The capacity of high nickel Li(NixCoyMn1-x-y)O2 (NCM, x ≥ 0.8) cathodes is known to rapidly decline, a serious problem that needs to be solved in a timely manner. It was reported that cathode materials with the {010} plane exposed toward the outside, i.e., a radial structure, can provide facile Li+ diffusion paths and stress buffer during repeated cycles. In addition, cathodes with a core-shell composition gradient are of great interest. For example, a stable surface structure can be achieved using relatively low nickel content on the surface. In this study, precursors of the high-nickel NCM were synthesized by coprecipitation in ambient atmosphere. Then, a transition metal solution for coprecipitation was replaced with a low nickel content and the coprecipitation reaction proceeded for the desired time. The electrochemical analysis of the core-shell cathode showed a capacity retention of 94 % after 100 cycles, compared to the initial discharge capacity of 184.74 mA h/g. The rate capability test also confirmed that the core-shell cathode had enhanced kinetics during charging and discharging at 1 A/g.
Extensive research is being carried out on Ni-rich Li(NixCoyMn1-x-y)O2 (NCM) due to the growing demand for electric vehicles and reduced cost. In particular, Ni-rich Li(NixCoyMn1-x-y-zAlz)O2 (NCMA) is attracting great attention as a promising candidate for the rapid development of Co-free but electrochemically more stable cathodes. Al, an inactive element in the structure, helps to improve structural stability and is also used as a doping element to improve cycle capability in Ni-rich NCM. In this study, NCMA was successfully synthesized with the desired composition by direct coprecipitation. Boron and tin were also used as dopants to improve the battery performance. Macro- and microstructures in the cathodes were examined by microscopy and X-ray diffraction. While Sn was not successfully doped into NCMA, boron could be doped into NCMA, leading to changes in its physicochemical properties. NCMA doped with boron revealed substantially improved electrochemical properties in terms of capacity retention and rate capability compared to the undoped NCMA.
Strontium lanthanum vanadate La1-xSrxVO3 (LSVO) is a promising anode material for electrochemical devices, especially for solid oxide fuel cells, thanks to its irregular electrical conductivity. However, the known synthesis methods are incapable of producing well-dispersed LSVO nanoparticles (NPs) with homogeneous size distribution, which partly impedes the applicability of the material. Thus, a new approach to synthesize LSVO NPs with such characteristics is of paramount importance. In the present work, we successfully prepare LSVO NPs with a high dispersion degree and homogeneous size distribution via a modified co-precipitation pathway, followed by hydrogen reduction at a temperature as low as 700 oC. The prepared LSVO NPs display uniform sizes in the range of 50 ~ 100 nm and do not contain any secondary phases, according to XRD analysis. The chemical mechanism of reactions that occur to form the LSVO is thoroughly highlighted. The work functions of NPs measured by the UPS analysis are in the 2.13 ~ 3.62 eV range, making the LSVO powders promising for use in thermionic devices. An explanation of the role of Sr substitution in work function values of LSVO is also proposed.
Ni1/3Co1/3Mn1/3(OH)2 powders have been synthesized in a continuously stirred tank reactor via a co-precipitation reaction between aqueous metal sulfates and NaOH using NH4OH as a chelating agent. The co-precipitation temperature is varied in the range of 30-80oC. Calcination of the prepared precursors with Li2CO3 for 8 h at 1000oC in air results in Li Ni1/3Co1/3Mn1/3O2 powders. Two kinds of obtained powders have been characterized by X-ray diffraction (XRD), scanning electron microscopy, particle size analyzer, and tap density measurements. The co-precipitation temperature does not differentiate the XRD patterns of precursors as well as their final powders. Precursor powders are spherical and dense, consisting of numerous acicular or flaky primary particles. The precursors obtained at 70 and 80oC possess bigger primary particles having more irregular shapes than those at lower temperatures. This is related to the lower tap density measured for the former. The final powders show a similar tendency in terms of primary particle shape and tap density. Electrochemical characterization shows that the initial charge/discharge capacities and cycle life of final powders from the precursors obtained at 70 and 80oC are inferior to those at 50oC. It is concluded that the optimum co-precipitation temperature is around 50oC.
As precursors of cathode materials for lithium ion batteries, Ni1/3Co1/3Mn1/3(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 NH4OH in air or nitrogen ambient. Calcination of the precursors with Li2CO3 for 8 h at 1,000°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 Ni1/3Co1/3Mn1/3(OH)2. Regardless of the atmosphere, the final powders exhibit the XRD patterns of LiNi1/3Co1/3Mn1/3O2 (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.
