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1.
Li4Ti5O12/Li2TiO3 composite nanofibers with the mean diameter of ca. 60 nm have been synthesized via facile electrospinning. When the molar ratio of Li to Ti is 4.8:5, the Li4Ti5O12/Li2TiO3 composite nanofibers exhibit initial discharge capacity of 216.07 mAh g?1 at 0.1 C, rate capability of 151 mAh g?1 after being cycled at 20 C, and cycling stability of 122.93 mAh g?1 after 1000 cycles at 20 C. Compared with pure Li4Ti5O12 nanofibers and Li2TiO3 nanofibers, Li4Ti5O12/Li2TiO3 composite nanofibers show better performance when used as anode materials for lithium ion batteries. The enhanced electrochemical performances are explained by the incorporation of appropriate Li2TiO3 which could strengthen the structure stability of the hosted materials and has fast Li+-conductor characteristics, and the nanostructure of nanofibers which could offer high specific area between the active materials and electrolyte and shorten diffusion paths for ionic transport and electronic conduction. Our new findings provide an effective synthetic way to produce high-performance Li4Ti5O12 anodes for lithium rechargeable batteries.  相似文献   

2.
Natural graphite treated by mechanical activation can be directly applied to the preparation of Li3V2(PO4)3. The carbon-coated Li3V2(PO4)3 with monoclinic structure was successfully synthesized by using natural graphite as carbon source and reducing agent. The amount of activated graphite is optimized by X-ray diffraction, scanning electron microscope, transmission electron microscope, Raman spectrum, galvanostatic charge/discharge measurements, cyclic voltammetry, and electrochemical impedance spectroscopy tests. Our results show that Li3V2(PO4)3 (LVP)-10G exhibits the highest initial discharge capacity of 189 mAh g?1 at 0.1 C and 162.9 mAh g?1 at 1 C in the voltage range of 3.0–4.8 V. Therefore, natural graphite is a promising carbon source for LVP cathode material in lithium ion batteries.  相似文献   

3.
The Li(Ni0.33Co0.33Mn0.33)O2 (LNCMO) cathode material is prepared by poly(vinyl pyrrolidone) (PVP)-assisted sol-gel/hydrothermal and poly(ethylene glycol)-block-poly(propylene glycol)-block-poly (ethylene glycol) (Pluronic-P123)-assisted hydrothermal methods. The compound prepared by PVP-assisted hydrothermal method shows a comparatively higher electrical conductivity of ~2?×?10?5 S cm?1 and exhibits a discharge capacity of 152 mAh g?1 in the voltage range of 2.5 to 4.4 V, for a C-rate of 0.2 C, whereas the compounds prepared by P123-assisted hydrothermal method and PVP-assisted sol-gel method show a total electrical conductivity in the order of 10?6 S cm?1 and result in poor electrochemical performance. The structural and electrical properties of LNCMO (active material) and its electrochemical performance are correlated. The difference in percentage of ionic and electronic conductivity contribution to the total electrical conductivity is compared by transference number studies. The cation disorder is found to be the limiting factor for the lithium ion diffusion as determined from ionic conductivity values.  相似文献   

4.
The novel Li3V2(PO4)3 glass-ceramic nanocomposites were synthesized and investigated as electrodes for energy storage devices. They were fabricated by heat treatment (HT) of 37.5Li2O–25V2O5–37.5P2O5?mol% glass at 450 °C for different times in the air. XRD, SEM, and electrochemical methods were used to study the effect of HT time on the nanostructure and electrochemical performance for Li3V2(PO4)3 glass-ceramic nanocomposites electrodes. XRD patterns showed forming Li3V2(PO4)3 NASICON type with monoclinic structure. The crystalline sizes were found to be in the range of 32–56 nm. SEM morphologies exhibited non-uniform grains and changed with variation of HT time. The electrochemical performance of Li3V2(PO4)3 glass-ceramic nanocomposites was investigated by using galvanostatic charge/discharge methods, cyclic voltammetry, and electrochemical impedance spectroscopy in 1 M H2SO4 aqueous electrolyte. The glass-ceramic nanocomposites annealed for 4 h, which had a lower crystalline size, exhibited the best electrochemical performance with a specific capacity of 116.4 F g?1 at 0.5 A g?1. Small crystalline size supported the lithium ion mobility in the electrode by decreasing the ion diffusion pathway. Therefore, the Li3V2(PO4)3 glass-ceramic nanocomposites can be promising candidates for large-scale industrial applications in high-performance energy storage devices.  相似文献   

