Controlling the Intercalation Chemistry to Design High-Performance Dual-Salt Hybrid Rechargeable Batteries

We have conducted extensive theoretical and experimental investigations to unravel the origin of the electrochemical properties of hybrid Mg²⁺/Li⁺ rechargeable batteries at the atomistic and macroscopic levels. By revealing the thermodynamics of Mg²⁺ and Li⁺ co-insertion into the Mo₆S₈ cathode host using density functional theory calculations, we show that there is a threshold Li⁺ activity for the pristine Mo₆S₈ cathode to prefer lithiation instead of magnesiation. By precisely controlling the insertion chemistry using a dual-salt electrolyte, we have enabled ultrafast discharge of our battery by achieving 93.6% capacity retention at 20 C and 87.5% at 30 C, respectively, at room temperature

Investigating Local Degradation and Thermal Stability of Charged Nickel-Based Cathode Materials through Real-Time Electron Microscopy

In this work, we take advantage of in situ transmission electron microscopy (TEM) to investigate thermally induced decomposition of the surface of Li_<i>x</i>Ni_0.8Co_0.15Al_0.05O₂ (NCA) cathode materials that have been subjected to different states of charge (SOC). While uncharged NCA is stable up to 400 °C, significant changes occur in charged NCA with increasing temperature. These include the development of surface porosity and changes in the oxygen K-edge electron energy loss spectra, with pre-edge peaks shifting to higher energy losses. These changes are closely related to O₂ gas released from the structure, as well as to phase changes of NCA from the layered structure to the disordered spinel structure, and finally to the rock-salt structure. Although the temperatures where these changes initiate depend strongly on the state of charge, there also exist significant variations among particles with the same state of charge. Notably, when NCA is charged to <i>x</i> = 0.33 (the charge state that is the practical upper limit voltage in most applications), the surfaces of some particles undergo morphological and oxygen K-edge changes even at temperatures below 100 °C, a temperature that electronic devices containing lithium ion batteries (LIB) can possibly see during normal operation. Those particles that experience these changes are likely to be extremely unstable and may trigger thermal runaway at much lower temperatures than would be usually expected. These results demonstrate that in situ heating experiments are a unique tool not only to study the general thermal behavior of cathode materials but also to explore particle-to-particle variations, which are sometimes of critical importance in understanding the performance of the overall system

Using Real-Time Electron Microscopy To Explore the Effects of Transition-Metal Composition on the Local Thermal Stability in Charged Li_<i>x</i>Ni_<i>y</i>Mn_<i>z</i>Co_{1–<i>y</i>–<i>z</i>}O₂ Cathode Materials

In this work, we use <i>in situ</i> transmission electron microscopy (TEM) to investigate the thermal decomposition that occurs at the surface of charged Li_<i>x</i>Ni_<i>y</i>Mn_<i>z</i>Co_{1–<i>y</i>–<i>z</i>}O₂ (NMC) cathode materials of different composition (with <i>y</i>, <i>z</i> = 0.8, 0.1, and 0.6, 0.2, and 0.4,and 0.3), after they have been charged to their practical upper limit voltage (4.3 V). By heating these materials inside the TEM, we are able to directly characterize near surface changes in both their electronic structure (using electron energy loss spectroscopy) and crystal structure and morphology (using electron diffraction and bright-field imaging). The most Ni-rich material (<i>y</i>, <i>z</i> = 0.8, 0.1) is found to be thermally unstable at significantly lower temperatures than the other compositionsthis is manifested by changes in both the electronic structure and the onset of phase transitions at temperatures as low as 100 °C. Electron energy loss spectroscopy indicates that (i) the thermally induced reduction of Ni ions drives these changes, and (ii) this is exacerbated by the presence of an additional redox reaction that occurs at 4.2 V in the <i>y</i>, <i>z</i> = 0.8, 0.1 material. Exploration of individual particles shows that there are substantial variations in the onset temperatures and overall extent of these changes. Of the compositions studied, the composition of <i>y</i>, <i>z</i> = 0.6, 0.2 has the optimal combination of high energy density and reasonable thermal stability. The observations herein demonstrate that real-time electron microscopy provide direct insight into the changes that occur in cathode materials with temperature, allowing optimization of different alloy concentrations to maximize overall performance