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A layered silicon disulfide (SiS2) was synthesized on a large-scale via a solid–gas phase reaction and applied as an anode material for Li-ion batteries and solid-state electrolytes for all-solid-state batteries.

Scalable production of LPSCl-based sulfide solid-electrolytes with high ionic conductivities using various green and sustainable solvents for commercializing all-solid-state batteries.

Heat generation and temperature of a battery is usually presented by an equation of current. This means that we need to adopt time domain calculation to obtain thermal characteristics of the battery. To avoid the complicated calculations using time domain, ‘state of charge (SOC)’ can be used as an independent variable. A SOC based calculation method is elucidated through the comparison between the calculated results and experimental results together. Experiments are carried for rapid resistive discharge of a large-capacitive lithium secondary battery to evaluate variations of cell potential, current and temperature. Calculations are performed based on open-circuit cell potential (SOC, T), internal resistance (SOC, T) and entropy (SOC) with specific heat capacity.

ANODE-free Li-metal batteries (AFLMBs) operating with Li of cathode material have attracted enormous attention due to their exceptional energy density originating from anode-free structure in the confined cell volume. However, uncontrolled dendritic growth of lithium on a copper current collector can limit its practical application as it causes fatal issues for stable cycling such as dead Li formation, unstable solid electrolyte interphase, electrolyte exhaustion, and internal short-circuit. To overcome this limitation, here, we report a novel dual-salt electrolyte comprising of 0.2 M LiPF6 + 3.8 M lithium bis(fluorosulfonyl) imide in a carbonate/ester co-solvent with 5 wt% fluoroethylene carbonate, 2 wt% vinylene carbonate, and 0.2 wt% LiNO3 additives. Because the dual-salt electrolyte facilitates uniform/dense Li deposition on the current collector and can form robust/ionic conductive LiF-based SEI layer on the deposited Li, a Li/Li symmetrical cell exhibits improved cycling performance and low polarization for over 200 h operation. Furthermore, the anode-free LiFePO4/Cu cells in the carbonate electrolyte shows significantly enhanced cycling stability compared to the counterparts consisting of different salt ratios. This study shows an importance of electrolyte design guiding uniform Li deposition and forming stable SEI layer for AFLMBs.

O substitution for S in argyrodite-type sulfide-based solid electrolytes enhances the stability by suppressing reaction with H2O and decomposition. O substitution modulates the electronic structures and then improves electrochemical performance.

A size-controlled high-quality sulphide solid electrolyte for all-solid-state Li batteries was prepared by a novel polar-to-nonpolar solvent exchange process.

Halide-doped sulfide solid electrolytes have attracted great attention due to their high lithium-ion conductivity, Li-metal compatibility, and deformability for use in all-solid-state Li batteries....

Vertically aligned Fe, S, and Fe-S doped anatase TiO2 nanotube arrays are prepared by electrochemical anodization process using an organic electrolyte in which lactic acid is added as an additive. In the electrolyte, nanotube layers of greater length (12 μm) and high order with inner diameter of approx. 90 nm and outer diameter of approx. 170 nm are achieved. Doping of Fe, S, and Fe-S via simple wet impregnation method substituted Ti and O sites with Fe and S, which leads to enhance the rate performance at high discharge current densities. Discharge capacities of TiO2 tubes increased from 82 mAh g-1 (bare) to 165 mAh g-1 for Fe-S doped TiO2 at high current densities of 0.3 mAcm-2 after 100 cycles with exceptional capacity retention of 85% after 100 cycles. Owing to the enhancement of thermodynamic and kinetic properties by doping of Fe-S, Li-diffusion increas2ed resulting in remarkable discharge capacities of 143 mAh g-1 and 89 mAh g-1 at a current density of 7.4 mA cm-2 and 19 mA cm-2, respectively.

