High-Throughput in Situ Pressure Analysis of Lithium-Ion Batteries.

Many degradation processes in lithium-ion batteries are accompanied by gas evolution and therefore lead to an increase in internal cell pressure. This causes serious safety concerns for state-of-the-art lithium-ion batteries, calling for a thorough investigation of the origin and the magnitude of such processes. Herein we introduce a multichannel in situ pressure measurement system that allows for the high-throughput quantification of gas evolution under realistic battery conditions. The capability of the system was demonstrated through its application on Li4Ti5O12 half cells. The pressure changes could be divided into an irreversible and a reversible part, where the latter is caused by the deposition and dissolution of elemental lithium during cycling. Comparison of the measured and the theoretical reversible pressure changes showed a close match, indicating the high accuracy of the system. Additionally, the irreversible part observed in the pressure changes was attributed to gas evolution, as confirmed by complementary measurements using differential electrochemical mass spectrometry. To show the practicality of the system, the temperature dependence of gas evolution in Li1+xNi0.6Co0.2Mn0.2O2 full cells was investigated. Enhanced gas evolution was observed at elevated temperature, which is partly attributed to the thermal decomposition of the conducting salt LiPF6.

Highly Reversible Sodiation of Tin in Glyme Electrolytes: The Critical Role of the Solid Electrolyte Interphase and Its Formation Mechanism.

Utilization of high-capacity alloying anodes is a promising yet extremely challenging strategy in building high energy density alkali-ion batteries (AIBs). Excitingly, it was very recently found that the (de-)sodiation of tin (Sn) can be a highly reversible process in specific glyme electrolytes, enabling high specific capacities close to the theoretical value of 847 mA h g-1. The unique solid electrolyte interphase (SEI) formed on Sn electrodes, which allows highly reversible sodiation regardless of the huge volume expansion, is herein demonstrated according to a series of in situ and ex situ characterization techniques. The SEI formation process mainly involves NaPF6 decomposition and the polymerization/oligomerization of the glyme solvent, which is induced by the catalytic effect of tin, specifically. This work provides a paradigm showing how solvent, salt, and electrode materials synergistically mediate the SEI formation process and obtains new insights into the unique interfacial chemistry between Na-alloying electrodes and glyme electrolytes, which is highly enlightening in building high energy density AIBs.

Gas Evolution in Lithium-Ion Batteries: Solid versus Liquid Electrolyte.

Gas evolution in conventional lithium-ion batteries using Ni-rich layered oxide cathode materials presents a serious issue that is responsible for performance decay and safety concerns, among others. Recent findings revealed that gas evolution also occurred in bulk-type solid-state batteries. To further clarify the effect that the electrolyte has on gassing, we report in this work-to the best of our knowledge-the first study comparing gas evolution in lithium-ion batteries with NCM622 cathode material and different electrolyte types, specifically solid (ß-Li3PS4 and Li6PS5Cl) versus liquid (LP57). Using isotopic labeling, acid titration, and in situ gas analysis, we show the presence of O2 and CO2 evolution in both systems, albeit with different cumulative amounts, and possible SO2 evolution for the lithium thiophosphate-based cells. Our results demonstrate the importance of considering gas evolution in solid-state batteries, especially the formation and release of highly corrosive SO2, due to side reactions with the electrolyte.

Phase Transformation Behavior and Stability of LiNiO2 Cathode Material for Li-Ion Batteries Obtained from In†Situ Gas Analysis and Operando X-Ray Diffraction.

