Particles in composite polymer electrolyte for solid-state lithium batteries: A review

Solid-state lithium batteries (SSLBs) have been identified as one kind of the most promising energy conversion and storage devices because of their safety, high energy density, and long cycling life. The development of solid-state electrolyte is vital to commercialize SSLBs. Composite polymer electrolyte (CPE), derived by compositing inorganic particles into solid polymer electrolyte has become the most practical species for SSLBs because it inherits the advantages of polymer electrolyte and simultaneously achieves enhanced ionic conductivity and mechanical properties. The characteristics of inorganic particles and their interaction with polymers strongly impact the performance of CPE, improving its ionic conductivity, mechanical properties, thermal and electrochemical stability, as well as interface compatibility with both electrodes. In this review, the effects of particle characteristics including its species, size, proportion, morphology on the ionic conductivity and mechanical properties of CPE are reviewed. Meanwhile, some novel composite strategies are also introduced including surface modification, hybridization, and alignment of particles in polymer matrices, as well as some new preparation methods of CPE. The interactions between particles and other components in CPE including polymer matrices or lithium salt are particularly focused herein to reveal the lithium conductive mechanism. Finally, a perspective on the direction of future CPE development for SSLBs is presented.     

Synthesis of Oligomeric Axially Bridged Ruthenium Phthalocyanines and 2,3-Naphthalocyanines

Bridged 2,3-naphthalocyaninatoruthenium oligomers {[MacRu(L)] _n } were synthesized and characterized using solid-state methods. For comparison, soluble t-butyl substituted phthalocyaninatoruthenium oligomers were prepared and their chain length examined by ¹H NMR spectroscopy. The powder conductivities of all bridged compounds ([MacRu(L)] _n ) were measured and the dependence of the conductivities on the bridging ligands is discussed.     

Alkaline Stable Anion Exchange Membranes Based on Cross-Linked Poly(arylene ether sulfone) Bearing Dual Quaternary Piperidines for Enhanced Anion Conductivity at Low Water Uptake

Alkaline stable anion exchange membranes based on the cross-linked poly(arylene ether sulfone) grafted with dual quaternary piperidine (XPAES-DP) units were synthesized. The chemical structure of the synthesized PAES-DP was validated using ¹H-NMR and FT-IR spectroscopy. The physicochemical, thermal, and mechanical properties of XPAES-DP membranes were compared with those of two linear PAES based membranes grafted with single piperidine (PAES-P) unit and conventional trimethyl amine (PAES-TM). XPAES-DP membrane showed the ionic conductivity of 0.021 S cm⁻¹ at 40 °C which was much higher than that of PAES-P and PAES-TM because of the possession of more quaternary ammonium groups in the cross-linked structure. This cross-linked structure of the XPAES-DP membrane resulted in a higher tensile strength of 18.11 MPa than that of PAES-P, 17.09 MPa. In addition, as the XPAES-DP membrane shows consistency in the ionic conductivity even after 96 h in 3 M KOH solution with a minor change, its chemical stability was assured for the application of anion exchange membrane fuel cell. The single-cell assembled with XPAES-DP membrane displayed a power density of 109 mWcm⁻² at 80 °C under 100% relative humidity.     

非均匀多孔介质有效热导率分析

本文采用控制容积法,界面调和平均导热系数值以及图形处理方法对典型非均匀多孔介质硬质聚氨酯泡沫材料的导热过程进行了分析与模拟计算。结果表明:多孔介质的内部结构是影响温度分布和热量传递的主要的因素,其影响程度与骨架和孔隙的导热系数,孔隙的大小和分布有关;计算得到的有效热导率值与文献中实验测量结果吻合较好。本文的研究结果可以推广到更为复杂的非均匀多孔介质的场合,从而可以进一步认识非均匀多孔介质中的导热规律,为工程计算提供更精确的计算方法。     

The Impact of Foaming Effect on the Physical and Mechanical Properties of Foam Glasses with Molecular-Level Insights

Foaming effect strongly impacts the physical and mechanical properties of foam glass materials, but an understanding of its mechanism especially at the molecular level is still limited. In this study, the foaming effects of dextrin, a mixture of dextrin and carbon, and different carbon allotropes are investigated with respect to surface morphology as well as physical and mechanical properties, in which 1 wt.% carbon black is identified as an optimal choice for a well-balanced material property. More importantly, the different foaming effects are elucidated by all-atomistic molecular dynamics simulations with molecular-level insights into the structure–property relationships. The results show that smaller pores and more uniform pore structure benefit the mechanical properties of the foam glass samples. The foam glass samples show excellent chemical and thermal stability with 1 wt.% carbon as the foaming agent. Furthermore, the foaming effects of CaSO₄ and Na₂HPO₄ are investigated, which both create more uniform pore structures. This work may inspire more systematic approaches to control foaming effect for customized engineering needs by establishing molecular-level structure–property–process relationships, thereby, leading to efficient production of foam glass materials with desired foaming effects.     

