Conversion‐type materials have been considered as potentially high‐energy‐density alternatives to commercially dominant intercalation‐based electrodes for rechargeable ion batteries and have attracted tremendous research effort to meet the performance for viable energy‐storage technologies. In situ transmission electron microscopy (TEM) has been extensively employed to provide mechanistic insights into understanding the behavior of battery materials. Noticeably, a great portion of previous in situ TEM studies has been focused on conversion‐type materials, but a dedicated review for this group of materials is missing in the literature. Herein, recent developments of in situ TEM techniques for investigation of dynamic phase transformation and associated structural, morphological, and chemical evolutions during conversion reactions with alkali ions in secondary batteries are comprehensively summarized. The materials of interest broadly cover metal oxides, chalcogenides, fluorides, phosphides, nitrides, and silicates with specific emphasis on spinel metal oxides and recently emerged 2D metal chalcogenides. Special focus is placed on the scientific findings that are uniquely obtained by in situ TEM to address fundamental questions and practical issues regarding phase transformation, structural evolution, electrochemical redox, reaction mechanism, kinetics, and degradation. Critical challenges and perspectives are discussed for advancing new knowledge that can bridge the gap between prototype materials and real‐world applications.
Cation-intercalation and conversion-type cathode materials for rechargeable aluminum batteries
The current research on cation-intercalation and conversion-type cathode materials for rechargeable aluminum batteries (RABs) is discussed in this critical review. The experimental evidence for Al 3+ intercalation in transition metal oxides, chalcogenides, MXene, and Prussian blue analogues in both chloroaluminate ionic liquids and aqueous electrolytes is analyzed to identify the true reaction mechanisms. Chevrel phase molybdenum sulfide (Mo 6 S 8 ) is the only proven intercalation material for RABs with unambiguous evidence, different understandings of the Al 3+ intercalation mechanism in Mo 6 S 8 are discussed. For conversion-type cathode materials, the discussion is focused on the conversion mechanism of metal chalcogenides, and the unique reversible oxidation mechanism of sulfur and selenium enabled by the chloroaluminate ionic liquid electrolytes. The reaction mechanisms of organic cathode materials are also discussed.
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- Award ID(s):
- 1751929
- NSF-PAR ID:
- 10318567
- Date Published:
- Journal Name:
- Materials Chemistry Frontiers
- Volume:
- 6
- Issue:
- 3
- ISSN:
- 2052-1537
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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The electronic structure and local coordination of binary (Mo 6 T 8 ) and ternary Chevrel Phases (M x Mo 6 T 8 ) are investigated for a range of metal intercalant and chalcogen compositions. We evaluate differences in the Mo L 3 -edge and K-edge X-ray absorption near edge structure across the suite of chalcogenides M x Mo 6 T 8 (M = Cu, Ni, x = 1–2, T = S, Se, Te), quantifying the effect of compositional and structural modification on electronic structure. Furthermore, we highlight the expansion, contraction, and anisotropy of Mo 6 clusters within these Chevrel Phase frameworks through extended X-ray absorption fine structure analysis. Our results show that metal-to-cluster charge transfer upon intercalation is dominated by the chalcogen acceptors, evidenced by significant changes in their respective X-ray absorption spectra in comparison to relatively unaffected Mo cations. These results explain the effects of metal intercalation on the electronic and local structure of Chevrel Phases across various chalcogen compositions, and aid in rationalizing electron distribution within the structure.more » « less
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The discovery of oxide electronics is of increasing importance today as one of the most promising new technologies and manufacturing processes for a variety of electronic and optoelectronic applications such as next-generation displays, batteries, solar cells, memory devices, and photodetectors[1]. The high potential use seen in oxide electronics is due primarily to their high carrier mobilities and their ability to be fabricated at low temperatures[2]. However, since the majority of oxide semiconductors are n-type oxides, current applications are limited to unipolar devices, eventually developing oxide-based bipolar devices such as p-n diodes and complementary metal-oxide semiconductors. We have contributed to a wide range of oxide semiconductors and their electronics and optoelectronic device applications. Particularly, we have demonstrated n-type oxide-based thin film transistors (TFT), integrating In 2 O 3 -based n-type oxide semiconductors from