Ni-rich layered oxide cathode materials, in particular the end member LiNiO2 , suffer from drawbacks such as high surface reactivity and severe structural changes during de-/lithiation, leading to accelerated degradation and limiting practical implementation of these otherwise highly promising electrode materials in Li-ion batteries. Among all known phase transformations occurring in LiNiO2 , the one from the H2 phase to the H3 phase at high state of charge is believed to have the most detrimental impact on the material's stability. In this work, the multistep phase transformation process and associated effects are analyzed by galvanostatic cycling, operando X-ray diffraction, and in situ pressure and gas analysis. The combined results provide thorough insights into the structural changes and how they affect the stability of LiNiO2 . During the H2-H3 transformation, the most significant change occurs in the c-lattice parameter, resulting in large mechanical stress in LiNiO2 . As for electrochemical stability, it suffers strongly in the H3 region. Oxygen evolution is observed not only during charge but also during discharge and found to be correlated with the presence of the H2 and H3 phases. Taken together, the experimental data improve the understanding of the degradation processes and the inherent instability of LiNiO2 in Li-ion cells when operated above around 75 % state of charge.

High-Entropy Oxides: Fundamental Aspects and Electrochemical Properties.

High-entropy materials, especially high-entropy alloys and oxides, have gained significant interest over the years due to their unique structural characteristics and correlated possibilities for tailoring of functional properties. The developments in the area of high-entropy oxides are highlighted here, with emphasis placed on their fundamental understanding, including entropy-dominated phase-stabilization effects and prospective applications, e.g., in the field of electrochemical energy storage. Critical comments on the different classes of high-entropy oxides are made and the underlying principles for the observed properties are summarized. The diversity of materials design, provided by the entropy-mediated phase-stabilization concept, allows engineering of new oxide candidates for practical applications, warranting further studies in this emerging field of materials science.

Origin of Carbon Dioxide Evolved during Cycling of Nickel-Rich Layered NCM Cathodes.

Gas formation caused by parasitic side reactions is one of the fundamental concerns in state-of-the-art lithium-ion batteries because gas bubbles might block local parts of the electrode surface, hindering lithium transport and leading to inhomogeneous current distributions. Here, we elucidate on the origin of CO2, which is the dominant gaseous species associated with the layered lithium nickel cobalt manganese oxide (NCM) cathode, by implementing isotope labeling and electrolyte substitution in differential electrochemical mass spectrometry-differential electrochemical infrared spectroscopy measurements. Li2CO3 on the NCM surface was successfully labeled with 13C via a process that involves its removal followed by intentional growth. In situ gas analytics on such NCM samples with 13C-labeled Li2CO3 clearly indicate that Li2CO3 decomposition contributes to CO2 evolution, especially during the first charge. At the same time, the greater contribution of electrolyte decomposition was indicated by the large amount of 12CO2 observed. Employment of butyronitrile as the electrolyte solvent in further measurements helped determine that the majority of electrolyte decomposition occurs via a reaction that involves the lattice oxygen of NCM.

Silicon Nanoparticles with a Polymer-Derived Carbon Shell for Improved Lithium-Ion Batteries: Investigation into Volume Expansion, Gas Evolution, and Particle Fracture.

Silicon (Si) and composites thereof, preferably with carbon (C), show favorable lithium (Li) storage properties at low potential, and thus hold promise for application as anode active materials in the energy storage area. However, the high theoretical specific capacity of Si afforded by the alloying reaction with Li involves many challenges. In this article, we report the preparation of small-size Si particles with a turbostratic carbon shell from a polymer precoated powder material. Galvanostatic charge/discharge experiments conducted on electrodes with practical loadings resulted in much improved capacity retention and kinetics for the Si/C composite particles compared to physical mixtures of pristine Si particles and carbon black, emphasizing the positive effect that the core-shell-type morphology has on the cycling performance. Using in situ differential electrochemical mass spectrometry, pressure, and acoustic emission measurements, we gain insights into the gassing behavior, the bulk volume expansion, and the mechanical degradation of the Si/C composite-containing electrodes. Taken together, our research data demonstrate that some of the problems of high-content Si anodes can be mitigated by carbon coating. Nonetheless, continuous electrolyte decomposition, particle fracture, and electrode restructuring due to the large volume changes during battery operation (here, ∼170% in the voltage range of 600-30 mV vs Li+/Li) remain as serious hurdles toward practical implementation.