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1. Perovskite Na-ion conductors developed from analogous Li _3x La _2/3−x TiO ₃ (LLTO): chemo-mechanical and defect engineering

   https://doi.org/10.1039/d1ta04252a  

   Lin, Yu-Ying ; Gustafson, William J. ; Murray, Shannon E. ; Shoemaker, Daniel P. ; Ertekin, Elif ; Krogstad, Jessica A. ; Perry, Nicola H. ( September 2021 , Journal of Materials Chemistry A)

   Na-ion conducting solid electrolytes can enable both the enhanced safety profile of all-solid-state-batteries and the transition to an earth-abundant charge-carrier for large-scale stationary storage. In this work, we developed new perovskite-structured Na-ion conductors from the analogous fast Li-ion conducting Li 3 x La 2/3− x TiO 3 (LLTO), testing strategies of chemo-mechanical and defect engineering. Na x La 2/3−1/3 x ZrO 3 (NLZ) and Na x La 1/3−1/3 x Ba 0.5 ZrO 3 (NLBZ) were prepared using a modified Pechini method with varying initial stoichiometries and sintering temperatures. With the substitution of larger framework cations Zr 4+ and Ba 2+ on B- and A-sites respectively, NLZ and NLBZ both had larger lattice parameters compared to LLTO, in order to accommodate and potentially enhance the transport of larger Na ions. Additionally, we sought to introduce Na vacancies through (a) sub-stoichiometric Na : La ratios, (b) Na loss during sintering, and (c) donor doping with Nb. AC impedance spectroscopy and DC polarization experiments were performed on both Na 0.5 La 0.5 ZrO 3 and Na 0.25 La 0.25 Ba 0.5 ZrO 3 in controlled gas environments (variable oxygen partial pressure, humidity) at elevated temperatures to quantify the contributions of various possible charge carriers (sodiummore »ions, holes, electrons, oxygen ions, protons). Our results showed that the lattice-enlarged NLZ and NLBZ exhibited ∼19× (conventional sintering)/49× (spark plasma sintering) and ∼7× higher Na-ion conductivities, respectively, compared to unexpanded Na 0.42 La 0.525 TiO 3 . Moreover, the Na-ion conductivity of Na 0.5 La 0.5 ZrO 3 is comparable with that of NaNbO 3 , despite having half the carrier concentration. Additionally, more than 96% of the total conductivity in dry conditions was contributed by sodium ions for both compositions, with negligible electronic conductivity and little oxygen ion conductivity. We also identified factors that limited Na-ion transport: NLZ and NLBZ were both challenging to densify using conventional sintering without the loss of Na because of its volatility. With spark plasma sintering, higher density can be achieved. In addition, the NLZ perovskite phase appeared unable to accommodate significant Na deficiency, whereas NLBZ allowed some. Density functional theory calculations supported a thermodynamic limitation to creation of Na-deficient NLZ in favor of a pyrochlore-type phase. Humid environments generated different behavior: in Na 0.25 La 0.25 Ba 0.5 ZrO 3 , incorporated protons raised total conductivity, whereas in Na 0.5 La 0.5 ZrO 3 , they lowered total conductivity. Ultimately, this systematic approach revealed both effective approaches and limitations to achieving super-ionic Na-ion conductivity, which may eventually be overcome through alternative processing routes.« less
2. Cycling of block copolymer composites with lithium-conducting ceramic nanoparticles

   https://doi.org/10.3389/fchem.2023.1199677  

   Patel, Vivaan ; Dato, Michael A. ; Chakraborty, Saheli ; Jiang, Xi ; Chen, Min ; Moy, Matthew ; Yu, Xiaopeng ; Maslyn, Jacqueline A. ; Hu, Linhua ; Cabana, Jordi ; et al ( June 2023 , Frontiers in Chemistry)

