Search NASA⌕ Search

Engineering topics

Su, Laisuo

Publications and source records attributed to Su, Laisuo.

At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

LaCl 3 -based sodium halide solid electrolytes with high ionic conductivity for all-solid-state batteries

To enable high performance of all solid-state batteries, a catholyte should demonstrate high ionic conductivity, good compressibility and oxidative stability. Here, a LaCl 3 -based Na + superionic conductor (Na 1–x Zr x La 1–x Cl 4 ) with high ionic conductivity of 2.9 × 10 –4 S cm –1 (30 °C), good compressibility and high oxidative potential (3.80 V vs. Na 2 Sn) is prepared via solid state reaction combining mechanochemical method. X-ray diffraction reveals a hexagonal structure (P6 3 /m) of Na 1–x Zr x La 1–x Cl 4 , with Na + ions forming a one-dimensional diffusion channel along the c-axis. First-principle calculations combining with X-ray absorption fine structure characterization etc. reveal that the ionic conductivity of Na 1–x Zr x La 1–x Cl 4 is mainly determined by the size of Na + -channels and the Na + /La 3+ mixing in the one-dimensional diffusion channels. When applied as a catholyte, the NaCrO 2 ||Na 0.7 Zr 0.3 La 0.7 Cl 4 ||Na 3 PS 4 ||Na 2 Sn all-solid-state batteries demonstrate an initial capacity of 114 mA h g –1 and 88% retention after 70 cycles at 0.3 C. In addition, a high capacity of 94 mA h g –1 can be maintained at 1 C current density.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Tuning the solvation structure with salts for stable sodium-metal batteries

Sodium-metal batteries are an appealing, sustainable, low-cost alternative to lithium metal batteries due to the high abundance and theoretical specific capacity (1,165 mA h g -1 ) of sodium. However, the poor compatibility of the electrolyte with the cathode and anode leads to unstable electrode-electrolyte interphases. Here we introduce the concept of using a salt as a diluent, which enables the use of a single non-flammable solvent, such as trimethyl phosphate. By using sodium nitrate (NaNO 3 ) salt as a model diluent, we report a 1.1 M NaFSI-NaNO 3 -trimethyl phosphate electrolyte that forms a stable interface with sodium-metal anode. In addition, the formation of robust cathode-electrolyte interphases on Na(Ni 0.3 Fe 0.4 Mn 0.3 )O 2 cathode facilitates smooth phase transitions, thus leading to stable cycle life with a capacity retention of 80% over 500 cycles at C/5 rate in Na||Na(Ni 0.3 Fe 0.4 Mn 0.3 )O 2 cells. Further, the work demonstrates a promising approach towards the development of safe, low-cost, sustainable high-performance sodium-metal batteries. Electrolytes with non-flammable solvents are important for the safe operation of sodium-metal batteries. Here the authors report an electrolyte engineering approach, employing salts as a diluent, to enhance interfacial stability and overall safety.

25 ENERGY STORAGE↗
DOE OSTI2023

Delineating the Impact of Transition‐Metal Crossover on Solid‐Electrolyte Interphase Formation with Ion Mass Spectrometry

Abstract Lithium‐metal batteries (LMB) employing cobalt‐free layered‐oxide cathodes are a sustainable path forward to achieving high energy densities, but these cathodes exhibit substantial transition‐metal dissolution during high‐voltage cycling. While transition‐metal crossover is recognized to disrupt solid‐electrolyte interphase (SEI) formation on graphite anodes, experimental evidence is necessary to demonstrate this for lithium‐metal anodes. In this work, advanced high‐resolution 3D chemical analysis is conducted with time‐of‐flight secondary‐ion mass spectrometry (TOF‐SIMS) to establish spatial correlations between the transition metals and electrolyte decomposition products found on cycled lithium‐metal anodes. Insights into the localization of various chemistries linked to crucial processes that define LMB performance, such as lithium deposition, SEI growth, and transition‐metal deposition are deduced from a precise elemental and spatial analysis of the SEI. Heterogenous transition‐metal deposition is found to perpetuate both heterogeneous SEI growth and lithium deposition on lithium‐metal anodes. These correlations are confirmed across various lithium‐metal anodes that are cycled with different cobalt‐free cathodes and electrolytes. An advanced electrolyte that is stable to higher voltages is shown to minimize transition‐metal crossover and its effects on lithium‐metal anodes. Overall, these results highlight the importance of maintaining uniform SEI coverage on lithium‐metal anodes, which is disrupted by transition‐metal crossover during operation at high voltages.

