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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 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

In-situ visualization of the transition metal dissolution in layered cathodes

Transition metal dissolution in layered cathodes is one of the most intractable issues that deteriorates the battery performance and lifetime. It not only aggravates the structure degradation in cathode, but also damages the solid electrolyte interphase in anode and even induce the formation of lithium dendrites. In this work, we investigate the dissolution behaviors of polycrystalline and single-crystalline layered cathode via operando X-ray imaging techniques. The described cathode particle morphology appears to have a significant impact on the evolution of the dissolution dynamics. As a mitigation strategy, we reveal that doping with trace amount of Zr in the layered cathode could improve its robustness against the transition metal dissolution. Our finding provides valuable insights for designing the next-generation highly-stable layered battery cathodes.

25 ENERGY STORAGE↗
DOE OSTI2024

Quantification of Commercially Planned Battery Component Supply in North America through 2035

There is the potential for rapid growth in battery manufacturing in North America in the coming years, as indicated by investment plans which companies have announced. Argonne National Laboratory is tracking these investment announcements to understand the availability of domestically produced battery cells and battery components over the next decade. We find that companies have made announcements for over 1,300 GWh/year of lithium-ion battery cell production by 2030, enough to conservatively supply ten million electric vehicles and expected growth in stationary grid storage. From 2021 to 2032, battery cell production is modeled to grow 28-fold. For each of the core battery components of lithium-ion batteries (cathodes, anodes, separators, electrolytes, and foils), we describe the current announced capacities for materials with respect to cell production and end-use demand, finding similar rapid growth for each.

25 ENERGY STORAGE↗
DOE OSTI2025

Lithium-Ion Batteries with Lithium Manganese Iron Phosphate Cathodes and Lithium Titanate Anodes: Linking Electrode Dynamics to Cell Performance

This study examines the electrochemical performance, impedance behavior, and aging mechanisms of lithium-ion cells pairing lithium manganese iron phosphate (LiMn 0.6 Fe 0.4 PO 4 , LMFP64) cathodes with lithium titanate (Li 4 Ti 5 O 12 , LTO) anodes. LMFP64 half-cells display distinct Fe and Mn redox plateaus at ∼3.5 and ∼4.1 V, respectively, and deliver excellent rate capability. Three-electrode measurements show that LMFP64 dominates cell impedance, which changes sharply across the Fe–Mn redox transition and decreases with increasing temperature (30 °C–50 °C). Voltage hysteresis arises mainly from the cathode, with higher C-rates shortening redox plateaus and broadening the transition region. Elevated temperature lowers impedance, especially near the Mn-redox and transition regions, but accelerates capacity fade. Post-cycling analyses of electrodes confirm structural stability of LMFP64 and indicate loss of lithium inventory (LLI) as the source of capacity fade. This LLI causes potential slippage between the LMFP64 and LTO electrodes, which decreases the Fe-redox plateau width. Long-term cycling highlights the critical role of electrode overhang: cathode overhang mitigates capacity fade by buffering lithium loss, whereas anode overhang cells experience faster capacity decline due to uncompensated lithium depletion. These results clarify LMFP64/LTO battery impedance evolution, thermal effects, and degradation pathways and provide insights for their applications in electric vehicles.

Area Specific Impedance↗
DOE OSTI2020

Cathode Electrolyte Diagnostics Based on Scanning Probe Microscopy

Various processes lead to degradation of cathodes in lithium-ion batteries. Questions remain regarding mechanisms of many of these processes. Probe microscopy methods including scanning electrochemical microscopy (SECM) are capable of directly probing processes at the cathode/electrolyte interface. SECM uses a small electrode to perform rapid electrochemical analysis of transient species generated at an active cathode/electrolyte interface. This paper discusses the background of the SECM instrument and its application to lithium-ion battery research. We also describe the application of SECM methods to the study of cathode degradation processes observed in lithium-ion batteries. Specifically, we focus on characterizing the dissolution of manganese from LiMn2O4 (LMO) based on recent debate in the literature. We describe experiments to observe and characterize the electrochemical properties of manganese complexes emerging from degrading LMO electrode materials.

