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At least 721 records · Page 40

Accelerated Modeling of Lithium Diffusion in Solid State Electrolytes using Artificial Neural Networks

Abstract Previous efforts to understand structure‐function relationships in high ionic conductivity materials for solid state batteries have predominantly relied on density functional theory (DFT‐) based ab initio molecular dynamics (MD). Such simulations, however, are computationally demanding and cannot be reasonably applied to large systems containing more than a hundred atoms. Here, an artificial neural network (ANN) is trained to accelerate the calculation of high accuracy atomic forces and energies used during such MD simulations. After carefully training a robust ANN for four and five element systems, nearly identical lithium ion diffusivities are obtained for Li 10 GeP 2 S 12 (LGPS) when benchmarking the ANN‐MD results with DFT‐MD. Applying the ANN‐MD approach, the effect of chlorine doping on the lithium diffusivity is calculated in an LGPS‐like structure and it is found that a dopant concentration of 1.3% maximizes ionic conductivity. The optimal concentration balances the competing consequences of effective atomic radii and dielectric constants on lithium diffusion and agrees with the experimental composition. Performing simulations at the resolution necessary to model experimentally relevant and optimal concentrations would be infeasible with traditional DFT‐MD. Systems that require a large number of simulated atoms can be studied more efficiently while maintaining high accuracy with the proposed ANN‐MD framework.

Rao, Karun K.↗

Li 2.9 Fe 0.9 Zr 0.1 Cl 6 as Redox-Active Catholyte for Solid-State Li-Ion Batteries

Solid electrolytes are one of the key challenges that hinder the commercialization of all-solid-state batteries. Most efforts have been made to advance the development of solid electrolytes as separators, while the development of catholytes, particularly redox-active catholytes, has been less extensively studied. The high loading of catholytes in composite cathodes, while facilitating ionic conduction, drastically decreases the energy density of the battery. Here, we report an alternative strategy to improve the energy density by using Li 2.9 Fe 0.9 Zr 0.1 Cl 6 as a redox-active catholyte. With a composite cathode containing uncoated LiCoO2 and Li 2.9 Fe 0.9 Zr 0.1 Cl 6 , the solid-state cell not only shows excellent rate capability and stable long-term cycling, benefiting from the high ionic conductivity of Li 2.9 Fe 0.9 Zr 0.1 Cl 6 , but also shows a high cathode specific capacity of ~153 mAh·g –1 . This study broadens the chemical space of the materials design for lithium-ion conductors with redox-active elements (e.g., Fe, Ti, V, and Cr), offering new opportunities to reduce the cost and improve the energy density for all-solid-state batteries.

36 MATERIALS SCIENCE↗

Electrochemically induced fracture in LLZO: How the interplay between flaw density and electrostatic potential affects operability

Fracture and short circuit in the Li 7 La 3 Zr 2 O 12 (LLZO) solid electrolyte are two key issues that prevent its adoption in battery cells. In this paper, we utilize phase-field simulations that couple electrochemistry and fracture to evaluate the maximum electric potential that LLZO electrolytes can support as a function of crack density. In the case of a single crack, we find that the applied potential at the onset of crack propagation exhibits inverse square root scaling with respect to crack length, analogous to classical fracture mechanics. Here, we further find that the short-circuit potential scales linearly with crack length. In the realistic case where the solid electrolyte contains multiple cracks, we reveal that failure fits the Weibull model. The failure distributions shift to favor failure at lower overpotentials as areal crack density increases. Furthermore, when flawless interfacial buffers are placed between the applied potential and the bulk of the electrolyte, failure is mitigated. When constant currents are applied, current focuses in near-surface flaws, leading to crack propagation and short circuit. We find that buffered samples sustain larger currents without reaching unstable overpotentials and without failing. Our findings suggest several mitigation strategies for improving the ability of LLZO to support larger currents and improve operability.

