• Title/Summary/Keyword: Spinel cathode

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Preparation and Characterization of $Li_4Ti_5O_{12}$ using Sol-Gel Method for Lithium Secondary Battery (Sol-Gel 방법을 이용한 리튬이차전지용 $Li_4Ti_5O_{12}$의 제조 및 특성)

  • Oh, Mi-Hyun;Kim, Han-Joo;Kim, Gyu-Sik;Kim, Young-Jae;Son, Won-Keun;Lim, Kee-Joe;Park, Soo-Gil
    • Proceedings of the KIEE Conference
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    • 2005.07c
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    • pp.1989-1991
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    • 2005
  • Lithium titanium oxide as anode material for energy storage prepared by novel synthesis method. $Li_4Ti_5O_{12}$ based spinel-framework structures are of great interest material for lithium-ion batteries. We describe here $Li_4Ti_5O_{12}$ a zero-strain insertion material was prepared by novel sol-gel method and by high energy ball milling (HEBM) of precursor to from nanocrystalline phases. According to the X-ray diffraction and scanning electron microscopy analysis, uniformly distributed $Li_4Ti_5O_{12}$ particles with grain sizes of 100nm were synthesized. Lithium cells, consisting of $Li_4Ti_5O_{12}$ anode and lithium cathode showed the 173 mAh/g in the range of $1.0{\sim}3.0V$. Furthermore, the crystalline structure of $Li_4Ti_5O_{12}$ didn't transfer during the lithium intercalation and deintercalation process.

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Properties of charge/discharge in synthesis method or substituting transition element for Li-Mn Oxide (전이금속 치환 및 합성방법에 따른 Li-Mn 산화물의 충방전 특성)

  • Jee, Mi-Jung;Choi, Byung-Hyun;Lee, Dae-Jin
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2007.06a
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    • pp.46-46
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    • 2007
  • There has been rapid progress in the portable electronics industry. which has led to a great increase for a demand of portable, lightweight power sources. Lithium 2'nd batteries have met these demand. and many studies on the cahtod materials for the lithium 2,nd batteries have been reported during the last decade. Possible candidates for the cathode materials for lithium 2,nd batteries are $LiCoO_2$, $LiNiO_2$, and $LiMn_2O_4$. Currently $LiCoO_2$ is widely used. but $LiMn_2O_4$ is an excellent alternative material in view of its several advantages such a low cost as well as the wasy availability of raw materials and environmental benignity. In this study, find the most suitable synthesis method that satisfied high capacitor and stability cycle character, etc in Li-Mn oxide for 2'nd batteries. And also made an experiment on doping the $LiMn_2O_4$ spinel with a small amount of metal ions has a remarkable effect on the electrochemical properties and characterics of powder, BET, PSA, Porosity, etc.

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Substitution of Fe-oxide for capacity improvement of $LiMn_2O_4$ cathode material ($LiMn_2O_4$ 양극 물질의 용량 특성 향상을 위한 Fe산화물 치환)

  • Lee, Dae-Jin;Jee, Mi-Jung;Choi, Byung-Hyun;Wai, Yin-Loo;Bae, Hyeon
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2007.11a
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    • pp.293-293
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    • 2007
  • 현재 활발하게 진행되고 있는 이차전지 양극 물질 중 저렴한 가격과 친환경성으로 각광받고 있는 $LiMn_2O_4$ spinel 산화물은 여러 장점에도 불구하고 용량 값이 기존 알려져 있던 Co-계 산화물에 비해 떨어지고 cycle 특성 역시 현저하게 이어진다. 이는 Mn이 전해액과의 반응에 있어 구조적인 안정성을 지니지 못하여 용출되어 나타나는 특성이다. 이번 연구에서는 Mn의 용출을 저지하고 용량의 향상을 이룰 수 있는 전이금속 중 Fe산화물을 치환하여 구조적 안정성을 갖도록 하였다. Fe산화물 치환을 통해 기본적 물성의 변화와 전기적 특성 변화를 측정하였고 공정에서의 온도 및 입도에 따른 영향도 확인하였다. Fe산화물은 Mn 자리의 3+와 4+의 자리에 치환되어 용량을 증대시키고 사이클 특성을 10회 기준으로 20%가량 향상시키는 효과를 가져왔다.

