Journal articles: 'Zn-MnO2 batteries'

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Durena, Ramona, and Anzelms Zukuls. "A Short Review: Comparison of Zinc–Manganese Dioxide Batteries with Different pH Aqueous Electrolytes." Batteries 9, no. 6 (June 5, 2023): 311. http://dx.doi.org/10.3390/batteries9060311.

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As the world moves towards sustainable and renewable energy sources, there is a need for reliable energy storage systems. A good candidate for such an application could be to improve secondary aqueous zinc–manganese dioxide (Zn-MnO2) batteries. For this reason, different aqueous Zn-MnO2 battery technologies are discussed in this short review, focusing on how electrolytes with different pH affect the battery. Improvements and achievements in alkaline aqueous Zn-MnO2 batteries the recent years have been briefly reviewed. Additionally, mild to acidic aqueous electrolyte employment in Zn-MnO2 batteries has been described, acknowledging their potential success, as such a battery design can increase the potential by up to 2 V. However, we have also recognized a novel battery electrolyte type that could increase even more scientific interest in aqueous Zn-MnO2 batteries. Consisting of an alkaline electrolyte in the anode compartment and an acidic electrolyte in the cathode compartment, this dual (amphoteric) electrolyte system permits the extension of the battery cell potential above 2 V without water decomposition. In addition, papers describing pH immobilization in aqueous zinc–manganese compound batteries and the achieved results are reported and discussed.

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Yadav, Gautam, Jinchao Huang, Meir Weiner, Shinju Yang, Kristen Vitale, Sanbir Rahman, Kevin Keane, and Sanjoy Banerjee. "Improvements in Performance and Cost Reduction of Large-Scale Rechargeable Zinc|Manganese Dioxide Batteries and a Future Roadmap Driven through Real World Applications." ECS Meeting Abstracts MA2022-01, no. 3 (July 7, 2022): 452. http://dx.doi.org/10.1149/ma2022-013452mtgabs.

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Zinc|Manganese Dioxide (Zn|MnO2) are widely available as primary batteries for use in small-scale consumer electronics because of its low cost and high energy density. The last decade has seen a resurgence in research to make this chemistry rechargeable by materials engineering, additives and experimenting with various electrolytes. These important contributions have showed that Zn|MnO2 has all the prerequisites to be a post-lithium solution for grid-scale storage. At Urban Electric Power, we have been commercializing proton-insertion Zn|MnO2 batteries in cylindrical and prismatic form factors between 70 to 140Ah nameplate capacity. These batteries contain improved materials and electrode designs with improved utilizations of the cathode and anode theoretical capacity. Both the cathode and anode can achieve 40 to 60% of their theoretical capacity, which is currently the best in alkaline electrolytes and scaled-up cells. These improvements not only reflect the performance but also the manufacturability of cells on a large scale. In this talk, we will present the methodological approach we pursued to achieve these performance metrics and reduce the cost to <$80/kWh. We also cycled these cells according to various protocols that represent real world applications. For example, we found that the newly improved Zn|MnO2 cells can achieve >6 years of performance for solar microgrid applications, which is better than lead acid batteries, the current battery of choice. We have also manufactured gelled Zn|MnO2 batteries that can be considered as “non-spillable” and thus, “non-hazardous” according to transportation regulations. These non-spillable cells manufacturing process and performance will also be presented in the talk. The talk will also expand on the future generations of Zn|MnO2 that are currently under development at Urban Electric Power like the conversion battery which access the complete 2nd electron capacity of the electrodes and the high voltage (>2.5V) battery. These batteries expand the application space of Zn|MnO2 batteries which make it a viable contender for post lithium-ion batteries.

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Wang, Xiao, Shuanghao Zheng, Feng Zhou, Jieqiong Qin, Xiaoyu Shi, Sen Wang, Chenglin Sun, Xinhe Bao, and Zhong-Shuai Wu. "Scalable fabrication of printed Zn//MnO2 planar micro-batteries with high volumetric energy density and exceptional safety." National Science Review 7, no. 1 (June 11, 2019): 64–72. http://dx.doi.org/10.1093/nsr/nwz070.

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Abstract The rapid development of printed and microscale electronics imminently requires compatible micro-batteries (MBs) with high performance, applicable scalability, and exceptional safety, but faces great challenges from the ever-reported stacked geometry. Herein the first printed planar prototype of aqueous-based, high-safety Zn//MnO2 MBs, with outstanding performance, aesthetic diversity, flexibility and modularization, is demonstrated, based on interdigital patterns of Zn ink as anode and MnO2 ink as cathode, with high-conducting graphene ink as a metal-free current collector, fabricated by an industrially scalable screen-printing technique. The planar separator-free Zn//MnO2 MBs, tested in neutral aqueous electrolyte, deliver a high volumetric capacity of 19.3 mAh/cm3 (corresponding to 393 mAh/g) at 7.5 mA/cm3, and notable volumetric energy density of 17.3 mWh/cm3, outperforming lithium thin-film batteries (≤10 mWh/cm3). Furthermore, our Zn//MnO2 MBs present long-term cyclability having a high capacity retention of 83.9% after 1300 cycles at 5 C, which is superior to stacked Zn//MnO2 batteries previously reported. Also, Zn//MnO2 planar MBs exhibit exceptional flexibility without observable capacity decay under serious deformation, and remarkably serial and parallel integration of constructing bipolar cells with high voltage and capacity output. Therefore, low-cost, environmentally benign Zn//MnO2 MBs with in-plane geometry possess huge potential as high-energy, safe, scalable and flexible microscale power sources for direction integration with printed electronics.

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Wruck, W. J., B. Reichman, K. R. Bullock, and W. ‐H Kao. "Rechargeable Zn ‐ MnO2 Alkaline Batteries." Journal of The Electrochemical Society 138, no. 12 (December 1, 1991): 3560–67. http://dx.doi.org/10.1149/1.2085459.

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Wang, Da Hui, Sha Zhang, and Ji Hong Xia. "Study on Mechanism of Desulfurization by Spent Zn-MnO₂ Batteries." Advanced Materials Research 402 (November 2011): 452–56. http://dx.doi.org/10.4028/www.scientific.net/amr.402.452.

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The mechanism of a novel desulfurization method using spent Zn-MnO2 batteries has been studied by X-ray diffraction(XRD), scanning electronic microscopy (SEM), energy dispersive spectrometry (EDS) and the experiments of SO2 absorption. The XRD results show that the positive electrode of spent Zn-MnO2 batteries consists of a mixture of α-MnO2, Mn2O3 and Mn3O4 phase. The SEM results show that micropores and microparticles are observed in the positive electrode surface, the relative content of zinc and graphite increases in the positive electrode after discharging according to EDS. The results of absorption experiments show that the electrolyte of spent batteries is of weak alkali which verifies the feasibility of absorbing SO2 using spent Zn-MnO2 batteries. Furthermore, the solution obtained by washing the positive electrode with low concentration ammonia is of much better desulfurization efficiency than that with distilled water directly, and 40°C is the optimum to absorb SO2 at a range of 30-70°C.

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Kankanallu, Varun, Xiaoyin Zheng, Cheng-Hung Lin, Nicole Zmich, Mingyuan Ge, and Yu-chen Karen Chen-Wiegart. "Elucidating MnO₂ Reaction Mechanism By Multi-Modal Characterization in Aqueous Zn-MnO₂ Batteries." ECS Meeting Abstracts MA2022-02, no. 4 (October 9, 2022): 401. http://dx.doi.org/10.1149/ma2022-024401mtgabs.

