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At least 91 records · Page 5

Upgrading the Performance and Stability of Lithium, Manganese-Rich Layered Oxide Cathodes with Combined-Formic Acid and Spinel Coating Treatment

We report improving sluggish rate performance and cycling stability of Li, Mn-rich cathode materials (LMR) is of great importance for practical implementation. Here, dual surface modification on LMR particles with formic acid washing and spinel coating improves the electrochemical performance. Dilute formic acid can remove the Li2CO3 surface impurities and selectively reduce Ni while significantly increasing specific surface area by ~32 %, unlocking more electrochemically active surfaces. Spinel coating enhances cycle stability by suppressing detrimental side reactions at electrode-electrolyte interfaces at high voltage. Post-annealing temperature was found to significantly affect the cathode performance. Higher temperature favors diffusion of transition metal (TM)/Li ions of the spinel coating from surface to the bulk, removing the coating by possible reconstruction into the layered structure and thus degrading the performance. The spinel coating also appears to increase Co 3+ segregation on the particle surface. Compared to the original material, the optimized sample demonstrates 47 % higher capacity retention at 3C and retains 89 % of initial capacity after 150 cycles at 0.5C. Besides, the specific energy density of 523 Wh kg -1 can be attained after 150 cycles at 0.5C. Moreover, the post-cycling analysis of modified sample verifies a better structural integrity with less particle cracking. Altogether, this study portrays an alternative strategy to overcome the shortcomings of LMR cathode materials.

25 ENERGY STORAGE↗

Cathode-Confined Polysulfide Retention-Release Reprograms Li 2 S Deposition in High-Loading Li–S Batteries

High-loading lithium-sulfur (Li-S) cells operated with lean electrolyte are limited by polysulfide crossover to Li metal and by transport-limited liquid-solid conversion that forms passivating Li 2 S films. Here, we show that a cathode-facing separator coating of carboxylated multiwalled carbon nanotubes acts as a cathode-confined polysulfide reservoir with intermediate binding. Early in discharge it captures newly generated polysulfides at the separator interface, suppressing shuttle reactions. As polysulfides are consumed, the reservoir buffers concentration gradients and feeds reactants back to the cathode, shifting Li 2 S deposition from burst-like film growth to progressive, three-dimensional, porous formation. Synchrotron XRD and S K-edge XANES, together with Scharifker–Hills nucleation analysis and depth-of-discharge EIS/DRT, substantiate this coupled transport–reaction control. With 4.3 mg S cm -2 and E/S = 5, cells reach 4.2 mAh cm -2 and retain 90% capacity over 100 cycles at 20 °C.

25 ENERGY STORAGE↗

Hollow cathodes with BaO impregnated, porous tungsten inserts and tips

The technology of impregnated materials is described and some inherently advantageous characteristics of impregnated cathodes are discussed. Thermionic emission measurements are presented for oxide coated and impregnated cathodes. Five cathode configurations with barium oxide impregnated porous tungsten inserts and/or tips have been fabricated and tested. Reliability, durability, and stability of operation are characterized. One of the cathodes has accumulated over 9000 operational hours, another has been cycled on and off more than 800 times.

Hudson, W. R.↗

Hollow cathodes with BaO impregnated, porous tungsten inserts and tips

The technology of impregnated materials is described and some inherently advantageous characteristics of impregnated cathodes are discussed. Thermionic emission measurements are presented for oxide coated and impregnated cathodes. Five cathode configurations with barium oxide impregnated porous tungsten inserts and/or tips have been fabricated and tested. Reliability, durability, and stability of operation are characterized. One of the cathodes has accumulated over 9000 operational hours, another has been cycled on and off more than 900 times.

