• Resources Recycling
• /
• v.26 no.3
• /
• pp.47-52
• /
• 2017

The concentrate of lepidolite, being treated by heavy medium separation (HMS), was ground with calcium sulphate hemihydrate (CSH, $CaSO_4{\cdot}1/2H_2O$) to investigate the mechanochemical effect for the Li leachability in water. This leachability increased, dramatically through the intensive grinding for the mixture, concentrate and CSH. The leachability of Li was improved from 4.48% to 93.5%. The grinding of the mixture destructed the crystal structure of the concentrate, and it might be formed to new compounds. As the result, Li in the concentrate can be extracted by water leaching at room temperature.

• Resources Recycling
• /
• v.30 no.6
• /
• pp.36-42
• /
• 2021

Spent lithium-ion batteries are treated by reduction-smelting at high temperatures to recover valuable metals. Solvent extraction and precipitation of the HCl leaching solution of reduction-smelted metallic alloys resulted in a filtrate containing Ni(II) and a small amount of Si(IV). Adsorption and precipitation experiments were conducted to recover pure Ni(II) compounds from the filtrate. Si(IV) was selectively loaded onto polyacrylamide, but this method did not efficiently filter the solution due to an increase in viscosity. The addition of Na₂CO₃ as a precipitant to the filtrate led to the simultaneous precipitation of Ni(II) and Si(IV). However, it was possible to recover nickel oxalate with a purity higher than 99.99% by selectively precipitating Ni(II) with the addition of Na₂C₂O₄ as a precipitant.

• Resources Recycling
• /
• v.31 no.3
• /
• pp.73-80
• /
• 2022

Reduction smelting of spent lithium-ion batteries at high temperature produces metallic alloys. Following solvent extraction of the leaching solutions of these metallic alloys with either sulfuric or hydrochloric acid, the raffinate is found to contain Ni(II), Co(II), Mn(II), and Si(IV). In this study, two cationic exchange resins (Diphonix and P204) were employed to investigate the loading behavior of these ions from synthetic sulfate and chloride solutions. Experimental results showed that Ni(II), Co(II), and Mn(II) could be selectively loaded onto the Diphonix resin from a sulfate solution of pH 3.0. With a chloride solution of pH 6.0, Mn(II) was selectively loaded onto the P204 resin, leaving Ni(II) and Si(IV) in the effluent. Elution experiments with H₂SO₄ and/or HCl resulted in the complete recovery of metal ions from the loaded resin.

• Journal of the Korean Electrochemical Society
• /
• v.7 no.3
• /
• pp.131-137
• /
• 2004

Sol-gel method which provides better electrochemical and physiochemical properties compared to the solid-state method was used to synthesize the material of $LiFe_yMn_{2-y}O_4$. Fe was substituted to increase the structural stability so that the effects of the substitution amount and sintering temperature were analyzed. XRD was used for the structural analysis of produced material, which in turn, showed the same cubic spinel structure as $LiMn_2O_4$ despite the substitution of $Fe^{3+}$. During the synthesis of $LiFe_yMn_{2-y}O_4$, as the sintering temperature and the doping amount of Fe(y=0.05, 0.1, 0.2)were increased, grain growth proceeded which in turn, showed a high crystalline and a large grain size, certain morphology with narrow specific surface area and large pore volume distribution was observed. In order to examine the ability for the practical use of the battery, charge-discharge tests were undertaken. When the substitution amount of $Fe^{3+}\;into\;LiMn_2O_4$ increased, the initial discharge capacity showed a tendency to decrease within the region of $3.0\~4.2V$ but when charge-discharge processes were repeated, other capacity maintenance properties turned out to be outstanding. In addition, when the sintering temperature was $800\~850^{\circ}C$, the initial capacity was small but showed very stable cycle performance. According to EVS(electrochemical voltage spectroscopy) test, $LiFe_yMn_{2-y}O_4(y=0,\;0.05,\;0.1,\;0.2)$ showed two plateau region and the typical peaks of manganese spinel structure when the substitution amount of $Fe^{3+}$ increased, the peak value at about 4.15V during the charge-discharge process showed a tendency to decrease. From the previous results, the local distortion due to the biphase within the region near 4.15V during the lithium extraction gave a phase transition to a more suitable single phase. When the transition was derived, the discharge capacity decreased. However the cycle performance showed an outstanding result.

