Utilizing Co 2+ /Co 3+ Redox Couple in P2-Layered Na 0.66 Co 0.22 Mn 0.44 Ti 0.34 O 2 Cathode for Sodium-Ion Batteries
Abstract not provided
Wang, Qin-Chao↗
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Electronic properties of Ir 3 Li and ultra-nanocrystalline lithium superoxide formation
Current lithium-oxygen (Li-O 2 ) batteries suffer from large charge overpotentials related to electronic resistivity of the insulating lithium peroxide (Li 2 O 2 ) discharge product. One potential solution to this challenge is the stabilization of the lithium superoxide (LiO 2 ) discharge intermediate, which has much higher electronic conductivity compared to Li 2 O 2 . Cathodes based on small iridium (Ir) nanoparticles have been recently used in a LiO 2 battery to successfully stabilize the LiO 2 product, however, the LiO 2 had a short lifetime. In the previous study, researchers found that the LiO 2 was stabilized on Ir 3 Li surfaces which were formed from Ir nanoparticles during battery operation. Little is known about the electronic properties of Ir 3 Li and its role in stabilizing LiO 2 product formation. This work provides the first study of the electronic properties of Ir 3 Li, which was thermally synthesized in bulk prior to implementation on the reduced graphene oxide (rGO) cathode of a Li-O 2 cell. Here, the bulk Ir 3 Li was found to have comparable electrical conductivity to Ir metal, possess metal-like magnetic properties, and has an affinity towards O 2 adsorption. The LiO 2 discharge product formed from the Li-O 2 battery discharge was characterized using Raman spectroscopy, titration, along with a comprehensive transmission electron microscopy (TEM) study. This analysis revealed the formation of ultra-nanocrystalline LiO 2 particles greater than 200 nm. This result was attributed to the use of large micron sized Ir 3 Li particles, which could stabilize larger LiO 2 particles compared to previous cathodes that utilized Ir nanoparticles that partially converted to Ir 3 Li during cycling. These results demonstrate that cathode properties can be modified to stabilize the bulk LiO 2 discharge product, which can be useful for the further development of LiO 2 -based Li-O 2 batteries.
25 ENERGY STORAGE↗
Status Report on the High-Temperature Steam Electrolysis Plant Model Developed in the Modelica Framework (FY17)
This report has been prepared as part of an effort to design and build a modeling and simulation (M&S) framework to assess the economic viability of a nuclear-renewable hybrid energy system (N-R HES). In order to facilitate dynamic M&S of such an integrated system, research groups in multiple national laboratories have been developing various subsystems as dynamic physics-based components using the Modelica programming language. In fiscal year 2015 (FY15), Idaho National Laboratory (INL) performed a dynamic analysis of two region-specific N-R HES configurations, including the gas-to-liquid (natural gas to Fischer-Tropsch synthetic fuel) and brackish water reverse osmosis desalination plants as industrial processes. In FY16, INL developed two additional subsystems in the Modelica framework: (1) a high-temperature steam electrolysis (HTSE) plant as a high priority industrial plant to be integrated with a light water reactor (LWR) within an N-R HES and (2) a gas turbine power plant as a secondary energy supply. In FY17, five new components (i.e., a feedwater pump, a multi-stage compression system, a sweep-gas turbine, flow control valves, and pressure control valves) have been incorporated into the HTSE system proposed in FY16, aiming to better realistically characterize all key components of concern. Special attention has been given to the controller settings based on process models (i.e., direct synthesis method), aiming to improve process dynamics and controllability. A dynamic performance analysis of the improved LWR/HTSE integration case was carried out to evaluate the technical feasibility (load-following capability) and safety of such a system operating under highly variable conditions requiring flexible output. The analysis (evaluated in terms of the step response) clearly shows that the FY17 model resulted in superior output responses with much smaller settling times and less oscillatory behavior in response to disturbances in the electric load than those observed with the FY16 model. Simulation results involving several case studies show that the suggested control scheme could maintain the controlled variables (including the steam utilization factor, cathode stream inlet composition, and temperatures and pressures of the process streams at various locations) within desired limits under various plant operating conditions. The results also indicate that the proposed HTSE plant could provide operational flexibility to participate in energy management at the utility scale by dynamically optimizing the use of excess plant capacity within an N-R HES.
