Cation-vacancy induced Li+ intercalation pseudocapacitance at atomically thin heterointerface for high capacity and high power lithium-ion batteries

It is challenging to create cation vacancies in electrode materials for enhancing the performance of rechargeable lithium ion batteries (LIBs). Herein, we utilized a strong alkaline etching method to successfully create Co vacancies at the interface of atomically thin Co_(3−x)O_(4)/graphene@CNT heterostructure for high-energy/power lithium storage. The creation of Co-vacancies in the sample was confirmed by high-resolution scanning transmission electron microscope (HRSTEM), X-ray photoelectron spectroscopy (XPS) and electron energy loss near-edge structures (ELNES). The obtained Co_(3−x)O_(4)/graphene@CNT delivers an ultra-high capacity of 1688.2 mAh g^(−1) at 0.2 C, excellent rate capability of 83.7% capacity retention at 1 C, and an ultralong life up to 1500 cycles with a reversible capacity of 1066.3 mAh g^(−1). Reaction kinetic study suggests a significant contribution from pseudocapacitive storage induced by the Co-vacancies at the Co_(3−x)O_(4)/graphene@CNT interface. Density functional theory confirms that the Co-vacancies could dramatically enhance the Li adsorption and provide an additional pathway with a lower energy barrier for Li diffusion, which results in an intercalation pseudocapacitive behavior and high-capacity/rate energy storage.

In situ induced cation-vacancies in metal sulfides as dynamic electrocatalyst accelerating polysulfides conversion for Li-S battery

Cation vacancy engineering is considered to be one of the effective methods to solve the issues of shuttling and sluggish redox kinetics of Li PSs owing to the intrinsic tunability of electronic structure.However,cation vacancies are few studied in the Li-S realm due to their complex and rigid preparation methods.In this work,one-step pyrolysis is reported to in situ introduce Fe-vacancies into iron sulfide(Fe_(0.96)S)as a sulfur host.For this host structure,Fe_(0.96)S is first employed as an adsorbent and catalyst in Li-S system.During the carbonization process,a tight contact structure of Fe_(0.96)S crystal and carbon network(Fe_(0.96)S@C)is in situ constructed,and the carbon layer as a conductor provides smooth electrons transfer pathways for redox reactions.Meanwhile,due to the introduction of Fe-vacancies in Fe S crystal,the adsorption capability and catalytic effect for Li PSs have been substantially enhanced.Moreover,the presence of Fe_(0.96)S crystal favors the mobility of electron and diffusion of Li+,which is revealed by the experiments and theoretical calculations.Through synergy respective advantages effect of Fe_(0.96)S and carbon,the Fe_(0.96)S@C-S cathode delivers high-rate capability at 5.0 C and stable long-life performance.Even under a high sulfur loading of 3.5 mg/cm^(2),the durable cyclic stability is still exhibited with the capacity retention of 93%over 400 cycles at 1.0 C,and the coulombic efficiency is≥98%.Noting that this strategy greatly simplifies the synthetic process of currently known cation-vacancy materials and furnishes a universal mentality for designing both divinable and astonishing new cation-vacancy materials.

Synthesis and Ionic Conduction of Cation-deficient Apatite La9.33-2x/3MxSi6O26 Doped with Mg, Ca, Sr

Apatite-type lanthanum silicate with special conduction mechanism via interstitial oxygen has attracted considerable interest in recent years. In this work, pure powder of La9.33 2x/3MxSi6O26 （M=Mg, Ca, Sr） is prepared by the sol-gel method with sintering at 1000℃. The powder is characterized by X-ray diffraction （XRD） and scanning electron micrograph （SEM）. The apatite can be obtained at relatively low temperature as compared to the conventional solid-state reaction method. The measurements of conductivity of a series of doped samples La9.33-2x/3MxSi6O26 （M=Ca, Mg, Sr） indicate that the type of dopant and the amount have a significant effect on the conductivity. The greatest decrease in conductivity is observed for Mg doping, following the Ca and the Sr doped apatites. The effect is ultimately attributed to the amount of oxygen interstitials, which is affected by the crystal lattice distortion arising from cation vacancies.