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Study on LiFePO4 Composite Cathode Materials to Enhance Thermal Stability of Hybrid Capacitor (하이브리드 커패시터의 열안정성 개선을 위한 LiFePO4 복합양극 소재에 관한 연구)

  • Kwon, Tae-Soon;Park, Ji-Hyun;Kang, Seok-Won;Jeong, Rag-Gyo;Han, Sang-Jin
    • Korean Chemical Engineering Research
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    • v.55 no.2
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    • pp.242-246
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    • 2017
  • The application of composite cathode materials including $LiFePO_4$ (lithium iron phosphate) of olivine crystal structure, which has high thermal stability, were investigated as alternatives for hybrid battery-capacitors with a $LiMn_2O_4$ (spinel crystal structure) cathode, which exhibits decreased performance at high temperatures due to Mn-dissolution. However, these composite cathode materials have been shown to have a reduction in capacity by conducting life cycle experiments in which a $LiFePO_4$/activated carbon cell was charged and discharged between 1.0 V and 2.3 V at two temperatures, $25^{\circ}C$ and $60^{\circ}C$, which caused a degradation of the anode due to the lowered voltage in the anode. To avoid the degradation of the anode, composite cathodes of $LiFePO_4/LiMn_2O_4$ (50:50 wt%), $LiFePO_4$/activated carbon (50:50 wt%) and $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ (50:50 wt%) were prepared and the life cycle experiments were conducted on these cells. The composite cathode including $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ of layered crystal structure showed stable voltage behavior. The discharge capacity retention ratio of $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ was about twice as high as that of a $LiFePO_4/LiMn_2O_4$ cell at thermal stability experiment for a duration of 1,000 hours charged at 2.3 V and a temperature of $80^{\circ}C$.

Synthesis and Electrochemical Performance of Mesoporous Hollow Sphere Shape LiMn2O4 using Silica Template (실리카 템플레이트를 이용하여 다공성 중공형태를 갖는 LiMn2O4 합성 및 전기화학적 특성 연구)

  • Ryu, Seong-Hyeon;Ryu, Kwang-Sun
    • Journal of the Korean Electrochemical Society
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    • v.14 no.3
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    • pp.184-190
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    • 2011
  • $LiMn_2O_4$ with mesoporous hollow sphere shape was synthesized by precipitation method with silica template. The synthesized $LiMn_2O_4$ has nanosized first particle and mesoporous hollow sphere shape. Silica template was removed by chemical etching method using NaOH solution. When the concentration of NaOH solution was increased, first particle size of manganese oxide was decrease and confirmed mesoporous hollow shpere shape. X-ray diffraction(XRD) patterns revealed that the synthesized samples has spinel structure with Fd3m space group. In case the ratio of silica and maganese salt increased, the size of first particles was decreased. The tetragoanal $LiMn_2O_4$ with micron size was synthesized at ratio of silica and manganese salt over 1 : 9. The prepared samples were assembled as cathode materials of Li-ion battery with 2032 type coin cell and their electrochemical properties are examined by charge-discharge and cyclic performance. Electrochemical measurements show that the nano-size particles had lower capacity than micron-size particles. But, cyclic performance of nano-size particles had better than that of micron-size particles.

Adipic Acid Assisted Sol-Gel Synthesis of Li1+x(Mn0.4Ni0.4Fe0.2)1-xO2 (0 < x < 0.3) as Cathode Materials for Lithium Ion Batteries

