• Clean Technology
• /
• v.28 no.2
• /
• pp.97-102
• /
• 2022

Lithium sulfur (Li-S) batteries have attracted considerable attention as a promising candidate for next-generation power sources due to their high theoretical energy density, low cost, and eco-friendliness. However, the poor electrical conductivity of sulfur and its insoluble discharging products (Li₂S₂/Li₂S), large volume changes, severe self-discharge, and dissolution of lithium polysulfide intermediates result in rapid capacity fading, low Coulombic efficiency, and safety risks, hindering Li-S battery commercial development. In this study, a three-dimensionally (3D) connected hierarchical porous carbon framework (HPCF) derived from waste sunflower seed shells was synthesized as a sulfur host for Li-S batteries via a chemical activation method. The natural 3D connected structure of the HPCF, originating from the raw material, can effectively enhance the conductivity and accessibility of the electrolyte, accelerating the Li⁺/electron transfer. Additionally, the generated micropores of the HPCF, originated from the chemical activation process, can prevent polysulfide dissolution due to the limited space, thereby improving the electrochemical performance and cycling stability. The HPCF/S cell shows a superior capacity retention of 540 mA h g^-1 after 70 cycles at 0.1 C, and an excellent cycling stability at 2 C for 700 cycles. This study provides a potential biomass-derived material for low-cost long-life Li-S batteries.

• Journal of the Korean Electrochemical Society
• /
• v.23 no.4
• /
• pp.105-112
• /
• 2020

Transition metal oxide, which undergoes a conversion reaction in the negative electrode material for a lithium-ion batteries, has a high specific capacity, but still has several critical problems. In this study, manganese pyrophosphate (Mn₂P₂O₇), nickel pyrophosphate (Ni₂P₂O₇), and carbon composite materials with pyrophosphates as novel negative electrode materials instead of transition metal oxide, are synthesized through simple solid-state reaction. The initial reversible capacity of Mn₂P₂O₇ and Ni₂P₂O₇ are 333 and 340 mAh g^-1, and when the composite materials are composed with carbon, the reversible capacity increases to 433 and 387 mAh g^-1, respectively. The initial Coulombic efficiency is also improved by about 10%. The Mn₂P₂O₇ and carbon composite material has the highest initial capacity and efficiency, and has the best cycle performance. Mn₂P₂O₇ containing polyanion, has a lower specific capacity due to the large mass of polyanion compared to MnO (manganese oxide). However, since Mn₂P₂O₇ shows a voltage curve with a slope, the charging (lithiation) voltage increases from 0.51 to 0.57 V (vs. Li/Li⁺), and the discharge (delithiation) voltage decreases from 1.15 to 1.01 V (vs. Li/Li⁺). Therefore, the voltage efficiency of the cell is improved because the voltage difference between charging and discharging is greatly reduced from 0.64 to 0.44 V, and the operating voltage of the full cell increases because the negative electrode potential is lowered during the discharging process.

• Korean Chemical Engineering Research
• /
• v.57 no.4
• /
• pp.559-564
• /
• 2019

Hierarchical $ZnCo_2O_4$ hollow nanofibers were prepared by electrospinning and subsequent heat-treatment process. The spinning solution containing polystyrene (PS) nanobeads was electrospun to nanofibers. During heat-treatment process, PS nanobeads in the composite were decomposed and therefore generated numerous pores uniformly in the structure, which facilitated the heat transfer and gas penetration into the structure. The resulting hierarchical $ZnCo_2O_4$ hollow nanofibers were applied as an anode material for lithium-ion batteries. The discharge capacity of the nanofibers was $815mA\;h\;g^{-1}$ ($646mA\;h\;cm^{-3}$) after the 300th cycle at a high current density of $1.0A\;g^{-1}$. However, $ZnCo_2O_4$ nanopowders showed the discharge capacity of $487mA\;h\;g^{-1}$ ($450mA\;h\;cm^{-3}$) after 300th cycle. The excellent lithium ion storage property of the hierarchical $ZnCo_2O_4$ hollow nanofibers was attributed to the synergetic effects of the hollow nanofiber structure and the $ZnCo_2O_4$ nanocrystals composing the shell. The hierarchical hollow nanofiber structure introduced in this study can be extended to various metal oxides for various applications, including energy storage.

