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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 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Topotaxially grown composite cathodes for cobalt-free high-energy long-life Li-ion batteries

The vehicle industry’s increasing demand for electrification necessitates the removal of expensive and rare cobalt from current high-energy batteries. However, eliminating cobalt poses challenges due to its vital role in maintaining the layered structural ordering and cycling stability of commonly used Li(NiMnCo)O 2 cathodes. As an alternative to conventional layered oxide designs, we report a lithium nickelate cathode with a composite structure comprising major stoichiometric layered and minor rocksalt phases within the same oxygen lattice. This material outperforms conventional designs by maintaining stable battery operation at voltages up to 4.8 V vs. Li|Li + , with 88% capacity retention after 1000 cycles at 2C. The topotaxial-growth-enabled interlock between the two components mitigates chemo-mechanical degradation, offering a promising pathway to cobalt-free cathodes. Additionally, we reveal a miscibility gap in the Li-Ni-O system that enables kinetic adjustment of composition and structure during sintering, thereby tuning the functionality of high-energy cathodes.

25 ENERGY STORAGE↗
DOE OSTI2024

Electrolytes and electrochemical devices

Disclosed herein are electrolytes and electrochemical devices. The electrochemical devices comprise cathodes that include nickel-rich layered lithium transition metal oxides, lithium-rich layered transition-metal oxides, lithium manganese-based spinel oxides, lithium polyanion-based compounds, and combinations thereof. The electrolytes include a lithium imide salt, an aprotic acyclic carbonate solvent, and an additive, wherein the additive comprises a metal salt, an aprotic solvent, or a combination thereof. The electrolyte can be stable at a voltage of 4.3 V or above vs. Li/Li+.

Manthiram, Arumugam↗
DOE OSTI2026

Stabilizing Cathode–Electrolyte Interphase of Nickel-Rich Single-Crystal Cathodes for Lithium-Ion Batteries

Nickel-rich single-crystal (SC) layered oxides are promising cathode candidates for next-generation lithium-ion batteries (LIBs) owing to their high energy density and structural robustness against intergranular cracking. However, their intrinsic surface reactivity with liquid electrolytes accelerates parasitic reactions at the cathode–electrolyte interphase (CEI), leading to transition-metal dissolution, gas generation, and impedance buildup. In this work, we synthesized SC-Li x Ni 0.9 Mn 0.05 Co 0.05 O 2 (NMC9055, 1 ≤ x ≤ 1.2) using a eutectic-assisted method and investigated interface stabilization strategies. A nickel-deficient Li x Ni 0.6 Mn 0.2 Co 0.2 O 2 (NMC622, 1 ≤ x ≤ 1.2) coating was applied via evaporation-based deposition to suppress CEI degradation pathways. Structural and compositional analyses confirmed uniform shell formation and preserved particle integrity. Half-cell electrochemical testing against lithium metal revealed ∼10% higher capacity retention and improved reversibility compared with pristine SC NMC9055, particularly under high-voltage operation. In conclusion, these results highlight the critical role of controlled surface chemistry in mitigating CEI instability in nickel-rich SC cathodes, offering a pathway toward enabling durable high-energy LIBs.

Coating processes↗
DOE OSTI2022

Ethylene Carbonate–Free Electrolytes for Stable, Safer High–Nickel Lithium–Ion Batteries

