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At least 73 records · Page 4

Catalytic Promotion of Transition-Metal-Doped Graphene Cathodes in Li-CO 2 Batteries

The Li-CO 2 battery is a promising energy storage system with impressive theoretical specific energy and discharge capacity. Graphene-based single-atom catalysts (SACs) provide high surface area and long-term electrochemical reactivity and stability, making SACs among the most promising cathode catalysts for these batteries. However, current Li-CO 2 systems have high reaction barriers, slowing the reaction and greatly increasing the overpotential. Improvement of the discharge/charge energetics requires atomic-level innovations in cathode design, such as alterations to the catalyst chemical structure. In this paper, we propose enhancing the SAC by using a Ti metal center, which is found to deliver the highest electrochemical Li + CO 2 activity among 3d transition metal candidates. Furthermore, we propose cathode surface coating with ionic liquids, since these environments promote the formation of reaction intermediates in the electrochemical conversion process. Here, our work provides insights to optimize electrode design for high-performance Li-CO 2 batteries, which can open new avenues to recycle greenhouse gases and achieve enhanced renewable energy storage.

25 ENERGY STORAGE↗

Co-Extrusion (CoEx) for Cost Reduction of Advanced High-Energy-and-Power Battery Electrode Manufacturing

Co-Extrusion (CoEx) is a deposition technology developed at PARC that uses engineered fluidic channels to cause multiple streams of dissimilar fluids to impart shape to one another. Here, we describe the use of CoEx to produce structured cathode electrode films to improve electrochemical performance of thick electrode films. CoEx enables us to create structured electrode films that have periodic regions of enhanced ionic conductivity, enabling higher utilization of thicker cathode films at high discharge rates. While increasing electrode thickness is a known method for increasing energy density of battery electrodes, this increase in energy density typically also results in reduced power density. This project, a collaboration between the Palo Alto Research Center, Oak Ridge National Laboratories, and Ford Motor Company, seeks to first validate the benefits of CoEx at the coin cell level, before performing the necessary R&D effort to scale production up to large (10+ Ah) pouch cells that will show increased energy density without a reduction in power density. We used conventional battery materials (commercially available NMC, PVDF, carbon black, and graphite) to produce structured electrodes via CoEx and compared them to thick and thin conventionally produced (unstructured) battery electrodes. CoEx electrodes show improved high rate performance compared to unstructured electrodes, resulting in higher energy density pouch cells compared to the baseline electrode of 7 and 11% in volumetric and gravimetric energy density, respectively. These electrodes also showed substantially improved electrochemical performance at high discharge rates compared to thick conventional electrodes.

25 ENERGY STORAGE↗

Cathode–Sulfide Solid Electrolyte Interfacial Instability: Challenges and Solutions

All-solid-state batteries are a candidate for next-generation energy-storage devices due to potential improvements in energy density and safety compared to current battery technologies. Due to their high ionic conductivity and potential scalability through slurry processing routes, sulfide solid-state electrolytes are promising to replace traditional liquid electrolytes and enable All-solid-state batteries, but stability of cathode-sulfide solid-state electrolytes interfaces requires further improvement. Herein we review common issues encountered at cathode-sulfide SE interfaces and strategies to alleviate these issues.

25 ENERGY STORAGE↗

An Oxygen‐Scavenger Sulfide Coating Enabling Long‐Term Stable Nickel‐Rich Cathodes

Oxygen release is a major issue associated with layer-structured metal oxide cathodes in lithium batteries, which can further cause a series of problems, such as irreversible phase transition, microcracking, and electrolyte decomposition. Eventually, these issues jointly result in cell performance degradation and safety hazards. Thus, it is very significant to tackle oxygen release for achieving long-term stable cyclability, but very challenging. Although intensive efforts have been invested to date, there still lacks a feasible solution. In this study, nanoscale ZrS 2 coatings are applied on prefabricated LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) cathodes directly via atomic layer deposition (ALD). Very encouragingly, we reveal that this ALD-deposited conformal ZrS 2 nanocoating can serve as an exceptional oxygen scavenger and then convert into a stable sulfate (Zr(SO 4 ) 2 ) coating. Such an in situ conversion is very beneficial and effective for protecting the electrolyte from decomposition. In addition, the resultant Zr(SO 4 ) 2 coating further inhibits undesirable reactions, stabilizes the interface between NMC811 and the electrolyte, suppresses microcracking, mitigates transition metal dissolution, and maintains the structural stability of the NMC811 cathode. Consequently, the ZrS 2 -coated NMC811 cathode has demonstrated extraordinary performance. Thus, this study advances the understanding of interface engineering while paving a new technical pathway for commercializing NMC811 cathodes.

