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At least 991 records · Page 55
All sourcesNASA NTRSDOE OSTI
DOE OSTI2014

Structural changes and thermal stability of charged LiNi x Mn y Co z O 2 cathode materials studied by combined in situ time-resolved XRD and mass spectroscopy

Thermal stability of charged LiNi x Mn y Co z O 2 (NMC, with x + y + z = 1, x:y:z = 4:3:3 (NMC433), 5:3:2 (NMC532), 6:2:2 (NMC622), and 8:1:1 (NMC811)) cathode materials is systematically studied using combined in situ time- resolved X-ray diffraction and mass spectroscopy (TR-XRD/MS) techniques upon heating up to 600 °C. The TR-XRD/MS results indicate that the content of Ni, Co, and Mn significantly affects both the structural changes and the oxygen release features during heating: the more Ni and less Co and Mn, the lower the onset temperature of the phase transition (i.e., thermal decomposition) and the larger amount of oxygen release. Interestingly, the NMC532 seems to be the optimized composition to maintain a reasonably good thermal stability, comparable to the low-nickel-content materials (e.g., NMC333 and NMC433), while having a high capacity close to the high-nickel-content materials (e.g., NMC811 and NMC622). The origin of the thermal decomposition of NMC cathode materials was elucidated by the changes in the oxidation states of each transition metal (TM) cations (i.e., Ni, Co, and Mn) and their site preferences during thermal decomposition. It is revealed that Mn ions mainly occupy the 3a octahedral sites of a layered structure (R3¯m) but Co ions prefer to migrate to the 8a tetrahedral sites of a spinel structure (Fd3¯m) during the thermal decomposition. Such element-dependent cation migration plays a very important role in the thermal stability of NMC cathode materials. The reasonably good thermal stability and high capacity characteristics of the NMC532 composition is originated from the well-balanced ratio of nickel content to manganese and cobalt contents. As a result, this systematic study provides insight into the rational design of NMC-based cathode materials with a desired balance between thermal stability and high energy density.

25 ENERGY STORAGE↗
DOE OSTI2020

Extended Interfacial Stability through Simple Acid Rinsing in a Li-Rich Oxide Cathode Material

Layered Li-rich Ni, Mn, Co (NMC) oxide cathodes in Li-ion batteries provide high specific capacities (>250 mAh/g) via O-redox at high voltages. However, associated high-voltage interfacial degradation processes require strategies for effective electrode surface passivation. Here, we show that an acidic surface treatment of a Li-rich NMC layered oxide cathode material leads to a substantial suppression of CO 2 and O 2 evolution, ~90% and ~100% respectively, during the first charge up to 4.8 V vs. Li +/0 . CO 2 suppression is related to Li 2 CO 3 removal as well as effective surface passivation against electrolyte degradation. This treatment does not result in any loss of discharge capacity and provides superior long-term cycling and rate performance compared to as-received, untreated materials. We also quantify the extent of lattice oxygen participation in charge compensation (“O-redox”) during Li + removal by a novel ex-situ acid titration. Our results indicate that the peroxo-like species resulting from O-redox originate on the surface at least 300 mV earlier than the activation plateau region around 4.5 V. X-ray photoelectron spectra and Mn -L X-ray absorption spectra of the cathode powders reveal a Li + deficiency and a partial reduction of Mn ions on the surface of the acid-treated material. More interestingly, although the irreversible oxygen evolution is greatly suppressed through the surface treatment, our O K-edge resonant inelastic X-ray scattering shows the lattice O-redox behavior largely sustained. The acidic treatment, therefore, only optimizes the surface of the Li-rich material and almost eliminates the irreversible gas evolution, leading to improved cycling and rate performance. This work therefore presents a simple yet effective approach to passivate cathode surfaces against interfacial instabilities during high-voltage battery operation.

