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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

New Insights into the High‐Performance Black Phosphorus Anode for Lithium‐Ion Batteries

Abstract Black phosphorus (BP) is a promising anode material in lithium‐ion batteries (LIBs) owing to its high electrical conductivity and capacity. However, the huge volume change of BP during cycling induces rapid capacity fading. In addition, the unclear electrochemical mechanism of BP hinders the development of rational designs and preparation of high‐performance BP‐based anodes. Here, a high‐performance nanostructured BP–graphite–carbon nanotubes composite (BP/G/CNTs) synthesized using ball‐milling method is reported. The BP/G/CNTs anode delivers a high initial capacity of 1375 mA h g −1 at 0.15 A g −1 and maintains 1031.7 mA h g −1 after 450 cycles. Excellent high‐rate performance is demonstrated with a capacity of 508.1 mA h g −1 after 3000 cycles at 2 A g −1 . Moreover, for the first time, direct evidence is provided experimentally to present the electrochemical mechanism of BP anodes with three‐step lithiation and delithiation using ex situ X‐ray diffraction (XRD), ex situ X‐ray absorption spectroscopy (XAS), ex situ X‐ray emission spectroscopy, operando XRD, and operando XAS, which reveal the formation of Li 3 P 7 , LiP, and Li 3 P. Furthermore, the study indicates an open‐circuit relaxation effect of the electrode with ex situ and operando XAS analyses.

Li, Minsi↗
NASA NTRS1991

Evaluation of lithium alloy anode materials for Li-TiS2 cells

A study was performed to select candidate lithium alloy anode materials and establish selection criteria. Some of the selected alloy materials were evaluated for their electrochemical properties and performance. This paper describes the criteria for the selection of alloys and the findings of the studies. Li-Si and Li-Cd alloys have been found to be unstable in the EC+2-MeTHF-based electrolyte. The Li-Al alloy system was found to be promising among the alloy systems studied in view of its stability and reversibility. Unfortunately, the large volume changes of LiAl alloys during charge/discharge cycling cause considerable 'exfoliation' of its active mass. This paper also describes ways how to address this problem. The rate of disintegration of this anode would probably be surpressed by the presence of an inert solid solution or a uniform distribution of precipitates within the grains of the active mass. It was discovered that the addition of a small quantity of Mn may improve the mechanical properties of LiAl. In an attempt to reduce the Li-Al alloy vs. Li voltage, it was observed that LiAlPb(0.1)Cd(0.3) material can be cycled at 1.5 mA/sq cm without exfoliation of the active mass.

Huang, C.-K.↗
DOE OSTI2023

Carbon Scaffold Architectures for Stable Lithium Metal Anodes

In light of the skyrocketing demand for electric vehicles and consequent need for high-performing lithium-ion batteries, there has been significant research into the creation of a battery with a lithium metal anode due to its high theoretical capacity and energy density. Unfortunately, nonuniform lithium deposition and consequent dendrite growth diminish performance and pose a safety risk. To combat this, lightweight carbon scaffolds are being developed to stabilize the electric field of these batteries and induce uniform deposition through rational design at the nano-, micro-, and meso- scales. However, there is a paucity of research on the impacts of macroscale scaffold topology on lithium cycling performance. Here, we report the creation of two graphite-based scaffolds with distinct 3D topologies: one a series of triangular prisms and one a series of rectangular prisms. Coin cells were made using these scaffolds and cycled at a current of 1mA/cm2 for 50 cycles to test the performance. The triangular topology was found to outperform the rectangular topology in terms of both potential magnitude and stability during cycling. Disassembling the cells revealed more even lithium deposition on the rectangular scaffold; however, some of the rectangular prisms were broken while all the triangular prisms remained intact. Last, future experiments are proposed regarding the scaffold spacing and mass of the cells in order to isolate the topological impact.

