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Electrochemical Properties of Cu Current Collector with Li0.5La0.5TiO3 or Si Thin Film as a Li Free Anode (Li0.5La0.5TiO3와 Si박막을 갖는 구리 집전체의 Li free 음극으로써의 전기화학적 특성)

  • Lee Jae-Jun;Kim Soo-Ho;Lee Jong-Min;Yoon Young-Soo
    • Journal of the Korean Electrochemical Society
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    • v.9 no.1
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    • pp.34-39
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    • 2006
  • Electrochemical properties of Cu foil current collector with a $Li_{0.5}La_{0.5}TiO_3$ Cu a Si thin film deposited by r.f sputtering as an anode for Li free battery were evaluated. The Cu foil current collectors were lied in and out of plasma during sputtering process. The X-ray diffraction results indicated that the as-deposited Si and $Li_{0.5}La_{0.5}TiO_3$ thin films in and out of plasma did not show any crystalline difference. The $Li_{0.5}La_{0.5}TiO_3$ film in plasma and Si film out of plasma showed better cyclability since crystalline $Li_{0.5}La_{0.5}TiO_3$ has much higher ionic conductivity and crystalline Si film is much sensitive far volume change during charge-discharge process. These results suggested that the deposition of amorphous Si on Cu foil current collector is much better for fabrication of Li free battery and it can be useful for the unique battery with a cycling number constraint of below 10.

An NMR Study on Complexation of Ortho-Xylyl-17-Crown-5 with $^{7}Li\;and\;^{23}Na$ Ions in Acetonitrile

  • 윤신영;안상두;이조웅
    • Bulletin of the Korean Chemical Society
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    • v.16 no.3
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    • pp.265-269
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    • 1995
  • Complexation of ortho-xylyl-17-crown-5 (X17C5) with alkali metal ions in acetonitrile was studied by 7Li and 23Na NMR spectroscopy. The complex formation constants of X17C5 with LiI, LiSCN, NaI, and NaSCN were determined by investigating the changes in the chemical shifts as a function of the concentration ratio of X17C5 to metal ion. It was found that X17C5 forms 1:1 complex with Li+ and Na+ ions and the log Kf's for the complexation with LiI, LiSCN, NaI, and NaSCN were determined to be 2.88, 2.43, 2.53, and 2.30, respectively. In particular, the kinetics of complexation of X17C5 with Na+ was investigated by the method of 23Na NMR lineshape analysis. Activation energies were determined from Arrhenius plot of the resultant rate constant data to be 25.4 kJ/mol for NaI and 15.1 kJ/mol for NaSCN. Other kinetic parameters were also calculated by employing the Eyring equation. The decomplexation rates measured were 1.82 × 104 M-1s-1 for NaI and 1.50 × 104 M-1s-1 for NaSCN. It is concluded that the decomplexation mechanism is predominantly a bimolecular cation exchange for both cases.

Electrochemical Properties of LiNiO$_2$/Li cell (LiNiO$_2$/Li cell의 전기화학적 특성)

  • 전대규;김철중;성창호;구할본
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 1997.11a
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    • pp.279-282
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    • 1997
  • The propose of this study is research and improvement of LiNiO$_2$as cathode material for Lithium secondary batteries. LiNiO$_2$is prepared by heating LiOH . $H_2O$ and Ni(OH)$_2$(mole ratio 1 : 1) on various heat condition. In the result of XRD mesurement, all LiNiO$_2$prepared at this study showed hexagonal structure. In Cyclic Voltammetry, LiNiO$_2$is not conspicous about oxidation peak but oxidation curve change steeply over 3.8V and reduction peak discover at 3.6V. In discharge capacities, specific capacity is higher $O_2$than air when preliminary heated and 75$0^{\circ}C$ than $700^{\circ}C$, 80$0^{\circ}C$ when heated. Therefore, when preliminary heat at $650^{\circ}C$ $O_2$and heat at 75$0^{\circ}C$ carried out, discharge property is the best.