Chemistry↗
DOE OSTI2023

Cracking vs. surface reactivity in high-nickel cathodes for lithium-ion batteries

High-nickel layered oxide cathodes LiNi x Mn y Co z O 2 (NMC) experience microcracks during cycling. This can expose fresh cathode surfaces for parasitic reactions and isolate active cathode material from the conductive electrode matrix, resulting in impedance increase and capacity fade. The commonly held belief attributes microcracks to anisotropic lattice volume changes of primary particles during cycling. Nevertheless, recent reports suggest that certain electrolytes might reduce microcracks in NMC cathodes during deep cycling. This raises a crucial question on the origin of microcracks: do microcracks exacerbate surface stability, or does poor surface stability contribute to microcrack formation? This perspective aims to provide context and expound this “chicken or egg” dilemma. We contend that the consequence of surface reactivity on the cycle life of high-Ni cathodes is more pronounced than that of particle cracking. Here, we hypothesize that particle cracking is more of a symptom of severe surface reactivity rather than a cause of capacity fade.

25 ENERGY STORAGE↗
DOE OSTI2023

Battery Charge Curve Prediction via Feature Extraction and Supervised Machine Learning

Real-time onboard state monitoring and estimation of a battery over its lifetime is indispensable for the safe and durable operation of battery-powered devices. In this study, a methodology to predict the entire constant-current cycling curve with limited input information that can be collected in a short period of time is developed. A total of 10 066 charge curves of LiNiO 2 -based batteries at a constant C-rate are collected. With the combination of a feature extraction step and a multiple linear regression step, the method can accurately predict an entire battery charge curve with an error of < 2% using only 10% of the charge curve as the input information. The method is further validated across other battery chemistries (LiCoO 2 -based) using open-access datasets. The prediction error of the charge curves for the LiCoO 2 -based battery is around 2% with only 5% of the charge curve as the input information, indicating the generalization of the developed methodology for predicting battery cycling curves. The developed method paves the way for fast onboard health status monitoring and estimation for batteries during practical applications.

25 ENERGY STORAGE↗
DOE OSTI2023

A High Energy–Density, Cobalt–Free, Low–Nickel LiNi 0.7 Mn 0.25 Al 0.05 O 2 Cathode with a High–Voltage Electrolyte for Lithium–Metal Batteries

Cobalt-free cathode materials have garnered increased attention for applications in next-generation batteries for electric vehicles, as cobalt is considered to have at a high supply chain risk. Here, the use of a localized saturated electrolyte (LSE) to enable stable cycling of a cobalt-free, low-nickel layered-oxide cathode LiNi 0.7 Mn 0.25 Al 0.05 O 2 (NMA-70) to higher voltages (4.6 V) in a lithium-metal battery is demonstrated. Compared to the baseline LP57 electrolyte, the LSE extends the cycle life from ≈100 cycles to ≈400 cycles before reaching 80% capacity retention. Visual indicators of cell degradation, such as product deposition, are observed on electrodes cycled in LP57. It is shown that cycling NMA-70 in LSE reduces the overall active material loss and overpotential growth during extended cycling. This is attributed to the formation of a beneficial fluorinated interphase layer, a lower degree of rock-salt phase formation, and a reduction in the gas evolution from the cathode surface. The decrease in gas evolution from the cathode cycled in LSE reflects a lower degree of electrolyte reactivity and an overall improvement in the safety characteristics of the cell. Furthermore, this study highlights the importance of a stable electrolyte to enable the high-voltage cycling of alternative, lower nickel, and cobalt-free cathodes.

25 ENERGY STORAGE↗
DOE OSTI2023

Operation of Layered LiCoO 2 to Higher Voltages with a Localized Saturated Electrolyte

The commercialization of lithium-ion batteries started with the layered LiCoO 2 (LCO) cathode for portable electronics, but only 50% of its theoretical capacity can be used in practical cells due to detrimental surface and bulk degradations when charged to high voltages. Here we demonstrate here that the stability of electrolyte plays a critical role in the performance of LCO at high voltages by employing a localized saturated electrolyte (LSE). With a cutoff voltage of 4.5 V, LCO achieves an initial 1C discharge capacity of 176 mA h g -1 and a capacity retention of 80% over 230 cycles. Even with a cutoff voltage of 4.6 V, LCO with 2% aluminum doping displays an initial discharge capacity of 189 mA h g -1 at 1C rate with 80% capacity retention over 137 cycles. With extensive analytical characterization, we show that the improved cycling stability stems from a suppression of the O3 to H1-3 phase transition as well as a robust inorganic-rich cathode-electrolyte interphase (CEI) facilitated by the LSE. This work highlights the importance of protecting the surface as well as the bulk with appropriate electrolytes for the high-voltage, higher-energy-density operation of LCO.