Hudson, W. R.↗

Work function lowering of LaB 6 by monolayer hexagonal boron nitride coating for improved photo- and thermionic-cathodes

We report a lowering of work function for lanthanum hexaboride (LaB 6 ) by monolayer hexagonal boron nitride (hBN) coating. Photoemission electron microcopy (PEEM) and thermionic emission electron microscopy (TEEM) both revealed that the hBN coated region of a LaB 6 (100) single crystal has a lower work function compared to the bare (i.e., non-coated) and graphene coated regions. A broad and uniform brighter image of the hBN coated region in PEEM was quantitatively supported by a 0.4 eV decrease in the work function in photoelectron spectra compared to the bare region. TEEM results were consistent in that the hBN coated region exhibited thermionic emission at 905 °C, whereas the bare and graphene coated regions did not. A larger decrease in the work function for hBN coated LaB 6 (100) compared to graphene coated LaB 6 (100) was qualitatively supported by our density functional theory calculations. Adding an oxide layer in the calculations improved consistency between the calculation and experimental results. We followed up our calculations with synchrotron-radiation x-ray photoelectron spectroscopy and confirmed the presence of an oxide layer on our LaB 6 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Roll-To-Roll Atomic Layer Deposition of Titania Nanocoating on Thermally Stabilizing Lithium Nickel Cobalt Manganese Oxide Cathodes for Lithium Ion Batteries

Conformal coating of ceramic layers (nm-thick) on Ni-rich layered cathode materials is an effective strategy for improving high-temperature longevity of Li-ion batteries (LIBs). In this work, we develop a roll-to-roll atomic layer deposition (R2R ALD) apparatus for growing uniform nanolayers of TiO 2 . We explore the effect of ALD parameters (temperature: 120–180 °C and line speed: 2–40 mm s –1 ) on the TiO 2 surface coating and subsequently investigate the electrochemical performance of the as-prepared cathodes. The capacity retention of TiO 2 -coated porous electrodes is substantially improved compared to that of the pristine cathode material for high-temperature cycling. Electrochemical impedance spectroscopy confirms that the ALD-TiO 2 coating suppresses the undesired side reactions initiated at the electrode/electrolyte interface, reduces charge transfer resistance, and ultimately facilitates the Li + transport through the composite cathode nanostructure. The robust design of the ALD-TiO 2 cathode material enables high-temperature operation (>55 °C) with enhanced specific capacity, superior rate capability, excellent cyclability, and ultra-high coulombic efficiency within a wide potential window (3.0–4.35 V). Furthermore, the R2R ALD technique developed in this work paves the way for large-scale fabrication of ceramic-coated cathode sheets with a production rate reaching 2.4 m min –1 for a continuous coating operation.

25 ENERGY STORAGE↗

Advancing Sodium-Ion Battery Cathodes: A Low-Cost, Eco-Friendly Mechanofusion Route from TiO 2 Coating to Ti 4+ Doping

Layered oxide battery cathodes often require extra stabilization strategies, such as surface coating or doping, to mitigate side reactions and enhance longevity. Conventional methods such as aqueous deposition and atomic layer deposition are costly and environmentally unfriendly and even damage the original structure, especially for air-sensitive sodium-ion battery (SIB) cathodes. Herein, we introduce an all-dry mechanofusion technique that modifies hydroxide precursors with TiO 2 coating before sintering with a sodium source. Using advanced characterizations including X-ray diffraction, neutron diffraction, and solid-state nuclear magnetic resonance for structural insights, X-ray absorption spectroscopy to study metal valence states, and transmission X-ray microscopy for nanoscale visualization of nickel oxidation states, we verified that postsintering transforms TiO 2 surface coating into Ti doping, leading to improved Ni-oxidation homogeneity, modified charge compensation, and enhanced thermal stability. Electrochemical tests reveal superior performance in capacity retention, rate capability, and air stability for these modified cathodes, with pouch cells maintaining over 85% capacity after 650 cycles. This method presents a sustainable, cost-effective route for advanced SIB cathode development.

36 MATERIALS SCIENCE↗

Performance of Different Water-Based Binder Formulations for Ni-Rich Cathodes Evaluated in LiNi 0.8 Mn 0.1 Co 0.1 O 2 //Graphite Pouch Cells

Water-based processing for lithium-ion battery electrodes is attractive due to its lower manufacturing cost and smaller environmental impact. However, multiple challenges associated with aqueous cathode processing have hindered commercial adoption. Polymer binders are an important component of the electrode, and thus the choice of binders can alter electrode cycling performance significantly. In this work, four different water-based binder combinations are investigated for Ni-rich LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811)-based cathodes, with a focus on the long-term electrochemical performance in practical-format full pouch cells. No additional pH-modulating additives were added to the aqueous cathode slurries, and no protective coatings were present on the cathode or aluminum current collector. Results are compared with the standard PVDF/NMP-based binder/solvent combination, used as a baseline. The influence of water-based binder type on slurry rheology and electrode microstructure are also discussed. All cells made by water-processing had worse rate performance compared to the baseline. However, the cell discharge capacity after 1000 U.S. Advanced Battery Consortium (USABC) cycles at C/3 charge/discharge rate was comparable to the baseline for two of the water-based cathode formulations (CMC & JSR, and LiPAA), demonstrating the potential viability of aqueous-processed Ni-rich cathodes at a commercial scale.

