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Nickel-rich layered oxides (LiNi1–x–yCoxMnyO2; (1 – x – y) ≥ 0.6), the high-energy-density cathode materials of lithium-ion batteries (LIBs), are seriously unstable at voltages higher than 4.5 V ve...

A redox-active mixed ion and electron conductor (redox-active MIEC) is presented as a binder for the lithium titanate anodes of lithium-ion batteries. The redox-active MIEC binder (symbolized by PT*-GmCn) was designed to be (1) electrically conductive along its conjugated thiophene backbone (PT = polythiophene), (2) redox-active from its succinimide moiety (* = redox-active) and (3) ionically conductive by adopting glyme (G) branches. It was superior to the practically used PVdF binder in terms of lithium ion diffusivity and electrical conductivity (1.4× and 15 000×, respectively). High capacity was guaranteed, particularly at high rates due to its MIEC nature of PT*-GmCn, while an additional capacity was achieved from its redox activity.

The reversibility of lithium plating/stripping should be guaranteed in lithium metal batteries. Seriously localized lithium growth during plating leads to the dendritic evolution of lithium metal due to the uneven current distribution on the electrically conductive surface. Artificial protective layers covering electrodes (e.g., polymer film on copper foil) have been used to narrow the gap of the current density between positions on the conductive surface. Herein, we incorporated an active ingredient to attract lithium ions into the dendrite-suppressing layer. Pyridinic nitrogen of graphitic carbon nitride (g-C3N4) served as the lithium ion affinity center. Conformation of the nitrogen changed from pyridinic to graphitic in the presence of lithium ions, which confirms the coordination of lithium ion to the pyridinic nitrogen. Moreover, lithium ion conduction was facilitated in the presence of g-C3N4 layer probably via a site-to-site hopping mechanism. Lithium metal was plated between the g-C3N4 layer and the copper current collector (or the lithium metal). The homogeneous lithium nucleation expected from the active role of the pyridinic nitrogen (lithium ion affinity and facilitated ionic conduction) suppressed the dendritic growth of lithium metal and decreased the overpotential required for the initial metal nucleation. Due to the top-down ion flux regulation on the uppermost surface (or tip) of lithium metal, the reversibility of lithium plating/stripping was dramatically improved.

Although bimetallic materials with various structures have been used as anodes for advanced lithium ion batteries, structural degradation, caused during electrochemical reactions, leads to a shorte...

Plating-stripping reversibility of lithium metal is improved by reinforcing the solid-electrolyte interphase layer by inorganic nanobeads. The outmost solid-electrolyte interphase shell is clearly identified, which is the passive layer formed on current collectors (or lithium metal) before the first lithium metal deposition. The outmost shell is intrinsically brittle and fragile so that it is easily broken by lithium metal dendrites growing along the progress of plating. Lithium metal deposit is not completely stripped back to lithium ions. On the other hand, lithium metal cells containing inorganic nanobeads in electrolyte show high reversibility between plating and stripping. The nanobeads are incorporated into the outmost shell during its formation. The nanobead-reinforced outmost shell having mechanically durable toughness suppresses dendritic growth of lithium metal, not allowing the dendrites to penetrate the shell. In addition to the mechanical effect of nanobeads, the LiF-rich solid-electrolyte interphase layer formation is triggered by HF generated by the reaction of the moisture adsorbed on oxide nanobeads with PF6−. The LiF-rich composition is responsible for facile lithium ion transfer through the passive layers.

Lithium metal has been considered as an anode material to improve energy densities of lithium chemistry-based rechargeable batteries (that is to say, lithium metal batteries or LMBs). Higher capacities and cell voltages are ensured by replacing practically used anode materials such as graphite with lithium metal. However, lithium metal as the LMB anode material has been challenged by its dendritic growth, electrolyte decomposition on its fresh surface, and its serious volumetric change. To address the problems of lithium metal anodes, herein, we guided and facilitated lithium ion transport along a spontaneously polarized and highly dielectric material. A three-dimensional web of nanodiameter fibers of ferroelectric beta-phase polyvinylidene fluoride (beta-PVDF) was loaded on a copper foil by electrospinning (PVDF#Cu). The electric field applied between the nozzle and target copper foil forced the dipoles of PVDF to be oriented centro-asymmetrically and then the beta structure induced ferroelectric polarization. Three-fold benefits of the ferroelectric nano-web architecture guaranteed the plating/stripping reversibility especially at high rates: (1) three-dimensional scaffold to accommodate the volume change of lithium metal during plating and stripping, (2) electrolyte channels between fibers to allow lithium ions to move, and (3) ferroelectrically polarized or negatively charged surface of beta-PVDF fibers to encourage lithium ion hopping along the surface. Resultantly, the beta-PVDF web architecture drove dense and integrated growth of lithium metal within its structure. The kinetic benefit expected from the ferroelectric lithium ion transport of beta-PVDF as well as the porous architecture of PVDF#Cu was realized in a cell of LFP as a cathode and lithium-plated PVDF#Cu as an anode. Excellent plating/stripping reversibility along repeated cycles was successfully demonstrated in the cell even at a high current such as 2.3 mA cm-2, which was not obtained by the nonferroelectric polymer layer.

