Electrolyte Concentration Regulation Boosting Zinc Storage Stability of High-Capacity K0.486V2O5 Cathode for Bendable Quasi-Solid-State Zinc Ion Batteries

Vanadium-based cathodes have attracted great interest in aqueous zinc ion batteries(AZIBs)due to their large capacities,good rate performance and facile synthesis in large scale.However,their practical application is greatly hampered by vanadium dissolution issue in conventional dilute electrolytes.Herein,taking a new potassium vanadate K0.486V2O5(KVO)cathode with large interlayer spacing(~0.95 nm)and high capacity as an example,we propose that the cycle life of vanadates can be greatly upgraded in AZIBs by regulating the concentration of ZnCl2 electrolyte,but with no need to approach“water-in-salt”threshold.With the optimized moderate concentration of 15 m ZnCl2 electrolyte,the KVO exhibits the best cycling stability with ~95.02% capacity retention after 1400 cycles.We further design a novel sodium carboxymethyl cellulose(CMC)-moderate concentration ZnCl2 gel electrolyte with high ionic conductivity of 10.08 mS cm^-1 for the first time and assemble a quasi-solid-state AZIB.This device is bendable with remarkable energy density(268.2 Wh kg^−1),excellent stability(97.35% after 2800 cycles),low self-discharge rate,and good environmental(temperature,pressure)suitability,and is capable of powering small electronics.The device also exhibits good electrochemical performance with high KVO mass loading(5 and 10 mg cm^-2).Our work sheds light on the feasibility of using moderately concentrated electrolyte to address the stability issue of aqueous soluble electrode materials.

Investigation on pumping oxygen characteristics of (Bi_2O_3)_(0.73)(Y_2O_3)_(0.27) solid electrolyte

（Bi2O3）0.73（Y2O3）0.27 fine powders prepared by wet chemical precipitation method were cold isostatically pressed to form solid electrolyte tubes, and sintered at 900 ℃ for 10 h in the air. Their pumping oxygen characteristics in non-dehydrated Ar gas were investigated, where a ZrO2 （Y2O3 stabilized） oxygen sensor was used to measure the oxygen partial pressure Po2. The results showed that the Po2 value reached magnitudes of 1×10^-2-1×10^-10 Pa at the applied pumping oxygen voltage of 0.5 V, 1×10^-37-1×10^-27 Pa at 1.0 V and 1×10^-53-1×10^47 Pa at 2.0 V within the temperature range from 550 to 650 ℃. Moreover, no cracks were found in the tested solid electrolyte tubes. Thus, the Bi2O3-Y2O3 system might be used in solid electrolyte oxygen pump for purifying gases.

La2Zr2O7 and MgO co-doped composite Li-Garnet solid electrolyte

Various solid electrolytes,such as sulfides(10^-3-10^-2 S cm^-1)and oxides(10^-4–10^-3 S cm^-1)are explored and developed to solve the safety problems in commercial Li-ion batteries using liquid flammable electrolytes.Metallic Li anode is required for pursuing high power density(>300 Wh kg^-1)for solid-state batteries[1,2].

Manipulating interfacial stability of LiNi0.5Co0.3Mn0.2O2 cathode with sulfide electrolyte by nanosized LLTO coating to achieve high-performance all-solid-state lithium batteries

All-solid-state lithium batteries(ASSLBs) based on sulfide solid-state electrolytes and high voltage layered oxide cathode are regarded as one of the most promising candidates for energy storage systems with high energy density and high safety.However,they usually suffer poor cathode/electrolyte interfacial stability,severely limiting their practical applications.In this work,a core-shell cathode with uniformly nanosized Li0.5La0.5TiO3(LLTO) electrolyte coating on LiNi0.5Co0.3Mn0.2O2(NCM532) is designed to improve the cathode/electrolyte interface stability.Nanosized LLTO coating layer not only significantly boosts interfacial migration of lithium ions,but also efficiently alleviates space-charge layer and inhibits the electrochemical decomposition of electrolyte.As a result,the assembled ASSLBs with high mass loading(9 mg cm-2)LLTO coated NCM532(LLTO@NCM532) cathode exhibit high initial capacity(135 mAh g^(-1)) and excellent cycling performance with high capacity retention(80% after 200 cycles) at 0.1 C and 25℃.This nanosized LLTO coating layer design provides a facile and effective strategy for constructing high performance ASSLBs with superior interfacial stability.

