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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 613 records · Page 34
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

In-situ preparation of Fe{sub 2}O{sub 3} hierarchical arrays on stainless steel substrate for high efficient catalysis

Hierarchical array catalysts with micro/nano structures on substrates not only possess high reactivity from large surface area and suitable interface, but intensify mass transfer through shortening the diffusion paths of both reactants and products for high catalytic efficiency. Herein, we first demonstrate fabrication of Fe{sub 2}O{sub 3} hierarchical arrays grown on stainless-steel substrates via in-situ hydrothermal chemical oxidation followed by heat treatment in N{sub 2} atmosphere. As a Fenton-like catalyst, Fe{sub 2}O{sub 3} hierarchical arrays exhibit excellent catalytic activity and life cycle performance for methylene blue (MB) dye degradation in aqueous solution in the presence of H{sub 2}O{sub 2}. The Fe{sub 2}O{sub 3} catalyst with unique hierarchical structures and efficient transport channels, effectively activates H{sub 2}O{sub 2} to generate large quantity of • OH radicals and highly promotes reaction kinetics between MB and • OH radicals. Immobilization of hierarchical array catalysts on stainless-steel can prevent particles agglomeration, facilitate the recovery and reuse of the catalysts, which is expected promising applications in wastewater remediation. - Graphical abstract: The in-situ synthesis of Fe{sub 2}O{sub 3} hierarchical arrays on stainless-steel substrates was reported for the first time, which exhibit excellent catalytic activity performance for methylene blue (MB) dye degradation in aqueous solution in the presence of H{sub 2}O{sub 2}. - Highlights: • Fe{sub 2}O{sub 3} hierarchical arrays was prepared by in-situ hydrothermal chemical oxidation. • F{sup −} ions play an important role in the formation of the Fe{sub 2}O{sub 3} hierarchical arrays. • Fe{sub 2}O{sub 3} hierarchical arrays show high catalytic activity to methylene blue degradation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Electrochemical properties of lithium polymer batteries with doped polyaniline as cathode material

Graphical abstract: -- Abstract: Polyaniline (PANI) was doped with different lithium salts such as LiPF{sub 6} and LiClO{sub 4} and evaluated as cathode-active material for application in room-temperature lithium batteries. The doped PANI was characterized by FTIR and XPS measurements. In the FTIR spectra, the characteristic peaks of PANI are shifted to lower bands as a consequence of doping, and it is more shifted in the case of PANI doped with LiPF{sub 6}. The cathodes prepared using PANI doped with LiPF{sub 6} and LiClO{sub 4} delivered initial discharge capacities of 125 mAh g{sup −1} and 112 mAh g{sup −1} and stable reversible capacities of 114 mAh g{sup −1} and 81 mAh g{sup −1}, respectively, after 10 charge–discharge cycles. The cells were also tested using polymer electrolyte, which delivered highest discharge capacities of 142.6 mAh g{sup −1} and 140 mAh g{sup −1} and stable reversible capacities of 117 mAh g{sup −1} and 122 mAh g{sup −1} for PANI-LiPF{sub 6} and PANI-LiClO{sub 4}, respectively, after 10 cycles. The cathode prepared with LiPF{sub 6} doped PANI shows better cycling performance and stability as compared to the cathode prepared with LiClO{sub 4} doped PANI using both liquid and polymer electrolytes.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Preparation and supercapacitor application of the single crystal nickel hydroxide and oxide nanosheets

Graphical abstract: The nickel hydroxide and nickel oxide nanosheets prepared using CTAB at room temperature exhibit a high specific capacitance, prompt charge/discharge rate. - Highlights: • The nickel hydroxide nanosheets were prepared using CTAB at room temperature. • Ni(OH){sub 2} nanosheet can be successfully converted to NiO nanosheet via calcination. • The NiO nanosheet has a specific capacitance of 388 F g{sup −1} at 5 A g{sup −1} in KOH solution. • Anneal temperature impacts capacitive properties as electrode. - Abstract: The single crystalline Ni(OH){sub 2} nanosheets were synthesized by a simple chemical precipitation method using nickel chloride as precursors and ammonia as precipitating agent. The Ni(OH){sub 2} nanosheets were successfully converted to NiO nanosheets via calcination under appropriate conditions. Analytical methods such as X-ray diffraction (XRD) spectra, scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), and Fourier transformed infrared (FTIR) spectra were employed to characterize the morphology and microstructure of the final products. The experimental results revealed that Ni(OH){sub 2} nanosheets were shape-preserved transformed to NiO nanosheets at 250 °C for 24 h. Ni(OH){sub 2} and NiO nanosheets were directly functionalized as supercapacitor electrodes for potential energy storage applications, whose charge–discharge properties, electrochemical impedance spectra, cyclic voltammetry, and cycle performance were examined. The experimental results show that the single-crystalline NiO nanosheets are a promising candidate for the supercapacitor electrode. They exhibit a high specific capacitance, prompt charge/discharge rate.

