• Applied Biological Chemistry
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• 제41권4호
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• pp.241-245
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• 1998

Two oxidation states of chromium commonly occur in natural soil/water systems, Cr(III) and Cr(VI). The oxidized form, Cr(VI), exists as the chromate ion and is more mobile and toxic than Cr(III). Therefore oxidation of Cr(III) by various Mn-oxides in natural systems is a very important environmental concern. Organic substances can inhibit the Cr(III) oxidation by binding, Cr(III) strongly and also by dissolving Mn-oxides. Most of Cr(III) oxidation studies were carried out using in vitro systems without organic substances which exist in natural soil/water systems. In this study effect of organic acids - oxalate and pyruvate - on Cr(III) oxidation by $birnessite({\delta}-MnO_2)$ was examined. The two organic acids significantly inhibited Cr(III) oxidation by birnessite. Oxalate showed more significant inhibition than pyruvate. As solution pH was lowered in the range of 3.0 to 5.0, the Cr(III) oxidation was more strongly depressed. Addition of more organic acids reduced the Cr(III) oxidation mare extensively. Different inhibition effects by the organic acids could be due to their ability of reductive dissolution of Mn-oxides and/or Cr(III) binding. Organic acids dissolved Mn-oxide during the Cr(III) oxidation by the oxide, Dissolution by oxalic acid was much greater than that by pyruvate, and the dissolution was more extensive at lower pH. Inhibition of Cr(III) oxidation was parallel to the dissolution of Mn-oxide by organic acids. Although the effect of Cr(III) binding by organic acids on Cr(III) oxidation is not known yet, Mn-oxide dissolution by organic acids could be a main reason for the inhibition of Cr(III) oxidation by Mn-oxide in presence of organic acids. Thus oxidation of Cr(III) to Cr(VI) by various Mn-oxides in natural systems could be much less than the oxidation estimated by in vitro studies with only Cr(III) and Mn-oxides.

• Bulletin of the Korean Chemical Society
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• 제32권11호
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• pp.3952-3958
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• 2011

The effect of sintering temperature on the electrochemical property of $LiMn_2O_4$ was investigated. Results showed that the particle size was increased at higher sintering temperatures while the initial capacity was decreased after high temperature sintering. Capacity fading, on the other hand, was suppressed at lower sintering temperatures since the sintering at higher temperatures (${\geq}800^{\circ}C$) increased the Mn ions with a lower oxidation state ($Mn^{+3}$), which induced structural instability during cycling due to dissolution of Mn ions into the electrolyte. In particular, $LiMn_2O_4$ sintered above $830^{\circ}C$ showed severe capacity fading (capacity loss was 38% of initial capacity) by lower coulombic efficiency due to the abnormally increased particle size.

• 전기화학회지
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• 제14권3호
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• pp.131-137
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• 2011

[ $LiMn_2O_4$ ] $Mn^{2+}$이온 용출현상 연구를 위한 간단하고 신속한 전기화학적 $Mn^{2+}$이온 분석법을 정립하였다. 이 분석법은 완충용액에서 $Mn^{2+}$이온이 $Mn^{4+}(MnO_2)$로 산화되는 원리를 이용한다. 최적조건 (pH 8.9 0.04 M $NH_3-NH_4Cl$ 완충용액 및 glassy carbon 작업전극)에서, Linear sweep voltammetry(LSV) 측정에 대해 $5{\mu}M-100{\mu}M$ (0.275-5.5 ppm) $Mn^{2+}$이온 범위에서, differential pulse voltammetry (DPV) 측정에 대해 $0.2{\mu}M-10{\mu}M$ (0.011-0.55 ppm) 범위에서 선형적 응답 특성을 확인하였다. 또한, 측정용액에 리튬 이차전지용 전해액 ($LiPF_6$, EC, EMC)이 첨가할 경우, 첨가량에 비례하여 $Mn^{2+}$ 이온의 산화 전류 감소하였는데, 이러한 감소의 주요 원인은 EMC보다는 $LiPF_6$와 EC성분임을 확인하였다.

