Evaluation of Electronic-Ionic Transport Properties of a Mg/Zr-Modified LiNi0.5Mn1.5O4 Cathode for Li-Ion Batteries.

There is an enormous drive for moving toward cathode material research in LIBs due to the proposal of zero-emission electric vehicles together with the restriction of cathode materials in design. LiNi0.5Mn1.5O4 (LNMO) attracts great research interests as high-voltage Co-free cathodes in LIBs. However, a more extensive study is required for LNMO due to its poor electrochemical performance, especially at high temperature, because of the instability of the LNMO interface. Herein, we design structural modifications using Mg and Zr to alleviate the above-mentioned drawbacks by limiting Mn dissolution and tailoring interstitial sites (which are shown by structural and electrochemical characterizations). This strategy enhances the cycle life up to 1000 cycles at both 25 and 50 °C. In addition, a thorough characterization by impedance spectroscopy is applied to give an insight into the electronic and ionic transport properties and the intricate phase transitions occurring upon oxidation and reduction.

Feasibility of Multifunctional Cellulose-Based Polysalt as a Polymer Matrix for Li Metal Polymer Batteries.

Li metal secondary batteries known for their high energy and power density are the much-awaited energy storage systems owing to the high specific capacity of Li metal. However, due to the instability of Li metal with common Li-ion battery electrolytes, a combination with a polymer electrolyte seems to be an effective strategy to alleviate the safety issues of employing Li metal and provide design conformity to the system. Current trends show improvements in different aspects, such as improving ionic conductivity, single-ion conductivity, mechanical stability, and electrochemical stability. A combination of all these properties has been a bottleneck for the development of polymer electrolytes for safe and efficient operation of all solid-state batteries. Herein, a multifunctional polysalt has been synthesized from green and sustainable materials, namely, ethyl cellulose, plasticized with adiponitrile, that contributes to meeting the critical properties enabling high compatibility with Li metal and a quasi-single-ion-conducting property while simultaneously acting as a matrix/filler for efficient operation of the cells. This multifunctional polymer matrix inhibits further decomposition of nitrile-based plasticizers on Li metal anodes with the formation of a favorable Li metal anode interface, thus enabling the utilization of high-voltage stable nitrile-based plasticizers (4.2 V) to be implemented as an electrolyte component for realization of high-voltage Li metal anode polymer batteries.

Dehydrofluorination Process of Poly(vinylidene difluoride) PVdF-Based Gel Polymer Electrolytes and Its Effect on Lithium-Sulfur Batteries.

Gel polymer electrolytes (GPEs) are emerging as suitable candidates for high-performing lithium-sulfur batteries (LSBs) due to their excellent performance and improved safety. Within them, poly(vinylidene difluoride) (PVdF) and its derivatives have been widely used as polymer hosts due to their ideal mechanical and electrochemical properties. However, their poor stability with lithium metal (Li0) anode has been identified as their main drawback. Here, the stability of two PVdF-based GPEs with Li0 and their application in LSBs is studied. PVdF-based GPEs undergo a dehydrofluorination process upon contact with the Li0. This process results in the formation of a LiF-rich solid electrolyte interphase that provides high stability during galvanostatic cycling. Nevertheless, despite their outstanding initial discharge, both GPEs show an unsuitable battery performance characterized by a capacity drop, ascribed to the loss of the lithium polysulfides and their interaction with the dehydrofluorinated polymer host. Through the introduction of an intriguing lithium salt (lithium nitrate) in the electrolyte, a significant improvement is achieved delivering higher capacity retention. Apart from providing a detailed study of the hitherto poorly characterized interaction process between PVdF-based GPEs and the Li0, this study demonstrates the need for an anode protection process to use this type of electrolytes in LSBs.

High-Temperature Thermal Reactivity and Interface Evolution of the NMC-LATP-Carbon Composite Cathode.