   Solid polymer and perovskite-type ceramic electrolytes have both shown promise in advancing solid-state lithium metal batteries. Despite their favorable interfacial stability against lithium metal, polymer electrolytes face issues due to their low ionic conductivity and poor mechanical strength. Highly conductive and mechanically robust ceramics, on the other hand, cannot physically remain in contact with redox-active particles that expand and contract during charge-discharge cycles unless excessive pressures are used. To overcome the disadvantages of each material, polymer-ceramic composites can be formed; however, depletion interactions will always lead to aggregation of the ceramic particles if a homopolymer above its melting temperature is used. In this study, we incorporate Li 0.33 La 0.56 TiO 3 (LLTO) nanoparticles into a block copolymer, polystyrene- b -poly (ethylene oxide) (SEO), to develop a polymer-composite electrolyte (SEO-LLTO). TEMs of the same nanoparticles in polyethylene oxide (PEO) show highly aggregated particles whereas a significant fraction of the nanoparticles are dispersed within the PEO-rich lamellae of the SEO-LLTO electrolyte. We use synchrotron hard x-ray microtomography to study the cell failure and interfacial stability of SEO-LLTO in cycled lithium-lithium symmetric cells. Three-dimensional tomograms reveal the formation of large globular lithium structures in the vicinity of the LLTO aggregates. Encasing themore »SEO-LLTO between layers of SEO to form a “sandwich” electrolyte, we prevent direct contact of LLTO with lithium metal, which allows for the passage of seven-fold higher current densities without signatures of lithium deposition around LLTO. We posit that eliminating particle clustering and direct contact of LLTO and lithium metal through dry processing techniques is crucial to enabling composite electrolytes.« less
3. (Digital Presentation) Activating the Ion Transmission at the Cathode-Electrolyte Interface in All-Solid-State Batteries

   https://doi.org/10.1149/MA2022-012384mtgabs  

   Zhang, Yuxuan ; Kivevele, Thomas ; Song, Han Wook ; Lee, Sunghwan ( July 2022 , ECS Meeting Abstracts)

   All-solid-state batteries (ASSBs) have garnered increasing attention due to the enhanced safety, featuring nonflammable solid electrolytes as well as the potential to achieve high energy density. 1 The advancement of the ASSBs is expected to provide, arguably, the most straightforward path towards practical, high-energy, and rechargeable batteries based on metallic anodes. 1 However, the sluggish ion transmission at the cathode-electrolyte (solid/solid) interface would result in the high resistant at the contact and limit the practical implementation of these all solid-state materials in real world batteries. 2 Several methods were suggested to enhance the kinetic condition of the ion migration between the cathode and the solid electrolyte (SE). 3 A composite strategy that mixes active materials and SEs for the cathode is a general way to decrease the ion transmission barrier at the cathode-electrolyte interface. 3 The active material concentration in the cathode is reduced as much as the SE portion increases by which the energy density of the ASSB is restricted. In addition, the mixing approach generally accompanies lattice mismatches between the cathode active materials and the SE, thus providing only limited improvements, which is imputed by random contacts between the cathode active materials and the SE during the mixingmore »process. Implementing high-pressure for the electrode and electrolyte of ASSB in the assembling process has been verified is a but effective way to boost the ion transmission ability between the cathode active materials and the SE by decreasing the grain boundary impedance. Whereas the short-circuit of the battery would be induced by the mechanical deformation of the electrolyte under high pressure. 4 Herein, we demonstrate a novel way to address the ion transmission problem at the cathode-electrolyte interface in ASSBs. Starting from the cathode configuration, the finite element method (FEM) was employed to evaluate the current concentration and the distribution of the space charge layer at the cathode-electrolyte interface. Hierarchical three-dimensional (HTD) structures are found to have a higher Li + transfer number (t Li+ ), fewer free anions, and the weaker space-charge layer at the cathode-electrolyte interface in the resulting FEM simulation. To take advantage of the HTD structure, stereolithography is adopted as a manufacturing technique and single-crystalline Ni-rich (SCN) materials are selected as the active materials. Next, the manufactured HTD cathode is sintered at 600 °C in an N 2 atmosphere for the carbonization of the resin, which induces sufficient electronic conductivity for the cathode. Then, the gel-like Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 (LATP) precursor is synthesized and filled into the voids of the HTD structure cathode sufficiently. And the filled HTD structure cathodes are sintered at 900 °C to achieve the crystallization of the LATP gel. Scanning transmission electron microscopy (STEM) is used to unveil the morphology of the cathode-electrolyte interface between the sintered HTD cathode and the in-situ generated electrolyte (LATP). A transient phase has been found generated at the interface and matched with both lattices of the SCN and the SE, accelerating the transmission of the Li-ions, which is further verified by density functional theory calculations. In addition, Electron Energy Loss Spectroscopy demonstrates the preserved interface between HTD cathode and SEs. Atomic force microscopy is employed to measure the potential image of the cross-sectional interface by the peak force tapping mode. The average potential of modified samples is lower than the sample that mix SCN and SEs simply in the 2D planar structure, which confirms a weakened space charge layer by the enhanced contact capability as well as the ion transmission ability. To see if the demonstrated method is universally applicable, LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811) is selected as the cathode active material and manufactured in the same way as the SCN. The HTD cathode based on NCM811 exhibits higher electrochemical performance compared with the reference sample based on the 2D planar mixing-type cathode. We believe such a demonstrated universal strategy provides a new guideline to engineer the cathode/electrolyte interface by revolutionizing electrode structures that can be applicable to all-solid-state batteries. Figure 1. Schematic of comparing of traditional 2D planar cathode and HTD cathode in ASSB Tikekar, M. D. , et al. , Nature Energy (2016) 1 (9), 16114 Banerjee, A. , et al. , Chem Rev (2020) 120 (14), 6878 Chen, R. , et al. , Chem Rev (2020) 120 (14), 6820 Cheng, X. , et al. , Advanced Energy Materials (2018) 8 (7) Figure 1« less
4. Designing Optimal Perovskite Structure for High Ionic Conduction

