• Applied Chemistry for Engineering
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• v.31 no.1
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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.

• Journal of Industrial and Engineering Chemistry
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• v.68
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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.

• KEPCO Journal on Electric Power and Energy
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• v.6 no.4
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• pp.461-466
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• 2020

There are many application fields of electrical energy storage such as load shifting, integration with renewables, frequency or voltage supports, and so on. Especially, the frequency regulation is needed to stabilize the electric power system, and there have to be more than 1 GW as power reserve in Korea. Ni-rich layered oxide cathode materials have been investigated as a cathode material for Li-ion batteries because of their higher discharge capacity and lower cost than lithium cobalt oxide. Nonetheless, most of them have been investigated using small coin cells, and therefore, there is a limit to understand the deterioration mode of Ni-rich layered oxides in commercial high energy Li-ion batteries. In this paper, the pouch-type 20 Ah-scale Li-ion full cells are fabricated using Ni-rich layered oxides as a cathode and graphite as an anode. Above all, two test conditions for the application of frequency regulation were established in order to examine the performances of cells. Then, the electrochemical performances of two types of Ni-rich layered oxides are compared, and the long-term performance and degradation mode of the cell using cathode material with high nickel contents among them were investigated in the frequency regulation conditions.

• Journal of Electrochemical Science and Technology
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• v.13 no.2
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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.

• Korean Journal of Materials Research
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• v.28 no.5
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• pp.273-278
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• 2018

Lithium-ion batteries have been considered the most important devices to power mobile or small-sized devices due to their high energy density. $LixCoO_2$ has been studied as a cathode material for the Li-ion battery. However, the limitation of its capacity impedes the development of high capacity cathode materials with Ni, Mn, etc. in them. The substitution of Mn and Ni for Co leads to the formation of solid solution phase $LiNi_xMn_yCo_{1-x-y}O_2$ (NMC, both x and y < 1), which shows better battery performance than unsubstituted $LiCoO_2$. However, despite a high discharge capacity in the Ni-rich compound (Ni > 0.8 in the metal site), poor cycle retention capability still remains to be overcome. In this study, aiming to improve the stability of the physical and chemical bonding, we investigate the stabilization effect of Ca in the Ni-rich layered compound $Li(Ni_{0.83}Co_{0.12}Mn_{0.05})O_2$, and then Ca is added to the modified secondary particles to lower the degree of cationic mixing of the final particles. For the optimization of the final grains added with Ca, the Ca content (x = 0, 2.5, 5.0, 10.0 at.%) versus Li is analyzed.

• Korean Journal of Materials Research
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• v.30 no.11
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• pp.636-640
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• 2020

Due to the serious air pollution problem, interest in eco-friendly vehicles is increasing. Solving the problem of pollution will necessitate the securing of high energy storage technology for batteries, the driving force of eco-friendly vehicles. The reason for the continuing interest in the transition metal oxide LiMO₂ as a cathode material with a layered structure is that lithium ions reveal high mobility in two-dimensional space. Therefore, it is important to investigate the effective intercalation and deintercalation pathways of Li⁺, which affect battery capacity, to understand the internal structure of the cathode particle and its effect on the electrochemical performance. In this study, for the cathode material, high nickel Ni_0.8Co_0.1Mn_0.1(OH)₂ precursor is synthesized by controlling the ammonia concentration. Thereafter, the shape of the primary particles of the precursor is investigated through SEM analysis; X-ray diffraction analysis is also performed. The electrochemical properties of LiNi_0.8Co_0.1Mn_0.1O₂ are evaluated after heat treatment.