Combination Effect of Cation Vacancies and O2 Adsorption on Ferromagnetism of Na0.5Bi0.5TiO3（100） Surface:ab initio Study

The combination effect of cation vacancies and O2 adsorption on ferromagnetism of Na0.5Bi0.5TiO3（100） surface is studied by using density functional theory. An ideal Na0.5Bi0.5TiO3（100） surface is non-magnetic and the cation vacancy could induce the magnetism. By comparing the formation energies for Na, Bi and Ti vacancy, the Na vacancy is more stable than the others. Therefore, we focus on the configuration and electric structure for the system of O2 molecule adsorption on the Na0.5Bi0.5TiO3（100） surface with a Na vacancy. Among the five physisorption configurations we considered, the most likely adsorption position is Na vacancy. The O2 adsorption enhances the magnetism of the system. The contribution of spin polarization is mainly from the O 2p orbitals. The characteristics of exchange coupling are also calculated, which show that the ferromagnetic coupling is favorable. Compared with the previous calculation results, our calculations could explain the room-temperature ferromagnetism of Na0.5Bi0.5TiO3 nanocrytalline powders more reasonably, because of taking into account adsorbed oxygen and cation vacancies. Moreover, our results also show that adsorption of O2 molecule as well as introduction of cation vacancies may be a promising approach to improve multiferroic materials.

Boosted sodium ion storage performance in MnO_(2):Understanding the bond angle-mediated orbital overlap in MnO_(6)units for fast charge transfer

Symmetric six oxygen-coordinated Mn structural units(MnO6)in MnO2 with small Mn–O orbital overlap hamper electron transfer rates during energy storage.Herein,we report a novel bond angle modulation strategy to manipulate Mn–O orbital overlap in MnO2 through the construction of Mn vacancies(MnO2-VMn),aiming at expediting electron transfer,and thus enhancing energy storage performance.Both experimental and theoretical results disclose that the amplification of Mn–O–Mn bond angles exclusively augments the Mn(dx2-y2)-O(py)orbital overlap and triggers the electron redistribution in MnO2-VMn,inducing an augmented Mn dx2-y2 electron occupation.This heightened presence of active electrons in the Mn dx2-y2 orbital paves the way for accelerating electron transfer and ion transfer in MnO2-VMn.Notably,MnO2-VMn delivers an improved specific capacitance of 425 F g−1 at 1 A g−1 and a superior rate capacity of 265 F g−1 at 20 A g−1.Furthermore,an asymmetric supercapacitor(MnO2-VMn//AC ASC)was fabricated,exhibiting a high energy density of 64.3 Wh kg−1 at a power density of 1000 W kg−1.Furthermore,theoretical insights uncover the profound implications of metal–oxygen–metal bond angle regulation on interatomic orbital overlap modulation.These revelations illuminate pathways for the design of advanced energy storage materials.

Synthesis and Conducting Properties of La10-x（SiO4）6O3-1.5x

The synthesis of silicate oxyapatitesLa10-x（SiO4）6O3-1.5x（x=0. 0.17, 0.33, 0.50 and 0.67） via a sol-gel method at 800 ℃ was reported. The apatite phases were characterized by X-ray diffraction （XRD） and conducting properties were studied by electrochemical impedance spectroscopy （EIS）. It is found that the conductivities are influenced by the amount of cation vacancies and interstitial oxygen. The conductivity of La9.33 （SiO4）6O2 with more cation vacancies is higher than that of La9.5 （SiO4）6O2.25. The conductivity of La10 （SiO4）6O3 with more interstitial oxygen is 7.98 ×10^-3 S·cm^-1, which is about 5 times higher than that of La9.33（SiO4）6O2 at 700℃. The electrical conductivity is almost independent of the oxygen partial pressure from 105 to 1 Pa, which suggests that the oxyapatites exhibit almost pure O^2- ion conduction over a wide range of oxygen partial pressure.

Structural and magnetic properties of La_(0.7)Sr_(0.1)Ag_xMnO_(3-δ) perovskite manganites

Ag-doped manganite powder samples, La0.7Sr0.1AgxMnO3 6 （x = 0.00, 0.025, 0.05, 0.075, and 0.10） were synthesized using the sol-gel method. X-ray diffraction patterns indicated that the samples had two phases with the R-3c perovskite being the dominant phase and Mn3O4 being the second phase. X-ray energy dispersive spectra indicated that the ratio of Ag to La was very close to that of the nominal composition in the samples. The specific saturation magnetizations at 300 K increased from 32.0 A.mZ/kg when x = 0.00 to 46.8 A-mZ/kg when x = 0.10. The Curie temperature, TC, of the samples increased from 310 K when x = 0.00 to 328 K when x = 0.10. Because the atomic concentration ratios of La, Sr, and Mn in the five samples were all the same and only the Ag concentration changed, the variations of the specific saturation magnetizations at 300 K and the Curie temperatures suggested that the Ag cations have been doped into the A sites of the perovskite phase in the samples.