  • Karthikeyan, Kaliyappan;Amaresh, Samuthirapandian;Son, Ju-Nam;Kim, Shin-Ho;Kim, Min-Chul;Kim, Kwang-Jin;Lee, Sol-Nip;Lee, Yun-Sung
    • Bulletin of the Korean Chemical Society
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    • v.34 no.1
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    • pp.89-94
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    • 2013
  • Layered $Li_{1+x}(Mn_{0.4}Ni_{0.4}Fe_{0.2})_{1-x}O_2$ (0 < x < 0.3) solid solutions were synthesized using solgel method with adipic acid as chelating agent. Structural and electrochemical properties of the prepared powders were examined by means of X-ray diffraction, Scanning electron microscopy and galvanostatic charge/discharge cycling. All powders had a phase-pure layered structure with $R\bar{3}m$ space group. The morphological studies confirmed that the size of the particles increased at higher x content. The charge-discharge profiles of the solid solution against lithium using 1 M $LiPF_6$ in EC/DMC as electrolyte revealed that the discharge capacity increases with increasing lithium content at the 3a sites. Among the cells, $Li_{1.2}(Mn_{0.32}Ni_{0.32}Fe_{0.16})O_2$ (x = 0.2)/$Li^+$ exhibits a good electrochemical property with maximum initial capacity of 160 $mAhg^{-1}$ between 2-4.5 V at 0.1 $mAcm^{-2}$ current density and the capacity retention after 25 cycles was 92%. Whereas, the cell fabricated with x = 0.3 sample showed continuous capacity fading due to the formation of spinel like structure during the subsequent cycling. The preparation of solid solutions based on $LiNiO_2-LiFeO_2-Li_2MnO_3$ has improved the properties of its end members.

The Influence of Impurities in Room Temperature Ionic Liquid Electrolyte for Lithium Ion Batteries Containing High Potential Cathode (고전압 리튬이차전지를 위한 LiNi0.5Mn1.5O4 양극용 전해질로써 상온 이온성 액체 전해질의 불순물 효과에 관한 연구)

  • Kim, Jiyong;Tron, Artur V.;Yim, Taeeun;Mun, Junyoung
    • Journal of the Korean Electrochemical Society
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    • v.18 no.2
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    • pp.51-57
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    • 2015
  • We report the effect of the impurities including water and bromide in the propylmethylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PMPyr-TFSI) on the electrochemical performance of lithium ion batteries. The several kinds of PMPyr-TFSI electrolytes with different amount of impurities are applied as the electrolyte to the cell with the high potential electrode, $LiNi_{0.5}Mn_{1.5}O_4$ spinel. It is found that the impurities in the electrolytes cause the detrimental effect on the cell performance by tracing the cycleability, voltage profile and Coulombic efficiency. Especially, the polarization and Coulombic efficiency go to worse by both impurities of water and bromide, but the cycleability was not highly influenced by bromide impurity unlike the water impurity.

Synthesis and Electrochemical Performance of Reduced Graphene Oxide/AlPO4-coated LiMn1.5Ni0.5O4 for Lithium-ion Batteries

  • Hur, Jaehyun;Kim, Il Tae
    • Bulletin of the Korean Chemical Society
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    • v.35 no.12
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    • pp.3553-3558
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    • 2014
  • The reduced graphene oxide(rGO)/aluminum phosphate($AlPO_4$)-coated $LiMn_{1.5}Ni_{0.5}O_4$ (LMNO) cathode material has been developed by hydroxide precursor method for LMNO and by a facile solution based process for the coating with GO/$AlPO_4$ on the surface of LMNO, followed by annealing process. The amount of $AlPO_4$ has been varied from 0.5 wt % to 1.0 wt %, while the amount of rGO is maintained at 1.0 wt %. The samples have been characterized by X-ray diffraction, scanning electron microscopy, and high-resolution transmission electron microscopy. The rGO/$AlPO_4$-coated LMNO electrodes exhibit better cyclic performance compared to that of pristine LMNO electrode. Specifically, rGO(1%)/$AlPO_4$(0.5%)- and rGO(1%)/$AlPO_4$(1%)-coated electrodes deliver a discharge capacity of, respectively, $123mAhg^{-1}$ and $122mAhg^{-1}$ at C/6 rate, with a capacity retention of, respectively, 96% and 98% at 100 cycles. Furthermore, the surface-modified LMNO electrodes demonstrate higher-rate capability. The rGO(1%)/$AlPO_4$(0.5%)-coated LMNO electrode shows the highest rate performance demonstrating a capacity retention of 91% at 10 C rate. The enhanced electrochemical performance can be attributed to (1) the suppression of the direct contact of electrode surface with the electrolyte, resulting in side reactions with the electrolyte due to the high cut-off voltage, and (2) smaller surface resistance and charge transfer resistance, which is confirmed by total polarization resistance and electrochemical impedance spectroscopy.