Ethylene carbonate (EC) is an important component in state-of-the-art electrolytes for lithium-ion batteries (LIBs). However, EC is highly susceptible to oxidation on the surface of high-nickel layered oxide cathodes, making it undesirable for next-generation high-energy-density LIBs. In this study, a simple, yet effective, EC-free electrolyte (20F1.5M-1TDI) is presented by adding 20 wt% fluoroethylene carbonate (FEC) and 1 wt% lithium 4,5-dicyano-2-(trifluoromethyl)imidazole (LiTDI) into 1.5 M LiPF 6 in an ethyl methyl carbonate (EMC) electrolyte. The 20F1.5M-1TDI electrolyte is found to efficiently passivate the graphite anode and stabilize high-nickel cathodes by a synergistic decomposition of FEC and LiTDI. The LiNi 0.9 Mn 0.05 Al 0.05 O 2 (NMA90)/graphite full cell with the 20F1.5M-1TDI electrolyte, therefore, exhibits an enhanced cycling stability and a suppressed voltage hysteresis growth compared to that with an EC-containing baseline electrolyte (1 M LiPF 6 in EC:EMC, 3:7 in weight, with 2 wt% vinyl carbonate). Advanced analytical tools, such as time-of-flight secondary ion mass spectrometry and X-ray photoelectron spectroscopy, are employed to understand the underlying working mechanism of the EC-free electrolyte. Furthermore, the present study clearly showcases the great potential of EC-free electrolytes as a straightforward, practical approach for LIBs with high-nickel cathodes.

electrode/electrolyte interface↗
DOE OSTI2023

Doping strategy for layered oxide electrode materials used in lithium-ion batteries

The present invention features a new way of doping layered cathode materials in lithium ion batteries. Using a “high entropy” doping strategy, more than four impurity elements can be introduced to the host materials. The present invention applies this high entropy doping strategy to a high nickel content layered oxide material and a lithium-manganese rich material. This new high entropy doping strategy allows the layered oxide materials used in the positive electrode of lithium ion battery to achieve high energy density, long life cycle and reduced reliance on the expensive and toxic cobalt, all of which are desired attributes for improving the performance of lithium ion batteries and reducing their cost.

Xin, Huolin↗
DOE OSTI2021

Crossover Effects in Batteries with High–Nickel Cathodes and Lithium–Metal Anodes

It is well understood that cathode-to-anode crossover, especially of transition-metal ions, can significantly impact the long-term cycling of lithium-ion batteries. The dissolved transition-metal ions in lithium-ion cells deposit on the graphite anode, disrupt the solid-electrolyte interphase (SEI), and catalyze further side reactions. Meanwhile, crossover effects in lithium-metal batteries have rarely been studied. This study is the first to investigate crossover effects in lithium-metal batteries with high-nickel layered-oxide cathodes. It is shown that the crossover of transition-metal ions from LiNi 0.9 Mn 0.05 Co 0.05 O 2 has minimal effect on the lithium-metal anode (LMA) due to the following reasons. The catalytic transition metals 1) have less effect on an inherently reactive LMA, 2) are diluted in a thicker SEI, and 3) are produced in overall lower quantity due to the limited cycle life of the LMA. Conversely, the LMA generates soluble decomposition products that cross over to the cathode even during early cycling. This crossover accelerates impedance growth and capacity fade at the cathode and is partially responsible for the mismatch between the performance of half and full-cells with layered-oxide cathodes. Finally, this study highlights the need for better battery design with LMA, potentially including electrolyte or cell modifications.

25 ENERGY STORAGE↗
DOE OSTI2020

High–Nickel NMA: A Cobalt–Free Alternative to NMC and NCA Cathodes for Lithium–Ion Batteries

High-nickel LiNi 1–x–y Mn x Co y O 2 (NMC) and LiNi 1–x–y Co x Al y O 2 (NCA) are the cathode materials of choice for next-generation high-energy lithium-ion batteries. Both NMC and NCA contain cobalt, an expensive and scarce metal generally believed to be essential for their electrochemical performance. Herein, a high-Ni LiNi 1–x–y Mn x Al y O 2 (NMA) cathode of desirable electrochemical properties is demonstrated benchmarked against NMC, NCA, and Al–Mg-codoped NMC (NMCAM) of identical Ni content (89 mol%) synthesized in-house. Despite a slightly lower specific capacity, high-Ni NMA operates at a higher voltage by ≈40 mV and shows no compromise in rate capability relative to NMC and NCA. In pouch cells paired with graphite, high-Ni NMA outperforms both NMC and NCA and only slightly trails NMCAM and a commercial cathode after 1000 deep cycles. Further, the superior thermal stability of NMA to NMC, NCA, and NMCAM is shown using differential scanning calorimetry. Here, considering the flexibility in compositional tuning and immediate synthesis scalability of high-Ni NMA very similar to NCA and NMC, this study opens a new space for cathode material development for next-generation high-energy, cobalt-free Li-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2024

