Synthetic Tailoring of Ionic Conductivity in Multicationic Substituted, High-Entropy Lithium Argyrodite Solid Electrolytes.

Superionic conductors are key components of solid-state batteries (SSBs). Multicomponent or high-entropy materials, offering a vast compositional space for tailoring properties, have recently attracted attention as novel solid electrolytes (SEs). However, the influence of synthetic parameters on ionic conductivity in compositionally complex SEs has not yet been investigated. Herein, the effect of cooling rate after high-temperature annealing on charge transport in the multicationic substituted lithium argyrodite Li6.5[P0.25Si0.25Ge0.25Sb0.25]S5I is reported. It is demonstrated that a room-temperature ionic conductivity of ∼12 mS cm-1 can be achieved upon cooling at a moderate rate, superior to that of fast- and slow-cooled samples. To rationalize the findings, the material is probed using powder diffraction, nuclear magnetic resonance and X-ray photoelectron spectroscopy combined with electrochemical methods. In the case of moderate cooling rate, favorable structural (bulk) and compositional (surface) characteristics for lithium diffusion evolve. Li6.5[P0.25Si0.25Ge0.25Sb0.25]S5I is also electrochemically tested in pellet-type SSBs with a layered Ni-rich oxide cathode. Although delivering larger specific capacities than Li6PS5Cl-based cells at high current rates, the lower (electro)chemical stability of the high-entropy Li-ion conductor led to pronounced capacity fading. The research data indicate that subtle changes in bulk structure and surface composition strongly affect the electrical conductivity of high-entropy lithium argyrodites.

Tuning Ion Mobility in Lithium Argyrodite Solid Electrolytes via Entropy Engineering.

The development of improved solid electrolytes (SEs) plays a crucial role in the advancement of bulk-type solid-state battery (SSB) technologies. In recent years, multicomponent or high-entropy SEs are gaining increased attention for their advantageous charge-transport and (electro)chemical properties. However, a comprehensive understanding of how configurational entropy affects ionic conductivity is largely lacking. Herein we investigate a series of multication-substituted lithium argyrodites with the general formula Li6+x[M1aM2bM3cM4d]S5I, with M being P, Si, Ge, and Sb. Structure-property relationships related to ion mobility are probed using a combination of diffraction techniques, solid-state nuclear magnetic resonance spectroscopy, and charge-transport measurements. We present, to the best of our knowledge, the first experimental evidence of a direct correlation between occupational disorder in the cationic host lattice and lithium transport. By controlling the configurational entropy through compositional design, high bulk ionic conductivities up to 18 mS cm-1 at room temperature are achieved for optimized lithium argyrodites. Our results indicate the possibility of improving ionic conductivity in ceramic ion conductors via entropy engineering, overcoming compositional limitations for the design of advanced electrolytes and opening up new avenues in the field.

Entropy-Mediated Stable Structural Evolution of Prussian White Cathodes for Long-Life Na-Ion Batteries.

The high-entropy approach is applied to monoclinic Prussian White (PW) Na-ion cathodes to address the issue of unfavorable multilevel phase transitions upon electrochemical cycling, leading to poor stability and capacity decay. A series of Mn-based samples with up to six metal species sharing the N-coordinated positions was synthesized. The material of composition Na1.65 Mn0.4 Fe0.12 Ni0.12 Cu0.12 Co0.12 Cd0.12 [Fe(CN)6 ]0.92 □0.08 ⋅ 1.09H2 O was found to exhibit superior cyclability over medium/low-entropy and conventional single-metal PWs. We also report, to our knowledge for the first time, that a high-symmetry crystal structure may be advantageous for high-entropy PWs during battery operation. Computational comparisons of the formation enthalpy demonstrate that the compositionally less complex materials are prone to phase transitions, which negatively affect cycling performance. Based on data from complementary characterization techniques, an intrinsic mechanism for the stability improvement of the disordered PW structure upon Na+ insertion/extraction is proposed, namely the dual effect of suppression of phase transitions and mitigation of gas evolution.

High-Entropy Lithium Argyrodite Solid Electrolytes Enabling Stable All-Solid-State Batteries.