   https://doi.org/10.1002/adma.201905178  

   Gao, Ran ; Jain, Abhinav C. P. ; Pandya, Shishir ; Dong, Yongqi ; Yuan, Yakun ; Zhou, Hua ; Dedon, Liv R. ; Thoréton, Vincent ; Saremi, Sahar ; Xu, Ruijuan ; et al ( November 2019 , Advanced Materials)

   Solid‐oxide fuel/electrolyzer cells are limited by a dearth of electrolyte materials with low ohmic loss and an incomplete understanding of the structure–property relationships that would enable the rational design of better materials. Here, using epitaxial thin‐film growth, synchrotron radiation, impedance spectroscopy, and density‐functional theory, the impact of structural parameters (i.e., unit‐cell volume and octahedral rotations) on ionic conductivity is delineated in La_0.9Sr_0.1Ga_0.95Mg_0.05O_3–δ. As compared to the zero‐strain state, compressive strain reduces the unit‐cell volume while maintaining large octahedral rotations, resulting in a strong reduction of ionic conductivity, while tensile strain increases the unit‐cell volume while quenching octahedral rotations, resulting in a negligible effect on the ionic conductivity. Calculations reveal that larger unit‐cell volumes and octahedral rotations decrease migration barriers and create low‐energy migration pathways, respectively. The desired combination of large unit‐cell volume and octahedral rotations is normally contraindicated, but through the creation of superlattice structures both expanded unit‐cell volume and large octahedral rotations are experimentally realized, which result in an enhancement of the ionic conductivity. All told, the potential to tune ionic conductivity with structure alone by a factor of ≈2.5 at around 600 °C is observed, which sheds new light on the rational design of ion‐conducting perovskite electrolytes.
5. Microstructural impacts on ionic conductivity of oxide solid electrolytes from a combined atomistic-mesoscale approach

   https://doi.org/10.1038/s41524-021-00681-8  

   Heo, Tae Wook ; Grieder, Andrew ; Wang, Bo ; Wood, Marissa ; Hsu, Tim ; Akhade, Sneha A. ; Wan, Liwen F. ; Chen, Long-Qing ; Adelstein, Nicole ; Wood, Brandon C. ( December 2021 , npj Computational Materials)

   Although multiple oxide-based solid electrolyte materials with intrinsically high ionic conductivities have emerged, practical processing and synthesis routes introduce grain boundaries and other interfaces that can perturb primary conduction channels. To directly probe these effects, we demonstrate an efficient and general mesoscopic computational method capable of predicting effective ionic conductivity through a complex polycrystalline oxide-based solid electrolyte microstructure without relying on simplified equivalent circuit description. We parameterize the framework for Li_7-xLa₃Zr₂O₁₂(LLZO) garnet solid electrolyte by combining synthetic microstructures from phase-field simulations with diffusivities from molecular dynamics simulations of ordered and disordered systems. Systematically designed simulations reveal an interdependence between atomistic and mesoscopic microstructural impacts on the effective ionic conductivity of polycrystalline LLZO, quantified by newly defined metrics that characterize the complex ionic transport mechanism. Our results provide fundamental understanding of the physical origins of the reported variability in ionic conductivities based on an extensive analysis of literature data, while simultaneously outlining practical design guidance for achieving desired ionic transport properties based on conditions for which sensitivity to microstructural features is highest. Additional implications of our results are discussed, including a possible connection between ion conduction behavior and dendrite formation.