• Journal of Electrochemical Science and Technology
• /
• v.12 no.4
• /
• pp.377-386
• /
• 2021

The Li-rich oxides are promising cathode materials due to their high energy density. However, characteristics such as low rate capability, unstable cyclic performance, and rapid capacity fading during cycling prevent their commercialization. These characteristics are mainly attributed to the phase instability of the host structure and undesirable side reactions at the cathode/electrolyte interface. To suppress the phase transition during cycling and interfacial side reactions with the reactive electrolyte, K (potassium) doping and Nb oxide coating were simultaneously introduced to a Li-rich oxide (Li_1.2Ni_0.13Co_0.13Mn_0.54O₂). The capacity and rate capability of the Li-rich oxide were significantly enhanced by K doping. Considering the X-ray diffraction (XRD) analysis, the interslab thickness of LiO₂ increased and cation mixing decreased due to K doping, which facilitated Li migration during cycling and resulted in enhanced capacity and rate capability. The K-doped Li-rich oxide also exhibited considerably improved cyclic performance, probably because the large K⁺ ions disturb the migration of the transition metals causing the phase transition and act as a pillar stabilizing the host structure during cycling. The Nb oxide coating also considerably enhanced the capacity and rate capability of the samples, indicating that the undesirable interfacial layer formed from the side reaction was a major resistance factor that reduced the capacity of the cathode. This result confirms that the introduction of K doping and Nb oxide coating is an effective approach to enhance the electrochemical performance of Li-rich oxides.

• Journal of the Korean Electrochemical Society
• /
• v.24 no.4
• /
• pp.120-132
• /
• 2021

Although the development of high-Nickel is being actively carried out to solve the capacity limitation and the high price of raw cobalt due to the limitation of high voltage use of the existing LiCoO₂, the deterioration of the battery characteristics due to the decrease in structural stability and increase of the Ni content. It is an important cause of delaying commercialization. Therefore, in order to increase the high stability of the Ni-rich ternary cathod material LiNi_0.6Co_0.2Mn_0.2O₂, precursor Ni_0.6Co_0.2Mn_0.2-x(OH)₂/xTiO₂ was prepared using a nanosized TiO₂ suspension type source for uniform Ti substitution in the precursor. It was mixed with Li₂CO₃, and after heating, the cathode active material LiNi_0.6Co_0.2Mn_0.2-xTi_xO₂ was synthesized, and the physical properties according to the Ti content were compared. Through FE-SEM and EDS mapping analysis, it was confirmed that a positive electrode active material having a uniform particle size was prepared through Ti-substituted spherical precursor and Particle Size Analyzer and internal density and strength were increased, XRD structure analysis and ICP-MS quantitative analysis confirmed that the capacity was effectively maintained even when the Ti-substituted positive electrode active material was manufactured and charging and discharging were continued at high temperature and high voltage.

• Journal of the Korean Electrochemical Society
• /
• v.16 no.3
• /
• pp.162-168
• /
• 2013

$Li_2MnO_3-LiMO_2$(M=Ni, Co, Mn) nano-composite is a promising cathode material for xEV application due to its high theoretic capacity. However high voltage operating system of $Li_2MnO_3-LiMO_2$(M=Ni, Co, Mn) has worked as a hurdle in its application because of the inherent demerits, such as cycle life degradation and gas evolution. In order to enhance cell performance of $Li_2MnO_3-LiMO_2$(M=Ni, Co, Mn)/graphite cell, we examined electrolyte mainly composed of FEC, fluroalkyl ether and $LiPF_6$ (F-based EL). F-based EL showed much better discharging retention ratio than 1.3 M $LiPF_6$ EC/EMC/DMC (3/4/3, v/v/v) (STD). Furthermore gas evolution, especially CO and $CO_2$ during $60^{\circ}C$ storage for 30 days was dramatically reduced owing to thermal stable SEI formation effect of F-based EL.