08 HYDROGEN↗
Identifying point defects and ordering in the high-entropy layered oxide Li 1.5 MO 3-δ (M=Mn, Al, Fe, Co, Ni) for energy storage applications
High-entropy layered oxides (HELOs) represent a very promising class of next-generation battery cathodes, combining the well-studied properties of layered cathode materials such as LiCoO 2 with the chemical tunability and stability of high-entropy materials. HELO materials often form particles with complex defects and domain structures, complicating accurate characterization of structure and cation mixing. Understanding disorder and order in HELO materials is necessary for understanding their performance and utility as cathodes. Here we demonstrate the characterization of the HELO Li 1.5 MO 3-δ (M = Mn, Al, Fe, Co, Ni), wherein X-ray powder diffraction, transmission electron microscopy imaging, and electron diffraction patterns are analyzed to reveal the presence of ordering in the HELO, with imaging and diffraction simulation employed to compare experimental results to atomic modeling. Finally, without rigorous characterization at the atomic scale, important features such as defect ordering can be easily overlooked and therefore remain unconsidered when interpreting experimental results.
36 MATERIALS SCIENCE↗
Polycarbonate‐Based Solid‐Polymer Electrolytes for Solid‐State Sodium Batteries
Solid-polymer electrolytes comprised of polypropylene carbonate (PPC) and varied sodium bis(fluorosulfonyl)imide (NaFSI) salt concentrations are investigated for implementation as a conductive solid polymer electrolyte into solid-state cathode composites utilizing a sodium-layered oxide active material. The ionic conductivity generally increases with NaFSI salt content, reaching ≈1 mS cm −1 at 80 °C at the highest salt concentration (PPC:NaFSI = 0.5:1). Through an all-in-one slurry casting method, Na 2/3 Ni 1/3 Mn 2/3 O 2 cathode composites are fabricated in which the dispersed PPC electrolyte acts as the primary binder. Enabled by a bilayer polymer electrolyte system, cycling performance with the PPC cathode electrolyte is optimized with respect to salt concentration and anode material. The best cyclability is achieved with a moderate salt concentration electrolyte (PPC:NaFSI = 5:1), showcasing an initial capacity of 83 mA h g −1 with a remarkable 80% capacity retention after 150 cycles at C/5 rate and 60 °C. The superior performance of the lower salt concentration electrolyte is attributed to better electrochemical stability, as confirmed by linear sweep voltammetry and online electrochemical mass spectrometry measurements. In conclusion, these results underscore the potential of carbonate-based polymer electrolytes and the importance of balancing electrolyte conductivity and stability in cell design.
25 ENERGY STORAGE↗
High temperature ceramic heat exchanger for solid oxide fuel cell
A ceramic heat exchanger with high effectiveness and low-pressure drop has been developed for application as a cathode air preheater for a Solid Oxide Fuel Cell (SOFC). At the operating conditions of SOFCs, typical metallic alloys as those used in commercial heat exchangers may undergo chromium volatilization, which is a known cathode degradation mechanism that reduces SOFC performance and life. Use of ceramics such as alumina or alumina-silicate instead of chromium-containing metal is one approach to eliminate the effects of chromium on the SOFC cathode. This project leverages the geometric design of a heat exchanger previously prototyped and tested [1] to fabricate a novel heat exchanger made from a ceramic material. All calculations of heat exchanger performance requirements are based on state of the art SOFC operating conditions. The alumina-silicate material selected to fabricate the modular prototype heat exchanger was made via a heat transfer based trade-off analysis that shows that for low pressure-drop devices, flow convection is the limiting heat transfer mechanism, and therefore wall conductivity becomes less relevant to heat transfer effectiveness. The modular design presented allows for incremental aggregation of modules to target a broad range of operating conditions typical of present and upcoming SOFC applications (e.g., 25 to 400 kWe). The completed prototype was subjected to a series of static leak/pressure tests, dynamic pressure drop tests both at ambient and realistic service temperature conditions, and finally to a matrix of heat transfer experiments to fully characterize its heat transfer effectiveness (including tests at hot gas temperatures up to 1033 K or 1400oF). The stand-alone system was demonstrated in the laboratory to successfully satisfy the design criteria at