A Cubic Mg2MnO4 Cathode for non-aqueous Magnesium Batteries

Ruiz, Rafaela; Vicente, C.; Rubio, Soledad; Stoyanova, Radostina; Zuo, Wenhua; Yang, Yong; Ortiz, Gregório F.

doi:10.1016/j.ensm.2022.02.047

Cited by 20 publications

(7 citation statements)

References 46 publications

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“…The electrolyte was 0.5 m Mg(TFSI) 2 (with 16% of water content) in DME (dimethoxymethane) as electrolyte as previously reported. [13,14] The cells were tested under controlled temperature between 25-27 °C. The Mg-cells and Na-cells were recorded at 5 mA g −1 .…”

Section: Methodsmentioning

confidence: 99%

“…The full extraction of Mg from the ordered (Mg) M1 (Mn) M2 SiO 4 phase takes place in two steps, at ≈4.0 and 3.0 V formally involving the multi-electron redox reactions of Mn 4+ /Mn 3+ and Mn 3+ /Mn 2+ redox pairs, respectively. [12][13][14] The extraction of Mg from M1 site with a Mg/Mn exchange of y = 0.25, that is, (Mg 0.75 Mn 0.25 ) M1 (Mg 0.25 Mn 0.75 ) M2 SiO 4 has been also carefully computed. In a first step, 0.50 Mg 2+ ions are extracted at 2.92 V, formally involving the Mn 3+ /Mn 2+ redox pair.…”

Section: Introductionmentioning

confidence: 99%

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Olivine‐Type MgMn_0.5Zn_0.5SiO₄ Cathode for Mg‐Batteries: Experimental Studies and First Principles Calculations

Vicente

Rubio

Ruiz

et al. 2023

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model to unveil enhanced reactions in lithium and magnesium battery fields. [2,3] One of the main limitations of the LFP is the limited capacity for one electron reaction and thus its energy density cannot get over to that of layered oxides. Therefore, alternative silicates with Li 2 MSiO 4 (M = Mn, Fe, Co, Ni) stoichiometry are currently studied due to the high theoretical capacity of 333 mA h g −1 . [4,5] Additionally, the redox potential should be successfully monitored by the redox (≈manganese) active species. Importantly, the main instabilities caused in the original Mn-tetrahedral environments, structural amorphization during alkali metal extraction and structural distortions should be abated. [5] This study compares different manganese silicates with Mn in octahedral environment to avoid the instabilities of Mn in tetrahedral sites. Specifically, MgMnSiO 4 is used as a model which has an olivine-type structure (similar to LFP) where Mg atoms occupy the so-called M1 site (as Li in LFP) while Mn atoms occupy the M2 site (Fe in LFP) (Scheme 1). The chemical formulation is thus (Mg) M1 (Mn) M2 SiO 4 . [6,7] Additionally, the comprehensive exchange of Mg and Mn in their respective sites gives the following cation distribution: (Mg 1-y Mn y ) M1 (Mg y Mn 1-y ) M2 SiO 4 , being the degree of exchange dependent on the sample thermal history. [8,9] This work aims to determine the structure and Mg extraction/insertion properties from/into (Mg) M1 (Mn 0.5 Zn 0.5 ) M2 SiO 4 . The replacement of half amount of Mn atoms in the octahedral sites by other divalent elements such as Zn 2+ could have an impact on the voltage and the energy density as foreseen by DFT calculations. The calculated voltage during Mg reaction for MgMnSiO 4 is ≈2.9 V, while the higher voltage of ≈3.2 V is obtained in the case of (Mg) M1 (Mn 0.5 M 0.5 ) M2 SiO 4 (M = Ca and Ni). However, the higher atomic weight of Ni penalizes its energy density, as compared with lighter elements such as M = Ca or Mg. The (Mg) M1 (Mn 0.5 Zn 0.5 ) M2 SiO 4 cathode achieves experimentally 120 mA h g −1 with an average voltage of ≈2 V. Results and Discussion Structure and Mg Extraction: Case of MgMnSiO 4The calculated unit cell parameters (a = 10.460( 5) Å, b = 6.134(3) Å, c = 4.817(2) Å, and V = 309.0(2) Å 3 ) from the refined X-ray diffraction (XRD) pattern are in good agreement with previous Magnesium driven reaction in olivine-type MgMn 0.5 Zn 0.5 SiO 4 structure is subject of study by experimental tests and density functional theory (DFT) calculations. The partial replacement of Mn in Oh sites by other divalent metal such as Zn to get MgMn 0.5 Zn 0.5 SiO 4 cathode is successfully developed by a simple sol-gel method. Its comparison with the well-known MgMnSiO 4 olivine-type structure with (Mg) M1 (Mn) M2 SiO 4 cations distribution serves as the basis of this study to understand the structure, and the magnesium extraction/insertion properties of novel olivine-type (Mg) M1 (Mn 0.5 Zn 0.5 ) M2 SiO 4 composition. This work foresees to extend the study to others dival...

