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At least 289 records · Page 16

A dual strategy for improving lithium storage performance, a case of Fe{sub 2}O{sub 3}

Graphical abstract: The α-Fe{sub 2}O{sub 3} nanoellipse with180–230 nm (edge length) and 140–170 nm (edge width) has been synthesize and tested as anode material for LIBs. The α-Fe{sub 2}O{sub 3} nanoellipse electrode with sodium alginate (SA) binder exhibits greatly enhanced performance for lithium storage. - Highlights: • α-Fe{sub 2}O{sub 3} nanoellipses were fabricated by a simple hydrothermal method with glycine. • The elliptical α-Fe{sub 2}O{sub 3}-SA electrode exhibits enhanced lithium storage performance. • The reason for the enhanced performance of elliptical α-Fe{sub 2}O{sub 3}-SA was investigated. - Abstract: In this paper, we developed a dual strategy, the nanostructure engineering of active material and the proper choice of binder, to achieve excellent lithium storage performance of transition metal oxides. α-Fe{sub 2}O{sub 3} nanoellipses with a mean size of 180–230 nm (edge length) and 140–170 nm (edge width) were fabricated by a simple hydrothermal method in the presence of glycine. When tested as anode material for lithium ion batteries (LIBs), the α-Fe{sub 2}O{sub 3} nanoellipse electrode with sodium alginate (SA) binder exhibits greatly enhanced performance for lithium storage. The capacity could be retained as high as 1164 mA h g{sup −1} at a current density of 100 mA g{sup −1} for over 60 cycles. Even cycled at high current densities of 2000–5000 mA g{sup −1}, high capacities of 443–628 mA h g{sup −1} can be achieved, whereas the electrode with the conventional poly(vinylidene fluoride) (PVDF) binder suffers from rapid capacity decay under the same test conditions.

36 MATERIALS SCIENCE↗

Large-format battery anodes comprising silicon particles

Large-scale anodes containing high weight percentages of silicon suitable for use in lithium-ion energy storage devices and batteries, and methods of manufacturing the same, are described. The anode material described herein can include a film cast on a current collector substrate, with the film including a plurality of active material particles and a conductive polymer membrane coated over the active material particles. In some embodiments, the conductive polymer membrane comprises polyacrylonitrile (PAN). The method of manufacturing the anode material can include preparation of a slurry including the active material particles and the conductive polymer material, casting the slurry on a current collector substrate, and subjecting the composite material to drying and heat treatments.

25 ENERGY STORAGE↗

Large-format battery anodes comprising silicon particles

Large-scale anodes containing high weight percentages of silicon suitable for use in lithium-ion energy storage devices and batteries, and methods of manufacturing the same, are described. The anode material described herein can include a film cast on a current collector substrate, with the film including a plurality of active material particles and a conductive polymer membrane coated over the active material particles. In some embodiments, the conductive polymer membrane comprises polyacrylonitrile (PAN). The method of manufacturing the anode material can include preparation of a slurry including the active material particles and the conductive polymer material, casting the slurry on a current collector substrate, and subjecting the composite material to drying and heat treatments.

Evans, Tyler↗

Boosting Sodium Storage in TiO 2 Nanotube Arrays through Surface Phosphorylation

In this paper, sodium–ion batteries (SIBs) offer a promise of a scalable, low–cost, and environmentally benign means of renewable energy storage. However, the low capacity and poor rate capability of anode materials present an unavoidable challenge. In this work, it is demonstrated that surface phosphorylated TiO 2 nanotube arrays grown on Ti substrate can be efficient anode materials for SIBs. Fabrication of the phosphorylated nanoarray film is based on the electrochemical anodization of Ti metal in NH 4 F solution and subsequent phosphorylation using sodium hypophosphite. The phosphorylated TiO 2 nanotube arrays afford a reversible capacity of 334 mA h g –1 at 67 mA g –1 , a superior rate capability of 147 mA h g –1 at 3350 mA g –1 , and a stable cycle performance up to 1000 cycles. In situ X–ray diffraction and transmission electron microscopy reveal the near–zero strain response and robust mechanical behavior of the TiO 2 host upon (de)sodiation, suggesting its excellent structural stability in the Na+ storage application.