• Journal of Electrochemical Science and Technology
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• 제5권3호
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• pp.87-93
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• 2014

The fluorine-substituted $0.3Li_2MnO_3{\cdot}0.7Li[Mn_{0.60}Ni_{0.25}Co_{0.15}]O_{2-x}F_x$ cathode materials were synthesized by using the transition metal precursor, $LiOH{\cdot}H_2O$ and LiF. This was to facilitate the movement of lithium ions by forming more compact SEI layer and to reduce the dissolution of transition metals. The $0.3Li_2MnO_3{\cdot}0.7Li[Mn_{0.60}Ni_{0.25}Co_{0.15}]O_{2-x}F_x$ cathode material was sphere-shaped and each secondary particle had $10{\sim}15{\mu}m$ in size. The fluorine-substituted cathodes initially delivered low discharge capacity, but it gradually increased until 50th charge-discharge cycles. These results indicated that fluorine substitution gave positive effects on the structural stabilization and resistance reduction in materials.

• 공업화학
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• 제10권6호
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• pp.832-837
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• 1999

수용액계에서 정극활물질의 안정성을 1 M LiOH 용액에서 Tafel plot를 통해서 측정하였으며, 이 때 $LiM_xMn_{2-x}O_4$(x=0.05~0.1) 전극은 100 mA에서 0.13~0.15 mV의 과전압으로 $LiMn_2O_4$ 전극보다 0.05 mV가 낮은 과전압을 나타냈다. 또한 전위변화에 따른 전해질의 전도도는 $LiM_xMn_{2-x}O_4$가 스피넬 구조의 $LiMn_2O_4$보다 높고 나타났으며, $Mn^{+2}$의 용해에 의한 용액저항은 상대적으로 낮게 나타났다.

• 한국전기화학회:학술대회논문집
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• 한국전기화학회 2002년도 전지기술심포지움
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• pp.57-65
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• 2002

The presence of tetragonal phase at the surface of $LiMn_2O_4$ pinicle due to a Jahn-Teller offset was previously reported to be one of the causes for capacity fading observed during cycling of $Li//Li_xMn_2O_4$ in 4V range. Further, it is reported that a Jahn-Teller effect in 4V range may be suppressed by substitution of Mn ions with Li ions or other transition metal ions. However, the direct evidence of the suppression of a Jahn-Teller effect in 4V range by substitution of Mn ions with other metal ions has not been reported. The dissolution and formation of surface film at the surface of $LiMn_2O_4$ electrodes also reportedly affect the capacity fading or rate capability. This study reports on the evidence of the onset and suppression of a Jahn-Teller effect in 4V range and the dissolution and formation of surface film at the surface of $LiMn_2O_4$ thin film electrodes using in situ bending beam method (BBM) in situ electrochemical quartz crystal microbalance (EQCM).

• 한국분말재료학회지
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• 제24권2호
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• pp.87-95
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• 2017

Lithium silicate, a lithium-ion conducting ceramic, is coated on a layer-structured lithium nickel manganese oxide ($LiNi_{0.7}Mn_{0.3}O_2$). Residual lithium compounds ($Li_2CO_3$ and LiOH) on the surface of the cathode material and $SiO_2$ derived from tetraethylorthosilicate are used as lithium and silicon sources, respectively. Powder X-ray diffraction and scanning electron microscopy with energy-dispersive spectroscopy analyses show that lithium silicate is coated uniformly on the cathode particles. Charge and discharge tests of the samples show that the coating can enhance the rate capability and cycle life performance. The improvements are attributed to the reduced interfacial resistance originating from suppression of solid-electrolyte interface (SEI) formation and dissolution of Ni and Mn due to the coating. An X-ray photoelectron spectroscopy study of the cycled electrodes shows that nickel oxide and manganese oxide particles are formed on the surface of the electrode and that greater decomposition of the electrolyte occurs for the bare sample, which confirms the assumption that SEI formation and Ni and Mn dissolution can be reduced using the coating process.