25 ENERGY STORAGE↗

LaCrO 3 -Coated La 0.6 Sr 0.4 Co 0.2 Fe0.8O3–δ Core–Shell Structured Cathode with Enhanced Cr Tolerance for Intermediate-Temperature Solid Oxide Fuel Cells

La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ (LSCF) is a common cathode material for intermediate temperature solid oxide fuel cells due to its excellent oxygen reduction reaction catalytic activity. However, the Cr-poisoning effect is a severe issue causing its electrochemical performance degrada-tion. To develop a LSCF-based cathode with excellent Cr-tolerance, LaCrO 3 -coated LSCF core-shell structured (LCr@LSCF) cathode was prepared via solution infiltration method. After coated by LCr shell, the long-term stability and Cr-tolerance were obviously improved, at the price of sacrificing some electrochemical performance. As a result, the development of LCr@LSCF cathode with eye-catching Cr-tolerance is of great significance to the commercialization of LSCF.

36 MATERIALS SCIENCE↗

Communication—Reduction of DC Resistance of Ni-Rich Lithium Transition Metal Oxide Cathode by Atomic Layer Deposition

A coating using Atomic layer deposition (ALD) of Al 2 O 3 was applied to Ni-rich lithium transition metal oxide cathode material. This ALD coating reduces the DC resistance (DCR) and increases the cycling performance of the Ni-rich cathode. Additionally, the reduced DCR comes from decreased solid electrolyte interphase (SEI) resistance on the anode, which is attributed to reduced transition metal deposition. This is due to the ALD coating preventing the direct contact between the cathode and the electrolyte, and therefore inhibits transition metal dissolution. This study suggests the promise of using ALD coating to reduce the DCR of Ni-rich cathode materials.

25 ENERGY STORAGE↗

High-Performance Low-Cobalt Cathode Materials for Li-ion Batteries

The layer-structured Li[Ni x Co y Mn 1-x-y ]O 2 (NCM) cathode materials have been the best choice for increasing electric vehicle driving distance per charge. The high Ni layered oxide represents successfully commercialized NCM cathodes (such as NCM622 and NCA) in lithium-ion batteries (LIBs) for EV applications due to their high energy density and acceptable cycling stability. However, the price of cobalt, the key element within LIBs for stability, has nearly tripled over the past few years due to increased demand from the cell phone industry. As mentioned in the DOE Funding Opportunity Announcement, the current materials shortage will also cause speculation for a future global shortage. Therefore, to meet the requirement and sustainability of the next-generation long-range and low-cost EVs, developing cathode materials with low-Co content to achieve higher energy density and lower cost is both essential and urgent. The overarching objective of this work is to develop stabilized NCM cathode materials with low Co content (namely LiNi x Co y Mn 1-x-y O 2 , y ≤ 0.04) to meet DOE’s goal of reducing Co loading below 50 mg Wh -1 while maintaining energy density greater than 600 Wh kg -1 based on cathode material. Via various dopings and coatings scalable methods, we explored and enhanced the cycling performance of low-cobalt cathodes. The final obtained NCM cathodes paired with graphite anode aim to deliver batteries with a high initial specific energy density of over 240 Wh kg -1 and a low capacity fading rate of less than 20% in 1000 cycles under a C/3 discharge rate. To accomplish this goal, a multidisciplinary team with several co-investigators has been formed from three organizations: The Pennsylvania State University (PSU), Oak Ridge National Laboratory (ORNL), and Pacific Northwest National Laboratory (PNNL). The PI and co-investigators are Dr. Donghai Wang (PI) from PSU with expertise in the synthesis of nanostructured materials and manipulation of interfacial properties of electrochemically active materials, Dr. Jagjit Nanda, with substantial knowledge of and expertise in state-of-the-art cathodes from ORNL, Dr. Chao-Yang Wang with significant experience in advanced cell design and fabrication and cell diagnostics from PSU, and Dr. Chongmin Wang with world-wide known expertise of advance atomic scale characterization of electrode materials from PNNL. Furthermore, this project will leverage and synergistically work with the current DOE-funded programs on battery materials at PSU and ORNL and electrode materials characterization at PNNL. During this funded period, we have accomplished milestones stated as follows: • Scale up production of LiFePO 4 (LFP) coated NCM811 with a production of 300g/batch. Fifteen (≥2 Ah) pouch cells with LFP-coated NCM811 cathode are delivered. Self-evaluated pouch cells in PSU show superior over 80% capacity retention performance even after 1500 cycles at C/3 rate. • Various cations (Al, Ti, Zr, and Mo) substitute cobalt in low-cobalt partially and Co-free cathodes. Their effects on crystal structure and electrochemical behavior are explored. • Phosphate compounds as coating materials represent promising surface protection precursors for low-cobalt cathode materials. Therefore, several metal phosphates were selected for improving the NMC cycling performance and are regarded as effective approaches for a scalable and practical surface protection method. • Production of NCM92, where Nickel content is 92% among transition metals, is scaled up from synthesis to coating and heat treatment procedures. Fifteen 2.7Ah pouch cells with Ti-doped NCM92 cathodes and industrial graphite anode are delivered to Idaho National Lab for testing.

