This review discusses how halide ion species have been used as charge carriers in both anion rocking‐chair and dual‐ion battery (DIB) systems. The anion rocking‐chair batteries based on fluoride and chloride have emerged over the past decade and are garnering increased research interest due to their large theoretical energy density values and the natural abundance of halide‐containing materials. Moreover, DIBs that use halide species as their anionic charge carrier are seen as one of the promising next‐generation battery technologies due to their low cost and high working potentials. Although numerous polyatomic anions have been studied as charge carriers, the use of single halide ions (i.e., F−and Cl−) and metal‐based superhalides (e.g., [MgCl3]−) as anionic charge carriers in DIBs has been considerably less explored. Herein, we provide an overview of some of the key advances and recent progress that has been made with regard to halide ion charge carriers in electrochemical energy storage. We offer our perspectives on the current state of the field and provide a roadmap in hopes that it helps researchers toward making new advances in these promising and emerging areas.
Although lithium-ion batteries have transformed energy storage, there is a need to develop battery technologies with improved performance. Fluoride-ion batteries (FIBs) may be promising alternatives in part due to their high theoretical energy density and natural elemental abundance. However, electrode materials for FIBs, particularly cathodes, have not been systematically evaluated, limiting rapid progress. Here, we evaluate ternary fluorides from the Materials Project crystal structure database to identify promising cathode materials for FIBs. Structures are further assessed based on stability and whether fluorination/defluorination occurs without unwanted disproportionation reactions. Properties are presented for pairs of fluorinated/defluorinated materials including theoretical energy densities, cost approximations, and bandgaps. We aim to supply a dataset for extracting property and structural trends of ternary fluoride materials that may aid in the discovery of next-generation battery materials.
more » « less- NSF-PAR ID:
- 10396556
- Publisher / Repository:
- Nature Publishing Group
- Date Published:
- Journal Name:
- Scientific Data
- Volume:
- 10
- Issue:
- 1
- ISSN:
- 2052-4463
- 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.
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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 Fluoride–ion batteries are a promising alternative to lithium–ion batteries with higher theoretical capacities and working voltages, but they have experienced limited success due to the poor ionic conductivities of known electrolytes and electrodes. Here, we report a high-throughput computational screening of 9747 fluoride-containing materials in search of fluoride-ion conductors. Via a combination of empirical, lightweight DFT, and nudged elastic band (NEB) calculations, we identified >10 crystal systems with high fluoride mobility. We applied a search strategy where calculations are performed in any order (decoupled), computational resources are reassigned based on need (dynamic), and predictive models are repeatedly updated (iterative). Unlike hierarchical searches, our decoupled, dynamic, and iterative framework (DDI) began by calculating high-quality barrier heights for fluoride-ion mobility in a large and diverse group of materials. This high-quality dataset provided a benchmark against which a rapid calculation method could be refined. This accurate method was then used to measure the barrier heights for 6797 fluoride–ion pathways. The final dataset has allowed us to discover many fascinating, high-performance conductors and to derive the design rules that govern their performance. These materials will accelerate experimental research into fluoride–ion batteries, while the design rules will provide an improved foundation for understanding ionic conduction.
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