25 ENERGY STORAGE↗
DOE OSTI2021

Molecular Layer Deposition of Crosslinked Polymeric Lithicone for Superior Lithium Metal Anodes

In this work, we for the first time developed a novel lithium-containing crosslinked polymeric material, a lithicone that enables excellent protection effects over lithium (Li) metal anodes. This new lithicone was synthesized via an accurately controllable molecular layer deposition (MLD) process, in which lithium tert -butoxide (LTB) and glycerol (GL) were used as precursors. The resultant LiGL lithicone was analyzed using a suite of characterizations. Furthermore, we found that the LiGL thichicone could serve as an exceptional polymeric protection film over Li metal anodes. Our experimental data revealed that the Li electrodes coated by this LiGL lithicone can achieve a superior cycling stability, accounting for an extremely long cyclability of >13,600 Li-stripping/plating cycles and having no failures so far in Li/Li symmetric cells at a current density of 5 mA/cm 2 and an areal capacity of 1 mAh/cm 2 . We found that, with a sufficient protection by this LiGL coating, Li electrodes could realize long-term stable cyclability with little formation of Li dendrites and solid electrolyte interphase. This novel LiGL represents a facile and effective solution to the existing issues of Li anodes and potentially paves a technically feasible route for lithium metal batteries.

Meng, Xiangbo↗
DOE OSTI2021

Tracking the evolution of processes occurring in silicon anodes in lithium ion batteries by 3D visualization of relaxation times

An unconventional electroanalytical method has been used for tracking processes in silicon anodes in lithium ion batteries: a 3D visualization of relaxation times. Impedance data of the electrodes were collected at different potentials and different cycles during cyclic voltammetry, and were treated by means of the Distribution of Relaxation Times (DRT) method. A 3D visualization of the results allowed to identify the formation of a solid electrolyte interphase on the anode, composed of two layers with different relaxation times. Such findings are not possible by conventional analysis of impedance data by modeling with equivalent circuits, nor by simple DRT alone. Additionally, it was possible to observe that the characteristic relaxation time of the lithiation of the Si anode becomes smaller upon cycling, indicating that the material experiences structural transformations that allow it to lithiate faster. The result is relevant to motivate the use of micron-sized particles in the anode.

25 ENERGY STORAGE↗
DOE OSTI2023

Anion modification for stable solid electrolyte interphase in anode-free lithium metal batteries

The durability of anode-free Li metal batteries is largely limited by the undesired Li plating/stripping irreversibility on the current collector due to the infinite volume change, uncontrollable Li dendrite growth, and continuous parasitic reactions between Li metal and the electrolyte. To address these challenges, the formation of a stable and robust solid electrolyte interphase (SEI) with high ionic conductivity and strong mechanical strength is critical. Here, we developed an advanced electrolyte by introducing LiNO 3 into the localized high concentration electrolyte (LHCE) with lithium bis(fluorosulfonyl)imide (LiFSI) salt, 1,2-dimethoxyethane (DME) solvent, and 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropylether (TFTE) diluent to in situ construct a LiF and Li x N y O z co-enriched passivation layer on the Cu current collector. The synergetic effect of high mechanical strength of LiF and high ionic conductivity of Li x N y O z endows the Li metal anode with a high Coulombic efficiency (CE) of 99.35%. In conclusion, in anode-free Li metal pouch cell using LiFePO 4 (LFP) as a cathode holds an exceptionally improved capacity retention under the charging/discharging rate of 1/3 C, demonstrating great promise for developing dendrite-free and safe Li metal batteries.

25 ENERGY STORAGE↗
DOE OSTI2021

Current Status and Future Directions of All-Solid-State Batteries with Lithium Metal Anodes, Sulfide Electrolytes, and Layered Ternary Oxide Cathodes

All-solid-state batteries (ASSBs) offer great promise as a next-generation energy storage technology with higher energy density, wider operating temperature range, and improved safety for electric vehicles. ASSBs employing lithium metal anodes (Li), sulfide-based solid-state electrolytes (SSE), and Ni-rich layered transition metal oxide cathodes (LiMO 2 , M = Ni, Mn, Co, Al) are particularly promising due to its superior electrochemical performance compared to other solid-electrolyte systems. However, the battery cycle life at high cathode mass loading and high current is still limited because the failure mechanism is not fully understood. Lithium dendrite growth at the anode or inside a solid electrolyte still represents as a serious risk of cell failure. Interfacial resistance increases attributed to electrolyte decomposition and interfacial void formation at both cathode–electrolyte and anode–electrolyte interfaces lead to gradual capacity fading. In this Review, we present the fundamental challenges and recent scientific understandings of each component in ASSBs. The novel diagnostic tools for these components, especially the interfaces buried under the surface that are often hard for characterization are mainly examined. Lastly, we offer a perspective for future research directions. We hope this Review will provide a timely snapshot of state-of-the-art research progress in ASSBs to accelerate the development of ASSBs.