二维CdO的低晶格热导率研究

寻求具有较小晶格热导率k_lat的高热电性能的二维材料具有重要意义。基于从头计算和声子玻耳兹曼输运理论,该研究首先对二维CdO结构进行优化,并通过计算声子谱验证了单层CdO的动力学稳定性。在此基础上详细研究了单层CdO的声子输运性质。计算表明在室温下单层CdO的晶格热导率k_lat约为5.7 W/(m·K),低于单层石墨烯、磷烯、黑磷和MoS₂等二维材料的晶格热导率。其中,Z方向声学模式(Z-direction acoustic, ZA),横声学支(transverse acoustic,TA),纵声学支(longitudinal acoustic, LA),Z方向光学模式(Z-direction optical, ZO),横光学支(transverse optical, TO),纵光学支(longitudinal optical, LO)对k_lat的百分比贡献分别为73.7％、13.9％、3.7％、2.8％、4.7％和1.2％。研究发现,ZA、TA、LA声学支和光学支之间的强散射是导致单层CdO低热导率的原因。本文计算结果可用于指导基于CdO的低维热电器件的设计。     

Electrical and Thermal Transport Properties of n-type Bi6Cu2Se4O6 (2BiCuSeO + 2Bi2O2Se)

New thermoelectric materials, n-type Bi₆Cu₂Se₄O₆ oxyselenides, composed of well-known BiCuSeO and Bi₂O₂Se oxyselenides, are synthesized with a simple solid-state reaction. Electrical transport properties, microstructures, and elastic properties are investigated with an emphasis on thermal transport properties. Similar to Bi₂O₂Se, it is found that the halogen-doped Bi₆Cu₂Se₄O₆ possesses n-type conducting transports, which can be improved via Br/Cl doping. Compared with BiCuSeO and Bi₂O₂Se, an extremely low thermal conductivity can be observed in Bi₆Cu₂Se₄O₆. To reveal the origin of low thermal conductivity, elastic properties, sound velocity, Grüneisen parameter, and Debye temperature are evaluated. Importantly, the calculated phonon mean free path of Bi₆Cu₂Se₄O₆ is comparable to the interlayer distance for BiO─CuSe and BiO─Se layers, which is ascribed to the strong interlayer phonon scattering. Contributing from the outstanding low thermal conductivity and improved electrical transport properties, the maximum ZT ≈0.15 at 823 K and ≈0.11 at 873K are realized in n-type Bi₆Cu₂Se_3.2Br_0.8O₆ and Bi₆Cu₂Se_3.6Cl_0.4O₆, respectively, indicating the promising thermoelectric performance in n-type Bi₆Cu₂Se₄O₆ oxyselenides.     

Influence of Electron–Phonon Interaction on the Lattice Thermal Conductivity in Single-Crystal Si

Lattice thermal conductivity can be reduced by introducing point defect, grain boundary, and nanoscale precipitates to scatter phonons of different wave-lengths, etc. Recently, the effect of electron–phonon (EP) interaction on phonon transport has attracted more and more attention, especially in heavily doped semiconductors. Here the effect of EP interaction in n-type P-doped single-crystal Si has been investigated. The lattice thermal conductivity decreases dramatically with increasing P doping. This reduction on lattice thermal conductivity cannot be explained solely considering point defect scattering. Further, the lattice thermal conductivity can be fitted well by introducing EP interaction into the modified Debye–Callaway model, which demonstrates that the EP interaction can play an important role in reducing lattice thermal conductivity of n-type P-doped single-crystal Si.     

Investigation on thermal conductivity of graphene/Si heterostructure with different defect ratios and sizes

The thermal conductivity (TC) of graphene/Si heterostructures with different defect ratios and sizes was investigated using the molecular dynamics method. As the defect ratio of heterostructure increased, the TC decreased first sharply and then slowly under a high temperature stage. The TC of heterostructure also showed a significant size effect. This phenomenon was explained by phonon dispersion and flip competition. The phonon density of states for the graphene heterostructure with different defect ratios and sizes was obtained to understand the thermal transport mechanism. Analysis showed that with the increase in the defect ratio and when the flexural modes of the heterostructure became weak, the longitudinal and transverse modes gradually dominated the phonon transport. This phenomenon can be explained that the Si atom vibration was harder in the vertical plane than that of graphene. The vibration mode hindered the heat carrier of graphene and affected heat transport to the heterostructure.     

Affinity foam fractionation of Trichoderma cellulase

Cellulase could not be selectively collected from fermentation broth by simple foam fractionation, because of the presence of other more surface-active compounds. A new approach of affinity foam fractionation was investigated for improvement. A hardwood hydrolysate (containing cellulose oligomers, substrates to cellulase) and two substrate analogs, i.e., carboxymethyl cellulose (CMC) and xylan hydrolysate, were added before the foaming process. The substrates and substrate analogs were indeed found to bind the cellulase selectively and form more hydrophobic complexes that partition more readily onto bubble surfaces. In this study, the effects of the type and concentration of substrate/analog as well as the presence of cells at different growth stages were examined. The foam fractionation properties evaluated included foaming speed, foam stability, foamate volume, and enrichment of filter paper unit (FPU) and individual cellulase components (i.e., endoglucanases, exoglucanases, and β-glucosidases). Depending on the broth and substrate/analog employed, the foamate FPU could be more than fourfold higher than the starting broth FPU. Addition of substrate/analog also deterred the enrichment of other extracellular proteins, resulting in the desired cellulase purification in the foamate. The value of E/P (enzyme activity-FPU/g/L of proteins) in the foamate reached as high as 18, from a lactose-based fermentation broth with original E/P of 5.6. Among cellulase components, exoglucanases were enriched the most and β-glucosidases the least. The study with CMC of different molecular weights (MW) and degrees of substitution (DS) indicated that the CMC with low DS and high MW performed better in cellulase foam fractionation.