Highly oxygen evolution reaction (OER)-active electrocatalysts often exhibit improved OER durability in the presence of carbon corrosion or oxidation (COR) in the literature. The activity-durability coincidence of OER electrocatalysts was theoretically understood by preferential depolarization in galvanostatic situations. At constant-current conditions for a system involving multiple reactions that are independent and competitive, the overpotential is determined most dominantly by the most facile reaction so that the most facile reaction is responsible for a dominant portion of the overall current. Therefore, higher OER activity improves durability by mitigating the current responsible for COR. The activity-durability coincidence was then proved experimentally by comparing between two catalysts of the same chemical identity (MnCo2O4) in different dimensions (5 and 100 nm in size). Carbon corrosion responsible for inferior durability was suppressed in the smaller-dimension catalyst (MnCo2O4 in 5 nm) having...

Perovskite oxides have received considerable attention as useful electro-catalysts for Li-air batteries due to their properties of excellent catalytic activity, electrical conductivity, and durability. The nanostructure can enhance the electrochemical performance of perovskite oxides by enlarging the catalytic active sites. In this study, nano-size Nd0.67Sr0.33CoO3-δ (NSC) perovskite particles with a particle size of 20–50 nm and a specific surface area of 12.759 m2 g−1 were successfully synthesized by a microemulsion method. The NSC perovskite particles exhibit excellent electrocatalytic activity particularly in the oxygen evolution reaction (OER) with a high limiting current density of 33.68 mA cm-2 at 0.9 V vs. (Hg/HgO). This excellent catalytic activity can be ascribed to the existence of Co3+ and the enlarged surface area. Co3+ provides catalytically active site by forming Co3+/4+ redox couple and the enlarged surface increases active sites for reactants and catalyst particles. In this regard, nano-size NSC particles prepared by the microemulsion route provide excellent and stable electrochemical performance in the hybrid Li-air battery.

Cost-effective and environmentally friendly seawater-electrolyte-based batteries exhibit high energy density and demonstrate immense potential for use in future energy storage devices; however, lack of high-performance negative and positive electrodes significantly challenges their practical applications. In this study, N-doped and N,S-doped carbon nanospheres (referred to as NCSs and NSCSs, respectively) are synthesized via the pyrolysis of melanosomes, which is a bio-inspired polymer. Electrocatalytic activity measurements reveal the bifunctionality of the prepared catalysts. NSCSs exhibit a distinctively higher performance than NCSs when used as an air electrode in seawater batteries under ambient conditions (referred to as static mode hereafter). Further, due to the introduction of air flow into the seawater electrolyte (referred to as flow mode hereafter), NSCSs exhibit an improved cell discharge potential. The high performance of the cell is attributed to the high surface area, bifunctional electrocatalytic activity, generation of new active sites, improvement of spin density in NSCSs, and continuous flow of air to the electrolyte. The cell in the flow mode exhibits an overpotential gap of 0.56 V, a round-trip efficiency of 84%, a maximum power density of 203 mW g−1, and an outstanding cycling stability up to 100 cycles. The developed synthetic method provides an effective, scalable approach for doping binary or ternary atoms into the carbon host matrix, which can motivate further experimental and theoretical studies of electrode materials in various energy storage devices. In addition, the concept and results obtained by the introduction of air flow into the electrolyte can lead to the improvement of cell performance in terms of electrical energy efficiency, which can be exploited in various metal–air batteries.

