All-in-one assembly based on 3D-intertangled and cross-jointed architectures of Si/Cu 1D-nanowires for lithium ion batteries

All-in-one assemblies of separator, electrode and current collector (SECA) for lithium ion batteries are presented by using 1D nanowires of Si and Cu (nwSi and nwCu). Even without binders, integrity of SECA is secured via structural joints based on ductility of Cu as well as entanglement of nwSi and nwCu. By controlling the ratio of the nanowires, the number of contact points and voids accommodating volume expansion of Si active material are tunable. Zero volume expansion and high energy density are simultaneously achievable by the architectureopen0

Nanoporous Films and Nanostructure Arrays Created by Selective Dissolution of Water-Soluble Materials.

Highly porous thin films and nanostructure arrays are created by a simple process of selective dissolution of a water-soluble material, Sr3Al2O6. Heteroepitaxial nanocomposite films with self-separated phases of a target material and Sr3Al2O6 are first prepared by physical vapor deposition. NiO, ZnO, and Ni1- x Mg x O are used as the target materials. Only the Sr3Al2O6 phase in each nanocomposite film is selectively dissolved by dipping the film in water for 30 s at room temperature. This gentle and fast method minimizes damage to the remaining target materials and side reactions that can generate impurity phases. The morphologies and dimensions of the pores and nanostructures are controlled by the relative wettability of the separated phases on the growth substrates. The supercapacitor properties of the porous NiO films are enhanced compared to plain NiO films. The method can also be used to prepare porous films or nanostructure arrays of other oxides, metals, chalcogenides, and nitrides, as well as films or nanostructures with single-crystalline, polycrystalline, or amorphous nature

Breathing silicon anodes for durable high-power operations

Silicon anode materials have been developed to achieve high capacity lithium ion batteries for operating smart phones and driving electric vehicles for longer time. Serious volume expansion induced by lithiation, which is the main drawback of silicon, has been challenged by multi-faceted approaches. Mechanically rigid and stiff polymers (e.g. alginate and carboxymethyl cellulose) were considered as the good choices of binders for silicon because they grab silicon particles in a tight and rigid way so that pulverization and then break-away of the active mass from electric pathways are suppressed. Contrary to the public wisdom, in this work, we demonstrate that electrochemical performances are secured better by letting silicon electrodes breathe in and out lithium ions with volume change rather than by fixing their dimensions. The breathing electrodes were achieved by using a polysaccharide (pullulan), the conformation of which is modulated from chair to boat during elongation. The conformational transition of pullulan was originated from its a glycosidic linkages while the conventional rigid polysaccharide binders have beta linkagesopen1

Superoxide stability for reversible Na-O2 electrochemistry

Stabilizing superoxide (O-2(-)) is one of the key issues of sodium-air batteries because the superoxide-based discharge product (NaO2) is more reversibly oxidized to oxygen when compared with peroxide (O-2(2-)) and oxide (O2-). Reversibly outstanding performances of sodium-oxygen batteries have been realized with the superoxide discharge product (NaO2) even if sodium peroxide (Na2O2) have been also known as the discharge products. Here we report that the Lewis basicity of anions of sodium salts as well as solvent molecules, both quantitatively represented by donor numbers (DNs), determines the superoxide stability and resultantly the reversibility of sodium-oxygen batteries. A DN map of superoxide stability was presented as a selection guide of salt/solvent pair. Based on sodium triflate (CF3SO3-)/dimethyl sulfoxide (DMSO) as a high-DN-pair electrolyte system, sodium ion oxygen batteries were constructed. Pre-sodiated antimony (Sb) was used as an anode during discharge instead of sodium metal because DMSO is reacted with the metal. The superoxide stability supported by the high DN anion/solvent pair (CF3SO3-/DMSO) allowed more reversible operation of the sodium ion oxygen batteries

A Biomimetic Superoxide Disproportionation Catalyst for Anti-Aging Lithium-Oxygen Batteries

Reactive oxygen species or superoxide (O2-) to damage or age biological cells is generated during metabolic pathways using oxygen as an electron acceptor in biological systems. Superoxide dismutase (SOD) protects cells from the superoxide-triggered apoptosis by converting superoxide to oxygen and peroxide. Lithium-oxygen battery (LOB) cells have the same aging problems caused by superoxide-triggered side reactions. We transplanted the function of SOD of biological systems into LOB cells. Malonic acid-decorated fullerene (MA-C60) was used as a superoxide disproportionation chemo-catalyst mimicking the function of SOD. As expected, MA-C60 as the superoxide scavenger improved capacity retention along charge/discharge cycles successfully. A LOB cell that failed to provide a meaningful capacity just after several cycles at high current (0.5 mA cm-2) with 0.5 mAh cm-2 cut-off survived up to 50 cycles after MA-C60 was introduced to electrolyte. Moreover, the SOD-mimetic catalyst increased capacity: e.g., more than six-fold increase at 0.2 mA cm-2. Experimentally observed toroidal morphology of the final discharge product of oxygen reduction (Li2O2) and density functional theory calculation confirmed that the solution mechanism of Li2O2 formation, more beneficial than the surface mechanism from the capacity-gain standpoint, was preferred in the presence of MA-C60

