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At least 127 records · Page 7

Photovoltaic Power Without Batteries for Continuous Cathodic Protection

The objective of this project was to successfully demonstrate that renewable energy can efficiently and economically replace dedicated non-renewable power sources. The COASTSYSTA designed, installed, and started up on 20 Jan. 1990, a state-of-the-art photovoltaic powered impressed current cathodic protection system (PVCPSYS) for steel and iron submerged structures. This system does not require any auxiliary/battery backup power. The PVCPSYS installed on 775 ft. of steel sheet piling of a Navy bulkhead is continuing to provide complete, continuous corrosion protection. This installation is well documented by COASTSYSTA and was verified on-site by the U.S. Army Corps of Engineers. The PVCPSYS uses only renewable energy and is environmentally clean. A patent is pending on the new technology. Other possible PVCPSYS applications are mothballed ships, docks, dams, locks, bridges, marinas, and pipelines. The Department of Defense Photovoltaic Review Committee and Sandia National Laboratories consider this successful and cost effective system a major advance in the application of photovoltaics.

Muehl, W. W., Sr.↗

Photovoltaic power without batteries for continuous cathodic protection

The COASTSYSTA designed, installed, and started up on 20 Jan. 1990, a state-of-the-art stand alone photovoltaic powered impressed current cathodic protection system (PVCPSYS) not requiring any auxiliary/battery backup power for steel and iron submerged structures. The PVCPSYS installed on 775' of steel sheet piling of a Navy bulkhead is continuing to provide complete, continuous corrosion protection. This has been well documented by COASTSYSTA and verified on-site by the U.S. Army Civil Engineering Research Laboratory, Champaign, Illinois and the Navy Energy Program Office-Photovoltaic Programs, China Lake, California. The Department of Defense (DoD) Photovoltaic Review Committee and Sandia National Laboratories consider this successful and cost effective system a major advance in the application of photovoltaic power. The PVCPSYS uses only renewable energy and is environmentally clean. A patent is pending on the new technology. Other possible PVCPSYS applications are mothballed ships, docks, dams, locks, bridges, marinas, offshore structures, and pipelines. The initial cost savings by installing a PVCPSYS vs. a conventional CP system was in excess of $46,000.00.

Muehl, W. W., Sr.↗

Factors Influencing Gas Evolution from High‐Nickel Layered Oxide Cathodes in Lithium‐Based Batteries

Abstract Gas evolution from high‐nickel layered oxide cathodes (>90% Ni) remains a major issue for their practical application. Gaseous species, such as CO 2 , O 2 , and CO, that are evolved at high states of charge (SOC) worsen the overall safety of batteries, as pressure build‐up within the cell may lead to cell rupture. Since these gasses are produced during cathode degradation, tracking the formation of gasses is also important in diagnosing cathode failure. Online electrochemical mass spectrometry (OEMS) is a powerful in situ technique to study gas evolution from the cathode during high‐voltage charge. However, the differences in the OEMS experimental setups between different groups make it challenging to compare results between groups. In this perspective, the various factors that influence gas evolution based on the OEMS results collected in this group are presented. The focus is on the conditions that lead to gas release, with a particular emphasis on reactive oxygen formation and subsequent chemical reactions with the electrolyte. Promising strategies, such as electrolytes, compositional tuning, and surface coatings that are effective at suppressing gas evolution from the cathode are highlighted. Critical insights into mitigating cathode degradation and gas evolution are provided to guide the development of safer, high‐energy batteries.

Chemistry↗

Developing low-cost rechargeable batteries: beyond traditional layered oxide cathodes for Li-ion and beyond Li-ion batteries

Here, the rising demand for energy storage systems, driven by the rapid adoption of electric vehicles and the global shift toward renewable energy, necessitates continuous efforts to lower the cost of current lithium-ion batteries (LIBs) and enhance the sustainability of existing battery chemistries. This feature article examines the key challenges associated with Ni- and Co-containing LIB cathodes and compares advancements in cathode development for non-traditional Li-ion and beyond Li-ion chemistries. First, a review of earth-abundant element containing disordered rock-salt cathodes is presented, with a discussion of key strategies such as compositional tuning and carbon coating to improve their electrochemical performance. Hurdles in developing oxide-based cathodes for Na- and K-ion batteries are also highlighted, followed by an in-depth overview of polyanion and Prussian blue cathodes for Na- and K-ion systems. Overall, this article provides a systematic perspective on the design of earth-abundant, low-cost, and sustainable cathode materials for both LIB and beyond LIB technologies.

