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CHEMICAL ENGINEERING JOURNAL · 2021 · IF 13.273

Rational reconfiguration of a gradient redox mediator with in-situ fabricated gel electrolyte for Li–air batteries

Yinwei Fu,Xiaofeng Lei,Huiming Yin,Xizheng Liu

Flexible lithium–air batteries (LABs) with a redox mediator (RM) in the electrolyte demonstrate enhanced round-trip efficiency. However, their cycle performance is unsatisfactory due to severe corrosion of the Li metal anode. Herein, we propose a two step gelatinization strategy to fabricate a gradient RMs (including LiI, TMPD, and DMPZ) gel electrolyte, in which the bare electrolyte gelatinization on the Li surface and then the electrolyte contained RMs sequentially gelled on the formed gel. The RMs mainly distributed at the surface and anchored at the cathode side. By suppressing the shuttle of RMs in the electrolyte and alleviating the passivation of the Li anode, the mid-charging potentials can reach 3.44 and 4.08 V at the 15th cycle with and without the LiI mediator, respectively. The energy efficiency is 63% even at the 150th cycle, whereas the corresponding energy efficiency are only 47% and 51% for the LABs with liquid and normal gel electrolytes, respectively. Moreover, the cycle life of the battery containing the gradient gel electrolyte is three times longer than that with the liquid electrolyte. The gel electrolyte further offers the flexibility of the device, and the laminated cells thus fabricated can readily operate under harsh bending conditions.

研究领域: 电化学 · 能源材料 · 纳米材料 · 界面化学 · 储能技术 · 先进电池 · 功能高分子 · 柔性电子
✓ 已验证 DOI 高影响因子
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International Journal of Electrochemical Science · 2023 ·Vol. 12 ·期 6 ·5421-5430 · IF 1.5

Membrane Separators Coated by TiO2-PMMA with Low Thermal Shrinkage Rate for Lithium-Ion Batteries

Yangyang Xi,Peng Zhang,Haining Zhang,Zhaohui Wan,Wenmao Tu,Haolin Tang

Composite membrane separators are fabricated by coating one side of microporous polyethylene membrane with poly(methyl methacrylate) modified titanate nanoparticles that are synthesized through emulsifier-free emulsion polymerization of methacrylate-functionalized titanate nanoparticles. The formed composite membrane separators exhibit great thermal-shrinking resistance due to the introduction of thermal resistant titanate nanoparticles. After immersed into electrolyte solution, the swelling poly(methyl methacrylate) microspheres leads to the formation of gel electrolyte, thus stabilizing the electrolyte. Moreover, the porous structure of the coated layer can facilitate the swelling of electrolyte and the transport of lithium ions. The thus-assembled lithium ion battery shows an improved cycle performance and rate capability.

研究领域: 材料科学 · 电化学 · 能源存储 · 高分子纳米复合材料 · 电池技术
✓ 已验证 DOI 高影响因子
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JOURNAL OF ALLOYS AND COMPOUNDS · 2023 · IF 6.2

Regulating the anion disorder and synthesizing the low-cost and high-performance Li6−xPS5−xCl1+x solid electrolytes

Chengyu Mo,Yutao Yang,Zhenyu Wang,Yanpeng Lv,Rongzheng Tian,Zixiang Zhao,Hongzhou Zhang,Chunliang Li,Lianqi Zhang,Yongan Yang,Dawei Song