25 ENERGY STORAGE↗

Structural Complexities in Sodium Ion Conductive Antiperovskite Revealed by Cryogenic Transmission Electron Microscopy

Here we use low-dose cryogenic transmission electron microscopy (cryo-TEM) to investigate the atomic-scale structure of antiperovskite Na 2 NH 2 BH 4 crystals by preserving the room-temperature cubic phase and carefully monitoring the electron dose. Via quantitative analysis of electron beam damage using selected area electron diffraction, we find cryogenic imaging provides 6-fold improvement in beam stability for this solid electrolyte. Cryo-TEM images obtained from flat crystals revealed the presence of a new, long-range-ordered supercell with a cubic phase. The supercell exhibits doubled unit cell dimensions of 9.4 Å × 9.4 Å as compared to the cubic lattice structure revealed by X-ray crystallography of 4.7 Å × 4.7 Å. The comparison between the experimental image and simulated potential map indicates the origin of the supercell is a vacancy ordering of sodium atoms. This work demonstrates the potential of using cryo-TEM imaging to study the atomic-scale structure of air- and electron-beam-sensitive antiperovskite-type solid electrolytes.

36 MATERIALS SCIENCE↗

Can a Coating Mitigate Molten Na Dendrite Growth in NaSICON Under High Current Density?

Alkali metals are among the most desirable negative electrodes for long duration energy storage due to their extremely high capacities. Currently, only high-temperature (>250 °C) batteries have successfully used alkali electrodes in commercial applications, due to limitations imposed by solid electrolytes, such as low conductivity at moderate temperatures and susceptibility to dendrites. Toward enabling the next generation of grid-scale, long duration batteries, we aim to develop molten sodium (Na) systems that operate with commercially attractive performance metrics including high current density (>100 mA cm –2 ), low temperature (<200 °C), and long discharge times (>12 h). In this work, we focus on the performance of NaSICON solid electrolytes in sodium symmetric cells at 110 °C. Specifically, we use a tin (Sn) coating on NaSICON to reduce interfacial resistance by a factor of 10, enabling molten Na symmetric cell operation with “discharge” durations up to 23 h at 100 mA cm –2 and 110 °C. Unidirectional galvanostatic testing shows a 70% overpotential reduction, and electrochemical impedance spectroscopy (EIS) highlights the reduction in interfacial resistance due to the Sn coating. Detailed scanning electron microscopy (SEM) and energy-dispersive spectroscopy (EDS) show that Sn-coated NaSICON enables current densities of up to 500 mA cm –2 at 110 °C by suppressing dendrite formation at the plating interface (Mode I). In conclusion, this analysis also provides a mechanistic understanding of dendrite formation at current densities up to 1000 mA cm –2 , highlighting the importance of effective coatings that will enable advanced battery technologies for long-term energy storage.

25 ENERGY STORAGE↗

Li 0.625 Al 0.125 H 0.25 Cl 0.75 O 0.25 Superionic Conductor with Disordered Rock-Salt Structure

Solid-state Li-ion conductors are of broad interest in electrochemical energy storage, especially in solid-state Li batteries that serve as a promising alternative for the next-generation safe and high-energy-density batteries. Exploring solid-state superionic conductors is significant for the development of solid-state Li batteries with high performance. Herein, we report a disordered rock-salt (A 1 B 1 )-structured solid electrolyte (Li 0.625 Al 0.125 H 0.25 )(Cl 0.75 O 0.25 ) (abbr. LAHCO) that was synthesized using Li 2 OHCl and LiAlCl 4 as precursors. Neutron diffraction reveals that Li, Al, and H atoms occupy the A sites and O and Cl atoms occupy the B sites in the A 1 B 1 structure for pure LAHCO. The LAHCO compound with excess LiAlCl 4 shows the highest Li + ionic conductivity of ~10 –4 S cm –1 at room temperature due to the disordering induced by configurational entropy as well as the entropy of mixing. Moreover, LAHCO–LiAlCl 4 solid electrolyte exhibits a stable polarization voltage under a current density of 5–50 μA cm –2 in Li symmetric cells. Furthermore, this work not only explicates the importance of Li-ion conductors with a rock-salt structure but also contributes toward the development of solid-state Li-ion conductors for broad applications.