• Environmental Engineering Research
• /
• v.25 no.1
• /
• pp.88-95
• /
• 2020

An investigation of rare metals recovery from LiNi_xCo_yMn_zO₂ cathode material of the end-of-life lithium-ion batteries is presented. To determine the influence of reductant on the leach process, the cathode material (containing Li 7.6%, Co 20.4%, Mn 19.4%, and Ni 19.3%) was leached in H₂SO₄ solutions either with or without H₂O₂. The optimal process parameters with respect to acid concentration, addition dosage of H₂O₂, temperature, and the leaching time were found to be 2.0 M H₂SO₄, 4 vol.% H₂O₂, 70℃, and 150 min, respectively. The yield of metal values in the leach liquor was > 99%. The leach liquor was subsequently treated by precipitation techniques to recover nickel as Ni(C₄H₇N₂O₂)₂ and lithium as Li₂CO₃ with stoichiometric ratios of 2:1 and 1.2:1 of dimethylglyoxime:Ni and Na₂CO₃:Li, respectively. Cobalt was recovered by solvent extraction following a 3-stage process using Na-Cyanex 272 at pH_eq ~5.0 with an organic-to-aqueous phase ratio (O/A) of 2/3. The loaded organic phase was stripped with 2.0 M H₂SO₄ at an O/A ratio of 8/1 to yield a solution of 114 g/L CoSO₄; finally recovered CoSO₄.xH₂O by crystallization. The process economics were analyzed and found to be viable with a margin of $476 per ton of the cathode material.

• Journal of the Korean Electrochemical Society
• /
• v.20 no.1
• /
• pp.7-12
• /
• 2017

Using a precursor of $LiNi_{0.6}Co_{0.2}Mn_{0.2}O_2$ as a starting material, a surface-modified cathode material was obtained by coating with KCl, where the added KCl reduces residual Li compounds such as $Li_2CO_3$ and LiOH, on the surface. The resulting electrochemical properties were investigated. The amounts of $Li_2CO_3$ and LiOH decreased from 8,464 ppm to 1,639 ppm and from 8,088 ppm to 6,287 ppm, respectively, with 1 wt% KCl added $LiNi_{0.6}Co_{0.2}Mn_{0.2}O_2$ that had been calcined at $800^{\circ}C$. X-ray diffraction results revealed that 1 wt% of KCl added $LiNi_{0.6}Co_{0.2}Mn_{0.2}O_2$ did not affect the parent structure but enhanced the development of hexagonal crystallites. Additionally, the charge transfer resistance ($R_{ct}$) decreased dramatically from $225{\Omega}$ to $99{\Omega}$, and the discharge capacity increased to 182.73mAh/g. Using atomic force microscopy, we observed that the surface area decreased by half because of the exothermic heat released by the Li residues. The reduced surface area protects the cathode material from reacting with the electrolyte and hinders the development of a solid electrolyte interphase (SEI) film on the surface of the oxide particles. Finally, we found that the introduction of KCl into $LiNi_{0.6}Co_{0.2}Mn_{0.2}O_2$ is a very effective method of enhancing the electrochemical properties of this active material by reducing the residual Li. To the best of our knowledge, this report is the first to demonstrate this phenomenon.

• Journal of the Korean Ceramic Society
• /
• v.43 no.3 s.286
• /
• pp.162-168
• /
• 2006

The perovskites with nominal compositions $La_{0.8}Sr_{0.2}Fe_{1-x}M_xO_3$ (M=Co, Mn, Ni, x=0.1-0.3) were fabricated by a solid-state reaction method as cathode materials of low-temperature operating Solid Oxide Fuel Cells (SOFCs). X-ray diffraction analysis and microstructure observation for the sintered samples were performed. The ac complex impedance were measured in the temperature range $600-900^{\circ}C$ in air and fitted with a Solatron ZView program. The electrical conductivity and polarization resistance of $La_{0.8}Sr_{0.2}Fe_{1-x}M_xO_3$ (M=Co, Mn, Ni, x=0.1-0.3) were characterized systematically. The porosities of the sintered samples were in the range of 25% to 38%. The polarization resistance of $La_{0.8}Sr_{0.2}Fe_{0.7}M_{0.3}O_3$ was $0.291{\Omega}cm^2\;at\;700^{\circ}C$.

• Korean Journal of Materials Research
• /
• v.12 no.4
• /
• pp.274-278
• /
• 2002

Discrete-variational(DV)-$X{\alpha}$ method was applied to investigate the electronic structures of spinel- type manganese oxide which is well known to the high performance adsorbent or cathode material for lithium ion. The results of DOS(density of states) and Mulliken population analysis showed that Li was nearly fully ionized and interactions between Mn and O were strong covalent bond. The effective charge of Li and Mn was +0.77 and +1.44 respectively and the overlap population between Mn and O was 0.252 in $LiMn_2O_4$. These results from DV-X$\alpha$ method were well coincided with the experimental result by XPS analysis and supported the feasibility of theoretical interpretation for the $LiMn_2O_4$ compound.

