Synthesis,structural and electrochemical properties of pulsed laser deposited Li(Ni,Co)O2 films

We report the epitaxial growth of the LiNi_1−yM_yO₂ films (M = Co, Co–Al) on heated nickel foil using pulsed laser deposition in oxygen environment from lithium-rich targets. The structure and morphology was characterized by X-ray diffractometry, electron scanning microscopy and Raman spectroscopy. Data reveal that the formation of oriented films is dependent on two important parameters: the substrate temperature and the gas pressure during ablation. The charge–discharge process conducted in Li-microcells demonstrates that effective high specific capacities can be obtained with films 1.35 μm thick. Stable capacities of 83 and 92 μAh cm⁻² μm are available in the potential range 4.2–2.5 V for LiNi_0.8Co_0.2O₂ and LiNi_0.8Co_0.15Al_0.05O₂ films, respectively. The self-diffusion coefficient of Li ions determined from galvanostatic intermittent titration experiments is found to be 4 × 10⁻¹² cm² s⁻¹.     

Stannum doping of layered LiNi3/8Co2/8Mn3/8O2 cathode materials with high rate capability for Li-ion batteries

Sn doped lithium nickel cobalt manganese composite oxide of LiNi_3/8Co_2/8Mn_3/8−xSn_xO₂ (0 ≤ x ≤ 0.10) was synthesized by stannum substitute of manganese to enhance its rate capability at first time. Its structure and electrochemical properties were characterized by X-ray diffraction (XRD), SEM, cyclic voltammetry (CV), galvanostatic intermittent titration technique (GITT) and charge/discharge tests. LiNi_3/8Co_2/8Mn_3/8−xSn_xO₂ had stable layered structure with α-NaFeO₂ type as x up to 0.05, meanwhile, its chemical diffusion coefficient D_Li of Li-ion was enhanced by almost one order of magnitude, leading to notable improvement of the rate capability of LiNi_3/8Co_2/8Mn_3/8O₂. The compound of x = 0.10 showed the best rate capability among Sn doped samples, but its discharge capacity reduced markedly due to secondary phase Li₂SnO₃ and increase of cation-disorder. The compound with x = 0.05 showed high rate capability with initial discharge capacity in excess of 156 mAh g⁻¹. It is a promising alternative cathode material for EV application of Li-ion batteries.     

The improved physical and electrochemical performance of LiNi0.35Co0.3−xCrxMn0.35O2 cathode materials by the Cr doping for lithium ion batteries

We have successfully prepared the layered structure LiNi_0.35Co_0.3−xCr_xMn_0.35O₂ with various Cr contents by a co-precipitation method. Many measurement methods have been applied to characterize the physical and electrochemical properties of LiNi_0.35Co_0.3−xCr_xMn_0.35O₂, such as XRD, SEM, BET and electrochemical test. SEM showed that the addition of Cr has obviously changed the morphologies of their particles and increased the size of grains. The specific surface area of LiNi_0.35Co_0.3−xCr_xMn_0.35O₂ decreases lineally from 4.9 m² g⁻¹ (x = 0) to 1.8 m² g⁻¹ (x = 0.1) with the increasing of Cr contents. Moreover, we have found that the Cr doping can greatly improve the density of the powder, which is beneficial to solve the problem of lower electrode density for these layered LiNi_0.35Co_0.3−xCr_xMn_0.35O₂ cathode materials. Electrochemical test indicated that the cycling performance of LiNi_0.35Co_0.3−xCr_xMn_0.35O₂ can be significantly improved with the increasing of Cr contents, although the initial discharge capacity of the sample has a little decrease.     

Rapid thermal annealing effect on surface of LiNi1−xCoxO2 cathode film for thin-film microbattery

The effect of rapid thermal annealing (RTA) on the surface of a LiNi_1−xCo_xO₂ cathode film is examined by means of scanning electron microscopy (SEM), atomic force microscopy (AFM) and auger electron spectroscopy (AES). It is found that the as-deposited LiNi_1−xCo_xO₂ film undergoes a surface reaction with oxygen in the air, due to the high activity of lithium in the film. AES spectra indicate that the surface layer consists of lithium and oxygen atoms. The RTA process at 500 °C eliminates the surface layer to some extent. An increase in annealing temperature to 700 °C results in complete elimination of the surface layer. The surface evolution of the LiNi_1−xCo_xO₂ film with increasing annealing time at 700 °C is examined by means of AFM examination. It is found that the surface layer, which is initially present in the form of an amorphous like-film, becomes agglomerated and then vaporizes after 5 min of annealing. A thin-film microbattery (TFB), fabricated by using the LiNi_1−xCo_xO₂ film without a surface layer, exhibits more stable cycliability and a higher specific discharge capacity of 60.2 μAh cm⁻² μm than a TFB with an unannealed LiNi_1−xCo_xO₂ film. Therefore, it is important to completely eliminate the surface layer in order to achieve high performance from all solid-state thin-film microbatteries.     