36 MATERIALS SCIENCE↗
DOE OSTI2013

A new strategy to diminish the 4 V voltage plateau of LiNi{sub 0.5}Mn{sub 1.5}O{sub 4}

Graphical abstract: The annealed sample LiNi{sub 0.5}Mn{sub 1.5}O{sub 4} cannot eliminate the 4-V voltage plateau completely. The Mg-doped compound LiNi{sub 0.5}Mn{sub 1.45}Mg{sub 0.05}O{sub 4} can effectively diminish the 4 V voltage plateau during charge and discharge process. - Highlights: • Mg-doped compound LiNi{sub 0.5}Mn{sub 1.45}Mg{sub 0.05}O{sub 4} was prepared. • The 4 V voltage plateau in the charge–discharge curves of LiNi{sub 0.5}Mn{sub 1.45}Mg{sub 0.05}O{sub 4} was diminished. • Compound LiNi{sub 0.5}Mn{sub 1.45}Mg{sub 0.05}O{sub 4} exhibited good electrochemical properties. - Abstract: As for spinel LiNi{sub 0.5}Mn{sub 1.5}O{sub 4}, there is 4 V voltage plateau in the charge–discharge profiles. This voltage plateau can be reduced by an annealing process, however it is hard to avoid it completely. In this study, a new strategy of partial substitution for Mn by Mg is applied. There is no 4 V voltage plateau in the charge–discharge profiles of Mg-doped compound LiNi{sub 0.5}Mn{sub 1.45}Mg{sub 0.05}O{sub 4}. This compound exhibits good electrochemical properties which can be used as cathode material of lithium ion batteries. At 1 C rate, it can deliver a capacity of around 129 mAh g{sup −1} and remain good cycle performance.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Investigation into the role of silica in lithium polysulfide adsorption for lithium sulfur battery

Highlights: • Amine functionalized silica nanoparticles (AFSN) were prepared. • Polysulfide adsorption studies were carried out with silica nanoparticles and AFSN. • Sulfur cathodes were prepared with SN and AFSN for Li–S batteries. • AFSN showed excellent polysulfide adsorption. - Abstract: A new type of sulfur electrodes with the ability for polysulfide adsorption was prepared by incorporating silica nanoparticles (SN) or amine functionalized silica nanoparticles (AFSN). AFSN was synthesized by a simple and cost-effective method. The functionalization and surface morphology of silica were confirmed with Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM), respectively. Polysulfide adsorption studies were carried out using UV–vis spectrometer, which confirmed the excellent adsorption of polysulfides by AFSN. Interaction of polysulfides with SN or AFSN was studied using FTIR and FT-Raman spectroscopy. The effective polysulfide adsorption by SN and AFSN leads to good and stable cycle performance of lithium sulfur cells. The results show that the incorporation of SN or AFSN with sulfur is a promising method to prepare cathode material for lithium sulfur batteries.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2015

Effects of sulfur loading on the corrosion behaviors of metal lithium anode in lithium–sulfur batteries

Highlights: • The effects of sulfur loading on the corrosion behaviors were investigated systematically. • The corrosion became severer with increasing sulfur loading or cycle times. • The corrosion films are porous and loose and cannot prevent further reaction between lithium and polysulfides. - Abstract: The corrosion behaviors in rechargeable lithium–sulfur batteries come from the reactions between polysulfides and metal lithium anode, and they are significantly influenced by the sulfur loading. While there are limited papers reported on the effects of sulfur loading on the corrosion behaviors. In this paper, the effects have been investigated systematically. The corrosion films consisted of insulating lithium ion conductors are loose and porous, so that the corrosive reactions cannot be hindered. The thickness of the corrosion layers, consequently, increased along with increasing sulfur loading or cycle times. For instance, the thickness of corrosion layers after 50 cycles was 98 μm in the cell with 5 mg sulfur while it reached up to 518 μm when the loading increased to 15 mg. The continuous deposition of corrosion products gave rise to low active materials utilization and poor cycling performance.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Synthesis of polyaniline shell on nickel oxide nanoflake arrays for enhanced lithium ion storage