25 ENERGY STORAGE↗
DOE OSTI2023

Ion Conducting Polymer Interfaces for Lithium Metal Anodes: Impact on the Electrodeposition Kinetics

Electrochemical cells that utilize metals (e.g., lithium, sodium, zinc) as anodes are under intense investigation as they are projected to replace the current lithium-ion batteries to serve as a more energy-dense option for commercial applications. In addition, metal electrodes provide opportunities for fundamental research of different phenomena, such as ion transport and electrochemical kinetics, in the complex environment of reactive metal-electrodeposition. In this work, computationally and experimentally the competing effects related to transport and kinetics during the metal electrodeposition process are examined. Using Brownian dynamics simulations, it is shown that slower deposition kinetics results in a more compact and uniform Li morphology. This finding is experimentally implemented by designing ion-containing polymeric coatings on the electrodes that simultaneously provide pathways for lithium-ion transport, while impeding the charge transfer (Li + + e - → Li) at heterogeneous surfaces. It is further shown that these ionic polymer interfaces can significantly extend the cell-lifetime of a lithium metal battery in both ether-based and carbonate-based electrolytes. Through theoretical and experimental investigations, it is found that a low kinetic to transport rate ratio is a major factor in influencing the Li plating morphology. The plating morphology can be further fine-tuned by increasing ionic conductivity.

36 MATERIALS SCIENCE↗
NASA NTRS1994

Improved Carbon Anodes For Rechargeable Lithium Cells

Carbon anodes for rechargeable lithium cells improved by choosing binder contents and fabrication conditions to achieve maximum porosity, uniform loading, and maximum reversible lithium capacity. Stacking electrodes under pressure during assembly of cells increases cyclability of lithium. Rechargeable, high-energy-density lithium cells containing improved carbon anodes find use in spacecraft, military, communications, automotive, and other demanding applications.

Huang, Chen-Kuo↗
DOE OSTI2023

Single‐Step Deformation Processing of Ultrathin Lithium Foil and Strip

Abstract Next‐generation, high‐efficiency energy storage and conversion systems require development of lithium metal batteries. But the high cost of production and constraints on thickness of lithium (anode) foils continue to limit adoption for integration into battery cell architectures. Here, a novel lithium anode manufacturing solution is demonstrated – single‐step production of ultrathin gauge foil formats directly from solid ingot. Hybrid cutting‐based deformation processes, involving large plastic strains and strain rates, produce foil to sub‐10 µm thickness, with surface quality even superior to present Li anode processing routes. Energy analysis shows the single‐stage processing is ≈50% more efficient than conventional processing by extrusion‐rolling. Through in situ force measurements and high‐speed imaging of the cutting it also characterize – for the first time – the flow stress of Li to strain rates of 800 sec −1 , revealing a power‐law relationship. The results present a paradigm shift in manufacturing and integration of solid lithium anodes for energy applications.

24 POWER TRANSMISSION AND DISTRIBUTION↗
DOE OSTI2025

Crossover Effects of Transition‐Metal Ions on Lithium‐Metal Anode in Localized High Concentration Electrolytes

Abstract The stability of the solid–electrolyte interphase (SEI) is critical to the cycle life of lithium‐metal batteries (LMBs). While the crossover effect of transition‐metal ions from cathode to anode is extensively studied in lithium‐ion batteries with graphite anodes, its impact on LMBs remains largely unexplored. Herein, this study investigates the electrochemical and chemical properties of SEI layers formed on lithium‐metal anodes in localized high‐concentration electrolytes (LHCEs) containing dissolved transition‐metal ions (Ni 2+ , Mn 2+ , and Co 2+ ). It is demonstrated that transition‐metal ions in LHCEs reduce the coulombic efficiency (CE) and significantly degrade the cycle life of LMBs. Time‐of‐flight secondary‐ion mass spectrometry (ToF‐SIMS) reveals that SEI structures differ depending on the dissolved TM ion, with Mn 2+ and Co 2+ inducing severe destabilization, and Ni 2+ exhibiting a less severe impact. These findings underscore the detrimental effects of transition‐metal crossover effects in LMB systems.