Electro-Chemo-Mechanical Evolution at the Garnet Solid Electrolyte–Cathode Interface

Solid-state batteries promise higher energy density and improved safety compared with lithium-ion batteries. However, electro-chemomechanical instabilities at the solid electrolyte interface with the cathode and the anode hinder their large scale implementation. Here, in this study, we focus on resolving electro-chemo-mechanical instability mechanisms and their onset conditions between a state-of-the-art cathode, LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622), and the garnet Li 7 La 3 Zr 2 O 12 (LLZO) solid electrolyte. We used thin-film NMC622 on LLZO pellets to place the interfacial region within the detection depth of the X-ray characterization techniques. The experimental probes of the near-interface region included in operando X-ray absorption spectroscopy and ex situ focused ion beam scanning electron microscopy. Electrochemical degradation was not observable during cycling at room temperature with 4.3 V versus Li/Li + charge voltage cutoff, or with stepwise potentiostatic hold up to 4.1 V versus Li/Li + . In contrast, secondary phases including reduced transition metal species (Ni 2+ , Co 2+ ) were found after cycling up to 4.3 V versus Li/Li + at 80 °C and during potentiostatic hold at 4.3 V versus Li/Li + (Ni 2+ ). Intergranular cracks between NMC622 grains and delamination at the NMC622|LLZO interface occurred readily after the first charge. These interface reaction products and mechanical failure lowered the capacity and cell efficiency due to partial loss of the NMC622 phase, partial loss of contact at the interface, and a higher polarization resistance. Electrochemical instability between delithiated NMC622 and LLZO could be mitigated by using a low charge voltage cutoff or cycling at lower temperature. Ways to engineer the mechanical properties to avoid crack deflection and delamination at the interface are also discussed for enhancing mechanical stability.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Impact of Anode to Cathode Crossover in Lithium‐metal Batteries With High‐Nickel Cathodes

The advancement of high-energy-density lithium-metal batteries (LMBs) is hindered by the chemical instability of both lithium-metal anode and high-nickel layered oxide cathodes. While cathode-to-anode crossover is well-documented, the reverse process of anode-to-cathode crossover remains underexplored. Here, we systematically investigate such crossovers and the degradation pathway in pouch cells with a localized high-concentration electrolyte, comparing NMC622, NMC811, and NMC90 cathodes paired with lithium-metal and graphite anodes. Despite delivering higher initial capacities, LMBs exhibit faster capacity fade under long-term cycling at 45 °C. To isolate cathode-side degradation, galvanostatic electrochemical impedance spectroscopy (GEIS) measurements of cycled cathodes paired with delithiated lithium iron phosphate (LFP) counter electrodes reveal significantly higher charge-transfer resistance in cathodes cycled with lithium-metal. Surface characterization via X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) reveals greater electrolyte decomposition on cathodes cycled with lithium metal, leading to thicker, more organic-rich cathode–electrolyte interphases (CEIs), consistent with the elevated charge-transfer resistance observed in GEIS measurements. Notably, NMC90 shows the most pronounced CEI thickening, linking higher cathode surface reactivity to greater susceptibility to anode-to-cathode crossover. This work presents compelling evidence of crosstalk degradation originating from lithium-metal anodes and underscores the importance of cross-interface stability for the design of durable LMBs.