• Journal of Electrochemical Science and Technology
• /
• v.13 no.2
• /
• pp.177-185
• /
• 2022

Electrochemical properties of LiMn₂O₄ cathode were investigated in three types of Zn-containing electrolytes: lithium-zinc sulfate electrolyte (1M ZnSO₄ / 2M Li₂SO₄), zinc sulfate electrolyte (2MZnSO₄) and lithium-zinc-manganese sulfate electrolyte (1MZnSO₄ / 2MLi₂SO₄ / 0.1MMnSO₄). Cyclic voltammetry measurements demonstrated that LiMn₂O₄ is electrochemically inactive in pure ZnSO₄ electrolyte after initial oxidation. The effect of manganese (II) additive in the zinc-manganese sulfate electrolyte on the electrochemical performance was analyzed. The initial capacity of LiMn₂O₄ is higher in presence of MnSO₄ (140 mAh g^-1 in 1 M ZnSO₄ / 2 M Li₂SO₄ / 0.1 M MnSO₄ and 120 mAh g^-1 in 1 M ZnSO₄ / 2MLi₂SO₄). The capacity increase can be explained by the electrodeposition of MnO_x layer on the electrode surface. Structural characterization of postmortem electrodes with use of XRD and EDX analysis confirmed that partially formed in pure ZnSO₄ electrolyte Zn-containing phase leads to fast capacity fading which is probably related to blocked electroactive sites.

• Journal of the Korean Electrochemical Society
• /
• v.9 no.2
• /
• pp.64-69
• /
• 2006

Cathode materials of Al-doped $Li(Ni_{1/3}Co_{1/3}Mn_{1/3-x}Al_x)O_2$ (x=0.0, 0.005, 0.01 0.05) for lithium ion batteries were synthesized with ultra-sonic spray pyrolysis method and single-step heat treatment. No secondary phases were found in all synthesized powders. The intensity ratio of $I_{003}\;to\;I_{104}$, however, slightly decreased and the particle size increased with the Al contents. The cells with bare, 0.5 and 1.0 at% Al-doped powders showed the initial discharge capacities of 182, 180 and $184mAhg^{-1}$ in a voltage range of $3.0\sim4.5V$ at 1C rate, and the capacity retentions of 81, 77 and 78% at the end of 30 cycles, respectively. But in the voltage range of $3.0\sim4.6V$, the Al-doping significantly enhanced the cycle stability. For example, the discharge capacity after 50 cycles was maintained to 70% in the 0.5 at% Al-doped sample compared to only 30% in no doped sample. The improvement of the cycle stability was thought to be due to $Mn^{3+}$ ion decrease as the Al doping from the XPS analysis results.

• Journal of the Korean Ceramic Society
• /
• v.34 no.6
• /
• pp.652-658
• /
• 1997

The phase stability in the interface of Sr-doped LaMnO3(LSM)/Gd-doped CeO2(CGO) was examined in this study in order to check the feasibility of using LSM as the cathode material in a low-temperature SOFC(solid oxide fuel cell) using CGO as the electrolyte. For the purpose, CGO powders of Ce0.82Gd0.18O0.91 and two LSM powders having different compositions, La0.9Sr0.1MnO3(LSM10) and La0.5Sr0.5MnO3(LSM50), were synthesized using Pechini method. Then, specimens having the LSM/CGO interface were prepared, heat-treated at 130$0^{\circ}C$ for up to 3 days, and analyzed by XRD and STEM/EDX. Face-centered cubic CGO powders of less than 10 nm size were obtained by calcination of polymeric precursor formed in the process at 45$0^{\circ}C$. Higher calcination temperature of $700^{\circ}C$ was necessary for monoclinic LSM10 and cubic LSM50 powders. LSM powders were coarser than CGO and observed to be in the range of 50~100 nm. No trace of LSM-CGO interaction product was found in the XRD pattern. Also it was known from the concentration profile in the vicinity of the interface that interdiffusion was occurred over only a small penetration depth of ~100 nm order.