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At least 127 records · Page 7

All sources NASA NTRS DOE OSTI

DOE OSTI2022

Experimental Observations for Anode Optimization of Oxide Reduction Equipment

The electrochemical behavior of several components has been investigated during the electrolysis of nickel oxide in LiCl-Li 2 O salt mixture at 650°C. The focus of this work is to improve anode design and shroud to increase current densities. The tested components were ceramic anode shroud porosity, porosity size, anode geometry, anode material, and metallic porous anode shroud. The goal of these experiments was to optimize and improve the reduction process. The highest contributors to higher current densities were anode shroud porosity and anode geometry.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

NASA NTRS1974

Coaxial anode wire for gas radiation counters

The design and characteristics of a gas radiation counter are discussed. The coaxial anode consists of an elongated central wire covered with an electrically insulating sleeve. Several longitudinally discontinuous segments of an electrically conductive coating are disposed about the insulating sleeve in a coaxial pattern along the length of the central wire. The conductive coating segments form a veto or rejection anode at each end of the central wire and a main or primary charge detecting anode between the ends. The segments are coupled together so that the primary charge detecting anode is connected to detection circuitry in anti-coincidence with the veto anodes. Background radiation detected by either of the veto anodes and the primary charge detecting anode is rejected and the sensitivity of the radiation counter device is increased.

Kraushaar, W. L.↗

NASA NTRS1991

Performance of a Dual Anode Nickel-Hydrogen Cell

Nickel-hydrogen batteries are presently being used for energy storage on satellites in low Earth orbit and in geosynchronous orbit, and have also been selected for use on the proposed Space Station Freedom. Development continues on the cell technology in order to improve the specific energy and lengthen the cycle life. An experimental study was conducted to compare the voltage performance of a nickel-hydrogen cell containing a dual anode with the standard cell design which uses a single hydrogen electrode. Since the principle voltage loss in a nickel-hydrogen cell is attributed to the mass transport and resistive polarization parameters of the nickel electrode, addition of a hydrogen electrode on the other side of the nickel electrode should reduce the electrochemical polarizations by a factor of two. A 3.5 in. diameter boilerplate cell with a single 30 mils thick nickel electrode was cycled under various current conditions to evaluate its performance with a single anode and then with a double anode. A layered separator consisting of one Zircar cloth separator and one radiation-grafted polyethylene separator were used between the electrodes. The electrolyte was 26% KOH, and the tests were done at room temperature. The discharge voltage characteristics were determined as a function of current and depth-of-discharge. At the 4C discharge rate and 50% DOD, the voltage of the dual anode cell was 100 mV higher than the single anode cell. At 75% DOD the dual anode cell voltage was about 130 mV higher than the standard cell design. Resistances of the two c ell designs obtained from the slope of the mid-discharge voltages plotted against various currents indicated that the dual anode cell resistance was one-half of the state-of-the-art cell.

Gahn, Randall F.↗

NASA NTRS2018

Three-Dimensional, Porous Anode for Use in Lithium-Ion Batteries and Method of Fabrication Thereof

A three-dimensional, porous anode material suitable for use in a lithium-ion cell. The three-dimensional, porous anode material includes active anode particles embedded within a carbon matrix. The porous structure of this novel anode material allows for the expansion and contraction of the anode without the anode delaminating or breaking apart, thus improving the life-cycle of the lithium-ion cell. An example of this three-dimensional porous anode material is a porous silicon-carbon composite formed using a bi-continuous micro-emulsion (BME) template.

Laicer, Castro↗

NASA NTRS2019

The Effect of Anode Position on Operation of a 25-A Class Hollow Cathode

The effect of the distance between a hollow cathode and a cylindrical anode on cathode operation is investigated for two anode geometries. Neutral flow simulations demonstrate that the anode diameter and distance from the cathode exit can elevate the downstream pressure as much as two orders of magnitude above what the cathode experiences while operating within a Hall thruster. Based on the results of this modeling, two axially-segmented cylindrical molybdenum anodes were constructed: a 64-mm diameter one that replicated the anode geometry used in recent NASA hollow cathode development testing and a larger 254-mm diameter one designed to reduce the neutral pressure in front of the cathode to thruster-like values. For each anode design, cathode performance was characterized for varying anode/cathode distance using metrics such as discharge voltage and oscillation magnitudes, and the ion voltage spectra were characterized using a radially-positioned retarding potential analyzer. It was found that as local neutral pressure decreased, discharge voltage and high-voltage ion content in the plume increased. For the 254-mm diameter anode, an ion voltage tail in excess of 200 V was found for nominal cathode flow rates. The implications of these results for standalone hollow cathode development tests are discussed.