25 ENERGY STORAGE↗

Rational Designed Mixed-Conductive Sulfur Cathodes for All-Solid-State Lithium Batteries

All-solid-state lithium–sulfur batteries (ASSLSBs) hold great promise for safe and high-energy-density energy storage. However, developing high-performance sulfur cathodes has been proven difficult due to low electronic and ionic conductivities and large volume change of sulfur during charge and discharge. Here, we reported an approach to synthesize sulfur cathodes with a mixed electronic and ionic conductivity by infiltrating a solution consisting of Li 3 PS 4 (LPS) solid electrolyte and S active material into a mesoporous carbon (CMK-3). This approach leads to a uniform dispersion of amorphous Li 3 PS 7 (L 3 PS) catholyte in an electronically conductive carbon matrix, enabling high and balanced electronic/ionic conductivities in the cathode composite. The inherent porous structure of CMK-3 also helps to accommodate the strain/stress generated during the expansion and shrinkage of the active material. In sulfide-based all-solid-state batteries with Li metal as the anode, this cathode composite delivered a high capacity of 1025 mAh g –1 after 50 cycles at 60 °C at 1/8C. This work highlights the important role of high and balanced electronic and ionic conductivities in developing high-performance sulfur cathodes for ASSLSBs.

25 ENERGY STORAGE↗

Li Stripping Behavior of Anode‐Free Solid‐State Batteries Under Intermittent‐Current Discharge Conditions

Anode‐free manufacturing holds promise to enable high energy densities and lower Lithium (Li)‐metal solid‐state batteries (LMSSBs). Nevertheless, in contrast to thick Li foil (>50 µm), the stripping capacity of in situ‐formed Li (10–30 µm) is limited due to diminished creep flow, resulting in reduced accessible capacity. This study explores the correlation between stripping capacity and surface roughness of garnet Li 7 La 3 Zr 2 O 12 (LLZO) solid electrolyte. The results reveal that stripping capacity can be enhanced through the surface modification of solid electrolytes. Additionally, this study scrutinizes the stripping behavior of in situ Li under intermittent‐current discharge conditions, which are more relevant to the operational conditions of electric vehicles (EVs). It is demonstrated that, when compared to constant‐current stripping, intermittent‐current stripping effectively suppresses void formation and enhances the stripping capacity of in situ Li by 40%. It is considered that the intermittent current inhibits the accumulation of Li vacancies, thereby delaying the void formation. These findings provide valuable insights into the development of high‐performance anode‐free LMSSBs for EVs.

25 ENERGY STORAGE↗

Au and Pt Diffusion in Electrodeposited Amorphous Sb 2 Te 3 Thin Films

Amorphous Sb 2 Te 3 thin films are synthesized using electrodeposition in different thicknesses to explore their solid electrolytic nature with respect to some noble metals. Au and Pt are used as the substrate materials and thermally diffused into the Sb 2 Te 3 films under passivated and nonpassivated conditions. Rutherford backscattering spectrometry is used to study the Au and Pt diffusion into the films as a function of depth. It is found that Au diffuses into the Sb 2 Te 3 thin films even at room temperature. In contrast, there is no observable diffusion of Pt at room temperature. At a higher temperature (i.e., 200 °C), both Au and Pt diffuse into the Sb 2 Te 3 thin films and Au diffusion is more significant than Pt. Overall, the findings suggest that amorphous Sb 2 Te 3 can be used as a good solid electrolyte to permit the diffusion of some noble metals such as Au and Pt.