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Influence of Ga Content on the Ionic Conductivity of Li1+XGaXTi2-X(PO4)3 Solid-State Electrolyte Synthesized by the Sol-Gel Method

  • Seong-Jin Cho;Jeong-Hwan Song
    • Korean Journal of Materials Research
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    • v.34 no.4
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    • pp.185-193
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    • 2024
  • In this study, NASICON-type Li1+XGaXTi2-X(PO4)3 (x = 0.1, 0.3 and 0.4) solid-state electrolytes for all-solid-state batteries were synthesized through the sol-gel method. In addition, the influence on the ion conductivity of solid-state electrolytes when partially substituted for Ti4+ (0.61Å) site to Ga3+ (0.62Å) of trivalent cations was investigated. The obtained precursor was heat treated at 450 ℃, and a single crystalline phase of Li1+XGaXTi2-X(PO4)3 systems was obtained at a calcination temperature above 650 ℃. Additionally, the calcinated powders were pelletized and sintered at temperatures from 800 ℃ to 1,000 ℃ at 100 ℃ intervals. The synthesized powder and sintered bodies of Li1+XGaXTi2-X(PO4)3 were characterized using TG-DTA, XRD, XPS and FE-SEM. The ionic conduction properties as solid-state electrolytes were investigated by AC impedance. As a result, Li1+XGaXTi2-X(PO4)3 was successfully produced in all cases. However, a GaPO4 impurity was formed due to the high sintering temperatures and high Ga content. The crystallinity of Li1+XGaXTi2-X(PO4)3 increased with the sintering temperature as evidenced by FE-SEM observations, which demonstrated that the edges of the larger cube-shaped grains become sharper with increases in the sintering temperature. In samples with high sintering temperatures at 1,000 ℃ and high Ga content above 0.3, coarsening of grains occurred. This resulted in the formation of many grain boundaries, leading to low sinterability. These two factors, the impurity and grain boundary, have an enormous impact on the properties of Li1+XGaXTi2-X(PO4)3. The Li1.3Ga0.3Ti1.7(PO4)3 pellet sintered at 900 ℃ was denser than those sintered at other conditions, showing the highest total ion conductivity of 7.66 × 10-5 S/cm at room temperature. The total activation energy of Li-ion transport for the Li1.3Ga0.3Ti1.7(PO4)3 solid-state electrolyte was estimated to be as low as 0.36 eV. Although the Li1+XGaXTi2-X(PO4)3 sintered at 1,000 ℃ had a relatively high apparent density, it had less total ionic conductivity due to an increase in the grain-boundary resistance with coarse grains.

A Study on the Phase Change of Cubic Bi1.5Zn1.0Nb1.5O7(c-BZN) and the Corresponding Change in Dielectric Properties According to the Addition of Li2CO3 (Li2CO3 첨가에 따른 입방정 Bi1.5Zn1.0Nb1.5O7(c-BZN)의 상 변화 및 그에 따른 유전특성 변화 연구)