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Aqueous Zn-ion batteries has attracted great attention in recent years, as a promising candidate for grid energy storage applications. An aqueous system offers intrinsic safety, high ionic conductivity contributing improved power capability and raw materials that are more earth abundant and environment friendly. Numerous promising reports haven been focusing on the Zn/MnO2 system owing to its low cost, moderate discharge potentials and with improved reversibility in the mild aqueous electrolyte. However, many questions remain unanswered regarding its reaction mechanism. The different reaction mechanisms including Zn+2 insertion, H+ insertion, chemical conversion reaction including the combined intercalation and conversion reaction mechanism, and the dissolution-deposition of the manganese oxide. In this work, we aim to unravel the reaction mechanism by a systematic multimodal synchrotron characterization. This work discusses the galvano-static charge-discharge process of aqueous Zn-MnO2 batteries using operando measurements, which provides us with a direct insight into the phenomenon and can be directly correlated to the battery's electrochemical response. The multimodal techniques include operando X-ray diffraction to study the structural phase change of the cathode active material, operando X-ray absorption spectroscopy to probe the local structure changes and transmission X-ray microscopy studies to observe the key morphological events. Overall, this multimodal approach gives us an insight into the reaction mechanism enabling us to better design Zn-MnO2 batteries for practical applications.

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Senthilkumar, S. T., Hussain Alawadhi, and Anis Allagui. "Enhancing aqueous Zn-Mn battery performance using Na⁺ ion conducting ceramic membrane." Journal of Physics: Conference Series 2751, no. 1 (April 1, 2024): 012005. http://dx.doi.org/10.1088/1742-6596/2751/1/012005.

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Abstract The low cell voltage and capacity of conventional Zn-MnO2 batteries often result in limited energy density. In this study, we assembled a Zn-MnO2 battery based on the acid-alkaline electrolyte decoupled concept and reversible MnO2/Mn2+ deposition/dissolution chemistry to increase the cell voltage and capacity. We used a Na+ ion conducting NASICON ceramic membrane in the battery to decouple the acid and alkaline electrolytes effectively. The assembled Zn-MnO2 battery demonstrated a cell voltage of 2.43 V and a coulombic efficiency (CE) of 90% at a current density of 0.2 mA/cm2. It also exhibited excellent rechargeability with continuous charge and discharge cycles. After 100 cycles, the battery exhibits a capacity of 0.36 mAh with a maximum CE of 93.42%. A study on the battery’s self-discharge performance showed that a maximum of 71% capacity could be recovered from the charged battery after 24 hours of rest. Finally, we fabricated a pouch-type acid-alkaline electrolyte decoupled Zn-MnO2 battery and examined its feasibility.

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Cho, Jungsang, Gautam Ganapati Yadav, Meir Weiner, Jinchao Huang, Aditya Upreti, Xia Wei, Roman Yakobov, et al. "Hydroxyl Conducting Hydrogels Enable Low-Maintenance Commercially Sized Rechargeable Zn–MnO2 Batteries for Use in Solar Microgrids." Polymers 14, no. 3 (January 20, 2022): 417. http://dx.doi.org/10.3390/polym14030417.

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Zinc (Zn)–manganese dioxide (MnO2) rechargeable batteries have attracted research interest because of high specific theoretical capacity as well as being environmentally friendly, intrinsically safe and low-cost. Liquid electrolytes, such as potassium hydroxide, are historically used in these batteries; however, many failure mechanisms of the Zn–MnO2 battery chemistry result from the use of liquid electrolytes, including the formation of electrochemically inert phases such as hetaerolite (ZnMn2O4) and the promotion of shape change of the Zn electrode. This manuscript reports on the fundamental and commercial results of gel electrolytes for use in rechargeable Zn–MnO2 batteries as an alternative to liquid electrolytes. The manuscript also reports on novel properties of the gelled electrolyte such as limiting the overdischarge of Zn anodes, which is a problem in liquid electrolyte, and finally its use in solar microgrid applications, which is a first in academic literature. Potentiostatic and galvanostatic tests with the optimized gel electrolyte showed higher capacity retention compared to the tests with the liquid electrolyte, suggesting that gel electrolyte helps reduce Mn3+ dissolution and zincate ion migration from the Zn anode, improving reversibility. Cycling tests for commercially sized prismatic cells showed the gel electrolyte had exceptional cycle life, showing 100% capacity retention for >700 cycles at 9.5 Ah and for >300 cycles at 19 Ah, while the 19 Ah prismatic cell with a liquid electrolyte showed discharge capacity degradation at 100th cycle. We also performed overdischarge protection tests, in which a commercialized prismatic cell with the gel electrolyte was discharged to 0 V and achieved stable discharge capacities, while the liquid electrolyte cell showed discharge capacity fade in the first few cycles. Finally, the gel electrolyte batteries were tested under IEC solar off-grid protocol. It was noted that the gelled Zn–MnO2 batteries outperformed the Pb–acid batteries. Additionally, a designed system nameplated at 2 kWh with a 12 V system with 72 prismatic cells was tested with the same protocol, and it has entered its third year of cycling. This suggests that Zn–MnO2 rechargeable batteries with the gel electrolyte will be an ideal candidate for solar microgrid systems and grid storage in general.

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Gao, Feifei, Wenchao Shi, Bowen Jiang, Zhenzhi Xia, Lei Zhang, and Qinyou An. "Ni/Fe Bimetallic Ions Co-Doped Manganese Dioxide Cathode Materials for Aqueous Zinc-Ion Batteries." Batteries 9, no. 1 (January 11, 2023): 50. http://dx.doi.org/10.3390/batteries9010050.

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The slow diffusion dynamics hinder aqueous MnO2/Zn batteries’ further development. Here, a Ni/Fe bimetallic co-doped MnO2 (NFMO) cathode material was studied by density functional theory (DFT) calculation and experimental characterization techniques, such as cyclic voltammetry (CV), galvanostatic intermittent titration technique (GITT) and electrochemical impedance spectra (EIS). The results indicated that the energy band structure and electronic state of MnO2 were effectively optimized due to the simultaneous incorporation of strongly electronegative Ni and Fe ions. Consequently, the NFMO cathode material exhibited a faster charge transfer and ion diffusion dynamics than MnO2 (MO), thus, the assembled NFMO/Zn batteries delivered excellent rate performance (181 mA h g−1 at 3 A g−1). The bimetallic ions co-doping strategy provides new directions for the development of oxide cathode materials towards high-performance aqueous zinc-ion batteries.

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Huang, Yalan, Wanyi He, Peng Zhang, and Xihong Lu. "Nitrogen-doped MnO2 nanorods as cathodes for high-energy Zn-MnO2 batteries." Functional Materials Letters 11, no. 06 (December 2018): 1840006. http://dx.doi.org/10.1142/s1793604718400064.

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The development of manganese dioxide (MnO[Formula: see text] as the cathode for aqueous Zn-MnO2 batteries is hindered by poor capacity. Herein, we propose a high-capacity MnO2 cathode constructed by engineering it with N-doping (N-MnO[Formula: see text] for a high-performance Zn-MnO2 battery. Benefiting from N element doping, the conductivity of N-MnO2 nanorods (NRs) electrode has been improved and the dissolution of the cathode during cycling can be relieved to some extent. The fabricated Zn-N-MnO2 battery based on the N-MnO2 cathode and a Zn foil anode presents an a real capacity of 0.31[Formula: see text]mAh[Formula: see text]cm[Formula: see text] at 2[Formula: see text]mA[Formula: see text]cm[Formula: see text], together with a remarkable energy density of 154.3[Formula: see text]Wh[Formula: see text]kg[Formula: see text] and a peak power density of 6914.7[Formula: see text]W[Formula: see text]kg[Formula: see text], substantially higher than most recently reported energy storage devices. The strategy of N doping can also bring intensive interest for other electrode materials for energy storage systems.

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Liu, Shuang, Wenyong Chen, Fantai Kong, Wenbin Tong, Yili Chen, and Shuanghong Chen. "The Origin of Capacity Degradation and Regulation Strategy in Aqueous Zn-MnO₂ Battery with Manganese Acetate." Journal of The Electrochemical Society 170, no. 3 (March 1, 2023): 030545. http://dx.doi.org/10.1149/1945-7111/acc693.

