Synthesis of Copper Birnessite, CuxMnOy·nH2O with Crystallite Size Control: Impact of Crystallite Size on Electrochemistry

Li, Yue Ru; Marschilok, Amy C.; Takeuchi, Esther S.; Takeuchi, Kenneth J.

doi:10.1149/2.0501602jes

Cited by 17 publications

(24 citation statements)

References 41 publications

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“…Birnessite-layered structure is of resurgent interest for battery applications as an ionic intercalation material373839 and with what appears to be some characteristics of a conversion electrode1415161727. Bi-δ-MnO 2 in alkaline electrolyte is synthesized either by an in-situ formation step1516264041 by discharging a mix of EMD with Bi 2 O 3 and recharging to its charged state to form Bi-δ-MnO 2 (see Methods section) or by ex situ synthesis methods141517232641424344.…”

Section: Resultsmentioning

confidence: 99%

“…The resulting composite material benefits from enhanced charge transfer and complete regeneration of layered materials on each cycle. The application of this methodology is not only limited to batteries but also applies to areas where layered materials are of interest like oxidation catalysts 36 , intercalation chemistry 37 38 39 and membranes for removal of heavy-metal ions 54 .…”

Section: Resultsmentioning

confidence: 99%

“…As a consequence, the electrode charge transfer characteristics are greatly improved. This holds promise of dramatically improving energy density and energy storage cost and safety, and amplifies recent interest in birnessite for design of catalysts 36 , lithium (Li) intercalation materials 37 38 39 and intercalation of metallic ions into layered structures 32 . A large-format rechargeable battery with high loadings of Cu 2+ -intercalated Bi-δ-MnO 2 paired with Zn anodes delivering ∼140 Wh l −1 is shown.…”

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Regenerable Cu-intercalated MnO2 layered cathode for highly cyclable energy dense batteries

et al. 2017

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Manganese dioxide cathodes are inexpensive and have high theoretical capacity (based on two electrons) of 617 mAh g−1, making them attractive for low-cost, energy-dense batteries. They are used in non-rechargeable batteries with anodes like zinc. Only ∼10% of the theoretical capacity is currently accessible in rechargeable alkaline systems. Attempts to access the full capacity using additives have been unsuccessful. We report a class of Bi-birnessite (a layered manganese oxide polymorph mixed with bismuth oxide (Bi2O3)) cathodes intercalated with Cu2+ that deliver near-full two-electron capacity reversibly for >6,000 cycles. The key to rechargeability lies in exploiting the redox potentials of Cu to reversibly intercalate into the Bi-birnessite-layered structure during its dissolution and precipitation process for stabilizing and enhancing its charge transfer characteristics. This process holds promise for other applications like catalysis and intercalation of metal ions into layered structures. A large prismatic rechargeable Zn-birnessite cell delivering ∼140 Wh l−1 is shown.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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confidence: 97%

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Regenerable Cu-intercalated MnO2 layered cathode for highly cyclable energy dense batteries

et al. 2017

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“…The change in d001 spacing of NaB is likely due to the ion exchange of Na + with Cu 2+ from the saline, leading to a transformation of a fraction of Na-birnessite into Cu-birnessite. 57 These observations demonstrate that when NaB/C electrode was cycled in a 100 ppm Cu 2+ saline, Cu 2+ ions were intercalated into the interlayer spacing of the pristine NaB during each ion adsorption operation, whereas a fraction of the intercalated Cu 2+ ions and the original stabilizing Na + ions were deintercalated from the interlayer region simultaneously in each ion desorption operation, leading to a gradual structural evolution of Na-birnessite to a mixture of poorly-crystallized Cu-birnessite, Cu-buserite, and the cycled Na-birnessite. 51,56,57 The phase transformation is also likely to occur in the cases of KB/C and MgB/C electrodes cycled in Cu 2+ saline (Figures S17B, 5A), although the peaks corresponding to the Cu-buserite in the XRD pattern of KB/C after 60 cycles are difficult to be identified (Figure S17B).…”

Section: Mechanisms For Copper Ions Sequestrationmentioning

confidence: 99%

Ion Exchange Conversion of Na-birnessite to Mg-buserite for Enhanced Cu2+ Removal via Membrane Capacitive Deionization (MCDI)

