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Synthetic Phosphate Analogues for Battery Applications

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Synthetic Phosphate Analogues for Battery Applications minerals Review Mineral-Inspired Materials: Synthetic Phosphate Analogues for Battery Applications Olga Yakubovich 1,* , Nellie Khasanova 2 and Evgeny Antipov 2,3 1 Department of Crystallography, Geological Faculty, M.V. Lomonosov Moscow State University, Leninskie Gory 1, 119991 Moscow, Russia 2 Chemical Faculty, M.V. Lomonosov Moscow State University, Leninskie Gory 1, 119991 Moscow, Russia; [email protected] (N.K.); [email protected] (E.A.) 3 Skolkovo Institute of Science and Technology, 3 Nobel Street, 143025 Moscow, Russia * Correspondence: [email protected]; Tel.: +7-903-975-91-06 Received: 28 April 2020; Accepted: 5 June 2020; Published: 7 June 2020 Abstract: For successful development of novel rechargeable batteries, considerable efforts should be devoted to identifying suitable cathode materials that will ensure a proper level of energy output, structural stability, and affordable cost. Among various compounds explored as electrode materials, structural analogues of minerals–natural stable inorganic solids–occupy a prominent place. The largest number of varieties of phosphate minerals occurs in rare metal granite pegmatites, and many of which contain transition metals as essential components. Transition metal phosphates are promising candidates for exploration as cathode materials due to a perfect combination of easily scalable synthesis, moderate-to-high voltage operation, thermal/chemical stability, and environmental safety. However, impurities usually presented in natural objects, and often inappropriate sample morphologies, do not permit the use of minerals as battery electrode materials. Nevertheless, the minerals of different classes, especially phosphates, are considered as prototypes for developing novel materials for battery applications. The crystal chemical peculiarities of the phosphate representatives that are most relevant in this aspect and the electrochemical characteristics of their synthetic analogues are discussed here. Keywords: phosphates; minerals; battery materials; cathode; synthetic analogous; crystal structure; electrochemistry; homeotypes; pegmatites; energy storage 1. Introduction “They created a rechargeable world”: the 2019 Nobel Prize in Chemistry was awarded to John B. Goodenough, M. Stanley Whittingham, and Akira Yoshino for their contribution to the development of lithium-ion batteries, which revolutionized our daily life and laid the foundation of a wireless fossil fuel-free society [1]. Ever-growing demands for energy and depleting of fossil fuels require utilizing renewable energy resources (solar, wind, geothermal). For accumulating the energy from these intermittent sources, we need highly efficient energy conversion and storage systems. Rechargeable batteries are the most efficient energy storage technology for a wide range of devices from portable electronics to electric vehicles and grids [2]. Meeting the future needs of our society requires a significant improvement of existing Li-ion technology and development of alternative Na- and K-ion batteries, and the main research task is to find suitable materials for electrodes. The discovered ability of synthetic triphylite LiFePO4 to reversibly de/intercalate lithium ions [3] has brought great attention to transition metal phosphates as electrode materials for Li-ion batteries. Phosphates are the most widespread minerals in the Earth’s crust after silicates and oxides. Their remarkable structural diversity allows for a large range of technological applications such Minerals 2020, 10, 524; doi:10.3390/min10060524 www.mdpi.com/journal/minerals Minerals 2020, 10, 524 2 of 30 as magnetic and nonlinear optical materials, catalysts, adsorbents, molecular sieves, phosphors, andMinerals biomaterials, 2020, 10, 524 to name but a few [4]. The advance of battery technologies promotes2 of 29 more sustainable and environmentally friendly energy production, storage, and consumption. Transition metalmagnetic phosphates and nonlinear are attractive optical here materials, due tocatalyst theirs, enhanced adsorbents, thermodynamic molecular sieves, and phosphors, kinetic stabilityand biomaterials, to name but a few [4]. The advance of battery technologies promotes more sustainable compared to oxides, higher operating potentials owing to the inductive effect of the phosphate group and environmentally friendly energy production, storage, and consumption. Transition metal for the same cation redox couples, and the environmental friendliness of their robust crystal structures. phosphates are attractive here due to their enhanced thermodynamic and kinetic stability compared toHowever, oxides, higher the mineral operating phases potentials may owing not be to suitable