Quest for Nonaqueous Multivalent Secondary Batteries: Magnesium and Beyond

Nearly all high energy density cathodes for rechargeable lithium batteries are well-ordered materials where lithium and other cations occupy distinct sites. Cation-disordered materials are generally disregarded as cathodes because lithium diffusion tends to be limited by their structures. The performance of Li1.211Mo0.467Cr0.3O2 shows that lithium diffusion can be facile in disordered materials. Using ab initio computations, we demonstrate that this unexpected behavior is due to percolation of certain diffusion channels that are active in disordered structures, but is unique to Li excess materials. This leads to a unified understanding of high performance in both layered and Li excess materials, and opens up an exciting new direction for designing disordered electrode materials with high capacity and high energy density.

http://science.sciencemag.org/content/sci/early/2014/01/08/science.1246432.full.pdf

Unlocking the potential of cation-disordered oxides for rechargeable lithium batteries

Safety concerns about organic media-based batteries are the key public arguments against their widespread usage. Aqueous batteries (ABs), based on water which is environmentally benign, provide a promising alternative for safe, cost-effective, and scalable energy storage, with high power density and tolerance against mishandling. Research interests and achievements in ABs have surged globally in the past 5 years. However, their large-scale application is plagued by the limited output voltage and inadequate energy density. We present the challenges in AB fundamental research, focusing on the design of advanced materials and practical applications of whole devices. Potential interactions of the challenges in different AB systems are established. A critical appraisal of recent advances in ABs is presented for addressing the key issues, with special emphasis on the connection between advanced materials and emerging electrochemistry. Last, we provide a roadmap starting with material design and ending with the commercialization of next-generation reliable ABs.

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Roadmap for advanced aqueous batteries: From design of materials to applications.

and Perspectives Sophie Carenco,†,‡,§,∥,⊥ David Portehault,*,†,‡,§ Ced́ric Boissier̀e,†,‡,§ Nicolas Meźailles, and Cleḿent Sanchez*,†,‡,§ †Chimie de la Matier̀e Condenseé de Paris, UPMC Univ Paris 06, UMR 7574, Colleg̀e de France, 11 Place Marcelin Berthelot, 75231 Paris Cedex 05, France ‡Chimie de la Matier̀e Condenseé de Paris, CNRS, UMR 77574, Colleg̀e de France, 11 Place Marcellin Berthelot, 75231 Paris Cedex 05, France Chimie de la Matier̀e Condenseé de Paris, Colleg̀e de France, 11 Place Marcellin Berthelot, 75231 Paris Cedex 05, France Laboratory Heteroelements and Coordination, Chemistry Department, Ecole Polytechnique, CNRS-UMR 7653, Palaiseau, France

Nanoscaled metal borides and phosphides: recent developments and perspectives

The rapidly expanding field of nonaqueous multivalent intercalation batteries offers a promising way to overcome safety, cost, and energy density limitations of state-of-the-art Li-ion battery technology. We present a critical and rigorous analysis of the increasing volume of multivalent battery research, focusing on a wide range of intercalation cathode materials and the mechanisms of multivalent ion insertion and migration within those frameworks. The present analysis covers a wide variety of material chemistries, including chalcogenides, oxides, and polyanions, highlighting merits and challenges of each class of materials as multivalent cathodes. The review underscores the overlap of experiments and theory, ranging from charting the design metrics useful for developing the next generation of MV-cathodes to targeted in-depth studies rationalizing complex experimental results. On the basis of our critical review of the literature, we provide suggestions for future multivalent cathode studies, including a...

Odyssey of Multivalent Cathode Materials: Open Questions and Future Challenges

The combination of a magnesium anode with a sulfur cathode is one of the most promising electrochemical couples because of its advantages of good safety, low cost, and a high theoretical energy density. However, magnesium sulfur batteries are still in a very early stage of research and development, and the discovery of suitable electrolytes is the key challenge for further improvement. Here, a new preparation method for non-nucleophilic electrolyte solutions using a two-step reaction in one-pot is presented, which provides a feasible way to optimize the physiochemical properties of the electrolyte for the application in magnesium sulfur batteries. The first use of modified electrolytes in glymes and binary solvents of glyme and ionic liquid shows beneficial effects on the performance of magnesium sulfur batteries. New insights into the reaction mechanism of electrochemical conversion between magnesium and sulfur are also investigated.

Performance Improvement of Magnesium Sulfur Batteries with Modified Non‐Nucleophilic Electrolytes

Recent progress in hydrogen storage alloys for nickel/metal hydride secondary batteries

Yolk–Shell NiS2 Nanoparticle‐Embedded Carbon Fibers for Flexible Fiber‐Shaped Sodium Battery

Non-nucleophilic electrolytes with outstanding electrochemical performances for magnesium batteries have been synthesized through the reaction between a bisamide magnesium and a Lewis acid in an aprotic solvent High anodic stability, good ionic conductivity, excellent cycling efficiency and the feasibility of the preparation make the in situ generated electrolyte very promising for the potential application in rechargeable magnesium batteries

Bisamide based non-nucleophilic electrolytes for rechargeable magnesium batteries

A key challenge of chloride ion batteries is to develop cathode materials that are stable in the electrolytes. Metal oxychlorides are presented as such a cathode material. The electrochemical performance and the reaction mechanisms of the BiOCl and FeOCl cathode were investigated. Both cathodes showed reversible reactions, including a major conversion reaction and a minor intercalation process, by chloride ion transfer during cycling.

Xiangyu Zhao

Papers

Performance Improvement of Magnesium Sulfur Batteries with Modified Non‐Nucleophilic Electrolytes

Recent progress in hydrogen storage alloys for nickel/metal hydride secondary batteries

Yolk–Shell NiS2 Nanoparticle‐Embedded Carbon Fibers for Flexible Fiber‐Shaped Sodium Battery

Bisamide based non-nucleophilic electrolytes for rechargeable magnesium batteries

Metal Oxychlorides as Cathode Materials for Chloride Ion Batteries