  • Yuseon Lee;Yunseok Kim;Seulwon Choi;Seongmin Han;Kyoungho Lee
    • Journal of the Microelectronics and Packaging Society
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    • v.30 no.4
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    • pp.79-85
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    • 2023
  • A novel low-temperature co-fired ceramic (LTCC) dielectric, composed of (1-4x)Bi1.5Zn1.0Nb1.5O7-3xBi2Zn2/3Nb4/3O7-2xLiZnNbO4 (x=0.03-0.21), was synthesized through reactive liquid phase sintering of Bi1.5Zn1.0Nb1.5O7-xLi2CO3 ceramic at temperatures ranging from 850℃ to 920℃ for 4 hours. During sintering, Li2CO3 reacted with Bi1.5Zn1.0Nb1.5O7, resulting in the formation of Bi2Zn2/3Nb4/3O7, and LiZnNbO4. The resulting sintered body exhibited a relative sintering density exceeding 96% of the theoretical density. By altering the initial Li2CO3 content (x) and consequently modulating the volume fraction of Bi1.5Zn1.0Nb1.5O7, Bi2Zn2/3Nb4/3O7, and LiZnNbO4 in the final sintered body, a sample with high dielectric constant (εr), low dielectric loss (tan δ), and the temperature coefficient of dielectric constant (TCε) characterized by NP0 specification (TCε ≤ ±30 ppm/℃) was achieved. As the Li2CO3 content increased from x=0.03 mol to x=0.15 mol, the volume fraction of Bi2Zn2/3Nb4/3O7 and LiZnNbO4 in the composite increased, while the volume fraction of Bi1.5Zn1.0Nb1.5O7 decreased. Consequently, the dielectric constant (εr) of the composite materials varied from 148.38 to 126.99, the dielectric loss (tan δ) shifted from 5.29×10-4 to 3.31×10-4, and the temperature coefficient of dielectric constant (TCε) transitioned from -340.35 ppm/℃ to 299.67 ppm/℃. A dielectric exhibiting NP0 characteristics was achieved at x=0.09 for Li2CO3, with a dielectric constant (εr) of 143.06, a dielectric loss (tan δ) value of 4.31×10-4, and a temperature coefficient of dielectric constant (TCε) value of -9.98 ppm/℃. Chemical compatibility experiment with Ag electrode revealed that the developed composite material exhibited no reactivity with the Ag electrode during the co-firing process.

Reaction Behavior of Li4+xTi5O12 Anode Material as Depth of Discharge

  • Cho, Woo-Suk;Song, Jun-Ho;Park, Min-Sik;Kim, Jae-Hun;Kim, Jeom-Soo;Kim, Young-Jun
    • Journal of Electrochemical Science and Technology
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    • v.1 no.2
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    • pp.85-91
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    • 2010
  • We have studied the origin of an additional plateau of $Li_{4+x}Ti_5O_{12}$ (LTO) observed at 0.7 V (vs. Li/$Li^+$). Some LTO has to be discharged down to below 1.0 V forming two-stage plateau (1.5 V and 0.7 V) in order to obtain most of capacity while others could achieve the same level of capacity at higher potential (1.0 V vs. Li/$Li^+$) forming one plateau (1.5 V). The particle size effect has been investigated as a possible reason of this. The 0.7 V plateau was gradually elongated with increasing the particle size. The structural variations and kinetic behaviors during discharge were carefully examined by in-situ XRD technique and OCV measurement. According to structural and electrochemical verifications, the kinetic limitation of $Li^+$ insertion is responsible primarily for the two-stage plateau which is related to the particle size of LTO rather than the formation of new intermediate phase during discharge. Herein, we propose a possible reaction model to elucidate this abnormal behavior of LTO below 1.0 V (Li/$Li^+$).

Ex-situ 7Li MAS NMR Study of Olivine Structured Material for Cathode of Lithium Ion Battery

  • Lee, Youngil;An, JiEun;Park, Seul-A;Song, HyeYeong
    • Journal of the Korean Magnetic Resonance Society
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    • v.18 no.2
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    • pp.63-68
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    • 2014
  • $^7Li$ nuclear magnetic resonance (NMR) spectra have been observed for $LiMPO_4$ (M = Fe, Mn) samples, as a promising cathode material of lithium ion battery. Observed $^7Li$ shifts of $LiFe_{1-x}Mn_xPO_4$ (x = 0, 0.6, 0.8, and 1) synthesized with solid-state reaction are compared with calculated $^7Li$ shift ranges based on the supertranferred hyperfine interaction of Li-O-M. Ex situ $^7Li$ NMR study of $LiFe_{0.4}Mn_{0.6}PO_4$ in different cut-off voltage for the first charge process is also performed to understand the relationship between $^7Li$ chemical shift and oxidation state of metals affected by delithiation process. The increment of oxidation state for metals makes to downfield shift of $^7Li$ by influencing the supertranferred hyperfine interaction.