Chemical and structural instabilities of lithium ion battery cathodes

The chemical and structural stabilities of various layered Li_1−xNi_1−y−zMn_yCo_zO₂ cathodes are compared by characterizing the samples obtained by chemically extracting lithium from the parent Li_1−xNi_1−y−zMn_yCo_zO₂ with NO₂BF₄ in an acetonitrile medium. The nickel- and manganese-rich compositions such as Li_1−xNi_1/3Mn_1/3Co_1/3O₂ and Li_1−xNi_0.5Mn_0.5O₂ exhibit better chemical stability than the LiCoO₂ cathode. While the chemically delithiated Li_1−xCoO₂ tends to form a P3 type phase for (1 − x) < 0.5, Li_1−xNi_0.5Mn_0.5O₂ maintains the original O3 type phase for the entire 0 ≤ (1 − x) ≤ 1 and Li_1−xNi_1/3Mn_1/3Co_1/3O₂ forms an O1 type phase for (1 − x) < 0.23. The variations in the type of phases formed are explained on the basis of the differences in the chemical lithium extraction rate caused by the differences in the degree of cation disorder and electrostatic repulsions. Additionally, the observed rate capability of the Li_1−xNi_1−y−zMn_yCo_zO₂ cathodes bears a clear relationship to cation disorder and lithium extraction rate.     

Effect of titanium substitution in layered LiNiO2 cathode material prepared by molten-salt synthesis

LiNi_1−xTi_xO₂ (0 ≤ x ≤ 0.1) compounds have been synthesized by a direct molten-salt method that uses a eutectic mixture of LiNO₃ and LiOH salts. According to X-ray diffraction analysis, these materials have a well-developed layered structure (R3-m) and are an isostructure of LiNiO₂. The LiNi_1−xTi_xO₂ (0 ≤ x ≤ 0.1) compounds have average particle sizes of 1–5 μm depending on the amount of Ti salt. Charge–discharge tests show that a LiNi_1−xTi_xO₂ (0 ≤ x ≤ 0.1) cathode prepared at 700 °C has an initial discharge capacity as high as 171 mA h g⁻¹ and excellent capacity retention in the range 4.3–2.8 V at a current density of 0.2 mA cm⁻².     

Synthesis and electrochemical properties of LiNi0.80(Co0.20−xAlx)O2 (x = 0.0 and 0.05) cathodes for Li ion rechargeable batteries

The effect of simultaneous cobalt as well as aluminum doping was studied to understand their effect on the phase formation behavior and electrochemical properties of solution derived lithium nickel oxide cathode materials for rechargeable batteries. The discharge capacities of LiNi_0.80Co_0.20O₂ and LiNi_0.80Co_0.15Al_0.05O₂ cathodes, measured at constant current densities of 0.45 mA cm⁻² in the cut-off voltage range of 4.3–3.2 V, were 100 and 136 mAh g⁻¹, respectively. LiNi_0.80Co_0.15Al_0.05O₂ had better cycleability than the LiNi_0.80Co_0.20O₂ cathodes. The retention of undesirable Li₂CO₃ phase both in LiNi_0.80Co_0.20O₂ and LiNi_0.80Co_0.15Al_0.05O₂ cathodes was argued to be responsible for the relatively lower discharge capacity of these materials.     

Crystal chemistry and electrochemical characterization of layered LiNi0.5−yCo0.5−yMn2yO2 and LiCo0.5−yMn0.5−yNi2yO2 (0 ≤ 2y ≤ 1) cathodes

The crystal chemistry and electrochemical performance of the layered LiNi_0.5−yCo_0.5−yMn_2yO₂ and LiCo_0.5−yMn_0.5−yNi_2yO₂ oxide cathodes for 0 ≤ 2y ≤ 1 have been investigated. Li₂MnO₃ impurity phase is observed for Mn-rich compositions with 2y > 0.6 in LiNi_0.5−yCo_0.5−yMn_2yO₂ and 2y < 0.2 in LiCo_0.5−yMn_0.5−yNi_2yO₂. Additionally, the Ni-rich compositions encounter a volatilization of lithium at the high synthesis temperature of 900 °C. Compositions around 2y = 0.33 are found to be optimum with respect to maximizing the capacity values and retention. The rate capabilities are found to bear a strong relationship to the cation disorder in the layered lattice. Moreover, the evolution of the X-ray diffraction patterns on chemically extracting lithium has revealed the presence of Li₂MnO₃ phase in addition to the layered phase for the composition LiNi_0.25Co_0.25Mn_0.5O₂ with an oxidation state of manganese close to 4+, which results in a large anodic peak at around 4.5 V due to the extraction of both lithium and oxygen.     