36 MATERIALS SCIENCE↗

A novel solid oxide electrolytic cell with reduced endothermic load for CO 2 electrolysis using (La 0.80 Sr 0.20 ) 0.95 MnO 3-δ cathode

CO 2 conversion to CO via solid oxide electrolysis provides a potentially efficient method for converting CO 2 into an industrially relevant product. A solid oxide electrolysis cell with (La 0.80 Sr 0.20 ) 0.95 MnO 3-δ (LSM) as the CO 2 reduction cathode, yttrium stabilized zirconia (YSZ) as electrolyte, and nickel as the H 2 oxidation anode was operated 800 °C and 850 °C. Thermogravimetric analysis of the LSM material showed no catalyst oxidation at operating temperatures allowing for CO 2 electrolysis without reducing safe gas. In addition, no cathode material mass gain was observed in the presence of CO suggesting little to no carbon deposition occurred above 750 °C. The formation rates of CO for the cell reached 1.15 mL∙min-1∙ cm -2 for an applied current of 150 mA∙cm -2 achieving a faradaic efficiency of 100 %. Furthermore, the cell displayed good stability in the short-term CO 2 electrolysis test with a nominal voltage drop of 4 mV h -1 for 10 h at 850°C. This study shows the feasibility of operating a solid oxide CO 2 electrolysis cell for CO production with H 2 at the anode to reduce endothermic process load.

(La0.80Sr0.20)0.95MnO3-δ↗

Tuning collective anion motion enables superionic conductivity in solid-state halide electrolytes

Halides of the family Li 3 MX 6 (M = Y, In, Sc and so on, X = halogen) are emerging solid electrolyte materials for all-solid-state Li-ion batteries. They show greater chemical stability and wider electrochemical stability windows than existing sulfide solid electrolytes, but have lower room-temperature ionic conductivities. Here, in this work, we report the discovery that the superionic transition in Li 3 YCl 6 is triggered by the collective motion of anions, as evidenced by synchrotron X-ray and neutron scattering characterizations and ab initio molecular dynamics simulations. Based on this finding, we used a rational design strategy to lower the transition temperature and thus improve the room-temperature ionic conductivity of this family of compounds. We accordingly synthesized Li 3 YCl x Br 6-x and Li 3 GdCl 3 Br 3 and achieved very high room-temperature conductivities of 6.1 and 11 mS cm -1 for Li 3 YCl 4.5 Br 1.5 and Li 3 GdCl 3 Br 3 , respectively. These findings open new routes to the design of room-temperature superionic conductors for high-performance solid batteries.

25 ENERGY STORAGE↗

Multiscale simulations of novel lithium electrolytes for improved processability and performance of solid-state batteries

In FY23, we performed atomic-scale simulations and developed analysis tools to understand the dynamic behaviors of Li ions and cation/anion components and predict mechanical properties in a new class of Li-ion solid electrolytes (SEs) developed by TRINA. Specifically, we revealed the transport characteristics of Li ions in anion sublattice, rotational dynamics of anion and cation components, and the effect of cation and anion on Li transport as well as interactions between cation and anions. The results imply that the transport characteristics in these soft materials may be affected by processing conditions significantly, which will offer the necessary insights to optimize these future SEs and accelerate the deployment of practical and easily processable Solid-state batteries (SSBs).

25 ENERGY STORAGE↗

Simulations with machine learning potentials identify the ion conduction mechanism mediating non-Arrhenius behavior in LGPS

Abstract Li 10 Ge(PS 6 ) 2 (LGPS) is a highly concentrated solid electrolyte, in which Coulombic repulsion between neighboring cations is hypothesized as the underlying reason for concerted ion hopping, a mechanism common among superionic conductors such as Li 7 La 3 Zr 2 O 12 (LLZO) and Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 (LATP). While first principles simulations using molecular dynamics (MD) provide insight into the Li + transport mechanism, historically, there has been a gap in the temperature ranges studied in simulations and experiments. Here, we used a neural network potential trained on density functional theory (DFT) simulations, to run up to 40-nanosecond long MD simulations at DFT-like accuracy to characterize the ion conduction mechanisms across a range of temperatures that includes previous simulations and experimental studies. We have confirmed a Li + sublattice phase transition in LGPS around 400 K, below which the ab -plane diffusivity D a b ∗ is drastically reduced. Concomitant with the sublattice phase transition near 400 K, there is less cation-cation (cross) correlation, as characterized by Haven ratios closer to 1, and the vibrations in the system are more harmonic at lower temperature. Intuitively, at high temperature, the collection of vibrational modes may be sufficient to drive concerted ion hops. However, near room temperature, the vibrational modes available may be insufficient to overcome electrostatic repulsion, thus resulting in less correlated ion motion and comparatively slower ion conduction. Such phenomena of a sublattice phase transition, below which concerted hopping plays a less significant role, may be extended to other highly concentrated solid electrolytes such as LLZO and LATP.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Low-temperature and high-rate-charging lithium metal batteries enabled by an electrochemically active monolayer-regulated interface