Enhancing the performance of carbon-based anode materials in Li-ion battery (LIB) systems is of considerable interest in terms of next-generation LIB host electrodes, because the unique reversible intercalation–de-intercalation process of such materials ultimately facilitates increases in LIB performance and longevity. This study explored the potential of a new class of carbon-based contorted hexabenzocoronene (c-HBC) as an anode material for high-performance LIB systems. The exploitation of the polymorphic crystalline nature of c-HBC resulted in successful development of a LIB anode based on a newly found crystal phase of trigonal R by solvent and subsequent thermal annealing. Our in-depth analysis based on cross-sectional transmission electron microscopy, grazing incidence X-ray diffraction, and computational investigation revealed further advantages of using contorted molecules in LIB systems. For instance, the resulting electrochemical characteristics using half-cell architecture clearly reflected single-stage Li insertion behavior associated with the large interspacing and short diffusion length of c-HBC molecule during the discharging process. In addition, the battery exhibited excellent rate capability and cycle endurance, highlighting the suitability of c-HBC as an anode material for high-performance LIBs.

We present a metal-ion-chelating organogel electrolyte, thermally gelated within cells, to solve the problems triggered by metal dissolution from cathodes of lithium ion batteries. The organogel significantly improved the capacity retention of lithium manganese oxide spinel during cycling. The organogel mitigated metal deposition on anodes by capturing metal ions (anode protection). Interestingly, the organogel inhibited metal dissolution by keeping dissolved metal ions highly concentrated around the cathode surface (cathode protection by Le Chatelier's principle).

Uniform zinc metal plating has been raised as a critical issue in zinc-based batteries. Randomly localized ions lead to severe zinc dendrite formation in liquid electrolyte due to nonuniform ion flux caused by electroconvective flow. One of the mitigating approaches is to use gel polymer electrolyte to regulate the ion flux for suppressing zinc dendrites by imparting viscoelasticity to the electrolyte and improving the ion transport along charged functional groups of polymer chains. However, to this date, the effectiveness of gel polymer electrolyte has been visualized using ex situ methods (e.g., scanning electron microscopy) that requires cell disassembly. And the underlying mechanism is poorly understood. Herein, we applied in situ optical microscopy with dark-field illumination and a transparent glass slide cell to visualize zinc metal plating in the gel polymer electrolyte. At a given current density, the morphological differences of plated zinc metal between the liquid and gel polymer electrolytes were compared. Our in situ optical microscopy platform successfully showed that the gel polymer electrolyte supported by cross-linked polyacrylic acid (PAA)/N,N’-methylenebisacrylamide (MBA) polymer framework significantly suppressed the dendrite formation in contrast to the liquid electrolyte during plating. In addition, at various current densities, the tendency of dendritic growth was observed and statistically compared in both electrolytes. The findings will be useful for future design of rechargeable zinc-based batteries.

Ruthenium oxide (RuO2) is the best oxygen evolution reaction (OER) electrocatalyst. Herein, we demonstrated that RuO2 can be also efficiently used as an oxygen reduction reaction (ORR) electrocatalyst, thereby serving as a bifunctional material for rechargeable Zn–air batteries. We found two forms of RuO2 (i.e. hydrous and anhydrous, respectively h-RuO2 and ah-RuO2) to show different ORR and OER electrocatalytic characteristics. Thus, h-RuO2 required large ORR overpotentials, although it completed the ORR via a 4e process. In contrast, h-RuO2 triggered the OER at lower overpotentials at the expense of showing very unstable electrocatalytic activity. To capitalize on the advantages of h-RuO2 while improving its drawbacks, we designed a unique structure (RuO2@C) where h-RuO2 nanoparticles were embedded in a carbon matrix. A double hydrophilic block copolymer-templated ruthenium precursor was transformed into RuO2 nanoparticles upon formation of the carbon matrix via annealing. The carbon matrix allowed overcoming the limitations of h-RuO2 by improving its poor conductivity and protecting the catalyst from dissolution during OER. The bifunctional RuO2@C catalyst demonstrated a very low potential gap (ΔEOER-ORR = ca. 1.0 V) at 20 mA cm−2. The Zn||RuO2@C cell showed an excellent stability (i.e. no overpotential was observed after more than 40 h).

Conversion-reaction-based anode materials for lithium ion batteries (LIBs) such as transition metal oxides have been considered as high-capacity alternatives to graphite. In the conversion reactions, interestingly, microparticles have been known to be superior to nanoparticles in terms of capacity retention along repeated cycles. In this work, a cross-linked two-component binder system of poly(acrylic acid) and carboxymethyl cellulose (PAA/CMC) was used for nanoparticular Co 3 O 4 . The binder was characterized by high modulus and strong bonding to the surface oxide of Co 3 O 4 . Even without carbon coating, the composite electrodes of nanoparticular Co 3 O 4 in the presence of PAA/CMC showed significantly enhanced cycle retention with improved reversibility of the conversion reaction.