As large format lithium ion batteries are used in EV and ESS applications, the temperature control of a battery is important to achieve a safe and long cycle life operation. To control the temperature properly, we need to know the heat generation characteristics. Heat generation of a battery mainly depends on the applied current, internal resistance, temperature and entropy of the battery. However, it is not easy to measure the entropy, because they depend on SOC and temperature simultaneously. Here, we suggested a new way to measure the entropy, on the assumption of adiabatic condition and calculate the heat generation. Internal resistance, specific heat capacity, OCCP values are also measured experimentally. The entropy (F ∂EOC ∂T−1) at a given SOC were measured from the variation of OCCP with temperature and expressed via a polynomial equation. The temperature dependence of the internal resistance were also expressed in the same procedure. The battery temperature variations calculated from the above parameters showed a good agreement with those from experiments. This suggested method provides a simple and reliable temperature estimation of lithium ion batteries.

The diffusivity and exchange current density are the two main parameters that determine both ionics and electrodics in the Newman’s battery model. Nonetheless, the values of both parameters are normally selected from eminent literatures or experimental data measured under specific conditions, furthermore, and they are occasionally overfitted to coincide with real electrochemical behaviors without sufficient consideration. Herein, the diffusivities and exchange current densities of a LiNi0.4Mn0.3Co0.3O2/Li half-cell are measured and applied to the electrochemical model using four different electrochemical techniques: galvanostatic intermittent titration technique (GITT), potentiostatic intermittent titration technique (PITT), electrochemical impedance spectroscopy (EIS), and cyclic voltammetry (CV). The model adopting the diffusivity and exchange current density measured in PITT and EIS, respectively, simulates the actual voltage and capacity profiles well with low errors without any fitting. Therefore, this case study helps us understand the effects of the essential parameters on the electrochemical behavior and the pros and cons of each measurement technique.

Instead of commercial lithium-ion batteries (LIBs) using organic liquid electrolytes, all-solid-state lithium-ion batteries (ASSBs) employing solid electrolytes (SEs) are promising for applications in high-energy–density power applications and electric vehicles due to their potential for improving safety and achieving high capacity. Although remarkable progress in SEs has been achieved and has resulted in high ionic conductivity, which now reaches values comparable to those of liquid electrolytes, the typical use of a slurry process for the fabrication of conventional ASSBs inevitably causes harmful reactions between sulfide materials and polar solvents. Here, we studied the efficient infiltration process of SE slurry into conventional composite LIB electrodes (NCM622) for achieving high-energy-density ASSBs via a scalable solution-based fabrication process. Two methods are proposed to ensure that SE materials are evenly distributed and sufficiently infiltrated into the porous structures of LIB electrodes. The LPSCl SE solutions were effectively infiltrated into the electrodes at higher processing temperatures and the temperature was subsequently optimized at above the boiling point of the ethanol solvent due to the dynamic motion of SE molecules via a convective flow during solvent vaporization. Moreover, the porous LIB composite electrodes with a mixture of active materials of different particle sizes formed and filled capillary pores resulting in a high electrode density. The LPSCl SE-infiltrated NCM622 electrodes that used this strategy could remarkably improve the initial discharge capacity of ASSBs to as high as 177 mAh/g. These ASSBs also showed excellent performance even at high loading values (about 17 mg/cm2), making them competitive with LIBs using conventional liquid electrolytes.

Sulfide-based lithium superionic conducting solid electrolytes for all-solid-state lithium batteries have received much attention due to their high safety, ionic conductivity, and compatibility. However, high-temperature treatment over a long time is needed to achieve high ionic conductivity. In this work, we have prepared the dual-halide-based Li7P2S8X type lithium superionic conductors by dry ball mill process and the high ionic conducting phase was achieved by low temperature (200℃) heat-treatment process. High ionic conducting halogen-halogen composition was arrived at through a series of optimization processes. Among the compositions tested, the Li7P2S8Br0.25I0.75 solid electrolyte exhibited a high ionic conductivity value of 6.16 mS cm−1, at room temperature. The ionic radius of the halogen element played an important role in the formation of the high ionic conducting phase. Further, the ionic conductivity of Li7P2S8I0.75Br0.25 solid electrolyte was improved by metal doping at P-site. The Sn-doped Li7P2S8I0.75Br0.25 solid electrolyte exhibited a high ionic conductivity value of 7.78 mS cm−1, at room temperature. The addition of large-sized Sn atoms extended the crystal lattice parameters and increased the Li-ions transport path. The partial substitution of Sn atoms at P-site was confirmed by NMR and Laser Raman analysis. The electrochemical stability of the prepared solid electrolyte was studied by cyclic voltammetry and DC charge-discharge analysis. The addition of a metal atom to the Li7P2S8Br0.25I0.75 solid electrolyte decreased the side reaction with the Li metals. Thus, low-temperature treated metal-doped Li7P2S8Br0.25I0.75 solid electrolytes are highly favourable for the fabrication of high-performance all-solid-state batteries. The fabricated all-solid-state battery using Sn doped Li7P2S8Br0.25I0.75 solid electrolyte exhibited the high specific capacity value of 170 mAh g−1 (0.1C), at room temperature.

