Effect of Graphite Layers on the Conformation and Thermal Conductivity of n-octadecane:A Molecular Dynamics Study

To understand the thermal conductivity improvement of the paraffin and graphite composite PCMs in micro-scale,the conformation characteristics of molecules with rising temperature was studied by molecular dynamics(MD)simulation.And then the structure and dynamics characteristics of the paraffin PCM,including the structural evolution,the self-diffusion coefficient,phase change properties and thermal conductivity,were analyzed.The results indicate that the distribution of the n-octadecane molecules is more regular in the region near the graphite layers,although the temperature is higher than the phase transition point,which means that the graphite layer has a significant absorption influence on the conformation of alkane molecules.Then,the self-diffusion coefficient of n-octadecane molecules increases with the increasing of temperature,which shows great agreement with the literature.Meanwhile,the self-diffusion coefficient of n-octadecane molecules staying far away from the graphite layers is larger than that of the molecules in the region near the graphite layer.In addition,the radial distribution function(RDF)was used to analyze the molecular interaction of the system at different temperatures.The sudden increase of R(ratio of the first peak value to the first valley value of the RDF)within the temperature range from 293 K to 313 K corresponds to the phase transition point,indicating that the solid-liquid phase transition occurs at the temperature range.Besides,the results indicate that the thermal conductivity of amorphous n-octadecane is about 2.5 times lower than that of the crystal n-octadecane with perfect structure.This investigation provides theoretical guidance for the study of the micro-mechanism of n-octadecane doped with graphite composite phase change materials.

Efficient ORR catalysts for zinc-air battery: Biomass-derived ultra-stable Co nanoparticles wrapped with graphitic layers via optimizing electron transfer

The poor stability of non-noble metal catalysts in oxygen reduction reaction(ORR) is a main bottleneck that limits their big-scale application in metal-air batteries. Herein, we construct a chainmail catalyst(Co-NC-AD) with outstanding stability, via the competitive complexation and post absorption strategy,consisting of highly graphitic layers wrapped uniform-size Co nanoparticles(Co-NPs). Experiments combined with density functional theory(DFT) calculations jointly confirmed that the electron transfer occurred from the inner Co-NPs to the external graphitic layers. It facilitated the adsorption process of oxygen molecules and the hybridization of the O-2 p and C-1 p orbitals, which accelerated the ORR reaction kinetics. Consequently, our prepared Co-NC-AD shows excellent ORR activity, offered with a more positive initial potential(E_(onset)= 0.95 V) and half-wave potential(E_(1/2)= 0.86 V). The remarkable stability and resistance of methanol poisoning are merited from the protection effect of stable graphitic layers. In addition, the high electrochemical performance of Co-NC-AD-based zinc-air battery demonstrates their potential for practical applications. Therefore, our work provides new ideas for the design of nanoconfined catalysts with high stability and activity.

Commercially Viable Hybrid Li-Ion/Metal Batteries with High Energy Density Realized by Symbiotic Anode and Prelithiated Cathode

The energy density of commercial lithium(Li)ion batteries with graphite anode is reaching the limit.It is believed that directly utilizing Li metal as anode without a host could enhance the battery’s energy density to the maximum extent.However,the poor reversibility and infinite volume change of Li metal hinder the realistic implementation of Li metal in battery community.Herein,a commercially viable hybrid Li-ion/metal battery is realized by a coordinated strategy of symbiotic anode and prelithiated cathode.To be specific,a scalable template-removal method is developed to fabricate the porous graphite layer(PGL),which acts as a symbiotic host for Li ion intercalation and subsequent Li metal deposition due to the enhanced lithiophilicity and sufficient ion-conducting pathways.A continuous dissolution-deintercalation mechanism during delithiation process further ensures the elimination of dead Li.As a result,when the excess plating Li reaches 30%,the PGL could deliver an ultrahigh average Coulombic efficiency of 99.5% for 180 cycles with a capacity of 2.48 m Ah cm^(-2) in traditional carbonate electrolyte.Meanwhile,an air-stable recrystallized lithium oxalate with high specific capacity(514.3 m Ah g^(-1))and moderate operating potential(4.7-5.0 V)is introduced as a sacrificial cathode to compensate the initial loss and provide Li source for subsequent cycles.Based on the prelithiated cathode and initial Li-free symbiotic anode,under a practical-level3 m Ah capacity,the assembled hybrid Li-ion/metal full cell with a P/N ratio(capacity ratio of Li Ni_(0.8)Co_(0.1)Mn_(0.1)O_(2) to graphite)of 1.3exhibits significantly improved capacity retention after 300 cycles,indicating its great potential for high-energy-density Li batteries.

Oxidization-induced structural optimization of Ni_(3)Fe-N-C derived from 3D covalent organic framework for high-efficiency and durable oxygen evolution reaction

NiFe composites have been regarded as promising candidates to replace commercial noble-based electrocatalysts for the oxygen evolution reaction(OER).However,their practical applications still suffer from poor conductivity,limited activity,durability.To address these issues,herein,by utilizing three-dimensional covalent organic framework(3D-COF)with porous confined structures and abundant coordinate N sites as the precursor,the partially oxidized Ni_(3)Fe nanoalloys wrapped by Ndoped carbon(N-C)layers are constructed via simple pyrolysis and subsequent oxidization.Benefiting from the 3D curved hierarchical structure,high-conductivity of Ni_(3)Fe and N-C layers,well-distributed active sites,the as-synthesized O-Ni_(3)Fe-NC catalyst demonstrates excellent activity and durability for catalyzing OER.Experimental and theoretical analyses disclose that both high-temperature oxidization and the OER process greatly promote the formation and exposure of the Ni(Fe)OOH active species as well as lower charge transfer resistance,inducing its optimized OER activity.The robust graphitized N-C layers with superior conductivity and their couplings with oxidized Ni_(3)Fe nanoalloys are beneficial for stabilizing catalytic centers,thereby imparting O-Ni_(3)Fe-N-C with such outstanding stability.This work not only provides a rational guidance for enriching and stabilizing high-activity catalytic sites towards OER but also offers more insights into the structural evolution of NiFe-based OER catalysts.

Towards the controlled CVD growth of graphitic B-C-N atomic layer films： The key role of B-C delivery molecular precursor

Graphene-like, ternary system B-C-N atomic layer materials promise highly tunable electronic properties and a plethora of potential applications. However, thus far, experimental synthesis of the B-C-N atomic layers normally yields a microscopic phase-segregated structure consisting of pure C and BN domains. Further, growing the truly ternary B-C-N phase layers with homogenous atomic arrangements has proven to be very challenging. Here, in designing a better- controlled process for the chemical vapor deposition （CVD） growth of B-C-N atomic layer films with the minimized C and BN phase segregation, we selected trimethyl borane （TMB）, a gaseous organoboron compound with pre-existing B--C bonds, as the molecular precursor to react with ammonia （NH3） gas that serves as the nitrification agent. The use of this unique B-C delivery precursor allows for the successful synthesis of high-quality and large-area B-C-N atomic layer films. Moreover, the TMB/NH3 reactant combination can offer a high level of tunability and control of the overall chemical composition of B-C-N atomic layers by regulating the relative partial pressure of two gaseous reactants. Electrical transport measurements show that a finite energy gap can be opened in the as-grown B-C-N atomic layers and its tunability is essentially dependent on the relative C to BN atomic compositions. On the basis of carefully controlled experiments, we show that the pre-existing B-C bonds in the TMB molecular precursor have played a crucial role in effectively reducing the C and BN phase segregation problem, thereby facilitating the formation of truly ternary B-C-N phase atomic layers.