Graphical abstract: Self-supported NiO/PANI core/shell arrays are prepared by successive electrodeposition methods and exhibit good lithium ion storage with high capacity & stable cycling life. - Highlights: • Construct self-supported porous NiO/PANI core/shell arrays. • Porous NiO/PANI composite arrays show high capacity and good cycling life. • Hierarchical porous structure is favorable for fast ion/electron transfer. - Abstract: Developing conducting polymer/oxide composites are of great importance to construct advanced electrochemical devices. In this work, we report a successive electrodeposition methods to fabricate polyaniline (PANI) on nickel oxide (NiO) nanoflake forming composite core-shell arrays. A thin layer of PANI of ∼10 nm is successfully coated on the surface of NiO nanoflake core. High porosity and enhanced conductivity are obtained in this composite electrode. As anode materials for lithium ion batteries, the NiO/PANI core-shell arrays exhibit weaker polarization and better cycling performance as compared to the bare NiO film. The second discharge capacity of NiO/PANI composite arrays is about 780 mAh g{sup −1} at 0.1 A g{sup −1}, higher than that of the bare NiO film (679 mAh g{sup −1}). The improvements of the electrochemical properties are attributed to the PANI, which forms a uniform conductive network leading to improved electrochemical performance.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Catalytic materials for lithium-sulfur batteries: mechanisms, design strategies and future perspective

Lithium-sulfur batteries (LSBs) are attractive candidates for post-lithium-ion battery technologies because of their ultrahigh theoretical energy density and low cost of active cathode materials. However, the commercialization of LSBs remains extremely challenging primarily due to poor cycling performance and safety concerns, which are inherently caused by low conductivity of S 8 and Li 2 S, severe polysulfide shuttling, and high polarization by solid Li 2 S 2 /Li 2 S deposition. Catalytic materials could facilitate the large-scale practical application of LSBs by overcoming all these challenges. In this review, we investigate the sulfur species evolution in LSBs and explore the roles of catalytic materials in charge/discharge processes, highlighting the catalysis of solid S 8 to liquid polysulfides and solid Li 2 S 2 to Li 2 S. Furthermore, we offer systematic strategies from atomic to macro levels, including defect engineering, morphology engineering and catalyst compositing, to enhance catalysis efficiency in terms of sulfur supercooling, fast charge transfer, thiosulfate generation, disulfide bond cleavage, tuneable Li 2 S growth and Li 2 S decomposition enhancement. Finally, the design and availability of the proposed catalytic materials will further advance LSB technology from coin cells and pouch cells to the subsequent commercialization scale.

25 ENERGY STORAGE↗
DOE OSTI2019

Carbon-pore-sheathed cobalt nanoseeds: An exceptional and durable bifunctional catalyst for zinc-air batteries

Exceptional and durable catalysts for Zinc-air batteries are plagued by nanoparticle agglomeration. As a proof-of-concept, we designed carbon-pore-sheathed cobalt nanoseeds by loading cobalt nanoparticles into N-doped defective carbon pores. Introduced N-doping, Co-N-C bond and graphitic/graphenic carbon defects endow the catalyst with exceptional catalytic activity. Most importantly, the design of Co confined within carbon pores effectively solved the dilemma of nanomaterial stability. By balancing the high catalytic activity and stable cyclability, this unique catalyst is among the outstanding bifunctional catalysts, with a high ORR half-wave potential of 0.847 V and a low OER potential at 10 mA/cm 2 of 1.593 V. As demonstrated in the full cell, a peak power density of 135 mW/cm 2 at a current density of 200 mA/cm 2 and 450 h of stable cycling performance without fading at a current density of 30 mA/cm 2 was delivered.

