Constructing high-toughness polyimide binder with robust polarity and ion-conductive mechanisms ensuring long-term operational stability of silicon-based anodes

Silicon-based materials have demonstrated remarkable potential in high-energy-density batteries owing to their high theoretical capacity.However,the significant volume expansion of silicon seriously hinders its utilization as a lithium-ion anode.Herein,a functionalized high-toughness polyimide(PDMI) is synthesized by copolymerizing the 4,4'-Oxydiphthalic anhydride(ODPA) with 4,4'-oxydianiline(ODA),2,3-diaminobenzoic acid(DABA),and 1,3-bis(3-aminopropyl)-tetramethyl disiloxane(DMS).The combination of rigid benzene rings and flexible oxygen groups(-O-) in the PDMI molecular chain via a rigidness/softness coupling mechanism contributes to high toughness.The plentiful polar carboxyl(-COOH) groups establish robust bonding strength.Rapid ionic transport is achieved by incorporating the flexible siloxane segment(Si-O-Si),which imparts high molecular chain motility and augments free volume holes to facilitate lithium-ion transport(9.8 × 10^(-10) cm^(2) s^(-1) vs.16 × 10^(-10) cm^(2) s~(-1)).As expected,the SiO_x@PDMI-1.5 electrode delivers brilliant long-term cycle performance with a remarkable capacity retention of 85% over 500 cycles at 1.3 A g^(-1).The well-designed functionalized polyimide also significantly enhances the electrochemical properties of Si nanoparticles electrode.Meanwhile,the assembled SiO_x@PDMI-1.5/NCM811 full cell delivers a high retention of 80% after 100 cycles.The perspective of the binder design strategy based on polyimide modification delivers a novel path toward high-capacity electrodes for high-energy-density batteries.

Phase field model for electric-thermal coupled discharge breakdown of polyimide nanocomposites under high frequency electrical stress

In contrast to conventional transformers, power electronic transformers, as an integral component of new energy power system, are often subjected to high-frequency and transient electrical stresses, leading to heightened concerns regarding insulation failures. Meanwhile, the underlying mechanism behind discharge breakdown failure and nanofiller enhancement under high-frequency electrical stress remains unclear. An electric-thermal coupled discharge breakdown phase field model was constructed to study the evolution of the breakdown path in polyimide nanocomposite insulation subjected to high-frequency stress. The investigation focused on analyzing the effect of various factors, including frequency, temperature, and nanofiller shape, on the breakdown path of Polyimide(PI) composites. Additionally, it elucidated the enhancement mechanism of nano-modified composite insulation at the mesoscopic scale. The results indicated that with increasing frequency and temperature, the discharge breakdown path demonstrates accelerated development, accompanied by a gradual dominance of Joule heat energy. This enhancement is attributed to the dispersed electric field distribution and the hindering effect of the nanosheets. The research findings offer a theoretical foundation and methodological framework to inform the optimal design and performance management of new insulating materials utilized in high-frequency power equipment.

3D Printed Integrated Gradient-Conductive MXene/CNT/Polyimide Aerogel Frames for Electromagnetic Interference Shielding with Ultra-Low Reflection

Construction of advanced electromagnetic interference(EMI)shielding materials with miniaturized,programmable structure and low reflection are promising but challenging.Herein,an integrated transition-metal carbides/carbon nanotube/polyimide(gradient-conductive MXene/CNT/PI,GCMCP)aerogel frame with hierarchical porous structure and gradient-conductivity has been constructed to achieve EMI shielding with ultra-low reflection.The gradient-conductive structures are obtained by continuous 3D printing of MXene/CNT/poly(amic acid)inks with different CNT contents,where the slightly conductive top layer serves as EM absorption layer and the highly conductive bottom layer as reflection layer.In addition,the hierarchical porous structure could extend the EM dissipation path and dissipate EM by multiple reflections.Consequently,the GCMCP aerogel frames exhibit an excellent average EMI shielding efficiency(68.2 dB)and low reflection(R=0.23).Furthermore,the GCMCP aerogel frames with miniaturized and programmable structures can be used as EMI shielding gaskets and effectively block wireless power transmission,which shows a prosperous application prospect in defense industry and aerospace.