• Korean Chemical Engineering Research
• /
• v.51 no.4
• /
• pp.411-417
• /
• 2013

To use as an anode material of lithium secondary battery, graphite-silicon composite powders are prepared by ball-milling with silicon nanoparticles (average diameter 100 nm, 0~50 wt%) and graphite powder (average diameter $15{\mu}m$) and their electrochemical properties are examined. As the silicon content increases, the graphite becomes smaller by the ball-milling and amorphous phase appears whereas the silicon do not suffer the change of nanocrystalline phases and embeds within the amorphous phase of graphite. Cyclic voltammetry at low scan rate reveals that typical oxidation peaks of graphite and silicon appear at 0.2~0.35 and 0.55~0.6 V, respectively, with higher reversibility for repeated cycles. In contrast, the high-scan-rate redox behavior is very irreversible for repeated cycles. High irreversible capacity is exhibited in the initial charging-discharging cycles, but it diminishes as the cycle number increases. The saturated discharge capacity achieves about 485 mAh $g^{-1}$ at 50th cycle for the composite of Si 20 wt%. This is due to the formation of amorphous graphite morphology by the adequate composition (C:Si=8:2 w/w), which efficiently buffers the volume change during alloying/dealloying between silicon and lithium.

• Korean Chemical Engineering Research
• /
• v.55 no.2
• /
• pp.242-246
• /
• 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 $80^{\circ}C$.

• Korean Chemical Engineering Research
• /
• v.60 no.3
• /
• pp.327-333
• /
• 2022

In this study, silicon/carbon nanotube/carbon (Si/CNT/C) composites for anode were prepared to improve the volume expansion of silicon used as a high-capacity anode material. Si/CNT were prepared by electrostatic attraction of the positively charged Si and negatively charged CNT and then hydrothermal synthesis was performed to obtain the spherical Si/CNT/C composites. Poly(vinylidene fluoride) (PVDF), polyacrylic acid (PAA), and styrene butadiene rubber (SBR) were used as binders for electrode preparation, and coin cell was assembled using 1.0 M LiPF₆ (EC:DMC:EMC = 1:1:1 vol%) electrolyte and fluoroethylene carbonate (FEC) additive. The physical properties of Si/CNT/C anode materials were analyzed using SEM, EDS, XRD and TGA, and the electrochemical performances of lithium-ion batteries were investigated by charge-discharge cycle, rate performance, dQ/dV and electrochemical impedance spectroscopy tests. Also, it was confirmed that both capacity and rate performance were significantly improved using the PAA/SBR binder and 10 wt% FEC-added electrolyte. It is found that Si/CNT/C have the reversible capacity of 914 mAh/g, the capacity retention ratio of 83% during 50 cycles and the rate performance of 70% in 2 C/0.1 C.

• Journal of the Korean Electrochemical Society
• /
• v.2 no.3
• /
• pp.123-129
• /
• 1999

