• Title/Summary/Keyword: 리튬 이차전지

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Microstructures and Electrochemical Properties of Si-M (M : Cr, Ni) as Alloy Anode for Li Secondary Batteries (리튬이차전지용 Si-M (M : Cr, Ni) 합금 음극의 미세구조와 전기화학적 특성)

  • Lee, Sung-Hyun;Sung, Jewook;Kim, Sung-Soo
    • Journal of the Korean Electrochemical Society
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    • v.18 no.2
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    • pp.68-74
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    • 2015
  • To compare the microstructure and electrochemical properties between two binary alloys (Cr-Si, Ni-Si), two composition of binary alloys with the same capacity were selected using phase-diagram and prepared by matrix-stabilization method to suppress the volume expansion of Si by inactive-matrix. Master alloys were made by Arc-melting followed by fine structured ribbon sample preparation by Rapid Solidification Process (RSP, Melt-spinning method) under the same conditions. Also powder samples were produced by wet grinding for X-Ray Diffraction (XRD) and electrochemical measurements. As predicted from the phase diagram, only active-Si and inactive-matrix ($CrSi_2$, $NiSi_2$) were detected. The results of Scanning Electron Microscope (SEM) and Transmission Electron Microscopy - Energy Dispersive X-ray Spectroscopy (TEM-EDS) show that Cr-Si alloy has finer microstructure than Ni-Si alloy, which was also predictable through phase diagram. The electrochemical properties related to microstructure were evaluated by coin type full- and half-cells. Separately, self-designed test-cells were used to measure the volume expansion of Si during reaction. Volume expansion of Cr-Si alloy electrode with finer microstructure was suppressed significantly and improved in cycle capability, in comparison Ni-Si alloy with coarse microstructure. From these, we could infer the correlation of microstructure, volume expansion and electrochemical degradation and these properties might be predicted by phase diagram.

Effect of Annealing Temperature on the Anode Properties of TiO2 Nanotubes for Rechargeable Lithium Batteries (열처리 온도에 따른 TiO2 나노튜브의 리튬이차전지 음전극 특성)

  • Choi, Min Gyu;Kang, Kun Young;Lee, Young-Gi;Kim, Kwang Man
    • Korean Chemical Engineering Research
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    • v.50 no.1
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    • pp.25-29
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    • 2012
  • $TiO_2$ nanotubes are prepared from rutile prticles via an alkaline hydrothermal synthesis and the consequent heat treatment at $300{\sim}500^{\circ}C$. The physical and electrochemical properties of the $TiO_2$ nanotubes are characterized for use as a anode material of rechargeable lithium battery. In particular, the microscale dusts as an impurity component occurred in the purification step after the hydrothermal reaction are completely removed to yield $TiO_2$ nanotube with a higher specific surface area and more obvious crystalline phases. As the annealing temperature increases, the specific surface area is slightly decreased due to some aggregation between the isotropically dispersed nanotubes. Highest initial discharge capacity of 250 mAh $g^{-1}$ is achieved for the $TiO_2$ nanotube annealed at $300^{\circ}C$, whereas the $400^{\circ}C$ $TiO_2$ nanotube shows the superior cycle performance and high-rate capability.

Investigation of Oxidation Methods of Organic Radical Polymer for Cathode Material in Lithium Ion Batteries (리튬이차전지 양극재인 유기라디칼 고분자의 산화법에 대한 연구)

  • Lee, Ilbok;Kim, Younghoon;Moon, Ji-Yeon;Lee, Chul Wee;Kim, Daeun;Ha, Kyoung-Su;Lee, Dong Hyun;Son, Hyungbin;Yoon, Songhun
    • Polymer(Korea)
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    • v.38 no.6
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    • pp.827-831
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    • 2014
  • An organic radical polymer (ORP) was prepared by radical polymerization and following oxidation into nitroxyl radical. Two different oxidation methods were employed and their radical concentrations were measured using electroparamagnetic resonance spectroscopy (EPR) and UV-visible absorption (UV-vis) spectroscopy. From these measurements, $H_2O_2-Na_2WO_4$ oxidation method exhibited a complete oxidation, which resulted in 97.6% spin concentration. Also, it was revealed that convenient and cheap UV-vis measurement was useful for preliminary radical concentration comparison. After applied as a cathode material in lithium ion batteries, ORP electrode showed a high initial capacity ($110mAh\;g^{-1}$), a good initial efficiency (96%), a very high rate performance (70% charging during 1.2 min) and stable cycle performance.

