Redox properties of alluaudite sodium cobalt manganese sulfates as high-voltage electrodes for rechargeable batteries

Marinova, D.; Kostov, V; Nikolova, Rositsa; Kukeva, R R; Zhecheva, E.; Stoyanova, Р.

doi:10.1039/c8cc01922c

Cited by 13 publications

(3 citation statements)

References 19 publications

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“…When Mn 2+ ions in Na 2+ δ Mn 2‐ δ /2 (SO 4 ) 3 are replaced with Co 2+ ions to form Na 2+ δ ( Co x Mn 1‐x ) 2‐ δ /2 (SO 4 ) 3 solid solutions, the operating potential increases above 4.7 V vs . Li/Li + couple . The high‐voltage operation of the Na 2+ δ ( Co x Mn 1‐x ) 2‐ δ /2 (SO 4 ) 3 alluaudite salt is related with reduced cationic deficiency on the 8 f alluaudite site, with redox properties of Co 2+ and Mn 2+ and stability of the alluaudite structure during Li + /Na + migration .…”

Section: Structural Matrices Suitable For Li+ Na+ and Mg2+ Intercalamentioning

confidence: 99%

“…Li/Li + couple . The high‐voltage operation of the Na 2+ δ ( Co x Mn 1‐x ) 2‐ δ /2 (SO 4 ) 3 alluaudite salt is related with reduced cationic deficiency on the 8 f alluaudite site, with redox properties of Co 2+ and Mn 2+ and stability of the alluaudite structure during Li + /Na + migration . Contrary to Co−Mn alluaudite solid solutions, the mixed sodium nickel‐manganese sulfates, Na 2 Ni x Mn 1‐x (SO 4 ) 2 , crystallizes in a large monoclinic unit cell, in which Ni x Mn 1‐x O 6 octahedra are bridged into pairs by edge‐ and corner sharing SO 4 2− groups .…”

Section: Structural Matrices Suitable For Li+ Na+ and Mg2+ Intercalamentioning

confidence: 99%

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Lithium versus Mono/Polyvalent Ion Intercalation: Hybrid Metal Ion Systems for Energy Storage

Stoyanova

Koleva

2018

The Chemical Record

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The energy storage by redox intercalation reactions is, nowadays, the most effective rechargeable ion battery. When lithium is used as intercalating agents, the high energy density is achieved at an expense of non-sustainability. The replacement of Li with cheaper monovalent ions enables to make greener battery alternatives. The utilization of polyvalent ions instead of Li permits to multiplying the battery capacity. Contrary to Li , the realization of quick and reversible intercalation of bigger monovalent and of polyvalent ions is a scientific challenge due to kinetic constraints, polarizing ion effects and Coulomb interactions. Herein we provide a vision how to make the intercalation of these ions feasible. The idea is to perform dual intercalation of ions having different charges, radii, preferred coordination and diffusion pathway topology. All these features are demonstrated by the recent knowledge on selective and non-selective intercalation properties of oxides and polyanion compounds with layered and tunnel structures. Based on dual intercalation properties, the fabrication of hybrid metal ion batteries is presented and discussed.

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Section: Structural Matrices Suitable For Li+ Na+ and Mg2+ Intercalamentioning

confidence: 99%

Section: Structural Matrices Suitable For Li+ Na+ and Mg2+ Intercalamentioning

confidence: 99%

Lithium versus Mono/Polyvalent Ion Intercalation: Hybrid Metal Ion Systems for Energy Storage

Stoyanova

Koleva

2018

The Chemical Record

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“…In the sodium family, several types of structures that are suitable for alkali intercalation have been identified depending on the ratio between sodium and transition metal ions: Na 2+2δ Fe/Mn 2−δ (SO 4 ) 3 with an alluaudite structure (SG C 2/ c ) [ 7 , 8 , 9 , 10 ]; eldfellite NaFe(SO 4 ) 2 with a layered structure [ 11 ]; Na 2 Mn 3 (SO 4 ) 4 with an orthorhombic structure (SG Cmc 21) [ 12 ]; Na 2 Fe(SO 4 ) 2 isostructural to α-Na 2 Co(SO4) 2 [ 13 ]; kröhnkite-type structure Na 2 Fe(SO 4 ) 2 ·2H 2 O [ 14 , 15 ]. The best electrochemical performance is observed for alluaudite Na 2+2δ Fe/Mn 2−δ (SO 4 ) 3 , whose potential of alkali intercalation increases after the replacement of Fe/Mn with cobalt or nickel ions [ 16 , 17 , 18 ]. Although Na 2 M 2 (SO 4 ) 3 adopts an alluaudite type of structure, the lithium analogues Li 2 M 2 (SO 4 ) 3 possess different crystal structures and electrochemical activities [ 19 ].…”

