A high surface area tunnel-type α-MnO2 nanorod cathode by a simple solvent-free synthesis for rechargeable aqueous zinc-ion batteries

Alfaruqi, Muhammad Hilmy; Islam, Saiful; Gim, Jihyeon; Song, Jinju; Kim, Sungjin; Pham, Duong; Jo, Jeonggeun; Xiu, Zhiliang; Mathew, Vinod; Kim, Jaekook

doi:10.1016/j.cplett.2016.02.067

Cited by 152 publications

(83 citation statements)

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“…Aqueous rechargeable zinc-ion batteries (ZIBs) are developed as a battery system, in which low-cost, non-toxic, and naturally abundant zinc metal is used as an anode and environment-friendly neutral aqueous Zn 2+ -containing solution serves as electrolyte [8]. In recent years, a series of high-performance cathode materials for ZIBs have also been studied such as Prussian blue analog [9][10][11], vanadium oxides [12][13][14][15][16][17][18][19], manganese oxides [20][21][22][23][24][25][26][27][28], and some metal sulfides [29][30][31]. Among these materials, MnO 2 is particularly concerned for its high theoretical specific capacity, low cost, eco-friendliness, and diverse crystallographic polymorphs (e.g., α-MnO 2 , δ-MnO 2 , and γ-MnO 2 ) [27,28,32].…”

Section: Introductionmentioning

confidence: 99%

Novel Insights into Energy Storage Mechanism of Aqueous Rechargeable Zn/MnO2 Batteries with Participation of Mn2+

et al. 2019

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HIGHLIGHTS• Pourbaix diagram of Mn-Zn-H 2 O system was used to analyze the charge-discharge processes of Zn/MnO 2 batteries.• Electrochemical reactions with the participation of various ions inside Zn/MnO 2 batteries were revealed.• A detailed explanation of phase evolution inside Zn/MnO 2 batteries was provided.ABSTRACT Aqueous rechargeable Zn/MnO 2 zinc-ion batteries (ZIBs) are reviving recently due to their low cost, non-toxicity, and natural abundance.However, their energy storage mechanism remains controversial due to their complicated electrochemical reactions. Meanwhile, to achieve satisfactory cyclic stability and rate performance of the Zn/MnO 2 ZIBs, Mn 2+ is introduced in the electrolyte (e.g., ZnSO 4 solution), which leads to more complicated reactions inside the ZIBs systems. Herein, based on comprehensive analysis methods including electrochemical analysis and Pourbaix diagram, we provide novel insights into the energy storage mechanism of Zn/MnO 2 batteries in the presence of Mn 2+ . A complex series of electrochemical reactions with the coparticipation of Zn 2+ , H + , Mn 2+ , SO 4 2− , and OH − were revealed. During the first discharge process, co-insertion of Zn 2+ and H + promotes the transformation of MnO 2 into Zn x MnO 4 , MnOOH, and Mn 2 O 3 , accompanying with increased electrolyte pH and the formation of ZnSO 4 ·3Zn(OH) 2 ·5H 2 O. During the subsequent charge process, Zn x MnO 4 , MnOOH, and Mn 2 O 3 revert to α-MnO 2 with the extraction of Zn 2+ and H + , while ZnSO 4 ·3Zn(OH) 2 ·5H 2 O reacts with Mn 2+ to form ZnMn 3 O 7 ·3H 2 O. In the following charge/discharge processes, besides aforementioned electrochemical reactions, Zn 2+ reversibly insert into/extract from α-MnO 2 , Zn x MnO 4 , and ZnMn 3 O 7 ·3H 2 O hosts; ZnSO 4 ·3Zn(OH) 2 ·5H 2 O, Zn 2 Mn 3 O 8 , and ZnMn 2 O 4 convert mutually with the participation of Mn 2+ . This work is believed to provide theoretical guidance for further research on high-performance ZIBs.

