乙烯硫脲-格氏试剂/THF电解液镁沉积-溶出性能

将乙烯硫脲与不同格氏试剂EtMgBr/THF、PhMgBr/THF、PhMgCl/THF反应制得了3种乙烯硫脲-格氏试剂/THF电解液. 通过循环伏安测试了在Pt电极的镁沉积-溶出性能. 结果表明,形成乙烯硫脲-格氏试剂/THF电解液不改变电解液的镁沉积-溶出性能,却拓宽了其电化学窗口. 如乙烯硫脲-PhMgBr/THF溶液的氧化分解电位可达2.3 V（vs. Mg/Mg²⁺）, 该电解液的电导率随溶液溶度增大先升后降,0.9 mol·L^-1时其电导率最高,可达615 μS·cm^-1. 比较乙烯硫脲-PhMgBr/THF在Pt、Ni、Cu和Al四种金属电极的电化学性能,发现在Ni电极的氧化分解电位最高,可达2.4 V（vs. Mg/Mg²⁺）,且具有良好的镁沉积-溶出性能. CR2016扣式电池的循环测试表明,Ni基底上的镁沉积-溶出电位较低,其循环效率可达到92%,适宜作为实用电池的集流体.     

PP14TFSI离子液体在可充镁电池电解液的应用

制备了可充镁电池电解质苯酚基镁盐,以四氢呋喃（THF）与N-甲基-N-丁基-哌啶-双三氟甲基磺酰胺（PP14TFSI）离子液体混合物代替四氢呋喃作为该电解质的溶剂. 当THF与PP₁₄TFSI体积配比为1:1时,该苯酚基镁盐电解液镁可逆溶出性能最佳,电化学窗口宽（2.7 V vs. Mg）,离子电导率高（7.77 mS·cm^-1）. 此外,热重测试表明离子液体的加入大大降低了THF溶剂的挥发性,提高了可充镁电池的安全性能. 四氢呋喃 + N-甲基-N-丁基-哌啶-双三氟甲基磺酰胺混合溶剂有望作为可充镁电池电解液的首选溶剂.     

苯硫酚盐基溶液的可充镁电池电解液

将4-甲基苯硫酚、4-异丙基苯硫酚和4-甲氧基苯硫酚(RSH)分别与格氏试剂C2H5MgCl/THF(四氢呋喃)反应制得的苯硫酚氯化镁(RSMgCl)(分别标记为MBMC、IPBMC和MOBMC)/THF和进一步与Lewis酸AlCl3反应制得的(RSMgCl)n-AlCl3/THF(n=1,1.5,2)苯硫酚盐基溶液用作可充镁电池电解液,采用循环伏安和恒电流充放电测试研究了电解液的镁沉积-溶出性能和氧化分解电位.结果表明,苯硫酚上的基团种类和RSMgCl与AlCl3的比例对其电化学性能有影响.其中,0.5 mol·L-1(IPBMC)1.5-AlCl3/THF溶液具有最佳的电化学性能,其氧化分解电位适宜(2.4 V(vs Mg/Mg2+)),镁沉积-溶出循环效率稳定,过电位低,电导率较高(2.48 mS·cm-1),与正极材料Mo6S8兼容性良好,且具有一定的空气稳定性,配制方便,有希望应用于实际的可充镁电池体系中.     

吡唑基镁卤化物/四氢呋喃可充镁电池电解液

将不同配比的吡唑与格氏试剂反应制得的吡唑基镁卤化物/四氢呋喃(THF)溶液用作可充镁电池电解液,采用循环伏安和恒电流充放电测试研究了该电解液的镁沉积-溶出性能和氧化分解电位;并通过X射线衍射(XRD)和扫描电镜(SEM)对沉积物的组分和形貌进行了分析.结果表明,吡唑上的取代基、吡唑与格氏试剂的反应配比对电解液的电化学性能都有影响.1 mol·L-11-甲基吡唑-PhMgCl(1:1摩尔比)/THF反应配制的电解液在不锈钢(SS)集流体的阳极氧化分解电位达到2.4 V(vs Mg/Mg2+),并具有镁沉积-溶出电位低、循环稳定性高、配制方便的特点,有希望应用于实际的可充镁电池体系中.     