Sulfide solid electrolytes have attracted wide attention due to their high ionic conductivity . Li 6 PS 5 Cl is one of the most promising electrolytes for all-solid-state lithium batteries with high-energy-density. It is reported that the disordered arrangement of Cl - in the aragonite structure has a significant effect on the conductivity of Li 6 PS 5 Cl. In this work, the disorder of anion sites is modestly regulated by adjusting the ratio of S and Cl in Li 6−x PS 5−x Cl 1+x electrolyte. In addition, to verify the commonality of this strategy, Li 5.6 PS 4.6 Cl 1.4 is prepared using self-made Li 2 S, and similar results are obtained. On this basis, the density of Li 5.6 PS 4.6 Cl 1.4 electrolyte sheet is improved by hot-pressing, which can successfully inhibit the growth of lithium dendrites . As expected, the ionic conductivity of the sulfide electrolyte and the electrochemical performance of the ASSLBs are greatly improved. A highest ionic conductivity of 8.2 × 10 −3 S cm −1 of Li 5.6 PS 4.6 Cl 1.4 is obtained at room temperature. A high capacity retention of 99.99 % is maintained for NCM811 @Li 2 O//Li 5.6 PS 4.6 Cl 1.4 //Li-In system after 400 cycles at 1 C with ultra-high cathode loading of 35.6 mg cm −2 . Besides, the cost of sulfide electrolytes can be reduced as the decreased usage of Li 2 S. This work proposes a novel synthesis method of low-cost and high-performance Li 6−x PS 5−x Cl 1+x electrolytes.

研究领域: 材料科学 · 电化学 · 能源存储 · 固态离子学 · 电池技术
✓ 已验证 DOI 高影响因子
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JOURNAL OF POWER SOURCES · 2024 · IF 8.1

A simple approach through reduction of Na2SO4 to prepare high-purity Na2S for sulfide electrolytes toward all-solid-state sodium batteries

Yufen Yan,Yayu Guo,Huadong Zheng,Liang Qi,Yutao Yang,Yanli Miao,Xixi Shi,Lianqi Zhang,Chunliang Li,Dawei Song

Development of sulfide solid-state electrolytes (SSEs) with high ionic conductivity plays a leading role in achieving all-solid-state sodium batteries (ASSSBs). As an important raw material for synthesizing sulfide SSEs, the purity of Na 2 S significantly affects the ionic conductivity and electrochemical properties of sulfide SSEs. In order to obtain high-purity and low-cost Na 2 S, a hydrogen reduction of industrial grade Na 2 SO 4 followed by ethanol purification has been successfully employed to synthesize and purify Na 2 S, which possesses a high purity of 98 %. Na 3 SbS 4 has been synthesized by as-synthesized Na 2 S (A-Na 2 S) and commercial Na 2 S (C–Na 2 S) by liquid-phase synthesis and solid-state reaction methods, respectively. The electrochemical properties indicate that Na 3 SbS 4 samples synthesized by A-Na 2 S possess higher ionic conductivity and lower Ea, and the assembled ASSSBs exhibit higher specific capacities, superior cycle and rate performance. At 0.5C, the assembled TiS 2 /Na 3 SbS 4 /NaSn ASSSB exhibits a high initial capacity of 211.4 mAh g −1 with capacity retention of 96.2 % after 360 cycles at room temperature. This work provides a simple approach for synthesizing high-purity Na 2 S at low cost, enabling the large-scale application of sulfide SSEs for ASSSBs.

研究领域: 材料科学 · 电化学 · 固态离子学 · 能源存储 · 无机合成 · 电池技术
✓ 已验证 DOI 高影响因子
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INTERNATIONAL JOURNAL OF HYDROGEN ENERGY · 2018 ·Vol. 43 ·期 45 ·20712-20720 · IF 4.229

Synthesis of PdV/C nanoparticles using phase transfer method for oxygen reduction in alkaline electrolytes

Biyao Jin,Yiqi Li,Lianhua Zhao

Bimetallic PdV/C nanoparticles have been synthesized by phase-transfer method for catalyzing the oxygen reduction reaction (ORR) in alkaline electrolytes . PdV/C nanoparticles with different V contents are spherical with a mean diameter of 3–4 nm, and the addition of V expands the lattice parameter of Pd as shown by XRD . XPS analysis indicated the binding energy of Pd 0 3d peak increased by ca. 1 eV. Density functional theory (DFT) calculations results shows d-band center of Pd down-shift after V-doping. Based on the electrocatalytic results, introducing V can improve the catalytic activity for ORR, methanol crossover tolerance and stability. Especially, Pd 4 V/C shows higher initial potential (E onset  = 1.027 V), excellent methanol crossover tolerance (98.03% retained) and long-term stability (81.30% retained), which are comparable with Pt/C JM . This work provides a new method of synthesizing PdV/C nanoparticles , which have the potential to be used as the cathode electrocatalysts for fuel cells.