Bao

Jin

et al. 2021

Preprint

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Layered manganese oxides (LMOs) have recently been demonstrated to be one of the most promising redox-active material platforms for electrochemical removal of heavy metal ions from solution via capacitive deionization (CDI). However, the impacts of phase transformation behaviors of the LMOs minerals, especially during the desalination operations, on the deionization performance of the LMOs/C electrodes have yet to be extensively evaluated. In this study, Mg-buserite derived from ion exchange of fresh Na-birnessite, Na- and K-birnessite were systematically evaluated as active electrode materials for removal of copper (Cu2+) ions from synthetic saline in a symmetric membrane capacitive deionization (MCDI) cell. In the cases of Na+, K+, Mg2+, and Ca2+ ions, the Mg-buserite/C electrode demonstrated the best deionization performance in terms of the salt and/or ion adsorption capacity, electrosorption rate, charge efficiency, and cycling stability, followed by K-birnessite/C, and then Na- birnessite/C. More importantly, the Mg-buserite/C electrode also exhibited the highest Cu2+ ion adsorption capacity (IAC) of 89.3 mg Cu2+/g active materials at a cell potential of 1.2 V in 500 mg L−1 CuCl2 solution, with an IAC retention as high as 96.3% after 60 electrosorption/desorption cycles. The underlying mechanisms for Cu2+ sequestration were investigated via ex-situ X-ray diffraction, indicating that the improving deionization performance toward Cu2+ from solution is mainly attributed to the expanded interlayer spacing through ion exchange of the original stabilizing Na+ ions of Na-birnessite with foreign Mg2+ ions, leading to a phase transformation from Na-birnessite into Mg-buserite that has larger ion diffusion channels and a higher ion storage capacity. Our work has demonstrated that expansion of interlayer spacing of LMOs minerals via ion exchange is a reliable and solid strategy for improving the desalination performance in CDI platforms, and provided insight for the rational design of smart electrodes for CDI applications towards heavy metal ion sequestration.

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“…69 The last diffractogram of Na-MnO 2 material, as shown in (Figure 1) had well-defined with symmetrical diffraction peaks (001) and (002) (JCPDS card #01-073-9669). 70 They indicated that material was single-phase mineral and well crystallized. This phase corresponds to the family of birnessite type sodium manganese, which has a layered structure with crystal water and Na + between the MnO 6 octahedral sheets.…”

Section: Xrd Of Mno 2 Lamellar and Nanostructuresmentioning

confidence: 99%

Elaboration of Lamellar and Nanostructured Materials Based on Manganese: Efficient Adsorbents for Removing Heavy Metals

Amarray¹,

Ghachtouli

Himi³

et al. 2020

ACSi

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The lamellar and nanostructured manganese oxide materials were chemically synthesized by soft and non-toxic methods. The materials showed a monophasic character, symptomatic morphologies, as well as the predominance of a mesoporous structure. The removal of heavy metals Cd(II) and Pb(II) by the synthesized materials Na-MnO2, Urchin-MnO2 and Cocoon-MnO2 according to the mineral structure and nature of the sites were also studied. Kinetically, the lamellar manganese oxide material Na-MnO2 was the most efficient of the three materials which had more vacancies in the MnO6 layers as well as in the space between the layers. The nanomaterials Urchin-MnO2 and Cocoon-MnO2 could exchange with the metal cations in their tunnels and cavities, respectively. The maximum adsorbed quantities followed the order (Pb(II): Na-MnO2 (297 mg/g)>Urchin-MnO2 (264 mg/g)>Cocoon-MnO2 (209 mg/g), Cd(II): Na-MnO2 (199 mg/g)>Urchin-MnO2 (191 mg/g)>Cocoon-MnO2 (172 mg/g)). Na-MnO2 material exhibited the best stability among the different structures, Na-MnO2 presented a very low amount of the manganese released. The results obtained showed the potential of lamellar manganese oxides (Na-MnO2) and nanostructures (Urchin-MnO2 and Cocoon-MnO2) as selective, economical, and stable materials for the removal of toxic metals in an aqueous medium.

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Synthesis of Copper Birnessite, Cu_xMnO_y·nH₂O with Crystallite Size Control: Impact of Crystallite Size on Electrochemistry

Cited by 17 publications

References 41 publications

Regenerable Cu-intercalated MnO2 layered cathode for highly cyclable energy dense batteries

Regenerable Cu-intercalated MnO2 layered cathode for highly cyclable energy dense batteries

Ion Exchange Conversion of Na-birnessite to Mg-buserite for Enhanced Cu2+ Removal via Membrane Capacitive Deionization (MCDI)

Elaboration of Lamellar and Nanostructured Materials Based on Manganese: Efficient Adsorbents for Removing Heavy Metals

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