We prepared the polyethylene oxide (PEO)-based composite membrane electrolytes which contained the specialized ionic liquids and the inorganic filler of Li7La3Zr2O12 (LLZO). Mixtures of ionic liquids and tetragonal inorganic fillers were used as additives to prepare composite electrolytes for an application of all solid-state lithium ion batteries (ASLBs). In order to improve the ionic conductivity of composite membranes, we studied the structural change and the electrochemical behaviors as a function of the amounts of solvated ionic liquids (ILs). The addition effect of solvated ILs showed the higher ionic conductivity such as 10−4 S/cm at 55 °C by reducing the crystalline character of polymer based composite, resulting in the enhanced ion conducting property. The hybrid composite membranes were successfully made in flexible form, and have an excellent thermal and electrochemical stability. Finally, the electrochemical performance of the half-cell was evaluated, and it was confirmed that the ion-conducting characteristics were influenced and controlled by the effect of ILs.

With the timely advent of the electric vehicle era, where battery stability has emerged as a major issue, all‐solid‐state batteries (ASSBs) have attracted significant attention as the game changer owing to their high stability. However, despite the introduction of a densely packed solid electrolyte (SE) layer, when Li is used to increase the energy density of the cell, the short‐circuit problem caused by Li protrusion is unavoidable. Furthermore, most strategies to control nonuniform Li growth are so complicated that they hinder the practical application of ASSBs. To overcome these limitations, this study proposes an Ag‐Li alloy anode via mass‐producible roll pressing method. Unlike previous studies reporting solid‐solution‐based metal alloys containing a small amount of lithiophilic Ag, the in situ formed and Ag‐enriched Ag‐Li intermetallic layer mitigates uneven Li deposition and maintains a stable SE/Ag‐Li interface, facilitating reversible Li operation. Contrary to Li cells showing frequent initial short‐circuit, the cell incorporating the Ag‐Li anode exhibits a better capacity retention of 94.3% for 140 cycles, as well as stable cycling even under 12 C. Through a facile approach enabling the fabrication of a large‐area anode with controllable Li growth, this study provides practical insight for developing ASSBs with stable cyclabilities., Compared to the sulfide‐based all‐solid‐state battery with Li metal anode exhibiting frequent initial short‐circuits, the cell incorporating Ag‐Li alloy anode fabricated via mass‐producible roll pressing method shows better cycle and rate performances, owing to the in situ formed Ag‐Li intermetallic layer physically controlling uneven Li deposition and chemically forming a stable solid electrolyte/Ag‐Li interface.

Vertically aligned Fe, S, and Fe-S doped anatase TiO2 nanotube arrays are prepared by an electrochemical anodization process using an organic electrolyte in which lactic acid is added as an additive. In the electrolyte, highly ordered TiO2 nanotube layers with greater thickness of 12 μm, inner diameter of approx. 90 nm and outer diameter of approx. 170 nm are successfully obtained. Doping of Fe, S, and Fe-S via simple wet impregnation method substituted Ti and O sites with Fe and S, which leads to enhance the rate performance at high discharge C-rates. Discharge capacities of TiO2 tubes increased from 0.13 mAh cm−2(bare) to 0.28 mAh cm−2 for Fe-S doped TiO2 at 0.5 C after 100 cycles with exceptional capacity retention of 85 % after 100 cycles. Owing to the enhancement of thermodynamic and kinetic properties by doping of Fe-S, Li-diffusion increased resulting in remarkable discharge capacities of 0.27 mAh cm−2 and 0.16 mAh cm−2 at 10 C, and 30 C, respectively.