Lohani, Harshita [Lawrence Berkeley National Labor↗

Unleashing the Potential of Fast Charging Batteries: Leveraging Anion Redox Chemistry in Ni- and Co-Free Cathodes

Designing Li-ion battery cathodes free from critical raw materials such as Co and Ni has a huge technological and societal impact. Though anion redox-based Li-rich oxide cathodes allow designing Co and Ni free cathode compositions, the Li-rich oxides witnessed voltage fade, voltage hysteresis, and irreversible oxygen release despite their high capacity. Conversely, anion redox through highly covalent chalcogenides (S/Se) is emerging due to the improved covalency between metal d and ligand p bands. Here, we investigate the tuning of multi-chalcogen (S/Se) p-band and redox-active metal d-band in a model Li-rich chalcogen composition Li 1.13 Ti 0.57 Fe 0.3 S 2-y Se y (y = 0 - 1) through in-depth electrochemical, X-ray spectroscopy, and DFT-based electronic structure investigations. Introducing the appropriate amount of Se p band character in anion redox sulfides increases interlayer distance and metal - ligand covalency without modifying the original crystal structure, promoting significant electrochemical reversibility through mixed anionic (Se 2- /Se n- , S 2- /S n- , wherein n<2) and cationic (Fe 2+ /Fe 3+ ) redox reactions. Here we show the detailed Fe, S, and Se redox contributions during Li insertion/extraction through X-ray Absorption (XAS) and Hard X-ray Photoemission Spectroscopy (HAXPES) measurements. The orbital tuning approach improves rate capability for more than 10 C charge-discharge rate, exhibiting more than 50% of its original capacity obtained at C/20 rate. The buffer cation in the lattice (Ti 4+ ) remains electrochemically inactive even after significant Se p-band introduction in the sulfide framework. Overall, this work takes advantage of multi-anion redox chemistry to uncover practically demanding fast charging-discharging characteristics in intercalation cathodes. The obtained knowledge of this design can be extended to other oxide and chalcogen cathodes for high performance Li-ion batteries.

25 ENERGY STORAGE↗

Unraveling the Synergistic effects of La and Al co-doping on Ni/Co-free P2-type Na 0.67 Mn 0.67 Fe 0.33 O 2 layered oxide cathodes for sodium-ion batteries

Recent developments in high-performance cathodes for sodium-ion batteries (SIBs) tend to mitigate use of critical Ni and Co active species to satisfy sustainability. P2-type layered oxide cathodes based on Mn and Fe promise high capacity, sustainability, and low cost on account of the abundance and multiple redox characteristics of Mn and Fe. However, their commercialization is still challenged due to poor cycling stability caused by phase changes emanating from inherent Jahn-Teller distortions. Herein, we propose a novel strategy of trivalent La and Al co-doping to alleviate the drawbacks, innovating a new cathode of Na 0.67 Mn 0.62 Al 0.05 Fe 0.31 La 0.02 O 2 (AlLa). The co-doped cathode delivers an impressive capacity of 128.7 mAh/g at 1C and 106.5 mAh/g at high rate of 5C with a good capacity retention of 85% after 100 cycles. These are superior to the unmodified material, whose specific capacity was 118.6 mAh/g at 1C and 61.1 mAh/g at 5C with a retention of only 65% after 100 cycles. The synergistic contribution from La and Al associated with their improved oxygen bonding, pillaring, and local electronic structural modification stemming from rigid Lasingle bondO and Alsingle bondO bonding resulted in the observed structural and electrochemical improvement. Overall, this research offers novel strategies for designing high-performance cathode materials for sodium-ion batteries.

25 ENERGY STORAGE↗

Cation Vacancies Enable Anion Redox in Li Cathodes

Conventional Li-ion battery intercalation cathodes leverage charge compensation that is formally associated with redox on the transition metal. Employing the anions in the charge compensation mechanism, so-called anion redox, can yield higher capacities beyond the traditional limitations of intercalation chemistry. Here, we aim to understand the structural considerations that enable anion oxidation and focus on processes that result in structural changes, such as the formation of persulfide bonds. Using a Li-rich metal sulfide as a model system, we present both first-principles simulations and experimental data that show that cation vacancies are required for anion oxidation. First-principles simulations show that the oxidation of sulfide to persulfide only occurs when a neighboring vacancy is present. To experimentally probe the role of vacancies in anion redox processes, we introduce vacancies into the Li 2 TiS 3 phase while maintaining a high valency of Ti. When the cation sublattice is fully occupied and no vacancies can be formed through transition metal oxidation, the material is electrochemically inert. Upon introduction of vacancies, the material can support high degrees of anion redox, even in the absence of transition metal oxidation. The model system offers fundamental insights to deepen our understanding of structure–property relationships that govern reversible anion redox in sulfides and demonstrates that cation vacancies are required for anion oxidation, in which persulfides are formed.