25 ENERGY STORAGE↗

Validating corrosion models: A comparison of governing equations

Experimental validation of Finite Element Method (FEM) models varying electrochemical governing equations, inclusion of chemical reactions, and time on the resultant damage profile for two galvanic couples is explored. Two anode materials (Magnesium AZ31 and Carbon Steel) in contact with a cathode (Stainless Steel 304 L) were modeled in/exposed to NaCl (1 and 0.1 M respectively for the anode materials) for up to one week. The physics approach, inclusion of chemical reactions, and the boundary conditions required to accurately represent the damage profile in FEM models depended on the galvanic couple materials and, ultimately, the corrosion rate. For high rates of corrosion (i.e., magnesium anode), the Nernst-Planck equation with Electroneutrality was sufficient to describe the damage, while, for low rates of corrosion (i.e., carbon steel anode), the Laplace equation was sufficient. In all cases, the most complete governing equation (Nernst-Planck-Poisson Equation) was not necessary to accurately describe the damage. Precipitation reactions in solution also played a critical role in the predicted damage profile, especially for high corrosion rate systems. Finally, for short time periods (< 6 h), the choice of governing equations does not significantly influence damage profile results. Overall, the choice of physics to reduce error in simulations relies on the boundary conditions, geometry, conductivity of the solution, electrochemical potential differences, and time of exposure. The above results are discussed with regard to accuracy and computational savings.

Carbon steel↗

SnCo–CMK nanocomposite with improved electrochemical performance for lithium-ion batteries

Highlights: • The SnCo–CMK nanocomposite was synthesized using mesoporous carbon as nano-reactor. • Ultrafine SnCo nanoparticles distribute both inside and outside of mesopore channels. • The SnCo–CMK nanocomposite is an alternative anode material for Li-ion intercalation. • A high reversible capacity of 562 mAh g{sup −1} is maintained after 60 cycles at 100 mA g{sup −1}. - Abstract: In the present work, SnCo–CMK nanocomposite was successfully synthesized for the first time via a simple nanocasting route by using mesoporous carbon as nano-reactor. The nanocomposite was then characterized by means of X-ray diffraction (XRD), thermogravimetric analysis (TG), N{sub 2} adsorption–desorption, scanning and transmission electron microscopy (SEM/TEM) respectively. Furthermore, the SnCo–CMK nanocomposite exhibited large reversible capacities, excellent cycling stability and enhanced rate capability when employed as an anode material for lithium-ion batteries. A large reversible capacity of 562 mA h g{sup −1} was obtained after 60 cycles at a current density of 0.1 A g{sup −1} which is attributed to the structure of ‘meso-nano’ SnCo–CMK composite. This unique structure ensures the intimate contact between CMK and SnCo nanoparticles, buffers the large volume expansion and prevents the aggregation of the SnCo nanoparticles during cycling, leading to the excellent cycling stability and enhanced rate capability.

36 MATERIALS SCIENCE↗

Scalable synthesis of nanoporous silicon microparticles for highly cyclable lithium-ion batteries

Nanoporous silicon is a promising anode material for high energy density batteries due to its high cycling stability and high tap density compared to other nanostructured anode materials. However, the high cost of synthesis and low yield of nanoporous silicon limit its practical application. Here, we develop a scalable, low-cost top-down process of controlled oxidation of Mg 2 Si in the air, followed by HCl removal of MgO to generate nanoporous silicon without the use of HF. By controlling the synthesis conditions, the oxygen content, grain size and yield of the porous silicon are simultaneously optimized from commercial standpoints. In situ environmental transmission electron microscopy reveals the reaction mechanism; the Mg 2 Si microparticle reacts with O 2 to form MgO and Si, while preventing SiO 2 formation. Owing to the low oxygen content and microscale secondary structure, the nanoporous silicon delivers a higher initial reversible capacity and initial Coulombic efficiency compared to commercial Si nanoparticles (3,033 mAh/g vs. 2,418 mAh/g, 84.3% vs. 73.1%). Synthesis is highly scalable, and a yield of 90.4% is achieved for the porous Si nanostructure with the capability to make an excess of 10 g per batch. Our synthetic nanoporous silicon is promising for practical applications in next generation lithium-ion batteries.