研究领域: 材料科学 · 电化学 · 纳米催化 · 能源材料 · 燃料电池 · 物理化学 · 表面科学
✓ 已验证 DOI 高影响因子
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JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS · 2015 ·Vol. 27 ·期 4 ·3549-3556 · IF 1.569

The electrochromic properties of mesoporous WO3–polythiophene film devices with composite electrolytes

Wang Lu,Yang Zhouyong,Ni Xiuyuan

We prepare the mesoporous polythiophene–WO 3 film through in situ polymerization which is initiated by WO 3 , and fabricate the electrochromic device with the composite film. The influences of the electrolyte ions, film morphologies and counter electrode on the electrochromism of the devices are explored by UV–Vis transmittance spectra and cyclic voltammetry tests. With the aim to enhance the contrast optical transmittance, we develop the binary composite electrolytes of LiClO 4 and N(C 4 H 9 ) 4 ClO 4 solution which can promote intercalation/deintercalation process. Besides that, we use polyethylene oxide as pore-forming agent on the polythiophene–WO 3 films, so that it will be easier for electrolyte ions to diffuse in the porous film. A NiO layer also has a complementary effect on the cathodic coloration films and increases the contrast optical transmittance remarkably. Equipped with the binary electrolyte and the NiO layer as the counter electrode, the film device exhibits high performance with the contrast optical transmittance (ΔT) of 62 % and the coloration efficiency of 212.6 cm 2 /C.

研究领域: 材料科学 · 电化学 · 功能材料 · 纳米材料 · 能源材料 · 表面科学
✓ 已验证 DOI 高影响因子
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REACTIVE & FUNCTIONAL POLYMERS · 2019 · IF 3.074

Templated synthesis of cyclic poly(ionic liquid)s

Qingquan Tang,Weiyi Zhang,Jiayin Yuan,Qiang Zhao

Charged cyclic polymers, e.g. cyclic DNAs and polypeptides , play enabling roles in organisms, but their synthesis was challenging due to the well-known “polyelectrolyte effect”. To tackle the challenge, we developed a templated method to synthesize a library of imidazolium and pyridinium based cyclic poly(ionic liquid)s. Cyclic templates, cyclic polyimidazole and poly(2-pyridine), were synthesized first through ring-closure method by light-induced Diels−Alder click reaction. Through quaternization of cyclic templates followed by anion metathesis, the cyclic poly(ionic liquid)s were synthesized, which paired with varied counter anions.

研究领域: 高分子化学 · 有机合成 · 功能材料 · 离子液体 · 生物医用材料
✓ 已验证 DOI 高影响因子
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Small · 2024 ·Vol. 21 ·期 4 ·2410657 · IF 13

2D MOF Structure Tuning Atomic Ru Sites for Efficient and Robust Proton Exchange Membrane Water Electrolysis

Jia Wang,De Wang,Zelin Zhao,Ganggang Chang,Wei Guo,Jun Xu,Yinyu Xiang,Junrui Li,Junsheng Li