25 ENERGY STORAGE↗
DOE OSTI2020

Probing the Thermal-Driven Structural and Chemical Degradation of Ni-Rich Layered Cathodes by Co/Mn Exchange

The intrinsic poor thermal stability of layered LiNi x Co y Mn 1-x-y O 2 (NCM) cathodes and the exothermic side reactions triggered by the associated oxygen release are the main safety threats for their large-scale implantation. In NCM family, it is widely accepted that Ni is the stability troublemaker, while Mn has long been considered as a structure stabilizer, whereas the role of Co remains elusive. Here, via Co/Mn exchange in Ni-rich LiNi 0.83 Co 0.11 Mn 0.06 O 2 cathode, we demonstrate that, the chemical and structural stability of the deep delithiated NCM cathodes are significantly affected by Co, rather than the widely reported Mn. Operando synchrotron X-ray characterization coupling with in situ mass spectrometry reveal that the Co 4+ reduces prior to the reduction of Ni 4+ , and could thus prolong the Ni migration by occupying the tetrahedra sites, and hence postpone the oxygen release and thermal failure. In contrast, the Mn itself is stable, but barely stabilizes the Ni 4+ . Our results highlight the importance of evaluating the intrinsic role of compositional tuning on Ni-rich/Co-free layered oxide cathode materials to guarantee the safe operation of high-energy Li-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2017

Intragranular cracking as a critical barrier for high-voltage usage of layer-structured cathode for lithium-ion batteries

LiNi 1/3 Mn 1/3 Co 1/3 O 2 (NMC333) layered cathode is often fabricated as secondary particles of consisting of densely packed primary particles, which offers advantage of high energy density and alleviation of cathode side reactions/corrosions, but introduces other drawbacks, such as intergranular cracking. Here, we report unexpected observations on the nucleation and growth of intragranular cracks in the commercial NMC333 layered cathode by using advanced S/TEM. We found that the formation of the intragranular cracks is directly associated with high voltage cycling, which is an electrochemically driven and diffusion controlled process. The intragranular cracks were noticed to be characteristically initiated from grain interior, a consequence of dislocation based crack incubation mechanism. This observation is in sharp contrast with the general theoretical models, predicting the initiation of intragranular cracks from grain boundaries or particle surface. As a result, our study indicates that maintain a structural stability is the key step toward high voltage operation of layered cathode materials.

25 ENERGY STORAGE↗
DOE OSTI2017

Insights into the structural effects of layered cathode materials for high voltage sodium-ion batteries

Cathode materials are critical to the energy density, power density and safety of sodium-ion batteries (SIBs). Herein, we performed a comprehensive study to elucidate and exemplify the interplay mechanism between phase structures, interfacial microstrain and electrochemical properties of layered-structured Na x Ni 1/3 Co 1/3 Mn 1/3 O 2 cathode materials for high voltage SIBs. The electrochemical test results showed that Na x Ni 1/3 Co 1/3 Mn 1/3 O 2 with an intergrowth P2/O3/O1 structure demonstrates better electrochemical performance and better thermal stability than Na x Ni 1/3 Co 1/3 Mn 1/3 O 2 with P2/O3 binary-phase integration and Na x Ni 1/3 Co 1/3 Mn 1/3 O 2 where only the P phase is dominant. This result is caused by the distinct interfacial microstrain development during the synthesis and cycling of the P2/O3/O1 phase. In operando high energy X-ray diffraction further revealed that the intergrowth P2/O1/O3 cathode can inhibit the irreversible P2–O2 phase transformation and simultaneously improve the structure stability of the O3 and O1 phases during cycling. Here, we believe that interfacial microstrain can serve as an indispensable bridge to guide future design and synthesis of high performance SIB cathode materials and other high energy battery materials.