the inductive for research effect of duethe phosphate to the unstable group for impurities the typicallysame presentcation redox in naturalcouples, samples.and the environmental At the same friendliness time, their of their crystal robust structures, crystal structures. often with such promisingHowever, features the as mineral low dimensionality, phases may not lack be ofsuitable a center for ofresearch symmetry, due to ion the di unstableffusion impurities channels may servetypically as excellent present reference in natural points samples. for theAt the development same time, oftheir new crystal materials. structures, The often useof with information such on chemicalpromising compositions, features as low structural dimensionality, features, lack and of a conditions center of symmetry, of mineral ion formation diffusion channels and alteration may in the Earth’sserve as crust excellent is essential reference for points understanding for the developm and adequateent of new interpretation materials. The ofuse the of information properties ofon their syntheticchemical analogues. compositions, Thus, structural crystal chemicalfeatures, and study cond ofitions transition of mineral metal formation phosphates and alteration with alkali in the atoms makesEarth's it possible crust is to essential determine for the understanding miscibility limits and adeq of soliduate solutionsinterpretation and toof findthe properties ways to control of their cation synthetic analogues. Thus, crystal chemical study of transition metal phosphates with alkali atoms ordering, defect concentration, and ion oxidation, which are important for creating electrochemically makes it possible to determine the miscibility limits of solid solutions and to find ways to control active materials. Moreover, phosphate-based materials provide ease of synthesis along with reliable cation ordering, defect concentration, and ion oxidation, which are important for creating electrochemicalelectrochemically characteristics. active materials. Moreover, phosphate-based materials provide ease of synthesis alongIn this with review, reliable we electrochemical will demonstrate characteristics. the definite attractiveness of minerals, mainly phosphates, as a sourceIn this of inspiration review, we forwill researchers demonstrate working the definite in the attractiveness field of battery of minerals, materials. mainly phosphates, as a source of inspiration for researchers working in the field of battery materials. 2. Background Information 2. Background Information Modern technologies require a tremendous amount of energy, and the problem of energy storage is now keyModern for the technologies world energy require supply. a tremendous A secondary amount (or rechargeable) of energy, and battery the problem is an electrochemical of energy energystorage storage is now device, key whichfor the convertsworld energy chemical supply. energy A secondary into electrical (or rechargeable) energy and battery vice versais an in a repeatedelectrochemical way. Among energy the storage present device, batteries, which Li-ion converts technology chemical is energy the best into due electrical to high energy delivered and vice energy density,versa long in a cycle repeated life, rateway. capability, Among the and present energy batteri efficiency.es, Li-ion The technology Li-ion battery is the (LIB) best comprises due to high one or delivered energy density, long cycle life, rate capability, and energy efficiency. The Li-ion battery more sequential or parallel single electrochemical cells consisting of two electrodes (anode and cathode) (LIB) comprises one or more sequential or parallel single electrochemical cells consisting of two and aelectrodes non-aqueous (anode electrolyte, and cathode) which and supports a non-aqueou the transports electrolyte, of charge which carriers supports between the transport the separated of electrodes.charge carriers The process between of the energy separated storage electrodes. is carried The process out through of energy the storage reversible is carried de/ intercalationout through of alkalithe metal reversible ions de/intercalation into the electrode of alkali materials. metal ions During into the charge, electrode the electronsmaterials. areDuring pumped charge, “uphill”, the thermodynamicallyelectrons are pumped speaking, "uphill", from thermodynamically a positive (cathode) speaking, to a from negative a positive (anode) (cathode) electrode to a negative through an external(anode) circuit; electrode ions also through flow towardan external the anodecircuit; butions through also flow the toward electrolyte the anode to complete but through the circuit the and keepelectrolyte the reaction to complete running (Figurethe circuit1). Theand oppositekeep the reaction process occursrunning during (Figure discharge: 1). The opposite
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