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JOURNAL OF POWER SOURCES · 2018 · IF 6.945

Lithiated Nafion as polymer electrolyte for solid-state lithium sulfur batteries using carbon-sulfur composite cathode

Jing Gao,Chunshui Sun,Lei Xu,Jian Chen,Chong Wang,Decai Guo,Hao Chen

Due to flexible property and light weight, the lithiated Nafion membrane swollen with PC (PC-Li-Nafion) has been employed as both solid-state electrolyte and separator to fabricate solid-state Li-S cells. The electrochemical measurements of PC-Li-Nafion membrane show that its Li-ion transference number is 0.928, ionic conductivity of 2.1 × 10 −4  S cm −1 can be achieved at 70 °C and its electrochemical window is 0 ∼ +4.1 V vs. Li + /Li. It is observed that the Li dendrites are suppressed by using PC-Li-Nafion membrane due to its single-ion conducting property. The amounts of Li-Nafion resin binder and conductive carbon in the cathode are optimized as 40% and 10% respectively to make a balance of ionic and electronic conductivities . A thin-layer Li-Nafion resin with a thickness of around 2 μm is fabricated between the cathode and PC-Li-Nafion membrane to improve the interfacial contact and further enhance the specific capacity of the cell. When measured at 70 °C, the Li-S cell delivers a reversible specific capacity of 1072.8 mAh g −1  (S) at 0.05 C and 895 mAh g −1  (S) at 1 C. The capacity retention at 1 C is 89% after 100 cycles. These results suggest that high-performance solid-state Li-S cells can be fabricated with the Li-Nafion polymer electrolyte .

研究领域: 电化学 · 能源材料 · 固态电池 · 聚合物电解质 · 锂离子电池 · 电极界面工程 · 储能技术
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SOLID STATE IONICS · 2019 · IF 2.886

Conformal, nanoscale γ-Al2O3 coating of garnet conductors for solid-state lithium batteries

Fan Deng,Yongmin Wu,Weiping Tang,Shufeng Song,Zhaoyin Wen,Masashi Kotobuki,Li Lu,Jianyao Yao,Ning Hu,Janina Molenda

The use of garnet-type conductors as electrolytes for safe lithium solid-state batteries is impeded by the lack of critical processing strategy to stabilize and densify the cubic lithium garnets. The synthesis and processing of dense cubic lithium garnets are typically depending on solid state reaction as a result of unintentional Al contamination from the alumina crucibles at temperatures up to 1230 °C. High Al concentration is also believed to induce the sluggish migration of lithium ions . Here, we demonstrate an ultrathin, conformal γ-Al 2 O 3 surface coating on garnet solids by a hybrid microemulsion solid-state method for accomplishing rational and controllable synthesis and processing of dense cubic garnets with low Al concentration. The γ-Al 2 O 3 coating demonstrates fast-ion conducting Al-doped Li 6.75 La 3 Zr 1.75 Ta 0.25 O 12 phase with low Al concentration (~0.17 mol per formula unit), low tetragonal-to-cubic phase transformation temperature of 500 °C, and total conductivity of ~4.4 × 10 − 4  S cm − 1 . Specifically, the desired microstructures of the sintered pellets with uniform grains are revealed. As a proof-of-concept, we demonstrate that the nanoscale γ-Al 2 O 3 modification garnet conductor Li 6.75 La 3 Zr 1.75 Ta 0.25 O 12 is available to suppress lithium dendrites in symmetric Li/γ-Al 2 O 3 coating Li 6.75 La 3 Zr 1.75 Ta 0.25 O 12 /Li cells during lithium plating/stripping at room temperature, with current densities of 0.026 to 0.5 mA cm − 2 . The Li/γ-Al 2 O 3 coating Li 6.75 La 3 Zr 1.75 Ta 0.25 O 12 /LiNi 0.5 Co 0.2 Mn 0.3 O 2 cell delivered a high initial discharge capacity of ~164.2 mAh g − 1 , more importantly, an outstanding cycling performance with a capacity retention of 90.16% after 30 cycles at 0.1C and room temperature. This new synthesis route and the utilization of nanoscale γ-Al 2 O 3 surface modification could open up new avenue to lithium garnet conductors with reliable synthesis for all-solid-state lithium batteries application.