Modulating surface cation vacancies of nickel-cobalt oxides as efficient catalysts for lithium-oxygen batteries

Rechargeable lithium-oxygen batteries(LOBs)have received incremental attention owing to their high energy density and applicability to mobile devices and electric vehicles.However,the lack of robust,low-cost,and environmentally benign bifunctional catalysts is a major impediment to the commercial application.The introduction of vacancies is one of the effective strategies to enhance the performance of cathode catalysts for lithium-oxygen batteries,but the preparation is complicated.In this work,needle-like microsphere cathode catalysts of nickel-cobalt oxide containing cationic vacancies are constructed by controlling the annealing temperature.It is demonstrated that the presence of cationic vacancies can modulate the electronic structure of the catalyst,reduce the energy barrier for the oxygen electrode re-action,meanwhile enhance the bifunctional catalytic activity.Impressively,the nickel-cobalt oxide-based LOB with cationic vacancies exhibits large specific capacity(12,205 mAh g^(-1)at 200 mA g^(-1))and good durability.This work provides worthwhile insight into the formation and catalytic enhancement mech-anism of transition metal oxide catalysts with cationic vacancies,and to some extent,the creation of efficient and low-cost oxygen electrocatalysts for LOBs.

Dual-metal precursors for the universal growth of non-layered 2D transition metal chalcogenides with ordered cation vacancies

Two-dimensional(2D)transition metal chalcogenides(TMCs)are promising for nanoelectronics and energy applications.Among them,the emerging non-layered TMCs are unique due to their unsaturated dangling bonds on the surface and strong intralayer and interlayer bonding.However,the synthesis of non-layered 2D TMCs is challenging and this has made it difficult to study their structures and properties at thin thickness limit.Here,we develop a universal dual-metal precursors method to grow non-layered TMCs in which a mixture of a metal and its chloride serves as the metal source.Taking hexagonal Fe_(1-x)S as an example,the thickness of the Fe_(1-x)S flakes is down to 3 nm with a lateral size of over 100 μm.Importantly,we find ordered cation Fe vacancies in Fe_(1-x)S,which is distinct from layered TMCs like MoS_(2) where anion vacancies are commonly observed.Low-temperature transport measurements and theoretical calculations show that 2D Fe_(1-x)S is a stable semiconductor with a narrow bandgap of60 meV.In addition to Fe_(1-x)S,the method is universal in growing various non-layered 2D TMCs containing ordered cation vacancies,including Fe_(1-x)Se,Co_(1-x)S,Cr_(1-x)S,and V_(1-x)S.This work paves the way to grow and exploit properties of non-layered materials at 2D thickness limit.

Hierarchically nanostructured Ni O-Co3O4 with rich interface defects for the electro-oxidation of 5-hydroxymethylfurfural

Ni-based electrocatalysts with strong redox abilities are active for the electrochemical oxidation of 5-hydroxymethylfurfural(HMF). Interface engineering is an efficient way to modulate the electronic structure, tune the intermediate adsorption, and expose more active sites. Herein, we increased the concentration of interfacial sites with rich defects in a 3D hierarchical nanostructured NiO-Co3O4 electrocatalyst and investigated its catalytic performance for HMF electro-oxidation. The interface effect created abundant cation vacancies, modulated the electronic properties of Co and Ni atoms, and raised the oxidation state of Ni species. The NiO-Co3O4 catalysts show superb HMF oxidation activities with a low onset potential of 1.28 VRHE.Meanwhile, in-situ surface-selective vibrational spectroscopy of sum-frequency generation was performed to study the reaction pathway during the oxidation process on the electrocatalysts. The current study offers an efficient way to create cation vacancies and proves the decisive role of cation vacancies in catalyzing the HMF electro-oxidation.

Intrinsic defects of nonprecious metal electrocatalysts for energy conversion: Synthesis, advanced characterization, and fundamentals

With the depletion of fossil fuels and environmental pollution, energy storage and conversion have become the focus of current research. Water splitting and fuel cell technologies have made outstanding contributions to energy conversion. However, the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) have slow kinetics, which limit the capacity of fuel cells. It is of great significance to develop catalysts for the OER and ORR and continuously improve their catalytic performance. Many studies have shown that intrinsic defects, especially vacancies (anion and cation vacancies), can effectively improve the efficiency of electrochemical energy storage and conversion. The introduction of intrinsic defects can generally expose more active sites, enhance conductivity, adjust the electronic state, and promote ion diffusion, thereby enhancing the catalytic performance. This review comprehensively summarizes the latest developments regarding the effects of intrinsic defects on the performance of non-noble metal electrocatalysts. According to the type of intrinsic defect, this article reviews in detail the regulation mechanism, preparation methods and advanced characterization techniques of intrinsic defects in different materials (oxides, non-oxides, etc.). Then, the current difficulties and future development of intrinsic defect regulation are analyzed and discussed thoroughly. Finally, the prospect of intrinsic defects in the field of electrochemical energy storage is further explored.