• Applied Chemistry for Engineering
• /
• v.28 no.5
• /
• pp.534-538
• /
• 2017

In this study, the molecular weight controlled pitches derived from pyrolyzed fuel oil (PFO) were prepared using solvent extraction and were carbonized. Electrochemical characteristics of lithium battery anode materials were investigated using these petroleum pitches. Three pitch samples prepared by the thermal reaction were 3903 (at $390^{\circ}C$ for 3 h), 4001 (at $400^{\circ}C$ for 1 h) and 4002 (at $400^{\circ}C$ for 2 h). The prepared hexane insoluble pitches were analysed by XRD, TGA, SEM and Gel permeation Chromatography (GPC). The electrochemical characteristics of the PFO-derived pitch as an anode material were investigated by constant current charge/discharge, cyclic voltammetry and electrochemical impedance tests. The coin cell using pitch (4001) and the electrolyte of $LiPF_6$ in organic solvents (EC : DMC = 1 : 1 vol%, VC 3 wt%) has better initial capacity (310 mAh/g) than that of other pitch coin cells. Also, this carbon anode showd a high initial efficiency of 82%, retention rate capability at 2 C/0.1 C of 90% and cycle retention of 85%. It was found that modified pitches improved the cycling and rate capacity performance.

• Proceedings of the Korean Vacuum Society Conference
• /
• 2010.08a
• /
• pp.302-303
• /
• 2010

Generally, the high energy lithium ion batteries depend intimately on the high capacity of electrode materials. For anode materials, the capacity of commercial graphite is unlike to increase much further due to its lower theoretical capacity of 372 mAhg-1. To improve upon graphite-based negative electrode materials for Li-ion rechargeable batteries, alternative anode materials with higher capacity are needed. Therefore, some metal anodes with high theoretic capacity, such as Si, Sn, Ge, Al, and Sb have been studied extensively. This work focuses on ternary Si-M1-M2 composite system, where M1 is Ge that alloys with Li, which has good cyclability and high specific capacity and M2 is Mo that does not alloy with Li. The Si shows the highest gravimetric capacity (up to 4000mAhg-1 for Li21Si5). Although Si is the most promising of the next generation anodes, it undergoes a large volume change during lithium insertion and extraction. It results in pulverization of the Si and loss of electrical contact between the Si and the current collector during the lithiation and delithiation. Thus, its capacity fades rapidly during cycling. Si thin film is more resistant to fracture than bulk Si because the film is firmly attached to the substrate. Thus, Si film could achieve good cycleability as well as high capacity. To improve the cycle performance of Si, Suzuki et al. prepared two components active (Si)-active(Sn, like Ge) elements film by vacuum deposition, where Sn particles dispersed homogeneously in the Si matrix. This film showed excellent rate capability than pure Si thin film. In this work, second element, Ge shows also high capacity (about 2500mAhg-1 for Li21Ge5) and has good cyclability although it undergoes a large volume change likewise Si. But only Ge does not use the anode due to its costs. Therefore, the electrode should be consisted of moderately Ge contents. Third element, Mo is an element that does not alloys with Li such as Co, Cr, Fe, Mn, Ni, V, Zr. In our previous research work, we have fabricated Si-Mo (active-inactive elements) composite negative electrodes by using RF/DC magnetron sputtering method. The electrodes showed excellent cycle characteristics. The Mo-silicide (inert matrix) dispersed homogeneously in the Si matrix and prevents the active material from aggregating. However, the thicker film than $3\;{\mu}m$ with high Mo contents showed poor cycling performance, which was attributed to the internal stress related to thickness. In order to deal with the large volume expansion of Si anode, great efforts were paid on material design. One of the effective ways is to find suitably three-elements (Si-Ge-Mo) contents. In this study, the Si based composites of 45~65 Si at.% and 23~43 Ge at.%, and 12~32 Mo at.% are evaluated the electrochemical characteristics and cycle performances as an anode. Results from six different compositions of Si-Ge-Mo are presented compared to only the Si and Ge negative electrodes.