基于静电纺丝和静电喷射技术的P(VDF-HFP)/Al_2O_3/P(VDF-HFP)复合隔膜的制备与电化学性能分析（英文）

通过静电纺丝和静电喷射技术,将三氧化二铝(Al_2O_3)纳米颗粒沉积在两层聚四氟乙烯六氟丙烯[P(VDF-HFP)]静电纺丝隔膜之间,制备出了具有"三明治"结构的P(VDF-HFP)/Al_2O_3/P(VDF-HFP)复合锂离子电池隔膜.分析了隔膜的形态结构、热收缩性能、拉伸性能、电化学性能以及隔膜在电池中的循环性能.测试结果表明,该复合隔膜比纯P(Vd F-HFP)膜拥有更高的吸液率,隔膜更容易吸收电解液从而形成凝胶聚合物电解质(GPEs).该复合隔膜的拉伸强度在4 MPa左右,相对应的断裂伸长率为261.57%.复合隔膜在室温下的离子电导率为1.61×10~(-3)S/cm,且表现出了较高的电化学稳定性(电化学稳定窗口达到5.4 V).在电池的循环测试中,使用钴酸锂(LiCoCO_2)作为正极材料,由该复合隔膜组装的电池的首次放电比容量达到了理想的水平,为145 m A·h·g~(-1).     

吡唑基镁卤化物/四氢呋喃可充镁电池电解液

将不同配比的吡唑与格氏试剂反应制得的吡唑基镁卤化物/四氢呋喃（THF）溶液用作可充镁电池电解液,采用循环伏安和恒电流充放电测试研究了该电解液的镁沉积-溶出性能和氧化分解电位;并通过X射线衍射（XRD）和扫描电镜（SEM）对沉积物的组分和形貌进行了分析. 结果表明,吡唑上的取代基、吡唑与格氏试剂的反应配比对电解液的电化学性能都有影响. 1 mol·L^-1 1-甲基吡唑-PhMgCl（1：1摩尔比）/THF反应配制的电解液在不锈钢（SS）集流体的阳极氧化分解电位达到2.4 V（vs Mg/Mg²⁺）,并具有镁沉积-溶出电位低、循环稳定性高、配制方便的特点,有希望应用于实际的可充镁电池体系中.     

新型锂盐Li[CF3BF3]电解液的制备与性能

制备了1种高纯度的新型锂盐三氟甲基三氟硼酸锂(Li[CF3BF3]),通过核磁共振(NMR)、元素分析(EA)及离子色谱(IC)对其结构进行表征和杂质分析.采取示差扫描量热(DSC)、交流阻抗(EIS)、循环伏安(CV)和扫描电镜(SEM)等方法研究了1 mol/L Li[CF3BF3]-EC/EMC/DMC(体积比5∶3∶2)电解液的物化和电化学性质.结果表明,Li[CF3BF3]基电解液的电导率和Li+迁移数远高于LiBF4,氧化电位高达5.91 V(vs.Li+/Li),在镍电极表面能观察到可逆的锂沉积-溶出过程,并对Al箔表现出优良的钝化性能.研究了Li[CF3BF3]基电解液的电导率与温度和浓度、黏度与浓度的变化规律,以及一系列浓度电解液的相变规律.Li/C半电池测试结果表明,—CF3取代LiBF4的1个F原子后,其衍生产物Li[CF3BF3]明显改善了电解液与人造石墨的相容性.     

碳酸乙烯酯添加剂对BMImBF4离子液体作为镁沉积—溶解电解液的改性研究

利用恒电流沉积-溶解、交流阻抗、XRD和SEM方法研究了在室温下EC(碳酸乙烯酯)添加剂对BMImBF₄离子液体作为镁沉积电解液的改善情况. 在Mg(CF₃SO₃)₂浓度为0.3 mol•L^－1的BMImBF₄电解液中加入w＝5%(质量分数)的EC后, 沉积—溶解循环过程更加稳定, 并且循环次数明显增加, 可以达到265次以上; 交流阻抗结果显示, 膜电阻和电荷转移电阻有所减少; 从SEM图可以观察到, 在沉积初期原本枝晶态的镁在加入EC后以颗粒状沉积. 可能是EC添加剂在反应中形成的低聚物覆盖在镁的表面, 抑制了枝晶的形成.     