This study was carried out for characterization of MIO synthesized in our laboratory by co-precipitation method and applied isotherm and kinetic models for adsorption properties. XRD analysis were conducted to find crystal structure of synthesized MIO. Further SEM and XPS analysis was performed before and after phosphate adsorption, and BET analysis for surface characterization. Phosphate stock solution was prepared by KH2PO4 for characterization of phosphate adsorption, and batch experiment was conducted using 50 ml conical tube. Langmuir and Freundlich models were applied based on adsorption equilibrium test of MIO by initial phosphate solution. Pseudo first order and pseudo second order models were applied for interpretation of kinetic model by temperature. Surface area and pore size of MIO were found 89.6 m2/g and 16 nm respectively. And, the determination coefficient (R2) value of Langmuir model was 0.9779, which was comparatively higher than that of Freundlich isotherm model 0.9340.
본 연구는 H2O2가 함유된 (Na2CO3-NaHCO3) 혼합 탄산염 계에서 사용후핵연료를 산화용해할 시 U과 함께 공용해 되는 Cs, Te, Tc, Mo 등의 핵분열생성물로부터 Cs과 Tc의 선택적 침전 제거 거동을 규명하였다. Cs과 Tc은 각각 장수명 핵종으로 지하에서의 빠른 핵종 이동성과 고방열성 등으로 최종 처분 시 처분 환경 을 저해하는 핵종으로 처분 안전성 제고 측면에서 이들의 제거는 중요한 과제 중의 하나이다. Cs과 Re (Tc대용원소)의 선택적 침전제로는 각각 NaTPB, TPPCl를 선정하였으며, NaTPB에 의한 Cs 침전 및 TPPCl에 의한 Re 침전 모두 5분 이내로 매우 빠르게 이루어졌으며, 온도를 50℃, 교반속도를 1000 rpm 까지 증가 시켜도 이들의 침전 속도에는 별 영향이 없었다. NaTPB 침전 및 TPPCl 침전에 있어 가장 중요한 요인은 침전 용액의 pH 이며, 특히 TPPCl에 의한 Re의 선택적 침전의 경우 낮은 pH 에서 Mo가 Re과 공침되므로 pH 9 이상에서 수행하는 것이 효과적이다. 그리고 [NaTPB]/[Cs] 및 [TPPCl]/[Re]의 몰 농도 비 1 이상에서 Cs 및 Re을 각각 99% 이상 선택적으로 침전 제거할 수 있었다.
가압 경수형 원자로 (pressurized light water reactor) 냉각재 계통 내의 주된 분식 생성물로 알려져 있는 nickel ferrite의 거동에 대해 고찰하기 위해 모의 nickel ferrite(Ni0.75Fe2.25O4)를 공침법으로 제조하였다. 수용액-pH-조절로는 am-monia 또는 potassium carbonate를, 공침물-세척제는 ammonia 수용액이나 potassium carbonate 수용액 또는 2차 증류수를 사용하였다. Nickel ferrite의 생성 및 수용액-pH-조절제와 공치물-세척제가 최종 생성물의 Ni-Fe 몰 비에 따른 수율 및 특성에 미치는 영향은 EDX, XPS, XRD 및 SEM으로 고찰하였다. 반응 전.후 Ni/Fe 몰 비에 따른 수율은, pH를 potassium carbon-ate로 조절한 후 2차 증류수로 공침물을 세척한 경우가 0.994로 가장 높이 나왔으며, pH-조절제로 potassium carbonate를 사용한 경우가 ammonia를 사용한 경우에 비해 높은 수율을 나타냈다. 이러한 차이는 공침 시에 수용액 내에서 ammonia가 보여주는 상대적으로 큰 Na2+←NH3 착화 효과와 더불어 공침물-세척제의 pH에 기인하는 것으로 해석하였다.
Various humic substances are widely distributed in natural water body, such as rivers and lakes and cause the yellowish or brownish color to water. The evidence that humic substances are precursors of THMs formation in chlorinated drinking water has been reported m the Jiteratures. For the reason of public health as well as aesthetics, needs for humic substances removal have been increased in the conventional water treatment processes. In this research, the characteristics of aluminium coagulation of humic acids and humic acids were investigated. The optimum pH and coagulants dosage to remove these materials simultaneously by coagulation were alto studied. The results are as followed; 1. UV-254 absorptiometry for measuring the concentration of aquatic humic acids showed good applicability and stable results. 2. The optimal pH range for humic acids removal by aluminium coagulation was 5 to 5.5, however, an increase in aluminium coagulant dosage could enhance the removal rate of humic acids in the wide pH range. 3. Coprecipitation of humic acids in the typical pH range of 6.5 to 8 in water treatment processes may require the sweep coagulation mechanism with the excess aluminium coagulant dosage. 4. Using PAC(poly aluminium chloride) or PASS(poly aluminium silica sulfate) as coagulants was able to expand the operating range for removing humic acids. 5. From the coagulation of humic substances(UV-254) and turbidity at pH range of 5.5 - 6.0 and alum dose of 86 ppm, the removal efficiency of turbidity from the reservoir water was above 90% and that of UV-254 was above 70%. 6. By using the reservoir water, the optimum condition of rapid mixing for simultaneous removal of turbidity and UV-254 absorbance was pH of 5.8 and LAS dose of 86 ppm, in this study.