Although the volume of antimony tremendously expands during the alloying reaction with sodium, it is considered a promising anode material for sodium-ion batteries (SIBs). Repeated volume changes along the sodiation/desodiation cycles encourage capacity fading by triggering pulverization accompanying electrolyte decomposition. Additionally, the low cation transference number of sodium ions is another hindrance for application in SIBs. In this work, a binder was designed for the antimony in SIB cells to ensure bifunctionality and improve (1) the mechanical toughness to suppress the serious volume change and (2) the transference number of sodium ions. A cross-linked composite of poly(acrylic acid) and cyanoethyl pullulan (pullulan-CN) was presented as the binder. The polysaccharide backbone of pullulan-CN was responsible for the mechanical toughness, while the cyanoethyl groups of pullulan-CN improved the lithium-cation transfer. The antimony-based SIB cells using the composite binder showed improved cycle life with enhanced kinetics. The capacity was maintained at 76% of the initial value at the 200th cycle of 1C discharge following 1C charge, while the capacity at 20C was 61% of the capacity at 0.2C, implying that the composite binder significantly improved the sodiation/desodiation reversibility of antimony.

Germanium nanoparticles were synthesized and subjected to study as anode materials for lithium ion batteries and sodium ion batteries. Laser pyrolysis of GeH4 was used to produce germanium nanoparticles and the average diameter of these nanoparticles was easily controlled by regulating sensitizer gas flow rates during the process. 60 and 10 nm diameter nanoparticles were synthesized and micron-size powder was purchased and these three pure germanium powder samples were tested as the anode materials of lithium ion batteries and sodium ion batteries in terms of cycle retention, long term cycles and the kinetics of reactions. Experimental results showed that the smallest powder sample which is synthesized, average 10 nm, exhibited excellent performances in both kinds of batteries. According to the results, the characteristics of batteries improved as the size of germanium powder decreased consistently. Pure germanium was thoroughly investigated as an anode of metal-ion batteries with regard to its powder size. The experimental data and synthesis approach of germanium nanoparticles suggested in this research would be a good example for the utilization of elemental germanium in high performance batteries.

It is demonstrated that the electroactivity of the oxygen reduction reaction (ORR) of Pt depends on the structure of a support. Highly conductive two-dimensional titanium carbide (Ti3C2) was selected as the support for Pt because of the expected strong metal-support interaction (SMSI) between Pt and Ti. To control the edge-to-basal ratio, the number of Ti3C2 layers was modulated by exfoliation. Pt nanoparticles (4 nm) were loaded on three different Ti3C2 supports including multi-, few-, and mono-layered Ti3C2 (22L-, 4L-, and 1L-Ti3C2, respectively). The edge-to-basal ratio of layered Ti3C2 increased as the number of layers increased. The edge-dominant support (22L-Ti3C2) donated more electrons to Pt than the basal-dominant supports (4L-Ti3C2 and 1L-Ti3C2). As a result, electron-rich Pt with less d-band vacancies (e.g., Pt/22L-Ti3C2) showed higher ORR activity. In addition, the electron transfer from the support to Pt inducing the strong interaction between Pt and Ti improved the durability of the ORR electroactivity of Pt.

Molecular structures of polysaccharide binders determining mechanical properties were correlated to electrochemical performances of silicon anodes for lithium-ion batteries. Glycosidic linkages (α and β) and side chains (-COOH and -OH) were selected and proven as the major factors of the molecular structures. Three different single-component polysaccharides were compared: pectin for α-linkages versus carboxylic methyl cellulose (CMC) for β-linkages from the linkage's standpoint, and pectin as a COOH-containing polymer and amylose as its non-COOH counterpart from the side chain's standpoint. Pectin was remarkably superior to CMC and amylose in cyclability and rate capability of battery cells based on silicon anodes. The pectin binder allowed volume expansion of silicon electrodes with keeping high porosity during lithiation due to the elastic nature caused by the chair-to-boat conformation in α-linkages of its backbone. Physical integrity of pectin-based electrodes was not challenged during repeated lithiation/delithiation cycles without crack development that was observed in rigid CMC-based electrodes. Covalent bonds formed between carboxylic side chains of pectin and silicon surface oxide prevented active silicon mass from being detached away from electric pathways. However, hydrogen bonds between hydroxyl side chains of amylose and silicon surface oxide were not strong enough to keep the silicon mass electrochemically active after cyclability tests.

