Enhanced electrochemical performance of La- and Zn-co-doped LiMn2O4 spinel as the cathode material for lithium-ion batteries

We report on the nanoparticle uptake into MCF10A neoT and PC-3 cells using flow cytometry, confocal microscopy, SQUID magnetometry, and transmission electron microscopy. The aim was to evaluate the influence of the nanoparticles?? surface charge on the uptake efficiency. The surface of the superparamagnetic, silica-coated, maghemite nanoparticles was modified using amino functionalization for the positive surface charge (CNPs), and carboxyl functionalization for the negative surface charge (ANPs). The CNPs and ANPs exhibited no significant cytotoxicity in concentrations up to 500???g/cm³ in 24?h. The CNPs, bound to a plasma membrane, were intensely phagocytosed, while the ANPs entered cells through fluid-phase endocytosis in a lower internalization degree. The ANPs and CNPs were shown to be co-localized with a specific lysosomal marker, thus confirming their presence in lysosomes. We showed that tailoring the surface charge of the nanoparticles has a great impact on their internalization.     

Structural and electrochemical investigation of Zn-doped LiCoO2 powders

A commercial cathode material (LiCoO₂) was modified by doping with Zn to improve its performance in lithium battery. The structure and morphology of the doped cathode material were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM). The synthesized samples were characterized using X-ray photoelectron spectra (XPS), used to investigate the elementary states on the system. The electrical conductivity variations of doped powders were measured in the temperature range between 30 and 150?°C. The 3?mol% Zn-doped LiCoO₂ sample shows the highest reversibility capacity (178?mA?h g^?1) after 30 cycles in the voltage window 3.0?C4.5?V.     

RF-sputtered LiCoO2 thick films: microstructure and electrochemical performance as cathodes in aqueous and nonaqueous microbatteries

Films of LiCoO₂ are prepared on metallized silicon substrates using RF-magnetron sputtering technique. The microstructural properties of the films are investigated by X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, and atomic force microscopy. The films deposited at a substrate temperature of 250 °C with subsequent annealing at 650 °C exhibited hexagonal layered structure with R $ \overline 3 $ m symmetry. The kinetics of lithium ions in LiCoO₂ film cathode host matrix and its cycleability are studied in aqueous Pt//LiCoO₂ and nonaqueous Li//LiCoO₂ cell. Both the electrochemical cells at same current density of 50 μA cm^?2 delivered the same initial discharge capacity of about 60 μA h?cm^?2 μm^?1 with a chemical diffusion coefficient of ca. 10^?11 cm² s^?1 for Li⁺ ions. The capacity fade rates for the Pt//LiCoO₂ and Li//LiCoO₂ cells, in average are 3.0 and 0.15 % per cycle, respectively, for the first 20 cycles. The Pt//LiCoO₂ cell is found to be advantageous for small number of cycles and is cost effective than the Li//LiCoO₂ cell.     

Silver-coated LiVPO4F composite with improved electrochemical performance as cathode material for lithium-ion batteries

Nano-structured LiVPO₄F/Ag composite cathode material has been successfully synthesized via a sol–gel route. The structural and physical properties, as well as the electrochemical performance of the material are compared with those of the pristine LiVPO₄F. X-ray diffraction (XRD) and scanning electron microscopy (SEM) reveal that Ag particles are uniformly dispersed on the surface of LiVPO₄F without destroying the crystal structure of the bulk material. An analysis of the electrochemical measurements show that the Ag-modified LiVPO₄F material exhibits high discharge capacity, good cycle performance (108.5 mAh g⁻¹ after 50th cycles at 0.1 C, 93% of initial discharge capacity) and excellent rate behavior (81.8 mAh g⁻¹ for initial discharge capacity at 5 C). The electrochemical impedance spectroscopy (EIS) results reveal that the adding of Ag decreases the charge-transfer resistance (R_ct) of LiVPO₄F cathode. This study demonstrates that Ag-coating is a promising way to improve the electrochemical performance of the pristine LiVPO₄F for lithium-ion batteries cathode material.     

