Confinement or dimensionality reduction is a novel strategy to reduce the lattice thermal conductivity and, consequently, to improve the thermoelectric conversion performance.

The major cause for capacity fading of silicon nanoparticle (SiNP)-based electrodes is the immense pressure applied toward the conductive networks during the charge/discharge process. While numerous efforts have been devoted to investigating different types of polymer binders, the rational design of an adhesive binder with pressure sensitivity has rarely been reported. Herein, a series of pressure-sensitive adhesives (PSAs) synthesized via copolymerization of 2-ethylhexyl acrylate (2-EHA) and acrylic acid (AA) are evaluated as polymer binders for SiNP-based electrodes. The balance between the density of interaction groups and viscoelastic properties is systematically investigated for efficient binding performance. The SiNP-based electrode using PSA with 20 mol % of 2-EHA (Si-PSA-20%) exhibits excellent electrochemical performance, achieving a capacity retention of 83% at the 100th cycle compared with 54% for Si-PAA after activation. Si-PSA-20% also delivers a superior cycling performance at a high current density (1731 mAh g −1 after 350 cycles vs 719 mAh g −1 after 150 cycles for Si-PAA, 1.8 A g −1 ) and at high mass loading of active materials (capacity retention of 74 vs 38% for Si-PAA after 100 cycles, SiNP content ∼1.2 mg cm −2 ). Atomic force microscopy (AFM), peel tests, and Car−Parrinello molecular dynamics (CPMD) simulations are employed to understand their binder performance. The novel design and systematical investigation of PSAs as binders will definitely be appealing for not only the Si electrode but also for other high-energy-density electrode materials.

We perform a systematic study of the lattice dynamics and the lattice thermal conductivity, κ, of monolayer group 13 monochalcogenides MX (M = Ga, In; X = S, Se, Te) by combining an iterative solution for linearized phonon Boltzmann transport equation and density functional theory. Among the competing factors influencing κ, harmonic parameters along with the atomic masses dominate over anharmonicity. An increase in atomic mass leads to a decrease in phonon frequencies and phonon group velocities and consequently in κ. At T = 300 K, the calculated κ values are 54.9, 48.1, 44.3, 25.0, 22.3, and 17.3 W m −1 K −1 for GaS, InS, GaSe, InSe, GaTe, and InTe monolayers, respectively. Further analysis of anharmonic scattering rates and average scattering matrix elements evidences that the anharmonicity characterized by the third-order IFCs in GaS and InS are the largest among all monolayer group 13 monochalcogenides despite the largest κ values. This is attributed to a strong interaction between nonbonding lone-pair s electrons around the S atom and adjacent bonding electrons. In addition, the κ of these monolayers further reduces to 50% for sample sizes 300−400 nm. Our findings provide fundamental insights into thermal transport in monolayer group 13 monochalcogenides and should stimulate further experimental exploration of thermal transport in these materials for possible theromoelectric and thermal management applications.

Resonance energy is one of the criteria to measure aromaticity. The effect of the use of different orbital models is investigated in the calculated resonance energies of cyclic conjugated hydrocarbons within the framework of the ab initio Valence Bond Self-Consistent Field (VBSCF) method. The VB wave function for each system was constructed using a linear combination of the VB structures (spin functions), which closely resemble the Kekulé valence structures, and two types of orbitals, that is, strictly atomic (local) and delocalized atomic (delocal) p-orbitals, were used to describe the π-system. It is found that the Pauling-Wheland's resonance energy with nonorthogonal structures decreases, while the same with orthogonalized structures and the total mean resonance energy (the sum of the weighted off-diagonal contributions in the Hamiltonian matrix of orthogonalized structures) increase when delocal orbitals are used as compared to local p-orbitals. Analysis of the interactions between the different structures of a system shows that the resonance in the 6π electrons conjugated circuits have the largest contributions to the resonance energy. The VBSCF calculations also show that the extra stability of phenanthrene, a kinked benzenoid, as compared to its linear counterpart, anthracene, is a consequence of the resonance in the π-system rather than the H-H interaction in the bay region as suggested previously. Finally, the empirical parameters for the resonance interactions between different 4n+2 or 4n π electrons conjugated circuits, used in Randić's conjugated circuits theory or Herdon's semi-emprical VB approach, are quantified. These parameters have to be scaled by the structure coefficients (weights) of the contributing structures.

In this work, the complexation of the bapbpy ligand to zinc dichloride is described (bapbpy = 6,6'-bis(2-aminopyridyl)-2,2'-bipyridine). The water-soluble, colorless complex [Zn(bapbpy)Cl]Cl·2H 2 O (compound 2·H 2 O) was synthesized; its X-ray crystal structure shows a mononuclear, pentacoordinated geometry with one chloride ligand in apical position. Upon excitation of its lowest-energy absorption band