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MnO2-based rechargeable aqueous zinc-ion batteries (ZIBs) have attracted wide attention as the next-generation large-scale, safe energy storage technology. However, the capacity decay process of Zn-MnO2 batteries remains poorly understood because of the complicated reaction mechanism, which may lead to incorrect interpretations and methods to improve the cycle stability. In this study, the capacity decay mechanism was demonstrated for Zn-MnO2 batteries with manganese acetate as an electrolyte additive. It is found that zinc hydroxide sulfate has a beneficial effect on the battery capacity, but the product ZnMn3O7·2H2O being converted from basic zinc sulfate is an irreversibility inert material and leads to a rapid capacity fading. Notably, with the increased low cutoff voltage (1.0 to 1.35 V), it exhibited a high capacity of 231 mA h g−1 at 200 mA g−1 and an excellent stability of 90.11% retention after 1000 cycles at 1000 mA g−1. Our results of the reaction mechanism and the strategy provide a new perspective for the development of fundamental science and applications for Zn-MnO2 battery.

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Spoerke, Erik D., Howard Passell, Gabriel Cowles, Timothy N. Lambert, Gautam G. Yadav, Jinchao Huang, Sanjoy Banerjee, and Babu Chalamala. "Driving Zn-MnO2 grid-scale batteries: A roadmap to cost-effective energy storage." MRS Energy & Sustainability 9, no. 1 (February 16, 2022): 13–18. http://dx.doi.org/10.1557/s43581-021-00018-4.

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Highlights Zn-MnO2 batteries promise safe, reliable energy storage, and this roadmap outlines a combination of manufacturing strategies and technical innovations that could make this goal achievable. Approaches such as improved efficiency of manufacturing and increasing active material utilization will be important to getting costs as low as $100/kWh, but key materials innovations that facilitate the full 2-electron capacity utilization of MnO2, the use of high energy density 3D electrodes, and the promise of a separator-free battery with greater than 2V potential offer a route to batteries at $50/kWh or less. Abstract Large-scale energy storage is certain to play a significant, enabling role in the evolution of the emerging electrical grid. Battery-based storage, while not a dominant form of storage today, has opportunity to expand its utility through safe, reliable, and cost-effective technologies. Here, secondary Zn–MnO2 batteries are highlighted as a promising extension of ubiquitous primary alkaline batteries, offering a safe, environmentally friendly chemistry in a scalable and practical energy dense technology. Importantly, there is a very realistic pathway to also making such batteries cost-effective at price points of $50/kWh or lower. By examining manufacturing examples at the Zn–MnO2 battery manufacturer Urban Electric Power, a roadmap has been created to realize such low-cost systems. By focusing on manufacturing optimization through reduced materials waste, scalable manufacturing, and effective materials selection, costs can be significantly reduced. Ultimately, though, coupling these approaches with emerging research and development advances to enable full capacity active materials utilization and battery voltages greater than 2V are likely needed to drive costs below a target of $50/kWh. Reaching this commercially important goal, especially with a chemistry that is safe, well-known, and reliably effective stands to inject Zn–MnO2 batteries in the storage landscape at a critical time in energy storage development and deployment. Graphical abstract

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Wu, Lisha, Ying Zhang, Ping Shang, Yanfeng Dong, and Zhong-Shuai Wu. "Redistributing Zn ion flux by bifunctional graphitic carbon nitride nanosheets for dendrite-free zinc metal anodes." Journal of Materials Chemistry A 9, no. 48 (2021): 27408–14. http://dx.doi.org/10.1039/d1ta08697a.

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14

Lahiri, Abhishek, and Arunabhiram Chutia. "Understanding Aluminium Electrochemistry in Aqueous and Aqueous-Ionic Liquid Mixtures for Aluminium-Ion Batteries." ECS Meeting Abstracts MA2023-02, no. 56 (December 22, 2023): 2715. http://dx.doi.org/10.1149/ma2023-02562715mtgabs.

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Among various batteries, Aluminium ion batteries are potential low-cost alternatives to Li-ion batteries, which possess highest theoretical volumetric capacity of 8056 mAh cm-3 and a modest gravimetric capacity of 2981 mAh g-1. 1 However, due to passive layer formation of Aluminium and lack of suitable cathode materials, there are major challenges to overcome in order to accomplish a suitable Al-ion battery. Here, we have studied the Al electrochemistry on electrodeposited MnO2 cathode and Zn anode in aqueous and aqueous-ionic liquid mixtures. Both from experiment and DFT calculations, we show that the presence of ionic liquid (1-ethyl-3-methylimidazolium trifluoromethanesulfonate) changes the Al solvation chemistry, which leads to a change in Al electrochemistry both on Zn and MnO2 (figure below). A strain-induced intercalation/deintercalation process was identified in MnO2 cathode leading to crack formation and capacity fading during Zn/Al-MnO2 battery cycling. By developing a MnO2-polymer matrix, a relatively stable average capacity of 150 mAh g-1 could be achieved over 50 cycles at a current density of 0.1 A g-1. Acknowledgement: The financial support by Royal Society grant (RGS\R2\212184) is gratefully acknowledged. References Faegh et al, Nat. Energy, 2021, 6, 21-29 Figure 1

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Zuo, Linqing, Haodong Sun, Xinhai Yuan, Juan Wen, Xi Chen, Shiyu Zhou, Yuping Wu, and Teunis van Ree. "Agar Acts as Cathode Microskin to Extend the Cycling Life of Zn//α-MnO2 Batteries." Materials 14, no. 17 (August 27, 2021): 4895. http://dx.doi.org/10.3390/ma14174895.

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The Zn/MnO2 battery is a promising energy storage system, owing to its high energy density and low cost, but due to the dissolution of the cathode material, its cycle life is limited, which hinders its further development. Therefore, we introduced agar as a microskin for a MnO2 electrode to improve its cycle life and optimize other electrochemical properties. The results showed that the agar-coating layer improved the wettability of the electrode material, thereby promoting the diffusion rate of Zn2+ and reducing the interface impedance of the MnO2 electrode material. Therefore, the Zn/MnO2 battery exhibited outstanding rate performance. In addition, the agar-coating layer promoted the reversibility of the MnO2/Mn2+ reaction and acted as a colloidal physical barrier to prevent the dissolution of Mn2+, so that the Zn/MnO2 battery had a high specific capacity and exhibited excellent cycle stability.

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Garcia, Eric M., Hosane A. Tarôco, Júlio O. F. Melo, Ana Paula C. M. Silva, and Ione M. F. Oliveira. "Electrochemical recycling of Zn from spent Zn–MnO2 batteries." Ionics 19, no. 11 (September 10, 2013): 1699–703. http://dx.doi.org/10.1007/s11581-013-0997-8.

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Kamenskii, Mikhail A., Filipp S. Volkov, Svetlana N. Eliseeva, Elena G. Tolstopyatova, and Veniamin V. Kondratiev. "Enhancement of Electrochemical Performance of Aqueous Zinc Ion Batteries by Structural and Interfacial Design of MnO2 Cathodes: The Metal Ion Doping and Introduction of Conducting Polymers." Energies 16, no. 7 (April 3, 2023): 3221. http://dx.doi.org/10.3390/en16073221.

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Aqueous zinc-ion batteries (AZIBs) and, in particular, Zn//MnO2 rechargeable batteries have attracted great attention due to the abundant natural resources of zinc and manganese, low cost, environmental friendliness, and high operating voltage. Among the various ways to improve the electrochemical performance of MnO2-based cathodes, the development of MnO2 cathodes doped with metal ions or composites of MnO2 with conducting polymers has shown such advantages as increasing the specific capacity and cycling stability. This mini-review focuses on the strategies to improve the electrochemical performance of manganese-based cathodes of AZIBs.