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Section: Introductionmentioning

confidence: 99%

Novel Insights into Energy Storage Mechanism of Aqueous Rechargeable Zn/MnO2 Batteries with Participation of Mn2+

et al. 2019

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“…In these structures, the basic structural unit MnO 6 octahedra is connected to each other by co‐angle/co‐edge, constructing chain, tunnel, layered structures with enough space accommodating foreign cations . Given this structural advantage, MnO 2 has been extensively investigated as favorable cathodes for batteries in the past several years, including Li‐ion batteries, Na‐ion batteries, K‐ion batteries, Mg‐ion batteries, and latest ZIB . Theoretically, MnO 2 can accommodate one Zn 2+ insertion per formula with a high theoretical capacity of approximately 616 mAh/g, in which the Mn 4+ is reduced to Mn 2+ .…”

Section: Manganese‐based Oxidesmentioning

confidence: 99%

Section: Manganese‐based Oxidesmentioning

confidence: 99%

“…[72][73][74][75] Given this structural advantage, MnO 2 has been extensively investigated as favorable cathodes for batteries in the past several years, including Li-ion batteries, 76,77 Na-ion batteries, 78 K-ion batteries, 79 Mg-ion batteries, [80][81][82] and latest ZIB. [83][84][85][86] Figure 4A). Some studies have successfully proved that β-MnO 2 has excellent zinc storage performance.…”

Section: Manganese Dioxidementioning

confidence: 99%

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Challenges and perspectives for manganese‐based oxides for advanced aqueous zinc‐ion batteries

Zhao

Zhu

Zhang

2019

InfoMat

302

156

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Li‐ion batteries (LIBs) with excellent cycling stability and high‐energy densities have already occupied the commercial rechargeable battery market. Unfortunately, the high cost and intrinsic insecurity induced by organic electrolyte severely hinder their applications in large‐scale energy storage. In contrast, aqueous Zn‐ion batteries (ZIBs) are being developed as an ideal candidate because of their cheapness and high security. Benefiting from high operating voltage and acceptable specific capacity, recently, manganese‐based oxides with different various crystal structures have been extensively studied as cathode materials for aqueous ZIBs. This review presents research progress of manganese‐based cathodes in aqueous ZIBs, including various manganese‐based oxides and their zinc storage mechanisms. In addition, we also discuss some optimization strategies that aim at improving the electrochemical performance of manganese‐based cathodes, and the design of flexible aqueous ZIBs based on manganese‐based cathodes (MZIBs). Finally, this review summarizes some valuable research directions, which will promote the further development of aqueous MZIBs.

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“…[1,4,5] Presently, several different categories of materials have been explored for use as cathodes, with the most popular ones being V oxide compounds, [4][5][6][7][8][9][10][11][12][13][14] Prussian blue analogues (PBA), [4,5,[15][16][17][18] and Mn oxide compounds. [4,5,[19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35] To a lesser extent, sustainable quinone analogs, metal sulfides, Chevrel phase compounds, and polyanion based compounds have also been explored. [4,5,36] Of the different materials explored for ZIB cathodes, the most commonly studied material is Mn oxide.…”

Section: Introductionmentioning

confidence: 99%

Electrodeposited Manganese Oxide on Carbon Paper for Zinc‐Ion Battery Cathodes

Dhiman

Ivey

2019

Batteries & Supercaps

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Nano‐crystalline, flake‐like Mn oxide was electrodeposited onto carbon paper (CP) using a pulsed electrodeposition technique. The electrodeposited Mn oxide was identified as Mn3O4 through a combination of X‐ray photoelectron spectroscopy (XPS), X‐ray diffraction (XRD), and Raman spectroscopy. The Mn3O4 on CP was used as a cathode for Zn‐ion batteries (ZIBs) and showed excellent cyclability at a current density of 1 A g−1 with a capacity retention of 139 % after 200 cycles. Electron microscopy was used to characterize the microstructural changes of the cathode at various stages during discharge/charge cycling. This work in combination with the electrochemical results suggests a two‐step reaction mechanism involving both intercalation and conversion reactions. The results demonstrate that electrodeposition of the cathode material is a simple, quick, and potentially scalable electrode synthesis method for producing high performing Zn‐ion electrodes without the use of binders or other additives.

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A high surface area tunnel-type α-MnO2 nanorod cathode by a simple solvent-free synthesis for rechargeable aqueous zinc-ion batteries

Cited by 152 publications

References 25 publications

Novel Insights into Energy Storage Mechanism of Aqueous Rechargeable Zn/MnO2 Batteries with Participation of Mn2+

Novel Insights into Energy Storage Mechanism of Aqueous Rechargeable Zn/MnO2 Batteries with Participation of Mn2+

Challenges and perspectives for manganese‐based oxides for advanced aqueous zinc‐ion batteries

Electrodeposited Manganese Oxide on Carbon Paper for Zinc‐Ion Battery Cathodes

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