Granulation of Bismuth Oxide by Alginate for Efficient Removal of Iodide in Water

The granulation of bismuth oxide (BO) by alginate (Alg) and the iodide adsorption efficacy of Alg–BO for different initial iodide concentrations and contact time values were examined. The optimal conditions for Alg–BO granulation were identified by controlling the weight ratio between Alg and BO. According to the batch iodide adsorption experiment, the Alg:BO weight ratio of 1:20 was appropriate, as it yielded a uniform spherical shape. According to iodide adsorption isotherm experiments and isotherm model fitting, the maximum sorption capacity (qm) was calculated to be 111.8 mg/g based on the Langmuir isotherm, and this value did not plateau even at an initial iodide concentration of 1000 mg/L. Furthermore, iodide adsorption by Alg–BO occurred as monolayer adsorption by the chemical interaction and precipitation between bismuth and iodide, followed by physical multilayer adsorption at a very high concentration of iodide in solution. The iodide adsorption over time was fitted using the intraparticle diffusion model. The results indicated that iodide adsorption was proceeded by boundary layer diffusion during 480 min and reached the plateau from 1440 min to 5760 min by intraparticle diffusion. According to the images obtained using cross-section scanning electron microscopy assisted by energy-dispersive spectroscopy, the adsorbed iodide interacted with the BO in Alg–BO through Bi–O–I complexation. This research shows that Alg–BO is a promising iodide adsorbent owing to its high adsorption capacity, stability, convenience, and ability to prevent secondary pollution

Shifting Target Reaction from Oxygen Reduction to Superoxide Disproportionation by Tuning Isomeric Configuration of Quinone Derivative as Redox Mediator for Lithium-Oxygen Batteries

Quinones having a fully conjugated cyclic dione structure have been used as redox mediators in electrochemistry. 2,5-Ditert-butyl-1,4-benzoquinone (DBBQ or DB-p-BQ) as a para-quinone derivative is one of the representative discharge redox mediators for facilitating the oxygen reduction reaction (ORR) kinetics in lithium-oxygen batteries (LOBs). Herein, we presented that the redox activity of DB-p-BQ for electron mediation was possibly used for facilitating superoxide disproportionation reaction (SODR) by tuning the isomeric config-uration of the carbonyl groups of the substituted quinone to change its reduction potentials. First, we expected a molecule having its reduction potential between oxygen/superoxide at 2.75 V versus Li/Li+ and superoxide/peroxide at 3.17 V to play a role of the SODR catalyst by transferring an electron from one superoxide (O-2(-)) to another superoxide to generate dioxygen (O2) and peroxide (O-2(2-)). By changing the isomeric configuration from para (DB-p-BQ) to ortho (DB-o-BQ), the reduction potential of the first electron transfer (Q/Q(-)) of the ditert-butyl benzoquinone shifted positively to the potential range of the SODR catalyst. The electrocatalytic SODR-promoting functionality of DB-o-BQ kept the reactive superoxide concentration below a harmful level to suppress superoxide-triggered side reaction, improving the cycling durability of LOBs, which was not achieved by the para form. The second electron transfer process (Q(-)/Q(2-)) of the DB-o-BQ, even if the same process of the para form was not used for facilitating ORR, played a role of mediating electrons between electrode and oxygen like the Q/Q(-) process of the para form. The ORR-promoting functionality of the ortho form increased the LOB discharge capacity and reduced the ORR overpotential

A Chemically and Electrochemically Bifunctional Mobile Catalyst for Anti-aging Lithium-Oxygen Batteries

Aprotic lithium-oxygen batteries (LOBs) have much higher energy density compared to today???s lithium ion batteries. However, highly reactive superoxide, the discharge intermediate of LOBs, triggers side reactions to deteriorate LOB performances. Also, high overpotential is required to oxidize the discharge product Li2O2 during charge due to the non-conductive nature of Li2O2. Herein, we present 4-carboxy-TEMPO as a bifunctional mobile catalyst soluble in LOB electrolytes for improving LOB performances. The roles of 4-carboxy-TEMPO is two-fold: (1) the chemo-catalyst to catalyze superoxide disproportionation reaction for suppressing the superoxide-triggered side reactions; and (2) the redox mediator to oxidize the discharge product Li2O2 in a kinetically effective way for reducing the overpotential during charge. As expected, the use of the mobile catalyst in LOB cells resulted in the 4-fold increase in cycle life from 50 cycles to 200 cycles, significantly reducing the overpotential during charge. Also, the discharge capacity increased 4-fold