cathode/electrolyte interface↗
DOE OSTI2024

Low-cost iron trichloride cathode for all-solid-state lithium-ion batteries

The dominant chemistries of lithium-ion batteries on the market today still rely on flammable organic liquid electrolytes and cathodes containing scarce metals, such as cobalt or nickel, raising safety, cost and environmental concerns. Here we show a FeCl 3 cathode that costs as little as 1% of the cost of a LiCoO 2 cathode or 2% of a LiFePO 4 cathode. Once coupled with a solid halide electrolyte and a lithium-indium (Li–In) alloy anode, it enables all-solid-state lithium-ion batteries without any liquid components. Notably, FeCl 3 exhibits two flat voltage plateaux between 3.5 and 3.8 V versus Li + /Li, and the solid cell retains 83% of its initial capacity after 1,000 cycles with an average Coulombic efficiency of 99.95%. Combined neutron diffraction and X-ray absorption spectroscopy characterizations reveal a Li-ion (de)intercalation mechanism together with a Fe 2+ /Fe 3+ redox process. Further, our work provides a promising avenue for developing sustainable battery technologies with a favourable balance of performance, cost and safety.

25 ENERGY STORAGE↗
DOE OSTI2020

Revealing Reaction Pathways of Collective Substituted Iron Fluoride Electrode for Lithium Ion Batteries

Metal fluorides present a high redox potential among the conversion-type compounds, which make them specially work as cathode materials of lithium ion batteries. To mitigate the notorious cycling instability of conversion-type materials, substitutions of anion and cation have been proposed but the role of foreign elements in reaction pathway is not fully evaluated. In this work, we explored the lithiation pathway of a rutile-Fe 0.9 Co 0.1 OF cathode with multimodal analysis, including ex situ and in situ transmission electron microscopy and synchrotron X-ray techniques. Our work revealed a prolonged intercalation–extrusion–cation disordering process during phase transformations from the rutile phase to rocksalt phase, which microscopically corresponds to topotactic rearrangement of Fe/Co–O/F octahedra. During this process, the diffusion channels of lithium transformed from 3D to 2D while the corner-sharing octahedron changed to edge-sharing octahedron. DFT calculations indicate that the Co and O cosubstitution of the Fe 0.9 Co 0.1 OF cathode can improve its structural stability by stabilizing the thermodynamic semistable phases and reducing the thermodynamic potentials. We anticipate that our study will inspire further explorations on untraditional intercalation systems for secondary battery applications.

25 ENERGY STORAGE↗
DOE OSTI2021

Electrolytes Polymerization‐Induced Cathode‐Electrolyte‐Interphase for High Voltage Lithium‐Ion Batteries

Abstract Lithium‐ion batteries (LIBs) based on LiNi x Co y Mn 1‐x‐y O 2 (NCM) cathode materials have been widely commercialized, because of their high energy density, favorable rate performance, and relatively low cost. However, with increased Ni content to further increase their energy density, their cycling stability deteriorates dramatically and thus fails to meet the commercial application requirements. The artificial cathode‐electrolyte‐interphase (CEI) is a promising approach to solve this problem. Here, a robust CEI is fabricated through in situ polymerization of ethylene carbonate induced by aluminum isopropoxide (AIP). By adding 1 wt.% AIP in a commercial electrolyte, the capacity retention of LiNi 0.8 Co 0.1 Mn 0.1 O 2 ||Li cell at 1 C rate has been significantly increased from 80.8% to 97.8% with a highly reversible capacity of 176 mA h g −1 after 200 cycles. AIP can be also used as an additive during the slurry‐making process, enabling a reversible capacity of 170 mA h g −1 for LiCoO 2 after 200 cycles even at a high charge cut‐off voltage of 4.6 V. It is confirmed that the in situ formed CEI layer can prevent the cathodes from cracking and reduce the irreversible phase transformation.