Superionic solid electrolytes (SEs) are essential for bulk-type solid-state battery (SSB) applications. Multicomponent SEs are recently attracting attention for their favorable charge-transport properties, however a thorough understanding of how configurational entropy (ΔSconf ) affects ionic conductivity is lacking. Here, we successfully synthesized a series of halogen-rich lithium argyrodites with the general formula Li5.5 PS4.5 Clx Br1.5-x (0≤x≤1.5). Using neutron powder diffraction and 31 P magic-angle spinning nuclear magnetic resonance spectroscopy, the S2- /Cl- /Br- occupancy on the anion sublattice was quantitatively analyzed. We show that disorder positively affects Li-ion dynamics, leading to a room-temperature ionic conductivity of 22.7 mS cm-1 (9.6 mS cm-1 in cold-pressed state) for Li5.5 PS4.5 Cl0.8 Br0.7 (ΔSconf =1.98R). To the best of our knowledge, this is the first experimental evidence that configurational entropy of the anion sublattice correlates with ion mobility. Our results indicate the possibility of improving ionic conductivity in ceramic ion conductors by tailoring the degree of compositional complexity. Moreover, the Li5.5 PS4.5 Cl0.8 Br0.7 SE allowed for stable cycling of single-crystal LiNi0.9 Co0.06 Mn0.04 O2 (s-NCM90) composite cathodes in SSB cells, emphasizing that dual-substituted lithium argyrodites hold great promise in enabling high-performance electrochemical energy storage.

Quantifying Degradation Parameters of Single-Crystalline Ni-Rich Cathodes in Lithium-Ion Batteries.

Single-crystal LiNix Coy Mnz O2 (SC-NCM, x+y+z=1) cathodes are renowned for their high structural stability and reduced accumulation of adverse side products during long-term cycling. While advances have been made using SC-NCM cathode materials, careful studies of cathode degradation mechanisms are scarce. Herein, we employed quasi single-crystalline LiNi0.65 Co0.15 Mn0.20 O2 (SC-NCM65) to test the relationship between cycling performance and material degradation for different charge cutoff potentials. The Li/SC-NCM65 cells showed >77 % capacity retention below 4.6 V vs. Li+ /Li after 400 cycles and revealed a significant decay to 56 % for 4.7 V cutoff. We demonstrate that the SC-NCM65 degradation is due to accumulation of rock-salt (NiO) species at the particle surface rather than intragranular cracking or side reactions with the electrolyte. The NiO-type layer formation is also responsible for the strongly increased impedance and transition-metal dissolution. Notably, the capacity loss is found to have a linear relationship with the thickness of the rock-salt surface layer. Density functional theory and COMSOL Multiphysics modeling analysis further indicate that the charge-transfer kinetics is decisive, as the lower lithium diffusivity of the NiO phase hinders charge transport from the surface to the bulk.

Probing the Lithium Substructure and Ionic Conductivity of the Solid Electrolyte Li4PS4I.

In search of high-performance solid electrolytes, various materials have been discovered in the past, approaching or even exceeding the ionic conductivity of conventional liquid electrolytes. Among the reported classes of superionic electrolytes for solid-state battery applications, lithium thiophosphates appear to be the most promising owing to their high ionic conductivity and mechanical softness. A recent example is the Li4PS4I phase (P4/nmm). Surprisingly, this material shows a comparatively low ionic conductivity at room temperature ranging from 10-4 to 10-5 S cm-1 despite having favorable structural characteristics. Because of discrepancies between experiment and theory regarding the Li-ion conductivity and polymorphism in Li4PS4I, we herein examine the crystal structure over a broad temperature range using ex situ and in situ X-ray and neutron powder diffraction techniques. We demonstrate the absence of polymorphic transitions, with a lithium redistribution at low temperatures though, and confirm the relatively poor room-temperature ionic conductivity despite the presence of a three-dimensional (3D) percolation network for facile charge transport.

High Entropy and Low Symmetry: Triclinic High-Entropy Molybdates.

Metal molybdates constitute a promising class of materials with a wide application range. Here, we report, to our knowledge for the first time, on the preparation and characterization of medium-entropy and high-entropy metal molybdates, synthesized by an oxalate-based coprecipitation approach. The high-entropy molybdate crystallizes in a triclinic structure, thus rendering it as high-entropy material with the lowest symmetry reported so far. This is noteworthy because high-entropy materials usually tend to crystallize into highly symmetrical structures. It is expected that application of the high-entropy concept to metal molybdates alters the material's characteristics and adds the features of high-entropy systems, that is, tailorable composition and properties. The phase purity and solid solution nature of the molybdates were confirmed by XRD, Raman spectroscopy, TEM, XPS, and ICP-OES.

