碳纳米管纸/纳米硅复合电极的锂离子电池性能

采用纳米硅和多壁碳纳米管(MWCNTs)复合材料作为活性材料,以纸纤维为基体,MWCNTs为导电剂制得的MWCNTs导电纸代替铜箔集流体应用于硅基锂离子电池。采用扫描电子显微镜、透射电子显微镜、恒流放电测试、电化学阻抗对复合材料的形貌和电化学性能进行分析。结果表明,采用MWCNTs导电纸-纳米硅复合的锂离子电池在80mA/g的电流密度下,循环50次后比容量达到约1000mAh/g,在2000mA/g大电流密度下仍保持好的循环稳定性。     

Evaluation of a cross-linked polyurethane acrylate as polymer electrolyte for lithium batteries

A cross-linked polyurethane acrylate (CL-PUA) was synthesized by end capping 2,6-toluene diisocyanate (TDI)/poly(ethylene glycol) (PEG) based prepolymer with hydroxybutyl methacrylate (HBMA). Differential scanning calorimetry (DSC) and Fourier transform infra-red (FT-IR) spectroscopy measurements reveal the possible presence of significant interactions between lithium ions and soft/hard segments of the CL-PUA, when CL-PUA was complexed with lithium perchlorate (LiClO₄). CL-PUA follows the VTF relationship for the ion transport. Predominant formation of contact ion pairs of LiClO₄ has been observed through AC conductivity and DSC measurements. The lithium stripping–plating process is a reversible and implies better electrochemical stability in the working voltage range. Also, CL-PUA electrolyte shows better compatibility with lithium metal as inferred from impedance measurements and has a good cationic transference number suitable to be used as a solid polymer electrolyte. The addition of HBMA into PU matrix improves tensile strength of the CL-PUA. Swelling measurements of CL-PUA with plasticizer showed better dimensional stability. Also, a cell was constructed using CL-PUA as electrolyte and the performance was assessed.     

The effect of acidic treatment on the lithium storage capacity of multi-walled carbon nanotubes

In this research, multi-walled carbon nanotubes (MWCNTs) were modified by nitric acidic treatment to improve their electrochemical performance. The electrochemical performance of MWCNTs was evaluated by charge and discharge cycles. Transmission electron microscopy (TEM), X-ray diffraction (XRD) and Raman spectrum analysis techniques were used to characterize the samples. The closed tip or cap structures of pristine MWCNT were opened and the nanotubes were chopped after acidic treatment, which is beneficial to improve the lithium ion insertion/extraction into/from MWCNTs and lithium storage capacity. The graphite crystallinity of acid treated MWCNTs reduced slightly and disordered carbon structures were introduced at the surface of MWCNTs, which led to the large initial irreversible capacity.     

PEO基固态聚合物电解质膜的静电纺丝制备及性能EI北大核心CSCD

PEO基固态聚合物电解质被认为是目前固态锂电池领域极具产业化前景的固态电解质。为适应工业化生产,采用静电纺丝技术制备PEO/LiClO_(4)固态聚合物电解质(SPE),研究纺丝电压、纺丝液质量浓度和锂盐含量对SPE纤维膜形貌和直径的影响。通过扫描电子显微镜观察SPE中纤维的形貌,利用Image J软件分析SPE纤维的直径。通过DSC,XRD,FTIR-ATR和拉伸测试等手段对静电纺丝制备的SPE纤维膜的组成、结构、性能等进行研究。结果表明:当纺丝电压为15 kV、PEO/LiClO_(4)纺丝液质量浓度为6%、[EO]∶[Li^(+)]=10∶1(摩尔比)时,静电纺丝方法制备的PEO/LiClO_(4) SPE纤维膜具有较好的纤维形貌,平均直径为557 nm,分布均一;当[EO]∶[Li^(+)]=10∶1时,SPE纤维膜中PEO的熔点仅为53.8℃,结晶度低至18.9%;电解质在30℃时的离子电导率达到5.16×10^(-5)S·cm^(-1),同时具备良好的电化学稳定性和界面稳定性。     

Thermal conductivity of polymer composites based on the length of multi-walled carbon nanotubes

