As a promising Li-ion battery cathode active material, lithium-rich manganese-based layer-structured oxides suffer from inferior cycle performance and poor rate capability. Herein, Nb-doped Li1.2Mn0.54Ni0.13Co0.13O2 is prepared by a sol-gel method, and the effects of Nb doping on its electrochemical performance are investigated. It is concluded that the Nb-doped Li1.2Mn0.54Ni0.13Co0.13O2, has a good layered structure along c-axis independent on the amount of Nb dopant and little cationic mixing. Nb doping for Li1.2Mn0.54Ni0.13Co0.13O2 has no obvious influence on its morphology. It is found that Nb doping can enhance the electrochemical activity of Li1.2Mn0.54Ni0.13Co0.13O2, such as improved rate performance and cycle performance under high rate conditions. Li1.2Mn0.54Ni0.13Co0.13O2 doped with 0.015 Nb shows the best cycle performance under the high rate with the capacity maintenance of 95.4% after 100 cycles under 5 C rate, which is higher than that of the undoped one by 10.5%.
Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) is a promising alternative to LiCoO2, as it is less expensive, more structurally stable, and has better safety characteristics. However, its capacity of 155 mAh g?1 is quite low, and cycling at potentials above 4.5 V leads to rapid capacity deterioration. Here, we report a successful synthesis of lithium-rich layered oxides (LLOs) with a core of LiMO2 (R-3m, M?=?Ni, Co) and a shell of Li2MnO3 (C2/m) (the molar ratio of Ni, Co to Mn is the same as that in NCM 111). The core–shell structure of these LLOs was confirmed by XRD, TEM, and XPS. The Rietveld refinement data showed that these LLOs possess less Li+/Ni2+ cation disorder and stronger M*–O (M*?=?Mn, Co, Ni) bonds than NCM 111. The core–shell material Li1.15Na0.5(Ni1/3Co1/3)core(Mn1/3)shellO2 can be cycled to a high upper cutoff potential of 4.7 V, delivers a high discharge capacity of 218 mAh g?1 at 20 mA g?1, and retains 90 % of its discharge capacity at 100 mA g?1 after 90 cycles; thus, the use of this material in lithium ion batteries could substantially increase their energy density.
Graphical Abstract Average voltage vs. number of cycles for the core–shell and pristine materials at 20 mA g?1 for 10 cycles followed by 90 cycles at 100 mA g?1
A porous, hollow, microspherical composite of Li2MnO3 and LiMn1/3Co1/3Ni1/3O2 (composition: Li1.2Mn0.53Ni0.13Co0.13O2) was prepared using hollow MnO2 as the sacrificial template. The resulting composite was found to be mesoporous; its pores were about 20 nm in diameter. It also delivered a reversible discharge capacity value of 220 mAh g?1 at a specific current of 25 mA g?1 with excellent cycling stability and a high rate capability. A discharge capacity of 100 mAh g?1 was obtained for this composite at a specific current of 1000 mA g?1. The high rate capability of this hollow microspherical composite can be attributed to its porous nature.
The three-dimensional porous Li3V2(PO4)3/nitrogen-doped reduced graphene oxide (LVP/N-RGO) composite was prepared by a facile one-pot hydrothermal method and evaluated as cathode material for lithium-ion batteries. It is clearly seen that the novel porous structure of the as-prepared LVP/N-RGO significantly facilitates electron transfer and lithium-ion diffusion, as well as markedly restrains the agglomeration of Li3V2(PO4)3 (LVP) nanoparticles. The introduction of N atom also has positive influence on the conductivity of RGO, which improves the kinetics of electrochemical reaction during the charge and discharge cycles. It can be found that the resultant LVP/N-RGO composite exhibits superior rate properties (92 mA h g?1 at 30 C) and outstanding cycle performance (122 mA h g?1 after 300 cycles at 5 C), indicating that nitrogen-doped RGO could be used to improve the electrochemical properties of LVP cathodes for high-power lithium-ion battery application.
Graphical abstract The three-dimensional porous Li3V2(PO4)3/nitrogen-doped reduced graphene oxide composite with significantly accelerating electron transfer and lithium-ion diffusion exhibits superior rate property and outstanding cycle performance.