Yang, Jixiang↗
DOE OSTI2021

An ultrathin solid-state electrolyte film coated on LiNi 0.8 Co 0.1 Mn 0.1 O 2 electrode surface for enhanced performance of lithium-ion batteries

We report layered Ni-rich oxide is a promising cathode material for lithium-ion batteries (LIBs) of high energy density, yet its poor electrochemical stability induced by electrode-electrolyte interfacial degradation has still needed to be addressed. Surface coating is one of the powerful techniques to tackle this issue, nevertheless, it has been extensively used on particle but not electrode regarding a larger area of protection. Herein, we have covered a nano-scaled layer of lithium phosphorus oxynitride (LiPON) on the electrode level of LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM) surface and found lower impedance, longer cycle life, and better safety for treated battery. Most notably, such an NCM-LiPON based 1.3 Ah pouch cell delivers an energy density of 364.4 Wh kg -1 (based on positive and negative materials), along with the retention of 80.0% over 745 cycles at 0.5 C-rate, which is 1.3 times longer than the bare one. This results from modification of both superficial cathode-electrolyte interphase (CEI) and structure stabilization of general particle surface, therefore, role of conformal coating upon electrode surface should be highlighted.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Positive Role of Fluorine Impurity in Recovered LiNi 0.6 Co 0.2 Mn 0.2 O 2 Cathode Materials

Lithium-ion battery (LIB) recycling is considered as an important component to enable industry sustainability. A massive number of LIBs in portable electronics, electric vehicles, and grid storage will eventually end up as wastes, leading to serious economic and environmental problems. Hence, tremendous efforts have been made to improve the hydrometallurgical recycling process because it is the most promising option for handling end-of-life LIBs owing to its wide applicability, low cost, and high productivity. Despite these advantages, some extra elements (Al, Fe, C, F, and so forth) remain as impurities in the removal process and are retained in the solution, which is a great challenge to obtain high-quality cathode materials. In this work, the impacts caused by fluorine impurity on the LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM622) cathode are intensively investigated via hydrometallurgical coprecipitation for the first time. Our results show that up to 1 at. % fluorine impurity brings a positive influence on the recovered material due to a higher Ni 2+ ratio on the surface of cathode particles. In addition, the presence of fluoride ions during coprecipitation could lead to the formation of holes in cathode particles, which improves the rate capability and cyclability dramatically. Compared to the virgin material, the capacity of the NCM622 material with 0.2 at. % fluorine impurity is boosted by ~8% (167.7 mA h/g) with a remarkable capacity retention of 98.0% after 100 cycles at 0.33 C. Besides, the cathode with 0.2 at. % fluorine impurity shows a far better rate performance, especially at high rates (~7% increased at 5 C) than that of virgin. Furthermore, these results convince that a low concentration of fluorine impurity is desirable in the hydrometallurgical recycling process. More importantly, this study offers implications in the design of high-performance NCM622 cathode materials via coprecipitation production with ion doping in the near future.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Thermal runaway mechanism of lithium-ion battery with LiNi 0.8 Mn 0.1 Co 0.1 O 2 cathode materials

Battery safety is critical to the application of lithium-ion batteries, especially for high energy density battery applied in electric vehicles. In this paper, the thermal runaway mechanism of LiNi 0.8 Co 0.1 Mn 0.1 O 2 based lithium-ion battery is illustrated. And the reaction between cathode and flammable electrolyte is proved as the trigger of the thermal runaway accident. In detail, with differential scanning calorimeter tests for battery components, the material combination contributing to thermal runaway was decoupled. Characterization with synchrotron X-ray diffraction and transmission electron microscopy with in-situ heating proved that the vigorous exothermic reaction is initiated by the liberated oxygen species. The pulse of highly active oxygen species reacted quickly with the electrolyte, accompanied with tremendous heat release, which accelerated the phase transformation of charged cathode. Also, the mechanism is verified by a confirmatory experiment when the highly active oxygen species were trapped by anion receptor, the phase transformation of the charged cathode was inhibited. Clarifying the thermal runaway mechanism of LiNi 0.8 Co 0.1 Mn 0.1 based lithium-ion battery may light the way to battery chemistries of both high energy density and high safety.