25 ENERGY STORAGE↗
DOE OSTI2021

Superior long-term cycling of high-voltage lithium-ion batteries enabled by single-solvent electrolyte

A new single-solvent electrolyte system comprising lithium bis(fluorosuflonyl) imide (LiFSI) and beta-fluorinated sulfone (TFPMS) was designed to enable very stable long-term cycling of high-voltage lithium-ion batteries. Compared to other fluorinated solvents such as alpha-fluorinated sulfone (FMES) and fluorinated carbonate (FEMC), which are prone to reduction on the graphite anode, the LiFSI-TFPMS system displayed outstanding compatibility with graphite. While regular carbonate and sulfone from the LiFSI electrolyte system are compatible with the graphite anode, their high solvating power not only induces severe corrosion on the aluminum cathode current collector at high voltage, but also renders a low aggregation level at a normal salt concentration (about 1.0 M), resulting in the formation of an unstable solid-electrolyte interphase (SEI) on the graphite anode. Owing to the low solvating power of TFPMS, the aggregation level of the LiFSI-TFPMS system is relatively high even at normal salt concentration, which not only facilitates the formation of a robust SEI by the sacrificial decomposition of LiFSI, but also suppresses the aluminum corrosion of the LiFSI electrolyte system at high voltage. Together with the high intrinsic anodic stability of TFPMS, the superior cycling performance of graphite parallel to LiNi 0.6 Co 0.2 Mn 0.2 O 2 cells was achieved by employing the non-flammable LiFSI-TFPMS single-solvent electrolyte system.

25 ENERGY STORAGE↗
DOE OSTI2022

Networks and interfaces as catalysts for polymer materials innovation

Autonomous experimental systems offer a compelling glimpse into a future where closed-loop, iterative cycles—performed by machines and guided by artificial intelligence (AI) and machine learning (ML)—play a foundational role in materials research and development. This perspective draws attention to the roles of networks and interfaces—of and between humans and machines—for the purpose of generating knowledge and accelerating innovation. Polymers, a class of materials with massive global impact, present a unique opportunity for the application of informatics and automation to pressing societal challenges. To develop these networks and interfaces in polymer science, the Community Resource for Innovation in Polymer Technology (CRIPT)—a polymer data ecosystem based on novel polymer data model, representation, search, and visualization technologies—is introduced. The ongoing co-design efforts engage stakeholders in industry, academia, and government to uncover rapidly actionable, high-impact opportunities to build networks, bridge interfaces, and catalyze innovation in polymer technology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Phase Stability and Kinetics of Topotactic Dual Ca 2+ –Na + Ion Electrochemistry in NaSICON NaV 2 (PO 4 ) 3

Recent reports of reversible calcium plating and stripping have rekindled interest in the development of Ca-ion batteries (CIBs) as next-generation energy storage devices. This technology has the potential to overcome the limitations of conventional Li-ion batteries, but CIBs are plagued by a paucity of suitable cathode materials. To date, NaSICON-structured NaV 2 (PO 4 ) 3 has been demonstrated as a successful cathode candidate, exhibiting reversible (de)intercalation of 0.6 mol Ca 2+ along with stable cycling performance. However, a complex multiphase mixture forms on discharge so the Ca-ion charge storage mechanism in the NaSICON framework is poorly understood. Here in this work, we report on an investigation of the structure and/or Na + /Ca 2+ environment(s) of a variety of chemically prepared NaSICON Ca x Na y V 2 (PO 4 ) 3 phases which were characterized using synchrotron XRD, SEM-EDS, 23 Na NMR, and TEM. Highly calciated CaV 2 (PO 4 ) 3 , Ca 1.5 V 2 (PO 4 ) 3 , and CaNaV 2 (PO 4 ) 3 phases can be prepared at high temperature, but -unlike Ca 0.6 NaV 2 (PO 4 ) 3 -these materials are electrochemically inactive. To better understand the fundamental factors impacting successful Ca 2+ electrochemistry in this system, DFT was employed to examine the Ca x Na y V 2 (PO 4 ) 3 phase diagram and Ca 2+ diffusion mechanism. Theoretical insights show that phase separation into Na-rich and Ca-rich phases is a reason for the capacity limitation and demonstrate that Na + ions in the host materials assist the migration of neighboring Ca 2+ ions, enabling reversible electrochemistry in Ca x Na y V 2 (PO 4 ) 3 . This investigation of fundamental principles affecting reversible Ca 2+ (de)intercalation in Ca x Na y V 2 (PO 4 ) 3 allows for the development of design principles to enable the discovery of a variety of successful cathodes for CIBs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