A cyanoresin organogel electrolyte, characterized by in situ gelation with no initiators or crosslinkers, was used for high-loading silicon batteries of 1.3 mgSi cm−2 (equivalent to 3.3 mA h cm−2). The organogel provided additional cohesion between the silicon particles and maintained electrode integrity even after pulverization, completely suppressing severe crack development and serious electrode thickness changes observed in liquid electrolytes. The capacity retention upon cycling was significantly improved in the organogel when compared with its liquid counterpart.

Germanium nanoparticles were synthesized and subjected to study as anode materials for lithium ion batteries and sodium ion batteries. Laser pyrolysis of GeH4 was used to produce germanium nanoparticles and the average diameter of these nanoparticles was easily controlled by regulating sensitizer gas flow rates during the process. 60 and 10 nm diameter nanoparticles were synthesized and micron-size powder was purchased and these three pure germanium powder samples were tested as the anode materials of lithium ion batteries and sodium ion batteries in terms of cycle retention, long term cycles and the kinetics of reactions. Experimental results showed that the smallest powder sample which is synthesized, average 10 nm, exhibited excellent performances in both kinds of batteries. According to the results, the characteristics of batteries improved as the size of germanium powder decreased consistently. Pure germanium was thoroughly investigated as an anode of metal-ion batteries with regard to its powder size. The experimental data and synthesis approach of germanium nanoparticles suggested in this research would be a good example for the utilization of elemental germanium in high performance batteries.

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− xMgxO 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.

Silicon, a promising high-capacity anode material of lithium ion batteries, suffers from its volume expansion leading to pulverization and low conductivities, showing capacity decay during cycling and low capacities at fast charging and discharging. In addition to popular active-material-modifying strategies, building lithium-ion-rich environments around silicon surface is helpful in enhancing unsatisfactory performances of silicon anodes. In this work, we accelerated lithium ion transport to silicon surface by using an organogel binder to utilize the electroactivity of silicon in a more efficient way. The cyanoethyl polymer (PVA-CN), characterized by high lithium ion transference number as well as appropriate elastic modulus with strong adhesion, enhanced cycle stability of silicon anodes with high coulombic efficiency even at high temperature (60 °C) as well as at fast charging/discharging rates.

The electric conductivity-dependence of the number of electrons transferred during the oxygen reduction reaction is presented. Intensive properties, such as the number of electrons transferred, are difficult to be considered conductivity-dependent. Four different perovskite oxide catalysts of different conductivities were investigated with varying carbon contents. More conductive environments surrounding active sites, achieved by more conductive catalysts (providing internal electric pathways) or higher carbon content (providing external electric pathways), resulted in higher number of electrons transferred toward more complete 4e reduction of oxygen, and also changed the rate-determining steps from two-step 2e process to a single-step 1e process. Experimental evidence of the conductivity dependency was described by a microscopic ohmic polarization model based on effective potential localized nearby the active sites.

A self-charging power cell (SCPC) is a structure that hybridizes the mechanisms for energy conversion and storage into one process through which mechanical energy can be directly converted into electrochemical energy. A key structure of an SCPC is the use of a polyvinylidene fluoride (PVDF) piezo-separator. Herein, we have fabricated a piezoelectric β-form PVDF separator with a highly porous architecture by introducing ZnO particles. The electrochemical charge/discharge performance of this SCPC was greatly enhanced at lower discharge rates compared to highly stretched (high-β-content) or less porous PVDF membranes. The lower charge-transfer resistance of this well-developed porous piezo-separator is the main factor that facilitated the transport of Li+ ions without sacrificing piezoelectric performance. This study reveals a novel approach for improving the performance of SCPCs.

Electrode materials having nanometer scale dimensions are expected to have property enhancements due to enhanced surface area and mass/charge transport kinetics. This is particularly relevant to intrinsically low electronically conductive materials such as lithium iron phosphate (LiFePO4), which is of recent research interest as a high performance intercalation electrode material for Li-ion batteries. Many of the reported works on LiFePO4 synthesis are unattractive either due to the high cost of raw materials or due to the complex synthesis technique. In this direction, synthesis of LiFePO4 directly from inexpensive FePO4 shows promise.The present study reports LiFePO4 nanostructures prepared from iron (III) phosphate (FePO4 x 2H2O) by precipitation-hydrothermal method. The sintered powder was characterized by X-ray diffractometry (XRD), X-ray photoelectron spectroscopy (XPS), Inductive coupled plasma-optical emission spectroscopy (ICP-OES), and Electron microscopy (SEM and TEM). Two synthesis methods, viz. bulk synthesis and anodized aluminum oxide (AAO) template-assisted synthesis are reported. By bulk synthesis, micro-sized particles having peculiar surface nanostructuring were formed at precipitation pH of 6.0 to 7.5 whereas typical nanosized LiFePO4 resulted at pH ≥ 8.0. An in-situ precipitation strategy inside the pores of AAO utilizing the spin coating was utilized for the AAO-template-assisted synthesis. The template with pores filled with the precipitate was subsequently subjected to hydrothermal process and high temperature sintering to fabricate compact rod-like structures.

