Effects of interlayer confinement and hydration on capacitive charge storage in birnessite

Boyd, Shelby; Ganeshan, Karthik; Tsai, Wan‐Yu; Wu, Tao; Saeed, Saeed; Jiang, De‐en; Balke, Nina; Duin, Adri C. T. van; Augustyn, Veronica

doi:10.1038/s41563-021-01066-4

Cited by 161 publications

(131 citation statements)

References 52 publications

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“…Manganese oxides with at least six different polymorphs labeled a, b, g, l, R, and d-MnO x 1,2 have been widely explored for various applications such as batteries, 3,4 supercapacitors, [5][6][7] heavy-metal adsorption, 8,9 and many more. [10][11][12] More recently, manganese oxides with a broad range of active-site configurations, nominal valence states, and nano-morphologies have been developed and tested as oxygen electrocatalysts, oxygen evolution reactions (OERs), and oxygen reduction reactions (ORRs) for some time.…”

Section: Introductionmentioning

confidence: 99%

Scalable, inexpensive, one-pot, facile synthesis of crystalline two-dimensional birnessite flakes

Badr

Montazeri

El-Melegy

et al. 2022

Matter

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Section: Introductionmentioning

confidence: 99%

Scalable, inexpensive, one-pot, facile synthesis of crystalline two-dimensional birnessite flakes

Badr

Montazeri

El-Melegy

et al. 2022

Matter

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“…23 Despite these observations, the charge transfer mechanism within intercalation compounds and the interactions between intercalants and the surrounding environment are still poorly understood. Our current understanding of charge transfer in layered materials comes from pioneering studies by Shpigel et al 24 and Boyd et al 25 who have identified the important role of ions and water molecules in charge storage even in the absence of intercalants. These observations imply that ions and water molecules may also play a crucial role in modulating charge transfer processes of redox active intercalants in layered materials.…”

Section: Introductionmentioning

confidence: 99%

Charge Transfer in Metallocene Intercalated Transition Metal Dichalcogenides

et al. 2022

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Intercalating redox active molecules into layered materials expands their functionality for emerging energy technologies. However, the mechanism of charge transfer to and from these small molecules within the confined environment of the layered host material and their role in charge storage are largely unexplored. Herein we examine charge transfer processes in metallocene intercalated transition metal dichalcogenides, including MoS2 and WS2. Combining experimental and computational analyses, we explore the orientation of the metallocene as a function of substitution pattern and study the influence of the metallocene redox potential on the electronic structure of MoS2 and WS2. We further examine the electrochemical response of these intercalated compounds via cyclic voltammetry. Our results show that the intercalated metallocene remains redox active and its redox potential is dramatically affected by the speciation and concentration of cations in the electrolyte. Our work provides a general strategy for studying the electronic and electrochemical responses of redox active intercalants in layered materials and highlights emergent phenomena regulating charge transfer that may be useful in energy storage and catalysis.

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“…This is consistent with quantification results, which suggest that redox processes at −30 °C have ≈10% higher contribution from the pseudocapacitive mechanism as compared with 20 °C, reaching as high as ≈90% at 0.5 mV s −1 (Figure 2f). Such nondiffusion pseudocapacitive processes are known to have faster kinetics and better stability, [ 21 ] and in fact enabled high rate performance with a high discharge capacity of 120 mAh g −1 in 3.0 m Zn(ClO 4 ) 2 at 5.0 C, representing a 46% retention compared with the capacity of 260 mAh g −1 at 0.1 C, significantly higher than the 23% retention in 1.0 m Zn(ClO 4 ) 2 (Figure S11, Supporting Information).…”

Section: Resultsmentioning

confidence: 99%

High‐Energy and Stable Subfreezing Aqueous Zn–MnO₂ Batteries with Selective and Pseudocapacitive Zn‐Ion Insertion in MnO₂

Gao

Tan

et al. 2022

Advanced Materials

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One major challenge of aqueous Zn–MnO2 batteries for practical applications is their unacceptable performance below freezing temperatures. Here the use of simple Zn(ClO4)2 aqueous electrolytes is described for all‐weather Zn–MnO2 batteries even down to −60 °C. The symmetric, bulky ClO4− anion effectively disrupts hydrogen bonds between water molecules and provides intrinsic ion diffusion even while frozen, and enables ≈260 mAh g−1 on MnO2 cathodes at −30 °C . It is identified that subfreezing cycling shifts the reaction mechanism on the MnO2 cathode from unstable H+ insertion to predominantly pseudocapacitive Zn2+ insertion, which converts MnO2 nanofibers into complicated zincated MnOx that are largely disordered and appeared as crumpled paper sheets. The Zn2+ insertion at −30 °C is faster and much more stable than at 20 °C, and delivers ≈80% capacity retention for 1000 cycles without Mn2+ additives. In addition, simple Zn(ClO4)2 electrolyte also enables a nearly fully reversible and dendrite‐free Zn anode at −30 °C with ≈98% Coulombic efficiency. Zn–MnO2 prototypes with an experimentally verified unit energy density of 148 Wh kg−1 at a negative‐to‐positive ratio of 1.5 and an electrolyte‐to‐capacity ratio of 2.0 are further demonstrated.

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Effects of interlayer confinement and hydration on capacitive charge storage in birnessite

Cited by 161 publications

References 52 publications

Scalable, inexpensive, one-pot, facile synthesis of crystalline two-dimensional birnessite flakes

Scalable, inexpensive, one-pot, facile synthesis of crystalline two-dimensional birnessite flakes

Charge Transfer in Metallocene Intercalated Transition Metal Dichalcogenides

High‐Energy and Stable Subfreezing Aqueous Zn–MnO₂ Batteries with Selective and Pseudocapacitive Zn‐Ion Insertion in MnO₂

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Effects of interlayer confinement and hydration on capacitive charge storage in birnessite

Cited by 161 publications

References 52 publications

Scalable, inexpensive, one-pot, facile synthesis of crystalline two-dimensional birnessite flakes

Scalable, inexpensive, one-pot, facile synthesis of crystalline two-dimensional birnessite flakes

Charge Transfer in Metallocene Intercalated Transition Metal Dichalcogenides

High‐Energy and Stable Subfreezing Aqueous Zn–MnO2 Batteries with Selective and Pseudocapacitive Zn‐Ion Insertion in MnO2

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Product

Resources

About

High‐Energy and Stable Subfreezing Aqueous Zn–MnO₂ Batteries with Selective and Pseudocapacitive Zn‐Ion Insertion in MnO₂