Synthesis and characterizations of Li[CrxLi(1−x)/3Mn2(1−x)/3]O2 (0.15 ≤ x ≤ 0.3) cathode materials in rechargeable lithium batteries

A series of Li[Cr_xLi_(1−x)/3Mn_2(1−x)/3]O₂ (0.15 ≤ x ≤ 0.3) cathode materials was prepared by citric acid-assisted, sol–gel process. Sub-micron sized particles were obtained and the X-ray diffraction (XRD) results showed that the crystal structure was similar to layered lithium transition metal oxides (R-3m space group). The electrochemical performance of the cathodes was evaluated over the voltage range 2.0–4.9 V at a current density of 7.947 mA g⁻¹. The Li_1.27Cr_0.2Mn_0.53O₂ electrode delivered a high reversible capacity of up to 280 mAh g⁻¹ during cycling. Li[Cr_xLi_(1−x)/3Mn_2(1−x)/3]O₂ yielded a promising cathode material.     

Study of the electrochemical properties of Ga-doped LiNi0.8Co0.2O2 synthesized by a sol–gel method

The effects of gallium doping on the structure and electrochemical properties of LiNi_0.8Co_0.2O₂ were investigated by X-ray diffraction, cyclic voltammetry and charge-discharge tests. LiNi_0.8Co_0.2−xGa_xO₂ (x = 0.01, 0.03, 0.05) was synthesized using a sol–gel method and it showed the average particle size less than 1 μm in diameter. Results showed that gallium-doping had no effect on the crystal structure (α-NaFeO₂) of the cathode material in the range x ≤ 0.05. On the other hand, two transitions at 3.7–3.9 and 4.2–4.7 V observed during the cycle test were merged into one when the amount of gallium doping increases to 0.05, implying that the enhanced capacity retention with gallium doping is attributed to the suppression of the phase transition of the cathode. However, the increase of gallium content in LiNi_0.8Co_0.2O₂ slightly decreases the initial discharge capacity.     

Layered Li(Ni0.5−xMn0.5−xM2x′)O2 (M′=Co,Al, Ti; x=0, 0.025) cathode materials for Li-ion rechargeable batteries

Layered Li(Ni_0.5−xMn_0.5−xM_2x′)O₂ materials (M′=Co, Al, Ti; x=0, 0.025) were synthesized using a manganese-nickel hydroxide precursor, and the effect of dopants on the electrochemical properties was investigated. Li(Ni_0.5Mn_0.5)O₂ exhibited a discharge capacity of 120 mAh/g in the voltage range of 2.8–4.3 V with a slight capacity fade up to 40 cycles (0.09% per cycle); by doping of 5 mol% Co, Al, and Ti, the discharge capacities increased to 140, 142, and 132 mAh/g, respectively, and almost no capacity fading was observed. The cathode material containing 5 mol% Co had the lowest impedance, 47 Ω cm², while undoped, Ti-doped, and Al-doped materials had impedance of 64, 62, and 99 Ω cm², respectively. Unlike the other dopants, cobalt was found to improve the electronic conductivity of the material. Further improvement in the impedance of these materials is needed to meet the requirement for powering hybrid electric vehicle (HEV, <35 Ω cm²). In all materials, structural transformation from a layered to a spinel structure was not observed during electrochemical cycling. Cyclic voltammetry and X-ray photoelectron spectroscopy (XPS) data suggested that Ni and Mn exist as Ni²⁺ and Mn⁴⁺ in the layered structure. Differential scanning calorimetry (DSC) data showed that exothermic peaks of fully charged Li_1−y(Ni_0.5−xMn_0.5−xM_2x′)O₂ appeared at higher temperature (270–290 °C) than LiNiO₂-based cathode materials, which indicates that the thermal stability of Li(Ni_0.5−xMn_0.5−xM_2x′)O₂ is better than those of LiNiO₂-based cathode materials.     

