Investigations into the superionic glass phase of Li4_{4}PS4_{4}I for improving the stability of high-loading all-solid-state batteries

In recent years, investigations into improving the performance of bulk-type solid-state batteries (SSBs) have attracted much attention. This is due, in part, to the fact that they offer an opportunity to outperform the present Li-ion battery technology in terms of energy density. Ni-rich Li$_{1+x}$(Ni$_{1-y-z}$Co$_{y}$Mn$_{z}$)$_{1-x}$O$_{2}$ (NCM) and lithium-thiophosphate-based solid electrolytes appear to be a promising material combination for application at the cathode side. Here, we report about exploratory investigations into the 1.5Li$_{2}$S/0.5P$_{2}$S$_{5}$/LiI phase system and demonstrate that a glassy solid electrolyte has more than an order of magnitude higher room-temperature ionic conductivity than the crystalline counterpart, tetragonal Li$_{4}$PS$_{4}$I with the P4/nmm space group (∼1.3 versus ∼0.2 mS cm$^{-1}$). In addition, preliminary results show that usage of the glassy 1.5Li$_{2}$S–0.5P$_{2}$S$_{5}$–LiI in pellet stack SSB cells with an NCM622 (60% Ni content) cathode and a Li$_{4}$Ti$_{5}$O$_{12}$ anode leads to enhanced capacity retention when compared to the frequently employed argyrodite Li$_{6}$PS$_{5}$Cl solid electrolyte. This indicates that, apart from interfacial instabilities, the stiffness (modulus) of the solid electrolyte and associated mechanical effects may also impact significantly the long-term performance. Moreover, SSB cells with the glassy 1.5Li$_{2}$S–0.5P$_{2}$S$_{5}$–LiI and high-loading cathode (∼22 mg$_{NCM622}$ cm$^{-2}$) manufactured using a slurry-casting process are found to cycle stably for 200 cycles at C/5 rate and 45 °C, with areal capacities in excess of 3 mA h cm$^{-2}$

Effect of surface carbonates on the cyclability of LiNbO3_{3}-coated NCM622 in all-solid-state batteries with lithium thiophosphate electrolytes

While still premature as an energy storage technology, bulk solid-state batteries are attracting much attention in the academic and industrial communities lately. In particular, layered lithium metal oxides and lithium thiophosphates hold promise as cathode materials and superionic solid electrolytes, respectively. However, interfacial side reactions between the individual components during battery operation usually result in accelerated performance degradation. Hence, effective surface coatings are required to mitigate or ideally prevent detrimental reactions from occurring and having an impact on the cyclability. In the present work, we examine how surface carbonates incorporated into the sol–gel-derived LiNbO$_{3}$ protective coating on NCM622 [Li$_{1+x}$(Ni$_{0.6}$Co$_{0.2}$Mn$_{0.2}$)$_{1-x}$O2] cathode material affect the efficiency and rate capability of pellet-stack solid-state battery cells with β-Li$_{3}$PS$_{4}$ or argyrodite Li$_{6}$PS$_{5}$Cl solid electrolyte and a Li$_{4}$Ti$_{5}$O$_{12}$ anode. Our research data indicate that a hybrid coating may in fact be beneficial to the kinetics and the cycling performance strongly depends on the solid electrolyte used

Design-of-experiments-guided optimization of slurry-cast cathodes for solid-state batteries

Laboratory research into bulk-type solid-state batteries (SSBs) has been focused predominantly on powder-based, pelletized cells and has been sufficient to evaluate fundamental limitations and tailor the constituents to some degree. However, to improve experimental reliability and for commercial implementation of this technology, competitive slurry-cast electrodes are required. Here, we report on the application of an approach guided by design of experiments (DoE) to evaluate the influence of the type/content of polymer binder and conductive carbon additive on the cyclability and processability of Li$_{1+x}$(Ni$_{0.6}$Co$_{0.2}$Mn$_{0.2}$)$_{1}$−xO$_{2}$ (NCM622) cathodes in SSB cells using lithium thiophosphate solid electrolytes. The predictions are verified by charge-discharge and impedance spectroscopy measurements. Furthermore, structural changes and gas evolution are monitored via X-ray diffraction and differential electrochemical mass spectrometry, respectively, in an attempt to rationalize and support the DoE results. In summary, the optimized combination of polymer binder and conductive carbon additive leads to high electrochemical performance and good processability

The Effect of Single versus Polycrystalline Cathode Particles on All‐Solid‐State Battery Performance