5.
Sn-doped Li-rich layered oxides of Li1.2Mn0.54-x Ni0.13Co0.13Sn x O2 have been synthesized via a sol-gel method, and their microstructure and electrochemical performance have been studied. The addition of Sn4+ ions has no distinct influence on the crystal structure of the materials. After doped with an appropriate amount of Sn4+, the electrochemical performance of Li1.2Mn0.54-x Ni0.13Co0.13Sn x O2 cathode materials is significantly enhanced. The optimal electrochemical performance is obtained at x = 0.01. The Li1.2Mn0.53Ni0.13Co0.13Sn0.01O2 electrode delivers a high initial discharge capacity of 268.9 mAh g?1 with an initial coulombic efficiency of 76.5% and a reversible capacity of 199.8 mAh g?1 at 0.1 C with capacity retention of 75.2% after 100 cycles. In addition, the Li1.2Mn0.53Ni0.13Co0.13Sn0.01O2 electrode exhibits the superior rate capability with discharge capacities of 239.8, 198.6, 164.4, 133.4, and 88.8 mAh g?1 at 0.2, 0.5, 1, 2, and 5 C, respectively, which are much higher than those of Li1.2Mn0.54Ni0.13Co0.13O2 (196.2, 153.5, 117.5, 92.7, and 43.8 mAh g?1 at 0.2, 0.5, 1, 2, and 5 C, respectively). The substitution of Sn4+ for Mn4+ enlarges the Li+ diffusion channels due to its larger ionic radius compared to Mn4+ and enhances the structural stability of Li-rich oxides, leading to the improved electrochemical performance in the Sn-doped Li1.2Mn0.54Ni0.13Co0.13O2 cathode materials.  相似文献   

6.
LiNi0.80Co0.15Al0.05O2 (NCA) is explored to be applied in a hybrid Li+/Na+ battery for the first time. The cell is constructed with NCA as the positive electrode, sodium metal as the negative electrode, and 1 M NaClO4 solution as the electrolyte. It is found that during electrochemical cycling both Na+ and Li+ ions are reversibly intercalated into/de-intercalated from NCA crystal lattice. The detailed electrochemical process is systematically investigated by inductively coupled plasma-optical emission spectrometry, ex situ X-ray diffraction, scanning electron microscopy, cyclic voltammetry, galvanostatic cycling, and electrochemical impedance spectroscopy. The NCA cathode can deliver initially a high capacity up to 174 mAh g?1 and 95% coulombic efficiency under 0.1 C (1 C?=?120 mA g?1) current rate between 1.5–4.1 V. It also shows excellent rate capability that reaches 92 mAh g?1 at 10 C. Furthermore, this hybrid battery displays superior long-term cycle life with a capacity retention of 81% after 300 cycles in the voltage range from 2.0 to 4.0 V, offering a promising application in energy storage.  相似文献   

