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.     

Structural and electrochemical properties of LiNi1/3Mn1/3Co1/3O2−xFx prepared by solid state reaction

A series of LiNi_1/3Mn_1/3Co_1/3O_2−xF_x (0 ≤ x ≤ 1) compounds was prepared by a solid state reaction and their characteristics were investigated by XRD, SEM, XPS, EIS, and charge–discharge test. The substitution of oxygen by fluorine produces change in the valences of the transition metal ions, thereby induces a complex change in the lattice parameters. Moreover, the fluorine doping of the LiNi_1/3Mn_1/3Co_1/3O₂ can promote the grain size growth and improve its crystallinity. The substituted samples with a low fluorine content can stabilize the interface between the surface layer of the active particles and the electrolyte after cycling, which is probably related to the improvement of the cyclic performance. A high fluorine content introduction into LiNi_1/3Mn_1/3Co_1/3O₂ significantly decreases its electrochemical properties, which is probably due to the formation of a new unstable interface as well as a structural instability caused by the nonequivilent substitution.     

Li(Ni1/3Co1/3Mn1/3)O2 as a suitable cathode for high power applications

The electrochemical performance of the layered Li(Ni_1/3Co_1/3Mn_1/3)O₂ material have been investigated as a promising cathode for a hybrid electric vehicle (HEV) application. A C/Li(Ni_1/3Co_1/3Mn_1/3)O₂ cell, cycled between 2.9 and 4.1 V at 1.5 C rate, does not show any sign of capacity fade up to 100 cycles, whereas at the 5 C rate, a loss of only 18% of capacity is observed after 200 cycles. The Li(Ni_1/3Co_1/3Mn_1/3)O₂ host cathode converts from the hexagonal to a monoclinic symmetry at a high state of charge. The cell pulse power capability on charge and discharge were found to exceed the requirement for powering a hybrid HEV. The accelerated calendar life tests performed on C/Li(Ni_1/3Co_1/3Mn_1/3)O₂ cells charged at 4.1 V and stored at 50 °C have shown a limited area specific impedance (ASI) increase unlike C/Li(Ni_0.8Co_0.2)O₂ based-cells. A differential scanning calorimetry (DSC) comparative study clearly showed that the thermal stability of Li(Ni_1/3Co_1/3Mn_1/3)O₂ is much better than that of Li(Ni_0.8Co_0.2)O₂ and Li(Ni_0.8Co_0.15Al_0.05)O₂ cathodes. Also, DSC data of Li(Ni_1/3Co_1/3Mn_1/3)O₂ cathode charged at 4.1, 4.3, and 4.6 V are presented and their corresponding exothermic heat flow peaks are discussed.     

Preparation and characterization of layered LiMn1/3Ni1/3Co1/3O2 as a cathode material by an oxalate co-precipitation method

The layered LiMn_1/3Ni_1/3Co_1/3O₂ cathode materials were synthesized by an oxalate co-precipitation method using different starting materials of LiOH, LiNO₃, [Mn_1/3Ni_1/3Co_1/3]C₂O₄·2H₂O and [Mn_1/3Ni_1/3Co_1/3]₃O₄. The morphology, structural and electrochemical behavior were characterized by means of SEM, X-ray diffraction analysis and electrochemical charge–discharge test. The cathode material synthesized by using LiNO₃ and [Mn_1/3Ni_1/3Co_1/3]C₂O₄·2H₂O showed higher structural integrity and higher reversible capacity of 178.6 mAh g⁻¹ in the voltage range 3.0–4.5 V versus Li with constant current density of 40 mA g⁻¹ as well as lower irreversible capacity loss of 12.9% at initial cycle. The rate capability of the cathode was strongly influenced by particle size and specific surface area.     

Synthesis and characterization of high tap-density layered Li[Ni1/3Co1/3Mn1/3]O2 cathode material via hydroxide co-precipitation

Li[Ni_1/3Co_1/3Mn_1/3]O₂ was prepared by mixing uniform co-precipitated spherical metal hydroxide (Ni_1/3Co_1/3Mn_1/3)(OH)₂ with 7% excess LiOH followed by heat-treatment. The tap-density of the powder obtained was 2.38 g cm⁻³, and it was characterized using X-ray diffraction (XRD), particle size distribution measurement, scanning electron microscope-energy dispersive spectrometry (SEM-EDS) and galvanostatic charge–discharge tests. The XRD studies showed that the material had a well-ordered layered structure with small amount of cation mixing. It can be seen from the EDS results that the transition metals (Ni, Co and Mn) in Li[Ni_1/3Co_1/3Mn_1/3]O₂ are uniformly distributed. Initial charge and discharge capacity of 185.08 and 166.99 mAh g⁻¹ was obtained between 3 and 4.3 V at a current density of 16 mA g⁻¹, and the capacity of 154.14 mAh g⁻¹ was retained at the end of 30 charge–discharge cycles with the capacity retention of 93%.     

