Effect of molecular sieves ZSM-5 on the crystallization behavior of PEO-based composite polymer electrolyte

Polarized optical microscopy (POM) results show that ZSM-5 has great influence on both the nucleation stage and the growth stage of PEO spherulites. Part of ZSM-5 particles can act as the nucleus of PEO spherulites and thus increase the amount of PEO spherulites. On the other hand, ZSM-5 can restrain the recrystallization tendency of PEO chains through Lewis acid–base interaction and hence decrease the growth speed of PEO spherulites. The increasing amount of PEO spherulites, decreasing size of PEO spherulites and the incomplete crystallization are all beneficial for creating more continuous amorphous phases of PEO, which is very important for the transporting of Li⁺ ions. An adequate amount of ZSM-5 can enhance the room temperature ionic conductivity of PEO-LiClO₄ based polymer electrolyte for more than two magnitudes.     

Enhanced electrochemical properties of nanocomposite polymer electrolyte based on copolymer with exfoliated clays

In this present work, a polymer electrolyte based on polymer/clay nanocomposite has been developed. Montmorillonite (MMT) clay was used as the filler, due to its special size in length and thickness, and its sandwich type structure. The obtained gel polymer electrolytes have high ionic conductivity up to 2.5 mS cm⁻¹ with high cationic transference number (about 0.64) at room temperature. The influences of the filler on the membrane morphology, the solvent uptake, the ionic conductivity, and the cation transport number were investigated, and thus the significant contribution from the exfoliated organophilic MMT was identified.     

A novel composite microporous polymer electrolyte prepared with molecule sieves for Li-ion batteries

Molecular sieves of NaY, MCM-41, and SBA-15 were used as fillers in a poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP) copolymer matrix to prepare microporous composite polymer electrolyte. The SBA-15-based composite polymer film was found to show rich pores that account for an ionic conductivity of 0.50 mS cm⁻¹. However, the MCM-41 and NaY composite polymer films exhibited compact structure without any pores, and the addition of MCM-41 even resulted in aggregation of fillers in the polymer matrix. These differences were investigated and interpreted by their different compatibility with DMF solvent and PVdF-HFP matrix. Results of linear sweep voltammetry (LSV), electrochemical impedance spectroscopy (EIS), X-ray diffraction (XRD) and differential scanning calorimetry (DSC) have revealed that the addition of SBA-15 has extended the electrochemical stability window of polymer electrolyte, enhanced the interfacial stability of polymer electrolyte with lithium electrode, and inhibited also the crystallization of PVdF-HFP matrix. Half-cell of Li/SBA-15-based polymer electrolyte/MCF was assembled and tested. The results have demonstrated that the coulombic efficiency of the first cycle was around 87.0% and the cell remains 94.0% of the initial capacity after 20 cycles, which showed the potential application of the composite polymer electrolyte in lithium ion batteries.     

Electrochemical properties of amorphous comb-shaped composite PEO polymer electrolyte

The electrochemical behaviour of a polyethylene oxide (PEO)-based composite polymer electrolyte are studied. The crystallinity of the PEO is suppressed by using a comb-shaped polymer to improve polymer chain mobility. An amorphous comb-shaped polymer, ‘TEC-24’, with a side-chain content of 24 mol%, is designed and fine silica powder is dispersed within it to enhance the mechanical properties above the melting point. The composite polymer electrolyte has an ionic conductivity of 1.6×10⁻⁴ and 1.6×10⁻³ S cm⁻¹ at 30 and 90 °C, respectively, with an electrochemical stability window close to 5.0 V, even at 80 °C (versus Li/Li⁺). The polymer electrolyte is evaluated using CuS as a cathode material and shows better cycle performance than that obtained with a liquid electrolyte.     

Ionanofluid plasticized electrolyte with improved electrical and electrochemical properties for high-performance lithium polymer battery

Herein, the electrochemical characteristics of Li/LiFePO₄ battery, comprising a new class of poly (ethylene oxide) (PEO) hosted polymer electrolytes, are reported. The electrolytes were prepared using lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) dopant salt and imidazolium ionic liquid-based nanofluid (ionanofluid) as the plasticizer. Morphological, thermophysical, electrical, and electrochemical properties of these newly developed electrolytes were studied. Using FT-IR spectroscopy, the interactions between dopant salt plasticizers and the host polymer, within the electrolytes, were evaluated. The optimized 30 wt% ionanofluid plasticized electrolyte exhibits a room temperature ionic conductivity of 6.33 × 10⁻³ S cm⁻¹, wide electrochemical voltage window (~4.94 V vs Li/Li⁺) along with a moderately high value of lithium-ion transference number (0.47). The values are substantially higher than that of similar wt% IL plasticized electrolyte (7.85 × 10⁻⁴ S cm⁻¹, ~4.44 V vs Li/Li⁺ and ~ 0.28, respectively). Finally, the Li/LiFePO₄ battery, comprising optimized 30 wt% ionanofluid plasticized electrolyte, delivers 156 mAh g⁻¹ discharge capacity at 0.1 C rate and able to retain its 92% value after 50 cycles. Such a superior battery performance as compared to the IL plasticized electrolyte cell (137 mAh g⁻¹ and 84% after 50 cycles at the same current rate) would endow this ionanofluid a very promising plasticizer to develop electrolytes for next-generation lithium polymer battery.     