7.
Vanadium pentoxide (V2O5) nanofibers (NFs) with a thin carbon layer of 3–5 nm, which wrapped on V2O5 nanoparticles, and integrated multiwalled carbon nanotubes (MWCNTs) have been fabricated via simple electrospinning followed by carbonization process and post-sintering treatment. The obtained composite displays a NF structure with V2O5 nanoparticles connected to each other, and good electrochemical performance: delivering initial capacity of 320 mAh g?1 (between 2.0 and 4.0 V vs. Li/Li+), good cycling stability (223 mAh g?1 after 50 cycles), and good rate performance (~?150 mAh g?1 at 2 A g?1). This can attribute to the carbon wrapped on the V2O5 nanoparticles which can not only enhance the electric conductivity to decrease the impendence of the cathode materials but also maintain the structural stability to protect the nanostructure from the corruption of electrolyte and the strain stress due to the Li-ion intercalation/deintercalation during the charge/discharge process. And, the added MWCNTs play the role of framework of the unique V2O5 coated by carbon layer and composited with MWCNT NFs (V2O5/C@MWCNT NFs) to ensure the material is more stable.  相似文献   

8.
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
  相似文献   

9.
The effect of chemical composition to ionic conductivity and activation energy of vitreous solid electrolytes (SE) based on Li2O-P2O5-LiF system (Li2O ≥ 45.4 mol %) was detected. The temperature effect to conductivity and activation energy was studied. An original technology was designed to prepare vitreous SEs in Li2O-P2O5-LiF system containing up to 20 mol % LiF and characterized with ionic conductivity up to 4.4 × 10?7 S cm?1 (24°C) and activation energy about 0.567 eV. The synthesized materials are characterized with high X-ray amorphism and technological performance.  相似文献   

10.
Li2ZnTi3O8/C nanocomposite has been synthesized using phenolic resin as carbon source in this work. The structure, morphology, and electrochemical properties of the as-prepared Li2ZnTi3O8 samples were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscope (TEM), Raman spectroscopy (RS), galvanostatic charge–discharge, and AC impedance spectroscopy. SEM images show that Li2ZnTi3O8/C was agglomerated with a primary particle size of ca. 40 nm. TEM images reveal that a homogeneous carbon layer (ca. 5 nm) formed on the surface of Li2ZnTi3O8 particles which is favorable to improve the electronic conductivity and inhibit the growth of Li2ZnTi3O8 during annealing process. The as-prepared Li2ZnTi3O8/C composite with 6.0 wt.% carbon exhibited a high initial discharge capacity of 425 and 159 mAh g?1 at 0.05 and 5 A g?1, respectively. At a high current density of 1 A g?1, 95.5 % of its initial value is obtained after 100 cycles.  相似文献   

11.
Cyclability of the Li|Li7La3Zr2O12 interface was tested by voltammetry under externally applied potential difference. It was found that the solid electrolyte synthesized in the study contains a minor amount of an impurity in the form of lithium carbonate. This impurity forms, when brought in contact with metallic lithium, carbon that pierces the whole volume of the ceramic separator and produces a channel for a flow of electrons through the material, which leads to a poor cyclability of the solid electrolyte. A possible way to solve the given problem is via a purposeful replacement of the carbonate in the intergrain space of Li7La3Zr2O12 with another crystalline or glassy plasticizer that possesses an acceptable unipolar lithium conductivity (no less than 10–6 S cm–1) and forms, when brought in contact with metallic lithium, no electrically conducting compound or a compound capable of reversibly intercalating/deintercalating lithium.  相似文献   

12.
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.
  相似文献   

13.
Herein, we demonstrate a safe, inexpensive, and stable cycle-life aqueous rechargeable Li-ion battery system using tavorite LiTiPO4F as anode and Li[Li0.2Co0.3Mn0.5]O2 as cathode in aqueous electrolyte using 2 M Li2SO4. These materials have been synthesized via a simple and an efficient method called RAPET (reaction under autogenic pressure at elevated temperature) method, and for the first time, we have evaluated the electrochemical properties of LiTiPO4F in aqueous electrolyte. Structural and morphological features have been characterized using X-ray diffraction and scanning electron microscopy techniques, and the electrochemical studies have been investigated by using cyclic voltammetry, galvanostatic charge/discharge studies, electrochemical impedance spectroscopic technique, potentiostatic intermittent titration techniques, and galvanostatic intermittent titration techniques. In galvanostatic charge/discharge studies, the capacity, cycle life, and columbic efficiency of LiTiPO4F have been tested in combination with Li [Li0.2Co0.3Mn0.5]O2 cathode. In particular, LiTiPO4F shows capacity of 82 mA h g?1, the capacity retention was maintained 90 % even after the 45th cycle.  相似文献   