A new anion receptor for improving the interface between lithium- and manganese-rich layered oxide cathode and the electrolyte

Surface degradation on cycled lithium-ion battery cathode particles is governed not only by intrinsic thermodynamic properties of the material but also, oftentimes more predominantly, by the side reactions with the electrolytic solution. A superior electrolyte inhibits these undesired side reactions on the cathode and at the electrolyte interface, which consequently minimizes the deterioration of the cathode surface. The present study investigates a new boron-based anion receptor, tris(2,2,2-trifluoroethyl)borate (TTFEB), as an electrolyte additive in cells containing a lithium- and manganese-rich layered oxide cathode, Li 1.16 Ni 0.2 Co 0.1 Mn 0.54 O 2 . Our electrochemical studies demonstrate that the cycling performance and Coulombic efficiency are significantly improved because of the additive, in particular, under elevated temperature conditions. Spectroscopic analyses revealed that the addition of 0.5 wt % TTFEB is capable of reducing the content of lithium-containing inorganic species within the cathode-electrolyte interphase layer and minimizing the reduction of tetravalent Mn4+ at the cathode surface. Furthermore, our work introduces a novel additive highly effective in improving lithium-ion battery performance, highlights the importance in preserving the surface properties of cathode materials, and provides new insights on the working mechanism of electrolyte additives.

25 ENERGY STORAGE↗
DOE OSTI2017

Correlations between Transition Metal Chemistry, Local Structure and Global Structure in Li 2 Ru 0.5 Mn 0.5 O 3 Investigated in a Wide Voltage Window

Li 2 Ru 0.5 Mn 0.5 O 3 , a high capacity lithium rich layered cathode material for lithium-ion batteries, was subject to comprehen-sive diagnostic studies including in situ/ex situ X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), pair distribu-tion function (PDF) and high resolution scanning transmission electron microscopy (STEM) analysis, to understand the cor-relations between transition metal chemistry, structure and lithium storage electrochemical behavior. Ru-Ru dimers have been identified in the as-prepared sample and found to be preserved upon prolonged cycling. Presence of these dimers, which are likely caused by the delocalized nature of 4d electrons, is found to favor the stabilization of the structure in a lay-ered phase. The in situ XAS results confirm the participation of oxygen redox into the charge compensation at high charge voltage, and the great flexibility of the covalent bond between Ru and O may provide great reversibility of the global struc-ture despite of the significant local distortion around Ru. In contrast, the local distortion around Mn occurs at low discharge voltage and is accompanied by a “layered to 1T” phase transformation, which is found to be detrimental to the cycle per-formances. It is clear that the changes of local structure around individual transition metal cations respond separately and differently to lithium intercalation/deintercalation. Here, cations with the capability to tolerate the lattice distortion will benefit for maintaining the integrality of the crystal structure and therefore is able to enhance the long-term cycling performance of the electrode materials.

25 ENERGY STORAGE↗
DOE OSTI2020

Calculated Reduction Potentials of Electrolyte Species in Lithium–Sulfur Batteries

In this work, reduction potentials of electrolyte molecules in the lithium–sulfur (Li/S) battery and their variations in several solvent environments are studied using the density functional theory method with Dunning’s triple-ζ correlation consistent basis set. Reliable reduction potential values are key for electrolyte additive design needed for suppressing polysulfide dissolution shuttle mechanism, resulting in poor cycle performance and severe self-discharge of the Li/S battery. Although isolated electrolyte molecules have reduction potentials outside the operating voltage range of the Li/S battery, complexation with other electrolyte species enables the electrolyte molecules to be reduced within the operating voltage range. Among the electrolyte species considered in this study, bis(fluorosulfonyl)imide (FSI – ) and fluoroethylene carbonate (FEC) yield reduction potentials within the expected range, suggesting the development of fluorine-containing additives as a promising line of research.