25 ENERGY STORAGE↗

Upcycling Mixed Spent Ni-Lean Cathodes into Ni-Rich Polycrystalline Cathodes

Sustainable battery recycling is vital for conserving resources and reducing environmental impacts. Current open- and closed-loop recycling strategies often focus on recovering individual components, making the reuse of mixed cathode materials a complex challenge. Meanwhile, the research on upcycling has been limited to using pristine cathode feedstocks and virgin materials for synthesis. Here, to address this issue, we present an upcycling approach for spent Ni-lean mixed cathode materials that integrate an upcycling hydrometallurgical recycling process with traditional hydrometallurgical methods. This strategy achieves a utilization of 92.31 mol % of recycled materials, enabling the regeneration of Ni-rich cathode materials while significantly reducing the reliance on virgin resources. The regenerated 83Ni cathode materials demonstrate physical properties comparable to those produced from virgin materials. Electrochemical evaluations using single-layer pouch cells show that both recycled and virgin cathodes exhibit initial specific capacity close to 201.1 mAh/g and maintain approximately 88 % capacity retention after 500 cycles. Additionally, 2Ah cells confirmed these findings, delivering 85 % capacity retention after about 900 cycles. Techno-economic analysis demonstrates notable environmental benefits, including reductions in greenhouse gas emissions and energy consumption, achieving 232.75 MJ/kg of product, which is 8.6 % lower than traditional methods and comparable to direct upcycling. Furthermore, the upcycling hydrometallurgical recycling process generates the highest profit, proving its economic viability. This scalable and versatile process is adaptable to varying transition metal compositions, facilitating a closed-loop recycling system that bridges mixed spent cathodes with next-generation cathode materials, and offers a sustainable solution for managing waste battery materials.

Hydrometallurgical recycling↗

Stable-Cycling Sustainable Na-Ion Batteries with Olivine Iron Phosphate Cathode in an Ether Electrolyte

Sustainable batteries using nontoxic, earth-abundant, and low-cost materials are key to decarbonization. Olivine NaFePO 4 fulfills these criteria, is attractive for Na-ion batteries, and can be derived from LiFePO 4 recycled from Li-ion battery wastes. Critical knowledge is needed for transforming LiFePO 4 to NaFePO 4 to enable such a sustainable, green engineering path toward high-performance Na-ion batteries. Herein, we report on the development of a stable-cycling, sustainable olivine iron phosphate-based Na-ion battery empowered by an improved understanding of materials transformation and electrolyte chemistry. First, we found that the conventional carbonate electrolyte with fluoroethylene carbonate additive causes an additional plateau (~2.4 V) at the end of the discharge process of the FePO 4 ||Na metal cell, leading to lower initial discharge capacity and voltage. This result shows that the voltage profile is influenced by not only intrinsic materials phase transformation during battery cycling but also the electrolyte additives and interphases formed. With the 1 M NaPF 6 diglyme electrolyte, we achieved an excellent capacity retention of 96% and 98% after 500 cycles at 1 and 5 C, respectively. Second, we chemically sodiated FePO 4 to form single-phase Na 0.9 FePO 4 . Na 0.9 FePO 4 ||hard carbon full cells demonstrated a remarkable capacity retention of ~84% at 3 and 5 C after 1000 cycles. The successful implementation of hard carbon, which can be derived from biomass waste, will further improve the sustainability of energy storage technologies. Our research demonstrates that electrolyte chemistry influences the voltage profile of phase-changing electrodes and provides effective electrolyte and full-cell design solutions for stable-cycling NaFePO 4 .