realistic operating conditions, showing a total pressure drop at the design flow of 8 g/sec of 6 kPa (vs. 3.45 kPa approximate requirement). It was also shown to have heat transfer effectiveness of 76% (with 73% being the design requirement). Moreover, the unit was shown to operate leak-free, and the ceramic elements and seals were capable of withstanding the thermal cycling resulting from the testing procedure. The heat exchanger was then integrated into a modified fuel cell test stand and tested at steady state operation. Unfortunately, the level of performance achieved was lower than expected based on laboratory performance tests. This appears to have been the result of an unforeseen loosening of a heat exchanger structural component, which resulted into a leak that prevented proper supply of hot gas to the heat exchanger. However, in general terms, the heat exchanger/fuel cell integration process provides confidence that a future application of the unit with a SOFC is feasible, assuming structural issues are addressed. It is considered that the difficulties encountered at the last stage of the program provided invaluable input in locating shortcomings of the mechanical design and integration approach. A portion of this work was presented at the ASME Power & Energy Conference, in Charlotte, NC, on June 28th 2016 in a paper entitled “Development of a Ceramic Heat Exchanger for Application as Solid Oxide Fuel Cell Cathode Air Preheater” and the corresponding paper was published in the Proceedings of the ASME 2016 Power & Energy Conference, Paper No.: PowerEnergy2016-59333 [8].
20 FOSSIL-FUELED POWER PLANTS↗
Degradation and Reliability Advancements in Tubular SOFC (Final Report)
The objective of this project is to improve the degradation and reliability of tubular SOFC and develop technologies applicable to stacks scalable to sub-MW system. The Phase II project scope encompasses the cell level technology development listed here and also bundle level degradation verification; 1. Incorporation of an inexpensive on-cell contamination gettering element in each cell to provide protection for cathode against Cr and S; 2. Enhance the electrical contact between Ag current collector and the lanthanum chromite based interconnection layer; 3. Improve the electrolyte layer sintering recipe to reduce the defect density and related anode oxidation problem
03 NATURAL GAS↗
Degradation and Reliability Advancements in Tubular SOFC (Final Report)
The objective of this project is to improve the degradation and reliability of tubular SOFC and develop technologies applicable to stacks scalable to sub-MW system. The Phase II project scope encompasses the cell level technology development listed below and also bundle level degradation verification. (1) Incorporation of an inexpensive on-cell contamination gettering element in each cell to provide protection for cathode against Cr and S. (2) Enhance the electrical contact between Ag current collector and the lanthanum chromite based interconnection layer. (3) Improve the electrolyte layer sintering recipe to reduce the defect density and related anode oxidation problem.
03 NATURAL GAS↗
Lithium inventory tracking as a non-destructive battery evaluation and monitoring method
Tracking the active lithium (Li) inventory in an electrode shows the true state of a Li battery, akin to a fuel gauge for an engine. However, non-destructive Li inventory tracking is currently unavailable. Here, in this work, we used the theoretical capacity of a transition metal oxide to convert capacity into a Li inventory analysis. The Li inventory in electrodes was tracked reliably to show how battery formulations and test methods affect performance. Contrary to capacity, Li inventory tracking reveals stoichiometric variations near the electrode–electrolyte interface. Verifiable results rationalized differences in measurements, clarifying and reducing interferences from cell formulations and experimental manipulations. By tracing four variables from formation to end-of-life, we characterize electrode and cell performance with a thermodynamic framework. Accurate rationalization of subtle differences in Li inventory utilization promises precise battery engineering, evaluation, failure analysis and risk mitigation. The method could be applicable from cell design optimization and fabrication to battery management, improving battery performance and reliability.
25 ENERGY STORAGE↗
A multi-functional interface derived from thiol-modified mesoporous carbon in lithium–sulfur batteries
Li–S batteries hold great promise as the utility of a thiol-based interface facilitates LiPS-trapping and improves the electrolyte wetting.