Geometry of carbon supports significantly affected electrochemical durability of Pt/C (platinum electrocatalyst supported by carbon) for oxygen reduction reaction (ORR). Carbon nano-onion (CNO) was used as the support, which is characterized by its nanosize (similar to Pt size) and high curvature. Superior ORR durability was guaranteed by Pt/CNO due to (1) its islands-by-islands configuration to isolate each Pt nanoparticle from its neighbors by CNO particles; (2) highly tortuous void structure of the configuration to suppress Ostwald ripening; and (3) the curvature-induced strong interaction between CNO and Pt. The finding that highly curved carbon surface encourages electron donation to catalysts was first reported.

Cellulose, which is one of the most-abundant and -renewable natural resources, has been extensively explored as an alternative substance for electrode materials such as activated carbons. Here, we demonstrate a new class of coffee-mediated green activation of cellulose as a new environmentally benign chemical-activation strategy and its potential use for all-paper flexible supercapacitors. A piece of paper towel is soaked in espresso coffee (acting as a natural activating agent) and then pyrolyzed to yield paper-derived activated carbons (denoted as “EK-ACs”). Potassium ions (K+), a core ingredient of espresso, play a viable role in facilitating pyrolysis kinetics and also in achieving a well-developed microporous structure in the EK-ACs. As a result, the EK-ACs show significant improvement in specific capacitance (131 F g–1 at a scan rate of 1.0 mV s–1) over control ACs (64 F g–1) obtained from the carbonization of a pristine paper towel. All-paper flexible supercapacitors are fabricated by assembling EK...

Single crystal silicon nanoparticles (Si-NPs) of 20 nm were produced via laser pyrolysis with a virtually complete conversion from SiH4 to Si-NPs. SF6 was used as the photosensitizer to transfer laser beam energy to silicon precursors, dramatically enhancing crystallinity of Si-NPs and their production efficiency. By using their well-developed crystalline structure, the directional volume expansion of Si-NPs was confirmed during lithiation. Lithiation/delithiation kinetics of our Si-NPs was superior to that of their amorphous counterparts due to the footprinted Li+ pathways formed during amorphization.

By coating nanoparticular lithium manganese oxide (LMO) spinel with a few layers of graphitic basal planes, the capacity of the material reached up to 220 mA h g(-1) at a cutoff voltage of 2.5 V. The graphitic layers 1) provided a facile electron-transfer highway without hindering ion access and, more interestingly, 2) stabilized the structural distortion at the 3 V region reaction. The gain was won by a simple method in which microsized LMO was ball-milled in the presence of graphite with high energy. Vibratory ball milling pulverized the LMO into the nanoscale, exfoliated graphite of less than 10 layers and combined them together with an extremely intimate contact. Ab initio calculations show that the intrinsically very low electrical conductivity of the tetragonal phase of the LMO is responsible for the poor electrochemical performance in the 3 V region and could be overcome by the graphitic skin strategy proposed.

The formation of a spinel Lix CoO2 layer in a Ni-rich secondary particle for lithium-ion batteries is reported by S. K. Kwak, J. Cho, and co-workers on page 4705, who find that the spinel-like Lix CoO2 layer, between layered primary particles, can enhance the mechanical strength of secondary particles by enhancing the interfacial binding energy among the grains. Moreover, the layer can effectively protect the unstable surface of the primary particles and offers a fast electron-ion pathway, resulting in overall enhancements of stability and kinetics in battery performance.

As high rate charge and discharge characteristics of energy storage devices become more important with the market of electric vehicles intensively growing, the kinetics of lithiation or delithiation of electrode materials for lithium ion batteries require enhancement. Graphites, the most widely used anode materials, have a limited power density at high discharge rates, while their alternatives, such as silicon and transition metal oxides, show even inferior rate capability. This work was motivated from an idea of what if the edge opening of graphite was zipped more open to lithium ions in the electrolyte. By edge-selective functionalization, the peripheral d-spacing of graphite (d(0)) was locally controlled. Larger values of d(0) led to higher capacity especially at high discharge rates. Around 2-fold enhancement of capacity or energy density was achieved at 50C discharge rate from 110 to 190 mAh g(-1) by exfoliating graphite locally in its edge region. Also, the d(0) dependency of delithiation kinetics confirmed that the electrochemical step of Li(+) influx into or efflux out of the interlayer space of graphite is possibly the rate-determining step of lithiation or delithiation.