Solvothermal synthesis and electrochemical performance of Ag-doped V6O13 as cathode material for lithium-ion battery

For the first time, belt-like V₆O₁₃ precursor was synthesized via a simple solvothermal method. Rod-like Ag-doped V₆O₁₃ was successfully synthesized by this method followed by heating at 350 °C. Both crystal domain size, electronic conductivity, and the lithium diffusion coefficient of the Ag-doped V₆O₁₃ samples are influenced by the added amount of AgNO₃. When the amount of AgNO₃ is 0.008 g, the product is rod-like particles, which are 0.1–0.3 μm wide and 1–2 μm long, and exhibits the best electrochemical performance. The enhanced electrochemical performance originates from its higher total conductivity, higher lithium diffusion coefficient, and better structural reversibility.     

Enhanced electrochemical performance of unique morphological LiMnPO4/C cathode material prepared by solvothermal method

The LiMnPO₄/C composite material with ordered olivine structure was synthesized in 1:1(v/v) enthanol–water mixed solvent in the presence of cetyltrimethylammonium bromide (CTAB) at 240 ^°C. Rod-like particle morphology of the resulting LiMnPO₄/C powder with a uniform particle dimension of 150 × 600 nm was observed by using scanning electron microscope and the amount of carbon coated on the particle surface was evaluated as 2.2wt% by thermogravimetric analysis, which is reported for the first time to date for LiMnPO₄/C composite. The measurement of the electrochemical performance of the material used in rechargeable lithium ion battery shows that the LiMnPO₄/C sample delivers an initial discharge capacity of 126.5 mA h g^?1 at a constant current of 0.01 C, which is 74% of the theoretical value of 170 mA h g^?1. The electrode shows good rated discharge capability and high electrochemical reversibility when compared with the reported results, which is verified further by the evaluation of the Li ion diffusion coefficient of 5.056×10^?14 cm²/s in LiMnPO₄/C.     

An investigation of silicon-doped LiCoO2 as cathode in lithium-ion secondary batteries

Powders of layered–structured LiCo_(1−x)Si_xO₂ (x = 0, 0.01, 0.05, 0.10, 0.35) were synthesized by a co-precipitation method followed by a 950 °C sintering. Their structures were analyzed by the X-ray diffraction (XRD) and scanning electron microscopy (SEM). Iodine titration method was also employed to measure the average valence of cobalt ions. With these powders as the active materials of positive electrodes versus lithium, the electrochemical behaviors of the cells were investigated using charge–discharge cycling, AC impedance spectroscopy and DC resistance measurement. It is found that the Si-doping results in the decrease of cobalt valence and the crystallite size. When the Si-content is less than 10%, pure LiCo_1−xSi_xO₂ phases are obtained. A second phase Li₂CoSiO₄ is also obtained when the Si-content is 35%. Among the five compositions, the non-doped LiCoO₂ exhibits a high initial specific capacity (about 150 and 185 mA h/g at a current density of 0.4 mA/cm² from 2.8 to 4.2 and from 2.8 to 4.5 V, respectively), but degrades in the following cycles; while the Si-doped LiCo_1−xSi_xO₂ electrodes especially LiCo_0.99Si_0.01O₂ show the best performance of long-life cycling. And all of the doped powders have better stability of the 3.6 V-plateau efficiency due to the improved stability effect on the cell impedance.     

Silyl-group functionalized organic additive for high voltage Ni-rich cathode material

To allow stable cycling of layered nickel-rich cathode material at high voltage, silyl-functionalized dimethoxydimethylsilane is proposed as a multi-functional additive. In contrast to typical functional additive, dimethoxydimethylsilane does not make artificial cathode-electrolyte interfaces by electrochemical oxidation because it is quite stable under anodic polarization. We find that dimethoxydimethylsilane mainly focuses on scavenging nucleophilic fluoride species that can be produced by electrolyte decomposition during cycling, leading to improving interfacial stability of both nickel-rich cathode and graphite anode. As a result, the cell cycled with dimethoxydimethylsilane-controlled electrolyte exhibits 65.7% of retention after 100 cycle, which is identified by systematic spectroscopic analyses for the cycled cell.     