25 ENERGY STORAGE↗

Chromium oxide coatings improve thermal emissivity of alumina

Chromium oxide coatings improve thermal radiation characteristics of alumina-coated heater-cathode systems in vacuum tubes. Chromium oxide is applied either as a surface layer or as a doping material. The new coatings eliminate the high temperature migration problems of carbon surface treatments.

Upshaw, V.↗

Suppressing strain propagation in ultrahigh-Ni cathodes during fast charging via epitaxial entropy-assisted coating

Surface reconstruction and the associated severe strain propagation have long been reported as the major cause of cathode failure during fast charging and long-term cycling. Despite tremendous attempts, no known strategies can simultaneously address the electro-chemomechanical instability without sacrificing energy and power density. Here we report an epitaxial entropy-assisted coating strategy for ultrahigh-Ni LiNi x Co y Mn 1-x-y O 2 (x ≥ 0.9) cathodes via an oriented attachment-driven reaction between Wadsley-Roth phase-based oxides and the layered-oxide cathodes. Further, the high anti-cracking and anti-corrosion tolerances as well as the fast ionic transport of the entropy-assisted surface effectively improved the fast charging/discharging capability, wide temperature tolerance and thermal stability of the ultrahigh-Ni cathodes. Comprehensive analysis from the primary and secondary particle level to the electrode level using multi-scale in situ synchrotron X-ray probes reveals greatly reduced lattice dislocations, anisotropic lattice strain and oxygen release as well as improved bulk/local structural stability, even when charging beyond the threshold state of charge (75%) of layered cathodes. Layered Ni-rich oxide cathodes are susceptible to challenges with surface reconstruction and strain propagation, limiting their cyclability. The authors propose a solution involving oriented attachment-driven reactions, utilizing Wadsley-Roth nanocrystals and layered oxide to induce an epitaxial entropy-assisted coating, effectively addressing these issues.

25 ENERGY STORAGE↗

Elucidating the Redox Behavior during Atomic Layer Deposition on Lithium-Ion Battery Cathode Materials

Atomic layer deposition (ALD) has emerged as a promising technology for applying ultrathin protective coatings on lithium-ion battery (LIB) cathode surfaces to improve their cycling stability. While there have been numerous reports evaluating the electrochemical performance of these surface-modified cathode materials, the chemical changes induced on the surface of the cathode materials upon ALD coating are not fully studied. This paper describes a systematic investigation to understand the interfacial changes of 12 different cathode materials upon coating with aluminum oxide (Al 2 O 3 ) using trimethyl aluminum (TMA) and H 2 O, and aluminum fluoride (AlF 3 ) using TMA and hydrogen fluoride pyridine (HFPy). Here, the surface composition of these cathode materials, which range from simple transition metal oxides (e.g. NiO and MnO) to complex multi-element cathode materials (e.g. LiNi x Mn 1-x-y Co y O 2 , NMC), was studied via X-ray photoelectron spectroscopy (XPS). The XPS measurements reveal that the transition metals in the cathode materials undergo selective oxidation/reduction depending upon the nature of the precursor, the coating, and the cathode material. The ability to chemically modify the surface of cathode materials via vapor-phase precursor adsorption will open new avenues to systematically control the interface of the cathode materials in LIBs that are not possible by conventional coating methods.