Li, Yun↗
Concentrated dual-cation electrolyte strategy for aqueous zinc-ion batteries
Rechargeable Zn-ion batteries are highly promising for stationary energy storage because of their low cost and intrinsic safety. However, due to the poor reversibility of Zn anodes and dissolution of oxide cathodes, aqueous Zn-ion batteries encounter rapid performance degradation when operating in conventional low-concentration electrolytes. Herein, we demonstrate that an aqueous Zn2+ electrolyte using a supporting Na salt at a high concentration is efficient to address these issues without sacrificing the power densities, cycling stability, and safety of zinc-ion batteries. We show that the high-concentration solute minimizes the number of free water molecules and the changes in the electronic state of the electrolyte. A combination of experimental and theoretical investigations reveals that a unique interphase, formed on the Zn anode, enables reversible and uniform Zn plating. Utilizing a cathode of sodium vanadate synthesized through a scalable strategy, the Zn–sodium vanadate battery with the concentrated bi-cation electrolyte shows improved cycling stability, decent rate performance, and low self-discharge. This work provides new insights on electrolyte engineering to achieve high-performance aqueous batteries.
25 ENERGY STORAGE↗
High Performance Cathode Recovery from Different Electric Vehicle Recycling Streams
For environmental and sustainability reasons, spent Li-ion batteries must be recovered and recycled so that the full promise of an electrified future is realized. Li-ion battery recycling streams pose a serious challenge to all existing recycling technologies due to their unknown and diverse chemistry. In this work, four representative recycling streams were used to demonstrate the flexibility of the recycling process developed at Worcester Polytechnic Institute (WPI) to accommodate a variable feed and generate consistent quality cathode material, LiNi 1/3 Mn 1/3 Co 1/3 O 2 (NMC111). Ni 1/3 Mn 1/3 CO 1/3( OH) 2 precursors derived from four recycling streams were produced by a hydroxide co-precipitation method in a continuous stirred tank reactor. It took two days for the co-precipitation reaction to reach steady state. A possible evolution of the precursor particles up to the steady state was proposed. Both the precursors and cathodes from these four different recycling streams exhibit similar morphology, particle size distribution, and tap density. Moreover, these recovered cathode materials display similar electrochemical properties. Surprisingly these recovered NMC111s have better rate capability than a commercial NMC111 prepared from virgin materials. The different chemical compositions of the incoming recycling streams were shown to have little observed effect on the recovered precursor and resultant cathode material generated by the WPI-developed recycling process with advantages including no sorting, low temperature, and high quality recovered battery materials. Therefore, the WPI-developed process applies to different spent Li-ion battery waste streams and is therefore general.
25 ENERGY STORAGE↗
High Active Material Loading in All‐Solid‐State Battery Electrode via Particle Size Optimization
Not Available
25 ENERGY STORAGE↗
Cobalt nanoparticle-encapsulated carbon nanowire arrays: Enabling the fast redox reaction kinetics of lithium-sulfur batteries
The commercial application of lithium-sulfur batteries is still impeded by the unsatisfying cyclability due to the sluggish reaction kinetics and shuttling effect of polysulfide intermediates. We develop a cobalt nanoparticle-encapsulated carbon nanowire arrays on carbon cloth (CC@Co-CNAs) to enable the fast redox reaction kinetics of the lithium sulfur batteries. The nanowire array-decorated carbon cloth as conductive matrix for sulfur active material could provide highly exposed cobalt nanoparticle active sites, owing to the high length-diameter ratio of the prepared CC@Co-CNAs. The binding affinity between the cobalt nanoparticle-incorporated materials and polysulfide intermediates is enhanced by Co-S bonds, which facilitates the redox reaction of active materials and consequently results in a high sulfur utilization for cathode especially with high sulfur loading. The lithium sulfur battery with CC@Co-CNAs as electrode materials delivers a high initial discharge capacity of 1228 mAh g –1 at 0.25 C, and a high initial discharge capacity of 807 mAh g –1 at 1C with a low capacity fading rate of 0.06% per cycle during 300 cycles. Furthermore, a discharge capacity of 958 mAhg –1 at 0.1 C is achieved for the cell even with a corresponding sulfur loading of 6.2 mg cm –2 .