Synthesis and electrochemical properties of layered $Li[Ni_xCo_{1-2x}Mn_x]O_2$ materials for lithium secondary batteries prepared by mechanical alloying (기계적 합금법을 이용한 리튬 2차 전지용 층상 양극물질 $Li[Ni_xCo_{1-2x}Mn_x]O_2$ 의 합성 및 전기화학적 특성에 관한 연구)

  • 박상호;신선식;선양국
    • Proceedings of the Korea Crystallographic Association Conference
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    • 2002.11a
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    • pp.16-16
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    • 2002
  • The presently commercialized lithium-ion batteries use layer structured LiCoO₂ cathodes. Because of the high cost and toxicity of cobalt, an intensive search for new cathode materials has been underway in recent years. Recently, a concept of a one-to-one solid state mixture of LiNO₂ and LiMnO₂, i.e., Li[Ni/sub 0.5/Mn/sub 0.5/]O₂, was adopted by Ohzuku and Makimura to overcome the disadvantage of LiNiO₂ and LiMnO₂. Li[Ni/sub 0.5/Mn/sub 0.5/]O₂ has the -NaFeO₂ structure, which is characteristic of the layered LiCoO₂ and LiNiO₂ structures and shows excellent cycleability with no indication of spinel formation during electrochemical cycling. Layered Li[Ni/sub x/Co/sub 1-2x/Mn/sub x/]O₂ (x = 0.5 and 0.475) materials with high homogeneity and crystallinity were synthesized using a mechanical alloying method. The Li[Ni/sub 0.475/Co/sub 0.05/Mn/sub 0.475/]O₂ electrode delivers a high discharge capacity of 187 mAh/g between 2.8 and 4.6 V at a high current density of 0.3 mA/㎠(30 mA/g) with excellent cycleability. The charge/discharge and differential capacity vs. voltage studies of the Li[Ni/sub x/Co/sub 1-2x/Mn/sub x/]O₂ (x = 0.5 and 0.475) materials showed only one redox peak up to 50 cycles, which indicates that structural phase transitions are not occurred during electrochemical cycling. The magnitude of the diffusion coefficients of lithium ions for Li[Ni/sub x/Co/sub 1-2x/Mn/sub x/]O₂(x = 0.5 and 0.475) are around 10/sup -9/ ㎠/s measured by the galvanostatic intermittent titration technique (GITT).

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The Studies of Structural Stability of LiNi0.5Mn1.5O4 Spinel (스피넬 LiNi0.5Mn1.5O4 양극 활물질의 구조 안정성 연구)

  • Park, Sung-Bin;Kim, Yool-Koo;Lee, Wan-Gyu;Cho, Won-Il;Jang, Ho
    • Korean Journal of Metals and Materials
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    • v.46 no.3
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    • pp.174-181
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    • 2008
  • The stability of the cathode materials for Li secondary battery is an important factor for its cyclability. The present paper focuses on the structural stability of $LiNi_{0.5}Mn_{1.5}O_4$ during lithiation/delithiation of Li ions and compared to that of $LiMn_{2}O_4$. $LiMn_{2}O_4$ and $LiNi_{0.5}Mn_{1.5}O_4$ powders are synthesized using a solgel method and their structural and electrochemical properties are investigated by XRD, SEM, and charge-discharge tests. $Li_xMn_2O_4$ and $Li_xNi_{0.5}Mn_{1.5}O_4$(x = 0.9,0.5,0.1) specimens are obtained after charge/discharge tests by controlling the cut-off voltage for XRD and TEM investigation. The charge-discharge tests shows that initial capacity of $LiNi_{0.5}Mn_{1.5}O_4$ is 125 mAh/g and that of LiMn2O4 is around 100 mAh/g. The capacity of $LiNi_{0.5}Mn_{1.5}O_4$ is maintained 95% of its initial capacity whereas the capacity of $LiMn_{2}O_4$ is maintained 65% of its initial capacity.