25 ENERGY STORAGE↗
DOE OSTI2018

Discovery of a high-pressure phase of rutile-like CoO 2 and its potential as a cathode material

Due to the structural failure of layered CoO 2 , there has been considerable effort to improve the reversible capacity of commercial LiCoO 2 cathode materials. Using a global structural search, we have discovered a rutile-like CoO 2 phase as the ground state at 50 GPa. The material is thermally, mechanically and dynamically stable, even after removing the pressure. We show that, when lithiated, this LiCoO 2 material can serve as an improved cathode material for Li-ion batteries. Its many advantages include good structural stability against transition metal migration and oxygen loss, one-dimensional channels for Li ion diffusion with variable energy barriers (0.36–0.86 eV), enhanced ionic mobility, and good intrinsic electronic conductivity brought about by its metallic band structure. Furthermore, with a voltage platform of 3.2–3.8 V, it provides better stability against conventional carbonate solvents than conventional layered cathode materials (>4.0 V). All these features demonstrate that the non-layered CoO 2 phase synthesized at high pressure would be a promising cathode material, providing a performance beyond that of the currently used layered phase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Oxygen redox chemistry in P2-Na 0.6 Li 0.11 Fe 0.27 Mn 0.62 O 2 cathode for high-energy Na-ion batteries

Owing to the abundance of raw material reserves and low cost, Na-ion batteries (NIBs) have successfully gained widespread attention from academic and industrial communities in the past few decades. However, the insufficient cathode energy density is still one of the critical bottlenecks restricting the development of NIBs. Following a strategy of introducing Li+ into the transition-metal (TM) layer to enhance the oxygen redox reaction, a novel layered cathode material P2-Na 0.6 Li 0.11 Fe 0.27 Mn 0.62 O 2 (NLFMO) was designed and successfully synthesized. This NLFMO cathode not only delivers a large initial reversible capacity of 207.3 mA h g -1 , but also shows a good cycling performance (104.2 mA h g -1 after 80 cycles) and rate capability (126.2 mA h g -1 at 1C). The ultrahigh capacity is contributed by both cationic (Fe 3+ /Fe 4+ and Mn 3+ /Mn 4+ ) and partially reversible anionic redox (O 2- /O n- ) reactions, revealed by in situ X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS) techniques. Moreover, no detrimental P2–O2 phase transition was observed in ex situ X-ray diffraction (XRD) patterns, confirming the high structural stability during Na + deintercalation/intercalation processes. These results provide valuable information about the high-energy density layered cathode materials based on anionic redox reactions for NIBs.

25 ENERGY STORAGE↗
DOE OSTI2024

An overview of various critical aspects of low-cobalt/cobalt-free Li-ion battery cathodes

Cathodes of lithium-ion batteries (LIBs) significantly impact the environmental footprint, cost, and energy performance of the battery-pack. Hence, sustainable production of Li-ion battery cathodes is critically required for ensuring cost-effectiveness, environmental benignity, consumer friendliness, and social justice. Battery chemistry largely determines individual cell performance as well as the battery pack cost and life cycle greenhouse gas emission. Continuous manufacturing platforms improve production efficiency in terms of product yield, quality and cost. Spent-battery recycling ensures the circular economy of critical elements that are required for cathode production. Innovations in fast-charging LIBs are particularly promising for sustainable e-mobility with a reduced carbon footprint. This article provides an overview of these research directions, emphasizing strategies for low-cobalt cathode development, recycling processes, continuous production and improvement in fast-charging capability.

25 ENERGY STORAGE↗
DOE OSTI2011

Mechanism of high luminous efficacy in plasma display panel with high secondary electron emission coefficient cathode material analyzed through three-dimensional fluid model simulation

The mechanism to realize high luminous efficacy in a plasma display panel fabricated with a cathode material possessing a high secondary electron emission coefficient ({gamma}) for Ne and Xe ions was studied via three-dimensional numerical simulation. When a high {gamma} cathode material is used, the increased electron heating efficacy is responsible for increasing vacuum ultraviolet (VUV) efficacy with 10% Xe content gas. However, the continued availability of sufficient secondary electrons during the dynamic moving phase of the cathode sheath in which the electric field remains weakened causes increasing VUV efficacy with 30% Xe content gas. It was found that the improvement of the luminous efficacy of the plasma display panel with a high {gamma} cathode material is maximized under the condition of high Xe content gas because of the simultaneous increase of the electron heating efficacy and Xe excitation efficacy.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2012

