• Current Applied Physics
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• 제18권11호
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• pp.1345-1351
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• 2018

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.

• Journal of Electrochemical Science and Technology
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• 제12권4호
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• pp.377-386
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• 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 Industrial and Engineering Chemistry
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• 제68권
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• pp.180-186
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• 2018

We report the discovery of Li-rich $Li_{1+x}[(Ni_{0.225}Co_{0.15}Mn_{0.625})_{1-y}V_y]O_2$ as a cathode material for rechargeable lithium-ion batteries in which a small amount of tetravalent vanadium ($V^{4+}$) is selectively and completely incorporated into the manganese sites in the lattice structure. The unwanted oxidation of vanadium to form a $V_2O_5-like$ secondary phase during high-temperature crystallization is prevented by uniformly dispersing the vanadium ions in coprecipitated $[(Ni_{0.225}Co_{0.15}Mn_{0.625})_{1-y}V_y](OH)_2$ particles. Upon doping with $V^{4+}$ ions, the initial discharge capacity (>$275mA\;h\;g^{-1}$), capacity retention, and voltage decay characteristics of the Li-rich layered oxides are improved significantly in comparison with those of the conventional undoped counterpart.

• Journal of the Korean Electrochemical Society
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• 제20권4호
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• pp.67-74
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• 2017

Layered Ni-rich NCM cathode materials $Li[Ni_xCo_{(1-x)/2}Mn_{(1-x)/2}]O_2$ ($x{\geq}0.6$) have advantages of high energy density and cost competitive over $LiCoO_2$. The discharge capacity of NCM increases proportionally to the Ni contents. However, there is a problem that it is difficult to realize the stable electrochemical performance due to cation mixing. In this study, synthesis conditions for the layered Ni-rich NCMs are investigated to achieve deliver the ones having good electrochemical performances. Synthesis parameters are atmosphere, lithium source, synthesis time, synthesis temperature and Li/M (M=transition metal) ratio. The degree of cation mixing gets worse as the Ni content is increased from $Li[Ni_{0.6}Co_{0.2}Mn_{0.2}]O_2$ (NCM6) to $Li[Ni_{0.8}Co_{0.1}Mn_{0.1}]O_2$ (NCM8). It is confirmed that higher level of cation mixing affects negatively on the electrochemical performance of NCMs. Optimum synthesis conditions are explored for NCMx (x=6, 7, 8) in order to reduce the cation mixing. Under optimized conditions for three representative NCMx, a high initial discharge capacity and a good cycle life are obtained for $180mAh{\cdot}g^{-1}$, 96.2% (50 cycle) in NCM6, $187mAh{\cdot}g^{-1}$, 94.7% (50 cycle) in NCM7, and $201mAh{\cdot}g^{-1}$, 92.7% (50 cycle) in NCM8, respectively.

• Applied Chemistry for Engineering
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• 제31권1호
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• pp.97-102
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• 2020

Recently, various degradation mechanisms of lithium secondary battery cathode materials have been revealed. As a result, many studies on overcoming the limitation of cathode materials and realizing new electrochemical properties by controlling the degradation mechanism have been reported. Li-rich layered oxide is one of the most promising cathode materials due to its high reversible capacity. However, the utilization of Li-rich layered oxide has been restricted, because it undergoes a unique atomic structure change during the cycle, in turn resulting in unwanted electrochemical degradations. To understand an atomic structure deterioration mechanism and suggest a research direction of Li-rich layered oxide, we deeply evaluated the atomic structure of 0.4Li₂MnO₃_0.6LiNi_1/3Co_1/3Mn_1/3O₂ Li-rich layered oxide during electrochemical cycles, by using an atomic-resolution analysis tool. During a charge process, Li-rich materials undergo a cation migration of transition metal ions from transition metal slab to lithium slab due to the structural instability from lithium vacancies. As a result, the partial structural degradation leads to discharge voltage drop, which is the biggest drawback of Li-rich materials.

• Korean Journal of Materials Research
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• 제32권4호
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• pp.210-215
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• 2022

Extensive research is being carried out on Ni-rich Li(Ni_xCo_yMn_1-x-y)O₂ (NCM) due to the growing demand for electric vehicles and reduced cost. In particular, Ni-rich Li(Ni_xCo_yMn_1-x-y-zAl_z)O₂ (NCMA) is attracting great attention as a promising candidate for the rapid development of Co-free but electrochemically more stable cathodes. Al, an inactive element in the structure, helps to improve structural stability and is also used as a doping element to improve cycle capability in Ni-rich NCM. In this study, NCMA was successfully synthesized with the desired composition by direct coprecipitation. Boron and tin were also used as dopants to improve the battery performance. Macro- and microstructures in the cathodes were examined by microscopy and X-ray diffraction. While Sn was not successfully doped into NCMA, boron could be doped into NCMA, leading to changes in its physicochemical properties. NCMA doped with boron revealed substantially improved electrochemical properties in terms of capacity retention and rate capability compared to the undoped NCMA.