25 ENERGY STORAGE↗
DOE OSTI2023

Stabilizing High–Nickel Cathodes with High–Voltage Electrolytes

Electrolytes connect the two electrodes in a lithium battery by providing Li + transport channels between them. Advanced electrolytes are being explored with high-nickel cathodes and the lithium-metal anode to meet the high energy density and cycle life goals, but the origin of the performance differences with different electrolytes is not fully understood. Here, the mechanisms involved in protecting the high-capacity, cobalt-free cathode LiNiO 2 with a model high-voltage electrolyte (HVE) are delineated. The kinetic barrier posed by a thick surface degradation layer with poor Li + -ion transport is found to be the major contributor to the fast capacity fade of LiNiO 2 with the conventional carbonate electrolyte. In contrast, HVE reduces the side reactions between the electrolyte and the electrodes, leading to a thinner nano-interphase layer comprised of more beneficial species. Crucially, the HVE leads to a different surface reorganization pathway involving the formation of a thinner nanoscale LiNi 2 O 4 spinel phase on the LiNiO 2 surface. Finally, with a high 3D Li + -ion and electronic conductivity, the spinel LiNi 2 O 4 reorganization nanolayer preserves fast Li + transport across the cathode–electrolyte interface, reduces reaction heterogeneity in the electrode and alleviates intergranular cracking within secondary particles, resulting in superior long-term cycle life.

25 ENERGY STORAGE↗
DOE OSTI2022

A Review on Application of Poly(3,4-ethylenedioxythiophene) (PEDOT) in Rechargeable Batteries

Since the very first patent on poly(3,4-ethylenedioxythiophene) (PEDOT) that was filed in 1988, this polymer has been widely utilized and has achieved great success owing to its high electrical conductivity and excellent stability. The application of the conducting polymer, PEDOT, in renewable energy devices, especially rechargeable batteries, is attracting increasing attention due to its potential to solve the energy and climate crisis. In this review, we summarize the research over the past few decades directed toward the application of PEDOT in rechargeable batteries aimed at improving their electrochemical performance. We focus on PEDOT synthesized via oxidative chemical vapor deposition (oCVD), a relatively new process known for its ability to grow conducting polymer thin films with uniform, pinhole-free properties, and controllable thickness and conformality. For a comparison purpose, PEDOT synthesized via solution-based methods is also briefly summarized. Finally, future research directions for applying oCVD PEDOT in rechargeable batteries are discussed. Introduction PEDOT Synthesis Methods Application of oCVD PEDOT in Rechargeable Batteries Applications of Solution-Based PEDOT in Rechargeable Batteries Conclusions and Outlook

25 ENERGY STORAGE↗
DOE OSTI2022

Lithium–Metal Batteries via Suppressing Li Dendrite Growth and Improving Coulombic Efficiency

Lithium–metal batteries (LMB) are recognized as one of the most promising candidates for the next generation of batteries due to their high energy density. Extensive studies have been refocused on the field in the past decade to make the technology commercially viable. Unfortunately, despite exciting progress that has been made, the practical application of LMBs is still hampered by the uncontrollable Li plating morphology and inferior Coulombic efficiency (CE) during cycling. Herein, first, the relevant research that has been carried out in the past decade (2010–2021) is briefly summarized and then the Li plating behaviors, mechanistic understanding of these behaviors, and strategies to suppress Li dendrite growth are discussed. Finally, the methods and techniques to improve Coulombic efficiency (CE) is discussed, especially the design of liquid electrolytes, and possible research directions for the future development of LMBs.

25 ENERGY STORAGE↗
DOE OSTI2022

Uncovering the Solvation Structure of LiPF 6 –Based Localized Saturated Electrolytes and Their Effect on LiNiO 2 –Based Lithium–Metal Batteries

Electrolytes play a critical role in stabilizing highly reactive lithium-metal anodes (LMAs) and high-voltage cathodes for rechargeable lithium-metal batteries (LMBs). Localized high concentration electrolytes (LHCEs) have achieved remarkable success in the context of LMBs. However, the state-of-the-art LHCEs are based on LiFSI salt, which is prohibitively expensive. Here, the utility of low-cost LiPF 6 salt in localized saturated electrolytes (LSEs) with a series of solvents and diluents in LMBs with cobalt-free LiNiO 2 cathode is systematically explored. Experimental and theoretical analyses reveal that the unique solvation structure formed not only changes the distribution of solvents and anions but also alters the atom–atom distances within them, leading to different reduction and oxidation stabilities compared to low-concentration electrolytes. In addition, LSEs help form LiF-rich interphase layers on the LMA and LiNiO 2 cathode, protecting the electrodes from degradation during cycling. Different LSEs also lead to differences in lithium plating morphology and impedance buildup during cycling, impacting the performance of LMBs. Finally, the solvent and diluent must be carefully selected for compatibility with a lithium salt when developing LHCEs and LSEs for LMBs.