25 ENERGY STORAGE↗
Probing Mg Migration in Spinel Oxides
Mg batteries utilizing oxide cathodes can theoretically surpass the energy density of current Li-ion technologies. The absence of functional devices so far has been ascribed to impeded Mg 2+ migration within oxides, which severely handicaps intercalation reactions at the cathode. Broadly, knowledge of divalent cation migration in solid frameworks is surprisingly deficient. In this paper, we present a combined experimental and theoretical study of Mg migration within three spinel oxides, which reveal critical features that influence it. Experimental activation energies for a Mg 2+ hop to an adjacent vacancy, as low as ~0.6 eV, are reported. These barriers are low enough to support functional electrodes based on the intercalation of M g2+ . Subsequent electrochemical experiments demonstrate that significant demagnesiation is indeed possible, but the challenges instead lie with the chemical stability of the oxidized states. Our findings enhance the understanding of cation transport in solid structures and renew the prospects of finding materials capable of high density of energy storage.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
High-Energy All-Solid-State Organic–Lithium Batteries Based on Ceramic Electrolytes
Recent studies have identified unique properties of organic battery electrode materials such as moderate redox potentials and mechanical softness which are uniquely beneficial for all-solid-state batteries based on ceramic electrolytes. Here, we further explore the promise of organic materials and demonstrate a sulfide electrolyte- based organic-lithium battery with a specific energy of 828 Wh kg –1 , rivaling the state-of- the-art of all-solid-state batteries. Two innovation steps are responsible for the accomplishment. First, the combination of lithium anode and the high-capacity cathode material pyrene-4,5,9,10-tetraone ensures a high theoretical specific energy. Second, the microstructure of the organic cathode is optimized with the introduction of cryomilling, a technique common to processing soft materials but not familiar to electrode fabrication. The cathode material utilization increases to 99.5% as a result, up from the 55–89% previously reported for ceramic electrolyte-based solid-state organic batteries. In conclusion, the improvement highlights the special requirements of solid-state organic electrodes for microstructural engineering while preserving the chemical integrity of components.
25 ENERGY STORAGE↗
Implications of Local Cathode Structure in Solid-State Batteries
Solid-state batteries (SSBs) are promising candidates for energy storage systems—specifically for automotive applications—owing to their higher energy density and supreme safety. SSBs currently must improve area-specific cathode loadings as well as the electro-chemo-mechanical stability at high voltages. Composite cathodes in SSBs are comprised of active material, ion and electronic conductors, binders, and electronic conducting materials. In addition to experimental limitations with engineering thick cathode architectures, low utilization and chemomechanical degradation of the cathodes limit the performance of composite cathodes. Composite cathodes must optimize several parameters simultaneously to achieve high performances that include loading, electrochemically active surface area, mechanical resilience, and porosity. This chapter summarizes the current state-of-the-art applications with regard to composite cathodes for SSBs and provides insights into cathode architectures using geometric packing models. Tailoring ion and electron transport pathways within the electrode while mitigating operational stresses is crucial for achieving energy-dense cathode structres for SSBs.
Dixit, Marm↗
Encapsulating Various Sulfur Allotropes within Graphene Nanocages for Long-Lasting Lithium Storage
The encapsulation of sulfur within carbon matrices is widely utilized in the cathode of a rechargeable lithium-sulfur battery, whose energy density largely depends on the design of the carbon structure. Here, an advanced graphene nanocage structure with the capability of hosting both cyclo-S-8 and smaller sulfur molecules (S2-4) is reported. The cage inner cavity is partially filled with S-8 to form a yolk-shell structure that enables free volumetric variation of S-8 during (de)lithiation. In the graphene shell of the cage, S-8 are downsized to S2-4 to activate extra sulfur loading sites within graphene layers. Importantly, the graphene shell exhibits inward volumetric variation upon (de)lithiation of the loaded S2-4, and the overall electrode strain is thus minimized. This prototyped design promises an ultimate solution to maximize sulfur loading in carbon matrices as well as to circumvent the polysulfide dissolution problem and boost the commercialization of lithium-sulfur batteries in the future.
Yuan, Yifei↗