Effect of sputtered lanthanum hexaboride film thickness on field emission from metallic knife edge cathodes

We report experiments and analysis of field emission from metallic knife-edge cathodes, which are sputter-coated with thin films of lanthanum hexaboride (LaB{sub 6}), a low-work function material. The emission current is found to depend sensitively on the thickness of the LaB{sub 6} layer. We find that films thinner than 10 nm greatly enhance the emitted current. However, cathodes coated with a thicker layer of LaB{sub 6} are observed to emit less current than the uncoated metallic cathode. This result is unexpected due to the higher work function of the bare metal cathode. We show, based on numerical calculation of the electrostatic potential throughout the structure, that the external (LaB{sub 6}/vacuum) barrier is reduced with respect to uncoated samples for both thin and thick coatings. However, this behavior is not exhibited at the internal (metal/LaB{sub 6}) barrier. In thinly coated samples, electrons tunnel efficiently through both the internal and external barrier, resulting in current enhancement with respect to the uncoated case. In contrast, the thick internal barrier in thickly coated samples suppresses current below the value for uncoated samples in spite of the lowered external barrier. We argue that this coating thickness variation stems from a relatively low (no higher than 10{sup 18} cm{sup -3}) free carrier density in the sputtered polycrystalline LaB{sub 6}.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Secondary-electrons-induced cathode plasma in a relativistic magnetron

Results of time- and space-resolved spectroscopic studies of cathode plasma during a S-band relativistic magnetron operation and a magnetically insulated diode having an identical interelectrode gap are presented. It was shown that in the case of the magnetron operation, one obtains an earlier, more uniform plasma formation due to energetic electrons' interaction with the cathode surface and ionization of desorbed surface monolayers. No differences were detected in the cathode's plasma temperature between the magnetron and the magnetically insulated diode operation, and no anomalous fast cathode plasma expansion was observed in the magnetron at rf power up to 350 MW.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2013

High-current long-duration uniform electron beam generation in a diode with multicapillary carbon-epoxy cathode

The results of reproducibly generating an electron beam with a current density of up to 5 kA/cm{sup 2}, without the cathode-anode gap being shorted by the plasma formed inside the cathode carbon-epoxy capillaries, in a ∼350 kV, ∼600 ns diode, with and without an external guiding magnetic field, are presented. The cathode sustained hundreds of pulses without degradation of its emission properties. Time- and space-resolved emissions of the plasma and spectroscopy analyses were used to determine the cathode plasma's density, temperature, and expansion velocity.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Cathode fall model and current-voltage characteristics of field emission driven direct current microplasmas

The post-breakdown characteristics of field emission driven microplasma are studied theoretically and numerically. A cathode fall model assuming a linearly varying electric field is used to obtain equations governing the operation of steady state field emission driven microplasmas. The results obtained from the model by solving these equations are compared with particle-in-cell with Monte Carlo collisions simulation results for parameters including the plasma potential, cathode fall thickness, ion number density in the cathode fall, and current density vs voltage curves. The model shows good overall agreement with the simulations but results in slightly overpredicted values for the plasma potential and the cathode fall thickness attributed to the assumed electric field profile. The current density vs voltage curves obtained show an arc region characterized by negative slope as well as an abnormal glow discharge characterized by a positive slope in gaps as small as 10 μm operating at atmospheric pressure. The model also retrieves the traditional macroscale current vs voltage theory in the absence of field emission.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2013

Cathode fall measurement in a dielectric barrier discharge in helium

A method based on the “zero-length voltage” extrapolation is proposed to measure cathode fall in a dielectric barrier discharge. Starting, stable, and discharge-maintaining voltages were measured to obtain the extrapolation zero-length voltage. Under our experimental conditions, the “zero-length voltage” gave a cathode fall of about 185 V. Based on the known thickness of the cathode fall region, the spatial distribution of the electric field strength in dielectric barrier discharge in atmospheric helium is determined. The strong cathode fall with a maximum field value of approximately 9.25 kV/cm was typical for the glow mode of the discharge.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2013