Tunable precipitation strategy to control the shape of nanoparticles of a three-component system is presented. The strategy is devised from understanding the effects of precursor addition sequences on the morphology of resultant precipitates. LiFePO4, one of the most potential candidate as a cathode material of lithium ion batteries for electric vehicles, was used as a representative model of the three (Li, Fe, and PO4)-component system. According to the precursor addition sequence, three different precipitation methods were adopted: coprecipitation (Copr) and two different types of sequential precipitations (Seq1 and Seq2). Solubility product (Ksp) of intermediate precipitates (Li3PO4 and Fe3(PO4)2) is the key parameter to help the precipitation processes understood. In Copr, the intermediate precipitates are formed simultaneously under Ksp-governed competition. In Seq1 and Seq2, Li3PO4 precipitates prior to Fe3(PO4)2. When Fe2+ is introduced into the suspension of Li3PO4, the preformed precipitate is sa...

The effect of poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) as a buffer layer was investigated in polymer solar cells (PSCs). Four different types of PEDOT:PSS were used: PH, PH500 and their DMSO (dimethylsulfoxide)-doped counterparts. The efficiency of PSCs was independent of the electric conductivity of the buffer layer as a bulk property while it was significantly related to interfacial properties between the buffer layer and a bulk-heterojunction (BHJ) layer. The interfacial properties included charge transfer resistance (RCT), hole mobility (μh) and contact angle (θ) of the solution of BHJ on the buffer layer. Lower RCT, higher μh and smaller θ led to the higher fill factor (up to 72%), enabling highly efficient PSCs with efficiency (η)=4.25%.

An oxygen reduction reaction (ORR) catalyst/support system is designed to have Pt nanoparticles nanoconfined in a nanodimensionally limited space. Holey crumpled reduced graphene oxide plates (hCR-rGO) are used as a carbon support for Pt loading. As expected from interparticular Pt-to-Pt distance of Pt-loaded hCR-rGO longer than that of Pt/C (Pt-loaded carbon black as a practical Pt catalyst), the durability of ORR electroactivity along cycles is improved by replacing the widely used carbon black with hCR-rGO. Unexpected morphological changes of Pt are electrochemically induced during repeated ORR processes. Spherical multifaceted Pt particles are evolved to {110}-dominant dendritic multipods. Nanoconfinement of a limited number of Pt within a nanodimensionally limited space is responsible for the morphological changes. The improved durability observed from Pt-loaded hCR-rGO originates from 1) dendritic pod structure of Pt exposing more active sites to reactants and 2) highly ORR-active Pt {110} planes dominant on the surface.

The chemically cross-linked gel polymer electrolytes supported by the microporous polyethylene membrane were prepared for application in lithium-ion polymer cells. The chemical cross-linking by tris(2-(acryloyloxy)ethyl) phosphate enhanced the electrochemical stability of the electrolyte and also promoted strong interfacial adhesion between the electrodes and the membrane. Lithium-ion polymer cells composed of a carbon anode and a lithium–cobalt oxide cathode were assembled by in situ chemical cross-linking, and their charge/discharge cycling performances were evaluated. Effect of the cross-linking agent on cycling performances of the cells has been investigated.

This work was supported by the Korea Energy Management Corporation (2005-C-CD11-P-04) and the Korea Research Foundation (KRF-2006-331-D00113).

A biopolymer composite consisting of polypyrrole, ABTS, and laccase (PAL) was electrodeposited onto the surface of an electrode and was shown to catalyze the reduction of dioxygen to water under acidic conditions. The catalytic activity of this biopolymer composite is highest at pH 4, decreasing with increasing pH. The activity of laccase immobilized within this polymer composite was found to be higher than laccase dissolved in solution when methanol was present or at elevated temperatures.

Porous structured materials have unique architectures and are promising for lithium-ion batteries to enhance performances. In particular, mesoporous materials have many advantages including a high surface area and large void spaces which can increase reactivity and accessibility of lithium ions. This study reports a synthesis of newly developed mesoporous germanium (Ge) particles prepared by a zincothermic reduction at a mild temperature for high performance lithium-ion batteries which can operate in a wide temperature range. The optimized Ge battery anodes with the mesoporous structure exhibit outstanding electrochemical properties in a wide temperature ranging from −20 to 60 °C. Ge anodes exhibit a stable cycling retention at various temperatures (capacity retention of 99% after 100 cycles at 25 °C, 84% after 300 cycles at 60 °C, and 50% after 50 cycles at −20 °C). Furthermore, full cells consisting of the mesoporous Ge anode and an LiFePO4 cathode show an excellent cyclability at −20 and 25 °C. Mesoporous Ge materials synthesized by the zincothermic reduction can be potentially applied as high performance anode materials for practical lithium-ion batteries.