Section: Introductionmentioning

confidence: 99%

Lithium Manganese Sulfates as a New Class of Supercapattery Materials at Elevated Temperatures

et al. 2023

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To make supercapattery devices feasible, there is an urgent need to find electrode materials that exhibit a hybrid mechanism of energy storage. Herein, we provide a first report on the capability of lithium manganese sulfates to be used as supercapattery materials at elevated temperatures. Two compositions are studied: monoclinic Li2Mn(SO4)2 and orthorhombic Li2Mn2(SO4)3, which are prepared by a freeze-drying method followed by heat treatment at 500 °C. The electrochemical performance of sulfate electrodes is evaluated in lithium-ion cells using two types of electrolytes: conventional carbonate-based electrolytes and ionic liquid IL ones. The electrochemical measurements are carried out in the temperature range of 20–60 °C. The stability of sulfate electrodes after cycling is monitored by in-situ Raman spectroscopy and ex-situ XRD and TEM analysis. It is found that sulfate salts store Li+ by a hybrid mechanism that depends on the kind of electrolyte used and the recording temperature. Li2Mn(SO4)2 outperforms Li2Mn2(SO4)3 and displays excellent electrochemical properties at elevated temperatures: at 60 °C, the energy density reaches 280 Wh/kg at a power density of 11,000 W/kg. During cell cycling, there is a transformation of the Li-rich salt, Li2Mn(SO4)2, into a defective Li-poor one, Li2Mn2(SO4)3, which appears to be responsible for the improved storage properties. The data reveals that Li2Mn(SO4)2 is a prospective candidate for supercapacitor electrode materials at elevated temperatures.

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Alluaudite Battery Cathodes

2020

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Rechargeable batteries have emerged as ubiquitous and indispensable technologies of the 21st century, propelling myriads of consumer electronics and ushering a new era of electric vehicles and stationary grid storage. Since the commercialization of Li‐ion batteries by SONY (approximately in the year 1991), the secondary battery sector has seen unprecedented growth with diverse applications touching global populations across socioeconomic strata. There is a steady quest to develop a wide range of batteries to cater diverse global demands from milliwatt‐scale electronics to megawatt‐scale grid‐storage applications. In this journey, Li‐ion batteries are complemented by various post‐Li‐ion chemistry (e.g., Na+, K+, Mg2+, Ca2+, and Al3+‐ion batteries), conversion mechanism‐based systems (e.g., Li–S, Na–S, and Li–O2) as well as renewed development of pre‐Li‐ion era technologies like aqueous batteries. Cathodes sit at the core with command over the net cost and performance of batteries. Various polyanionic cathodes have been developed to date, often guided by structure of naturally occurring minerals. One such mineral system is alluaudite, named after French geologist François Alluaud. The current article portrays the discovery and development of the alluaudite class of polyanionic cathode materials for rechargeable batteries. The structure and electrochemical properties of various alluaudite insertion materials are gauged along with possible future perspectives.

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Redox properties of alluaudite sodium cobalt manganese sulfates as high-voltage electrodes for rechargeable batteries

Abstract: This is the first experimental evidence for the operation of sodium cobalt-manganese sulfate, Na2+2δ(Co0.63Mn0.37)2−δ(SO4)3, at potentials higher than 4.0 V vs. Li/Li+.

Cited by 13 publications

References 19 publications

Lithium versus Mono/Polyvalent Ion Intercalation: Hybrid Metal Ion Systems for Energy Storage

Lithium versus Mono/Polyvalent Ion Intercalation: Hybrid Metal Ion Systems for Energy Storage

Lithium Manganese Sulfates as a New Class of Supercapattery Materials at Elevated Temperatures

Alluaudite Battery Cathodes

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