Effects of Lewis-acid polymer on the electrochemical properties of alkylphosphate-based non-flammable gel electrolyte

Non-flammable polymer gel electrolytes (NPGE) consisting of 1.0 mol dm⁻³ (=M) LiBF₄/EC + DEC + TEP (55:25:20 volume ratio) + PVdF-HFP (EC: ethylene carbonate, DEC: diethyl carbonate, TEP: triethylphosphate, PVdF-HFP: poly(vinyledenefluoride-co-hexafluoropropylene)) have been developed for rechargeable lithium batteries. The effects of addition of Lewis-acid polymer (LAP) with different mole ratio in NPGE have been studied. The addition of LAP improved physico-chemical properties of NPGE, viz ionic conductivity and lithium ion transport number, as well as mechanical and thermal properties. The ionic conductivity of the gel electrolyte containing LAP reached that of the base solution electrolyte (1.0 M LiBF₄/EC + DEC + TEP (55:25:20)) along with better mechanical properties. Interfacial resistance at Li-metal electrode/NPGE was also improved by introducing LAP in the gel.     

Four volts class solid lithium polymer batteries with a composite polymer electrolyte

Polyethylene oxide (PEO)-based polymer electrolytes with BaTiO₃ as a filler have been examined as electrolytes in 4 V class lithium polymer secondary batteries. A mixture of 90 wt.% LiN(CF₃SO₂)₂–10 wt.% LiPF₆ was found to be the best candidate as the salt in PEO, and showed high electrical conductivity, good corrosion resistance to the aluminum current collector and low interfacial resistance between the lithium metal anode and the polymer electrolyte. The cyclic performance of the cell, Li/[PEO₁₀–(LiN(CF₃SO₂)₂–10 wt.% LiPF₆)]–10 wt.% BaTiO₃/LiNi_0.8Co_0.2O₂/Al, showed good charge–discharge cycling performance. The observed capacity fading on charging up to 4.2 V at 80 °C in the cell was about 0.28% per cycle in the first 30 cycles, compared to that of 0.5% for the polymer electrolyte without LiPF₆ in the lithium salt.     

Ionic conductivity and electrochemical properties of cross-linked solid polymer electrolyte using star-shaped siloxane acrylate

A star-shaped siloxane acrylate with a different number of repeating units of oligo(ethylene oxide) (EO) was synthesized as a cross-linker of solid polymer electrolytes. The cross-linked solid polymer electrolytes blended with the ionic conducting plasticizers, such as low molecular weight poly(ethylene oxide)dimethyl ether (PEGDME) were prepared by the in situ thermal curing of the star-shaped siloxane acrylate. Different morphologies of the cross-linked polymer electrolytes were observed according to the number of repeating units of EO (n) in the cross-linker. A micro-phase separated solid polymer electrolyte was obtained when the n of cross-linker was 1. When the n of cross-linker was larger than 1, homogeneously blended solid polymer electrolytes were prepared. The ionic conductivity was measured to be 6.3 to 7.8 × 10⁻⁴ S cm⁻¹ with 80 wt.% PEGDME at 30 °C. The ionic conductivity of the micro-phase separated solid polymer electrolyte was slightly higher than that of the homogeneously blended solid polymer electrolyte. The electrochemical stability window of the resulting solid polymer electrolyte could be extended to up to 4.8 V versus Li/Li⁺ reference electrode.     

Hydrogen sorption properties of Pd-doped carbon molecular sieves

Decoration with transition metal catalysts has been reported to enhance H₂ storage capacity of carbon materials at ambient temperature. Furthermore, it has been proposed that surface oxygen groups may improve the process. In this study, a carbon molecular sieve was subjected to controlled oxidation and consequent doping with Pd nanoparticles. The H₂ sorption performance of the pristine and oxidized, undoped and doped materials was examined at 298 K up to 20 bar. It was found that the non-oxidized carbon-Pd composite did not show any spillover based sorption increase. On the other hand the oxidized samples reveal a slight enhancement that could be attributed to a weak chemisorption process initiated by the so-called ‘‘spillover’’ effect. Overall, the contribution of spillover to the total hydrogen storage capacity of this system (under the conditions studied) was not found to be of great significance.     