The Influence of Oxygen Gas Flow Rate on Growth of Tin Dioxide Nanostructures (이산화주석 나노구조물의 성장에서 산소가스 유량이 미치는 영향)

  • Kim, Jong-Il;Kim, Ki-Chul
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.19 no.10
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    • pp.1-7
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    • 2018
  • Tin dioxide, $SnO_2$, is applied as an anode material in Li-ion batteries and a gas sensing materials, which shows changes in resistance in the presence of gas molecules, such as $H_2$, NO, $NO_2$ etc. Considerable research has been done on the synthesis of $SnO_2$ nanostructures. Nanomaterials exhibit a high surface to volume ratio, which means it has an advantage in sensing gas molecules and improving the specific capacity of Li-ion batteries. In this study, $SnO_2$ nanostructures were grown on a Si substrate using a thermal CVD process with the vapor transport method. The carrier gas was mixed with high purity Ar gas and oxygen gas. The crystalline phase of the as-grown tin oxide nanostructures was affected by the oxygen gas flow rate. The crystallographic property of the as-grown tin oxide nanostructures were investigated by Raman spectroscopy and XRD. The morphology of the as-grown tin oxide nanostructures was confirmed by scanning electron microscopy. As a result, the $SnO_2$ nanostructures were grown directly on Si wafers with moderate thickness and a nanodot surface morphology for a carrier gas mixture ratio of Ar gas 1000 SCCM : $O_2$ gas 10 SCCM.

Electrochemical Characteristics of the Silicon Thin Films on Copper Foil Prepared by PECVD for the Negative Electrodes for Lithium ion Rechargeable Battery (PECVD법으로 구리 막 위에 증착된 실리콘 박막의 이차전지 음전극으로서의 전기화학적 특성)

  • Shim Heung-Taek;Jeon Bup-Ju;Byun Dongjin;Lee Joong Kee
    • Journal of the Korean Electrochemical Society
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    • v.7 no.4
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    • pp.173-178
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    • 2004
  • Silicon thin film were synthesized from silane and argon gas mixture directly on copper foil by rf PECVD and then lithium ion batteries were prepared from them employed as the negative electrodes without any further treatment. In the present study, two different kinds of silicon thin films, amorphous silicon and copper silicide were prepared by changing deposition temperature. Amorphous silicon film was prepared below $200^{\circ}C$, but copper silicide film with granular shape was formed by the reaction between silicon radical and diffused copper ions under elevating temperature above $400^{\circ}C$. The amorphous silicon film gives higher capacity than copper silicide, but the capacity decreases sharply with charge-discharge cycling. This is possibly due to severe volume changes. The cyclability is improved, however, by employing the copper silicide as a negative electrode. The copper silicide plays an important role as an active material of the electrode, which mitigates volume change cause by the existence of silicon and copper chemical bonding and provides low electrical resistance as well.

Enhanced Cycle Performance of Bi-layer Structured LMO-NCM Positive Electrode at Elevated Temperature (겹층구조의 LMO-NCM 복합양극을 통한 고온 사이클 수명개선 연구)

  • Yoo, Seong Tae;Ryu, Ji Heon
    • Journal of the Korean Electrochemical Society
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    • v.25 no.4
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    • pp.184-190
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    • 2022
  • Spinel LiMn2O4 (LMO) and layered LiNi0.5Co0.2Mn0.3O2 (NCM) are widely used as positive electrode materials for lithium-ion batteries. LMO and NCM positive electrode materials have a complementary properties. LMO has low cost and high safety and NCM materials show a relatively high specific capacity and better cycle life even at elevated temperature. Therefore, the LMO and NCM active materials are blended and used as a positive electrode in large-size batteries for electric vehicles (xEV). In this study, the cycle performance of a blended electrode prepared by simply mixing LMO and NCM and a bi-layer electrode in which two electrode layers aree sequentially coated are compared. The bi-layer electrode prepared by composing the same ratio of both active materials has similar capacity and cycle performance to the blend electrode. However, the LN electrode coated with LMO first and then NCM is the best in the full cell cycle performance at elevated temperature, and the NL electrode, in which NCM is first coated with LMO has a faster capacity degradation than the blended electrode because LMO is mainly located on the top of the electrode adjacent to electrolyte and graphite negative electrode. Also, the LSTA (linear sweep thermmametry) analysis results show that the LN bi-layer electrode in which the LMO is located inside the electrode has good thermal stability.

Electrochemical Characteristics of Transition Metal Pyrophosphate as Negative Electrode Materials through Solid-state Reaction (고상법으로 합성된 리튬이온 이차전지용 음극물질로서 전이금속 피로인산화물의 전기화학적 특성)

  • Hong, Min Young;An, Sang-Jo;Ryu, Ji Heon
    • Journal of the Korean Electrochemical Society
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    • v.23 no.4
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    • pp.105-112
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    • 2020
  • Transition metal oxide, which undergoes a conversion reaction in the negative electrode material for a lithium-ion batteries, has a high specific capacity, but still has several critical problems. In this study, manganese pyrophosphate (Mn2P2O7), nickel pyrophosphate (Ni2P2O7), and carbon composite materials with pyrophosphates as novel negative electrode materials instead of transition metal oxide, are synthesized through simple solid-state reaction. The initial reversible capacity of Mn2P2O7 and Ni2P2O7 are 333 and 340 mAh g-1, and when the composite materials are composed with carbon, the reversible capacity increases to 433 and 387 mAh g-1, respectively. The initial Coulombic efficiency is also improved by about 10%. The Mn2P2O7 and carbon composite material has the highest initial capacity and efficiency, and has the best cycle performance. Mn2P2O7 containing polyanion, has a lower specific capacity due to the large mass of polyanion compared to MnO (manganese oxide). However, since Mn2P2O7 shows a voltage curve with a slope, the charging (lithiation) voltage increases from 0.51 to 0.57 V (vs. Li/Li+), and the discharge (delithiation) voltage decreases from 1.15 to 1.01 V (vs. Li/Li+). Therefore, the voltage efficiency of the cell is improved because the voltage difference between charging and discharging is greatly reduced from 0.64 to 0.44 V, and the operating voltage of the full cell increases because the negative electrode potential is lowered during the discharging process.