The structural and electrochemical effects of electrospun V2O5 with selected redox-inactive dopants (namely Na+, Ba2+ and Al3+) have been studied. The electrospun materials have been characterised via a range of analytical methods including X-ray diffraction, X-ray photoelectron spectroscopy, Brunauer-Emmett-Teller surface area measurements and scanning and transmission electron microscopy. The incorporation of dopants in V2O5 was further studied with computational modelling. Structural analysis suggested that the dopants had been incorporated into the V2O5 structure with changes in crystal orientation and particle size, and variations in the V4+ concentration. Electrochemical investigations using potentiodynamic, galvanostatic and impedance spectroscopy analysis showed that electrochemical performance might be dependent on V4+ concentration, which influenced electronic conductivity. Na+- or Ba2+-doped V2O5 offered improved conductivities and lithium ion diffusion properties, whilst Al3+ doping was shown to be detrimental to these properties. The energetics of dopant incorporation, calculated using atomistic simulations, indicated that Na+ and Ba2+ occupy interstitial positions in the interlayer space, whilst Al3+ is incorporated in V sites and replaces a vanadyl-like (VO)3+ group. Overall, the mode of incorporation of the dopants affects the concentration of oxygen vacancies and V4+ ions in the compounds, and in turn their electrochemical performance.
In this study, we analyze the effect of Tb3+ concentration on the structural and optical properties of CaF2 terbium-doped thin films deposited on soda-lime glass substrates with an indium tin oxide (ITO)-sputtered coating by means of electrochemical processes. Compositional results showed that thin films have excess of F, which is believed to be the source for defect formation. XRD results showed not only shifting and widening of the CaF2 peaks as a function of [Tb3+] increase in the electrolitic solution but also an additional peak when high [Tb3+] are used, promoting thus the formation of secondary phases such as NaTbF4. According to photoluminescence (PL) results, when using UV excitation (λ?=?325 nm), CaF2:Tb3+ thin films presented green emission (5D4?→?7FJ, where J?=?6, 5, 4, 3, 2, 1, 0). Besides, PL studies not only allowed us to establish the quenching for Tb3+ concentration in the CaF2 matrix, but they also showed that there are no changes in intensity or peak position attributed to the presence of cubic NaTbF4 because its emission coincides with that of CaF2 terbium-doped thin films.
Graphical abstract Increase of [Tb3+] in the CaF2 solution and the presence of Na+ promotes a competition effect between CaF2:Tb3+ and NaTbF4 phases under equal deposition conditions
Within a temperature range of 120–330 K, 7Li NMR spectra in Li0.6CoO2 are obtained. It is shown that as the temperature increases, both smooth and stepwise variation of 7Li NMR contact shifts occurs. The observed effects are explained by the occupation of the excited levels of cobalt ions. The stepwise change of the resonance line width depending on the temperature is revealed. It is driven by the features of the diffusive motion of lithium ions. The calculation of the 1H NMR line shape provides the determination of the ratio of one-, two-, and three-spin proton clusters in Li0.6CoO2·xH2O. 相似文献
In this work, Bi3.64Mo0.36O6.55 nanoparticles (NPs) were successfully prepared by a facile hydrothermal method and utilized in pseudocapacitor for the first time. Within a redox potential range from ?1.0 to 0 V vs. Hg/HgO in a 1 M aqueous KOH solution by cyclic voltammetry (CV), chronopotentiometry (CP) and AC impendence, the specific capacitance could reach 998 F g?1 at 1 A g?1, which is possibly ascribed to the higher Bi content of Bi3.64Mo0.36O6.55 NPs. Furthermore, the Bi3.64Mo0.36O6.55 NP electrode exhibited good cycle stability maintaining over 85 % after 5000 cycles. These results demonstrated Bi3.64Mo0.36O6.55 NPs might be a promising electrode material for pseudocapacitor.
