Mesoporous Germanium Anode Materials for Lithium-Ion Battery with Exceptional Cycling Stability in Wide Temperature Range.

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.

2D PdTe2 Thin-Film-Coated Current Collectors for Long-Cycling Anode-Free Rechargeable Batteries.

The practical implementation of anode-free batteries is limited by factors such as lithium dendrite growth and low cycling Coulombic efficiency (CE). In this study, the improvement in the electrochemical performance of anode-free rechargeable lithium batteries bearing a Cu current collector (CC) coated with PdTe2 thin films is reported. The optimized thickness and sputtering heating conditions of the PdTe2 layer are 15 nm and 473.15 K, respectively. Upon deposition on a CC, PdTe2 works as a seed layer that considerably improves the CE in half-cells, owing to its unique 2D structure that reduces the nucleation overpotential. A further contribution to the high performance is brought about by a CuTe interphase between the coating layer and Cu CC formed during heating. Such an interphase contributes to the high CE by improving the uniformity of the current density distribution on the CC that suppresses lithium dendrite growth. A low nucleation overpotential and uniform current density distribution, in turn, result in a smooth morphology of the plated Li. The full cell obtained with the PdTe2-coated CC exhibits a capacity retention of 70.7% after the 100th cycle, with an average CE of 99.65% at a 0.2C rate─an outstanding result in view of the rapid development of lithium-ion batteries.

Metal-Ion Chelating Gel Polymer Electrolyte for Ni-Rich Layered Cathode Materials at a High Voltage and an Elevated Temperature.

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 versus Li/Li+ and temperatures higher than 50 °C. Herein, we demonstrated that the failure mechanism of a nickel-rich layered oxide (LiNi0.6Co0.2Mn0.2O2) behind the instability was successfully suppressed by employing cyanoethyl poly(vinyl alcohol) having pyrrolidone moieties (Pyrd-PVA-CN) as a metal-ion-chelating gel polymer electrolyte (GPE). The metal-ion-chelating GPE blocked the plating of transition-metal ions dissolved from the cathode by capturing the ions (anode protection). High-concentration metal-ion environments developed around the cathode surface by the GPE suppressed the irreversible phase transition of the cathode material from the layered structure to the rock-salt structure (cathode protection). Resultantly, the capacity retention was significantly improved at a high voltage and a high temperature. Capacity retention and coulombic efficiency of a full-cell configuration of a nickel-rich layered oxide with graphite were significantly improved in the presence of the GPE especially at a high cutoff voltage (4.4 V) and an elevated temperature (55 °C).

Gel/Solid Polymer Electrolytes Characterized by In Situ Gelation or Polymerization for Electrochemical Energy Systems.

A gel polymer electrolyte (GPE) is a liquid electrolyte (LE) entrapped by a small amount of polymer network less than several wt%, which is characterized by properties between those of liquid and solid electrolytes in terms of the ionic conductivity and physical phase. Electrolyte leakage and flammability, demerits of liquid electrolytes, can be mitigated by using GPEs in electrochemical cells. However, the contact problems between GPEs and porous electrodes are challenging because it is difficult to incorporate GPEs into the pores and voids of electrodes. Herein, the focus is on GPEs that are gelated in situ within cells instead of covering comprehensive studies of GPEs. A mixture of LE and monomer or polymer in a liquid phase is introduced into a pre-assembled cell without electrolyte, followed by thermal gelation based on physical gelation, monomer polymerization, or polymer cross-linking. Therefore, GPEs are formed omnipresent in cells, covering the pores of electrode material particles, and even the pores of separators. As a result, different from ex situ formed GPEs, the in situ GPEs have no electrode/electrolyte contact problems. Functional GPEs are introduced as a more advanced form of GPEs, improving lithium-ion transference number or capturing transition metals released from electrode materials.

Superoxide stability for reversible Na-O2 electrochemistry.

Stabilizing superoxide (O2-) 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 (O22-) 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 ([Formula: see text] -/DMSO) allowed more reversible operation of the sodium ion oxygen batteries.

Coffee-Driven Green Activation of Cellulose and Its Use for All-Paper Flexible Supercapacitors.

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-ACs/carbon nanotube mixture-embedded paper towels (as electrodes), poly(vinyl alcohol)/KOH mixture-impregnated paper towels (as electrolytes), and polydimethylsiloxane-infiltrated paper towels (as packaging substances). The introduction of the EK-ACs (as an electrode material) and the paper towel (as a deformable and compliant substrate) enables the resulting all-paper supercapacitor to provide reliable and sustainable cell performance as well as exceptional mechanical flexibility. Notably, no appreciable loss in the cell capacitance is observed after repeated bending (over 5000 cycles) or multiple folding. The coffee-mediated green activation of cellulose and the resultant all-paper flexible supercapacitors open new material and system opportunities for eco-friendly high-performance flexible power sources.

Li-Ion Battery Cathodes: Enhancing Interfacial Bonding between Anisotropically Oriented Grains Using a Glue-Nanofiller for Advanced Li-Ion Battery Cathode (Adv. Mater. 23/2016).

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.

Enhancing Interfacial Bonding between Anisotropically Oriented Grains Using a Glue-Nanofiller for Advanced Li-Ion Battery Cathode.

Formation of a glue-nanofiller layer between grains, consisting of a middle-temperature spinel-like Lix CoO2 phase, reinforces the strength of the incoherent interfacial binding between anisotropically oriented grains by enhancing the face-to-face adhesion strength. The cathode treated with the glue-layer exhibits steady cycling performance at both room-temperature and 60 °C. These results represent a step forward in advanced lithium-ion batteries via simple cathode coating.

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 architecture.

A physical organogel electrolyte: characterized by in situ thermo-irreversible gelation and single-ion-predominent conduction.

Electrolytes are characterized by their ionic conductivity (σ(i)). It is desirable that overall σ(i) 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 σ(i) leading to inferior cell performances. Here we present an organogel polymer electrolyte characterized by a high liquid-electrolyte-level σ(i) (~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°C without any initiators and crosslinkers, showing the behavior of lower critical solution temperature. During gelation, σ(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.