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Shi, Xin, Xinyue Liu, Xianshuo Cao, Xiaoning Cheng, and Xihong Lu. "Oxygen functionalized interface enables high MnO₂ electrolysis kinetics for high energy aqueous Zn-MnO₂ decoupled battery." Applied Physics Letters 121, no. 14 (October 3, 2022): 143903. http://dx.doi.org/10.1063/5.0116388.

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Aqueous Zn-based batteries show great potential in large scale energy storage system due to their low-cost and high-safety merits. However, the practical application of Zn-based batteries is restricted by their inferior energy and power densities, which is resulted from the low output voltage and poor reaction kinetics of cathode materials. To address the above issues, we propose a decoupled aqueous Zn–Mn battery with high-rate and high-voltage by using oxygen functionalized carbon nanotubes (OCNTs) substrate. The functional interface can greatly improve the wettability of the electrode, promote the ion transport capability, and facilitate the rapid deposition/dissolution of MnO2/Mn2+. Consequently, the OCNTs/MnO2 electrode can deliver a high capacity of 9.2 mA h cm−2 and superior capacity retention of 86.6% at an ultrahigh current density of 200 mA cm−2. When coupled with Zn anode, the Zn//OCNTs/MnO2 decoupled full battery exhibits a high discharge plateau (∼2.45 V) and area specific capacity (1.96 mA h cm−2) at a current density of 2 mA cm−2. Moreover, the outstanding peak power density of 13.4 kW kg−1 and peak energy density of 564.4 W h kg−1 can be achieved for Zn//OCNTs/MnO2 battery (based on the mass of active material involved in the reaction on the positive and negative electrodes during charge and discharge), far beyond currently reported aqueous electrochemical energy storage devices. This work provides a train of thoughts for the development of high energy and power density aqueous batteries.

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Rudhziah, Siti, Salmiah Ibrahim, and Mohamed Nor Sabirin. "Polymer Electrolyte of PVDF-HFP/PEMA-NH₄CF₃So₃-TiO₂ and its Application in Proton Batteries." Advanced Materials Research 287-290 (July 2011): 285–88. http://dx.doi.org/10.4028/www.scientific.net/amr.287-290.285.

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In this study, composite polymer electrolytes were prepared by addition of titanium oxide, TiO2nanofiller into polyvinylidene fluoride-co-hexafluoropropylene/polymethyl methacrylate-ammonium triflate (PVDF-HFP/PEMA-NH4CF3SO3) complex. The effect of TiO2on conductivity of the complex was examined using impedance spectroscopy. The highest room temperature conductivity of 1.32 × 10-3S cm-1was shown by the system containing 5 wt % of TiO2. This system was used for the fabrication of proton batteries with the configurations of (Zn + ZnSO4.7H2O + C + PTFE)/PVDF-HFP/PEMA-NH4CF3SO3-(5wt%)TiO2/(MnO2 + C + PTFE) and (Zn + ZnSO4.7H2O + C + PTFE)/PVDF-HFP/PEMA-NH4CF3SO3-(5wt%)TiO2/(MnO2 + PbO2+ C + PTFE). The performance of the batteries indicated potential application of the electrolyte system in proton batteries.

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Vijayakumar, Vidyanand, Arun Torris, Maria Kurian, Megha Mary Mathew, Meena Ghosh, Ajay B. Khairnar, Manohar V. Badiger, and Sreekumar Kurungot. "A sulfonated polyvinyl alcohol ionomer membrane favoring smooth electrodeposition of zinc for aqueous rechargeable zinc metal batteries." Sustainable Energy & Fuels 5, no. 21 (2021): 5557–64. http://dx.doi.org/10.1039/d1se00865j.

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Sulfonated polyvinyl alcohol ionomer membrane for aqueous rechargeable zinc-metal batteries shows its superiority over the non-ionomer counterpart, ensuring smooth Zn electrodeposition and better cycling stability in MnO2‖Zn cells.

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Huang, Lanxiang, Yilin Chen, Pu Deng, Bo Zhao, Xufeng Luo, Chang Chen, and Yu Hu. "Manganese vacancies and tunnel pillars synergistically improve the electrochemical performance of MnO₂ in aqueous Zn ion batteries." RSC Advances 13, no. 43 (2023): 30511–19. http://dx.doi.org/10.1039/d3ra05074b.

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Decrease of AOS of Mn and higher BE value of O 1s suggest that doped Nb5+ created Mn vacancies and as tunnel pillars enhanced the stability of MnO2. Both synergistically improved electrochemical performance of MnO2 in aqueous Zn ion batteries.

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Li, Bing, Jianwei Chai, Xiaoming Ge, Tao An, Poh-Chong Lim, Zhaolin Liu, and Yun Zong. "Sheet-on-Sheet Hierarchical Nanostructured C@MnO2 for Zn-Air and Zn-MnO2 Batteries." ChemNanoMat 3, no. 6 (April 7, 2017): 401–5. http://dx.doi.org/10.1002/cnma.201700043.

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Chomkhuntod, Praeploy, Kanit Hantanasirisakul, Salatan Duangdangchote, Nutthaphon Phattharasupakun, and Montree Sawangphruk. "The charge density of intercalants inside layered birnessite manganese oxide nanosheets determining Zn-ion storage capability towards rechargeable Zn-ion batteries." Journal of Materials Chemistry A 10, no. 10 (2022): 5561–68. http://dx.doi.org/10.1039/d1ta09968j.

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Rechargeable aqueous Zn–MnO2 batteries have been considered as one of the promising alternative energy technologies due to their high abundance, environmental friendliness, and safety of both Zn–metal anodes and manganese oxide cathodes.

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Liu, Cheng, Wenhai Wang, Ashley Black Serra, Vlad Martin Diaconescu, Lorenzo Stievano, Laura Simonelli, and Dino Tonti. "Tracking Mn and Zn in Rechargeable Aqueous Zn-MnO2 Batteries By Operando X-Ray Absorption." ECS Meeting Abstracts MA2023-02, no. 55 (December 22, 2023): 2705. http://dx.doi.org/10.1149/ma2023-02552705mtgabs.

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Zn-MnO2 batteries with mildly acidic electrolytes are a promising chemistry for large scale storage thanks to their remarkable energy density, low cost, and high safety. This is mainly obtained thanks to the high capacity of the Zn metal anode, and the nonflammable character of the aqueous electrolyte. MnO2 is one of the most common cathode of choice, not only for being Earth-abundant, but also because it can undergo a two-electron mechanism, which is however complex and still not fully understood. There is currently agreement in considering for discharge a MnO2 dissolution, leading to soluble Mn2+ and simultaneous precipitation of Zinc Hydroxide Sulfate (ZHS, ZnSO4[Zn(OH2)]3·xH2O). When charging the process is not simply reverted. In fact, a distinct electrochemical profile is observed, with at least two distinct plateaus and a third, apparently pseudocapacitive stage (Figure 1a). A similar multistage profile is observed during the second discharge. Although such profile is characteristic and observed with different MnO2 phases and architectures, the underlying mechanism remains elusive, as it seems to involve mainly poorly crystallized phases. We studied the mechanism by operando X-ray absorption (XAS) at the Mn and Zn K-edges to follow speciation simultaneously and quantitatively in the cathode and in the electrolyte via principal component analysis. Beam intensity needed appropriate regulation to avoid interference with the experiment. Simultaneous X-ray diffraction allowed precise correlation with the MnO2 dissolution and ZHS formation. We found evidence of Mn(III) intermediate occurring during local bond reorganization, which is inferred by the significant evolution of the absorption fine structure region (EXAFS) of the Mn K-edge (Figure 1b). In contrast, minor Zn spectral changes reflect primarily processes of precipitation and dissolution, suggesting that no Zn-Mn mixed phases form during cycling. Figure 1

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Luo, Lei, Zhaorui Wen, Guo Hong, and Shi Chen. "Reliable lateral Zn deposition along (002) plane by oxidized PAN separator for zinc-ion batteries." RSC Advances 13, no. 50 (2023): 34947–57. http://dx.doi.org/10.1039/d3ra05177c.