Guo, Zezhou [Materials Science and Engineering Pro↗
DOE OSTI2023

Catalytic Graphitization of Biocarbon for Lithium‐Ion Anodes: A Minireview

Abstract The demand for electrochemical energy storage is increasing rapidly due to a combination of decreasing costs in renewable electricity, governmental policies promoting electrification, and a desire by the public to decrease CO 2 emissions. Lithium‐ion batteries are the leading form of electrochemical energy storage for electric vehicles and the electrical grid. Lithium‐ion cell anodes are mostly made of graphite, which is derived from geographically constrained, non‐renewable resources using energy‐intensive and highly polluting processes. Thus, there is a desire to innovate technologies that utilize abundant, affordable, and renewable carbonaceous materials for the sustainable production of graphite anodes under relatively mild process conditions. This review highlights novel attempts to realize the aforementioned benefits through innovative technologies that convert biocarbon resources, including lignocellulose, into high quality graphite for use in lithium‐ion anodes.

25 ENERGY STORAGE↗
DOE OSTI2021

Complementary Electrolyte Design for Li Metal Batteries in Electric Vehicle Applications

In this report a complementary electrolyte system with 0.8 M lithium bis(fluorosulfonylimide) (LiFSI) salt and 2 wt % lithium perchlorate (LiCLO4) additive in fluoroethylene carbonate (FEC)/ethyl methyl carbonate (EMC) solution enables not only stable cycling of lithium metal batteries (LMBs) with practical loading (<30 μm lithium anode, cathode loading > 4 mAh/cm 2 ) but also outstanding degradation stability toward the end of cycle life when compared to the conventional electrolyte. Although the use of LiFSI salt can increase the electrolyte conductivity and lengthen the cycle life of LMBs, the aged lithium anode morphology formed by the sacrificial decomposition of LiFSI is highly porous, leading to an abrupt cell capacity drop toward the end of cycling. Moreover, the inability to stop aluminum corrosion by the LiFSI-based electrolyte also causes cracking of the cathode tab during prolonged cycling. It is observed that a highly porous aged lithium consumed electrolyte at a higher rate, leading to the dry-out of electrolyte solvents. On the contrary, dense aged lithium anode morphology increased the localized current applied on the lithium, causing the formation of lithium dendrite. Thus, porosity control is the key to enhance battery performance. In this complementary system, LiClO 4 was introduced as an advanced additive to not only improve the capacity retention rate but also mitigate the abrupt capacity drop toward the end of cycle life because LiClO 4 acted as a pore astringent reducing the porosity of the aged lithium metal anode to the desired level. Moreover, the addition of LiClO 4 can also suppress the AI corrosion, allowing stable high-voltage cycling of LMBs. The synergistic effect of combining LiFSI salt and a LiClO 4 additive leads to an electrolyte system that can facilitate the application of high-energy LMBs with practical electrode loading.

25 ENERGY STORAGE↗
DOE OSTI2026

Establishing the Stability of Cross-Linked Poly(ethylene oxide) Blended with Poly(pentyl malonate) against Lithium Metal Anodes

This work focuses on an electrolyte obtained by infusing linear poly(pentyl malonate) (PPM) chains into cross-linked poly(ethylene oxide) (PEO). A lithium salt is added to enable ion transport. Obtaining this electrolyte is only possible because PPM is miscible with PEO irrespective of salt concentration. The properties of this electrolyte are compared against two benchmarks: an electrolyte obtained by infusing linear PEO into cross-linked PEO and cross-linked PEO with no added linear polymer. Measurements of storage moduli and ion transport efficacies are found to be similar across the three electrolytes, suggesting similar stability behavior against lithium metal anodes, based on current theoretical models. Instead, the PPM infused electrolyte outperforms the other two electrolytes. In the cycling tests, the current supported by the PPM infused electrolyte was a factor of 20 higher than that of the PEO infused electrolyte and a factor of 4 higher than that of the cross-linked PEO electrolyte. In the unidirectional plating experiments, the other two electrolytes fail after about 4 h or less, while the PPM containing electrolyte did not fail during the 140 h testing period. Insight into the nature of failure modes was obtained using synchrotron hard X-ray microtomography.