Synthesis and electrochemical properties of Mo-doped Li[Ni1/3Mn1/3Co1/3]O2 cathode materials for Li-ion battery

The layered Li[Ni_(1−x)/3Mn_(1−x)/3Co_(1−x)/3Mo_x]O₂ cathode materials (x = 0, 0.005, 0.01, and 0.02) were prepared by a solid-state pyrolysis method (700, 800, 850, and 900 °C). Its structure and electrochemical properties were characterized by XRD, SEM, XPS, cyclic voltammetry, and charge/discharge tests. It can be learned that the doped sample of x = 0.01 calcined at 800 °C shows the highest first discharge capacity of 221.6 mAh g⁻¹ at a current density of 20 mA g⁻¹ in the voltage range of 2.3–4.6 V, and the Mo-doped samples exhibit higher discharge capacity and better cycle-ability than the undoped one at room temperature.     

Study of cobalt-doped lithium–nickel oxides as cathodes for MCFC

Cobalt substituted lithium–nickel oxides were synthesized by a solid-state reaction procedure using lithium nitrate, nickel hydroxide and cobalt oxalate precursor and were characterized as cathodes for molten carbonate fuel cell (MCFC). LiNi_0.8Co_0.2O₂ cathodes were prepared using non-aqueous tape casting technique followed by sintering in air. The X-ray diffraction (XRD) analysis of sintered LiNi_1−xCo_xO₂ indicated that lithium evaporation occurs during heating. The lithium loss decreases with an increase of the cobalt content in the mixed oxides. The stability studies showed that dissolution of nickel into the molten carbonate melt is smaller in the case of LiNi_1−xCo_xO₂ cathodes compared to the dissolution values reported in the literature for state-of-the-art NiO. Pore volume analysis of the sintered electrode indicated a mean pore size of 3 μm and a porosity of 40%. A current density of 160 mA/cm² was observed when LiNi_0.8Co_0.2O₂ cathodes were polarized at 140 mV. The electrochemical impedance spectroscopy (EIS) studies done on LiNi_0.8Co_0.2O₂ cathodes under different gas conditions indicated that the rate of the cathodic discharge reaction depends on the O₂ and CO₂ partial pressures.     

Characterization of Zn- and Fe-substituted LiMnO2 as cathode materials in Li-ion cells

Layered LiMn_1−xM_xO₂ (M = Zn or Fe) (0 ≤ x ≤ 0.3) samples are synthesized from the corresponding sodium analogues by an ion-exchange method using LiBr in n-hexanol at 160 °C. The samples are subjected to physicochemical and electrochemical characterization. X-ray diffraction data indicate the formation of layered structures for the LiMn_1−xZn_xO₂ samples up to x = 0.3 and for LiMn_1−xFe_xO₂ samples up to x = 0.2. Among these, LiMn_0.95Zn_0.05O₂ and LiMn_0.95Fe_0.05O₂ provide the highest capacity values of 180 and 193 mAh g⁻¹, respectively. Both Zn- and Fe-substituted samples display good capacity retention up to 30 charge–discharge cycles. Electrochemical impedance spectroscopy and galvanostatic intermittent titration data corroborate the results obtained from cyclic volatmmetry and charge–discharge cycling.     

Effect of sulfur and nickel doping on morphology and electrochemical performance of LiNi0.5Mn1.5O4−xSx spinel material in 3-V region

The effect of nickel and sulfur substitution for manganese and oxygen on the structure and electrochemical properties of the LiNi_0.5Mn_1.5O_4−xS_x is examined. The LiNi_0.5Mn_1.5O_4−xS_x (x = 0 and 0.05) compounds are successfully synthesized at 500 and 800 °C by co-precipitation using the metal carbonate (Ni_0.5Mn_1.5)CO₃ as a precursor. The resulting powder with sulfur doping exhibits different morphology from a Ni-only doped spinel in terms of particle size and surface texture. The LiNi_0.5Mn_1.5O_4−xS_x (x = 0 and 0.05) powders are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and galvanostatic charge–discharge cycling. The nickel- and sulfur-doped spinel displays excellent capacity retention and rate capability in the 3-V region, compared with Ni-only doped spinel material.     

Effects of aluminum on the structural and electrochemical properties of LiNiO2

LiNi_1−yAl_yO₂ (0.10≤y≤0.50) compounds have been synthesized by a coprecipitation method. The characterization of the samples by X-ray and neutron diffraction, associated with Rietveld refinement analysis, has shown that for all materials, about 5% extra-nickel ions are present in the interslab space. Charge−discharge cycling of LiNi_1−yAl_yO₂ as positive electrode material in lithium cells has shown that aluminum substitution suppresses all the phase transitions observed for the LiNiO₂ system. Good cycling stability was observed, but the capacity decreases from 125 to 100 mAh/g by increasing the aluminum amount from 10 to 25% (3–4.15 V range; C/20 rate).     

