bluuebunny/crossref_metadata_2025_split huggingface dataset:
Influence of the Stretching on the Ionic Conductivity of Solid Polymer Electrolyte
Authors: Jeanne-Brou Roselyne , de Moor Gilles , Charvin Nicolas , Flandin Lionel , Bouchet Renaud , Devaux Didier 
Published: December 2020

Conventional Li-ion batteries contain flammable liquid based electrolytes that can leak and react violently with the environment leading to a fire.[1] A solution is to replace the liquid electrolyte by a Solid Polymer Electrolytes (SPEs). Indeed, SPEs are of interest thanks to their flexibility, process easiness, lack of volatile compounds, and chemical and electrochemical stability toward one the most promising anode material, i.e. Li metal.[2]
Among the variety of SPEs reported in literature, Poly(ethylene oxide) (PEO) doped with a Li salt is the most studied polymer electrolyte.[3] Indeed, PEO contains ether coordination sites that efficiently dissociate Li salts and its flexible macromolecular backbone enables ionic transport. Ionic conduction in SPEs depends for a large part on the dynamics of the polymer chains (ref. Devaux et al. SSI 2012). Therefore, a fine understanding of the relationship between polymer chain conformation and ionic conductivity is necessary to pave the way toward an optimized SPE. The goal being to produce a SPE suitable for a Li metal battery operating at room temperature.
In this study, we report first on a setup designed to stretch SPE coupled with impedance spectroscopy in controlled Argon atmosphere. As an example, Figure 1 shows the impedance spectra under Argon at room temperature of a SPE made of high molecular weight PEO laden with LiTFSI (EO:Li =25) at different elongations (ε). Then, in-plane and through-plane conductivity of SPEs have been compared. 3 different type of SPEs has been studied of i) reference PEO/LiTFSI, ii) block copolymer electrolyte comprising polystyrene and PEO blocks (ref. Bouchet et al, Macromolecules 2014), and iii) composite electrolytes where PEO or the block copolymer is mixed with inorganic particles.

References

[1] D. Lisbona, T. Snee, Process Saf.
Environ., 89 (2011) 434.
[2] W. Xu et al., Energy Environ. Sci., 7 (2014) 513.
[3] R C. Agrawal, G. P. Pandey, J. Phys, D, 41 (2008) 223001.

Figure 1
Advanced Hybrid Electrodes Based on Polyoxometalate–Activated Carbon for Electrochemical Energy Storage in Li-Ion Batteries
Authors: Bosch Georg-Maximilian , Treffehn Patrick , Dsoke Sonia 
Published: December 2020

For fast charging and speeding up an electric vehicle, the high power of supercapacitors is needed. Driving a long distance can be realized by the high capacity of a battery. A combination of the advantages of supercapacitors and batteries in one material can bring novel possibilities for electric mobility in the future. Therefore, hybrid materials have attracted much attention in recent years, since they can simultaneously deliver high power and high energy density [1]. Polyoxometalates (POMs), for example, the α-Kegging type: y H+·[XM12O40]-y, are well known as very stable towards oxidation and reduction. These materials show fast and reversible multi-electron transfer reactions [2], and can, therefore, be considered as a promising candidate. In previous experiments, the properties of the POM were optimized for the use in an organic electrolyte by temperature treatment, and the cycling stability of the material improved by 20-times [3].
In this work, activated carbon (AC) was used to prepare POM@AC hybrid material. Due to the absorption properties of the activated carbon, the maximum POM amount was 45 %-wt. The high- temperature optimization of the POM was achieved in one step together with the activated carbon. The combination and optimization of the two materials enables increased cycling stability, as well as a higher capacity with respect to the two single materials (Fig.1). SEM revealed a smaller POM particle size. Therefore the increased capacity can be related to a higher surface of the active material. Further, the hybrid material was characterized by XRD, TGA-DSC, and electrochemically.
Future experiments will focus on increasing the amount of POM on the activated carbon. A higher percentage of POM in the hybrid material, as well as a better distribution of the particles on the surface, can lead to an increase in capacity.

Acknowledgment

This work contributes to the research performed at CELEST (Center for Electrochemical Energy Storage Ulm-Karlsruhe).
[1] M. Genovese, K. Lian, Polyoxometalate modified inorganic–organic nanocomposite materials for energy storage applications: A review, Curr. Opin. Solid State Mater. Sci. 19 (2015) 126–137.
[2] M. Sadakane, E. Steckhan, Electrochemical properties of polyoxometalates as electrocatalysts, Chem. Rev. 98 (1998) 219–237.
[3] G.-M. Bosch, S. Dsoke, Paper in progress, (2020).