Stable operation of rechargeable lithium (Li)-based batteries at low temperatures is vital for cold-climate applications but is plagued with dendritic Li plating and unstable solid-electrolyte interphase (SEI). Here we report high-performance Li-metal batteries under low-temperature and high-rate-charging conditions. This is realized by utilizing a self-assembled monolayer of electrochemically active molecules on current collectors that regulates the nanostructure and composition of SEI and deposition morphology of Li metal anodes. A multilayer SEI containing a LiF-rich inner phase and amorphous outer layer effectively seals the Li surface in contrast to the conventional impassive SEI at low temperatures. As a result, galvanic Li corrosion and self-discharge were suppressed; stable Li deposition was realized from -60º to 45ºC; and a Li|LiCoO 2 cell with a capacity of 2.0 mAh cm -2 displayed a 200-cycle life at -15ºC with a recharge time of 45 minutes.

25 ENERGY STORAGE↗

Ionic-Based Electrochemical Gas Sensors for Low-Cost, High-Sensitivity SO2 Detection

Sulfur dioxide (SO2) is a toxic gas associated with adverse health and environmental effects that necessitate reliable monitoring techniques. Here, we report the development of an all-solid-state electrochemical sensor utilizing a lithium borate (Li3BO3) solid electrolyte capable of subppm of SO2 detection. While subppm of SO2 sensing has been previously demonstrated in other solid-state electrolyte systems─such as stabilized zirconia, natrium super ionic conductors (NASICON) under mixed-potential conditions─here we establish Li3BO3 as an alternative solid electrolyte enabling equilibrium potentiometric sensing in an all-solid architecture. This sensor demonstrates a detection limit of at least 0.25 ppm, surpassing the human-olfactory threshold and meeting the rigorous requirements for industrial and personal monitoring applications. The sensing mechanism relies on the formation of Li2SO4 on the electrode surface, as evidenced by multimodal characterization techniques, including Raman spectroscopy, scanning electron microscopy (SEM), and scanning transmission electron microscopy (STEM). The strong linear correlation between the open-circuit potential (OCV) and the logarithm of SO2 concentration between 0.25 and 2 ppm indicates that the response is Nernstian in nature.

Lagunas, Francisco (ORCID:000000026377683X)↗

Understanding the Origin of the Nonpassivating Behavior of Si-Based Anodes during the Initial Cycles

In this contribution, we combined electrochemical cycling and X-ray photoelectron spectroscopy (XPS) to understand the nonpassivating behavior of the solid electrolyte interphase (SEI) on Si anodes during the first cycles. Based on galvanostatic measurements, we show that the irreversible capacity loss is reduced after the first cycle, and it stays almost constant from the second cycle onwards. XPS was used to determine the root causes of the Coulombic inefficiency, showing that the rate of decomposition of the organic solvents strongly decreased after the first cycle, whereas the rate of salt decomposition is almost unchanged between cycles. We determine that the inhibition of the decomposition reaction of the organic solvent is responsible for the lower Coulombic loss during the second electrochemical cycle in comparison to the first, whereas the nonpassivating behavior toward the salt decomposition is one of the main causes of capacity loss upon cycling. Here, we further revisit the role of cracking in contributing to capacity loss. Whereas high volumetric expansion remains an issue plaguing the performance of Si anodes, our chronoamperometry studies reveal that the SEI formed on Si anodes does not passivate even when the electrode is fully expanded, and no additional surface is exposed. Overall, our work establishes the need to address the chemical and electrochemical instability of the SEI on the Si anode in addition to the more notorious issue of cracking.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Lithium-ion battery physics and statistics-based state of health model