碳酸乙烯酯添加剂对BMImBF4离子液体作为镁沉积—溶解电解液的改性研究

利用恒电流沉积-溶解、交流阻抗、XRD和SEM方法研究了在室温下EC(碳酸乙烯酯)添加剂对BMImBF₄离子液体作为镁沉积电解液的改善情况. 在Mg(CF₃SO₃)₂浓度为0.3 mol•L^－1的BMImBF₄电解液中加入w＝5%(质量分数)的EC后, 沉积—溶解循环过程更加稳定, 并且循环次数明显增加, 可以达到265次以上; 交流阻抗结果显示, 膜电阻和电荷转移电阻有所减少; 从SEM图可以观察到, 在沉积初期原本枝晶态的镁在加入EC后以颗粒状沉积. 可能是EC添加剂在反应中形成的低聚物覆盖在镁的表面, 抑制了枝晶的形成.     

基于静电纺丝和静电喷射技术的P(VDF-HFP)/Al2O3/P(VDF-HFP)复合隔膜的制备与电化学性能分析

通过静电纺丝和静电喷射技术, 将三氧化二铝(Al₂O₃)纳米颗粒沉积在两层聚四氟乙烯六氟丙烯[P(VDF-HFP)]静电纺丝隔膜之间, 制备出了具有“三明治”结构的P(VDF-HFP)/Al₂O₃/P(VDF-HFP)复合锂离子电池隔膜. 分析了隔膜的形态结构、 热收缩性能、 拉伸性能、 电化学性能以及隔膜在电池中的循环性能. 测试结果表明, 该复合隔膜比纯P(VdF-HFP)膜拥有更高的吸液率, 隔膜更容易吸收电解液从而形成凝胶聚合物电解质(GPEs). 该复合隔膜的拉伸强度在4 MPa左右, 相对应的断裂伸长率为261.57%. 复合隔膜在室温下的离子电导率为1.61×10^-3 S/cm, 且表现出了较高的电化学稳定性(电化学稳定窗口达到5.4 V). 在电池的循环测试中, 使用钴酸锂(LiCoCO₂)作为正极材料, 由该复合隔膜组装的电池的首次放电比容量达到了理想的水平, 为145 mA·h·g^-1.     

A Self‐Healing Integrated All‐in‐One Zinc‐Ion Battery

The self‐healing of zinc‐ion batteries (ZIBs) will not only significantly improve the durability and extend the lifetime of devices, but also decrease electronic waste and economic cost. A poly(vinyl alcohol)/zinc trifluoromethanesulfonate (PVA/Zn(CF₃SO₃)₂) hydrogel electrolyte was fabricated by a facile freeze/thaw strategy. PVA/Zn(CF₃SO₃)₂ hydrogels possess excellent ionic conductivity and stable electrochemical performance. Such hydrogel electrolytes can autonomously self‐heal by hydrogen bonding without any external stimulus. All‐in‐one integrated ZIBs can be assembled by incorporating the cathode, separator, and anode into hydrogel matrix since the fabrication of PVA/Zn(CF₃SO₃)₂ hydrogel is a process of converting the liquid to quasi‐solid state. The ZIBs show an outstanding self‐healing and can recover electrochemical performance completely even after several cutting/healing cycles.     

GelatinnZn(CF3SO3)2 Polymer Electrolytes for Electrochromic Devices

The present work is focused on gelatin‐based electrolytes doped with a range of concentration of zinc triflate (Zn(CF₃SO₃)₂). The transparent‐thin‐film samples have been represented by the notation Gelatin_nZn(CF₃SO₃)₂, where n represents the zinc triflate salt concentration in the electrolyte membranes from 0.00 wt% to 10.93 wt% . The samples have been characterized by conductivity measurements, thermal analysis, cyclic voltammetry, X‐ray diffraction (XRD), polarized optical microscopy (POM) and scanning electron microscopy (SEM). The gelatin‐based electrolytes were also tested as ionic conductors in electrochromic devices with the glass/ITO/WO₃/gelatin‐based electrolyte/CeO₂‐TiO₂/ITO/glass configuration.     