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Oxidized polyacrylonitrile (OPAN) separator promotes Zn2+ transference and regulates Zn growth along (002) plane in Zn//MnO2 batteries. The symmetric cell cycles 1300 hours or 65% DOD and the full cell cycles >5000 times with little decay.

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Tang, Zhichu, Wenxiang Chen, Zhiheng Lyu, and Qian Chen. "Size-Dependent Reaction Mechanism of λ-MnO₂ Particles as Cathodes in Aqueous Zinc-Ion Batteries." Energy Material Advances 2022 (February 9, 2022): 1–12. http://dx.doi.org/10.34133/2022/9765710.

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Manganese dioxide (MnO2) with different crystal structures has been widely investigated as the cathode material for Zn-ion batteries, among which spinel λ-MnO2 is yet rarely reported because Zn-ion intercalation in spinel lattice is speculated to be limited by the narrow three-dimensional tunnels. In this work, we demonstrate that Zn-ion insertion in spinel lattice can be enhanced by reducing particle size and elucidate an intriguing electrochemical reaction mechanism dependent on particle size. Specifically, λ-MnO2 nanoparticles (NPs, ~80 nm) deliver a high capacity of 250 mAh/g at 20 mA/g due to large surface area and solid-solution type phase transition pathway. Meanwhile, severe water-induced Mn dissolution leads to the poor cycling stability of NPs. In contrast, micron-sized λ-MnO2 particles (MPs, ~0.9 μm) unexpectedly undergo an activation process with the capacity continuously increasing over the first 50 cycles, which can be attributed to the formation of amorphous MnOx nanosheets in the open interstitial space of the MP electrode. By adding MnSO4 to the electrolyte, Mn dissolution can be suppressed, leading to significant improvement in the cycling performance of NPs, with a capacity of 115 mAh/g retained at 1 A/g for over 500 cycles. This work pinpoints the distinctive impacts of the particle size on the reaction mechanism and cathode performance in aqueous Zn-ion batteries.

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Osenberg, Markus, Ingo Manke, André Hilger, Nikolay Kardjilov, and John Banhart. "An X-ray Tomographic Study of Rechargeable Zn/MnO2 Batteries." Materials 11, no. 9 (August 21, 2018): 1486. http://dx.doi.org/10.3390/ma11091486.

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We present non-destructive and non-invasive in operando X-ray tomographic investigations of the charge and discharge behavior of rechargeable alkaline-manganese (RAM) batteries (Zn-MnO2 batteries). Changes in the three-dimensional structure of the zinc anode and the MnO2 cathode material after several charge/discharge cycles were analyzed. Battery discharge leads to a decrease in the zinc particle sizes, revealing a layer-by-layer dissolving behavior. During charging, the particles grow again to almost their initial size and shape. After several cycles, the particles sizes slowly decrease until most of the particles become smaller than the spatial resolution of the tomography. Furthermore, the number of cracks in the MnO2 bulk continuously increases and the separator changes its shape. The results are compared to the behavior of a conventional primary cell that was also charged and discharged several times.

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Cho, Jungsang, Damon E. Turney, Gautam Ganapati Yadav, Michael Nyce, Bryan R. Wygant, Timothy N. Lambert, and Sanjoy Banerjee. "Use of Hydrogel Electrolyte in Zn-MnO2 Rechargeable Batteries: Characterization of Safety, Performance, and Cu2+ Ion Diffusion." Polymers 16, no. 5 (February 28, 2024): 658. http://dx.doi.org/10.3390/polym16050658.

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Achieving commercially acceptable Zn-MnO2 rechargeable batteries depends on the reversibility of active zinc and manganese materials, and avoiding side reactions during the second electron reaction of MnO2. Typically, liquid electrolytes such as potassium hydroxide (KOH) are used for Zn-MnO2 rechargeable batteries. However, it is known that using liquid electrolytes causes the formation of electrochemically inactive materials, such as precipitation Mn3O4 or ZnMn2O4 resulting from the uncontrollable reaction of Mn3+ dissolved species with zincate ions. In this paper, hydrogel electrolytes are tested for MnO2 electrodes undergoing two-electron cycling. Improved cell safety is achieved because the hydrogel electrolyte is non-spillable, according to standards from the US Department of Transportation (DOT). The cycling of “half cells” with advanced-formulation MnO2 cathodes paired with commercial NiOOH electrodes is tested with hydrogel and a normal electrolyte, to detect changes to the zincate crossover and reaction from anode to cathode. These half cells achieved ≥700 cycles with 99% coulombic efficiency and 63% energy efficiency at C/3 rates based on the second electron capacity of MnO2. Other cycling tests with “full cells” of Zn anodes with the same MnO2 cathodes achieved ~300 cycles until reaching 50% capacity fade, a comparable performance to cells using liquid electrolyte. Electrodes dissected after cycling showed that the liquid electrolyte allowed Cu ions to migrate more than the hydrogel electrolyte. However, measurements of the Cu diffusion coefficient showed no difference between liquid and gel electrolytes; thus, it was hypothesized that the gel electrolytes reduced the occurrence of Cu short circuits by either (a) reducing electrode physical contact to the separator or (b) reducing electro-convective electrolyte transport that may be as important as diffusive transport.

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You, Kun, Yifei Yuan, Xiuxian Liao, Wenjun Song, Xuedong He, Huile Jin, and Shun Wang. "Electrochemical Study of Polymorphic MnO2 in Rechargeable Aqueous Zinc Batteries." Crystals 12, no. 11 (November 10, 2022): 1600. http://dx.doi.org/10.3390/cryst12111600.

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Manganese dioxide is regarded as a promising energy functional material due to its open tunnel structure with enormous applications in energy storage and catalysis. In this paper, α-MnO2 with a 2 × 2 tunnel structure and β-MnO2 with a 1 × 1 tunnel structure were hydrothermally synthesized, which possess characteristic tunnel structures formed by the interconnected unit structure of [MnO6] octahedrons. With regards to their different tunnel dimensions, the specific mechanism of ion intercalation in these two phases and the effect on their performance as aqueous Zn-MnO2 battery cathodes are explored and compared. Comprehensive analyses illustrate that both α-MnO2 and β-MnO2 provide decent capacity in the aqueous battery system, but their intrinsic stability is poor due to the structural instability upon cycling. At the same time, experiments show that α-MnO2 has a better rate performance than β-MnO2 under larger currents, thus implying that the former has a broader application in this aqueous battery system.

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Chen, Junyan, Yang Zhou, Mohammad S. Islam, Xinying Cheng, Sonya A. Brown, Zhaojun Han, Andrew N. Rider, and Chun H. Wang. "Carbon fiber reinforced Zn–MnO2 structural composite batteries." Composites Science and Technology 209 (June 2021): 108787. http://dx.doi.org/10.1016/j.compscitech.2021.108787.

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Freitas, M. B. J. G., V. C. Pegoretti, and M. K. Pietre. "Recycling manganese from spent Zn-MnO2 primary batteries." Journal of Power Sources 164, no. 2 (February 2007): 947–52. http://dx.doi.org/10.1016/j.jpowsour.2006.10.050.

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Liu, Xiaoyu, Jin Yi, Kai Wu, Yong Jiang, Yuyu Liu, Bing Zhao, Wenrong Li, and Jiujun Zhang. "Rechargeable Zn–MnO2 batteries: advances, challenges and perspectives." Nanotechnology 31, no. 12 (January 8, 2020): 122001. http://dx.doi.org/10.1088/1361-6528/ab5b38.

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Ismail, Yanny Marliana Baba, Habsah Haliman, and Ahmad Azmin Mohamad. "Hydroponics Polymer Gels for Zn-MnO2 Alkaline Batteries." International Journal of Electrochemical Science 7, no. 4 (April 2012): 3555–66. http://dx.doi.org/10.1016/s1452-3981(23)13977-0.