14.
Here a novel material for methane adsorption was synthesized and studied, which is a graphene-like two-dimensional (2D) carbide (Ti2C, a member of MXenes), formed by exfoliating Ti2AlC powders in a solution of lithium fluoride (LiF) and hydrochloric acid (HCl) at 40 °C for 48 h. Based on first-principles calculation, theoretically perfect Ti2C with O termination has a specific surface area (SSA) of 671 m2 g?1 and methane storage capacity is 22.9 wt%. Experimentally, 2.85 % exfoliated Ti2C with mesopores shown methane capacity of 11.58 cm3 (STP: 0 °C, 1 bar) g?1 (0.82 wt%) under 5 MPa and the SSA was 19.1 m2 g?1. For Ti2C sample intercalated with NH3·H2O, the adsorbed amount was increased to 16.81 cm3 (STP) g?1 at same temperature. At the temperature of 323 K, the adsorbed amount of as-prepared Ti2C was increased to 52.76 cm3 (STP) g?1. For fully exfoliated Ti2C, the methane capacity was supposed to be 28.8 wt% or 1148 V (STP)v?1. Ti2C theoretically has much larger volume methane capacity than current methane storage materials, though its SSA is not very high.  相似文献   

15.
Properties of CF x /Li and CF x /Na cells were examined while using galvanostatic charging/discharging, electrochemical impedance spectroscopy and scanning electron microscopy (SEM). The capacity during the first cycle was as high as ca. 1000 mAh g?1. Such an electrode is suitable for primary CF x /Li and CF x /Na batteries. SEM images of CF x cathode showed that during discharging it was transformed into amorphous carbon and LiF or NaF crystals (of diameter of ca. 5–20 μm). These systems (C?+?LiF or C?+?NaF) cannot be reversibly converted back into CF x /Li or CF x /Na, respectively. Exchange current densities are between 10?7 Acm?2 and 10?9 Acm?2 when working with LiPF6 and NaPF6 electrolytes (1.12?×?10?7 Acm?2 and 6.82?×?10?9 Acm?2, respectively). Those values are low and indicate that the charge transfer process may be the rate-determining step. Activation energies for the charge transfer process were 57 and 72 kJ mol?1 for CF x /LiPF6 and CF x /NaPF6 systems, respectively. Higher activation energy barrier for the CF/Na+?+?e??→?C?+?NaF reaction results in lower observed exchange current density in comparison to the system with lithium ions.  相似文献   

16.
Within the density functional theory the electronic structure of triple molybdates Li2M3Al(MoO4)4, where M = Cs, Rb, is studied for the first time. It is found that all molybdates studied belong to wide band insulators with a band gap of ~4 eV. Quadrupole frequencies and asymmetry parameters of the electric field gradient near magnetic 7Li, 27Al, 87Rb, and 133Cs nuclei are calculated and experimental NMR spectra are interpreted.  相似文献   