• Carbon letters
• /
• v.26
• /
• pp.18-24
• /
• 2018

Pollution of chloride ion-reinforced concrete can trigger active corrosion processes that reduce the useful life of structures. Multifunctional materials used as a counter-electrode by electrochemical techniques have been used to rehabilitate contaminated concrete. Cement-based pastes added to carbonaceous material, fibers or dust, have been used as an anode in the non-destructive Electrochemical Chloride Extraction (ECE) technique. We studied the performance of the addition of Carbon Fiber (CF) in a cement-graphite powder base paste used as an anode in ECE of concretes contaminated with chlorides from the preparation of the mixture. The experimental parameters were: 2.3% of free chlorides, 21 days of ECE application, a Carbon Fiber Volume Fraction (CFVF) of 0.1, 0.3, 0.6, 0.9%, a lithium borate alkaline electrolyte, a current density of $4.0A/m^2$ and a cement/graphite ratio of 1.0 for the paste. The efficiency of the ECE in the traditional technique using metal mesh as an anode was 77.6% and for CFVF of 0.9% it was 90.4%, with a tendency to increase to higher percentages of the CFVF in the conductive cement-graphite paste, keeping the pH stable and achieving a homogeneous ECE in the mass of the concrete contaminated with chlorides.

• Corrosion Science and Technology
• /
• v.19 no.1
• /
• pp.31-36
• /
• 2020

An efficient wet process approach to modifying natural graphite (NG) electrodes for Li-ion batteries is introduced in this paper. With homogeneous mixing and thermal decomposition of NG with diammonium phosphate ((NH₄)₂HPO₄), phosphorus and nitrogen were successfully incorporated into the surface layer of NG particles. Electron microscopy and X-ray photoelectron spectroscopy analyses demonstrated that the surface was well modified by this process. As a result, the treated NG electrodes exhibited much improved electrochemical performance over pristine NG at two different temperatures: 25 ℃ and 50 ℃. Excellent capacity retention of 95.6% was obtained after 100 cycles at 50 ℃. These enhanced properties were confirmed in a morphology analysis on the cross-sections of the NG electrodes after galvanostatic cycling. The improved cycle and thermal stabilities can be attributed to the surface treatment with phosphorus and nitrogen; the treatment formed a stable solid electrolyte interphase layer that performed well when undergoing Li insertion and extraction cycling.

• Proceedings of the KIPE Conference
• /
• 2010.11a
• /
• pp.351-353
• /
• 2010

본 논문에서는 쉽고 빠르게 정확한 리튬 이온 배터리 모델을 구현할 수 있는 방법을 제시하고 있으며, 구현된 모델을 MATLAB(R)/Simulink(R)환경에서 검증한다. 모델을 구현함에 있어서 절차를 간소화하기 위해 비선형 개방 전압은 배터리 충전 및 방전 전압의 평균으로 근사하고, 배터리 내부 비선형 파라미터는 방전 초기에 발생하는 과도응답을 측정한 이산 데이터를 곡선 접합하여 구한다. 구현된 모델을 이용하여 시뮬레이션을 하고 이를 실험 데이터와 비교해본 결과, 평균 절대오차는 기존 연구보다 0.1% 낮은 0.091%로 측정되었다. 측정된 오차의 수준은 본 논문에서 제안한 방법이 파라미터 추출에 필요한 시간을 단축하고 시뮬레이션 모델을 쉽게 구현 가능하게 함에도 불구하고 여전히 리튬 이온 배터리의 출력 특성을 정확하게 예측함을 보여준다.