Unlike commercial lithium-ion batteries, the high cost and low ionic conductivity of solid electrolytes (SEs) continues to be a big hurdle in commercially available all-solid-state batteries (ASSBs). Rather than the conventional dry-process and high-energy ball milling processes, the productive solution synthesis of bulk-type SEs is the most crucial issue in the successful application of high-energy-density ASSBs. In this study, the way is paved to overcome the hurdle for commercial lithium phosphorus sulfide chloride (LPSCl) SEs via a readily processable bulk-type solution-based synthesis without acquiring any high-energy ball-milling processes. By incorporating an elemental sulfur additive during the preparation process, Li

All-solid-state batteries (ASSBs) have lately received enormous attention for electric vehicle applications because of their exceptional stability by engaging all-solidified cell components. However, there are many formidable hurdles such as low ionic conductivity, interface instability, and difficulty in the manufacturing process, for its practical use. Recently, carbon, one of the representative conducting agents, turns out to largely participate in side reactions with the solid electrolyte, which finally leads to the formation of insulating side products at the interface. Although the battery community mentioned that parasitic reactions are presumably attributed to carbon itself or the generation of electronic conducting paths lowering the kinetic barrier for reactions, the underlying origin for such reactions as well as appropriate solutions have not been provided yet. In this study, for the first time, it is verified that the functional group on carbon is an origin for causing negative effects on interfacial stability and a graphitized hollow nanocarbon as a promising solution for improving-electrochemical performance is introduced. This work offers an invaluable lesson that a relatively minor part, such as a conducting agent, in ASSBs sometimes gives more positive impact on improving electrochemical performance than huge efforts for resolving other parts.

We demonstrated the successful water treatment performance of a continuous-flow tubular TiO 2 nanotube reactor made of Ti pipe where a TiO 2 nanotube (TNT) layer was directly formed on the inner wall by an electrochemical anodization process. A cylindrical UV lamp was inserted into the pipe to irradiate the inner TNT surface as a light source. To optimize the thickness of TNT layer on Ti pipe, TNT layers with 1, 5 and 10 μm thickness were prepared and their photocatalytic activities were tested for the degradation of various organic substrates (acid orange 7 (AO7), dichloroacetate (DCA), and 4-chlorophenol (4-CP)) under UV illumination. The TNT layer with 10 μm thickness showed the highest photocatalytic activity, with first-order removal rate constants ( k :min −1 ) of 0.019, 0.039, and 0.025 for AO7, 4-CP, and DCA, respectively. The directly formed TNTs (10 μm thickness) on Ti pipes in the continuous-flow tubular TNT reactor, having a strong adhesiveness and a high surface area, enabled the successful degradation of organic compounds and to have kept the activity without decrease during the repeated cycles and long-term experiments. The photocatalytic performance of the tubular TNT reactor was tested with a higher concentration, smaller volume ([4-CP] 0 = 100 μM, solution vol. = 15 mL) and a lower concentration, larger volume ([4-CP] 0 = 20 μM, solution vol. = 100 mL) in the circulation-flow mode (20 mL min −1 ). A good performance was achieved under the low intensity UV illumination (≈2 mW cm −2 ) with a half-life of ca. 50 min and ca. 11 h with 80% and 79% removal of TOC for the above two test conditions, respectively. The proposed tubular TNT reactor can be an effective option in the design of continuous flow-type photocatalytic reactors for practical water purification.

Titanium (Ti) and its alloys are mainly used for dental and orthopedic applications due to their excellent biocompatibility and mechanical properties. However, their intrinsic bioinertness often quotes as a common complaint for biomedical applications. Herein, we produced nanopattern Ti surfaces with 10 nm nanopores in 120 nm dimples by electrochemical nanopattern formation (ENF), and evaluated the osteogenic differentiation of human mesenchymal stem cells (hMSCs) on the nanopattern Ti surfaces. The ENF surfaces were obtained by removing the TiO2 nanotube (NT) layers prepared by an anodization process. To determine the in vitro effects of the ENF surface, cell proliferation assay, alkaline phosphatase activity assay, alizarin red staining, western blotting, and immunocytochemistry were performed. Atomic force microscopy and scanning electron microscopy analysis show that the ENF surface has an ultrafine surface roughness with highly aligned nanoporous morphology. hMSCs on ENF surfaces exhibit increased proliferation and enhanced osteogenic differentiation as compared to the ordered TiO2 nanotubular and compact TiO2 surfaces. Surface modification with the ENF process is a promising technique for fabricating osteointegrative implant materials with a highly bioactive, rigid and purified nano surfaces.