The anisotropic development of thermal conductivity in polymer composites was evaluated by measuring the isotropic, in-plane and through-plane thermal conductivities of composites containing length-adjusted short and long multi-walled CNTs (MWCNTs). The thermal conductivities of the composites were relatively low irrespective of the MWCNT length due to their high contact resistance and high interfacial resistance to polymer resins, considering the high thermal conductivity of MWCNTs. The isotropic and in-plane thermal conductivities of long-MWCNT-based composites were higher than those of short-MWCNT-based ones and the trend can accurately be calculated using the modified Mori-Tanaka theory. The in-plane thermal conductivity of composites with 2 wt% long MWCNTs was increased to 1.27 W/m·K. The length of MWCNTs in polymer composites is an important physical factor in determining the anisotropic thermal conductivity and must be considered for theoretical simulations. The thermal conductivity of MWCNT polymer composites can be effectively controlled in the processing direction by adjusting the length of the MWCNT filler.     

Preparation,characterization and properties of polycaprolactone diol-functionalized multi-walled carbon nanotube/thermoplastic polyurethane composite

Multi-walled carbon nanotubes (MWCNTs) were chemically functionalized to prepare thermoplastic polyurethane (PU) composites with enhanced properties. In order to achieve a high compatibility of functionalized MWCNTs with the PU matrix, polycaprolactone diol (PCL), as one of PU’s monomers, was selectively grafted on the surface of MWCNTs (MWCNT–PCL), while carboxylic acid groups functionalized MWCNTs (MWCNT–COOH) and raw MWCNTs served as control. Both MWCNT–COOH and MWCNT–PCL improved the dispersion of MWCNTs in the PU matrix and interfacial bonding between them at 1 wt% loading fraction. The MWCNT–PCL/PU composite showed the greatest extent of improvement, where the tensile strength and modulus were 51.2% and 33.5% higher than those of pure PU respectively, without sacrificing the elongation at break. The considerable improvement in both mechanical properties and thermal stability of MWCNT–PCL/PU composite should result from the homogeneous dispersion of MWCNT–PCL in the PU matrix and strong interfacial bonding between them.     

Multiwall carbon-nanotube-doped ion conducting polymer electrolyte for electrochemical application

Electrical, structural and optical properties of a composite containing a polymer electrolyte (namely polyethylene oxide complexed with sodium iodide) and multiwall carbon nanotube (MWCNT) are reported. The films of these composites were ‘solution casted’ using the viscous solution of polyethylene oxide (PEO) complexed with sodium iodide (NaI) in desired ratios and characterised using various techniques. The conductivity versus composition plot in PEO:NaI shows conductivity maxima at 12?wt% NaI concentration while in MWCNTs doped polymer electrolyte it occurs at 40?wt% MWCNTs concentration. The surface morphology by scanning electron microscopy (SEM) shows the enhancement in amorphous reason by MWCNTs doping which is a well-known favourable condition for conductivity enhancement. The differential scanning calorimetry shows that dispersal of MWCNTs reduces the crystallinity of polymer electrolyte that is well-supported by our polarised optical micrographs and SEM measurements.     

Conducting polymer‐coated, palladium‐functionalized multi‐walled carbon nanotubes for the electrochemical sensing of hydroxylamine

Electrochemical sensors of hydroxylamine were fabricated on glassy carbon electrodes (GCEs) by the electropolymerization of 3,4‐ethylenedioxypyrrole (EDOP) and 3,4‐ethylenedioxythiophene (EDOT) on palladium (Pd) nanoparticles attached to thiolated multi‐walled carbon nanotubes (MWCNTs), denoted as PEDOP/MWCNT‐Pd/GCE and PEDOT/MWCNT‐Pd/GCE. The sensors were characterized by field emission scanning electron microscopy and electrochemical impedance spectroscopy. They showed strong catalytic activity toward the oxidation of hydroxylamine. Cyclic voltammetry and amperometry were used to characterize the sensors' performances. The detection limits of hydroxylamine by PEDOP/MWCNT‐Pd/GCE and PEDOT/MWCNT‐Pd/GCE were 0.22 and 0.24 μM (S/N = 3), respectively. The sensors' sensitivity, selectivity, and stability were also investigated.     

