Eight 6FDA-TFDB polyimide(PI)samples with absolute molecular weights ranging from 1.25 × 10^5 g mol^-1 to 3.11 × 10^5 g mol^-1 are obtained by precipitation fractionation.Rheological experiments are conducted to determine the influence of molecular weight on the associating behavior of PI in A/X-dimethylformamide(DMF)solutions in a broad volume fraction,including abnormal steady shear flow,solution heterogeneity,and scaling behavior.Abnormal flow behaviors,i.e.,multi-region shear thinning and weak shear thickening,are studied,and these behaviors have not been reported in literature.The heterogeneity of PI/DMF solutions is examined by dynamic rheological test.By plotting qsp versus four concentration regions of l-IV can be distinguished for all PI samples with various molecular weights.The scaling results in different concentration regions are in good agreement with the associative polymer theory proposed by Rubinstein and Semenov.The scaling exponents do not show molecular weight dependence in concentration regions I and II.In concentration regions Ⅲ and Ⅳ,the scaling exponents change little when the molecular weight is below 242 k but increase when the molecular weight increases from 242 k to 311 k.This work can help us to understand polyimide solution properties from dilute to semidilute entangled solutions,and will guide the polyimide solution preparation for different processing.
Hong-Xiang ChenEn-Song ZhangMei HongWei LiuXue-Min DaiQuan ChenXue-Peng QiuXiang-Ling Ji
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
Functional polymeric materials with electrical bi-stable states possess significant potential for high-density data storage due to their nanoscale memory site,threedimensional-stacking ability and intrinsic flexibility.Aromatic polyimides bearing donor-acceptor(D-A)skeleton could form the charge transfer complex(CTC)under an electrical field,leading to their feasibility as memory materials.Three novel porphyrinated polyimides DATPP-DSDA,Zn-DATPP-DSDA and Mn-DATPP-DSDA were designed and synthesized for information memory applications.Metal ions with different electron configurations at 3 d orbital have a determining influence on memory behaviors of polyimides:nonvolatile write-once-read-many-times memory(WORM)for DATPP-DSDA,volatile static random access memory(SRAM)for Zn-DATPP-DSDA,but no memory performance for Mn-DATPP-DSDA.By comparing the contribution of orbital transition and hole-electron distribution of chargetransfer excited states,roles of metal ions in regulating memory types were discussed.Molecular simulation results indicate that the Zn ion could play a bridge role in paving the route for excited electrons from a D to an A,while a trap role for the Mn ion in hindering this process.This study proves the feasibility of the strategy for modulating the memory behaviors of porphyrinated polyimides by varying the central metal ion and provides the exact effects of various metal ions on regulating charge transfer processes.
Jiacong GuoYankun ZhangGuofeng TianDeyang JiShengli QiDezhen WuWenping Hu
The thermal and mechanical properties of the chemically imidized polyimide(CIPI) films and thermally imidized polyimide(TIPI) films were investigated systematically. Experimental results indicated that the CIPI films show dramatically enhanced tensile strength and modulus with obviously reduced coefficient of thermal expansion(CTE) in comparison with TIPI films. These enhancements results from the high in-plane orientation and close packing of the CIPI backbones. Compared with thermal imidization which starts at about 140 °C, the chemical imidization activated by acetic anhydride and isoquinoline initiates the cyclization even at room temperature.The resulting imide rings restrict the mobility of polymer chains and lead to the in-plane orientation with solvent evaporation.Additionally, fewer small molecules remain in the films after treated at 120 °C by chemical imidization than by thermal imidization. The polymer chain plasticization caused by the evaporation of small molecules at high temperature is obviously restricted. Moreover, the partially imidized polymer inhibits the decomposition of mainchains that occurs at subsequent high temperature process, being beneficial to the formation of high molecular weight PI films. Hence, chemical imidization pathway shows apparent advantage to produce PI films with great combined properties, including high modulus, strength and toughness, as well as high thermal dimension stability etc.
Zhen-He WangXing ChenHai-Xia YangJiang ZhaoShi-Yong Yang
A series of polyimide（PI）/multi-walled carbon nanotube（MWCNT） composite fibers were prepared by copolymerizing a mixture of monomers and carboxylic-functionalized MWCNTs, followed by dry-jet wet spinning, thermal imidization, and hot-drawing process. The content of the carboxylic groups of MWCNTs significantly increased when treated with mixed acid, whereas their length decreased with treatment time. Both the carboxylic content and length of MWCNTs influenced the mechanical properties of the composite fibers. Fiber added with 0.1 wt% MWCNTs treated for 4 h exhibited the best mechanical properties, i.e., 1.4 GPa tensile strength and 14.30% elongation at break, which were 51% and 32% higher than those of pure PI fibers, respectively. These results indicated that a suitable MWCNT content strengthened and toughened the resultant PI composite fibers, simultaneously. Moreover, raising draw ratio resulted in the increase of tensile strength and tensile modulus of the composite fibers.
A series of polyimide fibers containing phosphorus element derived from （3-aminophenyl） methyl phosphine oxide （DAMPO） diamine was exposed to an artificial atomic oxygen environment which simulated the space environment in low earth orbit （LEO）. The mass loss, surface morphology, chemical composition, and mechanical properties of the fibers before and after atomic oxygen （AO） exposure were compared in detail with a blank sample. Results showed that the phosphor-containing fibers demonstrated lower mass change and less tensile strength reduction. SEM results showed that the fibers with phosphorous element had relatively dense surface after AO exposure. Meanwhile, XPS results indicated that a passivated phosphate layer, which could protect the following under-layer from attacking by AO, was formed on the surface of the fibers. These results indicated that the incorporation of diamine （DAMPO） into the main chains could protect the fibers for avoiding further erosion from AO exposure. Hence, the phosphor-containing PI fibers exhibits potential application in space fields.