Synthesis and electrochemical studies of LiMn1−xCuXO4 cathode material

LiMn_1.8Cu_0.2O₄ was investigated in order to improve the electrochemical properties of LiMn₂O₄. We report the synthesis and characterization of materials prepared by solid-state reaction. The structural properties evaluated by the X-ray diffraction and vibrational spectroscopy show that a single phase was formed. Conductivity of LiMn_1.8Cu_0.2O₄ cathode is found to be 8×10⁻⁶ S/cm at 25 °C. The cyclic voltammetry data shows the reversibility of the electrode material. Paper presented at the 7th Euroconference on Ionics, Calcatoggio, Corsica, France, Oct. 1–7, 2000.     

Enhanced rate performance of polypyrrole-coated sulfur/MWCNT cathode material: a kinetic study by electrochemical impedance spectroscopy

Lithium-sulfur batteries have a poor cyclability and inferior rate capability due to the shuttle effect of lithium polysulfides. To solve these problems, a sulfur-coated MWCNT composite (S/MWCNT) was coated with conductive polypyrrole (PPy) to trap the polysulfides and facilitate charge and lithium ion transport. From the contact angle measurement, it is found that the PPy coating improves the wettability of the S/MWCNT composite. Compared with the bare S/MWCNT composite, the PPy-coated S/MWCNT composite cathode exhibited improved cycle stability and high-rate performance. A reversible discharge capacity of 671 mAh g^?1 was maintained after 50 cycles at 3 C for the PPy-coated composite. The effect of PPy coating on kinetic property was investigated by electrochemical impedance spectroscopy (EIS). The electrolyte resistance, surface film resistance, charge transfer resistance, lithium ion diffusion coefficient, and exchange current density were evaluated from the EIS measurements. The EIS results reveal that the PPy coating increases both Li ion diffusion into the cathode and exchange current density. The as-prepared PPy-coated S/MWCNT composite can be considered to be a promising candidate for high capacity and high-rate performance cathode material.     

Characterization of a LiCoO2 thin film cathode grown by pulsed laser deposition

A highly (003)-oriented pure LiCoO₂ thin film cathode, without Co₃O₄ impurities, was grown on a stainless steel substrate by pulsed laser deposition and characterized by electrochemical testing, scanning electron microscopy (SEM), ex situ X-ray diffraction (XRD), Raman and X-ray photoelectron spectroscopy (XPS). The initial reversible discharge capacity of the LiCoO₂ thin film cathode reached 52.5?μAh/cm²µm and capacity loss was about 0.18% per cycle at a current density of 12.74?μA/cm². The chemical diffusion coefficient of the Li⁺ ion was estimated to be about 4.7?×?10^?11?cm²/s from cyclic voltammetric (CV) scans. Ex situ XRD revealed that the spacing of crystalline planes expanded about 0.09?Å when charged to 4.2?V, corresponding to Li_0.5CoO₂, lower than the value for composite powder LiCoO₂ electrodes. XPS results showed that the number of low-coordinated oxygen ions increased relative to the removal of Li⁺ ions.     

The NaCrS2 cathode material. IV. Effect of vanadium substitution on its physical properties and electrochemical performance in secondary Li cells

The introduction of 0.10–0.15 eq/mol of V³⁺ into the layered structure of NaCrS₂ substantially raises its conductivity and lowers its magnetic susceptibility without changing its crystal lattice parameters or nucleating a new phase, this implying considerable changes in the electron band structure of the dichalcogenide. When used as a cathode in a Li cell the partially desodiated vanadium substituted thiochromite exhibits a considerable increase in the equilibrium potential as compared to that of the nonsubstituted compound. Chemical and X-ray analysis reveal that in single phase samples (V³⁺0.15 eq/mol) practically all the V³⁺ ions are incorporated into the disulfide slabs, replacing equivalent amounts of Cr³⁺. It is demonstrated that the partially desodiated host structure Na_0.2Cr_0.9V_0.1S₂ can reversibly intercalate up to 1 eq Li/mole. The energy density, power capability and cycle life of this layered compound make it an attractive cathode material for secondary Li cells.     