Hybrid polymer electrolyte for Li–O_2 batteries

Li–O_2 batteries have attracted much attention because of their high specific energy. However, safety problem generated mainly from the flammable organic liquid electrolytes have hindered the commercial use of Li–O_2 batteries. One of the competitive alternatives is polymer electrolytes due to their flexibility and non-flammable property. Moreover, the hybrid polymer electrolyte with enhanced electrochemical properties would be achieved by incorporating inorganic filler, liquid plasticizer and redox mediator into the polymer. While most researches of the hybrid polymer electrolyte focused on Li-ion batteries, few of them took account into its application in Li–O_2 batteries. In this review, we mainly discuss hybrid polymer electrolytes for Li–O_2 batteries with different composition. The critical issues including conductivity and stability of electrolytes are also discussed in detail. Our review provides some insights of hybrid polymer electrolytes for Li–O_2 batteries and offers necessary guidelines for designing the suitable hybrid polymer electrolyte for Li–O_2 batteries as well.

Decomposition pathway and stabilization of ether-based electrolytes in the discharge process of Li-O_(2) battery

Ether-based electrolytes with relatively high stability are widely used in Li-O_(2) batteries (LOBs) with high energy density.However,they are still prone to be attacked by reactive oxygen species.Understanding the degradation chemistry of ether-based solvent induced by reactive oxygen species is significant importance toward selection of stable electrolytes for LOBs.Herein,we demonstrate that a great amount of H_(2) gas evolves on the Li anode during the long-term discharge process of LOBs,which is due to the electrolyte decomposition at the oxygen cathode.By coupling with in-situ and ex-situ characterization techniques,it is demonstrated that O_(2)^(-) induces the H-abstraction of tetraethylene glycol dimethyl ether(TEGDME) to produce a large amount of H_(2)O at cathode,and this H_(2)O migrates to Li anode and produce H_(2) gas.Based on the established experiments and spectra,a possible decomposition pathway of TEGDME caused by O_(2)^(-)at the discharge process is proposed.And moreover,three types of strategies are discussed to inhibit the decomposition of ether-based electrolytes,which should be highly important for the fundamental and technical advancement for LOBs.

Study on Kinetics of O_2/CO_2 Reaction in Cs_2CO_3 Electrolyte on Porous Pt/C Electrode

fuel cell with porous Pt/C electrodes is used to study O2/CO2 reaction in Cs2CO3 electrolyte and a Hg/HgO reference electrode is used to measure anodic and cathodic polarization during electrolysis. Steadystate polarization curves are obtained at 290-308K with various CO2/O2 mixtures. Kinetic analysis in the linear overpotential region indicates that (logjo/logP) is 0.02 for CO2 and 0.24 for O2. The reaction orders are 1/4 in CO2 and 3/8 in O2 in the cathodic direction, and -3/4 in CO2 and -1/8 in O2 in the anodic direction.

Highly reinforce the interface stability using 2-Phenyl-1H-imidazole-1-sulfonate electrolyte additive to enhance the high temperature performance of LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)/graphite batteries

This work develops 2-Phenyl-1H-imidazole-1-sulfonate(PHIS)as a multi-functional electrolyte additive for H2O/HF scavenging and film formation to improve the high temperature performance of LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)/graphite batteries.After 450 cycles at room temperature(25℃),the discharge capacity retentions of batteries with blank and PHIS-containing electrolyte are 56.03%and 94.92%respectively.After 230 cycles at high temperatures(45℃),their values are 75.30%and 88.38%respectively.The enhanced electrochemical performance of the batteries with PHIS-containing electrolyte is supported by the spectroscopic characterization and theoretical calculations.It is demonstrated that this PHIS electrolyte additive can facilitate the construction of the electrode interface films,remove the H2O/HF in the electrolyte,and improve the electrochemical performance of the batteries.This work not only develops a sulfonate-based electrolyte but also can stimulate new ideas of functional additives to improve the battery performance.