Hall, Scott J.↗

NASA NTRSDate not supplied

The Effect of Anode Configuration on the Plasma Plume of a 25-A class Hollow Cathode

The effect of anode configuration on the plasma plume properties of a 25-A class hollow cathode are experimentally characterized. At a nominal operating condition of 20.8 A and 14.7 sccm of xenon, the cathode was operated with two axially-segmented anodes of different diameters at varying distance from the cathode. A fast, reciprocating motion stage was used to rapidly insert an ion saturation probe and an emissive probe on cathode centerline, and from those measurements, spatial profiles of plasma density, plasma potential, and electron temperature were calculated. For both anode diameters, maximum plasma potential and electron temperature increased with increasing anode distance. However, the 64-mm diameter anode was found to be significantly more sensitive to position, with measurements indicating that parameters changed continuously with position instead of an instantaneous mode change at a certain critical distance. The 254-mm diameter, in contrast, showed much more similar plasma property profiles across the range of anode positions tested and much smaller changes per unit increase in distance. These results are discussed in the context of assessing anode design for component-level cathode tests.

Space propulsion↗

NASA NTRSDate not supplied

The Effect of Anode Configuration on the Plasma Plume of a 25-A class Hollow Cathode

space propulsion↗

DOE OSTI2021

System and method for removing water and hydrogen from anode exhaust

A fuel cell system includes an anode configured to output an anode exhaust stream comprising hydrogen, carbon dioxide, and water; and a membrane dryer configured to receive the anode exhaust stream, remove water from the anode exhaust stream, and output a membrane dryer outlet stream. The membrane dryer includes a first chamber configured to receive the anode exhaust stream; a second chamber configured to receive a purge gas; and a semi-permeable membrane separating the first chamber and the second chamber. The semi-permeable membrane is configured to allow water to diffuse therethrough, thereby removing water from the anode exhaust stream. The membrane dryer may further be configured to remove hydrogen from the anode exhaust stream.

Jolly, Stephen↗

DOE OSTI2022

Nanoscale Three-Dimensional Imaging of Degradation in Composite Si-Containing Anodes

The use of silicon (Si) in next-generation lithium-ion battery (LIB) anodes has the potential to dramatically improve electrochemical performance over current LIB graphite (Gr) anodes, due to silicon’s higher specific capacity.1 However, widespread implementation of Si-containing anodes is inhibited by issues such as significant Si volume expansion during lithiation and an unstable solid-electrolyte interphase (SEI), resulting in unreliable performance and poor cycle life. Currently, composite anodes with both Si and graphite active materials are used to increase capacity and mitigate some of the limitations associated with Si. In composite electrodes with a heterogeneous distribution of components with varying electrical properties (including Si, Gr, conductive carbon additive, and binder), it is important to understand the local distribution of each component to correlate with electrochemical processes, particularly localized degradation and heterogeneous aging, and to optimize performance. To investigate Si-containing composite anodes in the nanoscale, we use scanning spreading resistance microscopy (SSRM), a form of scanning probe microscopy (SPM) that probes local electronic resistivity. By examining the intrinsic electronic resistivity contrast between the anode components, separate phases can be distinguished and understood within the composite structure.2 This work studies the effect of electrochemical cycling in two different electrolytes on component distribution and aging by comparing the electrical and structural evolution of composite Si-graphite electrodes and SEI before and after charge-discharge cycling. 1. W. J. Zhang. A review of the electrochemical performance of alloy anodes for lithium-ion batteries J. Power Sources 196 13–24 (2011). 2. C. Stetson, Z. Huey, A. Downard, Z. Li, B. To, A. Zakutayev, C.-S. Jiang, M. Al-Jassim, D. Finegan, S.-D. Han and S. DeCaluwe: Three-Dimensional Mapping of Resistivity and Microstructure of Composite Electrodes for Lithium-Ion Batteries. ACS Nano Letters Accepted (2020).

ADVANCED PROPULSION SYSTEMS↗

DOE OSTI2023

3-D composite anodes for Li-ion batteries with high capacity and fast charging capability

An anode for a lithium ion battery is disclosed includes a first major face, a second major face that, together with the first major face, defines a thickness of the anode, and at least one carbonaceous electrochemically active lithium host material distributed between the first and second major faces of the anode. The at least one carbonaceous electrochemically active lithium host material is selected from the group consisting of graphite, hard carbon, or a blend of graphite and hard carbon. The anode additionally defines a plurality of vertical channels extending at least partially through the thickness of the anode. A lithium-ion batter that includes the disclosed anode and a method of charging a lithium-ion battery that includes the disclosed anode are also disclosed.