Nanoparticled Li(Ni1/3Co1/3Mn1/3)O2 as cathode material for high-rate lithium-ion batteries

Nanoparticle of Li(Ni_1/3Co_1/3Mn_1/3)O₂ with size smaller than 40 nm was obtained by non-aqueous system co-precipitation method. The particle morphology and crystal plane orientation were observed by TEM and HRTEM. Electrochemical properties of this nanostructued material were studied with experiment cells. The results show that the material has high capacity of 160 mAh g⁻¹ and excellent rate capability for charge and discharge. For the 50C and 100C rate, its capacity remains above 100 mAh g⁻¹ after tens of cycles.     

Effects of synthesis conditions on the structural and electrochemical properties of layered Li[Ni1/3Co1/3Mn1/3]O2 cathode material via the hydroxide co-precipitation method LIB SCITECH

The uniform layered Li[Ni_1/3Co_1/3Mn_1/3]O₂ cathode material for lithium ion batteries was prepared by using (Ni_1/3Co_1/3Mn_1/3)(OH)₂ synthesized by a liquid phase co-precipitation method as precursor. The effects of calcination temperature and time on the structural and electrochemical properties of the Li[Ni_1/3Co_1/3Mn_1/3]O₂ were systemically studied. XRD results revealed that the optimal prepared conditions of the layered Li[Ni_1/3Co_1/3Mn_1/3]O₂ were 850 °C for 18 h. Electrochemical measurement showed that the sample prepared under the above conditions has the highest initial discharge capacity of 162.1 mAh g⁻¹ and the smallest irreversible capacity loss of 9.2% as well as stable cycling performance at a constant current density of 16 mA g⁻¹ between 3 and 4.3 V versus Li at room temperature.     

Electrochemical performances of lithium-ion polymer battery using LiNi1/3Co1/3Mn1/3O2 as cathode materials

In this work, a gel polymer electrolyte (GPE) was prepared using polyoxyalkylene glycol acrylate (POAGA) as a macromonomer. LiNi_1/3Mn_1/3Co_1/3O₂/GPE/graphite cells were prepared and their electrochemical properties were evaluated at various current densities and temperatures. The ionic conductivity of the GPE was more than 6.2 × 10⁻³ S cm⁻¹ at room temperature. The GPE had good electrochemical stability up to 5.0 V versus Li/Li⁺. POAGA-based cells were showed good electrochemical performances such as rate capability, low-temperature performance, and cycleability. No leakage of the electrolyte or an explosion was observed at the overcharge test.     

Improvement of 12 V overcharge behavior of LiCoO2 cathode material by LiNi0.8Co0.1Mn0.1O2 addition in a Li-ion cell

The 12 V overcharge instability of the LiCoO₂ cathode material was improved by the physical blending it with LiNi_0.8Co_0.1Mn_0.1O₂. Even though a Li-ion cell containing a LiCoO₂ cathode did not exhibit thermal runaway at 12 V at the 1 C overcharging rate, it showed thermal runaway at the 2 C overcharging rate, and the cell surface temperature reached more than 400 °C. However, the LiCoO₂ cell containing 40, 50, and 60 wt.% LiNi_0.8Co_0.1Mn_0.1O₂ did not exhibit thermal runaway at the 2 C overcharging rate. In conclusion, 60 wt.% LiNi_0.8Co_0.1Mn_0.1O₂ in the LiCoO₂ cathode showed the lowest cell surface temperature of <90 °C even at a 3 C overcharging rate.     

Electrochemical performance of SrF2-coated LiNi1/3Co1/3Mn1/3O2 cathode materials for Li-ion batteries

SrF₂-coated LiNi_1/3Co_1/3Mn_1/3O₂ cathode materials with improved cycling performance over 2.5–4.6 V were investigated. The structural and electrochemical properties of the materials were studied using X-ray diffraction (XRD), scanning electron microscope (SEM), charge–discharge tests and electrochemical impedance spectra (EIS). The results showed that the crystalline SrF₂ with about 10–50 nm particle size is uniformly coated on the surface of LiNi_1/3Co_1/3Mn_1/3O₂ particles. As the coating amount increased from 0.0 to 2.0 mol%, the initial capacity and rate capability of the coated LiNi_1/3Co_1/3Mn_1/3O₂ decreased slightly owing to the increase of the charge-transfer resistance; however, the cycling stability was improved by suppressing the increase of the resistance during cycling. 4.0 mol% SrF₂-coated LiNi_1/3Co_1/3Mn_1/3O₂ showed remarkable decrease of the initial capacity. 2.0 mol% coated sample exhibited the best electrochemical performance. It presented an initial discharge capacity of 165.7 mAh g⁻¹, and a capacity retention of 86.9% after 50 cycles at 4.6 V cut-off cycling.     