• Journal of Electrochemical Science and Technology
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• 제7권2호
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• pp.179-184
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• 2016

The interface between the surface of a cathode material and the electrolyte gives rise to surface reactions such as solid electrolyte interface (SEI) and chemical side reactions. These reactions lead to increased surface resistance and charge transfer resistance. It is consequently necessary to improve the electrochemical characteristics by suppressing these reactions. In order to suppress unnecessary surface reactions, we coated cathode material using polypropylene (PP). The PP coating layer effectively reduced the SEI film that is generated after a 4.3 V initial charging process. By mitigating the formation of the SEI film, the PP-coated Li[(Ni_0.6Co_0.1Mn_0.3)_0.36(Ni_0.80Co_0.15Al0.05)_0.64)]O₂(NCS) electrode provided enhanced transport of Li⁺ ions due to reduced SEI resistance (R_SEI) and charge transfer resistance (R_ct). The initial charge and discharge efficiency of the PP-coated NCS electrode was 96.2 % at a current density of 17 mA/g in a voltage range of 3.0 ~ 4.3 V, whereas the efficiency of the NCS electrode was only 94.7 %. The presence of the protective PP layer on the cathode improved the thermal stability by reducing the generated heat, and this was confirmed via DSC analysis by an increased exothermic peak.

• Journal of Industrial Technology
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• 제42권1호
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• pp.1-5
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• 2022

Although the mileage of electric vehicles can be increased based on the excellent energy density of the LiNi_0.9Co_0.05Mn_0.05O₂, it is known that the reason for limiting its use is the low lifespan and poor surface stability due to the structural deformation of the LiNi_0.9Co_0.05Mn_0.05O₂. To improve the structural stability of LiNi_0.9Co_0.05Mn_0.05O₂, electrochemical performance is improved by La coating on the surface. La-modified LiNi_0.9Co_0.05Mn_0.05O₂ shows an initial capacity of 210.6 mAh/g, a capacity retention rate of 89.9 % after 50 cycles, and a retention rate of 52.5% at 6.0 C. These are superior performances than the pristine sample, because the structural stability of the LiNi_0.9Co_0.05Mn_0.05O₂ cathode is improved by the La coating.

• Journal of Electrochemical Science and Technology
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• 제15권1호
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• pp.161-167
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• 2024

Despite the important role of manganese (Mn) in cobalt-free, Ni-rich cathode materials, existing reports on the effects of Mn as a substitute for cobalt are not consistent. In this work, we analyzed the performance of cathodes comprised of Li(Ni_1-xMn_x)O₂ (LNMO). Both beneficial and detrimental results occurred as a result of the Mn substitution. We found that a complex interplay of effects (Li/Ni mixing driven by magnetic frustration, grain growth suppression, and retarded lithium insertion/extraction kinetics) influenced the performance and was intimately related to calcination temperature. This indicates the importance of establishing an optimal reaction temperature for the development of high-performance LNMO.

• Journal of Electrochemical Science and Technology
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• 제13권2호
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• pp.269-278
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• 2022

Utilization of high-voltage electrolyte additive(s) at a small fraction is a cost-effective strategy for a good solid electrolyte interphase (SEI) formation and performance improvement of a lithium-rich layered oxide-based high-energy lithium-ion cell by avoiding the occurrence of metal-dissolution that is one of the failure modes. To mitigate metal-dissolution, we explored fluorinated dual-additives of fluoroethylene carbonate (FEC) and di(2,2,2-trifluoroethyl)carbonate (DFDEC) for building-up of a good SEI in a 4.7 V full-cell that consists of high-capacity silicon-graphite composite (15 wt% Si/C/CF/C-graphite) anode and Li_1.13Mn_0.463Ni_0.203Co_0.203O₂ (LMNC) cathode. The full-cell including optimum fractions of dual-additives shows increased capacity to 228 mAhg^-1 at 0.2C and improved performance from the one in the base electrolyte. Surface analysis results find that the SEI stabilization of LMNC cathode induced by dual-additives leads to a suppression of soluble Mn²⁺-O formation at cathode surface, mitigating metal-dissolution event and crack formation as well as structural degradation. The SEI and structure of Si/C/CF/C-graphite anode is also stabilized by the effects of dual-additives, contributing to performance improvement. The data give insight into a basic understanding of cathode-electrolyte and anode-electrolyte interfacial processes and cathode-anode interaction that are critical factors affecting full-cell performance.