36 MATERIALS SCIENCE↗

Lithicone‐Protected Lithium Metal Anodes for Lithium Metal Batteries with Nickel‐Rich Cathode Materials

The high energy density advantage of lithium (Li) metal batteries (LMBs) makes them increasingly desirable; however, problems such as strong reactivity and dendrite growth of Li metal anode limit their practical uses. In this work, a novel Li‐containing glycerol (LiGL) or lithicone protection layer on a 50 μm thick Li metal anode is employed for improving the performance of LMBs. This LiGL layer was accurately deposited via a molecular layer deposition (MLD) process at 150 °C, using lithium tert‐butoxide and glycerol as precursors. The as‐formed LiGL coating layer is highly tunable in its thickness by simply adjusting MLD cycles and shows a good stability and outstanding ionic transport properties. The LiGL layer is found to effectively mitigate side reactions and enhance cycling stability in both symmetric cells and full cells. Specifically, the LMBs with LiGL@Li anode of 400 MLD cycles and LiNi 0.6 Mn 0.2 Co 0.2 O 2 cathode enable a capacity retention of ≈87%, much higher than ≈35% of the cells with bare Li after 200 cycles at a charge/discharge current density of 2.1 mA cm −2 . This work paves a feasible way for practical LMBs with improved capacity and stability through applying an innovative protection layer on Li metal anodes.

25 ENERGY STORAGE↗

New secondary batteries utilizing electronically conductive polymer cathodes

The objectives of this project are to characterize the transport properties in electronically conductive polymers and to assess the utility of these films as cathodes in lithium/polymer secondary batteries. During this research period, progress has been made in a literature survey of the historical background, methods of preparation, the physical and chemical properties, and potential technological applications of polythiophene. Progress has also been made in the characterization of polypyrrole flat films and fibrillar films. Cyclic voltammetry and potential step chronocoulometry were used to gain information on peak currents and potentials switching reaction rates, charge capacity, and charge retention. Battery charge/discharge studies were also performed.

Martin, Charles R.↗

Revealing the Roles of CuF 2 /NiF 2 Incorporation in the Electrochemical Performance of FeF 3 Cathodes in Solid‐State Batteries

Mixed metal fluorides have been considered as a promising candidate to lower the voltage hysteresis of conversion-type iron fluoride cathodes, but their cycling stability is limited due to transition metal dissolution and interphase growth in liquid electrolyte batteries. Here, we study the role of incorporating CuF 2 and NiF 2 in the electrochemical performance of FeF 3 cathode in halide-based solid-state batteries to test whether we can transfer the kinetic benefit of low voltage hysteresis to solid-state batteries while using solid electrolyte to eliminate transition metal dissolution and stabilize the interphase. Synchrotron X-ray absorption spectroscopy results indicated the redox reactions are attributed to Cu 0 /Cu + and Fe 0 /Fe 2+ in 25CuF 2 -75FeF 3 and Ni 0 /Ni 2+ and Fe 0 /Fe 3+ in 10NiF 2 -90FeF 3 . While no apparent improvement in electrode kinetics can be observed, the incorporation of CuF 2 and NiF 2 can largely improve the cycling stability of FeF 3 cathodes. In conclusion, the results demonstrate the advantages of using solid-state concept to improve the cycling stability of conversion-type cathodes.

25 ENERGY STORAGE↗

Navigating thermal stability intricacies of high-nickel cathodes for high-energy lithium batteries

High-nickel oxide cathodes, LiNi x M 1−x O 2 (x ≥ 0.8), are preferred in automotive lithium batteries, but they face thermal instability challenges. Inconsistent literature reports and unstandardized testing protocols further complicate quantitative assessments of the thermal stability of these cathodes. Here, we present here a statistical thermal analysis based on the differential scanning calorimetry measurements of 15 representative cathode materials with different compositions, morphologies and states of charge. The findings reveal that each cathode has a critical state of charge that defines its safe operating limit, which is affected by the metal–oxygen bond strength and surface reactivity. The thermal runaway temperature is dictated by the layered Li 1−x NiO 2 to LiNi 2 O 4 spinel-like phase transition, which is thermodynamically determined by the metal–oxygen bond covalency and kinetically influenced by the cation mixing and particle size. Raman spectroscopy is used to predict the thermal runaway temperature on the basis of the linear relationship between them. Finally, we propose a thermal stability index to quantify cathode thermal stability as a guide for developing safer high-nickel cathodes.

batteries↗

ε-VOPO 4 cathode for lithium ion batteries

The epsilon polymorph of vanadyl phosphate, ε-VOPO 4 , made from the solvothermally synthesized H 2 VOPO 4 , is a high density cathode material for lithium-ion batteries optimized to reversibly intercalate two Li-ions to reach the full theoretical capacity at least 50 cycles with a coulombic efficiency of 98%. This material adopts a stable 3D tunnel structure and can extract two Li-ions per vanadium ion, giving a theoretical capacity of 305 mAh/g, with an upper charge/discharge plateau at around 4.0 V, and one lower at around 2.5 V.