Construction of all-organic low dielectric polyimide hybrids via synergistic effect between covalent organic framework and cross-linking structure

Polyimide(PI)is a promising electronic packaging material,but it remains challenging to obtain an all-organic PI hybrid film with decreased dielectric constant and loss without modifying the monomer.Herein,a series of allorganic PI hybrid films were successfully prepared by introducing the covalent organic framework(COF),which could induce the formation of the cross-linking structure in the PI matrix.Due to the synergistic effects of the COF fillers and the cross-linking structure,the PI/COF hybrid film containing 2 wt%COF exhibited the lowest dielectric constant of 2.72 and the lowest dielectric loss(tanδ)of 0.0077 at 1 MHz.It is attributed to the intrinsic low dielectric constant of COF and a large number of mesopores within the PI.Besides,the cross-linking network of PI prevents the molecular chains from stacking and improves the fraction of free volume(FFV).The molecular dynamics simulation results are well consistent with the dielectric properties data.Furthermore,the PI/COF hybrid film with 5 wt%COF showed a significant enhancement in breakdown strength,which increased to 412.8 kV/mm as compared with pure PI.In addition,the PI/COF hybrid film achieve to reduce the dielectric constant and thermal expansion coefficient(CTE).It also exhibited excellent thermal,hydrophobicity,and mechanical performance.The all-organic PI/COF hybrid films have great commercial potential as next-generation electronic packaging materials.

Polyimides as Promising Materials for Lithium-Ion Batteries:A Review

Lithium-ion batteries(LIBs)have helped revolutionize the modern world and are now advancing the alternative energy field.Several technical challenges are associated with LIBs,such as increasing their energy density,improving their safety,and prolonging their lifespan.Pressed by these issues,researchers are striving to find effective solutions and new materials for next-generation LIBs.Polymers play a more and more important role in satisfying the ever-increasing requirements for LIBs.Polyimides(PIs),a special functional polymer,possess unparalleled advantages,such as excellent mechanical strength,extremely high thermal stability,and excellent chemical inertness;they are a promising material for LIBs.Herein,we discuss the current applications of PIs in LIBs,including coatings,separators,binders,solid-state polymer electrolytes,and active storage materials,to improve high-voltage performance,safety,cyclability,flexibility,and sustainability.Existing technical challenges are described,and strategies for solving current issues are proposed.Finally,potential directions for implementing PIs in LIBs are outlined.

A Metal-free Polyimide Photocatalyst for the Oxidation of Amines to Imines

Polyimide(PI) is an organic polymer material with good stability and diverse sources that has attracted widespread attention in the field of photocatalysis. In this study, a series of PI photocatalysts were synthesized by a thermal polymerization approach using pyromellitic dianhydride(PMDA) and various diamine monomers(melamine(MA), 4,4′-oxydianiline, and melem) as the precursors as well as different heating rates. The effects of the diamine precursor and heating rate on the structure, composition, morphology, and optical properties of the as-prepared PI materials were systematically investigated by various characterization techniques. The selective photo-oxidation of benzylamine was used as a model reaction to evaluate the photocatalytic activities of the resulting PI samples for the oxidation of amines to imines. The results revealed that the PI sample prepared using MA and PMDA as the precursors and a heating rate of 7 ℃/min(MA-PI-7) exhibited the best catalytic performance, with 98% benzylamine conversion and 98% selectivity for N-benzylidene benzylamine after 4 h of irradiation. Several benzylamine derivatives and heterocyclic amines also underwent the photo-oxidation reaction over the MA-PI-7 catalyst to afford the corresponding imines with good activity. In addition, MA-PI-7 exhibited good stability over four successive photocatalytic cycles.

Novel polyimide binder for achieving high-rate capability and long-term cycling stability of LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2) cathode via constructing polar and micro-branched crosslinking network structure

LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)material,as the promising cathode candidate for next-generation highenergy lithium-ion batteries,has gained considerable attention for extremely high theoretical capacity and low cost.Nevertheless,the intrinsic drawbacks of NCM811 such as unstable structure and inevitable interface side reaction result in severe capacity decay and thermal runaway.Herein,a novel polyimide(denoted as PI-Om DT)constructed with the highly polar and micro-branched crosslinking network is reported as a binder material for NCM811 cathode.The micro-branched crosslinking network is achieved by using 1,3,5-Tris(4-aminophenoxy)benzene(TAPOB)as a crosslinker via condensation reaction,which endows excellent mechanical properties and large free volume.Meanwhile,the massive polar carboxyl(-COOH)groups provide strong adhesion sites to active NCM811 particles.These functions of PIOm DT binder collaboratively benefit to forming the mechanically robust and homogeneous coating layer with rapid Li+diffusion on the surface of NCM811,significantly stabilizing the cathode structure,suppressing the detrimental interface side reaction and guaranteeing the shorter ion-diffusion and electron-transfer paths,consequently enhancing electrochemical performance.As compared to the NCM811 with PVDF binder,the NCM811 using PI-Om DT binder delivers a superior high-rate capacity(121.07 vs.145.38 m Ah g^(-1))at 5 C rate and maintains a higher capacity retention(80.38%vs.91.6%)after100 cycles at 2.5–4.3 V.Particularly,at the high-voltage conditions up to 4.5 and 4.7 V,the NCM811 with PI-Om DT binder still maintains the remarkable capacity retention of 88.86%and 72.5%after 100 cycles,respectively,paving the way for addressing the high-voltage operating stability of the NCM811 cathode.Moreover,the full-charged NCM811 cathode with PI-Om DT binder exhibits a significantly enhanced thermal stability,improving the safety performance of batteries.This work opens a new avenue for developing high-energy NCM811 based lithium-ion batteries with long cycle-life and superior safety performance using a novel and effective binder.

Extraordinary Ultrahigh-Capacity and Long Cycle Life Lithium-Ion Batteries Enabled by Graphitic Carbon Nitride-Perylene Polyimide Composites

Graphitic carbon nitride(g-C_(3)N_(4))is widely used in organic metal-ion batteries owing to its high porosity,facile synthesis,stability,and high-rate performance.However,pristine g-C_(3)N_(4)nanosheets exhibit poor electrical conductivity,irreversible metal-ion storage capacity,and short-term cycling owing to their high concentration of graphitic-N species.Herein,a series of 3,4:9,10-perylenetetracarboxylic diimide-coupled g-C_(3)N_(4)composite anode materials,CN-PI_(x)(x=0.2,0.5,0.75,and 1),was investigated,which exhibited an unusually high surface nitrogen content(23.19-39.92 at.%)and the highest pyridinic-N,pyrrolic-N,and graphitic-N contents reported to date.The CN-PI_(1)anode delivers an unprecedented and continuously increasing ultrahigh discharging capacity of exceeding 8400 mAh g^(-1)(1.96 mWh cm^(-2))at 100 mA g^(-1)with high specific energy density(E_(sp))of~7700 Wh kg^(-1)and the volumetric energy density(E_(v))of~14956 Wh L-1 and an excellent long-term stability(414 mAh g^(-1)or 0.579 mWh cm^(-2)at 1 A g^(-1)).Furthermore,the activation of the CN-PI_(x)electrodes contributes to their superior electrochemical performance,resulting from the fact that the Li+is not only stored in the CN-PI_(x)composites but also CN-PI_(x)activated the Li^(0)adlayer on the CN-PI_(1)-Cu heterojunction as an SEI layer to avoid the direct contact of Li^(0)phase and the electrolyte.The CN-PI_(1)full cell with LiCoO_(2)as the cathode delivers a discharge capacity of~587 mAh g^(-1)at a 1 A g^(-1)after 250 cycles with a Coulombic efficiency nearly 99%.This study provides a strategy to develop N-doped g-C_(3)N_(4)-based anode materials for realizing long-lasting energy storage devices.

Recyclability and Self-Healing of Dynamic Cross-Linked Polyimide with Mechanical/Electrical Damage

Recyclability and self-healing are two most critical factors in developing sustainable polymers to deal with environmental pollution and resource waste.In this work,a dynamic cross-linked polyimide insulation film with full closed-loop recyclability is successfully prepared,which also possesses good self-healing ability after being mechanical/electrical damaged depending on the Schiff base dynamic covalent bonds.The recycled and self-healed polyimide film still maintain its good tensile strength(r t)>60 MPa with Young’s modulus(E)>4 GPa,high thermal stability with glass transition temperature(T g)>220℃,and outstanding insulation property with breakdown strength(E 0)>358 kV mm^(-1),making it a very promising low energy consumption and high temperature resistant insulation material.The strategy of using Schiff base dynamic covalent bonds for reversible repairing the structure of high T g polyimides promotes the wider application of such sustainable and recyclable material in the field of electrical power and micro-electronics.