Preparation and properties of composite electrolyte

在复合电解质的设计中,采用结构承载相和离子导电相相结合的方式来满足结构化锂离子电池对强度和电性能的综合要求。首先确定环氧树脂为结构承载相的基体以获得良好的力学性能,利用液态和固态两种不同的造孔剂在基体内构筑连通孔隙,再通过在连通孔隙中填充凝胶态电解质或吸附液态电解质的方式提高离子导通率。综合考虑结构承载相力学性能和吸液率,得出以下结论：环氧树脂/萘/DBP/SiO₂质量比为20:20:4:1时,制得的样品力学性能和吸液率较佳。通过对复合聚合物电解质样品的阻抗分析测试,实验所制备的样品离子电导率最高可达1.6×10^-3 S/cm,满足结构化锂离子电池电性能需求。     

Novel composite polymer electrolyte for lithium air batteries

Hydrophobic ionic liquid–silica–PVdF-HFP polymer composite electrolyte is synthesized and employed in lithium air batteries for the first time. Discharge performance of lithium air battery using this composite electrolyte membrane in ambient atmosphere shows a higher capacity of 2800 mAh g⁻¹ of carbon in the absence of O₂ catalyst, whereas, the cell with pure ionic liquid as electrolyte delivers much lower discharge capacity of 1500 mAh g⁻¹. When catalyzed by α-MnO₂, the initial discharge capacity of the cell with composite electrolyte can be extended to 4080 mAh g⁻¹ of carbon, which can be calculated as 2040 mAh g⁻¹ associated with the total mass of the cathode. The flat discharge plateau and large discharge capacity indicate that the hydrophobic ionic liquid–silica–PVdF-HFP polymer composite electrolyte membrane can effectively protect lithium from moisture invasion.     

Electrochemical testing of industrially produced PEO-based polymer electrolytes

The present report describes the results of the electrochemical tests performed on polyethyleneoxide-based polymer electrolyte thin films industrially manufactured by blown-extrusion. The polymer electrolyte composition was PEO₂₀ LiCF₃SO₃: 16.7% γLiAlO₂. The polymer electrolyte film was tested to evaluate the ionic conductivity as well as the interfacial properties with lithium metal anodes. The work was developed within the advanced lithium polymer electrolyte (ALPE) project, an Italian project devoted to the realization of lithium polymer batteries for electric vehicle applications, in collaboration with Union Carbide.     

High discharge capacity solid composite polymer electrolyte lithium battery

In this study, a series of nanocomposite polymer electrolytes (CPEs), PAN/LiClO₄/SAP, with high conductivity are prepared based on polyacrylonitrile (PAN), LiClO₄ and low content of the silica aerogel powder (SAP) prepared by the sol-gel method with ionic liquid (IL) as the template. The effect of addition of SAP on the properties of the CPEs is investigated by FTIR, AC impedance, linear sweep voltagrams and cyclic voltammetry measurements as well as the charge-discharge performance. It is found that the ionic conductivity of the CPE is significantly improved by addition of SAP. The maximum ambient ionic conductivity of CPEs is about 12.5 times higher than that without addition of SAP. The results of the voltammetry measurements of CPE-3, which contained 3 wt% of SAP, show that the anodic and cathodic peaks are well maintained after 100 cycles, showing excellent electrochemical stability and cyclability over the potential range between 0 V and 4 V vs. Li/Li⁺. Besides, the room temperature discharge capacity measured at 0.5C for the coin cell based on CPE-3 is 120 mAh g⁻¹ and the capacity is retained after 20 cycles discharge, indicating the potential for practical use. This is perhaps the first report of the room temperature charge-discharge performance on the solid composite polymer electrolyte to the best of our knowledge.     

Thermal and electrochemical stability of cathode materials in solid polymer electrolyte

Thermal stability of cathode materials, including LiCoO₂, LiNiO₂, LiMn₂O₄, V₂O₅, V₆O₁₃, and Li_xMnO₂ in contact with poly(ethylene oxide) (PEO) based solid polymer electrolyte was systemically investigated by means of thermal analysis in combination with X-ray diffraction technique (XRD). The differential scanning calorimetry (DSC) analysis showed significant exothermic reaction of both LiNiO₂ and LiCoO₂ in contact with the polymer electrolyte. LiMn₂O₄ was less reactive compared with LiNiO₂ and LiCoO₂. V₂O₅, V₆O₁₃, and Li_xMnO₂ were also found less reactive, especially in their discharge states. The XRD results indicated that the thermal decomposition products of the cathode material were the low valance metal oxides, suggesting the exothermic reaction was an oxidation reaction of the polymer electrolyte with active material. The decomposition temperature is somehow dependent on the potential of the cathode active materials. Cyclic voltammetry reveals that PEO based solid polymer electrolyte is stable up to 5.0 V versus Li/Li⁺ at a blocking electrode, whereas it decomposes at ca 3.8 V when contacted with a carbon composite electrode.     