25 ENERGY STORAGE↗
DOE OSTI2020

Nature of Terminating Hydroxyl Groups and Intercalating Water in Ti 3 C 2 T x MXenes: A Study by 1 H Solid-State NMR and DFT Calculations

Since the discovery of two-dimensional transition metal carbides, referred to as MXenes, research efforts targeted their applications in energy storage, as lithium-ion batteries and supercapacitors. This interest is attributable to MXenes’ large volumetric capacitance, high rate handling capability and stable cycling performance, which largely rely on surface chemistry provided by the terminating groups, such as -OH, -O, and -F. However, the atomic-scale characterization of these surface terminations challenges the diffraction methods. Solid-state (SS)NMR spectroscopy, especially 1 H SSNMR, is a promising approach for scrutinizing the surface terminations and the intercalated water in an atomistic-scale, yet only a few SSNMR studies in MXenes have been reported to date offering conflicting results and limited understanding of -OH terminations. Here, we used 1 H SSNMR experiments in concert with the DFT calculations of NMR parameters to identify multiple types of -OH groups, residing on the external and internal surfaces, in a commonly studied MXene, Ti 3 C 2 T x . The study also identifies bulk-like water trapped between the MXene flakes and interfacial water stranded on the surface. Lastly, two-dimensional 1 H -1 H correlation spectra elucidated the water-surface interactions and the mechanism of de-intercalation of water upon annealing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Highly Conductive Iodine and Fluorine Dual-Doped Argyrodite Solid Electrolyte for Lithium Metal Batteries

Sulfide-type argyrodite solid electrolytes (SEs) with halide doping have attracted serious interest. Although other halides such as Cl and Br have been found to enhance Li-ion transport in argyrodites, the direct synthesis of efficiently conductive Li 6 PS 5 I without postprocessing has rarely been investigated. In this work, we report the one-step synthesis of highly conductive Li 6 PS 5 I with an impressive ionic conductivity of 2.5 × 10 –4 S cm –1 at room temperature through a solvent-based method. Moreover, by introducing F – to partially replace I – , hybrid-doped argyrodites Li 6 PS 5 F x I 1–x (x = 0.25, 0.5, 0.75) have been synthesized. Li 6 PS 5 F 0.25 I 0.75 achieves the highest conductivity of 3.5 × 10 –4 S cm –1 due to the energetic preference for anion-disordering among F – /I – and S 2– , which facilitate faster Li transport as supported by density functional theory (DFT) calculations. With higher F content in argyrodites, Li 6 PS 5 F 0.75 I 0.25 displays the best electrochemical stability toward Li metal, as evidenced by long-term stable cycling in Li symmetric cells up to 1100 h. Solid-state Li metal batteries with an active cathode of Li 4 Ti 5 O 12 (LTO) display an initial specific capacity of 140 mAh g –1 and remain at 105 mAh g –1 after 200 cycles, suggesting great battery cycling performance. Furthermore, this research has developed new compositions in the argyrodite SE family which could lead to advancements in the development of solid-state Li metal batteries.

25 ENERGY STORAGE↗
DOE OSTI2018

On Disrupting the Na + -Ion/Vacancy Ordering in P2-Type Sodium–Manganese–Nickel Oxide Cathodes for Na + -Ion Batteries

An investigation of the electrochemical and structural properties of layered P2-Na 0.62 Mn 0.75 Ni 0.25 O 2 is presented. The effect of changing the Mn:Ni ratio (3:1) from what is found in Na 0.67 Mn 0.67 Ni 0.33 O 2 (2:1) and consequently the introduction of a third metal center (Mn 3+ ) was investigated. X-ray diffraction ( in-situ and powder) revealed the lack of Na+-ion/vacancy ordering at the relevant sodium contents (x = 0.33, 0.5 and 0.67). The Mn 3+ in Na 0.62 Mn 0.75 Ni 0.25 O 2 introduces defects into the Ni-Mn inter-plane charge order that in turn disrupts the ordering within the Na-plane. The material underwent a P2-O2 and P2-P2’ phase transition at high (4.2 V) and low (~ 1.85 V) voltages, respectively. The material was tested at several different voltage ranges in order to understand the effect of the phase transitions on the capacity retention. Interestingly, the inclusion of both phase transitions demonstrated comparable cycling performance to when both phase transitions were excluded. As a result, excellent rate performance was demonstrated between 4.3 – 1.5 V with a specific capacity of 120 mAh/g delivered at 500 mA/g current density.

25 ENERGY STORAGE↗