25 ENERGY STORAGE↗
DOE OSTI2021

Time-Resolved X-ray Operando Observations of Lithiation Gradients across the Cathode Matrix and Individual Oxide Particles during Fast Cycling of a Li-Ion Cell

Lithiated transition metal oxides serve as active materials in the positive electrode (cathode) of lithium-ion cells. During electrochemical cycling, lithium ions intercalate and deintercalate into these oxide particles. This behavior causes two types of lithiation gradients to emerge: (i) a bulk gradient across the depth of the cathode matrix (averaged over individual oxide particles) and (ii) a microscopic gradient across the particles themselves, which also depends on their location in the electrode. Here we show how both gradients can be studied using operando X-ray diffraction during 4C charge and 4C discharge. The oxide (de)lithiation is estimated from the unit cell parameters by indexing the X-ray diffraction spectra. By fitting the lithiation profiles with orthogonal polynomials, the bulk gradients across the electrode thickness are quantified. These gradients develop as the current flows through the cell and dissipate during open-circuit and potentiostatic-hold periods. Further details of lithiation dynamics can be obtained through shape analysis of the Bragg peaks. In particular, from electrochemical model simulations, we show that the width and skewness of the (003) peak track (de)lithiation fronts moving across the individual oxide particles.

(003) peak↗
DOE OSTI2024

Cost‐Effective Layered Oxide – Olivine Blend Cathodes for High‐Rate Pulse Power Lithium‐Ion Batteries

Abstract Sustainability and supply‐chain concerns require lithium‐ion batteries (LIBs) free from critical minerals, such as nickel and cobalt. While recent advances provide encouraging signs that cobalt can be removed, the question remains how much Ni can be removed from Co‐free layered oxide cathodes before sacrificing critical performance metrics. This study highlights the effect of reducing Ni by benchmarking several Co‐free cathodes with decreasing Ni content. Keeping the energy density the same by increasing the charge voltage, cathodes below 80% Ni content exhibit worsened capacity fade due to increasing oxygen release and electrolyte decomposition. Charge transfer and diffusion kinetics are also hindered with increasing Mn content and exacerbated by resistive surface phases formed at high voltages, rendering lower‐Ni, Co‐free cathodes less competitive than high‐Ni cathodes for high energy and power applications. It is demonstrated blending layered oxide with olivine as an effective alternative to deliver energy density and cycling stability comparable to lower‐Ni cathodes with moderate charging voltages. Blending with 30 wt% olivine LiMn 0.5 Fe 0.5 PO 4 (LMFP) virtually eliminates the diffusion limitation of layered oxides at low state‐of‐charge, with enhanced pulse power characteristics rivaling the high‐Ni counterparts. Cathode blending can further reduce the overall Ni content and cost without the performance limitations of lower‐Ni, Co‐free cathodes.

Lee, Steven↗
DOE OSTI2025

Manganese‐Based Spinel Cathodes: A Promising Frontier for Solid‐State Lithium‐Ion Batteries

Recently, all-solid-state lithium-ion batteries (ASSLIBs), which exhibit improved safety and enhanced energy density compared to conventional commercialized lithium-ion batteries (LIBs), thereby have garnered extensive research interest. Among the promising cathode candidates, Mn-based spinel cathodes LiMn 2 O 4 (LMO) and LiNi 0.5 Mn 1.5 O 4 (LNMO), with the unique characteristics of low cost, structural stability, and 3D Li-ion diffusion channels, have demonstrated excellent performance in LIBs and presented great potential in ASSLIBs applications. However, several challenges, including structural degradations, poor interfacial contact, large interfacial resistance, and Mn-dissolution/diffusion during the electrochemical cycling, hinder their practical applications and commercialization in the ASSLIBs. Particularly, the high-voltage LNMO cathodes suffer from the challenge of electrochemical incompatibility with most of the solid-state electrolytes (SSEs). Herein, the spinel structure, the electrochemical behavior, and the structural degradation of the LMO/LNMO are explored. The characteristics and recent progress of the mitigating strategies to the challenges of various SSEs, including polymer-, oxide-, composite-, sulfide-, halide-, and LiPON-based SSEs, are introduced when paired with LMO/LNMO. Finally, the directions for future research to advance Mn-based spinel cathodes and fulfill the requirements of the next-generation ASSLIBs are also discussed.

