganese Dissolution in Mn2O3 Cathode with Controllable Ni2+ Incorporation for High‐Performance Zinc Ion Battery , 2021, Advanced Functional Materials.

[13]  Shangpeng Gao,et al.  Superior-Performance Aqueous Zinc-Ion Batteries Based on the In Situ Growth of MnO2 Nanosheets on V2CTX MXene. , 2021, ACS nano.

[14]  David M. Reed,et al.  Crossroads in the renaissance of rechargeable aqueous zinc batteries , 2021 .

[15]  Chen-Xuan Xu,et al.  Electrolytes speed up development of zinc batteries , 2021, Rare Metals.

[16]  F. Pan,et al.  Preintercalation Strategy in Manganese Oxides for Electrochemical Energy Storage: Review and Prospects , 2020, Advanced materials.

[17]  R. Hu,et al.  MnO Stabilized in Carbon‐Veiled Multivariate Manganese Oxides as High‐Performance Cathode Material for Aqueous Zn‐Ion Batteries , 2020, ENERGY & ENVIRONMENTAL MATERIALS.

[18]  Naiqing Zhang,et al.  Intercalation Pseudocapacitive Zn2+ Storage with Hydrated Vanadium Dioxide toward Ultrahigh Rate Performance , 2020, Advanced materials.

[19]  Yaoxin Zhang,et al.  Defect Engineering in Manganese‐Based Oxides for Aqueous Rechargeable Zinc‐Ion Batteries: A Review , 2020, Advanced Energy Materials.

[20]  Hongbo Geng,et al.  Boosting transport kinetics of cobalt sulfides yolk-shell spheres by anion doping for advanced lithium and sodium storage. , 2020, ChemSusChem.

[21]  Ya-li Guo,et al.  Multi-functional Mo-doping in MnO2 nanoflowers toward efficient and robust electrocatalytic nitrogen fixation , 2020 .

[22]  C. Yuan,et al.  Surface/Interface Structure Degradation of Ni‐Rich Layered Oxide Cathodes toward Lithium‐Ion Batteries: Fundamental Mechanisms and Remedying Strategies , 2019, Advanced Materials Interfaces.

[23]  Jiang Zhou,et al.  Oxygen Defects in β-MnO2 Enabling High-Performance Rechargeable Aqueous Zinc/Manganese Dioxide Battery , 2019, iScience.

[24]  C. Zhi,et al.  A Flexible Solid‐State Aqueous Zinc Hybrid Battery with Flat and High‐Voltage Discharge Plateau , 2019, Advanced Energy Materials.

[25]  Tongchao Liu,et al.  Correlation between manganese dissolution and dynamic phase stability in spinel-based lithium-ion battery , 2019, Nature Communications.

[26]  S. Kheawhom,et al.  δ-MnO2 nanoflower/graphite cathode for rechargeable aqueous zinc ion batteries , 2019, Scientific Reports.

[27]  Rajankumar L. Patel,et al.  Joint Charge Storage for High‐Rate Aqueous Zinc–Manganese Dioxide Batteries , 2019, Advanced materials.

[28]  Yitai Qian,et al.  Ultrathin δ-MnO2 nanosheets as cathode for aqueous rechargeable zinc ion battery , 2019, Electrochimica Acta.

[29]  Guozhao Fang,et al.  Suppressing Manganese Dissolution in Potassium Manganate with Rich Oxygen Defects Engaged High‐Energy‐Density and Durable Aqueous Zinc‐Ion Battery , 2019, Advanced Functional Materials.

[30]  J. Xue,et al.  Defect Engineering of Oxygen‐Deficient Manganese Oxide to Achieve High‐Performing Aqueous Zinc Ion Battery , 2019, Advanced Energy Materials.

[31]  A. Du,et al.  Tailoring Crystal Structure of FA0.83Cs0.17PbI3 Perovskite Through Guanidinium Doping for Enhanced Performance and Tunable Hysteresis of Planar Perovskite Solar Cells , 2018, Advanced Functional Materials.

[32]  H. Fan,et al.  Recent Advances in Zn‐Ion Batteries , 2018, Advanced Functional Materials.

[33]  Xiaoping Yang,et al.  Hierarchical heterostructure of interconnected ultrafine MnO2 nanosheets grown on carbon-coated MnO nanorods toward high-performance lithium-ion batteries , 2017 .

[34]  W. Chu,et al.  Effective Interlayer Engineering of Two-Dimensional VOPO4 Nanosheets via Controlled Organic Intercalation for Improving Alkali Ion Storage. , 2017, Nano letters.

[35]  Jun Chen,et al.  Rechargeable aqueous zinc-manganese dioxide batteries with high energy and power densities , 2017, Nature Communications.

[36]  Jianwen Liang,et al.  Wet‐Chemical Synthesis of Hollow Red‐Phosphorus Nanospheres with Porous Shells as Anodes for High‐Performance Lithium‐Ion and Sodium‐Ion Batteries , 2017, Advanced materials.

[37]  W. Cheikhrouhou-Koubaa,et al.  Effect of elaborating method on magnetocaloric properties of La0.7Ca0.2Ba0.1MnO3 manganite , 2016 .

[38]  Pengfei Yan,et al.  Reversible aqueous zinc/manganese oxide energy storage from conversion reactions , 2016, Nature Energy.

[39]  J. Gim,et al.  A layered δ-MnO2 nanoflake cathode with high zinc-storage capacities for eco-friendly battery applications , 2015 .

[40]  Joseph Paul Baboo,et al.  Electrochemically Induced Structural Transformation in a γ-MnO2 Cathode of a High Capacity Zinc-Ion Battery System , 2015 .

[41]  Xufeng Zhou,et al.  Towards High‐Voltage Aqueous Metal‐Ion Batteries Beyond 1.5 V: The Zinc/Zinc Hexacyanoferrate System , 2015 .

[42]  J. Tarascon,et al.  Towards greener and more sustainable batteries for electrical energy storage. , 2015, Nature chemistry.

[43]  Jun Liu,et al.  Materials Science and Materials Chemistry for Large Scale Electrochemical Energy Storage: From Transportation to Electrical Grid , 2013 .

[44]  Feiyu Kang,et al.  Energetic zinc ion chemistry: the rechargeable zinc ion battery. , 2012, Angewandte Chemie.

[45]  B. Dunn,et al.  Electrical Energy Storage for the Grid: A Battery of Choices , 2011, Science.

[46]  Han-Yi Chen,et al.  MnO2 cathode materials with the improved stability via nitrogen doping for aqueous zinc-ion batteries , 2022 .