Direct detection redox mechanisms of polyimide electrode by EPR spectroscopy

Recently,a study reported on the use of in situ electron paramagnetic resonance(EPR)spectroscopy to investigate two consecutive single-electron processes in polyimide and directly diagnose typical electrochemical reactions of carbonyl-based organic electrode in Li-ion batteries(LIBs).This research offers the important experimental clue for studying specific electron conversion routes of multi-electron transfer reactions in LIB materials[1].

基于MEMS技术的集成压力-湿度传感器

设计了一种高灵敏度的集成压力和湿度传感单元的芯片。压力传感单元基于SOI和蛇形电阻结构。室温下,传感器在载压范围为3~129 kPa内灵敏度为0.026 mV/kPa,与有限元仿真基本吻合。传感器在25~120℃范围内的热灵敏度漂移为0.004‰FS/℃,热零点漂移为0.25%FS/℃。湿度传感单元采用的叉指电极和电容式结构,引入含氟PI作湿度敏感膜。设计Mo电阻加热结构加快传感器降湿过程,缩短降湿时间近32%。在10%~90%RH的湿度范围,含氟PI湿度传感器的灵敏度为0.121 pF/%RH,略低于无氟PI器件。含氟基团的引入,使得传感器的湿滞较无氟PI降低16%。“电容-湿度”曲线呈指数分布,相关系数R^(2)=0.996。测试结果发现,湿度传感单元和压力传感单元拥有良好的独立工作性能。

纺丝液配制对PI/TiO_(2)活性碳纳米纤维膜吸附性能的影响

以均苯四甲酸酐(PMDA)、4,4′-二氨基二苯醚(ODA)及纳米TiO_(2)为原料,采用静电纺丝及热酰亚胺化的方法制备聚酰亚胺/二氧化钛(PI/TiO_(2))复合纳米纤维膜,在高温下对PI/TiO_(2)复合纳米纤维膜进行活化处理,通过正交试验研究了PMDA与ODA摩尔比、纳米TiO_(2)含量及纺丝液含量对PI/TiO_(2)活性碳纳米纤维膜吸附性能的影响。结果表明:PMDA与ODA摩尔比为1.03∶1、TiO_(2)质量分数为3%、纺丝液质量分数为22%时,活性碳纳米纤维薄膜的吸附性能最佳。

不同温度下聚酰亚胺薄膜的蠕变性能

为研究聚酰亚胺薄膜的蠕变黏弹性本构关系模型,选用厚度25μm的聚酰亚胺膜材料,初始应力选取极限抗拉强度的50%,在23、 50、 80、 110、 140、 170℃下进行单轴蠕变拉伸实验,分析不同温度下膜材料蠕变的变化规律.用经典Kelvin、经典Maxwell、 Burgers、三参数广义Kelvin、五参数广义Kelvin蠕变本构模型对数据进行拟合,分析拟合效果.结果表明,聚酰亚胺膜材料具有明显的黏弹性,初始应力对聚酰亚胺膜材料的蠕变性能影响显著,初始应力越大,黏弹性越明显.五参数广义Kelvin模型能够较好地预测聚酰亚胺膜材料的蠕变性能,可决系数均超过0.98,Burgers模型次之,其余3种模型的拟合可决系数为0.708~0.958,拟合结果满足实际工程需要.

HFBAPP/6FDA/BPADA含氟苯醚型聚酰亚胺薄膜的制备与性能研究

以2,2-双[4-(4-氨基苯氧基)苯基]六氟丙烷(HFBAPP)为二胺单体,2,2′-双(3,4-二羧酸)六氟丙烷二酐(6FDA)和双酚A型二醚二酐(BPADA)为二酐单体制备了一系列HFBAPP/6FDA/BPADA含氟苯醚型PI薄膜。通过改变二酐单体比例,分析比较醚键与三氟甲基对PI薄膜综合性能的影响。结果表明:随着三氟甲基含量的升高和醚键含量的降低,HFBAPP/6FDA/BPADA含氟苯醚型PI薄膜的光学性能和热学性能提高,而力学性能下降,玻璃化转变温度最高可达247.3℃,800℃时的残炭率最高可达56.3%,可见光范围内的透光率最高可达88.2%,拉伸强度最高可达84.7 MPa。