新型PEO/LPOS复合聚合物电解质的制备与性能研究

将具有较高电导率和稳定性的硫化物电解质LPOS引入PEO基聚合物中,制备一种新型PEO/LPOS复合聚合物电解质。研究结果表明,1%LPOS的添加能显著改善PEO基聚合物电解质的电导率、锂离子迁移数和电化学稳定性。与纯PEO基电解质相比,新制备的复合聚合物电解质PEO18-LiTFSI-1%LPOS室温电导率由   6.18×106 S/cm提高至1.60×105 S/cm,提高了158%。80 ℃表现出最佳电导率为1.08×103 S/cm,电化学窗口提高至4.7 V,同时具有非常良好的对锂稳定性。以新型复合电解质组装的LiFePO4/Li全固态锂电池表现出良好的循环稳定性,在60 ℃ 1 C下循环50周后放电比容量仍维持在105 mA•h/g以上。     

A novel composite gel polymer electrolyte for rechargeable lithium batteries

Composite polymer electrolyte (PE) films comprising of thermoplastic polyurethane (TPU) and polyacrylonitrile (PAN) (denoted as TPU–PAN) have been prepared by two different processes. Scanning electron microscope (SEM) of the films reveal the differences in morphology between them. The electrochemical properties of composite electrolyte films incorporating LiClO₄–propylene carbonate (PC) were studied. TPU–PAN based gel PE shows high ionic conductivity at room temperature. Thermogravimetric analysis informs that the composite electrolyte possesses good thermal stability with a decomposition temperature higher than 300 °C. Electrochemical stability in the working voltage range from 2.5 to 4.5 V was evident from cyclic voltammetry. Cycling performances of Li/PE/LiCoO₂ cells were also performed to test the suitability of the composite electrolyte in batteries.     

Mechanical properties of a reinforced composite polymer electrolyte membrane and its simulated performance in PEM fuel cells

The hygro-thermo-mechanical properties and response of a class of reinforced perfluorosulfonic acid membranes (PFSA), that has potential application as an electrolyte in polymer fuel cells, are investigated through both experimental and numerical modeling means. A critical set of material properties, including Young's modulus, proportional limit stress, break stress and break strain, is determined for a range of temperature and humidity levels in a custom-built environmental test apparatus. The swelling strains are also determined as functions of temperature and humidity level. To elucidate the mechanical response and the potential effect these properties have on the mechanical durability, mechanics-based simulations are performed using the finite element method (ABAQUS). The results indicate that the relatively high strength of the experimental membrane, in combination with its relatively low in-plane swelling due to water absorption, should have a positive influence on membrane durability, potentially leading to longer life times for polymer electrolyte membrane fuel cells (PEMFC).     

Enhanced diffusion in polymer electrolyte membrane fuel cells using oscillating flow

This study investigates the enhancement of the oxygen diffusion rate at the cathode of a proton exchange membrane fuel cell (PEMFC) due to pure oscillating flow. A unit cell of PEMFC using hydrogen fuel and oscillating air was tested. The experimental results show that the non-dimensional effective diffusivity varies linearly with the square of the Womersley number, when the Womersley number is close to unity. The non-dimensional effective diffusivity varies linearly with the Womersley number itself when the Womersley number is much larger than unity. Similar trend has been confirmed from the theoretical approach. Under the experimental conditions in this study, the reaction rate of oxygen increased linearly with respect to the sweep distance. The experimental results showed that a power density of 115.4 mW/cm² was obtained from the unit cell with oscillating flow, which is comparable to that obtained with forced flow. Therefore, an oscillating flow is found to be able to increase the concentration of the oxygen in the channel of PEMFCs, and consequently enhances mass-transfer, similarly to the use of forced flow using blowers or compressors.     

Characteristics of composite bipolar plates for polymer electrolyte membrane fuel cells

As alternative bipolar plate materials for polymer electrolyte membrane fuel cell (PEMFC), two types of carbon composite were developed and characterized. Electrical and physical properties of the currently used graphite and newly developed carbon composites were evaluated in terms of bulk and contact resistance, flexural strength, density, gas tightness, water absorption, and depth deviation of the flow channel. The test results showed that the carbon composites were very promising candidates for PEMFC bipolar plate material. In single cell tests, the carbon composite bipolar plates exhibited good initial and long-term performance compared with the graphite bipolar plates.