Graphical abstract The fabrication of uniform Bi3.64Mo0.36O6.55 nanoparticles with a diameter of 100 nm were succefully reported by a facial hydrothermal method, which exhibits a extraordinary electronic performance with 998 F g-1 at 1 A g-1 and cycling stability
LiNi1-x-yCoxMnyO2 (NCM) with excessive lithium is known to exhibit high rate capability and charge–discharge cycling durability. However, the practical usage of NCM is difficult, because the positive electrode slurry is unstable and battery cells swell due to the alkaline residual lithium compound generated on the surface of NCM particles. To reduce the residual lithium compound, ammonium metatungstate (AMT) added to NCM is studied, and the effect is investigated by scanning electron microscopy, aberration-corrected scanning transmission electron microscopy, X-ray diffractometry, synchrotron X-ray diffractometry, and several electrochemical measurements. It is found that the AMT modification reduces the amount of alkaline residual lithium compound and improves the rate capability due to the ~1-nm-thick W-rich layer generated on the NCM surface.
A direct adsorption method for the synthesis of Cu2+-doped CdTe quantum dot (QD)-sensitized TiO2 nanotubes (TNTAs) for use as a photoanode is reported in this study. The influences of the molar concentration of Cu2+, the sensitization temperature, the sensitization time, and the loop index on the photovoltaic performance of the CdTe:Cu2+/TNTAswas investigated. Scanning electron microscopy images showed that the CdTe:Cu2+ QDs are well dispersed on the TNTA surface. UV–vis adsorption measurements showed that the visible absorption of the TNTAs was enhanced by the CdTe:Cu2+ QD sensitization. Whereas the power conversion efficiency (PCE) of the bare TNTAs was 0.11%, the maximum PCE of the CdTe:5%Cu2+/TNTAs was 3.70% with a sensitization time of 5.0 h, a sensitization temperature of 60 °C, and a loop index of 2. Therefore, CdTe:5%Cu2+/TNTAs may be employed in quantum-dot-sensitized solar cells.
Graphical abstract The conversion efficiency of the CdTe: 5%Cu2+/TiO2 nanotube arrays can reach a maximum of 3.7%, which is enhanced by 33-fold, on comparison with bare TiO2 nanotube arrays (0.11%).
We obtained Tannin-4-azobenzoic acid (azo dye) by the conventional method of diazotization and coupling of aromatic amines. The properties of the azo dye were characterized via ultraviolet-visible (UV–vis), infrared (IR), and nuclear magnetic resonance (NMR) spectroscopy. Nanocrystalline titanium dioxide (TiO2) thin films were deposited by hydrothermal method onto fluorine-doped tin (IV) oxide (FTO)-coated glass substrate at 353 K for 4 h. The as-deposited and annealed films were characterized for structural, morphological, optical, thickness, and wettability properties. The synthesized metal free azo dye was used to sensitize the prepared TiO2 thin film with thickness of 26 μm. The photoelectrochemical (PEC) performance of TiO2 sensitized with the azo dye was evaluated in polyiodide (0.1 M KI + 0.01 M I2 + 0.1 M KCl) electrolyte at 40 mW cm?2 illumination intensity. The cell yielded a short circuit current of 2.82 mA, open circuit voltage of 314.3 mV, a fill factor of 0.30, and a photovoltaic conversion efficiency value of 0.64%.
LiMn2O4 is one of the most promising cathode materials due to its high abundance and low cost. However, the practical application of LiMn2O4 is greatly limited owing to its low volumetric energy density. Therefore, increasing its energy density is an urgent problem to be resolved. Herein, using the simple and mass production preferred solid-state reaction, surficial Nb-doped LiMn2O4 composed of the truncated octahedral or spherical-like primary particles are successfully synthesized. Auger electron spectroscopy (AES) and X-ray diffraction (XRD) characterizations confirm that most of Nb5+ enrich in the surficial layer of the particles to form a LiMn2-xNbxO4 phase. This kind of doping can increase the specific discharge capacity of LiMn2O4 materials. Contrast with the pristine LiMn2O4, the discharge capacity of LiMn1.99Nb0.01O4-based 18650R-type battery increases from 1497 to 1705 mAh with the volumetric energy density increasing by ~?13.9%, benefiting from the joint increments of the specific discharge capacity from 119.5 to 123.7 mAh g?1 and the compacted density from 2.81 to 3.10 g cm?3. Furthermore, the capacity retention after 500 cycles at 1 C (1500 mA) is also improved by 17.1%.