Developing cost-effective ruthenium (Ru)-based HER electrocatalysts as alternatives to commercial Pt/C is crucial for the advancement of proton exchange membrane water electrolysis (PEMWE). However, the strong hydrogen adsorption of Ru-based catalysts restricts its activity. Herein, a strategy is reported to tune the electronic structure and improve mass transfer by implanting Ru atoms onto the (002) facet of two-dimensional zeolitic imidazolate framework-67 (Ru@ L ZIF (002) ) to optimize the d -band center ( ε d ) of Ru and the hydrogen spillover behavior. Benefiting from the ultrathin nanosheet structure and optimized ε d of Ru, the over-strong H adsorption energy is weakened and the electron/mass transfer is facilitated. Ru@ L ZIF (002) exhibits an overpotential of 9.2 mV at 10 mA cm −2 and a long-lasting stability of 35 days at 100 mA cm −2 . The mass activity and price activity of Ru@ L ZIF (002) is 2.9 and 14.7 times higher than Pt/C, respectively. More impressively, Ru@ L ZIF (002) delivers a cell voltage of 2.01 V at a high current density of 4 A cm −2 in PEMWE. The excellent long-term durability of 1200 hours operating at 4 A cm −2 with an ultralow decay rate of 7.5 × 10 −3 mV h −1 has been achieved, making it promising as a cost-effective alternative to Pt/C catalyst for PEMWE applications.

研究领域: 电催化 · 材料科学 · 能源化学 · 纳米材料 · 电化学工程 · 可持续能源技术
✓ 已验证 DOI 高影响因子
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JOURNAL OF POWER SOURCES · 2017 · IF 6.395

Composite electrolytes of polyethylene oxides/garnets interfacially wetted by ionic liquid for room-temperature solid-state lithium battery

Hanyu Huo,Ning Zhao,Jiyang Sun,Fuming Du,Yiqiu Li,Xiangxin Guo

Paramount attention has been paid on solid polymer electrolytes due to their potential in enhancement of energy density as well as improvement of safety. Herein, the composite electrolytes consisting of Li-salt-free polyethylene oxides and 200 nm-sized Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 particles interfacially wetted by [BMIM]TF 2 N of 1.8 μL cm −2 have been prepared. Such wetted ionic liquid remains the solid state of membrane electrolytes and decreases the interface impedance between the electrodes and the electrolytes. There is no release of the liquid phase from the PEO matrix when the pressure of 5.0 × 10 4  Pa being applied for 24 h. The interfacially wetted membrane electrolytes show the conductivity of 2.2 × 10 −4  S cm −1 at 20 °C, which is one order of magnitude greater than that of the membranes without the wetted ionic liquids. The conduction mechanism is related to a large number of lithium ions releasing from Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 particles and the improved conductive paths along the ion-liquid-wetted interfaces between the polymer matrix and ceramic grains. When the membranes being used in the solid-state LiFePO 4 /Li and LiFe 0.15 Mn 0.85 PO 4 /Li cells at 25 °C, the excellent rate capability and superior cycle stability has been shown. The results provide a new prospect for solid polymer electrolytes used for room-temperature solid-state lithium batteries .

研究领域: 材料科学 · 电化学 · 能源材料 · 固态电池 · 高分子电解质 · 离子传导机制
✓ 已验证 DOI 高影响因子
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CARBOHYDRATE POLYMERS · 2018 · IF 5.158

Chitosan derivative-based self-healable hydrogels with enhanced mechanical properties by high-density dynamic ionic interactions

Ningxiao Yuan,Lu Xu,Bo Xu,Jianhao Zhao,Jianhua Rong

Chitosan derivative-based self-healable hydrogels with enhanced mechanical properties are reported, which were prepared by polymerization of acrylic acid (AAc) in 2-hydroxypropyltrimethyl ammonium chloride chitosan (HACC) solution. The PAAc/HACC hydrogels exhibit tensile fracture stress as high as 3.31 MPa and a Young's modulus of 2.53 MPa. They can maintain their original shape after 30 repeated compression cycles under various strain conditions, with a compression stress of more than 60 MPa at 99% strain. The damaged PAAc/HACC hydrogels can heal together in the presence of a NaCl salt solution with a self-healing efficiency of up to 61%. In addition, the PAAc/HACC hydrogels have high ionic conductivity and can serve as electrolytes for supercapacitors. The analysis suggests that all these good properties of the PAAc/HACC hydrogels mainly result from their high-density dynamic ionic interactions structure.