集流体对可充镁电池电解液电化学性能的影响

系统研究了铂、镍、不锈钢(SS)、铜、铝五种金属集流体和碳纤维、石墨箔、碳布三种碳纸集流体对“一代” (Mg(AlCl₂BuEt)₂/THF)、“二代” ((PhMgCl)₂-AlCl₃/THF)可充镁电池电解液阳极氧化分解电位和镁沉积-溶出性能的影响。金属镍、不锈钢、铜、铝作为可充镁电池正极的集流体时, 充电至一定电压时自身均会发生腐蚀。其中, 镍和不锈钢可用作充电电压在2.1V(vs Mg/Mg²⁺)以下正极材料的集流体; 铜可用作充电电压在1.8V(vs Mg/Mg²⁺)以下正极材料的集流体。碳集流体比金属集流体具有更高的稳定性, 其中, 碳布作为集流体, 适用于充电电压在2.25V(vs. Mg)(对“一代”电解液)和2.95V(vs Mg/Mg²⁺)(对“二代”电解液)以下的正极材料。     

Preparation and characterization of pva based solid polymer electrolytes for electrochemical cell applications

Solid polymer electrolyte films containing poly(vinyl alcohol) (PVA) and magnesium nitrate (Mg(NO3)2) were prepared by solution casting technique and characterized by using XRD, FTIR, DSC and AC impedance spectroscopic analysis. The amorphous nature of the polymer electrolyte films has been confirmed by XRD. The complex formation between PVA and Mg salt has been confirmed by FTIR. The glass transition temperature decreases with increasing the Mg salt concentration. The AC impedance studies are performed to evaluate the ionic conductivity of the polymer electrolyte films in the range of 303 383 K, and the temperature dependence seems to obey the Arrhenius behavior. Transport number measurements show that the charge transport is mainly due to ions. Electrochemical cell of configuration Mg/(PVA + Mg(NO3)2) (70:30)/(I2 + C + electrolyte) has been fabricated. The discharge characteristics of the cell were studied for a constant load of 100 kΩ.     

Properties of composite solid polymer electrolyte using hyperbranched polymer with ether-linkage

The cross-linked composite solid polymer electrolytes composed of poly(ethylene oxide), lithium salt (LiN(SO₂CF₃)₂), and a hyperbranched polymer whose repeating units were connected by ether-linkage (hyperbranched polymer (HBP)-2) were prepared, and their ionic conductivity, thermal properties, electrochemical stability, mechanical property, and chemical stability were investigated in comparison with the non-cross-linked or cross-linked composite solid polymer electrolytes using hyperbranched polymers whose repeating units were connected by ester-linkage (HBP-1a, 1b). The cross-linked composite solid polymer electrolyte using HBP-2 exhibited higher ionic conductivity than the non-cross-linked and cross-linked composite solid polymer electrolytes using HBP-1a and HBP-1b, respectively. The structure of the hyperbranched polymer did not have a significant effect on the thermal properties and electrochemical stability of the composite solid polymer electrolytes. The tensile strength of the cross-linked composite solid polymer electrolyte using HBP-2 was lower than that of the cross-linked composite solid polymer electrolyte using HBP-1b, but higher than that of the non-cross-linked composite solid polymer electrolyte using HBP-1a. The HBP-2 with ether-linkage showed higher chemical stability against alkaline hydrolysis compared with HBP-1a with ester-linkage.     

FT-IR and FT-Raman spectroscopy study of di-urethanesil hybrids doped with Mg(CF3SO3)2

In the present work di-urethane cross-linked poly(oxyethylene) (POE)/siloxane hybrids (di-urethanesils) incorporating magnesium triflate (Mg(CF₃SO₃)₂) with 100 ≥ n ≥ 2 (where n, composition, is the molar ratio of oxyethylene repeat units per Mg²⁺ ion) have been characterized by Fourier transform infrared and Raman spectroscopy to elucidate the Mg²⁺/POE, Mg²⁺/urethane, Mg²⁺/CF₃SO₃⁻ and hydrogen bonding interactions. The Mg²⁺ ions bond to POE chains and to the carbonyl oxygen atoms of the urethane linkages over the whole range of salt content studied. A crystalline POE/Mg(CF₃SO₃)₂ complex of unknown stoichiometry is formed at n = 5. “Free” and weakly coordinated CF₃SO₃⁻ ions are present in all the materials examined. Contact ion pairs emerge at n ≤ 20 and higher ionic aggregates appear at n ≤ 5.     

