A Novel Layered WO3 Derived from An Ion Etching Engineering for Ultrafast Proton Storage in Frozen Electrolyte

Aqueous proton batteries/pseudocapacitors are promising candidates for next‐generation electrochemical energy storage. However, their development is impeded by the lack of suitable electrode materials that facilitate rapid transport and storage of protons. Herein, an open‐layered hydrous tungsten oxide (WO3·nH2O) with larger layer spacing from Aurivillius Bi2WO6 via ion etching is proposed. Particularly, the WO3·nH2O electrode possesses a unique multi‐level nanostructure and presents superior rate performance (254 F g−1 at 1000 mV s−1, surpassing most carbon‐based electrode materials known). In situ X‐ray Diffraction combined with crystallography study demonstrate that the open layered structure with negligible structural strain enables fast and reversible (de)intercalation of protons during electrochemical reaction. Furthermore, a full proton pseudocapacitor (Prussian blue analogues//WO3·nH2O) operating in a wide temperature range from −40 to 25 °C is fabricated. This device can deliver 70% of the room‐temperature capacitance and stably cycle with negligible capacitance fading over 5000 cycles even in the solid‐phase electrolyte at −20 °C. This study provides a valuable strategy to design electrode materials with layered structures for the development of high‐performance aqueous proton batteries/pseudocapacitors at low temperatures.

[1]  Chen Zhao,et al.  Synergistic co-reaction of Zn2+ and H+ with carbonyl groups towards stable aqueous zinc–organic batteries , 2022, Energy Storage Materials.

[2]  Xiaogang Zhang,et al.  Electrochemical Proton Storage: From Fundamental Understanding to Materials to Devices , 2022, Nano-Micro Letters.

[3]  H. Tan,et al.  Layer-by-Layer Assembly of CeO2-x@C-rGO Nanocomposites and CNTs as a Multifunctional Separator Coating for Highly Stable Lithium-Sulfur Batteries. , 2022, ACS applied materials & interfaces.

[4]  X. Lou,et al.  Synthesis of Nitrogen‐Doped KMn8O16 with Oxygen Vacancy for Stable Zinc‐Ion Batteries , 2022, Advanced science.

[5]  Zaichun Liu,et al.  High performance aqueous Prussian blue analogue-hydrogen gas hybrid batteries , 2021 .

[6]  Xiaogang Zhang,et al.  A Fast Proton‐Induced Pseudocapacitive Supercapacitor with High Energy and Power Density , 2021, Advanced Functional Materials.

[7]  Yan Yu,et al.  Harnessing the Volume Expansion of MoS3 Anode by Structure Engineering to Achieve High Performance Beyond Lithium‐Based Rechargeable Batteries , 2021, Advanced materials.

[8]  Yongjiu Lei,et al.  Hierarchically structured Ti3C2T MXene paper for Li-S batteries with high volumetric capacity , 2021 .

[9]  X. Lou,et al.  Construction of Co–Mn Prussian Blue Analog Hollow Spheres for Efficient Aqueous Zn‐ion Batteries , 2021, Angewandte Chemie.

[10]  Jongwoo Lim,et al.  A new high-voltage calcium intercalation host for ultra-stable and high-power calcium rechargeable batteries , 2021, Nature Communications.

[11]  Zhiqiang Niu,et al.  Ultralow Temperature Aqueous Battery with Proton Chemistry. , 2021, Angewandte Chemie.

[12]  Jens Leker,et al.  Post-lithium-ion battery cell production and its compatibility with lithium-ion cell production infrastructure , 2021, Nature Energy.

[13]  Peng Li,et al.  A universal strategy towards high–energy aqueous multivalent–ion batteries , 2021, Nature Communications.

[14]  Joonhee Moon,et al.  Sub-micro droplet reactors for green synthesis of Li3VO4 anode materials in lithium ion batteries , 2020, Nature Communications.

[15]  Huiqing Yu,et al.  3-D hierarchical micro/nano-structures of porous Bi2WO6: Controlled hydrothermal synthesis and enhanced photocatalytic performances , 2021 .

[16]  Kang Xu,et al.  A rechargeable zinc-air battery based on zinc peroxide chemistry , 2020, Science.

[17]  F. Pan,et al.  Optimizing Ion Pathway in Titanium Carbide MXene for Practical High‐Rate Supercapacitor , 2020, Advanced Energy Materials.

[18]  Y. Gogotsi,et al.  Low-Temperature pseudocapacitive energy storage in Ti3C2T MXene , 2020 .

[19]  Alexander B. Brady,et al.  Fast Proton Insertion in Layered H2W2O7 via Selective Etching of an Aurivillius Phase , 2020, Advanced Energy Materials.

[20]  R. Ma,et al.  Layered materials for supercapacitors and batteries: Applications and challenges , 2020 .

[21]  C. Zhi,et al.  Non-metallic charge carriers for aqueous batteries , 2020, Nature Reviews Materials.

[22]  Haocheng Guo,et al.  Ultrahigh Areal Capacity Hydrogen‐Ion Batteries with MoO3 Loading Over 90 mg cm−2 , 2020, Advanced Functional Materials.

[23]  Jun Lu,et al.  A Non-aqueous Proton Electrolyte Enables Stable Cycling of Proton Electrodes. , 2020, Angewandte Chemie.