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Wei, Zhaohuan, Jun Cheng, Rui Wang, Yang Li, and Yaqi Ren. "From spent Zn–MnO2 primary batteries to rechargeable Zn–MnO2 batteries: A novel directly recycling route with high battery performance." Journal of Environmental Management 298 (November 2021): 113473. http://dx.doi.org/10.1016/j.jenvman.2021.113473.

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Chomkhuntod, Praeploy, and Montree Sawangphruk. "Understanding the Effect of Pre-Intercalated Cations on Zn-Ion Storage Mechanism of Layered Birnessite Manganese Oxide for Aqueous Zn-ionBatteries." ECS Meeting Abstracts MA2022-01, no. 1 (July 7, 2022): 25. http://dx.doi.org/10.1149/ma2022-01125mtgabs.

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With the rapid growth of energy consumption, tremendous research efforts have been dedicated to achieving sustainable and green energy storage systems, owing to environmental concerns. Over the past few years, rechargeable aqueous zinc-ion batteries (ZIBs) have become a compelling alternative to lithium-ion batteries (LIBs). Although LIBs have been successfully commercialized due to their high energy density, their organic-based electrolytes are highly volatile and flammable. Therefore, aqueous Zn-ion batteries have emerged as promising energy storage devices, owing to the benefits of water-based electrolytes such as low-cost, high safety, and high-power density as well as the advantages of zinc metal such as its natural abundance, low redox potential (-0.76 V vs standard hydrogen electrode), and high theoretical capacity (840 mAh g-1). Among cathode materials, birnessite manganese oxide (δ-MnO2) is one of the promising intercalation cathode materials for ZIBs due to its layered structure, which can facilitate H+/Zn2+ diffusion, leading to enhanced rate performance and improved capacity. However, the δ-MnO2 also suffers from some critical drawbacks such as structural phase transformations and collapse of the layered structure, resulting in poor cycling stability. To address these issues, a pre-intercalation strategy has been proved as an effective way to stabilize the layered MnO2 by using various organic polymers and metal cations such as polyaniline, Li+, K+, and Ca2+. In this work, we studied the effect of charge density of pre-intercalated cation on the Zn2+ storage mechanism of the δ-MnO2 in a mild aqueous electrolyte of 1 M ZnSO4. Overall, the results showed that a small amount of highly charged pre-intercalant (Al3+) can efficiently stabilize the layered structure of the δ-MnO2, resulting in more accommodation space for Zn2+ insertion, which can lead to improved capacity for the Al-MnO2 of 210 mAh g-1 at 0.1 A g-1. Apart from high capacity, the Al-MnO2 also exhibits excellent cycling stability with a capacity retention of 84% after 2000cycles at 2 A g-1. This is because highly charged intercalants can induce a reduction of binding energy between Zn2+ and host structure, leading to a highly reversible (de)intercalation of Zn2+ and stable structure of the δ-MnO2 during charge/discharge, which was confirmed by ex-situ XRD and DFT calculations. KEYWORDS: rechargeable aqueous Zn-ion batteries, birnessite manganese oxide, intercalation

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Li, Gang, Hai Liang, Haifang Ren, Linhan Zhou, and Mohamed Hashem. "Enhanced High-Performance Aqueous Zinc Ion Batteries with Copper-Doped α-MnO₂ Nanosheets Cathodes." Journal of Nanoelectronics and Optoelectronics 18, no. 8 (August 1, 2023): 931–37. http://dx.doi.org/10.1166/jno.2023.3484.

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Aqueous zinc ion batteries (ZIBs) have garnered considerable interest due to their eco-friendly nature, cost-efficiency, and remarkable safety features, making them a compelling contender for next-generation energy storage systems. Within the extensive array of cathode materials investigated for ZIBs, manganese-based materials stand out for their notable attributes, including low toxicity and high voltage. Nevertheless, their widespread application has been impeded by challenges related to poor cycling stability, low electrical conductivity, and intricate energy storage mechanisms. In this study, we present a novel approach to address these challenges by synthesizing copper-doped α-MnO2 nanosheets through a facile hydrothermal route. The resulting cathode material exhibits remarkable electrochemical properties when integrated into Zn/MnO2 batteries. At a low current density of 0.1 Ag−1, these batteries demonstrate an impressive reversible capacity of 445 mAh g−1, signifying their substantial energy storage capabilities. Furthermore, even when subjected to a demanding high current density of 1 Ag−1, they exhibit an exceptional cycling life of up to 1000 cycles, highlighting the enhanced durability of the copper-doped α-MnO2 nanowire cathode. This research paves the way for the development of high-performance Zn/MnO2 batteries, leveraging the advantages of manganese-based cathode materials while mitigating their inherent limitations. These findings represent a significant step forward in the development of environmentally sustainable and economically viable energy storage solutions, offering hope for a more sustainable energy future.

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Tao, Jiayou, Jie Liao, Zhijun Zou, Gaohua Liao, Chang Li, and Sanjie Liu. "Polypyrrole-Coated Manganese Dioxide Nanowires and Multi-Walled Carbon Nanotubes as High-Performance Electrodes for Zinc-Ion Batteries." Journal of Nanoelectronics and Optoelectronics 16, no. 4 (April 1, 2021): 522–27. http://dx.doi.org/10.1166/jno.2021.2979.

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Free-standing films based on MnO2@multi-walled carbon nanotubes (MWCNTs)@Polypyrrole (PPy) have been fabricated for aqueous zinc-ion batteries. A simple hydrothermal method was adopted to synthesize ß-MnO2 nanowires. PPy coated the ß-MnO2 nanowires@MWCNTs composite by an in-situ polymerization process. Free-standing films of ß-MnO2@MWCNTs@PPy composite were prepared by a convenient vacuum-assisted filtration. A zinc-ion battery is fabricated with a zinc foil anode and a ß-MnO2@MWCNTs@PPy composite cathode. The Zn//ß-MnO2@ MWCNTs@PPy system in ZnSO4@MnSO4 aqueous electrolyte exhibits high electrochemical performances, such as an initial capacity of 258.5 mAh g-1 at 0.2 A g-1, and about 74.6% retention after 100 cycles with near 100% Coulombic efficiency. The strategy of conductive polymer coating makes the technology of rechargeable zinc-ion batteries (ZIBs) very promising and provides opportunities of organic-inorganic composite materials for energy storage applications.

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Brito, Paulo S. D., Sandra Patrício, Luiz F. Rodrigues, and César A. C. Sequeira. "Electrodeposition of Zn–Mn alloys from recycling Zn–MnO2 batteries solutions." Surface and Coatings Technology 206, no. 13 (February 2012): 3036–47. http://dx.doi.org/10.1016/j.surfcoat.2011.11.036.

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Wang, Lei, Qiyuan Wu, Alyson Abraham, Patrick J. West, Lisa M. Housel, Gurpreet Singh, Nahian Sadique, et al. "Silver-Containing α-MnO2 Nanorods: Electrochemistry in Rechargeable Aqueous Zn-MnO2 Batteries." Journal of The Electrochemical Society 166, no. 15 (2019): A3575—A3584. http://dx.doi.org/10.1149/2.0101915jes.

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Wang, Kehuang, Mingliang Shangguan, Yibo Zhao, Haoran Tian, Fu Wang, Jinliang Yuan, and Lan Xia. "Flexible and Stable N-Isopropylacrylamide/Sodium Alginate Gel Electrolytes for Aqueous Zn-MNO2 Batteries." Batteries 9, no. 8 (August 15, 2023): 426. http://dx.doi.org/10.3390/batteries9080426.