后处理工艺对POSS-PMMA_8改性凝胶聚合物电解质性能的影响

为解决凝胶聚合物电解质(GPE)的离子电导率低、力学性能差等问题,通过静电纺丝制备星型笼型低聚倍半硅氧烷-聚甲基丙烯酸甲酯(POSS-PMMA_8)改性聚甲基丙烯酸甲酯-聚丙烯腈-聚偏氟乙烯(PMMA-PANPVDF)得到聚合物纺丝薄膜(POSS-PMMA_8/PMMA-PAN-PVDF)M1,将聚合物纺丝薄膜M1在120℃热处理得到聚合物纺丝薄膜M2,或热压并预氧化处理得到聚合物纺丝薄膜M3,将其浸泡于电解液中活化得到POSS-PMMA_8/PMMA-PAN-PVDF的GPE。对不同状态聚合物纺丝薄膜M1、M2、M3的形貌、孔隙率、吸液率、力学性能及其GPE的电导率和电化学稳定窗口进行测试。结果发现,相比于M1,M2的拉伸强度及GPE的电导率分别提高9.2%及181.1%,电化学窗口增至5.3 V;而M3的拉伸强度和GPE电导率分别较M1增加193.7%、20.2%,电化学窗口增至5.5V。     

Preparation and properties of chitosan nanocomposite films reinforced by poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) treated carbon nanotubes

Carbon nanotube-based nanocomposites of chitosan were successfully prepared by a simple solution-evaporation method. Multiwalled carbon nanotubes (MWCNTs) were treated by poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate)(PEDOT-PSS) in water before mixed with a chitosan solution to improve the dispersion of MWCNTs and interfacial compatibility between MWCNTs and chitosan. The morphological and mechanical properties of the prepared PEDOT-PSS/MWCNT/chitosan nanocomposites have been characterized with field emission scanning electron microscopy (FESEM) and tensile tests. MWCNTs were observed to be homogeneously dispersed throughout the chitosan matrix. As compared with the neat chitosan, the tensile strength and modulus of the nanocomposite were greatly improved by about 61% and 34%, respectively, with incorporation of only 0.5 wt.% of MWCNTs into the chitosan matrix. The comparison of mechanical properties for PEDOT-PSS/MWCNT/chitosan and pristine MWCNT/chitosan nanocomposites has been made. The hardness of the nanocomposites was also evaluated by nanoindentation.     

Aliphatic Polycarbonate‐Based Solid‐State Polymer Electrolytes for Advanced Lithium Batteries: Advances and Perspective

Conventional liquid electrolytes based lithium‐ion batteries (LIBs) might suffer from serious safety hazards. Solid‐state polymer electrolytes (SPEs) are very promising candidate with high security for advanced LIBs. However, the quintessential frailties of pristine polyethylene oxide/lithium salts SPEs are poor ionic conductivity (≈10⁻⁸ S cm⁻¹) at 25 °C and narrow electrochemical window (<4 V). Many innovative researches are carried out to enhance their lithium‐ion conductivity (10⁻⁴ S cm⁻¹ at 25 °C), which is still far from meeting the needs of high‐performance power LIBs at ambient temperature. Therefore, it is a pressing urgency of exploring novel polymer host materials for advanced SPEs aimed to develop high‐performance solid lithium batteries. Aliphatic polycarbonate, an emerging and promising solid polymer electrolyte, has attracted much attention of academia and industry. The amorphous structure, flexible chain segments, and high dielectric constant endow this class of polymer electrolyte excellent comprehensive performance especially in ionic conductivity, electrochemical stability, and thermally dimensional stability. To date, many types of aliphatic polycarbonate solid polymer electrolyte are discovered. Herein, the latest developments on aliphatic polycarbonate SPEs for solid‐state lithium batteries are summarized. Finally, main challenges and perspective of aliphatic polycarbonate solid polymer electrolytes are illustrated at the end of this review.     