Initial electrochemical characteristics of $LiCoO_2$ electrode for lithium ion battery with various content of super s black as conductive material were evaluated through the charge/discharge with the potential range of 4.3V to 2.0V versus $Li^+/Li^+$. The rate of C/4 and C/2 by the 3 electrode test cell composed with an electrolytic solution of 1 mol/l $LiPF_6/EC+DEC(1:3\;by\; weight)$. Lithium was used as reference electrode. High impedance charge behavior was observed at early stage of charge. In the case of $3\%w/w$ of super s black as conductive material, the specific resistance of the high impedance releasing was $3.82\;{\Omega}\;{\cdot}\;g-LiCoCo_2$ at the current density of $0.5 mA/cm^2$, which corresponds 7 times of the specific resistance of electrode $(0.728 g-LiCoO_2)$. At second charge, the specific resistance of the high impedance releasing was 63 mn · g-Lico02, which corresponds 12eio of the specific resistance of electrode and only $1.7\%$ of that of the first charge. The first charge and discharge specific capacities at C/4 rate were 160-161 and $153\~155mAh/g-LiCoO_2$, respectively, to lead $95.4\~96.4\%$ of coulombic efficiencies and ca. $6 mAh/g-LiCoO_2$ of initial irreversible specific capacity. Specific resistance at the end of charge and rest showed low value at content of super s black between 2 and $7\%w/w$, which agreed with characteristics of irreversible specific capacity. Capacity densities were reduced by the increasing the content of conductive material. They were 447 and 431mAh/ml when 2 and $2.9\%w/w$ of super s black were used, respectively, at the rate of C/4.

• Applied Chemistry for Engineering
• /
• v.27 no.4
• /
• pp.444-448
• /
• 2016

Hollow silicon/carbon (H-Si/C) composites as anode materials for lithium ion batteries were investigated to overcome the large volume expansion. H-Si/C composites were prepared as follows; hollow $SiO_2\;(H-SiO_2)$ was prepared by adding $NaBH_4$ to $SiO_2$ synthesized using $st{\ddot{o}}ber$ method followed by magnesiothermic reduction and carbonization of phenolic resin. The H-Si/C composites were analyzed by XRD, SEM, BET and EDX. To improve the capacity and cycle performance, the electrochemical characteristics of H-Si/C composites synthesized with various $NaBH_4$ contents were investigated by charge/discharge, cycle, cyclic voltammetry and impedance tests. The coin cell using H-Si/C composite ($SiO_2:NaBH_4=1:1$ in weight) in the electrolyte of $LiPF_6$ dissolved in organic solvents (EC : DMC : EMC = 1 : 1 : 1 vol%) has better capacity (1459 mAh/g) than those of other composition coin cells. It is found that the coin cell ($SiO_2:NaBH_4=1:1$ in weight) has an excellent capacity retention from 2nd cycle to 40th cycle.

• Korean Chemical Engineering Research
• /
• v.62 no.1
• /
• pp.19-26
• /
• 2024

In this study, the electrochemical properties of SiOx@C composite materials were prepared to alleviate volume expansion and cycle stability of silicon and to increase the capacity of anode material for LIBs. SiO₂ particles of 100, 200, and 500 nm were synthesized by the Stӧber method, and reduced to SiOx (0≤x≤2) through the magnesiothermic reduction method. Then, SiOx@C anode materials were synthesized by carbonization of PVC on SiOx. The physical properties of prepared SiOx and SiOx@C anode materials were analyzed by XRD, SEM, TGA, Raman spectroscopy, XPS and BET. The electrochemical properties were investigated by cycling performance, rate performance, CV and EIS test. As a result, the SiOx@C-7030 manufactured by coating carbon at SiOx : C = 70 : 30 on a 100 nm SiOx with the smallest particle size showed the best electrochemical properties with a discharge capacity of 1055 mAh/g and a capacity retention rate of 81.9% at 100 cycles. It was confirmed that cycle stability was impoved by reducing particle size and carbon coating.

• Journal of the Korean Geotechnical Society
• /
• v.23 no.4
• /
• pp.125-132
• /
• 2007

The oedometer, radial CRS and Rowe cell tests, composite discharge capacity tests and smear effect tests are carried out to estimate the parameters for the reliability-based design of vertical drain method. Also the sensitivity analysis, the probabilistic and deterministic solutions of radial consolidation theory are presented. The result of probabilistic analysis was compared to that of deterministic analysis using the tested and estimated parameters. The results indicated that the drain spacing in the deterministic method is larger than that in the probabilistic method because the former does not consider the uncertainties in the geotechnical property. The divergence of two methods is dependent on the probability of achieving target degree of consolidation by a given time and the coefficient of variation (COV) of the coefficient of horizontal consolidation ($c_h$).