Temperature-assisted densification methods are typically used in oxide-based solid-state batteries to suppress resistive interfaces. However, chemical reactivity among the different cathode components (which include a catholyte, the conducting additive, and the electroactive material) still represents a major challenge and processing parameters need thus to be carefully selected. In this study, we evaluate the impact of temperature and heating atmosphere in the LiNi0.6Mn0.2Co0.2O2 (NMC), Li1+xAlxTi2-xP3O12 (LATP), and Ketjenblack (KB) system. A rationale of the chemical reactions between components is proposed from the combination of bulk and surface techniques and overall involves a cation redistribution in the NMC cathode material that is accompanied by the loss of lithium and oxygen from the lattice enhanced by LATP and KB, which act as lithium and oxygen sinks. The final result is the formation of several degradation products, starting at the surface, that lead to a rapid capacity decay above 400 °C. Both the reaction mechanism and threshold temperature depend on the heating atmosphere, with the air atmosphere being more favorable compared to oxygen or any other inert gases.

Monolithic All-Solid-State High-Voltage Li-Metal Thin-Film Rechargeable Battery.

The substitution of an organic liquid electrolyte with lithium-conducting solid materials is a promising approach to overcome the limitations associated with conventional lithium-ion batteries. These constraints include a reduced electrochemical stability window, high toxicity, flammability, and the formation of lithium dendrites. In this way, all-solid-state batteries present themselves as ideal candidates for improving energy density, environmental friendliness, and safety. In particular, all-solid-state configurations allow the introduction of compact, lightweight, high-energy-density batteries, suitable for low-power applications, known as thin-film batteries. Moreover, solid electrolytes typically offer wide electrochemical stability windows, enabling the integration of high-voltage cathodes and permitting the fabrication of higher-energy-density batteries. A high-voltage, all-solid-state lithium-ion thin-film battery composed of LiNi0.5Mn1.5O4 cathode, a LiPON solid electrolyte, and a lithium metal anode has been deposited layer by layer on low-cost stainless-steel current collector substrates. The structural and electrochemical properties of each electroactive component of the battery had been analyzed separately prior to the full cell implementation. In addition to a study of the internal solid-solid interface, comparing them was done with two similar cells assembled using conventional lithium foil, one with thin-film solid electrolyte and another one with thin-film solid electrolyte plus a droplet of LP30 liquid electrolyte. The thin-film all-solid state cell developed in this work delivered 80.5 mAh g-1 in the first cycle at C/20 and after a C-rate test of 25 cycles at C/10, C/5, C/2, and 1C and stabilized its capacity at around 70 mAh g-1 for another 12 cycles prior to the start of its degradation. This cell reached gravimetric and volumetric energy densities of 333 Wh kg-1 and 1,212 Wh l-1, respectively. Overall, this cell showed a better performance than its counterparts assembled with Li foil, highlighting the importance of the battery interface control.

Stable non-corrosive sulfonimide salt for 4-V-class lithium metal batteries.

Rechargeable lithium metal (Li0) batteries (RLMBs) are considered attractive for improving Li-ion batteries. Lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) has been extensively used as a conducting salt for RLMBs due to its advantageous stability and innocuity. However, LiTFSI-based electrolytes are corrosive towards aluminium (Al0) current collectors at low potentials (>3.8 V versus Li/Li+), thereby excluding their application in 4-V-class RLMBs. Herein, we report on a non-corrosive sulfonimide salt, lithium (difluoromethanesulfonyl)(trifluoromethanesulfonyl)imide (LiDFTFSI), that remarkably suppresses the anodic dissolution of the Al0 current collector at high potentials (>4.2 V versus Li/Li+) and significantly improves the cycling performance of Li(Ni1/3Mn1/3Co1/3)O2 (NMC111) cells. In addition, this sulfonimide salt results in the growth of an advantageous solid electrolyte interphase on the Li0 electrode. The replacement of either LiTFSI or LiPF6 with LiDFTFSI endows a Li0||NMC111 cell with superior cycling stability and capacity retention (87% at cycle 200), demonstrating the decisive role of the salt anion in dictating the electrochemical performance of RLMBs.