17.
Homogeneous p-type cobalt (II) oxide (CoO) nanoparticles were successfully deposited on n-type three-dimensional branched TiO2 nanorod arrays (3D-TiO2) through photochemical deposition and thermal decomposition to form a novel CoO/3D-TiO2 p-n heterojunction nanocomposite. Due to the narrow band gap of CoO nanoparticles (~2.4 eV), the as-synthesized CoO/3D-TiO2 exhibited an excellent visible light absorption. The amounts of deposited CoO nanoparticles obviously influence the hydrogen production rate in the photoelectrochemical (PEC) water splitting. The as-synthesized CoO/3D-TiO2-5 obtains the highest PEC hydrogen production rate of 0.54 mL h?1 cm?2 after five-time CoO deposition cycles (at a potential of 0.0 V vs Ag/AgCl). The photocurrent density of CoO/3D-TiO2-5 is 1.68 mA cm?1, which is ca. 2.5 times greater than that of pure 3D-TiO2. The results showed that the formation of internal electrical-field between the CoO/3D-TiO2 heterojunction, which has a direction from n-type TiO2 to p-type CoO, facilitated the charge separation and transfer and resulted in a high efficiency and stable PEC activity.  相似文献   

18.
Transport properties of ionic salt CsH5(PO4)2 are studied by the impedance method. The salt’s bulk conductivity ranges from 10?8 to 10?4 S cm?1 in the temperature interval 90 to 145°C. The apparent activation energy is high (1.6–2.0 eV). The conductivity is slightly anisotropic: it is maximum in the [001] direction and minimum in the [100] direction (~5.6 and 1 times × 10?6 S cm?1, respectively, at 130°C). The conductivity of polycrystalline samples is higher by 1–2 orders of magnitude, and the activation energy drops to 1.05 eV due to the formation of a pseudoliquid layer with a high proton mobility at the intercrystallite boundary. The salt’s thermodynamic properties are examined by differential scanning calorimetry and thermogravimetry. No phase transitions are discovered in the salt up to the melting point (151.6°C), with the melting enthalpy equal to ~34 kJ mol?1. The crystallization occurs at lower temperatures (107°C) and the crystallization enthalpy (?18 kJ mol?1) is lower than the melting enthalpy. The melting is accompanied by slow decomposition of the salt. Factors affecting the proton transport in the salt are analyzed.  相似文献   

19.
Spherical Li[Ni1/3Co1/3Mn1/3]O2 cathode materials with different microstructure have been prepared by a continuous carbonate co-precipitation method using LiOH⋅H2O, Li2CO3, CH3COOLi⋅2H2O and LiNO3 as lithium source. The effects of Li source on the physical and electrochemical properties of Li[Ni1/3Co1/3Mn1/3]O2 are investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical measurements. The results show that the morphology, tap density and high rate cycling performance of Li[Ni1/3Co1/3Mn1/3]O2 spherical particles are strongly affected by Li source. Among the four Li sources used in this study, LiOH⋅H2O is beneficial to enhance the tap density of Li[Ni1/3Co1/3Mn1/3]O2, and the tap density of as-prepared sample reaches 2.32 g cm−3. Meanwhile, Li2CO3 is preferable when preparing the Li[Ni1/3Co1/3Mn1/3]O2 with high rate cycling performance, upon extended cycling at 1 and 5C rates, 97.5% and 92% of the initial discharge capacity can be maintained after 100 cycles.  相似文献   

20.
Tavorite-structured lithium transition metal fluorophosphates have been considered as a good alternative to olivine-type cathode for lithium-ion batteries due to its exceptional ionic conductivity and excellent thermal stability. In this work, nearly monodisperse LiFePO4F nanospheres with high purity are successfully synthesized by a solid-state route associated with chemically induced precipitation method for the first time. The synthesized LiFePO4F presents nearly monodisperse nanospheres particles with average particle size of ~?500 nm. Cyclic voltammetry data exhibit a clear indication of the Fe3+/Fe2+ redox couple that involves a two-phase transition. Its electrochemical behaviors are examined by galvanostatic charge-discharge. The results show that the initial discharge capacity is 110.2 mAh g?1 at 0.5 C, after 200 cycles is still retained 104.0 mAh g?1 with the retention rate of 94.4%. The excellent cycle performance is mainly attributed to the uniform nanospheres-like morphology which is not only beneficial to shorten the transport distance of ions and electrons, but also improve the interface area between electrode and electrolyte, and thus improve the kinetics of Li ions.  相似文献   

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