25 ENERGY STORAGE↗
DOE OSTI2021

Layered Heterostructure Ionogel Electrolytes for High‐Performance Solid‐State Lithium‐Ion Batteries

Abstract Ionogel electrolytes based on ionic liquids and gelling matrices offer several advantages for solid‐state lithium‐ion batteries, including nonflammability, wide processing compatibility, and favorable electrochemical and thermal properties. However, the absence of ionic liquids that are concurrently stable at low and high potentials constrains the electrochemical windows of ionogel electrolytes and thus their high‐energy‐density applications. Here, ionogel electrolytes with a layered heterostructure are introduced, combining high‐potential (anodic stability: >5 V vs Li/Li + ) and low‐potential (cathodic stability: <0 V vs Li/Li + ) imidazolium ionic liquids in a hexagonal boron nitride nanoplatelet matrix. These layered heterostructure ionogel electrolytes lead to extended electrochemical windows, while preserving high ionic conductivity (>1 mS cm −1 at room temperature). Using the layered heterostructure ionogel electrolytes, full‐cell solid‐state lithium‐ion batteries with a nickel manganese cobalt oxide cathode and a graphite anode are demonstrated, exhibiting voltages that are unachievable with either the high‐potential or low‐potential ionic liquid alone. Compared to ionogel electrolytes based on mixed ionic liquids, the layered heterostructure ionogel electrolytes enable higher stability operation of full‐cell lithium‐ion batteries, resulting in significantly enhanced cycling performance.

Hyun, Woo Jin↗
DOE OSTI2024

Effects of Calcination Conditions on the Structural and Electrochemical Behaviors of High‐Nickel, Cobalt‐Free LiNi 0.9 Mn 0.1 O 2 Cathode

Abstract Eliminating cobalt from high‐nickel layered oxide cathodes lowers the cost of lithium‐ion batteries for electric vehicles. However, cobalt‐free cathodes with high Mn 4+ and Ni 2+ contents are prone to Li/Ni mixing after synthesis, potentially compromising battery energy density, rate capability, and cycling stability. Without cobalt facilitating cation ordering in the layered structure, the degree of Li/Ni mixing in cobalt‐free cathodes depends heavily on the calcination conditions. In this study, a systematic exploration of calcination temperatures and LiOH ratio for LiNi 0.9 Mn 0.1 O 2 (NM‐90) provides detailed insights into the optimal synthesis conditions for high‐capacity cobalt‐free cathodes with extended cycle life. Surprisingly, high Li/Ni mixing does not necessarily lead to poor cycling stability whereas low Li/Ni mixing does not guarantee a long cycle life. More importantly, although excessive calcination temperature can further decrease Li/Ni mixing, it does not necessarily enhance capacity. Instead, the pernicious effects from the H2 → H3 phase transition are amplified due to a pronounced two‐phase reaction. An extensive suite of chemical and structural characterization methods uncovers a correlation between elevated calcination temperature, phase transformation, cation ordering, and capacity fading behavior: “overcooking” high‐nickel, cobalt‐free cathodes induce structural arrangement toward that of LiNiO 2 , with exacerbated lattice distortion and surface instability accelerating capacity fade.

Lee, Steven↗
DOE OSTI2020

Long-Term Cyclability of NCM-811 at High Voltages in Lithium-Ion Batteries: an In-Depth Diagnostic Study

