Construction of phosphorus-doping with spontaneously developed selenium vacancies: Inducing superior ion-diffusion kinetics in hollow Cu_(2)Se@C nanospheres for efficient sodium storage

Achieving high-efficiency sodium storage in metal selenides is still severely constrained in consideration of their inferior electronic conductivity and inadequate Na^(+)insertion pathways and active sites.Heteroatom doping accompanied by spontaneously developed lattice defects can effectively tune electronic structure of metal selenides,which give a strong effect to motivate fast charge transfer and Na^(+)accessibility.Herein,we finely designed and successfully constructed a fascinating phosphorus-doped Cu_(2)Se@C hollow nanosphere with abundant vacancy defects(Cu_(2)P_(x)Se_(1-x)@C)through a combination strategy of selenization of Cu_(2)O nanosphere template,self-polymerization of dopamine,and subsequent phosphorization treatment.Such exquisite composite possesses enriched active sites,superior conductivity,and sufficient Na^(+)insertion channel,which enable much faster Na^(+)diffusion rates and more remarkable pseudocapacitive features,Satisfyingly,the Cu_(2)P_(x)Se_(1-x)@C composites manifest the supernormal sodium-storage capabilities,that is,a reversible capacity of 403.7 mA h g^(-1) at 1.0 A g^(-1) over 100 cycles,and an ultrastable cyclic lifespan over 1000 cycles at 20.0 A g^(-1) with a high capacity-retention of about249.7 mA h g^(-1).The phase transformation of the Cu_(2)P_(x)Se_(1-x)@C involving the intercalation of Na^(+)into Cu_(2)Se and the following conversion of NaCuSe to Cu and Na2Se were further demonstrated through a series of ex-situ characterization methods.DFT results demonstrate that the coexistence of phosphorusdoping and vacancy defects within Cu_(2)Se results in the reduction of Na^(+)adsorption energy from-1.47to-1.56 eV improving the conductivity of Cu_(2)Se to further accelerate fast Na^(+)mobility.

Gradient nanostructured tungsten and the thermal shock response

In fusion reactor or spallation neutron source environment,damage of tungsten components begins at the surface.To enhance the surface toughness,strength,and hardness of tungsten,a nano-to-micro sc ale lamellar gradient surface layer(thickness up to~50μm)was produced on as-rolled pure tungsten using a dry-sliding surface treatment.The dry-sliding temperature and time were established by observing the grain-size evolution from room temperature to 750℃and the coefficient of friction on the surface layer after sliding from 10 to 50 min.The grains changed into a slender fibrous structure at 250℃,which is higher than the ductile-brittle transition temperature but lower than the dynamic recrystallization temperature(750℃).The coefficient of friction of the surface layer decreased with sliding time and stabilized at approximately 50 min,indicating near-s aturation of the surface refinement.After repetitive thermal loads of 10,20,and 30 MW·m^(-2)on the gradient modified layer,it exhibited mainly recrystallization and grain growth.The proportion of low-angle grain boundaries(<10°)reached50.6,42.2,and 17.3%,respectively,and the hardness decreased to 602,582,and 488HV.A heat load of 30 MW·m^(-2)was the threshold for the fast grain growth.Compared with unmodified tungsten,the recrystallization and grain growth are relatively slow.Besides,the gradient layer could suppress the formation of pits and protrusions in the as-rolled tungsten sample.