All-solid-state lithium batteries (ASSLBs) based on sulfide solid electrolytes (SEs) have received great attention because of the high ionic conductivity of the SEs, intrinsic thermal safety, and higher energy density achievable with a Li metal anode. However, studies on practical slurry-cast composite electrodes show an extremely limited battery performance than the binder-free pelletized electrodes because of the poor interfacial robustness between the active materials and SEs by the presence of a polymeric binder. Here, we employ a low-temperature post-sintering process for the slurry-cast composite electrodes in order to overcome the binder-induced detrimental effects on the electrochemical performance. The LiI-doped Li3PS4 SEs are chosen because the addition of iodine not only improves the Li-ion conductivity and Li metal compatibility but also lowers the glass-transition and crystallization temperatures. Low-temperature post-sintering of composite cathodes consisting of a LiNi0.6Co0.2Mn0.2O2-active material, LiI-doped Li3PS4 SE, polymeric binder, and conducting agent shows a significantly improved electrochemical performance as compared to a conventional slurry-cast electrode containing pre-annealed SEs. Detailed analyses by electrochemical impedance spectroscopy and galvanostatic intermittent titration technique confirm that post-sintering effectively reduces the interfacial resistance and enhances the chemomechanical robustness at solid-solid interfaces, which enables the development of practical slurry-cast ASSLBs with sulfide SEs.

This Letter shows that copper nanowires grow through the diffusion-controlled reduction of dihydroxycopper(I), Cu(OH)2(-). A combination of potentiostatic coulometry, UV-visible spectroscopy, and thermodynamic calculations was used to determine the species adding to growing Cu nanowires is Cu(OH)2(-). Cyclic voltammetry was then used to measure the diffusion coefficient of Cu(OH)2(-) in the reaction solution. Given the diameter of a Cu nanowire and the diffusion coefficient of Cu(OH)2(-), we calculated the dependence of the diffusion-limited growth rate on the concentration of copper ions to be 26 nm s(-1) mM(-1). Independent measurements of the nanowire growth rate with dark-field optical microscopy yielded 24 nm s(-1) mM(-1) for the growth rate dependence on the concentration of copper. Dependence of the nanowire growth rate on temperature yielded a low activation energy of 11.5 kJ mol(-1), consistent with diffusion-limited growth.

This article reports the fabrication of copper–platinum core–shell nanowires by electroplating platinum onto copper nanowires, and the first demonstration of their use as a transparent, conducting electrocatalyst for the hydrogen evolution reaction (HER). Cu–Pt core–shell nanowire networks exhibit mass activities up to 8 times higher than carbon-supported Pt nanoparticles for the HER. Electroplating minimizes galvanic replacement, allowing the copper nanowires to retain their conductivity, and eliminating the need for a conductive substrate or overcoat. Cu–Pt core–shell nanowire networks can thus replace more expensive transparent electrodes made from indium tin oxide (ITO) in photoelectrolysis cells and dye sensitized solar cells. Unlike ITO, Cu–Pt core–shell nanowire films retain their conductivity after bending, retain their transmittance during electrochemical reduction, and have consistently high transmittance (>80%) across a wide optical window (300–1800 nm).