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Olivine‐Type MgMn_0.5Zn_0.5SiO₄ Cathode for Mg‐Batteries: Experimental Studies and First Principles Calculations

Vicente

Rubio

Ruiz

et al. 2023

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“…Spinel Mn-based oxides show great structural stability and have been widely applied in LIBs, MIBs [60,61], and so on. LiMn 2 O 4 and LiNi 0.5 Mn 1.5 O 4 are, at present, the main spinel Mn-based oxides for lithium batteries.…”

Section: Spinel Mn-based Oxidesmentioning

confidence: 99%

Low-Cost Mn-Based Cathode Materials for Lithium-Ion Batteries

Yi¹,

Liang

Qian³

et al. 2023

Batteries

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Due to a high energy density and satisfactory longevity, lithium-ion batteries (LIBs) have been widely applied in the fields of consumer electronics and electric vehicles. Cathodes, an essential part of LIBs, greatly determine the energy density and total cost of LIBs. In order to make LIBs more competitive, it is urgent to develop low-cost commercial cathode materials. Among all cathode materials, Mn-based cathode materials, such as layered LiNi0.5Mn0.5O2 and Li-rich materials, spinel LiMn2O4 and LiNi0.5Mn1.5O4, olivine-type LiMnPO4 and LiMn0.5Fe0.5PO4, stand out owing to their low cost and high energy density. Herein, from the perspective of industrial application, we calculate the product cost of Mn-based cathode materials, select promising candidates with low cost per Wh, and summarize the structural and electrochemical properties and improvement strategies of these low-cost Mn-based cathode materials. Apart from some common issues for Mn-based cathode materials, such as Jahn–Teller distortions and Mn dissolution, we point out the specific problems of each material and provide corresponding improvement strategies to overcome these drawbacks.

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“…(d) Long-term cyclic stability at 0.5 A g –1 . (e) Electrochemical performance comparison with other rechargeable Mg batteries, including nonaqueous Mg metal batteries (NAMMB) and aqueous Mg-ion batteries (AMIB). ,,− This work is the only aqueous Mg metal battery (AMMB) reported to date.…”

Section: (De-)intercalation Of Mg2+ In the Cuhcf Cathodementioning

confidence: 99%

Reversibility of a High-Voltage, Cl^–-Regulated, Aqueous Mg Metal Battery Enabled by a Water-in-Salt Electrolyte

et al. 2022

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Rechargeable Mg batteries are a promising post-Li-ion battery technology, but their development has been critically hampered by the passivating nature of Mg, particularly in aqueous solutions. Due to a quick dismissal of its reversibility, the use of Mg anodes in aqueous electrolytes has been overlooked, and most researchers focus on nonaqueous systems instead. In this work, reversible, aqueous Mg battery chemistry has been realized for the first time, via the conversion of its impermeable passivation film to a conductive metallic oxide complex, facilitated by Cl– regulation and the suppression of the hydrogen evolution reaction using a MgCl2 water-in-salt (WIS) electrolyte. When coupled with copper hexacyanoferrate as the cathode, the full battery exhibits an impressive voltage plateau of 2.4–2.0 V and a stability of over 700 cycles with a Coulombic efficiency of up to 99% at 0.5 A g–1. Mg dissolution and deposition have proven reversible in the aqueous MgCl2 WIS electrolyte.

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A Cubic Mg2MnO4 Cathode for non-aqueous Magnesium Batteries

Cited by 20 publications

References 46 publications

Olivine‐Type MgMn_0.5Zn_0.5SiO₄ Cathode for Mg‐Batteries: Experimental Studies and First Principles Calculations

Olivine‐Type MgMn_0.5Zn_0.5SiO₄ Cathode for Mg‐Batteries: Experimental Studies and First Principles Calculations

Low-Cost Mn-Based Cathode Materials for Lithium-Ion Batteries

Reversibility of a High-Voltage, Cl^–-Regulated, Aqueous Mg Metal Battery Enabled by a Water-in-Salt Electrolyte

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A Cubic Mg2MnO4 Cathode for non-aqueous Magnesium Batteries

Cited by 20 publications

References 46 publications

Olivine‐Type MgMn0.5Zn0.5SiO4 Cathode for Mg‐Batteries: Experimental Studies and First Principles Calculations

Olivine‐Type MgMn0.5Zn0.5SiO4 Cathode for Mg‐Batteries: Experimental Studies and First Principles Calculations

Low-Cost Mn-Based Cathode Materials for Lithium-Ion Batteries

Reversibility of a High-Voltage, Cl–-Regulated, Aqueous Mg Metal Battery Enabled by a Water-in-Salt Electrolyte

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Product

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Olivine‐Type MgMn_0.5Zn_0.5SiO₄ Cathode for Mg‐Batteries: Experimental Studies and First Principles Calculations

Olivine‐Type MgMn_0.5Zn_0.5SiO₄ Cathode for Mg‐Batteries: Experimental Studies and First Principles Calculations

Reversibility of a High-Voltage, Cl^–-Regulated, Aqueous Mg Metal Battery Enabled by a Water-in-Salt Electrolyte