Relationship between CO_2 Sensor Voltage Response and Phase Equilibrium of Solid Electrolyte Na,K-β/β″-Al_2O_3

A type of CO2 sensor based on oxygen concentration cell was designed as following: Cell I: Pt | Au, O2, CO2| Na2CO3(Au)|NKBA(Au)|YSZ|O2, CO2|Pt or Cell lI: Pt|Au, O2, CO2|K2CO3(Au)|NKBA(Au)|YSZ|O2, CO2|Pt. (Na,K-β/β'-AI2O3 is named by NKBA). The sensor signal is consistent with the Nernstian slope within the region of phase equilibrium for Na, K-β/β'-AI2O3 material. The relationship between CO2 sensor voltage response and phase equilibrium of solid electrolyte Na, K-β/β-AI2O3 is discussed in this paper.

V-L EQUILIBRIUM OF WEAK ELECTROLYTE SOLUTION OF THE NH_3-CO2-H_2O,NH_3-H_2S-H_2O AND NH_3-SO_2-H_2O SYSTEM

In this paper we have systematically studied V-L equilibrium in ternary aqueous solutions containingvolatile electrolytes by introducing a ternary interaction term into Edwards generalized molecular thermody-namic model and optimizing several adjustable parameters.The program PARA9 with flexible functions ofdoing a series of calculations has been developed and carried out on a TQ-16 computer.It can be usedeither for directly calculating the V-L equilibrium or for optimizing the adjustable parameters.For the sys-toms（NH3-CO3-H2O3,NH3-H2S-H2O and NH3-SO2-H2O）satisfactory results have been obtained withrelative mean deviation of 5-10%.Besides,several sets of adjustable parameters and valuable information ofactivity coefficients,equilibrium concentrations of ions and molecules in solutions are obtained.

Protective electrode/electrolyte interphases for high energy lithium-ion batteries with p-toluenesulfonyl fluoride electrolyte additive

High energy density lithium-ion batteries using Ni-rich cathode(such as LiNi0.6Co0.2Mn0.2O2) suffer from severe capacity decay.P-toluenesulfonyl fluoride(pTSF) has been investigated as a novel film-forming electrolyte additive to enhance the cycling performances of graphite/LiNi0.6Co0.2Mn0.2O2 pouch cell.In comparison with the baseline electrolyte,a small dose of pTSF can significantly improve the cyclic stability of the cell.Theoretical calculations together with experimental results indicate that pTSF would be oxidized and reduced to construct protective interphase film on the surfaces of LiNi0.6Co0.2Mn0.2O2 cathode and graphite anode,respectively.These S-containing surface films derived from pTSF effectively mitigate the decomposition of electrolyte,reduce the interphasial impedance,as well as prevent the dissolution of transition metal ions from Ni-rich cathode upon cycling at high voltage.This finding is beneficial for the practical application of high energy density graphite/LiNi0.6Co0.2Mn0.2O2 cells.

Effects of Yttrium Ion on Formation Mechanism of ZrO_2-Y_2O_3 Ceramic Coatings Formed by Plasma Electrolytic Oxidation on Al-12Si Alloy

ZrO2-Y2O3 ceramic coating was produced by plasma electrolytic oxidation （PEO） on ZAlSil2Cu3Ni2 alloy. The microstructure and phase composition of the coating were investigated by SEM and XRD.： The results show that adding an appropriate amount of yttrium ion can improve the growing rate of ceramic coating at different oxidation stages and decrease arc voltage. The thickness of ZrO2-Y2O3 coating is 16 μn thicker than that of ZrO2 coating and the maximum oxidation rate improves by 0.6 μm/min. In addition, the arc voltage decreases from 227 to 172 V. It can be seen that the rate of oxidation firstly increases to some extent and then decreases with the content of yttrium ion increasing. The growth rate reaches the maximum while the content of yttrium ion is 0.05 g-L-1The maximum thickness is 90 μm.Compared to ZrO2 coating, the micropores of ZrO2-Y2O3 coating are less and the ceramic layer is repeatedly deposited by ZrO2 and Y2O3 ceramic particles. Meanwhile, the binding force between coating and substrate is better and the coating is uniform and compact. The ceramic layer is mainly composed of c-Y0.15Zr0.85O1.93□0.07, m-ZrO2, α-Al2O3, ,γ-Al2O3 and Y2O3. It is indicated that ZrO2 has beert fully stabilized by yttrium ion through the formation of solid solution.