Ion velocities in direct current arc plasma generated from compound cathodes

Arc plasma from Ti-C, Ti-Al, and Ti-Si cathodes was characterized with respect to charge-state-resolved ion energy. The evaluated peak velocities of different ion species in plasma generated from a compound cathode were found to be equal and independent on ion mass. Therefore, measured difference in kinetic energies can be inferred from the difference in ion mass, with no dependence on ion charge state. The latter is consistent with previous work. These findings can be explained by plasma quasineutrality, ion acceleration by pressure gradients, and electron-ion coupling. Increasing the C concentration in Ti-C cathodes resulted in increasing average and peak ion energies for all ion species. This effect can be explained by the “cohesive energy rule,” where material and phases of higher cohesive energy generally result in increasing energies (velocities). This is also consistent with the here obtained peak velocities around 1.37, 1.42, and 1.55 (10{sup 4} m/s) for ions from Ti{sub 0.84}Al{sub 0.16}, Ti{sub 0.90}Si{sub 0.10}, and Ti{sub 0.90}C{sub 0.10} cathodes, respectively.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Numerical simulation of the sustaining discharge in radio frequency hollow cathode discharge in argon

In this paper, a two-dimensional fluid model was developed to study the radio frequency (RF) hollow cathode discharge (HCD) in argon at 1 Torr. The evolutions of the particle density distribution and the ionization rate distribution in RF HCD at 13.56 MHz indicate that the discharge mainly occurs inside the hollow cathode. The spatio-temporal distributions of the ionization rate and the power deposition within the hollow cathode imply that sheath oscillation heating is the primary mechanism to sustain the RF HCD, whereas secondary electron emission plays a negligible role. However, as driving frequency decreases, secondary electron heating becomes a dominant mechanism to sustain the discharge in RF hollow cathode.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2014

Sharp transition between two regimes of operation of dc discharge with two anodes and thermionic emission from cathode

In a dc discharge plasma with two anodes and thermionic emission from cathode, the two anodes are used for plasma control. The main anode is placed between the cathode and the other auxiliary anode has a circular opening for passing electron current from the cathode to the second anode. It is experimentally demonstrated that a plasma may exhibit a sudden transition between two quasi-stable conditions as one increases the cathode-electron current collected by the auxiliary anode through an aperture, i.e., hole, in the main anode. In one regime, a bright glowing “ball-shaped double layer” appears on the plasma side having a potential drop of 10–15 eV and concomitant ionization in the neighboring region attached to the opening. The second regime is characterized by a uniform potential profile in plasma and an absence of the ball-shaped double layer. The transition between these regimes is accompanied by a significant change in plasma properties, such as the electron energy distribution function (EEDF). Controlling the EEDF is a valuable capability in technological applications. Increasing the gas pressure leads to the elimination of the first regime for sufficiently high gas pressure, the threshold being a few Torr. The disappearance of a regime transition can be explained by invoking an EEDF transition, from being nonlocal at low pressure to becoming local at high pressure. Local EEDF is determined by local values of electric field. Nonlocal EEDF is determined by electric field values elsewhere, and the electron can travel without energy loss over a path much longer than the discharge dimension.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2014

Cathodes - Technological review

Lithium cobalt oxide (LiCoO{sub 2}) was already used in the first commercialized Li-ion battery by SONY in 1990. Still, it is the most frequently used cathode material nowadays. However, LiCoO{sub 2} is intrinsically unstable in the charged state, especially at elevated temperatures and in the overcharged state causing volume changes and transport limitation for high power batteries. In this paper, some technological aspects with large impact on cell performance from the cathode material point of view will be reviewed. At first it will be focused on the degradation processes and life-time mechanisms of the cathode material LiCoO{sub 2}. Electrochemical and structural results on commercial Li-ion batteries recorded during the cycling will be discussed. Thereafter, advanced nanomaterials for new cathode materials will be presented.

25 ENERGY STORAGE↗