In contrast to monovalent lithium or sodium ions, the reversible insertion of multivalent ions such as Mg and Al into electrode materials remains an elusive goal. Here, we demonstrate a new strategy to achieve reversible Mg and Al insertion in anatase TiO, achieved through aliovalent doping, to introduce a large number of titanium vacancies that act as intercalation sites. We present a broad range of experimental and theoretical characterizations that show a preferential insertion of multivalent ions into titanium vacancies, allowing a much greater capacity to be obtained compared to pure TiO. This result highlights the possibility to use the chemistry of defects to unlock the electrochemical activity of known materials, providing a new strategy for the chemical design of materials for practical multivalent batteries.
Designing active and stable electrocatalysts with economic efficiency for acidic oxygen evolution reaction is essential for developing proton exchange membrane water electrolyzers. Herein, we report on a cobalt oxide incorporated with iridium single atoms (Ir-Co3O4), prepared by a mechanochemical approach. Operando X-ray absorption spectroscopy reveals that Ir atoms are partially oxidized to active Ir>4+ during the reaction, meanwhile Ir and Co atoms with their bridged electrophilic O ligands acting as active sites, are jointly responsible for the enhanced performance. Theoretical calculations further disclose the isolated Ir atoms can effectively boost the electronic conductivity and optimize the energy barrier. As a result, Ir-Co3O4 exhibits significantly higher mass activity and turnover frequency than those of benchmark IrO2 in acidic conditions. Moreover, the catalyst preparation can be easily scaled up to gram-level per batch. The present approach highlights the concept of constructing single noble metal atoms incorporated cost-effective metal oxides catalysts for practical applications.
Since the report of electrochemical activity of LiFePO4 from Goodenough's group in 1997, it has attracted considerable attention as cathode material of choice for lithium‐ion batteries. It shows excellent performance such as the high‐rate capability, long cyclability, and improved safety. Furthermore, the raw materials cost of LiFePO4 are lower and abundant compared with conventional Li‐ion battery oxides compounds. The lithium extraction from LiFePO4 operates as biphase mechanism accompanied by a relatively large volume change of ∼6.8%, even though, nanosized LiFePO4 shows exceptionally high‐rate capability during cycling. In the aim to explain this remarkable feature, recent reports using cutting‐edge techniques, such as in situ high‐resolution synchrotron X‐ray diffraction, explained that the origin of the observed high‐rate performance in nanosized LiFePO4 is the absence of phase separation during battery operation at high current densities. In this review, the importance of understanding lithium insertion mechanisms towards explaining the significantly fast‐charging performance of LiFePO4 electrode is highlighted. In particular, phase separation mechanisms, are unclear and deserve considerable attention. Several proposed models for Li diffusion and phase separation in LiFePO4 are summarized. In addition, the crystallographic aspects, defect structures of LiFePO4 are also reviewed. Finally, the status of development of other olivine‐type LiMPO4 (M = Co, Mn, and Ni) are summarized.
Aluminium batteries constitute as afe and sustainable high-energy-density electrochemical energy-storage solution. Viable Al-ion batteries require suitable electrode materials that can readily intercalate high-charge Al 3+ ions.H ere,w e investigate the Al 3+ intercalation chemistry of anatase TiO 2 and howc hemical modifications influence the accommodation of Al 3+ ions.W eu se fluoride-and hydroxide-doping to generate high concentrations of titanium vacancies.T he coexistence of these hetero-anions and titanium vacancies leads to acomplex insertion mechanism, attributed to three distinct types of host sites:n ative interstitial sites,s ingle vacancy sites,a nd paired vacancy sites.W edemonstrate that Al 3+ induces astrong local distortion within the modified TiO 2 structure,which affects the insertion properties of the neighbouring host sites.O verall, specific structural features induced by the intercalation of highly polarising Al 3+ ions should be considered when designing new electrode materials for polyvalent batteries.
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