Structural Design of Ionic Conduction Paths in Molecular Crystals for Selective and Enhanced Lithium Ion Conduction

The molecular crystals [Li{N(SO₂CF₃)₂}{C₆H₄(OCH₃)₂}₂] and [Li{N(SO₂CF₃)₂}{C₆F₂H₂(OCH₃)₂}₂] with solid‐state lithium ion conductivity have been synthesized by the addition of two equivalents of 1,2‐dimethoxybenzene or 1,2‐difluoro‐4,5‐dimethoxybenzene to Li{N(SO₂CF₃)₂}, respectively. Single‐crystal X‐ray diffraction analysis revealed the formation of ionic conduction paths with an ordered arrangement of lithium ions in these crystal structures, afforded by the self‐ assembled stacking of molecular‐based channels consisting of N(SO₂CF₃)₂ anion and 1,2‐dimethoxybenzene frameworks as a result of intermolecular aromatic and hydrogen interactions. These compounds show selective lithium ion conductivity as the anions behave as a component unit of the conduction paths. The relationship between the crystal structure and ionic conductivity of the molecular crystals provides a clue to the development of novel solid electrolytes based on molecular crystals showing fast and selective lithium ion conduction.     

Mg-ion conducting gel polymer electrolyte membranes containing biodegradable chitosan: Preparation,structural, electrical and electrochemical properties

A biodegradable gel polymer electrolyte system based on chitosan/magnesium trifluoromethanesulfonate/1-ethyl-3-methylimidazolium trifluoromethanesulfonate (CA/Mg (Tf)₂/EMITf) is developed. The structure, thermal performance, mechanical properties, ionic conductivity, relaxation time, electrochemical stability and ionic transport number of the membranes are analyzed by various techniques. The ion migration mainly depends on the complexation and decomplexation of Mg²⁺ with amine band (NH₂) in chitosan. The 90CA-10Mg (Tf)₂ system plasticized with 10% EMITf (relative to the amount of 90CA-10Mg (Tf)₂) is identified as the optimum one and the temperature dependence of ionic conductivity obeys the Arrhenius rule. Moreover, the relaxation time of the electrolyte is very short, being just 1.25 × 10⁻⁶ s, and its electrochemical stability window is quite wide, being up to 4.15 V. The anodic oxidation and cathodic reduction of Mg at the Mg-electrode/electrolyte interface is facile, and the ionic transference number of this electrolyte is 0.985, indicating that it could be a potential electrolyte candidate for Mg-ion devices.     

Probing the effect of anion structure on the physical properties of cationic 1,2,3‐triazolium‐based poly(ionic liquid)s

To extensively explore the influence of anion structure on the physical properties of poly(ionic liquid)s (PILs) a series of PILs having main‐chain 1,2,3‐triazolium cations was synthesized via copper(I)‐catalyzed azide‐alkyne 1,3‐dipolar cycloaddition (CuAAC) followed by N‐alkylation with iodomethane and anion metathesis with different metal salts, that is, Li(CF₃SO₂)₂N, Li(CF₃CF₂SO₂)₂N, K(FSO₂)₂N, K(CF₃SO₂)N(CN), Ag(CN)₂N, and sodium 4,5‐dicyano‐1,2,3‐triazolate. To isolate the effect of anion on physical properties of PILs, a common iodide precursor was used to maintain constant the average degree of polymerization (DP_n) and chain dispersity. Detailed structure/properties relationship analyses demonstrated a lack of correlation between anion chemical structure, ionic conductivity, and glass transition temperatures. Among synthesized series, the PIL derivative having bis(trifluoromethylsulfonyl)imide counter anion showed the best compromise in performance: low glass transition temperature (T_g = ?68 °C), high thermal stability (T_onset = 340 °C) and superior ionic conductivity (σ_DC = 8.5 × 10^{? 6} S/cm at 30 °C), which makes it an interesting candidate for various key modern electrochemical applications. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2191–2199