• Title/Summary/Keyword: Li-air battery cathode

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A Mechanism Study on Formation and Reduction of Residual Li of High Nickel Cathode for Lithium-ion Batteries (층상계 하이니켈 양극재의 잔류 리튬 생성 및 저감 메커니즘 연구)

  • MinWook, Pin;Beom Tak, Na;Tae Eun, Hong;Youngjin, Kim
    • Journal of Industrial Technology
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    • v.42 no.1
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    • pp.7-12
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    • 2022
  • High nickel layered oxide cathodes are gaining increasing attention for lithium-ion batteries due to their higher energy density and lower cost compared to LiCoO2. However, they suffer from the formation of residual lithium on the surface in the form of LiOH and Li2CO3 on exposure to ambient air. The residual lithium causes notorious issues, such as slurry gelation during electrode preparation and gas evolution during cell cycling. In this review, we investigate the residual lithium issues through its impact on cathode slurry instability based on deformed polyvinylidene fluoride (PVdF) as well as its formation and reduction mechanism in terms of inherently off-stoichiometric synthesis of high nickel cathodes. Additionally, new analysis method with anhydrous methanol was introduced to exclude Li+/H+ exchange effect during sample preparation with distilled water. We hope that this review would contribute to encouraging the academic efforts to consider practical aspects and mitigation in global high-energy-density lithium-ion battery manufacturers.

Synthesis of polycrystalline powder of $Li_xNi_{1-y}Co_yO_2$ via the PVA-precursor method : the effect of synthetic variation on the electrochemical property of the lithium ion battery (PVA-전구체법을 적용한 $Li_xNi_{1-y}Co_yO_2$ 다결정성 분말의 합성 : 합성조건에 따른 리튬이온전지의 전기화학적 특성 고찰)

  • Kim Sue Joo;Song Me Young;Kwon Hye Young;Park Seon Hui;Park Dong Gon;Kweon Ho-Jin
    • Journal of the Korean Electrochemical Society
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    • v.2 no.1
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    • pp.5-12
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    • 1999
  • By the PVA-precursor method, polycrystalline powder of $Li_xNi_{1-y}Co_yO_2$, cathode material for lithium battery, was synthesized. Using the powder as the cathode material, lithium ion batteries were fabricated, whose electrochemical properties were measured. The effect of changing synthetic conditions, such as PvA/metal mole ratio, concentration of PVA, degree of polymerization of PVA, pyrolysis condition, and metal stoichiometry, on the battery performance was investigated. Considering the initial performance of the cell, the optimum stoichiometry of the $Li_xNi_{1-y}Co_yO_2$, synthesized by the PVA-precursor method was observed to be x: 1.0 and y=0.26. A minor phase of $Li_2CO_3$, which was generated by the residual carbon in the powder precursor, deteriorated the performance of the cell. In order to eliminate the minor phase, the precursor had to be pyrolyzed under the flow of dry air. Annealing the powder at $500^{\circ}C$ under the flow of dry air also eliminated the minor phase, and the performance of the cell was largely improved by the treatment.

Characteristics of Ni1/3Co1/3Mn1/3(OH)2 Powders Prepared by Co-Precipitation in Air and Nitrogen Atmospheres (공기와 질소 분위기에서 공침법으로 합성된 Ni1/3Co1/3Mn1/3(OH)2 분말의 특성 비교)

  • Choi, Woonghee;Park, Se-Ryen;Kang, Chan Hyoung
    • Journal of Powder Materials
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    • v.23 no.2
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    • pp.136-142
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    • 2016
  • As precursors of cathode materials for lithium ion batteries, $Ni_{1/3}Co_{1/3}Mn_{1/3}(OH)_2$ powders are prepared in a continuously stirred tank reactor via a co-precipitation reaction between aqueous metal sulfates and NaOH in the presence of $NH_4OH$ in air or nitrogen ambient. Calcination of the precursors with $Li_2CO_3$ for 8 h at $1,000^{\circ}C$ in air produces dense spherical cathode materials. The precursors and final powders are characterized by X-ray diffraction (XRD), scanning electron microscopy, particle size analysis, tap density measurement, and thermal gravimetric analysis. The precursor powders obtained in air or nitrogen ambient show XRD patterns identified as $Ni_{1/3}Co_{1/3}Mn_{1/3}(OH)_2$. Regardless of the atmosphere, the final powders exhibit the XRD patterns of $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ (NCM). The precursor powders obtained in air have larger particle size and lower tap density than those obtained in nitrogen ambient. NCM powders show similar tendencies in terms of particle size and tap density. Electrochemical characterization is performed after fabricating a coin cell using NCM as the cathode and Li metal as the anode. The NCM powders from the precursors obtained in air and those from the precursors obtained in nitrogen have similar initial charge/discharge capacities and cycle life. In conclusion, the powders co-precipitated in air can be utilized as precursor materials, replacing those synthesized in the presence of nitrogen injection, which is the usual industrial practice.