Lithium garnets: Synthesis,structure, Li+ conductivity,Li+ dynamics and applications

Inorganic solid fast Li⁺ conductors based batteries are expected to overcome the limitations over safety concerns of flammable organic polymer electrolytes based Li⁺ batteries. Hence, an all-solid-state Li⁺ battery using non-flammable solid electrolyte have attracted much attention as next-generation battery. Therefore, in the development of all-solid-state lithium rechargeable batteries, it is important to search for a solid electrolyte material that has high Li⁺ conductivity, low electronic conductivity, fast charge transfer at the electrode interface and wide electrochemical window stability against potential electrodes and lithium metal. Hence, significant research effort must be directed towards developing novel fast Li⁺ conductors as electrolytes in all-solid-state lithium batteries. Among the reported inorganic solid Li⁺ conductive oxides, garnet-like structural compounds received considerable attention in recent times for potential application as electrolytes in all-solid-state lithium batteries. The focus of this review is to provide comprehensive overview towards the importance of solid fast lithium ion conductors, advantages of lithium garnets over other ceramic lithium ion conductors and understanding different strategies on synthesis of lithium garnets. Attempts have also been made to understand relationship between the structure, Li⁺ conduction and Li⁺ dynamics of lithium garnets. The status of lithium garnets as solid electrolyte in electrochemical devices like all-solid state lithium battery, lithium-air battery and sensor are also discussed.     

直接挥发法制备无纺布增强型聚合物电解质

以N,N-二甲基-甲酰胺(DMF)为溶剂, 采用直接挥发法制备无纺布增强型聚偏氟乙烯-六氟丙烯(PVDF-HFP)聚合物电解质, 并以锂为负极制备了聚合物电池.用扫描电子显微镜、交流阻抗和循环伏安对所制聚合物膜性能进行了表征,用充放电实验对所制聚合物电池电化学性能进行了测试.实验结果表明,直接挥发法制得的聚合物膜孔穴丰富,微孔呈蜂窝状,吸液率为280%,电化学稳定窗口为4.5V,浸取电解液后室温离子电导率为1.5mS/cm;以LiCoO2为正极制得的聚合物电池0.1C充放电, 放电平台为3.9V左右, 首次放电容量为137.5mAh/g,20次循环后容量保持在134mAh/g以上,充放电库仑效率高于95%,0.5C放电时放电平台为3.7V,0.5和1C放电分别能保持0.1C放电容量的96%和93%.     

PVDF-HFP基复合多孔聚合物电解质膜的研制

聚偏氟乙烯-六氟丙烯共聚物(PVDF-HFP)多微孔膜在锂离子电池领域中具有很好的应用前景.采用Bellcore制膜法,用纳米材料对PVDF-HFP为基质的聚合物微孔膜材料进行了改性.利用XRD,SEM,交流阻抗等测试手段对电解质膜的晶体结构、微观形貌、电化学性能等进行了表征.结果表明:改性后聚合物电解质膜的孔隙率增加、结晶度降低,PVDF-HFP/SiO2和PVDF-HFP/Al2O3聚合物电解质隔膜的电导率(20℃)分别达到2.762×10-3S/cm和3.517×10-3S/cm,相应的离子迁移数分别为0.80和0.82.     

碳纳米管多微孔集流体对氧化锡锂离子电池性能的影响

以纸纤维为基体,多壁碳纳米管(MWCNTs)为导电剂,采用真空抽滤法制得多微孔结构的导电纸。将MWCNTs导电纸作为负极集流体代替铜箔应用于氧化锡锂离子电池。采用场发射扫描电镜(SEM)进行表征。SEM显示,Sn O2均匀地分布在MWCNTs构建的三维导电网络的孔隙中。对循环后的MWCNTs导电纸负载Sn O2极片进行EDS元素分析,结果表明,三维多微孔集流体能充分均匀吸附Sn O2浆料,从而保证基体材料的结构稳定性和化学稳定性。电化学测试表明,MWCNTs导电纸作为负极材料Sn O2的集流体能够有效改善电池性能。在100 m A/g电流密度放电时,60次循环后比容量为580 m Ah/g,逐渐增大电流密度时电池比容量下降较为平缓,库伦效率保持在97%以上。     

A Single-Ion Conducting Borate Network Polymer as a Viable Quasi-Solid Electrolyte for Lithium Metal Batteries

Lithium-ion batteries have remained a state-of-the-art electrochemical energy storage technology for decades now, but their energy densities are limited by electrode materials and conventional liquid electrolytes can pose significant safety concerns. Lithium metal batteries featuring Li metal anodes, solid polymer electrolytes, and high-voltage cathodes represent promising candidates for next-generation devices exhibiting improved power and safety, but such solid polymer electrolytes generally do not exhibit the required excellent electrochemical properties and thermal stability in tandem. Here, an interpenetrating network polymer with weakly coordinating anion nodes that functions as a high-performing single-ion conducting electrolyte in the presence of minimal plasticizer, with a wide electrochemical stability window, a high room-temperature conductivity of 1.5 × 10⁻⁴ S cm⁻¹, and exceptional selectivity for Li-ion conduction (t_Li+ = 0.95) is reported. Importantly, this material is also flame retardant and highly stable in contact with lithium metal. Significantly, a lithium metal battery prototype containing this quasi-solid electrolyte is shown to outperform a conventional battery featuring a polymer electrolyte.     