25 ENERGY STORAGE↗
DOE OSTI2022

High-efficiency, anode-free lithium–metal batteries with a close-packed homogeneous lithium morphology

Anode-free lithium–metal batteries (LMBs) are ideal candidates for high-capacity energy storage as they eliminate the need for a conventional graphite electrode or excess lithium–metal anode. Current anode-free LMBs suffer from low Coulombic efficiency (CE) due to poor lithium stripping efficiency. Advanced electrolyte development is a promising route to maximize lithium plating and stripping CE and minimize capacity fade. However, a poor understanding of the mechanisms by which advanced electrolytes improve performance hampers progress in the practical development of anode-free LMBs. Here, we use synchrotron techniques and other tools to analyze the influence of three commercially available electrolytes on the composition, heterogeneity, kinetics, morphology, and electrochemistry of anode-free LMBs. Advanced electrolytes improve the electrochemical performance of anode-free LMBs by forming much denser and better-packed Li morphologies on a Cu current collector than on the conventional electrolyte. Li plates uniformly over the electrode area with the advanced electrolytes rather than in a few active sites. Inactive crystalline Li with heterogeneous distribution dominates the capacity degradation of anode-free cells, especially with the conventional electrolyte, indicating that reducing the amount of “dead” crystalline Li will significantly improve the cycling stability of anode-free cells. Finally, the understanding of the Li plating and stripping process obtained from this work will accelerate the development of anode-free LMBs with high efficiency.

25 ENERGY STORAGE↗
DOE OSTI2021

Multiscale operando X-ray investigations provide insights into electro-chemo-mechanical behavior of lithium intercalation cathodes

The electrochemical performance and cycle life of lithium-ion batteries (LIBs) depend on the electrochemical, chemical, and mechanical behavior of electrodes and electrolytes. Despite extensive studies conducted previously, challenges exist to decouple these behaviors, capture the evolution of electro-chemo-mechanical behavior in realistic conditions, and correlate atomic-scale stress evolution to micro-scale bulk mechanical degradation. Here, we report multiscale operando techniques to investigate polydisperse battery electrodes by integrating volume-averaged quantitative synchrotron X-ray scattering with high-resolution transmission X-ray microscopy (TXM). The former provides us information spanning a wide spatial range, from Angstrom-level atomic structures to micrometer-level particle scales, while the latter provides time-resolved 2D images of the particles during cycling. The complementarity of the two operando techniques is demonstrated by an over-lithiation test of LiCoO 2 electrodes, where particles crack and eventually pulverize. Additionally, the techniques are applied to study LiCoO 2 cycling stability from 3.0 V to 4.5 V. Operando X-ray scattering result shows nanometer-scale features keep forming in LiCoO 2 electrodes during cycling, resulting in an increased projected area observed by the TXM experiment. The formation of such features is inhibited by a polymer coating on the electrode, leading to vastly improved cycling stability. The polymer coating alleviates LiCoO 2 surface deterioration, reduces side product generation, and inhibits LiCoO 2 particles volume expansion during the cycling test. These operando multimodal X-ray techniques presented herein thus offer a novel, multiscale diagnostic modality for studying existing and emerging battery materials, aiding the development of next-generation LIBs.

25 ENERGY STORAGE↗
DOE OSTI2020

Engineering lithium-ion battery cathodes for high-voltage applications using electromagnetic excitation

Microwave radiation (MWR), a type of electromagnetic excitation source, reduces the synthesis temperature and processing time for chemical reactions compared to traditional synthesis methods. Recently, we demonstrated that MWR can engineer ceramics with different crystal phases compared to traditional methods [ Journal of Materials Chemistry A 5 , 35 (2017)]. Here, we further apply the MWR-assisted technique to improve the electrochemical performance of LiCoO 2 cathodes by engineering TiO 2 and ZrO 2 ceramic coatings. Electrochemical tests suggest that the TiO 2 coating improves the rate capability of the LiCoO 2 electrode. Both TiO 2 and ZrO 2 coatings improve the high-voltage (4.5 V) cycling stability of LiCoO 2 . The capacity remaining is improved from 52.8 to 84.4% and 81.9% by the TiO 2 coating and the ZrO 2 coating, respectively, after 40 cycles. We compare these results with existing studies that apply traditional methods to engineer TiO 2 /ZrO 2 on LiCoO 2 , and find that the MWR-assisted method shows better performance improvement. X-ray photoelectron spectroscopy measurements suggest that the improved cycling stability arises from the formation of metal fluorides that protect the electrode from side reactions with electrolytes. This mechanism is further supported by the reduced Co dissolution from TiO 2 /ZrO 2 -coated LiCoO 2 electrode after cycling. This study provides a new toolbox facilitating the integration of many delicate, low melting point materials like polymers into battery electrodes.

25 ENERGY STORAGE↗