Mg6MnO8 as a Magnesium-Ion Battery Material: Defects, Dopants and Mg-Ion Transport

Kuganathan, Navaratnarajah; Gkanas, Evangelos I.; Chroneos, Alexander

doi:10.3390/en12173213

Cited by 10 publications

(9 citation statements)

References 51 publications

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“…The experimental observation of diffusion pathways and their energetics is challenging. In that respect, computational modelling has been useful in providing valuable information on migration pathways and their activation energies [44][45][46][47][48]. We identified two Ca local hops (A and B), as shown in Figure 2.…”

Section: Calcium Ion Diffusionmentioning

confidence: 99%

Defects and Dopants in CaFeSi2O6: Classical and DFT Simulations

Kuganathan

Chroneos

2020

Energies

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Calcium (Ca)-bearing minerals are of interest for the design of electrode materials required for rechargeable Ca-ion batteries. Here we use classical simulations to examine defect, dopant and transport properties of CaFeSi2O6. The formation of Ca-iron (Fe) anti-site defects is found to be the lowest energy process (0.42 eV/defect). The Oxygen and Calcium Frenkel energies are 2.87 eV/defect and 4.96 eV/defect respectively suggesting that these defects are not significant especially the Ca Frenkel. Reaction energy for the loss of CaO via CaO Schottky is 2.97 eV/defect suggesting that this process requires moderate temperature. Calculated activation energy of Ca-ion migration in this material is high (>4 eV), inferring very slow ionic conductivity. However, we suggest a strategy to introduce additional Ca2+ ions in the lattice by doping trivalent dopants on the Si site in order to enhance the capacity and ion diffusion and it is calculated that Al3+ is the favourable dopant for this process. Formation of Ca vacancies required for the CaO Schottky can be facilitated by doping of gallium (Ga) on the Fe site. The electronic structures of favourable dopants were calculated using density functional theory (DFT).

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Section: Calcium Ion Diffusionmentioning

confidence: 99%

Defects and Dopants in CaFeSi2O6: Classical and DFT Simulations

Kuganathan

Chroneos

2020

Energies

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“…In addition to manganese dioxide, other manganese oxides such as, MnO, Mn 2 O 3 , Mn-based perovskites [142] and the various oxide derivatives (e.g., Mg 6 MnO 8 , [143] Ca 2 MnO 4 [144] ) have also been studied in rechargeable battery systems. Research regarding MnO mainly focuses on SIBs.…”

Section: Other Mn-based Oxidesmentioning

confidence: 99%

Manganese‐Based Materials for Rechargeable Batteries beyond Lithium‐Ion

Zhang

Sun

et al. 2021

Advanced Energy Materials

109

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etc., is essentially crucial to help combat these hazards and build a sustainable society. Among them, rechargeable battery has been regarded as a key technology. In the past decade, we have witnessed that the prevailing lithium-ion batteries (LIBs) made our society more portable, intelligent, and cleaner. [17][18][19] Nevertheless, the limited lithium resources and rising cost hinder their applications in the long run, especially in the field of large-scale stationary energy storage for renewable energy resources (e.g., solar, tide, and wind power). Thus, it is a huge stimulus for researchers to explore more sustainable rechargeable battery systems, which are expected to involve abundant and nontoxic metals to reduce the cost and impacts on environment.Diversified rechargeable batteries such as, the monovalent sodium-ion batteries (SIBs), [20][21][22][23][24] potassium-ion batteries (PIBs), [25][26][27] bivalent zinc-ion batteries (ZIBs), [28][29][30][31] magnesium-ion batteries (MIBs), [32][33][34][35] calcium-ion batteries (CIBs), [36][37][38][39] and trivalent aluminum-ion batteries (AIBs), [40][41][42] have emerged and shown great energy storage promise. As depicted in Figure 1a, those nonlithium metals are much more abundant than Li, especially Al, Ca, Na, K, and Mg, all of which rank the top-8 abundant elements in earth crust. For SIBs and PIBs, since Al would not form alloys with Na and K, Al foil can be used as anode collector, which further lowers the prices of SIBs and PIBs. On the other hand, the higher standard potential of Na/Na + (−2.71 V vs standard hydrogen electrode, SHE) and K/K + (−2.93 V) and their heavier atomic weights make energy densities of SIBs and PIBs intrinsically lower than that of LIBs. For multivalent-ion batteries, the multielectron transfer enables their volumetric capacities (e.g., 5857 and 8056 mA h cm −3 for Zn and Al, respectively) higher than that of Li (2042 mA h cm −3 ). [43,44] Additionally, the small cation radius of Zn 2+ (0.74 Å), Mg 2+ (0.72 Å), and Al 3+ (0.54 Å) indicate that many intercalation electrode materials typical in LIBs may be also potential hosts for reversible intercalation of these multivalent ions. Combining all the above merits, one can anticipate that these emerging rechargeable batteries would be considered as promising alternatives to LIBs.In quest of safe, cost-effective, and high-performance rechargeable batteries, two technical routes have been

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“…Si and Si � Al Þ are not stable and they aggregate to form clusters (Al 0 Si : Si � Al ) X without an energy penalty. In many oxide materials, the anti-site defect has been identified experimentally and theoretically [38][39][40][41]. The O Frenkel is identified as the second most favorable defect energy process.…”

Section: Si Andsi �mentioning

confidence: 99%

Defects, diffusion and dopants in the ceramic mineral “Lime- Feldspar”

Suthaharan

Iyngaran

Kuganathan

et al. 2021

Journal of Asian Ceramic Societies

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Calcium aluminosilicate, CaAl 2 Si 2 O 8 , is a promising ceramic material that has found applications in several areas, such as glass production and petrology. Atomistic scale simulation techniques are used to study the intrinsic defects, Ca-ion migration paths and doping behavior in CaAl 2 Si 2 O 8 . The most favorable defect is the Al-Si anti-site in agreement with the experimental observation. The O-Frenkel is the second most favorable defect. The Ca-Frenkel is higher in energy only by 0.62 eV than the O-Frenkel. Long-range Ca-ion migration is observed in the ac plane with the activation energy of 2.84 eV suggesting that Ca-ion diffusion in this material is slow. The prominent isovalent dopant on the Ca site is the Sr, which was experimentally substituted on the Ca site to prevent phase transformation. The formation of Ca interstitials and oxygen vacancies is favored by Fe 3+ doping on the Si site. The favorable tetravalent dopant on the Si site and the Al site to form Ca vacancies is the Ge.

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Mg6MnO8 as a Magnesium-Ion Battery Material: Defects, Dopants and Mg-Ion Transport

Cited by 10 publications

References 51 publications

Defects and Dopants in CaFeSi2O6: Classical and DFT Simulations

Defects and Dopants in CaFeSi2O6: Classical and DFT Simulations

Manganese‐Based Materials for Rechargeable Batteries beyond Lithium‐Ion

Defects, diffusion and dopants in the ceramic mineral “Lime- Feldspar”

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