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Rechargeable aqueous Zn-ion batteries (ZIBs) have attracted considerable attention owing to their high theoretical capacity of 820 mA h g−1, low cost and intrinsic safety. However, the electrolyte leakage and the instability issues of Zn negative electrodes originating from side reactions between the aqueous electrolyte and Zn negative electrode not only restrict the battery stability, but also result in the short circuit of aqueous ZIBs. Herein, we report a flexible and stable N-isopropylacrylamide/sodium alginate (N-SA) gel electrolyte, which possesses high mechanical strength and high ionic conductivity of 2.96 × 10−2 S cm−1, and enables the Zn metal negative electrode and MnO2 positive electrode to reversibly and stably cycle. Compared to the liquid electrolyte, the N-SA hydrogel electrolyte can effectively form a uniform Zn deposition and suppress the generation of irreversible by-products. The assembled symmetric Zn/Zn cells at a current density of 1 mA cm−2 (capacity: 1 mAh cm−2) show a stable voltage profile, which maintains a low level of about 100 mV over 2600 h without an obvious short circuit or any overpotential increasing. Specially, the assembled Zn/N-SA/MnO2 batteries can deliver a high specific capacity of 182 mAh g−1 and maintain 98% capacity retention after 650 cycles at 0.5 A g−1. This work provides a simple method to fabricate high-performance SA-based hydrogel electrolytes, which illustrates their potential for flexible batteries for wearable electronics.

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Tran, Lan-Huong, Kulchaya Tanong, Ahlame Dalila Jabir, Guy Mercier, and Jean-François Blais. "Hydrometallurgical Process and Economic Evaluation for Recovery of Zinc and Manganese from Spent Alkaline Batteries." Metals 10, no. 9 (September 1, 2020): 1175. http://dx.doi.org/10.3390/met10091175.

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An innovative, efficient, and economically viable process for the recycling of spent alkaline batteries is presented herein. The developed process allows for the selective recovery of Zn and Mn metals present in alkaline batteries. The hydrometallurgical process consists of a physical pre-treatment step for separating out the metal powder containing Zn and Mn, followed by a chemical treatment step for the recovery of these metals. Sulfuric acid was used for the first leaching process to dissolve Zn(II) and Mn(II) into the leachate. After purification, Mn was recovered in the form of MnO2, and Zn in its metal form. Furthermore, during the second sulfuric acid leaching, Na2S2O5 was added for the conversion of Mn(IV) to Mn(II) (soluble in the leachate), allowing Mn to be recovered as MnCO3. Masses of 162 kg of Zn metal and 215 kg of Mn (both in the form of MnO2 and MnCO3) were recovered from one ton of spent alkaline batteries. The direct operating costs (chemicals, labor operation, utilities, energy) and indirect costs (amortization, interest payment) required for a plant treating 8 tons of spent batteries per day was calculated to be $CAD 726 and $CAD 534 per ton, respectively, while the total revenue from the sale of the metals was calculated at $CAD 1359.6 per ton of spent batteries. The development of this type of cost-effective industrial process is necessary for a circular economy, as it contributes to addressing environment- and energy-related issues, and creates opportunities for the economic utilization of metals.

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Liu, Yi, Yuyin Zhang, and Xiang Wu. "Polypyrrole Film Decorated Manganese Oxide Electrode Materials for High-Efficient Aqueous Zinc Ion Battery." Crystals 13, no. 10 (September 28, 2023): 1445. http://dx.doi.org/10.3390/cryst13101445.

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Aqueous zinc-ion batteries (AZIBs) have raised wide concern as a new generation energy storage device due to their high capacity, low cost, and environmental friendliness. It is a crucial step to develop the ideal cathode materials that match well with the Zn anode. In this work, we report polypyrrole-(PPy)-encapsulated MnO2 nanowires as cathode materials for AZIBs. The assembled Zn//MnO2@PPy batteries deliver a reversible capacity of 385.7 mAh g−1 at a current density of 0.1 A g−1. Also, they possess an energy density of 192 Wh kg−1 at a power density of 50 W kg−1. The cells show long-term cycling stability, with a retention rate of 96% after 1000 cycles. The outstanding electrochemical performance indicates their potential applications in large-scale energy storage.

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Yadav, Gautam, Meir Weiner, Aditya Upreti, Jinchao Huang, Xia Wei, Timothy N. Lambert, Noah B. Schorr, Nelson Bell, and Sanjoy Banerjee. "The Advent of Aqueous >2.85V Zn-MnO₂ Batteries: Uncovering Novel Mechanisms in This New High Voltage Chemistry." ECS Meeting Abstracts MA2022-01, no. 1 (July 7, 2022): 22. http://dx.doi.org/10.1149/ma2022-01122mtgabs.

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Alkaline zinc (Zn)-manganese dioxide (MnO2) batteries are ubiquitous, safe, cheap and used in several applications that require only a single discharge. Its impact in the developing world has been significant where its affordability has helped consumers with low to medium economic background power several of their household devices and flashlights when grid reliability has been poor. Its single discharge is enough to deliver an energy density of ~400Wh/L. However, its promising characteristics are outweighed by its limited use in the next generation of green energy technologies because of the irreversibility of its active materials and its low nominal voltage of ~1.3V. The application of battery energy storage in these next generation of technologies like grid-storage, electric vehicles and personal electronics is extremely vital to decarbonize our future. Currently, expensive, toxic and flammable lithium-ion and lead acid batteries dominate these fields. If Zn-MnO2 batteries could be made rechargeable with an increase in its nominal voltage and capacity utilized, it could be serious contender to the dominant lithium-ion and lead acid batteries. In this presentation, we report on an innovative approach where we solve the two aforementioned issues by redesigning the battery system to have two electrolytes that are decoupled from each other(1). The two electrolytes are aqueous-based, where the cathode and anode are immersed in mildly acidic solutions and alkaline solutions, respectively. Operating in decoupled electrolytes allows the chemistry to widen its potential window and access voltages of >2.85V, while also allowing the respective electrodes operate efficiently and reversibly in their respective electrolyte system. The neutralization of these electrolytes is prevented by gelation of the alkaline electrolyte, which removes the need of expensive ion-exchange membranes. As a demonstration of this concept, we have developed Zn-MnO2 batteries reaching voltages >2.85V that are able to access the theoretical capacity (617mAh/g) of MnO2. This translates to energy densities 2 to 3 times greater than the commercially available alkaline batteries that can be recharged multiple times at costs that are comparable to primary batteries (~$20-30/kWh). G. Yadav et al., ACS Energy Lett. 2019, 4(9), 2144-2146.

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Zhu, Ruijie, Sho Kitano, Daniel King, Chunyu Zhu, Yoshitaka Aoki, and Hiroki Habazaki. "High Strength Hydrogel Enables Dendrite-Free Zn Metal Anodes and High-Capacity Zn-MnO₂ Batteries." ECS Meeting Abstracts MA2022-01, no. 4 (July 7, 2022): 560. http://dx.doi.org/10.1149/ma2022-014560mtgabs.