• Journal of Electrochemical Science and Technology
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• 제13권2호
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• pp.269-278
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• 2022

Utilization of high-voltage electrolyte additive(s) at a small fraction is a cost-effective strategy for a good solid electrolyte interphase (SEI) formation and performance improvement of a lithium-rich layered oxide-based high-energy lithium-ion cell by avoiding the occurrence of metal-dissolution that is one of the failure modes. To mitigate metal-dissolution, we explored fluorinated dual-additives of fluoroethylene carbonate (FEC) and di(2,2,2-trifluoroethyl)carbonate (DFDEC) for building-up of a good SEI in a 4.7 V full-cell that consists of high-capacity silicon-graphite composite (15 wt% Si/C/CF/C-graphite) anode and Li_1.13Mn_0.463Ni_0.203Co_0.203O₂ (LMNC) cathode. The full-cell including optimum fractions of dual-additives shows increased capacity to 228 mAhg^-1 at 0.2C and improved performance from the one in the base electrolyte. Surface analysis results find that the SEI stabilization of LMNC cathode induced by dual-additives leads to a suppression of soluble Mn²⁺-O formation at cathode surface, mitigating metal-dissolution event and crack formation as well as structural degradation. The SEI and structure of Si/C/CF/C-graphite anode is also stabilized by the effects of dual-additives, contributing to performance improvement. The data give insight into a basic understanding of cathode-electrolyte and anode-electrolyte interfacial processes and cathode-anode interaction that are critical factors affecting full-cell performance.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2001년도 춘계학술대회 논문집 센서 박막재료
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• pp.18-22
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• 2001

Spinel $LiMn_{2-y}Mn_{y}O_4$ powder was prepared solid-state method by calcining the mixture of $LiOH{\cdot}H_2O$, $MnO_2$ and MgO at $800^{\circ}C$ for 36h. To investigate the effect of temperature for cycle behaviour of cathode material during cycling, charge-discharge experiments and initial impedance spectroscopy performed by the condition of the charge-discharge temperature. Initial charge-discharge capacity was gradually increased by rising charge-discharge temperature. However, capacity was suddenly decreased at high temperature during cycling. Capacity at low temperature was almost constant during cycling. It confirmed because Mn dissolution is more serious at high temperature than at low temperature.

• 한국세라믹학회지
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• 제37권12호
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• pp.1204-1211
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• 2000

Mn-Zn 페라이트 소결체와 SiO$_2$-PbO-ZnO 삼성분계 유리와의 계면반응에서 페라이트와 유리에 각각 첨가된 ZnO가 계면반응에 미치는 영향을 조사하였다. SiO$_2$-PbO-ZnO 삼성분계 유리에 첨가된 ZnO 함량이 낮은 경우 페라이트와의 접합계면에서 생성되는 중간상은 Pb$_2$(Mn,Fe)$_2$Si$_2$O$_{9}$와 Pb$_{8}$(Mn,Fe)Si$_{6}$O$_{21}$의 고용체였으며, ZnO 농도가 증가함에 따라 중간상은 사라졌다. 유리속의 ZnO 성분이 증가함에 따라 페라이트 소결체 쪽의 계면부근에 Zn의 농도가 증가하는 특이한 분포가 나타났다. 이는 유리 속에 첨가된 Zn 이온의 높은 활동도로 인해 페라이트에 포함된 Zn 이온의 용해반응이 선택적으로 억제되어 나타난 것으로 생각된다. 페라이트에 첨가된 ZnO 함량이 낮은 경우 SiO$_2$-PbO 이성분계 유리와의 접합계면에서 페라이트의 용해에 따른 침식과 입계를 통한 유리의 침투가 심하게 일어났으며, ZnO 함량이 증가함에 따라 계면을 통한 상호확산과 반응이 억제되었다.