Anthraquinone derivative as high-performance anode material for sodium-ion batteries using ether-based electrolytes

Organic materials, especially the carbonyl compounds, are promising anode materials for room temperature sodium-ion batteries owing to their high reversible capacity, structural diversity as well as eco-friendly synthesis from bio-mass. Herein, we report a novel anthraquinone derivative, C_(14)H_6 O_4 Na_2 composited with carbon nanotube(C_(14)H_6 O_4 Na_2-CNT), used as an anode material for sodium-ion batteries in etherbased electrolyte. The C_(14)H_6 O_4 Na_2-CNT electrode delivers a reversible capacity of 173 mAh g^(-1) and an ultra-high initial Coulombic efficiency of 98% at the rate of 0.1 C. The capacity retention is 82% after 50 cycles at 0.2 C and a good rate capability is displayed at 2 C.Furthermore, the average Na insertion voltage of 1.27 V vs. Na^+/Na makes it a unique and safety battery material, which would avoid Na plating and formation of solid electrolyte interface. Our contribution provides new insights for designing developed organic anode materials with high initial Coulombic efficiency and improved safety capability for sodium-ion batteries.

Formation mechanism of Al2O3/MoS2 nanocomposite coating by plasma electrolytic oxidation(PEO)

In this study,an Al2O3/MoS2 nanocomposite coating was created on an aluminum 1050 substrate using the plasma electrolytic oxidation method.The zeta potential measurements showed that small MoS2 particles have negative potential and move toward the anode electrode.The nanoparticles of MoS2 were found to have a zeta potential of-25 mV,which prevents suspension in the solution.Thus,to produce an Al2O3/MoS2 nanocomposite,one has to use the microparticles of MoS2.The X-ray diffraction analyses showed that the produced coatings containedα-Al2O3,γ-Al2O3,and MoS2,and that the size of MoS2 particles can be reduced to 30 nm.It was observed that prolonged suspension in the electrolyte results in an enhanced formation of an Al2O3/MoS2 nanocomposite.Using the results,it was hypothesized that the mechanism of the formation of the Al2O3/MoS2 nanocomposite coating on the aluminum 1050 substrate is based on electrical energy discharge.

Synthesis and Characterization of a Novel Polymer Electrolyte for Lithium-ion Battery

A novel polymer electrolyte with the formula of Li2B4O7-PVA for lithium-ion battery was synthesized and its ion conductivity and mechanical properties were also tested. It is found that the conductivity of the prepared polymer electrolytes is higher than that of LiClO4/PEO or LiClO4/EC-DMC by two or three orders in magnitude and a large delocalized bond formed in Li2B4O7-PVA lead to transportation of Li ion easier, this electrolyte possesses high thermo-stability and can be used under 200C.

Impact of Separator Thickness on Temperature Distribution in Single Polymer Electrolyte Fuel Cell Based on 1D Heat Transfer

It is known from the New Energy and Industry Technology Development Organization (NEDO) roam map Japan, 2017 that the polymer electrolyte fuel cell (PEFC) power generation system is required to operate at 100°C for application of mobility usage from 2020 to 2025. This study aims to clarify the effect of separator thickness on the distribution of the temperature of reaction surface (Treact) at the initial temperature of cell (Tini) with flow rate, relative humidity (RH) of supply gases as well as RH of air surrounding cell of PEFC. The distribution of Treact is estimated by means of the heat transfer model considering the H2O vapor transfer proposed by the authors. The relationship between the standard deviation of Treact-Tini and total voltage obtained in the experiment is also investigated. We can know the effect of the flow rate of supply gas as well as RH of air surrounding cell of PEFC on the distribution of Treact-Tini is not significant. It is observed the wider distribution of Treact-Tini provides the reduction in power generation performance irrespective of separator thickness. In the case of separator thickness of 1.0 mm, the standard deviation of Treact-Tini has smaller distribution range and the total voltage shows a larger variation compared to the other cases.