Lyophobized Ordered Mesoporous Silica Additives for Li-O2 Battery Cathode

  • Roev, Victor;Ma, Sang Bok;Lee, Dong Joon;Im, Dongmin
    • Journal of Electrochemical Science and Technology
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    • v.5 no.2
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    • pp.58-64
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    • 2014
  • The surface of an ordered mesoporous silica (OMS) was functionalized using 1H,1H,2H,2H-perfluorooctyltrimethoxysilane at $20^{\circ}C$ and $60^{\circ}C$. It was shown that only elevated temperature allows lyophobic properties on the walls of OMS, eventually preventing pore flooding with nonaqueous electrolytes. The functionalized OMSs (OMS-F) were characterized with various techniques: wettability test, $N_2$ sorption measurement, high-resolution transmission electron microscopy (HR-TEM). Cathodes of $10mg/cm^2$ loading were prepared with a commercial Pt/C catalyst and polyvinylidene fluoride (PVDF, 2.5 wt.%) binder using a typical doctor blade method on a commercial gas diffusion layer (GDL) in the presence or in the absence of OMS-F additives. Subsequent discharge-charge curves were taken in a 1M LiTFSI-TEGDME electrolyte at 60oC in pure oxygen atmosphere. It was found that the discharge capacity was significantly affected by OMS-F: 5 wt.% of additive extended discharge capacity by a factor 1.5. On the other hand, a similar OMS material but synthesized at $20^{\circ}C$ did not show lyophobic properties and deteriorated cathode capacity.

Physicochemical Behaviors of Oxygen and Sulfur in Li Batteries (리튬 전지에서 산소, 황의 물리화학적 거동)

  • Park, Dong-Won;Kim, Jin Won;Kim, Jongwon;Lee, Jaeyoung
    • Applied Chemistry for Engineering
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    • v.23 no.3
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    • pp.247-252
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    • 2012
  • Of late, the development of advanced batteries with high power density and capacity has been indispensible for pushing ahead with much wider applications to electric vehicles and smart IT devices. However, a conventional Li-ion battery contains a limited energy density due to various technological challenges such that other types of Li batteries including Li-S and Li-air have been extensively studied due to their interestingly high energy capacities. Sulfur and oxygen, of which both are cathode materials, showing similar physicochemical characteristics have widely been available which may also contribute to the commercialization of these batteries. In this review, we introduce some perspectives in improving these advanced Li batteries through several approaches such as the provision of porous cathode structures, the optimization of cathode-electrolyte interfaces and the modification of Li anodes.

Synthesis of LiMn2O4 Powders Using Li-Ion Secondary Battery by SHS Process (SHS합성법에 의한 리튬이온이차전지용 정극활물질 LiMn2O4 의 제조)

  • Jang, Chang-Hyun;Nersisyan, Hayk;Kim, Jung-Han;Won, Chang-Whan
    • Journal of the Korean Ceramic Society
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    • v.42 no.7 s.278
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    • pp.503-508
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    • 2005
  • A simple and effective method for the synthesis of LiMn$_{2}$O$_{4}$ powder as a cathode material for lithium secondary battery is reported. Micrometer size LiMn$_{2}$O$_{4}$ was prepared by combustion synthesis technique employing initial mixture of l.l LiNO$_{3}$ -1.3Mn-0.7MnO$_{2}$-1NaCl composition. Parametric study of the combustion process including molar ratio of Mn/MnO$_{2}$ and NaCl concentration were carried out under air atmosphere. The combustion products obtained were additionally heat treated at the temperature 900$^{\circ}C$ and the washed by distilled water. The results of charging-discharging characteristics revealed that LiMn$_{2}$O$_{4}$ cell synthesized in the presence of NaCl had a high capacity and much better reversibility than one formed without NaCl An approximate chemical mechanism for LiMn$_{2}$O$_{4}$ formation is proposed.

Electrochemical Properties of Spinel $LiMn_2O_4$ Synthesized at Various Heat Treatment for Lithium lon Battery (리튬 이온 전지용 스피넬 $LiMn_2O_4$의 열처리 온도에 따른 전기 화학적 특성)

  • Han, Tae-Hee;Min, Hyung-Sik;Han, Byoung-Sung
    • The Transactions of the Korean Institute of Electrical Engineers C
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    • v.48 no.3
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    • pp.179-184
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    • 1999
  • In the past ten years, $LiMn_2O_4$-based spinels have been extensively studied as positive electrode materials for lithium-ion batteries. To improve the cycle performance of spinel $LiMn_2O_4$ as the cathode of 4V class lithium secondary batteries, spinel phases $LiMn_2O_4$ were prepared at various temperatures ranging form 600-900$^{\cire}C$ in air. The results showed that charge.dischare capacity of $LiMn_2O_4$ varied at 1st temperature from $200^{\circ}C to 600^{\circ}C$ increase with increasing temperature. $LiMn_2O_4$ synthesized at 2nd temperature $750^{\circ}C$excellent charge.discharge capacity, efficiency and cyclability compared to the samplesynthesized different temperatures. The value of lst charge.discharge capacity was 121mAh/g, 118mAh/g, Also, the efficiency value was about 97%.