25 ENERGY STORAGE↗

Investigation of SiO x anode fading mechanism with limited capacity cycling

Silicon suboxide (SiO x ) is one of the promising anode materials for the next-generation lithium-ion batteries. However, SiO x has a severe capacity fading problem during cycling. It is thus desired to investigate the detailed fading mechanisms of SiO x anode materials. In this study, limited capacity cycling was employed to examine the electrochemical behaviors of the SiO x anode, and the lithiation/delithiation cycling was limited within a range of 10% theoretical capacity. This strategy minimizes the volume variation of SiO x materials upon charging/discharging, which helps to reveal their decay factors other than volume fluctuation. It is demonstrated that the instability of the SiO x surface during cycling was likely a parallel factor of active material fading, which seems to cause unfavored electrode interface rearrangements with lowered electric conductivity.

electric vehicles↗

A Novel Approach to Synthesize Micrometer-Sized Porous Silicon as a High Performance Anode for Lithium-Ion Batteries

Porous structured silicon (p-Si) has been recognized as one of the most promising anodes for Li-ion batteries. However, many available methods to synthesize p-Si are difficult to scale up due to their high production cost. Here we introduce a new scalable approach to obtain spherical micrometer-sized silicon with unique porous structure by using a microemulsion and magnesiothermic reduction method. The spherical micron-sized p-Si particles prepared by this approach consist of highly aligned nano-sized silicon and exhibit a tap density close to that of bulk Si particles. They have demonstrated significantly improved electrochemical stability compared to nano-Si. Well controlled void space and a highly graphitic carbon coating on the p-Si particles enable good stability of the structure and low overall resistance, thus resulting in a Si-based anode with high capacity (~1467 mAh g-1 at 1C), enhanced cycle life (200 cycles with 90% capacity retention), and high rate capability (~650 mAh g-1 at 5C). This scalable approach may also be generalized to prepare other hierarchical structured high capacity anode materials for constructing high energy density lithium ion batteries.

Jia, Haiping↗

Tailored Organic Electrode Material Compatible with Sulfide Electrolyte for Stable All‐Solid‐State Sodium Batteries

Abstract All‐solid‐state sodium batteries (ASSSBs) with nonflammable electrolytes and ubiquitous sodium resource are a promising solution to the safety and cost concerns for lithium‐ion batteries. However, the intrinsic mismatch between low anodic decomposition potential of superionic sulfide electrolytes and high operating potentials of sodium‐ion cathodes leads to a volatile cathode–electrolyte interface and undesirable cell performance. Here we report a high‐capacity organic cathode, Na 4 C 6 O 6 , that is chemically and electrochemically compatible with sulfide electrolytes. A bulk‐type ASSSB shows high specific capacity (184 mAh g −1 ) and one of the highest specific energies (395 Wh kg −1 ) among intercalation compound‐based ASSSBs. The capacity retentions of 76 % after 100 cycles at 0.1 C and 70 % after 400 cycles at 0.2 C represent the record stability for ASSSBs. Additionally, Na 4 C 6 O 6 functions as a capable anode material, enabling a symmetric all‐organic ASSSB with Na 4 C 6 O 6 as both cathode and anode materials.

Chi, Xiaowei↗

Size dependent polaronic conduction in hematite

Lithium Ion Batteries have been attracted as the major renewable energy source for all portable electronic devices because of its advantages like superior energy density, high theoretical capacity, high specific energy, stable cycling and less memory effects. Recently, α-Fe{sub 2}O{sub 3} has been considered as a potential anode material due to high specific capacity, low cost, high abundance and environmental benignity. We have synthesized α-Fe{sub 2}O{sub 3} with various sizes by using the ball milling and sol-gel procedure. Here, we report the dc conductivity measurement for the crystallite size ranging from 15 nm to 50 nm. It has been observed that the enhancement in the polaronic conductivity nearly two orders in magnitude while reducing the crystallite size from bulk into nano scale level. The enhancement in the conductivity is due to the augmented to compressive strain developed in the material which leads to pronounced decrease in the hopping length of polarons. Thus, nanocrystaline α-Fe{sub 2}O{sub 3} may be a better alternative anode material for lithium ion batteries than earlier reported systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NiF2/NaF:CaF2/Ca Solid-State High-Temperature Battery Cells