稳态法联合检测CO_2和O_2的全固态电化学传感器研究

基于O2 和CO2 在Au微电极上的稳态电化学响应特性和新型高分子固体聚合物电解质研究 ,构建了一类全新的固态电化学传感器 ,实现了常温下气体O2 和CO2 的联合检测 ,不仅消除了常规电化学传感器中电解液渗漏或干涸对器件性能的影响 ,而且具有体积小、结构紧凑。

稀土氧化物Gd_(2)O_(3)、Nd_(2)O_(3)、Sm_(2)O_(3)和Dy_(2)O_(3)在KCl-LiCl-Li_(2)O熔盐中的电解

采用循环伏安法和计时电位法研究了Li_(2)O在KCl-LiCl熔盐中的电化学行为,并利用卷积伏安法计算了923 K下O_(2)-在KCl-LiCl熔盐中的扩散系数(D),得到D=0.5×10^(-5) cm^(2)/s。以Gd_(2)O_(3)、Nd_(2)O_(3)、Sm_(2)O_(3)和Dy_(2)O_(3)为阴极,在KCl-LiCl-Li_(2)O(w=1%)熔盐中进行电解(恒电压3.40 V、电解温度923 K、电解时间25 h)。通过X射线衍射分析(XRD),证实稀土氧化物被部分还原为金属,并分析了电解过程中可能发生的反应。同时利用PRS模型(该模型可将固态阴极内离子的极限扩散速率与固态氧化物孔隙P、金属/氧化物摩尔体积R、阴极还原后的体积收缩率S等参数关联)分析了这些稀土氧化物的电解还原模型,得到Gd_(2)O_(3)、Nd_(2)O_(3)、Sm_(2)O_(3)和Dy_(2)O_(3)的最优孔隙率分别为18.7%、24.2%、30.6%、16.7%,最短电解时间分别为133、157、143、119 h,将这些结果与电解实验结果进行对比,发现阴极的孔隙率和电解时间均不满足金属氧化物完全被还原的要求,并给出了相应的解释。

Mo-Bi-S@CNTs纳米双金属硫化物电催化CO_(2)还原制取甲醇的性能

采用水热法原位合成碳纳米管(CNTs)负载Mo-Bi-S纳米颗粒的复合催化剂(Mo-Bi-S@CNTs),考察了水热温度对催化剂形貌结构和CO2电催化性能的影响。结果表明:水热温度为200℃时制备的Mo-Bi-S@CNTs催化剂的颗粒尺寸较小,约为10~15 nm,并且能够均匀地负载在CNTs上。同时,该催化剂在[NH2-emim]BF4-H2O(ω=40%)电解液中展现出了较为优异的电催化性能。在过电位为-0.3 V vs.SCE时,作为主产物甲醇的法拉第转化效率高达63.0%;恒电位下连续运行6 h电流密度保持在-13.5 mA/cm^(2)左右。研究结果表明Mo-Bi-S@CNTs-200℃是一种具有良好应用前景的CO_(2)还原电催化剂。

Thermodynamic modeling and phase diagram prediction of salt lake brine systems.Ⅰ. Aqueous Mg^2+–Ca^2+–Cl^- binary and ternary systems

Salt lake brine is a complex salt-water system under natural environment.Although many models can express the thermodynamic properties and phase equilibrium of electrolyte aqueous solution,the multi-temperature characteristics and predictability are still the goals of model development.In this study,a comprehensive thermodynamic model system is re-established based on the eNRTL model and some improvements:(1) new expression of long-range electrostatic term with symmetrical reference state is proposed to handle the electrolyte solution covering entire concentration range;(2) the temperature dependence of the binary interaction parameters is formulated with a Gibbs Helmholtz expression containing three temperature coefficients,the liquid parameters,which associated with Gibbs energy,enthalpy,and heat capacity contribution;and(3) liquid parameters and solid species data are regressed from properties and solubility data at full temperature range.Together the activity coefficient model,property models and parameters of liquid and solid offer a comprehensive thermodynamic model system for the typical bittern of MgCl2-CaCl2-H2 O binary and ternary systems,and it shows excellent agreement with the literature data for the ternary and binary systems.The successful prediction of complete phase diagram of ternary system shows that the model has the ability to deal with high concentration and high non-idealitv system,and the ability to extrapolate the temperature.