The effects of partial substitution of Cr for Ni on the electrochemical properties of Mg1.75Al0.25Ni1−xCrx (0 ≤ x ≤ 0.3) electrode alloys

In this paper, the substitution of different amounts of Cr for Ni in the hydrogen storage electrode alloy of Mg_1.75Al_0.25Ni has been carried out to form quaternary Mg_1.75Al_0.25Ni_1−xCr_x (0 ≤ x ≤ 0.3) alloys by means of solid diffusion method (DM). The XRD profiles exhibited that the quaternary alloys still kept the same main phase of Mg₃AlNi₂ (S.G. Fd3m) as that of ternary Mg_1.75Al_0.25Ni alloy. The electrochemical studies found that Cr substituted quaternary alloy reached its maximum discharge capacity (165 mAh g⁻¹) after 2 cycles, which was larger than that of the Mg_1.75Al_0.25Ni alloy (154 mAh g⁻¹). Among these quaternary alloys, the Mg_1.75Al_0.25Ni_0.9Cr_0.1 electrode alloy was found possessing the highest cycling capacity retention rate. Cyclic voltammetry (CV) results and anodic polarization curves demonstrated that appropriate content (x lower than 0.1) of Cr effectively improved the reaction activity of electrode and inhibited the cycling capacity degradation to some degree. Electrochemical impedance spectroscopy (EIS) analyses indicated that the increase of Cr content would raise the polarization resistance R_p on the particle surface of these quaternary alloys.     

Electrochemical performance behavior of combustion-synthesized LiNi0.5Mn0.5O2 lithium-intercalation cathodes

LiNiO₂, partially substituted with manganese in the form of a LiNi_0.5Mn_0.5O₂ compound, has been synthesized by a gelatin assisted combustion method [GAC] method. Highly crystalline LiNi_0.5Mn_0.5O₂ powders with R3m symmetry have been obtained at an optimum temperature of 850 °C, as confirmed by PXRD studies. The presence of cathodic and anodic CV peaks exhibited by the LiNi_0.5Mn_0.5O₂ cathode at 4.4 and 4.3 V revealed the existence of Ni and Mn in their 2+ and 4+ oxidation states, respectively. The synthesized LiNi_0.5Mn_0.5O₂ cathode has been subjected to systematic electrochemical performance evaluation, via capacity tapping at different cut-off voltage limits (3.0–4.2, 3.0–4.4 and 3.0–4.6 V) and the possible extraction of deliverable capacity under different current drains (0.1C, 0.5C, 0.75C and 1C rates). The LiNi_0.5Mn_0.5O₂ cathode exhibited a maximum discharge capacity of 174 mAh g⁻¹ at the 0.1C rate between 3.0 and 4.6 V. However, a slightly decreased capacity of 138 mAh g⁻¹ has been obtained in the 3.0–4.4 V range, when discharged at the 1C rate. On the other hand, extended cycling at the 0.1C rate encountered an acceptable capacity fade in the 3.0–4.4 V range (<10%) for up to 50 cycles.     

Electrochemical properties of iodine-containing lithium manganese oxide spinel

Iodine-containing, cation-deficient, lithium manganese oxides (ICCD-LMO) are prepared by reaction of MnO₂ with LiI. The MnO₂ is completely transformed into spinel-structured compounds with a nominal composition of Li_1−δMn_2−2δO₄I_x. A sample prepared at 800 °C, viz. Li_0.99Mn_1.98O₄I_0.02, exhibits an initial discharge capacity of 113 mA h g⁻¹ with good cycleability and rate capability in the 4-V region. Iodine-containing, lithium-rich lithium manganese oxides (ICLR-LMO) are also prepared by reaction of LiMn₂O₄ with LiI, which results in a nominal composition of Li_1+xMn_2−xO₄I_x. Li_1.01Mn_1.99O₄I_0.02 shows a discharge capacity of 124 mA h g⁻¹ on the first cycle and 119 mA h g⁻¹ a on the 20th cycle. Both results indicate that a small amount of iodine species helps to maintain cycle performance.     

Advanced manganese oxide material for rechargeable lithium cells

A family of potassium-doped manganese oxide materials were synthesized with the stoichiometric formula Li_0.9−XK_XMn₂O₄, where X = 0.0–0.25 and evaluated for their viability as a cathode material for a rechargeable lithium battery. A performance maximum was found at X = 0.1 where the initial specific capacity for the lithium–potassium-doped manganese dioxide electrochemical couple was 130 mAh g⁻¹ of active cathode material. The discharge capacity of the system was maintained through 90 cycles (95% initial capacity). Additionally, the capacity was maintained at greater than 90% initial discharge through 200 cycles. Other variants demonstrated greater than 75% initial discharge through 200 cycles at comparable capacity.