Ordered mesoporous metal oxides for electrochemical applications: correlation between structure, electrical properties and device performance.

Ordered mesoporous metal oxides with a high specific surface area, tailored porosity and engineered interfaces are promising materials for electrochemical applications. In particular, the method of evaporation-induced self-assembly allows the formation of nanocrystalline films of controlled thickness on polar substrates. In general, mesoporous materials have the advantage of benefiting from a unique combination of structural, chemical and physical properties. This Perspective article addresses the structural characteristics and the electrical (charge-transport) properties of mesoporous metal oxides and how these affect their application in energy storage, catalysis and gas sensing.

Li7GeS5Br-An Argyrodite Li-Ion Conductor Prepared by Mechanochemical Synthesis.

In recent years, the search for glassy and ceramic Li+ superionic conductors has received significant attention, mainly due to the renaissance of interest in all-solid-state batteries. Here, we report the mechanochemical synthesis of metastable Li7GeS5Br, which is, to the best of our knowledge, the first compound of the Li2S-GeS2-LiBr system. Applying combined synchrotron X-ray diffraction and neutron powder diffraction, we show Li7GeS5Br to crystallize in the F4̅3m space group and to be isostructural with argyrodite-type Li6PS5Br, but with a distinct difference in the S2-/Br- site disorder (and improved anodic stability). Electrochemical impedance spectroscopy indicates an electrical (ionic) conductivity of 0.63 mS cm-1 at 298 K, with an activation energy for conduction of 0.43 eV. This is supported by temperature-dependent 7Li pulsed-field gradient-nuclear magnetic resonance spectroscopy measurements. Overall, the results demonstrate that novel (metastable) argyrodite-type solid electrolytes can be prepared via mechanochemistry that are not accessible by conventional solid-state synthesis routes.

Tailoring the protonic conductivity of porous yttria-stabilized zirconia thin films by surface modification.

Porous yttria-stabilized zirconia (YSZ) thin films were prepared by pulsed laser deposition to investigate the influence of specific surface area on the electronic, oxygen ion, and protonic transport properties. Electrochemical impedance spectroscopy was carried out as a function of temperature, oxygen activity and humidity of the surrounding atmosphere. At high humidity, protons on the surface of the porous YSZ thin films lead to increased conductivity, even for temperatures up to 700 °C. With increasing relative humidity, the activation energy of proton transport decreases because of changes in the transport mechanism from Grotthuss-type to vehicle-type transport. By coating the porous YSZ films with an amorphous titania (TiO2) layer of only a few nanometer thickness using atomic layer deposition, the protonic contribution to conductivity is significantly reduced. Depositing an 18 nm-thick anatase TiO2 surface layer, the protonic conductivity contribution increases again, which can be attributed to enhanced capillary condensation because of the lower pore size. Interestingly, the filling of pores is accompanied by a decrease in proton mobility. Theses results demonstrate the significant effect that the porosity and the surface properties have on the protonic transport and further provide new design principles for developing nanostructured proton-conducting oxides.

There and Back Again-The Journey of LiNiO2 as a Cathode Active Material.

This Review provides a comprehensive overview of LiNiO2 (LNO), almost 30 years after its introduction as a cathode active material. We aim to highlight the physicochemical peculiarities that make LNO a complex material in every aspect. We specifically stress the effect of the Li off-stoichiometry (Li1-z Ni1+z O2 ) on every property of LNO, especially the electrochemical ones. The key instability issues that plague the compound and the strategies that have been implemented so far to overcome them are discussed in detail. Finally, the open questions that remain to be addressed by the scientific community are summarized, and the research directions that seem the most promising to enable LNO to be fully exploited are elucidated.

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.

Improving the capacity of lithium-sulfur batteries by tailoring the polysulfide adsorption efficiency of hierarchical oxygen/nitrogen-functionalized carbon host materials.