研究领域: 材料科学 · 电化学 · 固态离子学 · 能源存储 · 纳米材料 · 电池技术
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DALTON TRANSACTIONS · 2023 ·Vol. 52 ·期 21 ·7143-7151 · IF 4

Mixed electronic and oxide ionic conduction and migration mechanisms in digermanate La2−xCaxGe2O7−x/2

Lu Liang,Xiaohui Li,Xiaoge Wang,Zhaoji Luo,Kun Lin,Qiang Li,Sihao Deng,Lunhua He,Xiaojun Kuang,Xianran Xing

Mixed electronic and oxide ionic conduction was enabled in digermanate-type La2−xCaxGe2O7−x/2 containing Ge3O10 chains and isolated GeO4 units by substitution of La3+ with Ca2+. The structure and solid solution limit of Ca doped La2Ge2O7 were studied by systematic experiments, including rotation electron diffraction (RED), X-ray diffraction (XRD) and neutron powder diffraction (NPD) experiments, etc. The preferred occupation of Ca2+ and oxygen vacancies was investigated by Rietveld analysis of the NPD data. The obtained conducting material La1.925Ca0.075Ge2O6.963 exhibits superior thermal stability and an order of magnitude improvement in conductivity compared to the parent La2Ge2O7 (∼9 × 10−5 S cm−1 at 1000 °C). BVEL calculations reveal that the oxygen vacancies were stabilized and transported within the framework of La2Ge2O7 by sharing oxygen and oxygen exchange between the adjacent Ge3O10 chains and GeO4 units, exhibiting a three-dimensional oxide ion transport nature.

研究领域: 无机化学 · 固态离子学 · 功能材料 · 结构化学 · 能源材料 · 晶体化学
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RSC Advances · 2014 ·Vol. 4 ·期 78 ·41398-41410 · IF 3.708

Cross-linked multiblock copoly(arylene ether sulfone) ionomer/nano-ZrO2 composite anion exchange membranes for alkaline fuel cells

Xiuhua Li,Jinxiong Tao,Guanghui Nie,Liuchan Wang,Liuhong Li,Shijun Liao

A series of cross-linked multiblock copoly(arylene ether sulfone) ionomer/nano-ZrO2 (CLQCPAES/nano-ZrO2) composite anion exchange membranes were prepared via block copolymerization, bromomethylation, ultrasonication blending, self-crosslinking, quaternization and alkalization. The structure, and the surface and cross section morphology of the CLQCPAES/nano-ZrO2 composite membranes were characterized by solubility tests, FT-IR, XRD and SEM analyses. The combination of the determined results revealed that the CLQCPAES/nano-ZrO2 composite membranes are a complex cross-linking networks of hydrophobic domains/hydrophilic domains/nano-ZrO2 with a clear zonal distribution of uniform nano-sized particles in the hydrophilic domains, when the nano-filler loading was below 7.5%. Basic performances of the CLQCPAES/nano-ZrO2 composite membranes were assessed to investigate their application in fuel cells in terms of the water uptake, swelling ratio, ion exchange capacity (IEC), hydroxide conductivity, thermal and mechanical properties, and alkaline stability. The modification of anion exchange membranes with multiblock ionomer structures, the use of a cross-linking technique and the introduction of nano-ZrO2 particles greatly enhanced the water uptake, hydroxide conductivity, mechanical properties and alkaline stability of the composite membranes. In particular, the CLQCPAES/7.5%ZrO2 membrane with an IEC value of 1.23 mmol g−1 exhibited the best comprehensive properties and constitutes a good potential candidate for an anion exchange membrane to be used in AEMFCs.

研究领域: 高分子材料科学 · 电化学 · 能源材料 · 膜科学与技术 · 燃料电池 · 纳米复合材料 · 功能高分子
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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
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JOURNAL OF NON-CRYSTALLINE SOLIDS · 2019 · IF 2.6

Enhancing ionic conductivity in Ag3PS4 via mechanical amorphization

Ang Qiao,Haizheng Tao,Yuanzheng Yue

Amorphous conductors with high ionic conductivity are a promising candidate as electrolytes in all-solid state batteries. In this work, we prepared amorphous Ag 3 PS 4 conductor via a chemo-mechanical milling process, and then characterized its structure and electrochemical properties . The results show that Ag + conductivity of the amorphous Ag 3 PS 4 was remarkably enhanced by three orders of magnitude compared to its crystalline counterpart. Furthermore, the amorphous sample exhibits lower activation energy ( E a ) for ionic conductivity as a function of temperature. Structural characterizations indicate that the tetrahedral [PS 4 ] units were retained in amorphous Ag 3 PS 4 , but the Ag + ions became more liberated than those in the crystalline state, leading to the enhanced migration of Ag + ions, thereby, the ionic conductivity in amorphous Ag 3 PS 4 is drastically increased. This work provides insight into the crucial role of the disorder in raising the ionic conductivity of amorphized chalcogenide materials containing mobile ions.

研究领域: 材料科学 · 固体化学 · 能源材料 · 电化学 · 无机非金属材料 · 固态电池 · 离子传导
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