Chen, Kuan-Hung↗

DOE OSTI2022

Flash Recycling of Graphite Anodes

The ever-increasing production of commercial lithium-ion batteries (LIBs) will result in a staggering accumulation of waste when they reach their end of life. A closed-loop solution, with effective recycling of spent LIBs, will lessen both the environmental impacts and economic cost of their use. Presently, <5% of spent LIBs are recycled and the regeneration of graphite anodes has, unfortunately, been mostly overlooked despite the considerable cost of battery-grade graphite. Here, in this work, an ultrafast flash recycling method to regenerate the graphite anode is developed and valuable battery metal resources are recovered. Selective Joule heating is applied for only seconds to efficiently decompose the resistive impurities. The generated inorganic salts, including lithium, cobalt, nickel, and manganese, can be easily recollected from the flashed anode waste using diluted acid, specifically 0.1 M HCl. The flash-recycled anode preserves the graphite structure and is coated with a solid-electrolyte-interphase-derived carbon shell, contributing to high initial specific capacity, superior rate performance, and cycling stability, when compared to anode materials recycled using a high-temperature-calcination method. Life-cycle-analysis relative to current graphite production and recycling methods indicate that flash recycling can significantly reduce the total energy consumption and greenhouse gas emission while turning anode recycling into an economically advantageous process.

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

Silicon Anodes with Improved Calendar Life Enabled By Multivalent Additives

Silicon is widely recognized as the most promising upgrade for graphite anodes due to its much higher capacity, natural abundance, and ability to be directly applied in the slurry-based, roll-to-roll production lines. However, in addition to the fast capacity decay, silicon anodes also suffer from inferior calendar life in practical applications due to the unstable solid-electrode interface (SEI). Until now, strategies to effectively improve the calendar life by tailored SEIs remain largely unclear, especially in high-Si content, zero-graphite anodes. Here, silicon anodes with superior calendar life are developed by adding small concentrations of multivalent salts into the baseline electrolyte. The Ca additive reacts with the F ions in the electrolyte, forming a layer of nanocrystalline CaF 2 that is closely coated around the silicon particles. The CaF 2 -enabled new SEI is strong and dense, which effectively protects the silicon core from side reactions, leading to lower capacity decay after calendar aging at high voltage. More importantly, the Ca additive is effective universally for all available commercial silicon or SiO sources. This study provides a feasible and low-cost solution for developing silicon anodes with long calendar life, paving the way towards commercially viable silicon anodes.

25 ENERGY STORAGE↗

DOE OSTI2020

The electrolyte comprising more robust water and superhalides transforms Zn-metal anode reversibly and dendrite-free

A great challenge for all aqueous batteries, including Zn-metal batteries, is the parasitic hydrogen evolution reaction on the low-potential anode. Herein, we report the formula of a highly concentrated aqueous electrolyte that mitigates hydrogen evolution by transforming water molecules more inert. The electrolyte comprises primarily ZnCl 2 and LiCl as an additive, both of which are inexpensive salts. The O–H covalent bonds in water get strengthened in a chemical environment that has fewer hydrogen bonding interactions and a greater number of Zn–Cl superhalides, as suggested by integrated characterization and simulation. As a result, the average Coulombic efficiency of zinc-metal anode is raised to an unprecedented >99.7% at 1 mA cm –2 . In the new electrolyte, the plating/stripping processes leave the zinc-metal anode dendrite-free, and the zinc-metal anode delivers stable plating/stripping cycles for 4000 hours with an areal capacity of 4 mAh cm –2 at 2 mA cm –2 . Furthermore, the high Coulombic efficiency of zinc-metal anode in the ZnCl 2 -LiCl mixture electrolyte is demonstrated in full cells with a limited anode. The V 2 O 5 ·H 2 O| |Zn full cell with an N/P mass ratio of 1.2 delivers a stable life of more than 2500 cycles, and the LiMn 2 O 4 | |Zn hybrid cell with an N/P mass ratio of 0.6 exhibits 1500 cycles in its stable life.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Insights into Chemical Prelithiation of SiO x /Graphite Composite Anodes through Scanning Electron Microscope Imaging

Initial Coulombic efficiency (ICE) is critical for determining the energy density of lithium-ion batteries (LIBs) used for practical applications; however, it is typically disregarded in anode research. We used SiO x and graphite composite anodes for commercial lithium-ion batteries in our preliminary research to achieve a balance between ICE, capacity, and cycling life. ICE reached 88%; however, it needs further improvement for commercial applications. Prelithiation is a process that involves the introduction of extra lithium ions into LIBs during their manufacturing to enhance the overall performance of the LIBs. We applied a chemical prelithiation method on our SiO x /graphite composite anodes, which comprised 95 wt % of the active material mass loading on the electrode. The ICE increased from 88% to 98% using an aryllithium reagent impregnation method within 2 min of prelithiation. The anode’s specific capacity density, rate, and cycle performance also significantly improved. Scanning electron microscopy (SEM) imaging enhanced by an osmium tetroxide staining method indicated that the P-anode contained a stable solid electrolyte interface (SEI) layer after the prelithiation process and cycling electrochemical test. The P-anode’s stable charge differential peak over 500 cycles also showcases a robust artificial SEI layer that was generated by the prelithiation procedure. Here, this prelithiation process has significant potential for adoption in the LIB industry’s current electrode manufacturing process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Progress of 3D network binders in silicon anodes for lithium ion batteries