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Introduction Rechargeable aqueous zinc-ion batteries (RAZIBs) have some inherent advantages such as intrinsic safety, low-cost and theoretically high energy density, making them a current topic of interest. The problem is, dendritic growth of zinc (Zn) metal during electrodeposition occurs whatever alkaline electrolyte or neutral electrolyte, which will break the separator and cause a short-circuit inside the battery. Unless a solution can be found to effectively limit the growth of dendrites, the real-world application of RAZIBs will be nowhere in sight. In this report, by using a glass fiber modified double network hydrogel consists of poly(2-acrylamido-2-methylpropanesulfonicacid)/polyacrylamide (PAMPS/PAM) as semi-solid-state electrolyte (coded as DNGF), we found the formation of Zn dendrites can be greatly alleviated. We attribute the elimination of Zn dendrites to a modified mechanical suppression effect. In addition, a Zn-MnO2 battery with high areal capacity (4.9 mAh cm-2) worked stably for 500 cycles with the help of DNGF. Experimental The obtained DNGF composite was prepared by the following steps: a piece of glass fiber contained PAMPS (PAMPS-GF) was soaked in a 3 mol L-1 acrylamide solution for 1 day, in order to thoroughly swell the PAMPS-GF skeleton with AM solution. 0.01 % N,N'-Methylenebisacrylamide (MBAA) was used as crosslinker. The AM-swollen PAMPS-GF was transferred to a glovebox and was polymerized by a 12 h UV irradiation. The high-capacity Zn-MnO2 battery was assembled by placing a Zn metal foil, a DNGF separator that was swollen by 2M ZnSO4 electrolyte (additive 0.2 M MnSO4) and an MnO2 cathode that consists of α-MnO2 nanowire and carbon black in a Swagelok cell. The cut-off voltage was set as 0.8 V - 1.8 V. Results and discussion The structure of DNGF is depicted in Figure 1a, the second network PAM entangled with the first-network PAMPS while the glass fiber is dispersed in the structure. The DNGF can sustain a stress of 6.9 MPa at a strain of 80%, which is 10 times higher than the PAM gel (Figure 1b). As shown in Figure 2, when DNGF is used as separator in a Zn-Zn symmetric cell, the electrodeposition of Zn crystal becomes uniform and flat. Here, we attribute the suppression of Zn dendrites to a modified mechanical suppression effect. Unlike the case in lithium-ion batteries, in which a stiff polymer separator can effectively prevent the uncontrollable growth of dendrites, the growth of Zn dendrites generally cannot be suppressed by using a polymer separator due to the shear modulus of conventional polymer cannot meet the demanded value (1.8 times higher than the anode metal).[1] The use of DNGF does not stop the upward growth of Zn crystal through the normal mechanical suppression effect, but it delays the growth of Zn dendrites and forces the deposited Zn crystals flat and uniform. As shown in Figure 3, when DNGF was used in a high-capacity Zn-MnO2 battery to protect the cell from short-circuit, the cell worked stably for 500 cycles. The success in the DNGF protected Zn-MnO2 batteries gives us an important information: even within real-world application requirements (e.g. electrode capacity > 4 mAh cm-2), using polymer with excellent mechanical properties as a separator still can suppress the growth of zinc dendrites via the modified mechanical suppression effect. [1] X. Zhang, A. Wang, X. Liu and J. Luo, Acc. Chem. Res., 2019, 52, 3223-3232 Figure 1

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Lin, Gang, Xiaoliang Zhou, Limin Liu, Huangmin Li, Di Huang, Jing Liu, Jie Li, and Zhaohuan Wei. "Performance improvement of aqueous zinc batteries by zinc oxide and Ketjen black co-modified glass fiber separators." RSC Advances 13, no. 10 (2023): 6453–58. http://dx.doi.org/10.1039/d2ra07745k.

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Co-modification of ZnO and KB is effective in improving the electrochemical performance of the cells. When the rate of ZnO and KB equals 6 : 3 in mass, the modified Zn//Zn and Zn//MnO2 showed excellent electrochemical performance.

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Madej, E., M. Espig, R. R. Baumann, W. Schuhmann, and F. La Mantia. "Optimization of primary printed batteries based on Zn/MnO2." Journal of Power Sources 261 (September 2014): 356–62. http://dx.doi.org/10.1016/j.jpowsour.2014.03.103.

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Li, Yun, Shanyu Wang, James R. Salvador, Jinpeng Wu, Bo Liu, Wanli Yang, Jiong Yang, Wenqing Zhang, Jun Liu, and Jihui Yang. "Reaction Mechanisms for Long-Life Rechargeable Zn/MnO2 Batteries." Chemistry of Materials 31, no. 6 (February 22, 2019): 2036–47. http://dx.doi.org/10.1021/acs.chemmater.8b05093.

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Noh, Jun Ho, Myoungeun Oh, Sunjin Kang, Hyeong Seok Lee, Yeong Jun Hong, Chaeyeon Park, Raeyun Lee, and Changsoon Choi. "Wearable and Washable MnO2−Zn Battery Packaged by Vacuum Sealing." Nanomaterials 13, no. 2 (January 7, 2023): 265. http://dx.doi.org/10.3390/nano13020265.

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Batteries are used in all types of electronic devices from conventional to advanced devices. Currently, batteries are evolving in the direction of extremely personalized yarn− or textile−structured textronic systems. However, the absence of a protective layer on such batteries is a critical limitation to their practical use. In this study, we developed a wearable and washable MnO2−Zn textile battery that maintains its electrochemical capacity under various external environmental conditions through a vacuum−sealed packaging. The packaged textile battery was fabricated by vacuuming a polymer envelope containing the battery, followed by heat sealing with a vacuum packaging machine. The interior and exterior regions of the textile battery are completely separated by the packaging sheath to preclude leakage and intrusion of substances. The resulting packaged textile battery exhibits stable capacity retention performance under varying temperature and humidity; mechanical deformations due to bending, twisting, rubbing, and pressing; and several mechanical, chemical, and their combined washing cycles. On the basis of these demonstrations, we expect that our vacuum−packaged textile battery will offer new possibilities for practical and convenient use of textronics.

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Yeşiltepe, Selçuk, Mehmet Buğdaycı, Onuralp Yücel, and Mustafa Şeşen. "Recycling of Alkaline Batteries via a Carbothermal Reduction Process." Batteries 5, no. 1 (March 19, 2019): 35. http://dx.doi.org/10.3390/batteries5010035.

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Primary battery recycling has important environmental and economic benefits. According to battery sales worldwide, the most used battery type is alkaline batteries with 75% of market share due to having a higher performance than other primary batteries such as Zn–MnO2. In this study, carbothermal reduction for zinc oxide from battery waste was completed for both vacuum and Ar atmospheres. Thermodynamic data are evaluated for vacuum and Ar atmosphere reduction reactions and results for Zn reduction/evaporation are compared via the FactSage program. Zn vapor and manganese oxide were obtained as products. Zn vapor was re-oxidized in end products; manganese monoxide and steel container of batteries are evaluated as ferromanganese raw material. Effects of carbon source, vacuum, temperature and time were studied. The results show a recovery of 95.1% Zn by implementing a product at 1150 °C for 1 h without using the vacuum. The residues were characterized by Atomic Absorption Spectrometer (AAS) and X-ray Diffraction (XRD) methods.

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Liao, Yanxin, Chun Yang, Qimeng Xu, Wenxuan Zhao, Jingwen Zhao, Kuikui Wang, and Hai-Chao Chen. "Ag-Doping Effect on MnO2 Cathodes for Flexible Quasi-Solid-State Zinc-Ion Batteries." Batteries 8, no. 12 (December 2, 2022): 267. http://dx.doi.org/10.3390/batteries8120267.

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Rechargeable aqueous Zn/MnO2 batteries are very potential for large-scale energy storage applications owing to their low cost, inherent safety, and high theoretical capacity. However, the MnO2 cathode delivers unsatisfactory cycling performance owing to its low intrinsic electronic conductivity and dissolution issue. Herein, we design and synthesize a Ag-doped sea-urchin-like MnO2 material for rechargeable zinc-ion batteries (ZIBs). Doping Ag was found to reduce charge transfer resistance, increase the redox activity, and improve the cycling stability of MnO2. The unique sea-urchin-like structure maintains rich active sites for charge storage. As a result, the Ag-doped MnO2-based ZIB presents a high reversible specific capacity to 315 mA h g−1 at 50 mA g−1, excellent rate performance, and a capacity retention of 94.4% when cycling over 500 cycles. An ex situ TEM test demonstrates the low-dissolution property of Ag-doped MnO2. A flexible quasi-solid-state ZIB is successfully assembled using Ag-doped MnO2 on graphite paper, which shows a stable specific capacity of 171 mA h g−1 at 1 A g−1 when cycled over 600 cycles. Our investigation demonstrates the significant role played by Ag doping in enhancing the ZIB performance of MnO2, and gives some insight into developing advanced active materials by heteroatom doping.

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Journal articles on the topic 'Zn-MnO2 batteries'

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