• Journal of Electrochemical Science and Technology
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• v.4 no.3
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• pp.102-107
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• 2013

The electrochemical properties of Mg-doped $LiFe_{0.48}Mn_{0.48}Mg_{0.04}PO_4$ and pure $LiFe_{0.5}Mn_{0.5}PO_4$ olivine cathodes are examined and the lattice parameters are refined by Rietveld analysis. The calculated atomic parameters from the refinement show that $Mg^{2+}$ doping has a significant effect in the olivine $LiFeMnPO_4$ structure. The unit cell volume is 297.053(2) ${\AA}^3$ for pure $LiFe_{0.5}Mn_{0.5}PO_4$ and is decreased to 296.177(1) ${\AA}^3$ for Mg-doped $LiFe_{0.48}Mn_{0.48}Mg_{0.04}PO_4$ sample. The doping of $Mg^{2+}$ cation with atomic radius smaller than $Mn^{2+}$ and $Fe^{2+}$ ion induces longer Li-O bond length in $LiO_6$ octahedra of the olivine structure. The larger interstitial sites in $LiO_6$ octahedra facilitate the lithium ion migration and also enhance the diffusion kinetics of olivine cathode material. The $LiFe_{0.48}Mn_{0.48}Mg_{0.04}PO_4$ sample with larger Li-O bond length delivers higher discharge capacities and also notably increases the rate capability of the electrode.

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

• Korean Journal of Materials Research
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• v.32 no.4
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• pp.216-222
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• 2022

The capacity of high nickel Li(Ni_xCo_yMn_1-x-y)O₂ (NCM, x ≥ 0.8) cathodes is known to rapidly decline, a serious problem that needs to be solved in a timely manner. It was reported that cathode materials with the {010} plane exposed toward the outside, i.e., a radial structure, can provide facile Li⁺ diffusion paths and stress buffer during repeated cycles. In addition, cathodes with a core-shell composition gradient are of great interest. For example, a stable surface structure can be achieved using relatively low nickel content on the surface. In this study, precursors of the high-nickel NCM were synthesized by coprecipitation in ambient atmosphere. Then, a transition metal solution for coprecipitation was replaced with a low nickel content and the coprecipitation reaction proceeded for the desired time. The electrochemical analysis of the core-shell cathode showed a capacity retention of 94 % after 100 cycles, compared to the initial discharge capacity of 184.74 mA h/g. The rate capability test also confirmed that the core-shell cathode had enhanced kinetics during charging and discharging at 1 A/g.

• Bulletin of the Korean Chemical Society
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• v.31 no.2
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• pp.355-359
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• 2010

A $Li[Co_{1/3}Ni_{1/3}Mn_{1/3}]O_2$ cathode was modified by applying a $ZrF_x$ coating. The surface-modified cathodes were characterized by XRD, SEM, EDS, TEM techniques. XRD patterns of $ZrF_x$-coated $Li[Co_{1/3}Ni_{1/3}Mn_{1/3}]O_2$ revealed that the coating did not affect the crystal structure of the parent powder. SEM and TEM images showed that $ZrF_x$ nano-particles were formed as a coating layer, and EDS data confirmed that $ZrF_x$ distributed uniformly on the surface the powder. Capacity retention of coated samples at high C rates was superior to that of pristine sample. However, as the coating concentration increases beyond the optimum concentration, the rate capability was deteriorated. Whereas, as the increase of coating concentration to 2.0 wt %, the cyclic performances of the electrodes under the severe conditions (high cut-off voltage, 4.8 V, and high measurement temperature, $55^{\circ}C$) were improved considerably.

• Journal of Electrochemical Science and Technology
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• v.9 no.3
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• pp.176-183
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• 2018

In this study, a $Li_2ZrO_3$ coated $Li[Ni_{0.8}Co_{0.15}Al_{0.05}]O_2$ (NCA) cathode was applied to an all-solid-state cell employing a sulfide-based solid electrolyte. Sulfide-based solid electrolytes are preferable for all-solid-state cells because of their high ionic conductivity and good softness and elasticity. However, sulfides are very reactive with oxide cathodes, and this reduces the stability of the cathode/electrolyte interface of all-solid-state cells. $Li_2ZrO_3$ is expected to be a suitable coating material for the cathode because it can suppress the undesirable reactions at the cathode/sulfide electrolyte interface because of its good stability and high ionic conductivity. Cells employing $Li_2ZrO_3$ coated NCA showed superior capacity to those employing pristine NCA. Analysis by X-ray photoelectron spectroscopy and electron energy loss spectroscopy confirmed that the $Li_2ZrO_3$ coating layer suppresses the propagation of S and P into the cathode and the reaction between the cathode and the sulfide solid electrolyte. These results show that $Li_2ZrO_3$ coating is promising for reducing undesirable side reactions at the cathode/electrolyte interface of all-solid-state-cells.