高压自紧式聚酰亚胺垫片密封性能影响因素分析及结构优化

为了解决液体火箭发动机在异常工况下的密封失效问题,建立了发动机充气阀阀芯密封结构的有限元模型,分析了密封结构参数、加工误差及卡滞偏斜对充气阀阀芯密封性能的影响,并进行了试验验证。结果表明:综合考虑可加工性、密封效果,圆阀座是充气阀的首选结构;在不同圆角半径下,圆角半径在0.35~0.45 mm范围内使用效果最佳;平面度偏差及卡滞偏斜在0~0.07 mm范围内对密封效果和使用寿命几乎没有影响。本研究可为航天军工用高精密密封的设计和优化提供参考,有助于提高我国高精密密封的技术水平。

高透明性聚酰亚胺薄膜专利技术研究与工业化进展

介绍了国内外高透明性聚酰亚胺(CPI)薄膜材料的研究现状,重点综述了含氟芳香族和脂环族两大类P1薄膜的研究进展,包括分子主链引入强电负性(含氟)取代基、脂环结构、非平面共轭结构、砜基、酯基、酰胺基及可聚合的无机纳米粒子等方法制备高透明性薄膜材料。同时,概述了国内外CPI薄膜的产业化现状,并对CPI薄膜的发展趋势和应用前景进行了展望。

聚酰亚胺纳米纤维滤膜的制备及性能分析

为探究亚胺化温度对聚酰亚胺(PI)纳米纤维性能的影响,将二胺单体4,4-二氨基二苯醚(ODA)和二酐单体均苯四甲酸酐(PMDA)溶于N,N-二甲基乙酰胺(DMAc)中,配制不同质量分数的聚酰胺酸(PAA)溶液,通过静电纺丝制成PAA纳米纤维滤膜,随后经过不同温度亚胺化处理形成PI纳米纤维滤膜,研究滤膜的微观形态、过滤性能、透气性能和透湿性能等。结果表明:PAA溶液质量分数为30%时,其纳米纤维形态最好;亚胺化温度为200℃时,滤膜的过滤效率为95.86%,阻力压降为610.56 Pa,过滤性能平衡关系最好,此时最大强度为3.24MPa,透气率为98.19 mm/s;亚胺化温度为190℃时,水接触角为95.26°,润湿性能最好;透湿性能随着亚胺化温度的升高而降低。

国产聚酰亚胺柔性覆铜板材料介电性能测评

介绍了聚酰亚胺柔性覆铜板的主要电性能指标及其典型应用场景,明确了柔性覆铜板介电性能测评流程。在完成谐振环仿真及设计后,开展ASG-TL00060UF2国产高性能聚酰亚胺柔性覆铜板与进口板材的常温和湿热试验,进行介电性能对比测试计算。最后给出了国产聚酰亚胺柔性覆铜板材料介电性能测评结论。

无色透明聚酰亚胺的研究进展

随着柔性光电器件的快速发展,对无色透明聚合物薄膜类柔性基材的性能要求越来越高。其中,作为高分子材料“金字塔”尖的聚酰亚胺(PI)因其优异的耐热性、机械性能、化学稳定性及介电性能成为最有力的候选者。因此,在保持传统有色PI优势性能的基础上,如何实现PI的无色透明化成为近些年的研究热点。本文分别从制备(包括制备方法和溶剂)和分子结构设计(如引入强电负性基团、脂环结构和大体积侧基等)两个方面,讨论了它们对无色透明PI(CPI)关键性能指标的影响,并进行了展望。

聚酰亚胺复合薄膜性能研究

为提高电池组金属外壳的耐腐蚀性能,向聚酰亚胺涂层中掺杂碳纳米管和石墨烯粉体,得到了聚酰亚胺复合涂层,并研究其在200℃下添加纳米碳材料前后的耐腐蚀性、导电性以及韧性变化。结果表明:聚酰亚胺在掺杂碳纳米管后,耐腐蚀性、导电性能以及力学性能均有所改善,尤其是导电性大幅提高,并且同时掺杂1%CNTs和0.5%石墨烯对聚酰亚胺性能提高最为显著,说明向聚酰亚胺中同时添加一维及二维纳米材料能更好地提高涂层的性能。