Prompted by its overwhelming benefits, silicon (Si) has evolved as one of the most promising anode materials for high-capacity lithium-ion batteries (LIBs). However, some of the intrinsic drawbacks such as low ionic conductivity and inevitable volume change during the alloying/dealloying process seriously hamper the commercialization of Si-based anodes in LIBs. Among the several strategies to overcome the challenges of the Si anode, the development of designed polymeric binders is imperative for enabling stable and satisfactory performance. The improved cell performance due to the designed binders is recognized as an economical and practical approach, especially from the industrial perspective. In addition to their conventional role in integrating electrode components, binders also play a significant role in alleviating the unfavorable phenomenon of volume expansion, and ultimately stabilizing the Si anode and Si-electrolyte interphase. The polymer architecture of the binders significantly influences the binder performance, and three-dimensional (3D) network binders are generally more effective at coping with the stress resulting from the huge volume change of the Si anode. To develop advanced 3D binders, substantial research efforts have been made including various crosslinking strategies in the past decade. In this review, we focus on diverse crosslinking methods including chemical-, physical-, and topological-crosslinking for rationally designing network binders for Si anodes and take a glance at dynamic interactions to construct healable binders for long-term stability.

25 ENERGY STORAGE↗

DOE OSTI2021

A chemical switch enabled autonomous two-stage crosslinking polymeric binder for high performance silicon anodes

Silicon (Si) is a promising high-capacity anode material for high-energy-density lithium-ion batteries. However, the drastic volumetric changes of Si upon lithiation/delithiation hinder the practical use of Si anodes. Although adhesive polymeric binders, such as poly(acrylic acid) (PAA), mitigate this issue, the cycling performance of the fabricated Si anodes is still far from meeting the criteria of practical applications. In this study, we present a novel polymeric binder system for Si anodes consisting of PAA, a chemical switch (ammonia, NH 3 ), and a crosslinker (branched polyethylenimine, PEI). The crosslinking between PAA and PEI is switched off in the slurry, which can then be turned on during electrode drying. Interestingly, the crosslinking reaction consists of two stages: ionic cross-linking (PAA-PEI-i) and covalent crosslinking (PAA-PEI-c) at a higher temperature (e.g., 130 °C). In half-cells, Si anodes fabricated using the PAA-PEI-c binder show a 67% increase in capacity retention compared to PAA anodes over 150 cycles at C/3 rate. The PAA-PEI-c binder also outperforms PAA in full cells. In addition, the chemical switch controlled crosslinking binder system also facilitates the slurry making process by avoiding early crosslinking. This system requires no additional steps compared to the conventional electrode lamination process, showing enormous potential for direct adoption in large-scale manufacturing.

25 ENERGY STORAGE↗

DOE OSTI2022

Enhancing Coking Tolerance and Stability of SOFC Anodes Using Atomic Layer Deposition (ALD) of Oxide Thin Films

The overall objective of this project was to use atomic layer deposition (ALD) to add modifiers to the surfaces of conventional Ni-YSZ cermet, solid oxide fuel cell (SOFC) anodes to enhance both their tolerance to hydrocarbon fuels by decreasing their propensity to form coke deposits, and to increase redox stability. Studies of the use of ALD to modify analogous supported metal powder catalysts were also added to the scope of the project in response to our industrial partner, Atrex going out of business. The initial portion of the program focused on designing and building the ALD reactor required for deposition of the oxide modifier films. Studies of the oxide modifier films on the coking tolerance and of redox properties of Ni-cermet anodes were then carried out. These studies demonstrated that while surface oxide modifiers were able to impart some coking resistance this only occurred for a relatively small range of operating conditions (e.g., temperature, steam-to-fuel ratio, etc.) and not at the level that would be required for operating in methane fuel at low steam-to-methane ratios. In light of this observation, we focused on assessing another approach to enhance anode coking resistance which eliminated bulk Ni from the anode. This approach made use of electronically conducting perovskite films to provide electrical conductivity in the anode, while using small amounts of Ni or other metals, such as Pt, deposited using ALD as the anode oxidation catalyst. This approach proved to be quite promising at both imparting coking resistance and redox stability.

03 NATURAL GAS↗