Siu, Carrie↗

An integrated in-situ coordination strategy enabling high-performance layered cathodes for sodium-ion batteries

O3-type layered transition metal oxide cathodes hold tremendous potential in sodium-ion batteries (SIBs) due to their low cost and high energy density. However, the structure instability associated with detrimental phase transitions and severe interface parasitic reactions exacerbate the material's electrochemical performance degradation. Herein, we develop an integrated in-situ coordination strategy via heteroatomic modulation inducing coherent epitaxial layer to collaboratively enhance the overall framework robustness from surface to bulk. The theoretical calculation and multiple in/ex-situ characterizations demonstrate the charge density around oxygen is redistributed, which promotes the electron localization, thus widening the NaO 2 lattice space and accelerating the Na + transport dynamics. Furthermore, the formed strengthened oxygen bond energy effectively distributes the long-range coordination of Mn 3+ O 6 octahedron, thereby alleviating Jahn-Teller distortion and local stress. Importantly, the in-situ formed conformal buffer layer dramatically relieves the adverse interface side reactions, facilitating the construction of robust cathode-electrolyte interface, which ameliorate the whole structure stability of designed materials. Consequently, the optimized NFMZ@NZO-1.0 exhibits the excellent cycling stability with 80.2% capacity retention after 300 cycles at 1C, and delivers a high discharge capacity of 107.1 mAh g −1 at 10C. In conclusion, this distinctive coupling strategy provides valuable insights for developing high-performance layered cathode materials in SIBs.

Coherent epitaxial layer↗

Delineating the kinetic limitations of Mn 2+/3+ redox in LiMn x Fe 1−x PO 4 cathodes for lithium-ion batteries

LiMn x Fe 1−x PO 4 (LMFP) cathodes offer higher energy density than LiFePO 4 due to a higher operating voltage. However, the kinetic limitations of the Mn 2+/3+ redox couple in LMFP restrict its practically achievable capacity and hinder the ability to achieve high energy density. While the shortcomings of Mn 2+/3+ redox are recognized, its behavior and the factors that impact it remain to be fully understood. We present here an in-depth kinetics study of LMFP by utilizing novel techniques, such as chronoamperometry and galvanostatic electrochemical impedance spectroscopy. Compared to moderate-Mn LMFP (40–60% Mn), high-Mn LMFP (80% Mn) experiences reduced capacity, poor rate capability, and heightened impedance during Mn 2+/3+ redox. The oxidation of Mn 2+ to Mn 3+ becomes more resistive during charge due to the formation of Jahn–Teller active Mn 3+ and the increasing charge-transfer insulating behavior of Mn x Fe 1−x PO 4 . However, the impedance associated with Mn 3+ to Mn 2+ reduction remains constant during discharge in the entire region. The protracted Mn2+ oxidation in high-Mn LMFP results in excessive impedance compared to that in moderate-Mn LMFP, even at low C-rates and high cycling temperatures. Despite the promise of high energy density, the extreme kinetic limitations inherent to high-Mn LMFP present a barrier.

25 ENERGY STORAGE↗

Probing Operando Electrochemical Strain Generation in α-NaFeO 2 Composite Cathodes during Cycling of Na-Ion Batteries

The transition metal oxide (TMO) cathodes in Na-ion batteries suffer from low-capacity retention. Chemo-mechanical instabilities lead to the deterioration of the electrochemical performance of TMO cathodes in Li-ion batteries. However, there is not much known about the chemo-mechanical instabilities in the TMO cathodes for Na-ion batteries. Understanding the governing forces behind the interplay between the electrochemical performance and mechanical stability in TMO cathodes is critical for the development of Na-ion batteries. Here, we synchronize the digital image correlation (DIC) technique with electrochemical analysis to capture the real-time deformation behavior of the α-NaFeO 2 cathodes during cycling. When the charge cutoff voltage is 3.6 V, the cathode experiences reversible deformations (except for the first cycle). There is negative strain (shrinkage) generation during Na extraction and positive strain (expansion) generation during the subsequent Na insertion. A detailed analysis of the potential-dependent strain rate evolution points out complicated phase transformations and nonequilibrium conditions in the α-NaFeO 2 cathodes during cycling. When the charge cutoff voltage was increased to 4.2 V, there was a rapid capacity loss and large plastic deformations in the α-NaFeO 2 cathodes. We provide an in-depth discussion about the possible mechanisms behind the chemo-mechanical instabilities in the α-NaFeO 2 . In conclusion, the correlation is critical to develop material-based strategies to mitigate instability mechanisms in TMO cathodes for Na-ion batteries.

Wable, Minal [University of Maryland Baltimore Cou↗