School of Materials Engineering, Purdue University, West Lafayette, IN 47907.
Department of Physics and Astronomy, Rutgers, The State University of New Jersey, Piscataway, NJ 08854;
Proc Natl Acad Sci U S A. 2018 Sep 25;115(39):9672-9677. doi: 10.1073/pnas.1805029115. Epub 2018 Aug 13.
Solid-state ion shuttles are of broad interest in electrochemical devices, nonvolatile memory, neuromorphic computing, and biomimicry utilizing synthetic membranes. Traditional design approaches are primarily based on substitutional doping of dissimilar valent cations in a solid lattice, which has inherent limits on dopant concentration and thereby ionic conductivity. Here, we demonstrate perovskite nickelates as Li-ion shuttles with simultaneous suppression of electronic transport via Mott transition. Electrochemically lithiated SmNiO (Li-SNO) contains a large amount of mobile Li located in interstitial sites of the perovskite approaching one dopant ion per unit cell. A significant lattice expansion associated with interstitial doping allows for fast Li conduction with reduced activation energy. We further present a generalization of this approach with results on other rare-earth perovskite nickelates as well as dopants such as Na The results highlight the potential of quantum materials and emergent physics in design of ion conductors.
固态离子穿梭在电化学器件、非易失性存储器、神经形态计算和利用合成膜的仿生学中具有广泛的应用前景。传统的设计方法主要基于在固体晶格中取代不同价态的阳离子,这对掺杂浓度和离子电导率有固有的限制。在这里,我们展示了钙钛矿镍酸盐作为锂离子穿梭体,同时通过莫特转变抑制了电子输运。电化学锂化的 SmNiO(Li-SNO)含有大量位于钙钛矿的间隙位的可移动 Li,每个单位晶胞中接近一个掺杂离子。与间隙掺杂相关的晶格膨胀允许快速的 Li 传导,并降低了活化能。我们进一步提出了一种推广这种方法的思路,得到了其他稀土钙钛矿镍酸盐以及 Na 等掺杂剂的结果。结果突出了量子材料和新兴物理在离子导体设计中的潜力。