Figure 1
Redox Synthesis and Characterization of Layered LiNi1/3Co1/3Mn1/3O2 for Rechargeable Lithium Ion Batteries
Authors: Song Moonsoo , Lee Seulgi , Mathew Vinod , Alfaruqi Muhammad Hilmy , Lee Jun , Kim Jaekook 
Published: December 2020

This study reports on the characterization of layered Li (Ni1/3Co1/3Mn1/3)O2 (x = 1.05 and 1.1) cathodes synthesized by a simple ambient temperature redox synthesis and post-heat treatment with added lithium sources.
Synchrotron XANES and ICP measurements were performed to confirm the change in oxidation state during the redox reaction and the successful control of the stoichiometric ratio of ternary transition metal oxides (Ni2+
0.33Co3+
0.35Mn4+
0.32Oy).
In the FE-SEM image, loosely aggregated particles with an average diameter of 60nm appeared in the intermediate product, and the particle size grew to several hundred nanometers after lithiation at elevated temperature.
The electrochemical performances at 14 mAg-1 in the potential range of 3.0–4.3V vs. Li/Li+ indicated that reasonable specific capacities and cycle performances are registered for all the prepared cathodes. especially, the Li1.05(Ni1/3Co1/3Mn1/3)O2 composition demonstrated the highest capacity retention value (~99%) after 50 cycles and better rate performances (104, 91, 76, and 67 mAhg-1) at high current densities (229, 457, 914, and 1429 mAg-1 respectively).
Stabilization of Li Metal Powder Anodes on Cu Foil Current Collectors Using Thin Carbon Interlayers
Authors: Jin Dahee , Roh Youngjoon , Lee Hongkyung , Ryou Myung-Hyun , Lee Yong Min 
Published: December 2020

Due to the highest theoretical capacity, the Li metal anode is considered to be the most ideal anode materials for large-scale batteries, if the problems related to Li dendrite growth can be overcome. Obviously, as most people know well, enlarging the surface area of the Li metal has quite an influence on lower the effective current density to suppress the lithium dendrite growth of lithium metal secondary batteries (LMSB). For this reason, lithium metal powder (LiMP) has attracted much attention for use in electrodes because of its 4.5 times higher surface area compared to lithium foil. However, the electrolyte can be fully penetrated to the LiMP electrode due to its porosity, which leads to galvanic corrosion between Cu foil and LiMP particles. Furthermore, repeated cycling deepens the delamination of lithium particles from Cu foil and results in excess dead lithium particles.
Herein, we address this problem by coating the submicron-thickness (~600 nm) carbon interlayer on Cu foil for the LiMP electrode. Despite the LiMP electrode that exists under the electrolyte, the nanoscale carbon interlayer plays an important role in enhancing the adhesive strength between LiMP particle and Cu foil. To confirm the role of the carbon interlayer, we succeeded in quantifying the adhesive strength at the Li/Cu interface for the first time using a surface and interfacial cutting analysis system (SAICAS). Furthermore, the seeding effect of the carbon interlayer in Li/Li symmetric cells and improving electrochemical performance in thin LiMP (40 μm) based cell.
Surface Double Coating of LiNiaCobAl1-a-bO2 (a > 0.85 ) Cathode with Tiox and Li2CO3 to Apply a Water-Based Hybrid Polymer Binder to Li-Ion Batteries’ Preparation
Authors: Watanabe Tatsuya , Hirai Kouji , Ando Fuma , Kurosumi Shoudai , Ugawa Shinsaku , Lee Hojin -J , Irii Yuta , Maki Fumihiko , Gunji Takao , Wu Jianfei , Ohsaka Takeo , Matsumoto Futoshi 
Published: December 2020