25 ENERGY STORAGE↗

Challenges and Strategies to Advance High-Energy Nickel-Rich Layered Lithium Transition Metal Oxide Cathodes for Harsh Operation

Nickel-rich layered lithium transition metal oxides (LiNi 1–x–y Co x Mn y O 2 and LiNi 1–x–y Co x Al y O 2 , x + y ≤ 0.2) are the most attractive cathode materials for the next generation lithium-ion batteries for automotive application. However, they suffer from structural/interfacial instability during repeated charge/discharge, resulting in severe performance degradation and serious safety concerns. Here we provide a comprehensive review about challenges and strategies to advance nickel-rich layered cathodes specifically for harsh (high-voltage, high-temperature, and fast charging) operations. Firstly, the degradation pathways of nickel-rich cathodes including surface/interface degradation, undesired cathode–electrolytes parasitic reactions, gas evolution, inter/intragranular cracking, and electrical/ionic isolation are discussed. Then, recent achievements in stabilizing the structure/interface of nickel-rich cathodes via surface coating, cation/anion doping, composition tailoring, morphology engineering, and electrolytes optimization are summarized. Moreover, challenges and strategies to improve the performance of Ni-rich cathodes at the electrode level are discussed. Outlook and perspectives to promote the practical application of nickel-rich layered cathodes toward automotive application are provided as well.

25 ENERGY STORAGE↗

Facile Surface Coatings for Performance Improvement of NMC811 Battery Cathode Material

High nickel content layered oxide LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) is a promising cathode material with a high theoretical capacity of 200 mAh g -1 for use in high energy density lithium-ion batteries. However, its surface can easily get passivated by LiOH and Li 2 CO 3 due to its surface residual Li 2 O being reacting with ambient moisture and CO 2 . Herein, NMC811 was treated in a 3.0 M solution of lithium bis(fluorosulfonyl)imide (LiFSI) in dimethyl carbonate (DMC) at 60 °C for 8 h, 16 h and 24 h, respectively, resulting in coating of the NMC811 surface with LiF due to the basic nature of those residual lithium salts that react with LiFSI. The facile treatment of NMC811 in LiFSI/DMC not only improves the cycling stability but also enhances the capacity of the Li/NMC811 cells, mainly because of the thinning of the Li 2 CO 3 layer as suggested by cyclic voltammograms and impedance analyses. This method opens a new avenue for activation of passivated NMC811 particles for practical battery applications.

25 ENERGY STORAGE↗

Galvanic corrosion of AZ31B joined to dual-phase steel with and without Zn layer by ultrasonic and friction stir welding

Galvanic corrosion of AZ31B joined with bare or Zn-coated DP590 steel by ultrasonic spot welding or linear friction stir welding was quantitatively studied by pre-defining anode and cathode in the lap joint samples. Corrosion volume and depth from Mg anode surfaces exposed to 0.1 M sodium chloride solution was analyzed as functions of cathode surface type and welding method. Characterization of as-welded joints was performed to identify any microstructural feature of the bonding zone that could impact galvanic corrosion behavior. COMSOL modeling with modified user subroutine was conducted to simulate the progression of Mg corrosion in the same joint and electrode configurations used for the corrosion experiments. The experimental results indicated that Zn-coated cathode surface can reduce Mg galvanic corrosion significantly as galvanic polarization and cathodic current on Zn-coated surface remained relatively low for Mg in the weld joints. COMSOL modeling described the growth of Mg galvanic corrosion in a reasonable manner but showed limitation by underestimating the corrosion volume as it did not capture self-corrosion.

36 MATERIALS SCIENCE↗