Compared to other oxide materials, the sol-gel deposition of an optically transparent LiNbO3 waveguiding film of sufficient thickness (approx. 1?μm) is complicated by the presence of a highly hydrolyzing Nb(V) in the starting solution. Thicker films require more concentrated solutions that are not easily achieved for such ions. This problem may be solved using strong chelating agents such as water-soluble polymers. To prepare a stable Er(III)/Yb(III)/Li(I)/Nb(V)/2-methoxyethanol solution with high metal concentration, we tested three such polymers: polyethylene glycol (PEG), polyacrylic acid (PAA) and polyvinyl alcohol (PVA), and compared them with already used polyvinylpyrrolidone (PVP). The solutions were spin-coated on crystalline sapphire substrates under a multi-step heating-deposition regime. Apart from Er3+/Yb3+ photoluminescence properties, we evaluated the influence of the film microstructure (SEM, AFM) on optical transparency and waveguiding ability in the UV/Vis/NIR region (transmission and m-line spectroscopy). Among the newly tested polymers, only PEG was able to prevent Nb(V) hydrolysis up to a maximum metal concentration of 0.6?mol/L. For PEG and PVP, the crystallization temperature of the deposited films (between 700?°C and 1000?°C) was compared. After further optimization of the heating-deposition process, we were able to prepare a transparent Er3+/Yb3+:LiNbO3 film thick enough to guide an optical signal in the NIR region. Thus, the use of PEG results is one of the very few non-hydrolytic sol-gel methods suitable for the preparation of not only luminescent, but also waveguiding Er3+/Yb3+:LiNbO3 structures.
A series of Ni0.37Co0.63S2-reduced graphene oxide nanocomposites with different graphene contents (NCS@rGO-x) has been successfully prepared via a facile one-step hydrothermal method and applied as the catalysts for the oxygen evolution reaction (OER) and degradation of organic pollutants. The XRD and FESEM analyses revealed that the phase structure and morphology of NCS nanoparticles were substantially influenced by the graphene contents. The phase structure of NCS nanoparticles gradually transformed from primary NiCo2S4 to Ni0.37Co0.63S2 and the morphology and size of NCS nanoparticles were found to become more regular and homogeneous with the increase of graphene concentration. On the NCS@rGO-x nanocomposites, the NCS@rGO-2 sample demonstrated the best catalytic activity toward the OER, which delivers a stable current density of 10 mA cm?2 at a small overpotential of ～276 mV (vs. RHE) with a Tafel slope as low as 48 mV dec?1. Furthermore, the NCS@rGO-2 sample showed the remarkable photocatalytic activity for degradation of methylene blue (MB), which may be attributed to the increased reaction sites and high separation efficiency of photogenerated charge carries due to the electronic interaction between NCS nanoparticles and rGO. All these impressive performances indicate that the NCS@rGO-2 nanocomposite is a promising catalyst in energy and environmental fields.
Graphical abstract A series of Ni0.37Co0.63S2-reduced graphene oxide nanocomposites with different graphene contents has been successfully prepared and applied as the catalysts for the oxygen evolution reaction (OER) and degradation of organic pollutants. The NCS@rGO-2 catalyst-modified stainless steel wire mesh (SSWM) electrode delivers a stable current density of 10 mA cm?2 at a small overpotential of ～276 mV (vs. RHE) with a Tafel slope as low as 48 mV dec?1. At the same time, the NCS@rGO-2 catalyst is also first investigated as an efficient photocatalyst for degradation of MB.
In this paper, the LiNi0.5Mn1.5O4 cathode materials of lithium-ion batteries are synthesized by a co-precipitation spray-drying and calcining process. The use of a spray-drying process to form particles, followed by a calcination treatment at the optimized temperature of 750 °C to produce spherical LiNi0.5Mn1.5O4 particles with a cubic crystal structure, a specific surface area of 60.1 m2 g?1, a tap density of 1.15 g mL?1, and a specific capacity of 132.9 mAh g?1 at 0.1 C. The carbon nanofragment (CNF) additives, introduced into the spheres during the co-precipitation spray-drying period, greatly enhance the rate performance and cycling stability of LiNi0.5Mn1.5O4. The sample with 1.0 wt.% CNF calcined at 750 °C exhibits a maximum capacity of 131.7 mAh g?1 at 0.5 C and a capacity retention of 98.9% after 100 cycles. In addition, compared to the LiNi0.5Mn1.5O4 material without CNF, the LiNi0.5Mn1.5O4 with CNF demonstrates a high-rate capacity retention that increases from 69.1% to 95.2% after 100 cycles at 10 C, indicating an excellent rate capability. The usage of CNF and the synthetic method provide a promising choice for the synthesis of a stabilized LiNi0.5Mn1.5O4 cathode material.