Dou, Yu [Concordia University, Montreal, QC (Canad↗
DOE OSTI2022

Delineating the Roles of Mn, Al, and Co by Comparing Three Layered Oxide Cathodes with the Same Nickel Content of 70% for Lithium-Ion Batteries

High-nickel layered oxides continue to prevail in the energy storage market as the frontmost cathode candidates for next-generation lithium-ion batteries. Demand and development of LiNi 1–x–y Mn x Co y O 2 (NMC) and LiNi 1–x–y Co x Al y O 2 (NCA) cathodes are rampantly increasing, particularly for the electric vehicle (EV) industry. However, the continued presence of cobalt in NMC and NCA cathodes raises global concerns due to geopolitical and ethical issues attributed to Co sourcing. We herein introduce a novel cobalt-free, high-nickel cathode LiNi 0.7 Mn 0.25 Al 0.05 O 2 (NMA70) and benchmark it against Co-containing LiNi 0.7 Mn 0.15 Co 0.15 O 2 (NMC70) as well as Co- and Al-free LiNi 0.7 Mn 0.3 O 2 (NM70) cathodes with equivalent 70% Ni contents that are all synthesized in-house. NMA70 displays a high initial C/10 capacity of 210 mA h g –1 , matching that of NMC70 in half cells with a cutoff voltage of 4.5 V. NMA70 also exhibits an impressive high-voltage full cell cycling performance with a cutoff voltage of 4.4 V with a nearly identical capacity retention of 83% compared to that of 82% for NMC70 after 300 cycles. Postmortem X-ray photoelectron spectroscopy (XPS), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), and electron energy loss spectroscopy (EELS) analyses indicate a thinner cathode–electrolyte interface (CEI) developed in NMA70 compared to that in NM70 and unveil a more robust solid-electrolyte interface (SEI) passivation on the graphite anode among all samples. The benefits of Al doping are additionally highlighted with enhanced high-voltage CEI and thermal stabilities in NMA70. Furthermore, this work assesses the roles of Mn, Al, and Co to demonstrate both the practicality and feasibility of synthesizing cobalt-free, high-nickel cathodes that are promising alternatives to current NMC- and NCA-based cathodes.

25 ENERGY STORAGE↗
DOE OSTI2022

Alternate Synthesis Method for High-Performance Manganese Rich Cation Disordered Rocksalt Cathodes

Cation-disordered rocksalt (DRX) cathodes have recently emerged as a promising class of cobalt-free, high-capacity cathodes for lithium-ion batteries. To facilitate their commercialization, the development of scalable synthesis techniques providing control over composition and morphology is critical. To this end, a sol-gel synthesis route to prepare Mn-rich DRX cathodes with high capacities is presented here. Several compositions with varied Mn content and nominal F doping are successfully prepared using this technique. In-situ X-ray diffraction measurements demonstrate that DRX formation proceeds at moderate temperature (800 °C) through the sol-gel route, which enables intimate mixing among reactive intermediate phases that form at lower temperatures. All synthesized compositions possess cation short-range order, as evidenced by neutron pair distribution function and electron diffraction analysis. These DRX materials demonstrate promising electrochemical performance with reversible capacities up to 275 mAh g. Compared to the baseline oxide (Li 1.2 Mn 0.4 Ti 0.4 O 2 ), the Mn-rich compositions exhibit improved cycling stability, with some showing an increase in capacity upon cycling. Finally, this study demonstrates the feasibility of preparing high-capacity DRX cathodes through a sol-gel based synthesis route, which may be further optimized to provide better control over the product morphology compared to traditional synthesis methods.

25 ENERGY STORAGE↗