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Cathodic Properties of $LiCoO_2$ Synthesized by a Sol-Gel Method for Lithium Ion Battery

  • 조봉준;정의덕;심윤보
    • Bulletin of the Korean Chemical Society
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    • v.19 no.1
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    • pp.39-44
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    • 1998
  • $LiCoO_2$ powder was synthesized in an aqueous solution by a sol-gel method and used as a cathode active material for a lithium ion rechargeable battery. The layered $LiCoO_2$ powders were prepared by igniting in air for 12 hrs at 600 ℃ $(600-LiCoO_2)$ and 850 ℃ $(850-LiCoO_2)$. The structure of the $LiCoO_2$ powder was assigned to the space group R bar 3 m (lattice parameters a=2.814 Å and c=14.04Å). The SEM pictures of $600-LiCoO_2$ revealed homogeneous and fine particles of about 1 μm in diameter. Cyclic voltammograms (CVs) of $600-LiCoO_2$ electrode displayed a set of redox peaks at 3.80/4.05 V due to the intercalation/deintercalation of the lithium ions into/out of the $LiCoO_2$ structure. CVs for the $850-LiCoO_2$ electrode had a major set of redox peaks at 3.88/4.13 V, and two small set of redox peaks at 4.18/4.42 V and 4.05/4.25 V due to phase transitions. The initial charge-discharge capacity was 156-132 mAh/g for the $600-LiCoO_2$ electrode and 158-131 mAh/g for the $850-LiCoO_2$ electrode at the current density of 0.2 mA/cm2. The cycleability of the cell consisting of the $600-LiCoO_2$ electrode was better than that of the $850-LiCoO_2$. The diffusion coefficient of the $Li^+$ ion in the $600-LiCoO_2$ electrode was calculated as $4.6{\times}10^{-8}\; cm^2/sec$.

Electrochemical Properties of Carbon/Manganese Oxide Composite Air Cathode for Lithium-Air Batteries (리튬-공기전지용 탄소/망간산화물 복합구조 공기극의 전기화학적 특성)

  • Lee, Sun-Young;Cha, Eun-Hee;Mho, Sun-Il;Ju, Jeh-Beck;Cho, Won-Il
    • Journal of the Korean Electrochemical Society
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    • v.15 no.3
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    • pp.198-205
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    • 2012
  • Carbon-supported manganese oxide composite were fabricated as an air cathode material for Li-air batteries by hydrothermal method. The composite materials of carbon and manganese oxide were investigated by the implementation of X-ray diffraction, FE-SEM and BET surface area measurer. The manganese oxide synthesized at $170^{\circ}C$ for 12 h has a rod like shape morphology with 40-50 nm long in size. A Lithium-air battery with coin type, of which electrodes are composed of cathode composite materials synthesized $170^{\circ}C$-12 h and lithium metal anode, reveals its first discharge capacity of 3,852 mAh/g and four discharge-charge cycles.

Effect of Calcination Temperatures on the Structure and Electrochemical Characterization of Li(Ni0.5Mn0.3Co0.2)O2 as Cathode Material by Supercritical Hydrothermal Synthesis Method (초임계 수열법으로 합성한 Li(Ni0.5Mn0.3Co0.2)O2 양극 활물질의 소성 온도영향에 따른 구조 및 전기화학적 특성)

  • Choo, Soyeon;Beom, YunGyeong;Kim, Sungsu;Han, Kyooseung
    • Journal of the Korean Electrochemical Society
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    • v.16 no.3
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    • pp.151-156
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    • 2013
  • As the cathode material for li-ion battery, $LiNi_{0.5}Mn_{0.3}Co_{0.2}O_2$ were synthesized by supercritical hydrothermal method and calcined $850^{\circ}C$ and $900^{\circ}C$ for 10hrs in air. The effect of temperature in the heat treatment on the powder and its performance were studied of xray diffraction pattern, SEM-image, physical properties and electrochemical behaviors. As a result, calcined at $900^{\circ}C$ material particle size more increase than calcined at $850^{\circ}C$ material, especially shows excellent electrochemical performance with initial reversible specific capacity of 163.84 mAh/g (0.1C/2.0-4.3V), 186.87 mAh/g (0.1C/2.0-4.5V) and good capacity retention of 91.49% (0.2C/2.0-4.3V) and 90.36% (0.2C/2.0-4.5V) after 50th charge/discharge cycle.