• Proceedings of the Materials Research Society of Korea Conference
• /
• 2011.05a
• /
• pp.5-5
• /
• 2011

The research and development of hybrid electric vehicle (HEV), plug-in hybrid electric vehicle (PHEV) and electric vehicle (EV) are intensified due to the energy crisis and environmental concerns. In order to meet the challenging requirements of powering HEV, PHEV and EV, the current lithium battery technology needs to be significantly improved in terms of the cost, safety, power and energy density, as well as the calendar and cycle life. One new technology being developed is the utilization of composite cathode by mixing two different types of insertion compounds [e.g., spinel $LiMn_2O_4$ and layered $LiMO_2$ (M=Ni, Co, and Mn)]. Recently, some studies on mixing two different types of cathode materials to make a composite cathode have been reported, which were aimed at reducing cost and improving self-discharge. Numata et al. reported that when stored in a sealed can together with electrolyte at $80^{\circ}C$ for 10 days, the concentrations of both HF and $Mn^{2+}$ were lower in the can containing $LiMn_2O_4$ blended with $LiNi_{0.8}Co_{0.2}O_2$ than that containing $LiMn_2O_4$ only. That reports clearly showed that this blending technique can prevent the decline in capacity caused by cycling or storage at elevated temperatures. However, not much work has been reported on the charge-discharge characteristics and related structural phase transitions for these composite cathodes. In this presentation, we will report our in situ x-ray diffraction studies on this mixed composite cathode material during charge-discharge cycling. The mixed cathodes were incorporated into in situ XRD cells with a Li foil anode, a Celgard separator, and a 1M $LiPF_6$ electrolyte in a 1 : 1 EC : DMC solvent (LP 30 from EM Industries, Inc.). For in situ XRD cell, Mylar windows were used as has been described in detail elsewhere. All of these in situ XRD spectra were collected on beam line X18A at National Synchrotron Light Source (NSLS) at Brookhaven National Laboratory using two different detectors. One is a conventional scintillation detector with data collection at 0.02 degree in two theta angle for each step. The other is a wide angle position sensitive detector (PSD). The wavelengths used were 1.1950 ${\AA}$ for the scintillation detector and 0.9999 A for the PSD. The newly installed PSD at beam line X18A of NSLS can collect XRD patterns as short as a few minutes covering $90^{\circ}$ of two theta angles simultaneously with good signal to noise ratio. It significantly reduced the data collection time for each scan, giving us a great advantage in studying the phase transition in real time. The two theta angles of all the XRD spectra presented in this paper have been recalculated and converted to corresponding angles for ${\lambda}=1.54\;{\AA}$, which is the wavelength of conventional x-ray tube source with Cu-$k{\alpha}$ radiation, for easy comparison with data in other literatures. The structural changes of the composite cathode made by mixing spinel $LiMn_2O_4$ and layered $Li-Ni_{1/3}Co_{1/3}Mn_{1/3}O_2$ in 1 : 1 wt% in both Li-half and Li-ion cells during charge/discharge are studied by in situ XRD. During the first charge up to ~5.2 V vs. $Li/Li^+$, the in situ XRD spectra for the composite cathode in the Li-half cell track the structural changes of each component. At the early stage of charge, the lithium extraction takes place in the $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ component only. When the cell voltage reaches at ~4.0 V vs. $Li/Li^+$, lithium extraction from the spinel $LiMn_2O_4$ component starts and becomes the major contributor for the cell capacity due to the higher rate capability of $LiMn_2O_4$. When the voltage passed 4.3 V, the major structural changes are from the $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ component, while the $LiMn_2O_4$ component is almost unchanged. In the Li-ion cell using a MCMB anode and a composite cathode cycled between 2.5 V and 4.2 V, the structural changes are dominated by the spinel $LiMn_2O_4$ component, with much less changes in the layered $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ component, comparing with the Li-half cell results. These results give us valuable information about the structural changes relating to the contributions of each individual component to the cell capacity at certain charge/discharge state, which are helpful in designing and optimizing the composite cathode using spinel- and layered-type materials for Li-ion battery research. More detailed discussion will be presented at the meeting.