High-nickel layered oxides, such as LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM-811), offer higher energy density than their low-nickel counterparts at a given voltage and are gaining major traction in automotive lithium-ion batteries for electric vehicles. Besides high-Ni content, higher charging voltages above 4.3 V vs Li + /Li boost the energy and represent another focus in battery development. Here, we investigate the long-term cyclability of NCM-811 in graphite pouch cells over 1000 deep cycles between 2.5–4.2, 2.5–4.4, and 2.5–4.5 V through a suite of sensitive characterization techniques. The NCM-811 full cells show severely deteriorated cyclability with higher charging voltages, from 78% at 4.2 V to 52 and 32% at 4.4 and 4.5 V, respectively. At 4.2 V, minor parasitic electrolyte oxidation as well as cathode Li/Ni mixing and cracking are revealed after cycling, while transition-metal dissolution and surface reconstruction into rock-salt NiO are virtually undetectable. At 4.4 and 4.5 V, transition-metal dissolution and crossover to the anode become much more pronounced and a primary contributor to the capacity fade, while significant surface NiO formation causes substantial voltage polarization, which is less noticeable at 4.2 V. Meanwhile, more severe electrolyte oxidation, Li/Ni mixing, and particle pulverization exacerbate the voltage and capacity fade. Finally, these results outline distinct challenges for stable high-Ni layered oxide cathodes in high-voltage Li-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2023

Demarcating the Impact of Electrolytes on High–Nickel Cathodes and Lithium–Metal Anode

The ever-growing demand for low-cost, high-energy-density lithium-ion batteries (LIBs) makes high-nickel layered oxide cathodes, especially LiNiO 2 (LNO), one of the most appealing candidates. However, poor structural and surface instability that leads to a short cycle life remains a formidable challenge. Herein, a systematic investigation of LNO performance in two different electrolytes (a conventional carbonate-based LP57 electrolyte and an ether-based localized high-concentration electrolyte (LHCE)) with different charge cut-off voltages is presented. These findings show that the cathode-electrolyte reactivity is the main factor dictating the performance degradation of LNO at high voltages rather than bulk integrity. While LHCE can provide good stability beyond 4.2 V with a robust, uniform solid–electrolyte interphase (SEI) layer on the Li-metal anode, there is no significant difference in cyclability at 4.15 V (96% capacity retention after 200 cycles) for both LP57 and LHCE. From LNO symmetric cells, carbonate-based electrolyte is found to be good for LNO stability while ether-based electrolyte is beneficial toward Li-metal anode. Furthermore, a suitable electrolyte or a low cut-off voltage is necessary to maintain a decent cycle life. Altogether, this work highlights the impact of electrolyte and cut-off voltage on LNO and Li-metal, which can help guide the development of cells based on LNO.

25 ENERGY STORAGE↗
DOE OSTI2023

Fluorinated High-Voltage Electrolytes To Stabilize Nickel-Rich Lithium Batteries

As state-of-the-art (SOA) lithium-ion (Li-ion) batteries approach their specific energy limit (~250 Wh kg -1 ), layer-structured, nickel-rich (Ni-rich) lithium transition metal oxide-based cathode materials, e. g., LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811), have attracted great interest owing to their practical high specific capacities (>200 mAhg -1 ). Coupled with their high average discharge voltages (~4 V vs Li/Li + ), Ni-rich cathode-based lithium batteries possess a great potential to achieve much higher specific energies (>350 Wh kg -1 at the cell level) than the SOA Li-ion counterparts. In addition, Ni-rich oxides are low-cost battery cathode materials due to their low cobalt contents. However, Ni-rich cathode-based lithium batteries suffer quick capacity degradations upon cycling, particularly at high upper cutoff voltages (e.g., ≥= 4.5 V vs Li/Li + ), due to crystal structure changes of the active cathode materials and parasitic side reactions at the electrolyte/electrode interfaces. In this study, a fluorinated-solvent-based, high-voltage stable electrolyte (HVE), i.e., 1 M Li bis(trifluoromethanesulfonyl)imide (LiTFSI) in fluoroethylene carbonate (FEC), bis(2,2,2-trifluoroethyl) carbonate (FDEC), and methyl (2,2,2-trifluoroethyl) carbonate (FEMC) with Li difluoro(oxalate)borate (LiDFOB) additive, was formulated and evaluated in Li/NMC811 battery cells. Further, to the best of our knowledge, this class of electrolyte has not been investigated for Ni-rich cathode-based lithium batteries. Li/NMC811 cells with HVE exhibited a superior long-term cycle performance stability, maintaining ~80% capacity after ~500 cycles at a high cutoff voltage of 4.5 V (vs Li/Li + ) than a baseline carbonate-solvent-based electrolyte (BE). The superior cycle stability of the Li/NMC811 cells is attributed to the inherently high-voltage stability of HVE, supported by the physical and electrochemical analyses. This conclusion is supported by our density functional theory (DFT) modeling where HVE shows a less tendency of deprotonation/oxidation than BE, leading to the observed cycle stability. The findings in this study are important to help tackle the technical challenges facing Ni-rich cathode-based lithium batteries to realize their high energy density potentials with a long cycle life.