Rapid preparation of high electrochemical performance LiFePO4/C composite cathode material with an ultrasonic-intensified micro-impinging jetting reactor

A joint chemical reactor system referred to as an ultrasonic-intensified micro-impinging jetting reactor (UIJR), which possesses the feature of fast micro-mixing, was proposed and has been employed for rapid preparation of FePO₄ particles that are amalgamated by nanoscale primary crystals. As one of the important precursors for the fabrication of lithium iron phosphate cathode, the properties of FePO₄ nano particles significantly affect the performance of the lithium iron phosphate cathode. Thus, the effects of joint use of impinging stream and ultrasonic irradiation on the formation of mesoporous structure of FePO₄ nano precursor particles and the electrochemical properties of amalgamated LiFePO₄/C have been investigated. Additionally, the effects of the reactant concentration (C = 0.5, 1.0 and 1.5 mol L⁻¹), and volumetric flow rate (V = 17.15, 51.44, and 85.74 mL min⁻¹) on synthesis of FePO₄·2H₂O nucleus have been studied when the impinging jetting reactor (IJR) and UIJR are to operate in nonsubmerged mode. It was affirmed from the experiments that the FePO₄ nano precursor particles prepared using UIJR have well-formed mesoporous structures with the primary crystal size of 44.6 nm, an average pore size of 15.2 nm, and a specific surface area of 134.54 m² g⁻¹ when the reactant concentration and volumetric flow rate are 1.0 mol L⁻¹ and 85.74 mL min⁻¹ respectively. The amalgamated LiFePO₄/C composites can deliver good electrochemical performance with discharge capacities of 156.7 mA h g⁻¹ at 0.1 C, and exhibit 138.0 mA h g⁻¹ after 100 cycles at 0.5 C, which is 95.3% of the initial discharge capacity.     

Effects of Ca doping on the electrochemical properties of LiNi0.8Co0.2O2 cathode material

LiNi_0.8Co_0.2O₂ and Ca-doped LiNi_0.8Co_0.2O₂ cathode materials were synthesized via a rheological phase reaction method. It is found that the Ca doping significantly improves reversible capacity, cycling performance, thermal stability and rate capability. The Ca-doped LiNi_0.8Co_0.2O₂ cathode material maintains nearly its initial discharge capacity up to 100 cycles at room temperature. It also delivers an initial discharge capacity of 183 mA h g^− 1 and still keeps 131 mA h g^− 1 even after 120 cycles at 60 °C. These results, together with the X-ray diffraction and electrochemical impedance spectroscopy analysis, reveal that Ca²⁺ ions occupy Li⁺ ion sites to form Ca_Li defects and lithium vacancies (V_Li′), which reduce the resistance and increases conductivity of LiNi_0.8Co_0.2O₂.     

Vibrational spectroscopy and electrochemical properties of LiNi0.7Co0.3O2 cathode material for rechargeable lithium batteries

We are reporting the synthesis and characterization of solid solutions of the LiNiO₂ and LiCoO₂ system. Substitution of cobalt for nickel in the LiNi_1−yCo_yO₂ phases provides significant improvements in the two-dimensionality of the crystal lattice and ease the large scale synthesis. This structural effect improves the reversibility of the lithium intercalation-deintercalation process. We have evaluated the vibrational spectra and electrochemical properties of LiNi_0.7Co_0.3O₂ (charge-discharge profiles and cyclic voltammetry) and compared the results with those of the end members, i.e., LiNiO₂ and LiCoO₂. The local environment of cations against oxygen neighboring atoms has been determined. Paper presented at the 4th Euroconference on Solid State Ionics, Renvyle, Galway, Ireland, Sept. 13–19, 1997     