Recently a water-based polymer binder has been getting much attention to simplify the production process of lithium ion batteries (LIBs) and reduce their cost. The surface of LiNiaCobAl1-a-bO2 (a > 0.85, NCA) cathode with a high voltage and high capacity was coated doubly with water-insoluble titanium oxide (TiOx) and Li2CO3 layers to protect the NCA surface from the damage caused by contacting it with water during its production process. The TiOx layer was at first coated on the NCA particle surface with a tumbling fluidized-bed granulating/coating machine for producing TiOx-coated NCA. However, the TiOx layer could not coat the NCA surface completely. In the next place, the coating of the TiOx-uncoated NCA surface with Li2CO3 layer was conducted by bubbling CO2 gas in the TiOx-coated NCA aqueous slurry on the ground that Li2CO3 is formed through the reaction between CO3
2- ions and LiOH residua on the TiOx-uncoated NCA surface, resulting in the doubly coated NCA particles (TiOx/Li2CO3-coated NCA particles). The Li2CO3 coating is considered to take place on the TiOx layer as well as the TiOx-uncoated NCA surface. The results (Fig.1) demonstrate that the double coating of the NCA surface with TiOx and Li2CO3 allows for a high water-resistance of the NCA surface and consequently the TiOx/Li2CO3-coated NCA particles cathode prepared with a water-based binder possesses the same charge/discharge performance as obtained with “water-uncontacted” NCA particles cathode prepared using the conventional organic solvent-based polyvinylidene difluoride binder.
Fig. 1 Charge/discharge cycle performance obtained with the cathodes prepared from (black circle) the slurry consisting of pristine NCA, PVdF and AB, (red circle) the water-based slurry consisting of TiOx/Li2CO3-coated NCA (the slurry was kept for 7 days under CO2 atmosphere), TRD202A, CMC and AB, (blue circle) the water-based slurry consisting of TiOx-coated NCA, TRD202A, CMC and AB and (green circle) the water-based slurry consisting of Li2CO3-coated NCA (the slurry was kept for 1 h under CO2 atmosphere), TRD202A, CMC and AB at the charging/discharging rate of 0.1 C at 25℃.

Figure 1
Effect of Na3BO3 Addition to Nasicon-Type Na3V2(PO4)3 single-Phase All-Solid-State Battery
Authors: Shirai Nobuaki , Nishio Akira , Inoishi Atsushi , Minami Hironari , Izumi Hiroaki , Okada Shigeto 
Published: December 2020

All-solid-state rechargeable batteries(ASSBs) have been attracting much attention in recent years as an alternative to conventional lithium ion batteries because ASSBs have various advantages such as safety with nonflammable inorganic electrolytes, high energy density. While solid electrolytes which show excellent conductivity of 10-2 S cm-1 were reported in the sulfide-based materials, particularly oxide-based solid-state cell shows large interfacial resistance and prevents commercialization of ASSBs. To address this issue, we have revealed NASICON-type Na3-xV2-xZrx(PO4)3 operates as “single-phase” all- solid-state batteries that were fabricated from a single material [1]. In addition, we have reported the addition of Li3BO3 to a single-phase all-solid-state battery using NASICON-type Li1.5Cr0.5Ti1.5(PO4)3 (LCTP) to improve the packing density and the lithium-ionic conductivity [2]. In this work, based on the above results, we investigate the effect of the addition of Na3BO3 to the NASICON-type Na3V2(PO4)3 (NVP) to enhance their electrochemical properties.
NVP were prepared using conventional solid-state reaction method. NaH2PO4 and V2O5 were mixed in a molar ratio of 3:1. The mixture were sintered twice at 900℃ for 20 h with intermediate regrinding. Both sintering were performed under Ar + H2 (5 vol.%) atmosphere. To obtain Na3BO3, NaOH and H3BO3 were mixed in a molar ratio of 3.2:1 inside an Ar-filled glove box and heated at 400℃ and 450℃ under Ar atmosphere. The obtained NVP was pelletized and annealed at 900℃ for 5 h under Ar + H2 atmosphere. To prepare a NVP-Na3BO3 composite pellet, NVP powder and Na3BO3 powder were mixed in a molar ratio of 95:5 and sintered under the same condition. A thin platinum layer was sputtered on both sides of the pellet as a current collector. Electrochemical measurements were carried out with HS cell (Hohsen Corp.) as the experimental cell.
Figure 1a and 1b show the SEM images of NVP and NVP-Na3BO3. As is clear from them, it is found that by Na3BO3 addition to NVP, many voids between the NVP particles are filled and the packing density is improved. Regarding the cyclability of the NVP-Na3BO3 single-phase cell, a reproducible strange behavior with increasing the utilization on cycling is observed as shown in Figure 1c. However, the similar behavior has been reported for other NVP single-phase batteries [1]. It seems that the conduction path in the system develops and the area that can be used as cathode/anode increases with repeated cycling.
Acknowledgement
This work was supported by Element Strategy Initiative of MEXT, Grant Number JPMXP0112101003.
References
[1] A. Inoishi, T. Omuta, E. Kobayashi, A. Kitajou, S. Okada, Adv. Mater. Interf., 4 (2017) 1600942.
[2] A. Nishio, A. Inoishi, A. Kitajou, S. Okada, J. Ceram. Soc. Japan,
127 (1) (2019) 18-21