The use of monolithic carbons with structural hierarchy and varying amounts of nitrogen and oxygen functionalities as sulfur host materials in high-loading lithium-sulfur cells is reported. The primary focus is on the strength of the polysulfide/carbon interaction with the goal of assessing the effect of (surface) dopant concentration on cathode performance. The adsorption capacity - which is a measure of the interaction strength between the intermediate lithium polysulfide species and the carbon - was found to scale almost linearly with the nitrogen level. Likewise, the discharge capacity of lithium-sulfur cells increased linearly. This positive correlation can be explained by the favorable effect of nitrogen on both the chemical and electronic properties of the carbon host. The incorporation of additional oxygen-containing surface groups into highly nitrogen-functionalized carbon helped to further enhance the polysulfide adsorption efficiency, and therefore the reversible cell capacity. Overall, the areal capacity could be increased by almost 70% to around 3 mA h cm-2. We believe that the design parameters described here provide a blueprint for future carbon-based nanocomposites for high-performance lithium-sulfur cells.

Gas Evolution in LiNi0.5Mn1.5O4/Graphite Cells Studied In Operando by a Combination of Differential Electrochemical Mass Spectrometry, Neutron Imaging, and Pressure Measurements.

The cycling performance and in operando gas analysis of LiNi0.5Mn1.5O4 (LNMO)/graphite cells with reasonably high loading, containing a "standard" carbonate-based electrolyte is reported. The gas evolution over the first couple of cycles was thoroughly investigated via differential electrochemical mass spectrometry (DEMS), neutron imaging and pressure measurements. The main oxidation and reduction products were identified as CO2, H2 and C2H4. In different sets of experiments graphite was substituted with delithiated LiFePO4 (LFP) and LNMO with LFP to distinguish between processes occurring at either anode or cathode and gain mechanistic insights. Both C2H4 and H2 were found to be mainly formed at the anode side, while CO2 is generated at the cathode. The results from DEMS analysis further suggest that the Ni redox couples play a profound role in the evolution of CO2 at the LNMO/electrolyte interface. Lastly, it is shown that the cycling stability and capacity retention of LNMO/graphite cells can be considerably improved by a simple cell formation procedure.

Online Continuous Flow Differential Electrochemical Mass Spectrometry with a Realistic Battery Setup for High-Precision, Long-Term Cycling Tests.

We describe the benefits of an online continuous flow differential electrochemical mass spectrometry (DEMS) method that allows for realistic battery cycling conditions. We provide a detailed description on the buildup and the role of the different components in the system. Special emphasis is given on the cell design. The retention time and response characteristics of the system are tested with the electrolysis of Li2O2. Finally, we show a practical application in which a Li-ion battery is examined. The value of long-term DEMS measurements for the proper evaluation of electrolyte decomposition is demonstrated by an experiment where a Li(1+x)Ni(0.5)Mn(0.3)Co(0.2)O2 (NMC 532)/graphite cell is cycled over 20 charge/discharge cycles.

Simple cathode design for Li­S batteries: cell performance and mechanistic insights by in operando X-ray diffraction.

Rechargeable batteries have been receiving increasing attention over the past several years, particularly with regard to the accelerated development of electric vehicles, but also for their potential in grid storage applications. Among the broad range of cathode active materials, elemental sulfur has the highest theoretical specific capacity, thereby making it one of the most promising positive electrode materials these days. In the present work, we show that already a simple cathode design (cathodes with a non-optimized composite microstructure) provides good electrochemical performance both in coin and pouch cells with sulfur loadings of 2 mg cm−2. Our research data demonstrate that (1) specific capacities of 1000 mA h g−1 can be achieved over 60 cycles at room temperature while the cyclability at elevated temperatures (here, θ > 40 °C) is poor, (2) the discharge is the kinetically rate-limiting process, (3) the major fraction of active sulfur in the electrode is lost during the formation cycle at C/50 and (4) the Li­S cells suffer from drying-out due to continuous electrolyte decomposition on the lithium metal anode. In addition, in operando X-ray diffraction shows Li2S formation (grain size of <10 nm) on discharge and the appearance of single phase ß-sulfur in the sub-100 nm size range ­ rather than the thermodynamically stable orthorhombic polymorph (α-sulfur) ­ by the end of the charge cycle.