Experiments and theoretical study have demonstrated the promise of all-solid-state, high-temperature electrochemical battery cells based on NiF2 as the active cathode material, CaF2 doped with NaF as the electrolyte material, and Ca as the active anode material. These and other all-solid-state cells have been investigated in a continuing effort to develop batteries for instruments that must operate in environments much hotter than can be withstood by ordinary commercially available batteries. Batteries of this type are needed for exploration of Venus (where the mean surface temperature is about 450 C), and could be used on Earth for such applications as measuring physical and chemical conditions in geothermal wells and oil wells. All-solid-state high-temperature power cells are sought as alternatives to other high-temperature power cells based, variously, on molten anodes and cathodes or molten eutectic salt electrolytes. Among the all-solid-state predecessors of the present NiF2/NaF:CaF2/Ca cells are those described in "Solid-State High-Temperature Power Cells" (NPO-44396), NASA Tech Briefs, Vol. 32, No. 5 (May 2008), page 40. In those cells, the active cathode material is FeS2, the electrolyte material is a crystalline solid solution of equimolar amounts of Li3PO4 and LiSiO4, and the active anode material is Li contained within an alloy that remains solid in the intended high operational temperature range.

West, William↗

New Insights on the Structure of Electrochemically Deposited Lithium Metal and Its Solid Electrolyte Interphases via Cryogenic TEM

Lithium metal has been considered as the “holy grail” anode material for rechargeable batteries though the dendritic growth and low Coulombic efficiency (CE) have crippled its practical use for decades. Its high chemical reactivity and low stability make it difficult to explore the intrinsic chemical and physical properties of the electrochemically deposited lithium (EDLi) and its accompanied solid electrolyte interphase (SEI). To prevent the dendritic growth and enhance the electrochemical reversibility, it is crucial to understand the nano- and meso- structures of EDLi. However, Li metal is very sensitive to beam damage and has low contrast for commonly used characterization techniques such as electron microscopy. Inspired by biological imaging techniques, this work demonstrates the power of cryogenic (cryo)- electron microscopy to reveal the detailed structure of EDLi and the SEI composition at the nano scale while minimizing beam damage during imaging. Surprisingly, the results show that the nucleation dominated EDLi (five minutes at 0.5 mA cm-2) is amorphous while there is some crystalline LiF present in the SEI. The EDLi grown from various electrolytes with different additives exhibits distinctive surface properties. Consequently, these results highlight the importance of the SEI and its relationship with the CE. Our findings not only illustrate the capabilities of cryogenic microscopy for beam (thermal)-sensitive materials, but it yields crucial structural information of the EDLi evolution with and without electrolyte additives.

electrochemical deposition↗

Enhanced Li- and Na-storage in Sb-Graphene nanocomposite anodes

Highlights: • Antimony-graphene nanocomposite (Sb-GNP) was prepared by a wet-chemical approach. • Sb-GNP exhibits the well-dispersed Sb nanoparticles anchored on the graphenes. • Sb-GNP shows highly reversible capacities in both Li- and Na-storage. - Abstract: Antimony-graphene nanocomposite (Sb-GNP) was prepared from commercially available graphene nanoplatelets (GNPs) by a simple wet-chemical route at room temperature, and systematically investigated as an anode material for both lithium- and sodium-ion batteries (LIBs and NIBs). The microstructural features of Sb-GNP, and of pure Sb nanoparticles prepared without addition of GNPs, were characterized using X-ray diffraction, field-emission scanning electron microscopy, and high-resolution transmission electron microscopy. The successful formation of a nanocomposite structure was observed for Sb-GNP; the Sb nanoparticles are well dispersed and anchored on graphene nanoplatelets without significant aggregation of Sb nanoparticles, in contrast to the pure Sb nanoparticles. Furthermore, galvanostatic studies revealed that Sb-GNP displays better Li- and Na-storage performance than the pure Sb nanoparticles when utilized as an anode material. The enhanced electrochemical performance can be attributed to the effects of nanocomposite formation with GNPs.