Electrochemical Performance of Hollow Silicon/Carbon Anode Materials for Lithium Ion Battery (리튬이차전지용 Hollow Silicon/Carbon 음극소재의 전기화학적 성능)

  • Jung, Min Ji;Lee, Jong Dae
    • Applied Chemistry for Engineering
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    • v.27 no.4
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    • pp.444-448
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    • 2016
  • Hollow silicon/carbon (H-Si/C) composites as anode materials for lithium ion batteries were investigated to overcome the large volume expansion. H-Si/C composites were prepared as follows; hollow $SiO_2\;(H-SiO_2)$ was prepared by adding $NaBH_4$ to $SiO_2$ synthesized using $st{\ddot{o}}ber$ method followed by magnesiothermic reduction and carbonization of phenolic resin. The H-Si/C composites were analyzed by XRD, SEM, BET and EDX. To improve the capacity and cycle performance, the electrochemical characteristics of H-Si/C composites synthesized with various $NaBH_4$ contents were investigated by charge/discharge, cycle, cyclic voltammetry and impedance tests. The coin cell using H-Si/C composite ($SiO_2:NaBH_4=1:1$ in weight) in the electrolyte of $LiPF_6$ dissolved in organic solvents (EC : DMC : EMC = 1 : 1 : 1 vol%) has better capacity (1459 mAh/g) than those of other composition coin cells. It is found that the coin cell ($SiO_2:NaBH_4=1:1$ in weight) has an excellent capacity retention from 2nd cycle to 40th cycle.

Characteristics of Copper Vanadium Oxide$(Cu_{0.5}V_2O_5)$ Cathode for Thin Film Microbattery (구리-바나듐 산화물 박막의 양극 특성 및 전 고상 전지의 제작)

  • Lim Y. C.;Nam S. C.;Park H. Y.;Yoon Y. S.;Cho W. I.;CHo B. W.;Chun H. S.;Yun K. S.
    • Journal of the Korean Electrochemical Society
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    • v.3 no.4
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    • pp.219-223
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    • 2000
  • All-solid state lithium rechargeable thin film batteries were fabricated with the configuration of$Cu_{0.5}V_2O_5/Lipon/Li$ using sequential thin film techniques. Copper vanadium oxide thin films and Lipon thin films were prepared by DC reactive dual source magnetron sputtering and RF magnetron sputtering, respectively. According to XRD analysis, we found out that copper vanadium oxide thin films were amorphous. The electrochemical behaviour of them was examined in half cell system using EC : DMC(1:1 in IM $LiPF_5$) liquid electrolyte. The ionic conductivity of Lipon thin film was $1.02\times10^{-6}S/cm$ at $25^{\circ}C$ and $Cu_{0.5}V_2O_5/Lipon/Li$ cell showed that the discharge capacity was about $50{\mu}Ah/cm^2{\mu}m$ beyond 500cyc1es.

Recovery of Rare Metals from the Waste Secondary Lithium Ion Battery Cathode Active Materials Using Lactic Acid and Oxalic acid (젖산과 옥살산을 이용한 폐 이차 리튬이온 전지 양극 활물질로부터 희유금속들의 회수)

  • Kim, Younjung;Han, Ji Sun;Choi, Sik Young;Oh, In-Gyung;Hong, Yong Pyo;Ryoo, Keon Sang
    • Journal of the Korean Chemical Society
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    • v.63 no.6
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    • pp.446-452
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    • 2019
  • We have developed a method that can leach Co, Mn, and Ni in the cathode active material safely using lactic acid. When cathode active material was leached by lactic acid, lactic acid showed the highest efficiency at 2 N than 1 N and above 4 N concentration. When the cathode active material was added incrementally into the solution of lactic acid, the maximum solubility was 30 g/L at 2 N concentration. Oxalic acid was added in the solution of lactic acid and it showed that rare metals represent the most economical recovery efficiency at 4 g/L. Based on this study, it was found that the optimal condition for recovery of rare metals from cathode active material is oxalic acid : cathode active material = 7 : 1 as a ratio of weight. In addition, it was observed that the precipitate produced by oxalic acid is a polynuclear crystalline material bonded with 3 components of Co, Ni, and Mn.