Figure 1
Application of Porous Carbon Material As Electrode Material of Polyvalent Cation Electric Double Layer Capacitor (EDLC) for High Capacity
Authors: Okamura Tsubasa , Nakagawa Kiyoharu 
Published: December 2020

An electric double layer capacitor (EDLC) is charged and discharged by the physical adsorption and desorption of electrolyte ions on the electrode surface. EDLC has the advantage that it can be charged and discharged at high speed and has a long life. EDLC is used in memory backup power supplies for personal computers and energy recovery systems for power regenerative brakes in hybrid vehicles and other applications. Therefore, higher energy density is required.
E = 1/2 CV2 ... (1)
Therefore, the energy density increases by increasing the electrostatic capacity and the potential. In the conventional adsorption and desorption of monovalent cations, only one electron can be transferred per cation. Therefore, by adsorption / desorption of divalent cations, two electrons can be exchanged for each cation. Therefore, it was considered that the capacitance can be increased by using an electrolyte solution of divalent cations.
In this study, Li + was used as the monovalent cation and Ca2 + was used as the divalent cation. As the anion, Li +, Ca2 + and ClO4
- and BF4
-, which have a stable anion structure, were used. An organic electrolyte with a wide potential window was used. Propylene carbonate (PC) and γ-butyrolactone (GBL), which are commonly used in EDLC research as a solvent for organic electrolytes, can dissolve the electrolyte used. Was used.
As a result, the capacitance increased when Ca2 + was used as the cation. This is thought to be due to the increase in electron transfer due to the use of the divalent cation. In addition, when GBL is used as the solvent, the electrostatic capacity is further increased. The capacity was increased. We considered that there was a difference in the solvation structure, and evaluated the solvation structure using Raman spectroscopy. As a result, when GBL was used, the coordination number of the solvent molecule decreased and solvation It was thought that the size of the electrode became smaller, the amount of adsorption to the electrode increased, and the capacitance increased.
Electrochemistry of Solvent-Free Liquid Quinones
Authors: Penn Emily E , Baclig Antoino C , Ganapathi Devi , Chueh William C. 
Published: December 2020

Redox flow batteries are a promising candidate for grid energy storage due favorable scaling and cyclability but are limited by low energy density due to poor solubility of active species in both aqueous and organic solvent. To increase the energy density we investigate the use of a solvent free liquid quinone electrolyte, resulting in high active species concentration (>10M). Well studied in aqueous and organic solvents, the electroreduction of quinones has been shown to strongly depend on the solvent [1] and supporting electrolyte [2]. The absence of inert solvent poses additional challenges due to mass transport and reaction effects in highly concentrated solutions [3]. Here we characterize the physical and electrochemical properties of 2,3,5-trimethyl-1,4-benzoquinone, ranging in concentration from a dilute solution in inert organic solvent to a highly concentrated solvent-free liquid quinone. Using ultramicroelectrode techniques, diffusion and redox kinetics are determined for solvated and solvent free liquid quinones to investigate the feasibility of this material for use as a solvent free redox flow battery electrolyte.
References:
[1] M. Quan, D. Sanchez, M. F. Wasylkiw, D. K. Smith, J. Am. Chem. Soc. 2007, 129, 42, 12847-12856
[2] D. Pletcher, H. Thompson, J. Chem. Soc., Faraday Trans. 1998, 94, 3445-3450
[3] R. B. Morris, K. F. Fischer, H. S. White, J. Phys Chem. 1988, 92, 5306-5313
Versatile Battery Insertion Materials: Crystal Structure and Electrochemistry
Authors: Sada Krishnakanth , Barpanda Prabeer 
Published: December 2020

