There is considerable interest in multivalent cation batteries, such as those based on magnesium, calcium or aluminium. Most attention has focused on magnesium. In all cases the metal anode represents a significant challenge. Recent work has shown that calcium can be plated and stripped, but only at elevated temperatures, 75 to 100 °C, with small capacities, typically 0.165 mAh cm, and accompanied by significant side reactions. Here we demonstrate that calcium can be plated and stripped at room temperature with capacities of 1 mAh cm at a rate of 1 mA cm, with low polarization (∼100 mV) and in excess of 50 cycles. The dominant product is calcium, accompanied by a small amount of CaH that forms by reaction between the deposited calcium and the electrolyte, Ca(BH) in tetrahydrofuran (THF). This occurs in preference to the reactions which take place in most electrolyte solutions forming CaCO, Ca(OH) and calcium alkoxides, and normally terminate the electrochemistry. The CaH protects the calcium metal at open circuit. Although this work does not solve all the problems of calcium as an anode in calcium-ion batteries, it does demonstrate that significant quantities of calcium can be plated and stripped at room temperature with low polarization.
A novel templating method to create 3D bicontinuous structured hybrid electrolytes with improved mechanical properties for all-solid-state lithium batteries.
In the search for active Lithium-ion battery materials with ever-increasing energy density, the limits of conventional auxiliary materials, such as binders and conducting additives are being tested. Binders adhere to active substances and current collectors, yielding an interconnected electrode structure that ensures mechanical integrity during the (de-)lithiation process. Even though the battery binder only accounts for a fraction of battery weight and cost, it is a bottleneck technology in the deployment of high energy density active materials that experience significant volume variation and side-reactions. This review paper discusses research on alternative binders derived from conducting polymers (CPs). The use of CPs in binders enables mechanically flexible electronic contacts with the active material with the goal of accommodating larger volume changes within the electrode. Following a summary of the reasoning behind the use of CP-based binders, their rational design is reviewed, including novel composite syntheses and chemical modifications. A new class of multifunctional CP-based binders exhibits promising properties such as high electronic conductivity, the ability for aqueous processing, and efficient binding that tackle the limiting features of traditional binders. The practical application of these binders in Li-ion batteries and beyond is summarized, yielding an outline of current achievements, and a discussion of remaining knowledge gaps and possible future development of such binders.
State‐of‐the‐art scanning probe microscopy (SPM) methods as applied to energy conversion and storage devices, specifically lithium‐ion batteries, are reviewed with an emphasis on the electroactive elements. The unique ability of SPM‐based methods to provide localized information has proven highly valuable for the in‐depth understanding of the fundamental mechanisms, processes, and degradation of lithium‐ion batteries (LIBs). As such, SPM analysis is poised to play a strong role in the competition for new higher performing LIBs, especially given the unprecedented choice and availability of SPM techniques tailored to provide physical and chemical information at the nanoscale.
Lithium‐rich transition metal cathodes can deliver higher capacities than stoichiometric materials by exploiting redox reactions on oxygen. However, oxidation of O2− on charging often results in loss of oxygen from the lattice. In the case of Li2MnO3 all the capacity arises from oxygen loss, whereas doping with Ni and/or Co leads to the archetypal O‐redox cathodes Li[Li0.2Ni0.2Mn0.6]O2 and Li[Li0.2Ni0.13Co0.13Mn0.54]O2, which exhibit much reduced oxygen loss. Understanding the factors that determine the degree of reversible O‐redox versus irreversible O‐loss is important if Li‐rich cathodes are to be exploited in next generation lithium‐ion batteries. Here it is shown that the almost complete eradication of O‐loss with Ni substitution is due to the presence of a less Li‐rich, more Ni‐rich (nearer stoichiometric) rocksalt shell at the surface of the particles compared with the bulk, which acts as a self‐protecting layer against O‐loss. In the case of Ni and Co co‐substitution, a thinner rocksalt shell forms, and the O‐loss is more abundant. In contrast, Co doping does not result in a surface shell yet it still suppresses O‐loss, although less so than Ni and Ni/Co doping, indicating that doping without shell formation is effective and that two mechanisms exist for O‐loss suppression.
Graphene oxide is regarded as a major precursor for graphene-based materials. The development of graphene oxide based derivatives with new functionalities requires a thorough understanding of its chemical reactivity, especially for canonical synthetic methods such as the Diels-Alder cycloaddition. The Diels-Alder reaction has been successfully extended with graphene oxide as a source of diene by using maleic anhydride as a dienophile, thereby outlining the presence of the cis diene present in the graphene oxide framework. This reaction provides fundamental information for understanding the exact structure and chemical nature of graphene oxide. On the basis of high-resolution (13) C-SS NMR spectra, we show evidence for the formation of new sp(3) carbon centers covalently bonded to graphene oxide following hydrolysis of the reaction product. DFT calculations are also used to show that the presence of a cis dihydroxyl and C vacancy on the surface of graphene oxide are promoting the reaction with significant negative reaction enthalpies.
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