研究领域: 高分子材料科学 · 生物医学工程 · 功能材料 · 组织工程 · 药物递送系统 · 再生医学 · 电化学器件
✓ 已验证 DOI 高影响因子
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2024 · IF 9.4

A self-healing composite solid electrolyte with dynamic three-dimensional inorganic/organic hybrid network for flexible all-solid-state lithium metal batteries

Ying Jiang,Kai Chen,Jinping He,Yuxue Sun,Xiaorong Zhang,Xiaoxing Yang,Haiming Xie,Jun Liu

Composite solid electrolytes (CSEs), which combine the advantages of solid polymer electrolytes and inorganic solid electrolytes, are considered to be promising electrolytes for all-solid-state lithium metal batteries. However, the current CSEs suffer from defects such as poor inorganic/organic interface compatibility, lithium dendrite growth, and easy damage of electrolyte membrane, which hinder the practical application of CSEs. Herein, a CSE (PBHL@LLZTO@DDB) with polyurethane (PBHL) as the polymer matrix and Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO) modified by silane coupling agent (DDB) as inorganic fillers (LLZTO@DDB) has been prepared. Disulfide bond exchange reactions between PBHL and LLZTO@DDB enable PBHL@LLZTO@DDB to form a dynamic three-dimensional (3D) inorganic/organic hybrid network, which promotes the uniform dispersion of LLZTO in PBHL@LLZTO@DDB, improves the Li + conductivity (1.24 ± 0.08 × 10 −4  S cm −1 at 30 ℃), and broadens the electrochemical stability window (5.16 V vs. Li + /Li). Moreover, a combination of hydrogen bonds and disulfide bonds endows PBHL@LLZTO@DDB with excellent self-healing properties. As such, both all-solid-state symmetric and full cells exhibit excellent cycle performance at ambient temperature. More importantly, the healed PBHL@LLZTO@DDB can almost completely restore its original electrochemical properties, indicating its application potential in flexible electronic products.

研究领域: 材料科学 · 电化学 · 能源存储 · 高分子化学 · 固态离子学
✓ 已验证 DOI 高影响因子
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IONICS · 2020 ·Vol. 26 ·期 9 ·4239-4246 · IF 2.394

Enhancement of cycling stability of all-solid-state lithium-ion batteries with composite polymer electrolytes incorporating Li6.25La3Zr2Al0.25O12 nanofibers

Zhang Yi,Feng Wei,Zhen Yichao,Zhao Peiyao,Wang Xiaohui,Li Longtu

Li 7 La 3 Zr 2 O 12 (LLZO) with cubic phase structure is a kind of lithium-ion-conducting nanoparticles. According to the previous studies, incorporation of c-LLZO can improve electrochemical properties of PEO-based composite polymer electrolytes (CPEs). Therefore, in our study, we synthesized a kind of room-temperature-stable cubic phase LLZAO (Li 6.25 La 3 Zr 2 Al 0.25 O 12 ) nanofibers, and we aimed to confirm the optimal content of LLZAO nanofibers in PEO-based CPEs. With the incorporating 10 wt% LLZAO nanofibers, ionic conductivity of CPEs are 9.87×10 −5  S cm −1 at 30 °C and 8.66×10 −4  S cm −1 at 60 °C. The Li/CPE incorporating 10 wt% LLZAO nanofibers/Li symmetric cell exhibits little voltage fluctuation in 1000 cycles under a current density of 0.5 mA cm −2 , demonstrating better cycling stability with long cycle life. The LiFePO 4 /CPE incorporating 10 wt% LLZAO nanofibers/Li cell has a high initial discharge-specific capacity of 155.6 mAh g −1 under 0.1 C rate at 60 °C and remains 94.5% of capacity after 100 cycles. This cell also has great cycling performance under 0.2 C and 0.5 C rate, indicating good rate performance. Our work indicates that incorporation of LLZAO nanofibers enhances electrochemical properties and cycling stability of PEO-based all-solid-state lithium-ion batteries.

研究领域: 材料科学 · 电化学 · 能源存储 · 固态电池 · 高分子材料 · 纳米材料 · 电化学能量转换
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