Enhanced electrochemical performances of LiNi0.5Co0.2Mn0.3O2 cathode material co-coated by graphene/TiO2

The electrochemical performances of LiNi_0.5Co_0.2Mn_0.3O₂ (NCM523) layered cathode material, such as poor rate capacity and cycling stability caused by undesirable intrinsic conductivity and low rate of lithium ion transportation, are not fairly good especially at elevated rate and cut-off voltage. To improve these properties, in this study, the co-coating layer of graphene and TiO₂ was constructed on NCM523 surface. The graphene/TiO₂ coating layer could effectively prevent hydrofluoric acid (HF) attacks, suppress the side reaction, accelerate the lithium ion diffusion and facilitate the electron migration. The enhancement of cycle performance and rate capacity was contributed to the uniform co-modified surface, interacting each other and thus exhibiting synergistic effects.     

Effect of mesoporous carbon containing binary conductive additives in lithium ion batteries on the electrochemical performance of the LiCoO2 composite cathodes

Binary conductive additives (BCA), formed by sonication of mesoporous carbon (MC) and acetylene black (AB), were used as conductive additives to improve the electrochemical performance of a LiCoO₂ composite cathode. The electrochemical performance of the LiCoO₂ composite cathode dispersed with BCA was investigated. The results showed that the electrochemical performance (including the discharge capacity, the discharge voltage and the total internal resistance) of a BCA loaded LiCoO₂ composite cathode was better than that of a cathode loaded with AB. The possible mechanism is that the MC in BCA can adsorb and retain electrolyte solution, which allows an intimate contact between the lithium ions and the cathode active material LiCoO₂ due to its large mesopore specific surface area. A simplified model was also proposed.     

Structure and electrochemical characteristics of LiFePO4 cathode materials for rechargeable Li-Ion batteries

Complex investigations of cathode materials for rechargeable lithium-ion batteries have been carried out using the following techniques: scanning electron microscopy, microanalysis, extended X-ray absorption fine structure (EXAFS) spectroscopy, Mössbauer spectroscopy, and porosimetry. Investigations have been performed on samples prepared according to the original technology at the St. Petersburg State Institute of Technology (Technical University) (SPbSTI (TU)) and on four commercial cathode materials. It has been established that there is a correlation between the nanostructured morphology of the cathode materials, their chemical composition, and electrochemical capacity. It has been found that the internal resistance of the LiFePO₄ cathode material is linearly dependent on the diffusion coefficient of lithium ions. The valence state and local coordination of Fe ions have been studied using the ⁵⁷Fe Mössbauer effect. It has been shown that more than 90% of the iron ions are in the valence state Fe²⁺. Based on the data available in the literature on the methods of synthesizing LiFePO₄ and data on the diagnosis of the studied samples, conclusions have been drawn about a modification of the synthesis for producing high-quality cathode materials for Li-ion batteries.     

Tuning electrochemical potential of LiCoO2 with cation substitution: first-principles predictions and electronic origin

With a goal to improve the performance of LiCoO₂ as a cathode material in Li-ion batteries, we simulate substitution of various elements (X = Be, Mg, Al, Ga, Si and Ti) for Co using first-principles density functional theory and predict changes in its electrochemical potential. While the electrochemical potential of LiCoO₂ is enhanced with substitution of Be, Mg, Al and Ga for Co, an opposite effect is predicted of Si and Ti substitution. We determine the electronic origin of these changes in electrochemical potential using (a) Bader method of topological analysis of charge density, (b) partial density of electronic states to estimate oxidation states of metal and oxygen, and charge re-distribution upon lithiation. We find that the distribution of electronic charge donated by Li is influenced by the nature of the X–O bond. A larger electron transfer to O (in XO₆ octahedron) upon lithiation leads to stronger Li intercalation and thereby higher electrochemical voltage. Our findings provide a platform for a rational design of cathode materials in Li batteries with enhanced voltage.