The morphology and crystallinity of electrode materials have a major effect on their charge carrier storage properties when applied in rechargeable batteries. While nanosizing electrode particles (with larger surface area) and maintaining electrode integrity are both good for performance enhancement, they seem to contradict each other and are challenging to balanced. Herein, electrode particles consisting of numerous nanograins with uniform crystalline orientation are designed to guarantee both high surface area and high structural integrity, allowing the significant improvement of Li+storage kinetics and performance. Applying this “mesocrystallizing” strategy to an NiCo2O4‐based anode, results in various degrees of pseudocapacitance response, the long‐term cyclability and rate performance of this material are also significantly enhanced. Impressively, the mesocrystalline NiCo2O4electrode exhibits a high specific capacity of 1403 mAh g–1after 200 cycles at 1.6 A g–1(a rate of 1.8 C). The growth mechanism of mesocrystalline materials with different morphologies is identified to be a topotactic structural transition process featuring a gradual edge‐to‐core corrosion process. This work presents an important synthetic clue to balance the morphology and crystallinity of battery electrode materials for their performance optimization and is expected to inspire future structural design for battery materials beyond the one prototyped here.
Relating the synthesis conditions of materials to their functional performance has long been an experience‐based trial‐and‐error process. However, this methodology is not always efficient in identifying an appropriate protocol and can lead to overlooked opportunities for the performance optimization of materials through simple modifications of the synthesis process. In this work, the authors systematically track the structural evolution in the synthesis of a representative disordered rock salt (a promising next‐generation Li‐ion cathode material) at the scale of both the long‐range crystal structure and the short‐range atomic structure using various in situ and ex situ techniques, including transmission electron microscopy, X‐ray diffraction, and pair distribution function analysis. An optimization strategy is proposed for the synthesis protocol, leading to a remarkably enhanced capacity (specific energy) of 313 mAh g−1(987 Wh kg−1) at a low rate (20 mA g−1), with a capacity of more than 140 mAh g−1retained even at a very high cycling rate of 2000 mA g−1. This strategy is further rationalized using ab initio calculations, and important opportunities for synthetic optimization demonstrated in this study are highlighted.
more » « less- NSF-PAR ID:
- 10445032
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Energy Materials
- Volume:
- 12
- Issue:
- 21
- ISSN:
- 1614-6832
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Ever-increasing demands for energy, particularly being environmentally friendly have promoted the transition from fossil fuels to renewable energy.1Lithium-ion batteries (LIBs), arguably the most well-studied energy storage system, have dominated the energy market since their advent in the 1990s.2However, challenging issues regarding safety, supply of lithium, and high price of lithium resources limit the further advancement of LIBs for large-scale energy storage applications.3Therefore, attention is being concentrated on an alternative electrochemical energy storage device that features high safety, low cost, and long cycle life. Rechargeable aqueous zinc-ion batteries (ZIBs) is considered one of the most promising alternative energy storage systems due to the high theoretical energy and power densities where the multiple electrons (Zn2+) . In addition, aqueous ZIBs are safer due to non-flammable electrolyte (e.g., typically aqueous solution) and can be manufactured since they can be assembled in ambient air conditions.4As an essential component in aqueous Zn-based batteries, the Zn metal anode generally suffers from the growth of dendrites, which would affect battery performance in several ways. Second, the led by the loose structure of Zn dendrite may reduce the coulombic efficiency and shorten the battery lifespan.5
Several approaches were suggested to improve the electrochemical stability of ZIBs, such as implementing an interfacial buffer layer that separates the active Zn from the bulk electrolyte.6However, the and thick thickness of the conventional Zn metal foils remain a critical challenge in this field, which may diminish the energy density of the battery drastically. According to a theretical calculation, the thickness of a Zn metal anode with an areal capacity of 1 mAh cm-2is about 1.7 μm. However, existing extrusion-based fabrication technologies are not capable of downscaling the thickness Zn metal foils below 20 μm.
Herein, we demonstrate a thickness controllable coating approach to fabricate an ultrathin Zn metal anode as well as a thin dielectric oxide separator. First, a 1.7 μm Zn layer was uniformly thermally evaporated onto a Cu foil. Then, Al2O3, the separator was deposited through sputtering on the Zn layer to a thickness of 10 nm. The inert and high hardness Al2O3layer is expected to lower the polarization and restrain the growth of Zn dendrites. Atomic force microscopy was employed to evaluate the roughness of the surface of the deposited Zn and Al2O3/Zn anode structures. Long-term cycling stability was gauged under the symmetrical cells at 0.5 mA cm-2for 1 mAh cm-2. Then the fabricated Zn anode was paired with MnO2as a full cell for further electrochemical performance testing. To investigate the evolution of the interface between the Zn anode and the electrolyte, a home-developed in-situ optical observation battery cage was employed to record and compare the process of Zn deposition on the anodes of the Al2O3/Zn (demonstrated in this study) and the procured thick Zn anode. The surface morphology of the two Zn anodes after circulation was characterized and compared through scanning electron microscopy. The tunable ultrathin Zn metal anode with enhanced anode stability provides a pathway for future high-energy-density Zn-ion batteries.
Obama, B., The irreversible momentum of clean energy.
Science 2017, 355 (6321), 126-129.Goodenough, J. B.; Park, K. S., The Li-ion rechargeable battery: a perspective.
J Am Chem Soc 2013, 135 (4), 1167-76.Li, C.; Xie, X.; Liang, S.; Zhou, J., Issues and Future Perspective on Zinc Metal Anode for Rechargeable Aqueous Zinc‐ion Batteries.