25 ENERGY STORAGE↗
DOE OSTI2020

Long-Life, Ultrahigh-Nickel Cathodes with Excellent Air Storage Stability for High-Energy Density Lithium-Based Batteries

With increased energy density and cost advantage, ultrahigh-nickel layered oxides (LiNi x M 1-x O 2 , x = 0.9 - 1.0) are becoming front-runner as cathodes for next-generation lithium-based batteries, yet their commercialization is blocked both by severe capacity fade and exponentially aggravated air degradation. Thus, it is imperative to find effective solutions to address these issues simultaneously. Here, a significant enhancement in both the cycling and air storage stability of the ultrahigh-Ni cathode LiNi 0.94 Co 0.06 O 2 is achieved via a distinctive phosphoric acid treatment strategy. The modified cathode displays remarkably improved capacity retention (from 36 % to 80 % after 1,000 cycles) and rate capability (from 0 to 105 mA h g -1 at 30C rate) in pouch cells. Impressively, the modified cathode, after air storage for 450 days, maintains the morphology and 92% of the initial capacity of the fresh sample with excellent cyclability. Comprehensive interphase and structural analyses reveal that the enhanced electrochemical performance is due to a highly stabilized electrode/electrolyte interphase that suppresses electrode corrosion and lattice reconstruction. The excellent air stability results from an adsorption-buffering effect enabled by phosphoric acid to air attack. Finally, the study demonstrates an engineering pathway to improve the cycling and air stability, facilitating the practical viability of high-capacity, affordable, ultrahigh-Ni cathodes in lithium-based batteries.

25 ENERGY STORAGE↗
DOE OSTI2020

Distinct Surface and Bulk Thermal Behaviors of LiNi 0.6 Mn 0.2 Co 0.2 O 2 Cathode Materials as a Function of State of Charge

Understanding how structural and chemical transformations take place in particles under thermal conditions can inform designing thermally robust electrode materials. Such a study necessitates the use of diagnostic techniques that are capable of probing the transformations at multiple length scales and at different states of charge (SOC). In this study, the thermal behavior ofLiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC-622) was examined as a function of SOC, using an array of bulk and surface-sensitive techniques. In general, thermal stability decreases as lithium content is lowered and conversion in the bulk to progressively reduced metal oxides (spinels, rock salt) occurs as the temperature is raised. Hard X-ray absorption spectroscopy (XAS) and X-ray Raman spectroscopy (XRS) experiments, which probe the bulk, reveal that Ni and Co are eventually reduced when partially delithiated samples (regardless of the SOC) are heated, although Mn is not. Surface-sensitive synchrotron techniques, such as soft XAS and transmission X-ray microscopy (TXM), however, reveal that for 50% delithiated samples, apparent oxidation of nickel occurs at particle surfaces under some circumstances. This is partially compensated by reduction of cobalt but may also be a consequence of redistribution of lithium ions upon heating. TXM results indicate the movement of reduced nickel ions into particle interiors or oxidized nickel ions to the surface or both. These experiments illustrate the complexity of the thermal behavior of NMC cathode materials. The study also informs the importance of investigating the surface and bulk difference as a function of SOC when studying the thermal behaviors of battery materials.

25 ENERGY STORAGE↗