Graphical Abstract Micro/nanostructured LiNi0.5Mn0.5O4 cathode materials with enhanced electrochemical performances for high voltage lithium-ion batteries are synthesized by a co-precipitation spray-drying and calcining routine and using carbon nanofragments (CNFs) as additive.
Generally adopted strategies to improve capacitance of the electrode materials are tuning various properties of the electrode material or increasing the cell voltage. While tuning the properties of the electrode material is tedious, increasing the cell voltage is restricted by the stability of the electrolyte. Herein, we report a facile approach to improve the capacitance of MnCO3 by the influence of SiOx nanofluid in the electrolyte. The capacitance properties of MnCO3 are studied in 0.1 M Mg(ClO4)2 electrolyte in the presence and in the absence of SiOx nanofluid. The presence of small amount of SiOx nanofluid in the electrolyte provides higher diffusivity and more conductive percolation paths for ions and thus decreases internal resistance and increases ionic conductivity of the electrolyte. As a result, 60% enhancement in the capacitance is witnessed for MnCO3. Further, nanofluid containing electrolyte is found to be stable over a month.
Sulfonated polyvinylchloride (SPVC) cation-exchange membranes were coated using chitosan solutions comprising different amounts of Fe3O4 nanoparticles. Influence of chitosan immobilization as well as nanofiller concentration on the electrochemical performance of the membranes was investigated. Electrochemical properties of the membranes including permselectivity, ionic permeability, and areal resistance were studied using an equipped electrodialysis setup and NaCl solution as model electrolyte. Scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) were employed for membrane characterization. Electrochemical performance of the SPVC membranes was improved by coating chitosan polymer. In addition, ionic permeability and permselectivity of the membranes were initially raised by increasing nanoparticles concentration from nil to 2 wt% and then decreased by further insertion of the nanofiller. The areal resistance of the plain SPVC membrane was decreased from 9.4 to 2.9 (ohm) by coating of chitosan solution including optimum value of nano-Fe3O4 due to electrical potential field enhancement across the membrane.
Herein, porous Li3V2(PO4)3/C microspheres made of nanoparticles are obtained by a combination of sol spray-drying and subsequent-sintering process. Beta-cyclodextrin serves as a special chelating agent and carbon source to obtain carbon-coated Li3V2(PO4)3 grains with the size of ca. 30–50?nm. The unique porous structure and continuous carbon skeleton facilitate the fast transport of lithium ion and electron. The Li3V2(PO4)3/C microspheres offer an outstanding electrochemical performance, which present a discharge capacity of 122?mAh?g?1 at 2?C with capacity retention of 96% at the end of 1000 cycles and a high-rate capacity of 113?mAh?g?1 at 20?C in the voltage window of 3.0–4.3?V. Moreover, the Li3V2(PO4)3/C microspheres also give considerable cycling stability and high-rate reversible capacity at a higher end-of-charge voltage of 4.8?V.
In the present work, Li+ conductor is synthesized via small doping of LiBH4 into “Li-free” compound (or solid solvent), NaI. The formation of solid solution between NaI and LiBH4 is confirmed by XRD measurement, and the solubility limit of LiBH4 exists between 6 to 13 mol%. The value of σ for 15NaI·LiBH4 (6 mol% LiBH4) showed 1.7 × 10?6 S/cm at room temperature, which is comparable to that for LiI. From the plot of log σT vs. 1000/T, an activation energy for Li+ conduction in NaI is estimated to be 0.68 and 0.32 eV for heating and cooling cycle, respectively. The results of AC impedance measurement and DC polarization test indicate that Li+ plays a major role in ionic conduction in NaI regardless of the slight molar fraction of Li+. The present results suggest that the expansion in the material choice for solid solvent and other alkali halides can also work as a base material for Li+ ion conductors. 相似文献