• Bulletin of the Korean Chemical Society
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• v.30 no.11
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• pp.2584-2588
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• 2009

The effect of $LaF_3$ coating on the structural and electrochemical properties of $Li[Ni_{0.3}Co_{0.4}Mn_{0.3}]O_{2}$ cathodes was investigated using XRD, SEM, TEM, and a cycler. The coating layer consisted of nano-sized particles attached nonuniformly to the surface of pristine powder. Despite the surface coating treatment, phase difference by $LaF_3$ coating was not detected. The discharge capacities of coated electrodes were a little lower than that of pristine sample at a 1 C rate. However, as the C rate increases, the capacity retention of the coated sample becomes obviously superior to that of the pristine sample. The cyclic performances of the electrodes in the voltage range of 4.8 $\sim$ 3.0 V were also improved by the surface coating. Such enhancement is attributed to the presence of the $LaF_3$ coating layer, which effectively suppressd the reaction between electrodes and electrolytes on the surface of the $Li[Ni_{0.3}Co_{0.4}Mn_{0.3}]O_{2}$ electrode.

• Applied Chemistry for Engineering
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• v.21 no.2
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• pp.211-216
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• 2010

$(NH_4)_{0.3}V_2O_5$ nanorods and $V_2O_5$ nanosheets have been synthesized by the reaction of $V_2O_5$ gel via homogeneous precipitation process employing urea and formic acid. The electrochemical and chemical characteristics of these nanomaterials have been investigated using TGA, SEM, FT-IR, XRD, and LSV. The interlayer distance of $(NH_4)_{0.3}V_2O_5$ was about $10.7{\AA}$, and that of $V_2O_5$ synthesized by using formic acid was $14.2{\AA}$. The surface morphology of $(NH_4)_{0.3}V_2O_5$ and $V_2O_5$ showed features that looked like nanorods and nanosheets, respectively. Specific capacity of $(NH_4)_{0.3}V_2O_5$ nanorods prepared at $95^{\circ}C$ was at least 280 mAh/g at 10 mA/g discharge rate.

• Journal of the Korean Electrochemical Society
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• v.5 no.1
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• pp.1-6
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• 2002

Silver doped vanadium pentoxides with a doping ratio Ag/V ranging from 0.03 to 0.11 were synthesized by sol-gel process, and $Li/Ag_xV_2O_5$ cell was investigated by the electrochemical methods. It appears to be amorphous layered material and entangled fibrous textures has been grown to form anisotropic corrugated fibrils. NMR measurements revealed that several different kinds of $Li^+$ ions exist in the lithium intercalated xerogel electrodes and the average cell potential was about 3.0V vs. $Li/Li^+$. The cell capacity of the silver doped $Ag_xV_2O_5$ xerogel cathodes was more than 359 mAh/g at discharge current 10mA/g and cycle efficiency $94\%$ was achieved.

• Applied Chemistry for Engineering
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• v.16 no.1
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• pp.107-111
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• 2005

We have performed a study on the electrochemical characteristics and nuclear ($^7Li$) magnetic resonance of $V_2O_5$ xerogels that have been synthesized by the sol-gel reaction of $V_2O_5$ powder with hydrogen peroxide. NMR measurements revealed that chemical shift of $Li^+$ ions varied as lithium ions were inserted into $V_2O_5$ xerogel and that several different sites for $Li^+$ ions existed in the $V_2O_5$ xerogel structure. The electrochemical properties of the xerogel electrodes did not depend much upon the concentration of $V_2O_5$ and HCl that were used for the synthesis of $V_2O_5$ gels. The specific capacity of $V_2O_5$ xerogels were about 140 mAh/g, similar to that of the xerogels prepared by the ion exchange method.

• Bulletin of the Korean Chemical Society
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• v.28 no.12
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• pp.2226-2230
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• 2007

As a cathode material of lithium rechargeable batteries, charged Li[Co0.1Ni0.15Li0.2Mn0.55]O2 electrodes, which were aged thermally at 25 oC and 90 oC respectively, were characterized by means of charge/discharger, impedance spectroscopy, and X-ray diffraction. The discharge capacity diminution of the electrodes aged at 25 oC and 90 oC for 1 week was 4% and 23%, respectively. The cell aged at 25 oC was recovered on cycling. However, the capacity loss after ageing at 90 oC was not recovered in a subsequent cycling test, which demonstrates that the reaction occurring during ageing at 90 oC is irreversible. A significant impedance increase of aged electrode at 90 oC is associated with irreversible capacity loss. The structural changes including phase transformation were not detected by XRD analysis, because it could be due to out of detection limit. After ageing, impedance was slightly decreased during subsequent cycling test. It could be explained the cyclic performance of aged sample is stable. The thermal stability was not deteriorated by ageing even at the high temperature of 90 oC.