binary cation materials to ternary cation species including InZnO, InGaZnO (IGZO), and InAlZnO. We have suggested channel/metallization contact strategies to achieve stable and high TFT performance[3, 4], identified vacancy-based native defect doping mechanisms[5], suggested interfacial buffer layers to promote charge injection capability[6], and established the role of third cation species on the carrier generation and carrier transport[7]. More recently, we have reported facile manufacturing of p-type SnOx through reactive magnetron sputtering from a Sn metal target[8]. The fabricated p-SnOx was found to be devoid of metallic phase of Sn from x-ray photoelectron spectroscopy and demonstrated stable performance in a fully oxide-based p-n heterojunction together with n-InGaZnO. The oxide-based p-n junctions exhibited a high rectification ratio greater than 10 3 at ±3 V, a low saturation current of ~2x10 -10 , and a small turn-on voltage of -0.5 V. In this presentation, we review recent achievements and still remaining issues in transition metal oxide semiconductors and their device applications, in particular, bipolar applications including p-n heterostructures and complementary metal-oxide-semiconductor devices as well as single polarity devices such as TFTs and memristors. In addition, the fundamental mechanisms of carrier transport behaviors and doping mechanisms that govern the performance of these oxide-based devices will also be discussed. ACKNOWLEDGMENT This work was 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. 20011028) by KRISS. K.N. was supported by Basic Science Research Program (NRF-2021R11A1A01051246) through the NRF Korea funded by the Ministry of Education. REFERENCES [1] K. Nomura et al. , Nature, vol. 432, no. 7016, pp. 488-492, Nov 25 2004. [2] D. C. Paine et al. , Thin Solid Films, vol. 516, no. 17, pp. 5894-5898, Jul 1 2008. [3] S. Lee et al. , Journal of Applied Physics, vol. 109, no. 6, p. 063702, Mar 15 2011, Art. no. 063702. [4] S. Lee et al. , Applied Physics Letters, vol. 104, no. 25, p. 252103, 2014. [5] S. Lee et al. , Applied Physics Letters, vol. 102, no. 5, p. 052101, Feb 4 2013, Art. no. 052101. [6] M. Liu et al. , ACS Applied Electronic Materials, vol. 3, no. 6, pp. 2703-2711, 2021/06/22 2021. [7] A. Reed et al. , Journal of Materials Chemistry C, 10.1039/D0TC02655G vol. 8, no. 39, pp. 13798-13810, 2020. [8] D. H. Lee et al. , ACS Applied Materials & Interfaces, vol. 13, no. 46, pp. 55676-55686, 2021/11/24 2021.more » « less
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Abstract Herein, a self‐charging mechanism of rechargeable aluminum (Al) batteries with Chevrel phase molybdenum sulfide (Mo6S8) cathode is reported. The results unambiguously reveal that the self‐charging is a spontaneous disproportionation of Al intercalated Mo6S8originated from the dynamic shift of Al between occupied sites during Al intercalating and resting. The theoretical study indicates that the fully Al intercalated Mo6S8in the format of Al4/3Mo6S8is kinetically accessible driven by electrochemical overpotential but thermodynamically unstable due to the repulsion between Al3+cations. This mechanism is a true self‐charging with no input of any form of energy, thus distinctly superior to the previously reported self‐charging mechanisms. Based on this discovery, a semi‐flow AlMo6S8battery is designed and demonstrated with long‐lasting discharge capability and high capacity.
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Because of the increasing demand, high-power, high-rate energy storage devices based on electrode materials have attracted immense attention. However, challenges remain to be addressed to improve the concentration-dependent kinetics of ionic diffusion and understand phase transformation, interfacial reactions, and capacitive behaviors that vary with particle morphology and scanning rates. It is valuable to understand the microscopic origins of ion transport in electrode materials. In this review, we discuss the microscopic transport phenomena and their dependence on ion concentration in the cathode materials, by comparing dozens of well-studied transition metal oxides, sulfides, and phosphates, and in the anode materials, including several carbon species and carbides. We generalize the kinetic effects on the microscopic ionic transport processes from the phenomenological points of view based on the well-studied systems. The dominant kinetic effects on ion diffusion varied with ion concentration, and the pathway- and morphology-dependent diffusion and capacitive behaviors affected by the sizes and boundaries of particles are demonstrated. The important kinetic effects on ion transport by phase transformation, transferred electrons, and water molecules are discussed. The results are expected to shed light on the microscopic limiting factors of charging/discharging rates for developing new intercalation and conversion reaction systems.more » « less
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/d1qm01267c