基于OMMT/PVDF-HFP的锂离子电池用复合聚合物电解质

对蒙脱石进行改性,并用直接挥发溶剂法制备有机蒙脱石/聚偏氟乙烯-六氟丙烯复合聚合物电解质。用扫描电子显微镜和X射线衍射等对所制电解质性能进行表征,用交流阻抗和充放电实验研究聚合物电池的电化学性质。结果表明：直接挥发溶剂法制得的复合聚合物膜呈蜂窝状,孔穴丰富,强度增加,浸取电解液后室温离子电导率为1.51 mS/cm,电化学稳定窗口为5.5V;以LiCoO₂为正极制得的聚合物电池0.1C充放电,50次循环后容量保持率达到95.3%,倍率放电能力较好,有机蒙脱石的加入可改善电池的电极界面性质,提高电池充放电循环性能。     

塑料锂离子电池用聚合物电解质性能表征

以导电聚合物作为电解质的塑料锂离子电池被认为是迄今锂电池发展最新水平，研制性能优良的聚合物电解质是生产该种锂离子电池的关键技术，因此对聚合物电解质的表征是必不可少的步骤，电导率，扩散系数，迁移数和电化学窗口是表征聚合物电解质的重要指标，文中介绍了塑料锂离子电池用聚合物电解质性能的表征方法，给出了交流阻抗，浓差极化，断电流，线性伏安扫描等实验方法，并对其作为分析和讨论。     

Highly enhanced thermal conductivity of thermoplastic nanocomposites with a low mass fraction of MWCNTs by a facilitated latex approach

The construction of a three-dimensional (3D) compactly interconnected carbon nanotube (CNT) network could offer a substantial increase in the thermal conductivity of the polymeric nanocomposite. In order to achieve desirable 3D conductive architectures in the polymeric matrix, a facilitated latex technique was employed to coat multi-walled CNT (MWCNT) onto micro-sized polymeric powders. The microstructure and rheological characterization study were conducted to evaluate the internal distribution of MWCNTs within the polymeric matrices. The crystallinity of the polymer, the kinetics of crystallization, and the influence of surface functionalization on thermal conductivity were also investigated. The selected steroid-based surfactant (sodium cholate) could improve the interfacial coupling of CNT-CNT and CNT-polymer to reduce the interfacial thermal resistances. Meanwhile, the 3D architecture of MWCNTs could provide a phonon transport pathway and accelerate the recrystallization process of semi-crystalline polymers. MWCNTs and the surfactant had a synergic effect on the enhancement of thermal conductivity of the nanocomposites.     

Li7P2S8I固态电解质的湿化学法制备及性能

对于全固态锂离子电池,固态电解质是制约电池性能的最重要因素之一。以四氢呋喃为反应溶剂,以P₂S₅,Li₂S和LiI为反应原材料,采用湿化学法及后续真空热反应方法成功制备出Li₇P₂S₈I固态电解质。通过同步热分析仪、粉末X射线衍射、拉曼光谱、扫描电子显微镜和能谱仪对所制备电解质样品的形貌、元素分布和物相组成进行表征分析。利用交流阻抗测试、循环伏安法和直流极化等手段研究了Li₇P₂S₈I固态电解质的电化学性能。不同温度对比分析结果表明Li₇P₂S₈I固态电解质的最佳热处理温度为230℃,在此条件下的制备产物具有纳米多孔结构且组成元素分布均匀。电化学测试表明该电解质在25℃下的离子电导率为1.63×10^-4 S·cm^-1,活化能为0.388 eV,电化学窗口达到5 V,锂离子迁移数高于0.999。该电解质与锂金属组装的对称电池可充放电稳定循环>262次(525 h),表明以此方法制备的Li₇P₂S₈I固态电解质与金属锂负极具有优异的电化学稳定性和化学相容性。