The capacity of nanoparticular LiMn2O4 (LMO) spinel can be improved up to 220 mAh/g at a cutoff voltage of 2.5 V by coating with a few layers of graphitic basal planes.

A 1D organic redox-active material is combined with another 1D conductive material for rechargeable batteries. Poly(vinyl carbazole) (or PVK) and poly(3,4-ethylenedioxythiophene) doped with poly(styrenesulfonate) (or PEDOT:PSS) are used as the redox-active and conductive 1D materials, respectively. Due to their extremely anisotropic geometry, the two polymers are expected to be inter-tangled with each other, showing a kinetically ideal model system in which each redox-active moiety of PVK is supposed to be directly connected with the conducting pathways of PEDOT:PSS. In addition to its role as a conductive agent providing kinetic benefits, PEDOT:PSS works as an efficient binder that guarantees enhanced electrochemical performances with only a tenth of the amount of a conventional binder (polyvinylidene fluoride or PVdF). The benefit of gravimetric energy density gain obtained using the conductive binder comes mainly from efficient spatial coverage of binding volume due to the low density of PEDOT:PSS. Towards realizing flexible all-polymer batteries, a quasi-all-polymer battery half-cell is designed using the PVK/PEDOT:PSS composite with a polymer gel electrolyte.

Electric conductivity of conducting polymers has been steadily enhanced towards a level worthy of being called its alias, "synthetic metal". PEDOT:PSS (poly(3,4-ethylenedioxythiophene) doped with poly(styrene sulfonate)), as a representative conducting polymer, recently reached around 3,000 S cm(-1), the value to open the possibility to replace transparent conductive oxides. The leading strategy to drive the conductivity increase is solvent annealing in which aqueous solution of PEDOT:PSS is treated with an assistant solvent such as DMSO (dimethyl sulfoxide). In addition to the conductivity enhancement, we found that the potential range in which PEDOT:PSS is conductive is tuned wider into a negative potential direction by the DMSO-annealing. Also, the increase in a redox-active fraction of charge carriers is proposed to be responsible for the enhancement of conductivity in the solvent annealing process.

Electrolytes are characterized by their ionic conductivity (sigma(i)). It is desirable that overall si results from the dominant contribution of the ions of interest (e. g. Li+ in lithium ion batteries or LIB). However, high values of cationic transference number (t(+)) achieved by solid or gel electrolytes have resulted in low sigma(i) leading to inferior cell performances. Here we present an organogel polymer electrolyte characterized by a high liquid-electrolyte-level sigma(i) (similar to 10(1) mS cm(-1)) with high t(+) of Li+ (>0.8) for LIB. A conventional liquid electrolyte in presence of a cyano resin was physically and irreversibly gelated at 60 degrees C without any initiators and crosslinkers, showing the behavior of lower critical solution temperature. During gelation, sigma(i) of the electrolyte followed a typical Arrhenius-type temperature dependency, even if its viscosity increased dramatically with temperature. Based on the Li+-driven ion conduction, LIB using the organogel electrolyte delivered significantly enhanced cyclability and thermal stability.

There are many practical difficulties in direct adsorption of polymers onto nanocrystalline inorganic oxide surface such as Al2O3 and TiO2 mainly due to the insolubility of polymers in solvents or polymer agglomeration during adsorption process. As an alternative approach to the direct polymer adsorption, we propose surface-bound polymerization of pre-adsorbed monomers. 6-(3-Thienyl)hexanoic acid (THA) was used as a monomer for poly[3-(5-carboxypentyl)thiophene-2,5-diyl] (PTHA). PTHA-coated nanocrystalline TiO2/FTO glass electrodes were prepared by immersing THA-adsorbed electrodes in FeCl3 oxidant solution. Characterization by ultraviolet/visible/infrared spectroscopy and thermal analysis showed that the monolayer of regiorandom-structured PTHA was successfully formed from intermolecular bonding between neighbored THA surface-bound to TiO2. The anchoring functional groups (-COOH) of the surface-crawling PTHA were completely utilized for strong bonding to the surface of TiO2.