Rechargeable battery technologies became the spotlight of global scientific research in the quest to address growing energy demand. Currently, Li-ion batteries are unanimously occupied consumer electronic sector. These are mostly depending on only two transition elements such as Cobalt (Co) and Nickel (Ni) in popular cathodes LiCoO2 and LiNi1/3Mn1/3Co1/3O2 (NMC). The resource constraints of Co and Ni have paved away for alternate redox chemistry. In this scenario, manganese and vanadium-based layered materials are promising to owe their low-cost, resource-friendly nature with high operational safety. Moreover, the multiple redox states associated with these transition metals are promising to design high energy density cathodes.
Here, we worked on the A2M3O7 (M= V, Mn) class of cathode materials. This family of materials exhibits polymorphism and multiple cationic redox properties. Further, bond valence sum energy calculations (BVSE) discovered a very low migration barrier of the alkali-ion (A) site. It inspired us to examine the intercalation properties of different ions including Li, Na, K and Zn. In each case, we observed interesting crystal chemistry with self-ion exchange property. The residual ions after self-ion exchange acted as pillars to lash out structural collapse during (de)intercalation. The ternary layered Na-Mn-O based metal oxide (Na2Mn3O7) was synthesized using different synthetic routes to tune the size and morphology of Na2Mn3O7 particles. The phase pure Na2Mn3O7 crystallizes in a triclinic layered structure (s.g. P-1). It consists of Mn in major +IV and minor +III oxidation states with electrochemically active Mn4+/Mn3+ redox center. The as-synthesized powder material worked as a versatile cathode for the Li, Na, K and Zn-ion batteries1-4. The systematic electrochemical studies were carried in both the aqueous and non-aqueous electrolytes. It delivered a reversible capacity of ~160, ~140, ~134 and ~330 mA h g-1 respectively with Li, Na, K and Zn metal foil as an anode in half-cell architectures. The detailed (de)intercalation mechanism along with diffusional studies of the various alkali-ions (Li/Na/K) along with Zn-ion will be described to present Na2Mn3O7 as a versatile cathode material.
References:

Adamczyk, V. Pralong, Chem. Mater., 2017, 11, 4645.

Sada, B. Senthilkumar, P. Barpanda, ACS Appl. Energy Mater., 2018, 12, 6719.

Sada, B. Senthilkumar, P. Barpanda, ACS Appl. Energy Mater., 2018, 10, 5410.

Sada, P. Barpanda, MRS Adv., 2019, 49, 2651-2657.
Synthesis and Electrical Properties of Mixed Anion Fluorosulfide Ba18F18in8S21
Authors: Tsukamoto Tomoki , Tachibana Shintaro , Orikasa Yuki 
Published: December 2020

Fluoride-ion batteries that utilize the multi-electron reaction of metal cation have the potential to far improve the energy density compared with the current lithium-ion batteries.1) In addition, the all-solid-state fluoride-ion battery that uses solid electrolyte is attracting great expectations as a battery system that has both safety and high energy density and that can open up new applications. The fluoride-ion solid conductors such as PbSnF4 and Ba1-xLaxF2+x have been widely studied for decades. Although PbSnF4 has a high ionic conductivity of 1.6 mS cm-1, the potential window is narrow, and a high voltage secondary battery cannot be realized by using PbSnF4. Although Ba1-xLaxF2+x has a wide potential window, the conductivity is 0.2 mS cm-1 at 50°C, which is not suitable for practical use at an ambient temperature. To our knowledge, a solid electrolyte that has both high ionic conduction and a wide potential window has not been found at present and the further development of materials is required.
In this study, we have extended the search area to mixed fluoride compounds containing sulfide ion due to its high polarizability. For the crystal structure of the fluorosulfide compound, Ba18F18In8S21 exhibits unique domain structure having Ba-F structure.2) We report the synthesis and electrical property of Ba18F18In8S21.
According the literature, 2) we prepared Ba18F18In8S21 by solid state synthesis. In an Ar atmosphere, BaS:BaF2:In:S = 3:3:4:6 were weighed in molar ratio and mixed in a mortar. The pelletized sample was sealed in vacuum and calcined at 800 °C. From the result of XRD, it was confirmed that the prepared samples contained Ba18F18In8S21 crystal phase with BaF2 and BaS impurities. Therefore, it is necessary to improve the synthesis condition. Since sulfur exhibits a boiling point of 444 °C and indium metal has a melting point of 156 °C, two atoms might be deficient during the calcination. Therefore, In2S3 was used without using sulfur powder and indium metal, and synthesis was performed at a lower temperature of 700 °C. XRD pattern of the latter prepared powder can be indexed with a space group of the reported Ba18F18In8S21, and the lattice constants were a = b = 22.152 Å and c = 12.642 Å. Although this value is equivalent to the literature,2) there was small amount of BaF2 impurity.
In order to evaluate the electrical property of the obtained sample, AC impedance measurement was performed by using two-electrode cell. The conductivity at 140 ° C was the order of 10-8 S cm-1.

M. Reddy, M. Fichtner, J. Mater. Chem.,
21
, 17059-17062 (2011).

Z.-Z. Luo, C.-S. Lin, W.-L. Zhang, H. Zhang, Z.-Z. He and W.-D. Cheng, CrystEngComm,
16
, 2788-2794 (2014).