Using the High-Entropy Approach to Obtain Multimetal Oxide Nanozymes: Library Synthesis, In Silico Structure-Activity, and Immunoassay Performance.

High-entropy nanomaterials exhibit exceptional mechanical, physical, and chemical properties, finding applications in many industries. Peroxidases are metalloenzymes that accelerate the decomposition of hydrogen peroxide. This study uses the high-entropy approach to generate multimetal oxide-based nanozymes with peroxidase-like activity and explores their application as sensors in ex vivo bioassays. A library of 81 materials was produced using a coprecipitation method for rapid synthesis of up to 100 variants in a single plate. The A and B sites of the magnetite structure, (AA')(BB'B'')2O4, were substituted with up to six different cations (Cu/Fe/Zn/Mg/Mn/Cr). Increasing the compositional complexity improved the catalytic performance; however, substitutions of single elements also caused drastic reductions in the peroxidase-like activity. A generalized linear model was developed describing the relationship between material composition and catalytic activity. Binary interactions between elements that acted synergistically or antagonistically were identified, and a single parameter, the mean interaction effect, was observed to correlate highly with catalytic activity, providing a valuable tool for the design of high-entropy-inspired nanozymes.

Morphology, microstructure, and magnetic properties of ordered large-pore mesoporous cadmium ferrite thin film spin glasses.

Herein, we report the synthesis, microstructure, and magnetic properties of cadmium ferrite (CdFe2O4) thin films with both an ordered cubic network of 18 nm diameter pores and single-phase spinel grains averaging 13 nm in diameter. These mesoporous materials were produced through facile polymer templating of hydrated nitrate salt precursors. Both the morphology and the microstructure, including cation site occupancy and electronic bonding configuration, were analyzed in detail by electron microscopy, grazing incidence small-angle X-ray scattering, Raman and X-ray photoelectron spectroscopy, and N2-physisorption. The obtained data demonstrate that the network of pores is retained up to annealing temperatures as high as 650 °C--the onset of crystallization is at ϑ = (590 ± 10) °C. Furthermore, they show that the polymer-templated samples exhibit a "partially" inverted spinel structure with inversion parameter λ = 0.40 ± 0.02. This differs from microcrystalline CdFe2O4 which shows virtually no inversion. Magnetic susceptibility studies reveal ferrimagnetic spin coupling below 147 K and further point to the likelihood of glassy behavior at low temperature (T(f) ≈ 60 K). In addition, analysis of room temperature magnetization data indicates the presence of sub-10 nm diameter superparamagnetic clusters in an otherwise paramagnetic environment.

Facile solid-state synthesis of a layered Co-free, Ni-rich cathode material for all-solid-state batteries.

Layered Ni-rich oxides are attractive cathode active materials for secondary battery applications. Combining them with inorganic superionic conductors and high-capacity anodes can significantly increase energy density. Herein we successfully synthesized spherical secondary particles of a Mn-substituted LiNiO2, LiNi0.95Mn0.05O2 (a Co-free NMX material), for use in bulk-type lithium-thiophosphate-based all-solid-state batteries.

In situ neutron diffraction to investigate the solid-state synthesis of Ni-rich cathode materials.

Studying chemical reactions in real time can provide unparalleled insight into the evolution of intermediate species and can provide guidance to optimize the reaction conditions. For solid-state synthesis reactions, powder diffraction has been demonstrated as an effective tool for resolving the structural evolution taking place upon heating. The synthesis of layered Ni-rich transition-metal oxides at a large scale (grams to kilograms) is highly relevant as these materials are commonly employed as cathodes for Li-ion batteries. In this work, in situ neutron diffraction was used to monitor the reaction mechanism during the high-temperature synthesis of Ni-rich cathode materials with a varying ratio of Ni:Mn from industrially relevant hydroxide precursors. Rietveld refinement was further used to model the observed phase evolution during synthesis and compare the behaviour of the materials as a function of temperature. The results presented herein confirm the suitability of in situ neutron diffraction to investigate the synthesis of batches of several grams of electrode materials with well-controlled stoichiometry. Furthermore, monitoring the structural evolution of the mixtures with varying Ni:Mn content in real time reveals a delayed onset of li-thia-tion as the Mn content is increased, necessitating the use of higher annealing temperatures to achieve layering.