[24]  Y. Gogotsi,et al.  Perspectives for electrochemical capacitors and related devices , 2020, Nature Materials.

[25]  G. Cao,et al.  Active Materials for Aqueous Zinc Ion Batteries: Synthesis, Crystal Structure, Morphology, and Electrochemistry. , 2020, Chemical reviews.

[26]  V. Presser,et al.  Pseudocapacitance: From Fundamental Understanding to High Power Energy Storage Materials. , 2020, Chemical reviews.

[27]  Yongyao Xia,et al.  Low‐Temperature Charge/Discharge of Rechargeable Battery Realized by Intercalation Pseudocapacitive Behavior , 2020, Advanced science.

[28]  Jun Lu,et al.  A High‐Rate Aqueous Proton Battery Delivering Power Below −78 °C via an Unfrozen Phosphoric Acid , 2020, Advanced Energy Materials.

[29]  Yongjiu Lei,et al.  Review of MXene electrochemical microsupercapacitors , 2020 .

[30]  M. Deschamps,et al.  First Example of Protonation of Ruddlesden–Popper Sr2IrO4: A Route to Enhanced Water Oxidation Catalysts , 2020, Chemistry of Materials.

[31]  W. Rao,et al.  A Universal Approach to Aqueous Energy Storage via Ultralow‐Cost Electrolyte with Super‐Concentrated Sugar as Hydrogen‐Bond‐Regulated Solute , 2020, Advanced materials.

[32]  Yonggang Wang,et al.  Solid-State Proton Battery Operated at Ultralow Temperature , 2020 .

[33]  Jun Chen,et al.  Aqueous Batteries Operated at - 50 °C. , 2019, Angewandte Chemie.

[34]  Danielle M. Butts,et al.  Achieving high energy density and high power density with pseudocapacitive materials , 2019, Nature Reviews Materials.

[35]  Chenglong Zhao,et al.  Building aqueous K-ion batteries for energy storage , 2019, Nature Energy.

[36]  G. Cao,et al.  Graphene-Encapsulated FeS2 in Carbon Fibers as High Reversible Anodes for Na+ /K+ Batteries in a Wide Temperature Range. , 2019, Small.

[37]  Tongchao Liu,et al.  Diffusion-free Grotthuss topochemistry for high-rate and long-life proton batteries , 2019, Nature Energy.

[38]  G. Yushin,et al.  Understanding the Exceptional Performance of Lithium‐Ion Battery Cathodes in Aqueous Electrolytes at Subzero Temperatures , 2018, Advanced Energy Materials.

[39]  Yan Yu,et al.  Ultrathin Ti2Nb2O9 Nanosheets with Pseudocapacitive Properties as Superior Anode for Sodium‐Ion Batteries , 2018, Advanced materials.

[40]  B. Dunn,et al.  Design and Mechanisms of Asymmetric Supercapacitors. , 2018, Chemical reviews.

[41]  F. Du,et al.  NH4+ Topotactic Insertion in Berlin Green: An Exceptionally Long-Cycling Cathode in Aqueous Ammonium-Ion Batteries , 2018, ACS Applied Energy Materials.

[42]  E. Salager,et al.  Proton Ion Exchange Reaction in Li3IrO4: A Way to New H3+xIrO4 Phases Electrochemically Active in Both Aqueous and Nonaqueous Electrolytes , 2018 .

[43]  Wei Chen,et al.  A manganese–hydrogen battery with potential for grid-scale energy storage , 2018 .

[44]  Yury Gogotsi,et al.  Guidelines for Synthesis and Processing of Two-Dimensional Titanium Carbide (Ti3C2Tx MXene) , 2017 .

[45]  V. Augustyn,et al.  Transition from Battery to Pseudocapacitor Behavior via Structural Water in Tungsten Oxide , 2017 .

[46]  Linda F. Nazar,et al.  Advances in lithium–sulfur batteries based on multifunctional cathodes and electrolytes , 2016, Nature Energy.

[47]  Yi Cui,et al.  The path towards sustainable energy. , 2016, Nature materials.

[48]  Zhengu Chen,et al.  Hierarchical Nanostructured WO3 with Biomimetic Proton Channels and Mixed Ionic-Electronic Conductivity for Electrochemical Energy Storage. , 2015, Nano letters.

[49]  Atsuo Yamada,et al.  Pseudocapacitance of MXene nanosheets for high-power sodium-ion hybrid capacitors , 2015, Nature Communications.

[50]  Yunfeng Lu,et al.  WO3 nanocrystals with tunable percentage of (0 0 1)-facet exposure , 2012 .

[51]  S. Pei,et al.  Tetragonal tungsten oxide nanobelts synthesized by chemical vapor deposition , 2010 .

[52]  Yongyao Xia,et al.  Large-scale synthesis of single-crystal hexagonal tungsten trioxide nanowires and electrochemical lithium intercalation into the nanocrystals , 2007 .

[53]  O. Terasaki,et al.  A layered tungstic acid H2W2O7 x nH2O with a double-octahedral sheet structure: conversion process from an aurivillius phase Bi2W2O9 and structural characterization. , 2003, Inorganic chemistry.