Lithium-thiophosphate-based all-solid-state batteries (ASSBs) are increasingly attracting attention for high-density electrochemical energy storage. In this work, the cycling performance of single and polycrystalline forms of LiNi$_{x}$Co$_{y}$Mn$_{z}$O$_{2}$ (NCM, with ≥83% Ni content) cathode active materials in ASSB cells with an Li$_{4}$Ti$_{5}$O$_{12}$ composite anode is explored, and the advantages and disadvantages of both morphologies are discussed. The virtual lack of grain boundaries in the quasi-single-crystalline material is found to contribute to improved stability by eliminating the tendency of Ni-rich NCM particles to crack during cycling, due to volume differences between the lithiated and delithiated phases. Although the higher crack resistance mitigates effects of chemical oxidation of the lithium thiophosphate solid electrolyte, the cells suffer from electrochemical side reactions occurring at the cathode interfaces. However, coating the single-crystal particles with a protective LiNbO$_{3}$ overlayer helps to stabilize the interface between cathode active material and solid electrolyte, leading to a capacity retention of 93% after 200 cycles (with q$_{dis}$ ≈ 160 mAh g$_{NCM}$$^{-1}$ or 1.7 mAh cm$^{-2}$ at C/5 rate and 45 °C). Overall, this work highlights the importance of addressing electro-chemo-mechanical phenomena in ASSB electrodes

Spinal Stenosis Presenting with Scrotal and Perianal Claudication

A 63-year-old gentleman presented with a one-year duration of progressive neurogenic claudication. However, unlike most patients who presents with leg symptoms, his pain was felt in his scrotal and perianal region. This was exacerbated with walking and standing, but he had immediate relief with sitting. An magnetic resonance imaging (MRI) was performed which showed severe central canal stenosis. An L3/4 and L4/5 surgical decompression and a transforaminal lumbar interbody fusion was performed, and the patient made good recovery with immediate resolution of symptoms. Although rare, spinal stenosis should be considered a differential when approaching a patient with perianal and scrotal claudication, even in the absence of leg claudication. An MRI is useful to confirm the diagnosis. This rare symptom may be a sign of severe cauda equina compression and we recommend decompression with predictable good results

Impact of the Chlorination of Lithium Argyrodites on the Electrolyte/Cathode Interface in Solid‐State Batteries

Lithium argyrodite-type electrolytes are regarded as promising electrolytes due to their high ionic conductivity and good processability. Chemical modifications to increase ionic conductivity have already been demonstrated, but the influence of these modifications on interfacial stability remains so far unknown. In this work, we study Li6PS5Cl and Li5.5PS4.5Cl1.5 to investigate the influence of halogenation on the electrochemical decomposition of the solid electrolyte and the chemical degradation mechanism at the cathode interface in depth. Electrochemical measurements, gas analysis and time-of-flight secondary ion mass spectrometry indicate that the Li5.5PS4.5Cl1.5 shows pronounced electrochemical decomposition at lower potentials. The chemical reaction at higher voltages leads to more gaseous degradation products, but a lower fraction of solid oxygenated phosphorous and sulfur species. This in turn leads to a decreased interfacial resistance and thus a higher cell performance

Advanced Nanoparticle Coatings for Stabilizing Layered Ni‐Rich Oxide Cathodes in Solid‐State Batteries

Improving the interfacial stability between cathode active material (CAM) and solid electrolyte (SE) is a vital step toward the development of high-performance solid-state batteries (SSBs). One of the challenges plaguing this field is an economical and scalable approach to fabricate high-quality protective coatings on the CAM particles. A new wet-coating strategy based on preformed nanoparticles is presented herein. Nonagglomerated nanoparticles of the coating material (≤5 nm, exemplified for ZrO$_{2}$) are prepared by solvothermal synthesis, and after surface functionalization, applied to a layered Ni-rich oxide CAM, LiNi$_{0.85}$Co$_{0.10}$Mn$_{0.05}$O$_{2}$ (NCM85), producing a uniform surface layer with a unique structure. Remarkably, when used in pelletized SSBs with argyrodite Li$_{6}$PS$_{5}$Cl as SE, the coated NCM85 is found to exhibit superior lithium-storage properties (q$_{dis}$ ≈ 204 mAh g$_{NCM85}$$^{-1}$ at 0.1 C rate and 45 °C) and good rate capability. The key to the observed improvement lies in the homogeneity of coating, suppressing interfacial side reactions while simultaneously limiting gas evolution during operation. Moreover, this strategy is proven to have a similar effect in liquid electrolyte-based Li-ion batteries and can potentially be used for the application of other, even more favorable, nanoparticle coatings