Nickel-rich cathodes↗

Functionalized carbon nanotubes for thermionic emission and cooling applications

Barium strontium oxide-coated carbon nanotubes (CNTs) were implemented as a work function lowering and field enhancing functional coating on a coiled tungsten filament to create a new thermionic cathode. This cathode resembles conventional oxide cathodes in structure. It has the same coiled tungsten filament as a conventional oxide cathode but uses barium strontium oxide-coated CNTs instead of the traditional barium strontium calcium oxide powder mixture as an emissive coating. The cathode produces a strong thermionic emission. At 1395 K and 2.5 V/μm, the thermionic emission current of 0.87 A or current density of 2.9 A/cm 2 was obtained from this oxide-coated CNT cathode. This level of emission is about three times as large as a conventional oxide cathode operating at similar temperature and field strength. Strong thermionic emissions from the cathode also lead to a large thermionic cooling effect. Temperature reduction as large as 90° was observed from the cathode surface when it was emitting electrons. Strong thermionic emission and a large cooling effect obtained are the result of the combination of the low work function of barium strontium oxide (1.6 eV) and the large field effect induced by the CNTs. Plasma enhanced chemical vapor deposition was used to grow CNTs, and magnetron sputtering deposition was used to deposit the barium strontium oxide functional coating; details of the cathode fabrication are presented to illustrate both the versatility of the processing techniques and the adaptability of barium strontium oxide-coated CNTs as a functional coating. Finally, measurements on thermionic emission and thermionic cooling of the cathode are also presented.

36 MATERIALS SCIENCE↗

Slot-die-coating operability windows for polymer electrolyte membrane fuel cell cathode catalyst layers

Roll-to-roll (R2R) slot-die coating of polymer electrolyte membrane fuel cell (PEMFC) catalyst layers represents a scalable deposition method for producing 10–20 m 2 ·min -1 of catalyst-coated gas diffusion layers (GDLs). This high-throughput production technique will help lower the cost of PEMFC catalyst layers. The uniformity of the wet layer applied by slot die deposition is affected by process parameters such as substrate speed, vacuum pressure applied at the upstream meniscus, gap between the slot die lips and substrate, ink rheology, and other ink and substrate properties. The set of conditions for producing a defect-free coating with a dilute ink typically requires little to no upstream vacuum pressure, so suitable operating conditions can be found easily through trial and error and operator intuition. However, the higher viscosity of more concentrated inks dramatically shifts the range of settings that result in a homogeneous coating to higher vacuum levels, which are harder to find through hit or miss. A predictive model showing the range of operable conditions decreases material wastage inherent in experimentally searching for suitable parameters. In this study, the defect-free coating parameter window is explored experimentally and theoretically for two concentrations of PEFC cathode inks. Both a full capillary hydrodynamic model and a computationally cheaper viscocapillary model successfully predict the experimentally determined coating window within the experimental and model uncertainty limits for inks with 5.3 wt% and 12.0 wt% solids ink while maintaining the 0.1 mg Pt ·cm -2 Pt areal loading target. Here, this paper demonstrates a viable pathway for meeting the $30/kW net ultimate cost target of the United States Department of Energy (U.S. DOE) Hydrogen Fuel Cells Technologies Office (HFTO). The concentrated ink lowers the thermal energy and capital expenditure (CapEx) budget of the coating process by decreasing the amount of time, energy, and floorspace required for drying the coating.

25 ENERGY STORAGE↗

Unveiling the critical role of interfacial ionic conductivity in all-solid-state lithium batteries

Advancement of all-solid-state lithium-ion (Li + ) batteries (ASSLIBs) has been hindered by the large interfacial resistance mainly originating from interfacial reactions between oxide cathodes and solid-state sulfide electrolytes (SEs). To suppress the interfacial reactions, an interfacial coating layer between cathodes and SEs is indispensable. However, the kinetics of interfacial Li + transport across the coating layer has not been well understood yet. Herein, we tune the interfacial ionic conductivity of the coating layer LiNb 0.5 Ta 0.5 O 3 (LNTO) by manipulating post-annealing temperature. It is found that the interfacial ionic conductivity determines interfacial Li + transport kinetics and enhancing the interfacial ionic conductivity can significantly boost the electrochemical performance of SE-based ASSLIBs. A representative cathode LiNi 0.5 Mn 0.3 Co 0.2 O 2 coated by LNTO with the highest interfacial ionic conductivity exhibits a high initial capacity of 152 mAh.g -1 at 0.1 C and 107.5 mAh.g -1 at 1C. This work highlights the importance of increasing interfacial ionic conductivity for high-performance SE-based ASSLIBs.

25 ENERGY STORAGE↗

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↗

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↗

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↗