A pseudo-2d model using COMSOL Multiphysics® software is developed to simulate performance and performance degradation of Li-ion batteries consisting of layered and olivine cathodes with graphite anode when subjected to peak shaving grid service. Multiple degradation pathways are considered, including solid electrolyte interphase (SEI) formation and breakdown at the anode, cathode dissolution and its synergistic effect on SEI formation at the anode. The model is validated by simulating commercial cylindrical cell performance. A global model is developed to simulate performance across all chemistries, along with individual chemistry models using global model parameters as initial values. There is good agreement between these models for various optimization parameters such as SEI equilibrium potential, cathode dissolution exchange current density, solvent diffusivity in the SEI and SEI ionic conductivity. To circumvent time constraints related to the COMSOL model, a 0d global model is developed which fits data well and provides more clarity on differences in cathode dissolution exchange current density. Again, good agreement for various optimization parameters is obtained among the COMSOL global & individual chemistry models and the 0-d model. The lessons learned from the physics-based model is used to develop a top down statistics-based model using current, voltage and anode volumetric change per mole lithium intercalated, along with their interactions as degradation predictors. This model predicts out of sample degradation for multiple grid services and electric vehicle drive cycle with high accuracy and provides the pathway to develop an efficient battery management system combining machine learning and findings from physics-based computationally intensive algorithms.

Crawford, Aladsair J.↗

Lithium Polymer Electrolytes and Solid State NMR

Research is being done at the Glenn Research Center (GRC) developing new kinds of batteries that do not depend on a solution. Currently, batteries use liquid electrolytes containing lithium. Problems with the liquid electrolyte are (1) solvents used can leak out of the battery, so larger, more restrictive, packages have to be made, inhibiting the diversity of application and decreasing the power density; (2) the liquid is incompatible with the lithium metal anode, so alternative, less efficient, anodes are required. The Materials Department at GRC has been working to synthesize polymer electrolytes that can replace the liquid electrolytes. The advantages are that polymer electrolytes do not have the potential to leak so they can be used for a variety of tasks, small or large, including in the space rover or in space suits. The polymers generated by Dr. Mary Ann Meador's group are in the form of rod -coil structures. The rod aspect gives the polymer structural integrity, while the coil makes it flexible. Lithium ions are used in these polymers because of their high mobility. The coils have repeating units of oxygen which stabilize the positive lithium by donating electron density. This aids in the movement of the lithium within the polymer, which contributes to higher conductivity. In addition to conductivity testing, these polymers are characterized using DSC, TGA, FTIR, and solid state NMR. Solid state NMR is used in classifying materials that are not soluble in solvents, such as polymers. The NMR spins the sample at a magic angle (54.7') allowing the significant peaks to emerge. Although solid state NMR is a helpful technique in determining bonding, the process of preparing the sample and tuning it properly are intricate jobs that require patience; especially since each run takes about six hours. The NMR allows for the advancement of polymer synthesis by showing if the expected results were achieved. Using the NMR, in addition to looking at polymers, allows for participation on a variety of other projects, including aero-gels and carbon graphite mat en als. The goals of the polymer electrolyte research are to improve the physical properties of the polymers. This includes improving conductivity, durability, and expanding the temperature range over which it is effective. Currently, good conductivity is only present at high temperatures. My goals are to experiment with different arrangements of rods and coils to achieve these desirable properties. Some of my experiments include changing the number of repeat units in the polymer, the size of the diamines, and the types of coil. Analysis of these new polymers indicates improvement in some properties, such as lower glass transition temperature; however, they are not as flexible as desired. With further research we hope to produce polymers that encompass all of these properties to a high degree.

Berkeley, Emily R.↗