Gido, Lily [University of California, Berkeley]↗
DOE OSTI2021

Evolution of Protrusions on Lithium Metal Anodes Stabilized by a Solid Block Copolymer Electrolyte Studied Using Time-Resolved X-ray Tomography

The growing demand for rechargeable batteries with higher energy densities has motivated research focused on enabling the lithium metal anode. A prominent failure mechanism in such batteries is short circuiting due to the uncontrolled propagation of lithium protrusions that often have a dendritic morphology. In this paper, the electrodeposition of metallic lithium through a rigid polystyrene- b -poly(ethylene oxide) (PS- b -PEO or SEO) block copolymer electrolyte was studied using hard X-ray microtomography. In this system, protrusions were approximately ellipsoidal globules: we take advantage of this simple geometry to quantify their growth as a function of polarization time and electrolyte salt concentration. The growth of 47 different globules was tracked with time to obtain average velocities of globule growth into the electrolyte. The globule diameter was a linear function of globule height in the electrolyte with a slope of about 6, independent of time and electrolyte salt concentration.

25 ENERGY STORAGE↗
DOE OSTI2021

Mechanical studies of the solid electrolyte interphase on anodes in lithium and lithium ion batteries

A stable solid electrolyte interphase (SEI) layer is key to high performing lithium ion batteries for metrics such as calendar and cycle life. The SEI must be mechanically robust to withstand large volumetric changes in anode materials such as lithium and silicon, so understanding the mechanical properties and behavior of the SEI is essential for the rational design of artificial SEI and anode form factors. The mechanical properties and mechanical failure of the SEI are challenging to study, because the SEI is thin at only ~ 10 – 200 nm thick and is air sensitive. Furthermore, the SEI changes as a function of electrode material, electrolyte and additives, temperature, potential, and formation protocols. A variety of in situ and ex situ techniques have been used to study the mechanics of the SEI on a variety of lithium ion battery anode candidates; however, there hasn't been a succinct review of the findings thus far. Because of the difficultly of isolating the true SEI and its mechanical properties, there have been a limited number of studies that can fully de-convolute the SEI from the anode it forms on. A review of past research will be helpful for culminating current knowledge and helping to inspire new innovations to better quantify and understand the mechanical behavior of the SEI. This review will summarize the different experimental and theoretical techniques used to study the mechanics of SEI on common lithium ion battery anodes and their strengths and weaknesses.

25 ENERGY STORAGE↗
DOE OSTI2022

Quantification of Dead Lithium on Graphite Anode under Fast Charging Conditions

A series of computational and experimental studies were conducted to understand the onset of lithium plating and subsequent quantification of dead lithium on graphite electrodes in the design of fast charging batteries. The experiments include titration and relaxation studies for detecting initiation of lithium metal plating for various SOC and C-rates, which are compared against the thermodynamically consistent phase field computational results. The collaborative study on "model graphite electrode" with 2.18 mAh cm-2 nominal capacity at 25 degrees C demonstrates: (1) the macroscopic voltage response during relaxation studies indicate the reintercalation of plated lithium into the graphite anode; (2) for SOC below 60% and low C-Rates, there is no dead lithium; (3) for SOC between 60% to 80%, and C-Rates in the range of 4C-6C show dead lithium both in experiments and simulations; (4) at 100% SOC and 4C-6C rates, large amounts of dead lithium are observed. The study presented here allows us to evaluate the effects of the physical properties of the electrochemical system on plating and stripping kinetics and the amount of dead lithium on graphite electrodes, which determines the cell capacity loss under fast charge.

batteries↗