Morphological,structural, and electrochemical characteristics of LiNi0.5Mn0.4M0.1O2 (M = Li,Mg, Co,Al)

LiNi_0.5Mn_0.4M_0.1O₂ (M = Li, Mg, Al, Co) compound was prepared by a solid-state reaction, and its structural, morphological and electrochemical properties were characterized by XRD, SEM, charge–discharge tests and EIS. The impacts of alien ion introduction on the structural, morphological and electrochemical properties of LiNi_0.5Mn_0.5O₂ depend on the dopants. The substitution of Li, Mg, and Co for Mn can enlarge the particle size and improve the crystallinity. LiNi_0.5Mn_0.4Li_0.1O₂ and LiNi_0.5Mn_0.4Co_0.1O₂ show increased reversible capacities as well as upgraded rate capabilities. LiNi_0.5Mn_0.4Li_0.1O₂ exhibits a retentive capacity of about 200 mAh g⁻¹ at 50 °C.     

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.     

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.     

Effect of Ag additive on the performance of LiNi1/3Co1/3Mn1/3O2 cathode material for lithium ion battery

The LiNi_1/3Co_1/3Mn_1/3O₂/Ag composite used for cathode material of lithium ion battery was prepared by thermal decomposition of AgNO₃ added to commercial LiNi_1/3Co_1/3Mn_1/3O₂ powders to improve the electrochemical performance of LiNi_1/3Mn_1/3Co_1/3O₂. Structure and morphology analysis showed that Ag particles were dispersed on the surface of LiNi_1/3Co_1/3Mn_1/3O₂ instead of entering the crystal structure. The results of charge–discharge tests showed that Ag additive could improve the cycle performance and high-rate discharge capability of LiNi_1/3Mn_1/3Co_1/3O₂. Extended analysis indicated that Ag was unstable in the commercial electrolyte at high potential. The improved electrochemical performance caused by Ag additive was associated not only with the enhancement of electrical conductivity of the material and the lower polarization of the cell, but also with the increased “c” parameter of LiNi_1/3Mn_1/3Co_1/3O₂ after repeated charge/discharge cycles and the compact and protective SEI layer formed on the surface of LiNi_1/3Mn_1/3Co_1/3O₂.     

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.     

LiNi1/3Co1/3Mn1/3O2/polypyrrole composites as cathode materials for high-performance lithium-ion batteries

Polypyrrole is successfully introduced to enhance the reaction stability and ionic conductivity of LiNi_1/3Co_1/3Mn_1/3O₂ material through an ultrasound dispersion method and applied as cathode materials for lithium-ion batteries. This polymer can significantly advance the electrochemical properties. Expectedly, the 8 wt.% LiNi_1/3Co_1/3Mn_1/3O₂/polypyrrole composite has lower mixing degree of Li⁺/Ni²⁺, higher c/a value, which delivers the first discharge capacity of 199.2 mAh g⁻¹, which abate to 121.3 mAh g⁻¹ in the 300th cycle at 0.2 C between 2.5 and 4.5 V. Even at 3 C, it continues to reveal a reversible capacity of 86.4 mAh g⁻¹ after 100 cycles. All the consequences implied that the 8 wt.% LiNi_1/3Co_1/3Mn_1/3O₂/polypyrrole verified a minor charge transfer resistance and better Li⁺ diffusion ability, hence establishing preferable rate and cycling performance compared with the primordial LiNi_1/3Co_1/3Mn_1/3O₂.     

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.     

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.     

Preparation and electrochemical/thermal properties of LiNi0.74Co0.26O2 cathode material

Electrochemical and thermal properties of LiNi_0.74Co_0.26O₂ cathode material with 5, 13 and 25 μm-sized particles have been studied by using a coin-type half-cell Li/LiNi_0.74Co_0.26O₂. The specific capacity of the material ranges from 205 to 210 mA h g⁻¹, depending on the particle size or the Brunauer, Emmett and Teller (BET) surface area. Among the particle sizes, the cathode with a particle size of 13 μm shows the highest specific capacity. Even though the material with a particle size of 5 μm exhibits the smallest capacity value of 205 mA h g⁻¹, no capacity fading was observed after 70 cycles between 4.3 and 2.75 V at the 1 C rate. Differential scanning calorimetry (DSC) studies of the charged electrode at 4.3 V show a close relationship between particle size (BET surface area) and thermal stability of the electrode, namely, a larger particle size (smaller BET surface area) leads to a better thermal stability of the LiNi_0.74Co_0.26O₂ cathode.     

LiNi0.8Co0.2O2 cathode materials synthesized by the maleic acid assisted sol–gel method for lithium batteries

A maleic acid assisted sol–gel method was employed to synthesize LiNi_0.8Co_0.2O₂ cathode materials, which are of interest for potential use in lithium batteries. Various synthesis conditions such as solvent, calcination time, calcination temperature, acid-to-metal ion ratio (R), and lithium stoichiometry were studied to determine the ideal conditions for preparing LiNi_0.8Co_0.2O₂ with the best electrochemical characteristics. The optimal synthesis conditions were found to be an ethanol solvent with a calcination time of 12 h at 800°C under flowing oxygen. The first discharge capacity of the material synthesized using the above conditions was 190 mAh/g, and the discharge capacity after 10 cycles was 183 mAh/g, at a 0.1 C rate between 3.0 and 4.2 V. Details of how varying initial synthesis conditions affected capacity and cycling performance of LiNi_0.8Co_0.2O₂ are discussed.