36 MATERIALS SCIENCE↗

Nickel-Tin Electrode Materials for Nonaqueous Li-Ion Cells

Experimental materials made from mixtures of nickel and tin powders have shown promise for use as the negative electrodes of rechargeable lithium-ion electrochemical power cells. During charging (or discharging) of a lithium-ion cell, lithium ions are absorbed into (or desorbed from, respectively) the negative electrode, typically through an intercalation or alloying process. The negative electrodes (for this purpose, designated as anodes) in state-of-the-art Li-ion cells are made of graphite, in which intercalation occurs. Alternatively, the anodes can be made from metals, in which alloying can occur. For reasons having to do with the electrochemical potential of intercalated lithium, metallic anode materials (especially materials containing tin) are regarded as safer than graphite ones; in addition, such metallic anode materials have been investigated in the hope of obtaining reversible charge/discharge capacities greater than those of graphite anodes. However, until now, each of the tin-containing metallic anode formulations tested has been found to be inadequate in some respect.

Ehrlich, Grant M.↗

Synthesis, characterization and mechanical properties of NiO - GDC20 (Ce{sub 0.8}Gd{sub 0.2}O{sub 1.9}) nano composite anode for solid oxide fuel cells

In the present research work, X (NiO) +1-X(Ce{sub 0.8}Gd{sub 0.2}O{sub 1.9}) where X = 30,40 and 45 wt% Nano Composite Anodes are synthesized for low temperature operating solid oxide fuel cells (SOFC). NiO and Ce{sub 0.8}Gd{sub 0.2}O{sub 1.9} (GDC20) are synthesized by sol-gel citrate method and the nanopowders of NiO, GDC20 were calcined from 650 °c to 750 °c. For anode materials, pelletized the nanocomposites of X(NiO)+ (1-X) GDC20 (X = 30,40,45 wt.%) and sintered at 1200 °c. systematic study of atomic structure, purity, phase and structural parameters such as Lattice parameters, crystallite size of as-synthesized nanopowders and anode materials were carried out by XRD and SEM. For mechanical strength, Vickers micro-hardness of anode composites were estimated and observed that micro-hardness of composites were increasing with NiO wt.% and the density of sintered samples, which is varying from 4.35 to 5.54 Gpa at 500g load.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

UiO-66 Metal–Organic Framework as an Anode for a Potassium-Ion Battery: Quantum Mechanical Analysis

The natural abundance of potassium in the earth’s crust is 1000 times higher than that of lithium, so energy technologies built on potassium are more sustainable. Potassium-ion batteries have attracted considerable attention because of their relatively low cost and high operating potential, but questions remain about the best anode material for such batteries. Here, in this paper, we report first-principles computations based on density functional theory to investigate the performance of the UiO-66 metal–organic framework as an anode material for potassium-ion batteries; the goal is to provide a fundamental understanding of metal–organic framework (MOF)-based electrodes to guide the design and development of high-performance potassium-ion batteries. Our study includes the stability and electronic properties of potassiated structures and the mechanisms of potassium intercalation and diffusion in the framework. The results indicate that UiO-66 has a maximum specific capacity of 644 mAh/g as the anode of a potassium-ion battery. During potassiation, we observe charge transfer from potassium to carbon or oxygen of UiO-66 near the intercalated K. During K diffusion, the K migrates along the UiO-66 framework with a maximal migration energy barrier of 0.377 eV in the optimal pathway, which is much lower than the barriers for Li and Na diffusion in UiO-66. The diffusion coefficient of K in the anode is several orders of magnitude larger than those of Li and Na. This favors potassium ions over lithium ions or sodium ions when UiO-66 is the anode.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