Energy & Environmental Materials 2020, 3 (2), 146-159.Jia, H.; Wang, Z.; Tawiah, B.; Wang, Y.; Chan, C.-Y.; Fei, B.; Pan, F., Recent advances in zinc anodes for high-performance aqueous Zn-ion batteries.
Nano Energy 2020, 70 .Yang, J.; Yin, B.; Sun, Y.; Pan, H.; Sun, W.; Jia, B.; Zhang, S.; Ma, T., Zinc Anode for Mild Aqueous Zinc-Ion Batteries: Challenges, Strategies, and Perspectives.
Nanomicro Lett 2022, 14 (1), 42.Yang, Q.; Li, Q.; Liu, Z.; Wang, D.; Guo, Y.; Li, X.; Tang, Y.; Li, H.; Dong, B.; Zhi, C., Dendrites in Zn-Based Batteries.
Adv Mater 2020, 32 (48), e2001854.Acknowledgment
This work was partially supported by the U.S. National Science Foundation (NSF) Award No. ECCS-1931088. S.L. and H.W.S. acknowledge the support from the Improvement of Measurement Standards and Technology for Mechanical Metrology (Grant No. 22011044) by KRISS.
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Abstract Despite the advantages of aqueous zinc (Zn) metal batteries (AZMB) like high specific capacity (820 mAh g−1and 5,854 mAh cm−3), low redox potential (−0.76 V vs. the standard hydrogen electrode), low cost, water compatibility, and safety, the development of practically relevant batteries is plagued by several issues like unwanted hydrogen evolution reaction (HER), corrosion of Zn substrate (insulating ZnO, Zn(OH)2, Zn(SO4)x(OH)y, Zn(ClO4)x(OH)yetc. passivation layer), and dendrite growth. Controlling and suppressing HER activity strongly correlates with the long‐term cyclability of AZMBs. Therefore, a precise quantitative technique is needed to monitor the real‐time dynamics of hydrogen evolution during Zn electrodeposition. In this study, we quantify hydrogen evolution using in situ electrochemical mass spectrometry (ECMS). This methodology enables us to determine a correction factor for the faradaic efficiency of this system with unmatched precision. For instance, during the electrodeposition of zinc on a copper substrate at a current density of 1.5 mA/cm2for 600 seconds, 0.3 % of the total charge is attributed to HER, while the rest contributes to zinc electrodeposition. At first glance, this may seem like a small fraction, but it can be detrimental to the long‐term cycling performance of AZMBs. Furthermore, our results provide insights into the correlation between HER and the porous morphology of the electrodeposited zinc, unravelling the presence of trapped H2and Zn corrosion during the charging process. Overall, this study sets a platform to accurately determine the faradaic efficiency of Zn electrodeposition and provides a powerful tool for evaluating electrolyte additives, salts, and electrode modifications aimed at enhancing long‐term stability and suppressing the HER in aqueous Zn batteries.
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Abstract Despite the advantages of aqueous zinc (Zn) metal batteries (AZMB) like high specific capacity (820 mAh g−1and 5,854 mAh cm−3), low redox potential (−0.76 V vs. the standard hydrogen electrode), low cost, water compatibility, and safety, the development of practically relevant batteries is plagued by several issues like unwanted hydrogen evolution reaction (HER), corrosion of Zn substrate (insulating ZnO, Zn(OH)2, Zn(SO4)x(OH)y, Zn(ClO4)x(OH)yetc. passivation layer), and dendrite growth. Controlling and suppressing HER activity strongly correlates with the long‐term cyclability of AZMBs. Therefore, a precise quantitative technique is needed to monitor the real‐time dynamics of hydrogen evolution during Zn electrodeposition. In this study, we quantify hydrogen evolution using in situ electrochemical mass spectrometry (ECMS). This methodology enables us to determine a correction factor for the faradaic efficiency of this system with unmatched precision. For instance, during the electrodeposition of zinc on a copper substrate at a current density of 1.5 mA/cm2for 600 seconds, 0.3 % of the total charge is attributed to HER, while the rest contributes to zinc electrodeposition. At first glance, this may seem like a small fraction, but it can be detrimental to the long‐term cycling performance of AZMBs. Furthermore, our results provide insights into the correlation between HER and the porous morphology of the electrodeposited zinc, unravelling the presence of trapped H2and Zn corrosion during the charging process. Overall, this study sets a platform to accurately determine the faradaic efficiency of Zn electrodeposition and provides a powerful tool for evaluating electrolyte additives, salts, and electrode modifications aimed at enhancing long‐term stability and suppressing the HER in aqueous Zn batteries.
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Abstract Organic materials with redox‐active oxygen functional groups are of great interest as electrode materials for alkali‐ion storage due to their earth‐abundant constituents, structural tunability, and enhanced energy storage properties. Herein, a hybrid carbon framework consisting of reduced graphene oxide and oxygen functionalized carbon quantum dots (CQDs) is developed via the one‐pot solvothermal reduction method, and a systematic study is undertaken to investigate its redox mechanism and electrochemical properties with Li‐, Na‐, and K‐ions. Due to the incorporation of CQDs, the hybrid cathode delivers consistent improvements in charge storage performance for the alkali‐ions and impressive reversible capacity (257 mAh g−1at 50 mA g−1), rate capability (111 mAh g−1at 1 A g−1), and cycling stability (79% retention after 10 000 cycles) with Li‐ion. Furthermore, density functional theory calculations uncover the CQD structure‐electrochemical reactivity trends for different alkali‐ion. The results provide important insights into adopting CQD species for optimal alkali‐ion storage.