Recently, lithium-ion batteries (LIBs) have been applied to large-scale devices such as electric vehicles and energy storage systems (ESSs), requiring high energy density and long cycle life. The use of organic electrolytes in lithium ion batteries in such large-scale devices has some safety issues. Organic electrolytes have a high ionic conductivity, but there are many risks of leakage, explosion and ignition due to the decomposition reaction of the electrolyte. As a promising solution to this issues, the use of a solid electrolyte have been proposed. In contrast to organic-based liquid electrolytes, all-solid-state lithium batteries (ASLBs) with a solid electrolyte are considered safe because of their non-flammability. These solid electrolytes have the advantages of high stability and high energy density, but they have a disadvantage of very low ionic conductivity at room temperature. In this work, we prepared sheet-type Li6PS5Cl-infiltrated electrode that has high capacity, even though it has high loading value. We propose two methods to ensure that SE materials are evenly distributed and sufficiently infiltrated into the porous structures of LIB electrode. First, we aimed to reveal the effects of solid electrolyte solution vaporization on the solid electrolyte content in the thick electrode for ASSBs. The performance of the cells at different temperatures were compared. Elevated temperature of SE solution arrive at vaporization point and it result in molecular motion, and it makes more LPSCl infiltrated into electrode. The NCM622 electrode infiltrated LPSCl at 90oC show reversible capacity of 177mAh/g (5.5mg/cm2) and 136mAh/g (17mg/cm2) at 0.05C, 55oC. We also prepared three different active materials having different particle size. The porous electrode which is made by mixing different sized active materials(DS-AM) absorbs SE solution. This absorb effects explain the capillary phenomena. The mixed DS-AM electrode demonstrated higher capacity than non-mixed DS-AM electrodes due to the improved ion transport path.

The lithium-ion battery (LIB) is the primary choice for many applications such as mobile electronics, electric vehicles, and stationary energy storage solutions due to its high energy density, high voltage and low self-discharge rate. Reported safety incidents related to LIBs have resulted in an increased attention toward the safety issue of the LIB. In the operation of LIBs, there are many sorts of field failures including overheat, overcharge, and short circuit. External short circuit (ESC) is a severe fault which causes the large current flow and high temperature rise in an LIB immediately. Modeling to predict the maximum current flow and temperature rise of an LIB under ESC fault is essential to design an effective fault detection and diagnosis system for the safety management of LIB. In this work, a modeling is performed to predict the electrical and thermal behaviors of an LIB cell under ESC conditions. The validation of the modeling approach is provided through the comparison of the modeling results for a 75Ah LIB cell from KOKAM with the experimental measurement data obtained from the ESC tests. The ESC tests were carried out using the external resistances of 0, 2, and 5 mΩ. Model predictions reasonably reproduce the experimental data.

Yazami1 reports on the thermodynamics of lithium ion battery. The understanding on heat generation of battery during charge and discharge and on heat dissipation is very important to maintain within appropriate temperature range2-4. Especially, it is highly important in the case of the battery of large capacity. Here, drastic discharge with external resistance was studied with experimental and computational approach applying evaluated parameters of entropy, internal resistance, specific heat and open circuit cell potential. The coulombic capacity of used cell was ca 100 Ah. A case of external short was presented as below figure. Acknowledgment: This study was supported by the KERI R&D program of MSIP/NST (18-12-N0103-01) and 18-02-N0108-02. References: Kazunori Ozawa, Lithium Ion Rechargeable Batteries, Ch. 5, Wiley-VCH Verlag GmbH & Co. KGaA, 2009. K. Maher, R. Yazami, Electrochimica Acta, 101 (2013) 71. K. Jalkanen, T. Aho, K. Vuorilehto, Journal of Power Sources 243 (2013) 354. D.H. Jeon, S.M. Baek, Energy Conversion and Management 52 (2011) 2973 Dong Hyup Jeon, Current Applied Physics 14 (2014) 196. Figure 1

The low performance or high cost of commercially available conductive inks limits the advancement of printed electronics. This article studies the explosion of metal wires in aqueous solutions as a simple, low-cost and environmentally friendly method to prepare metallic nanoparticles consisting of Cu and Cu alloys for use in affordable, highly conductive inks. Addition of 0.2 M ascorbic acid to an aqueous explosion medium prevented the formation of Cu2O shells around Cu nanoparticles and allowed for the printing of conductive lines directly from these nanoparticles with no post-treatment. Cu alloy nanoparticles were generated from metal wires that were alloyed as purchased, or from two wires of different metals that were twisted together. Cu nanoparticles alloyed with 1% Sn, 5% Ag, 5% Ni and 30% Ni had electrical conductivities similar to Cu but unlike Cu, remained conductive after 24 hrs at 85 °C and 85% RH.