Synthesis and Characteristics of LiCoO2 Powders Prepared by SHS Process (자전연소합성법을 이용한 리튬이차전지용 양극활물질 LiCoO2의 제조 및 특성)

  • ;;;Hayk H. Nersisyan
    • Journal of the Korean Ceramic Society
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    • v.41 no.5
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    • pp.388-394
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    • 2004
  • LiCoO$_2$ as the cathode activity material for lithium secondary battery was prepared from a homogeneously mixed powder of LiNO$_3$/Co by SHS process under argon gas. The characteristics of powder including electrochemical properties were investigated according to various reaction conditions. The reaction temperature/velocity and the size of LiCoO$_2$ were controlled by Li/Co molar ratio and a cooling rate of the specimen, respectively. The maximum discharge capacity was 145 mAh/g on 1.05 Li/Co molar ratio and the relatively stable cycling characteristic with 6.4% of capacity fading was obtained after 10th charging-discharging test.

Crystal Structures and Electrochemical Properties of LiNi1-xMgxO2 (0≤x≤0.1) for Cathode Materials of Secondary Lithium Batteries (리튬 이차전지의 양극 활물질 LiNi1-xMgxO2 (0≤x≤0.1)의 결정구조 및 전기화학적 특성)

  • Kim, Deok-Hyeong;Jeong, Yeon Uk
    • Korean Journal of Metals and Materials
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    • v.48 no.3
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    • pp.262-267
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    • 2010
  • $LiNi_{1-x}Mg_xO_2$(x=0, 0.025, 0.05, 0.075, 0.1) samples were synthesized by the solid-state reaction method. The crystal structure was analyzed by X-ray powder diffraction and Rietveld refinement. $LiNi_{1-x}Mg_xO_2$samples give single phases of hexagonal layered structures with a space group of R-3m. The calculated cation-anion distances and angles from the Rietveld refinement were changed with Mg contents in $LiNi_{1-x}Mg_xO_2$. The thicknesses of $NiO_2$ slabs were increased and the distances between the $NiO_2$ slabs were decreased with the increase in Mg contents in the samples. The electrical conductivities of sintered $LiNi_{1-x}Mg_xO_2$ samples were around $10^{-2}$ S/cm at room temperature. The electrochemical performances of $LiNi_{1-x}Mg_xO_2$were evaluated by coin cell test. Compared to $LiNiO_2$, $LiNi_{0.95}Mg_{0.05}O_2$ exhibited improved high-rate capability and cyclability due to the well-ordered layered structure by doping of Mg ion.

MAS-NMR Studies in Mixed Alkali Silicate Glasses with low Fe2O3 Content (미소량의 Fe2O3를 첨가시킨 혼합 알칼리 Silicate 유리들의 MAS-NMR 연구)

  • Kang, Myoung-Jin;Shim, Moon-Sik
    • Journal of Korean Ophthalmic Optics Society
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    • v.1 no.1
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    • pp.1-14
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    • 1996
  • The mixed alkali silicate glasses doped 0.1 mol% $Fe_2O_3$ are fabricated for studying the effect of transition metal oxides, which is related to the $Li^-$ ion movement in Magic-Angle-Spinning NMR. We have investigated the spin-lattice relaxation times in the room temperature and measured the $^7Li$ MAS-NMR spectrum with temperature. When the $Fe_2O_3$ oxides are added in alkali silicate glasses, the width of spectrum is changed a little but the line shape is hardly varied. For this reason, we can think that the mixed alkali effects are shown sufficiently in the spin-spin relaxation processes. However, it is not mixed alkali effects in this case. The activation energy of $Li^-$ ions are diminished in mixed alkali glasses. From the analysis of $Li^-$ diffusion environment, spin-lattice relaxation time and the nuclear magnetization, it is confirmed that the alkali mixed effects are not shown in $^7Li$ spin-lattice relaxation processes.

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