• Journal of Electrochemical Science and Technology
• /
• v.13 no.2
• /
• pp.208-212
• /
• 2022

In this paper, we report the effects of temperature on the deterioration of graphite-based negative electrodes during the longterm cycling of lithium-ion batteries (LIBs). After cycling 75 Ah pouch-type LIB full cells at temperatures of 45℃ (45-Cell) and 25℃ (25-Cell) until their end of life, we expected to observe changes in the negative electrode according to the temperature. The thickness of the negative electrode of the cell was greater after cycling; that of the electrode of 45-Cell (144 ㎛) was greater than that of the electrode of 25-Cell (109 ㎛). Cross-sectional scanning electron microscopy analysis confirmed that by-products caused this increase in the thickness of the negative electrode. The by-products that formed on the surface of the negative electrode during cycling increased the surface resistance and decreased the electrical conductivity. Voltage profiles showed that the negative electrode of 25-Cell exhibited an 84.7% retention of the initial capacity, whereas that of 45-Cell showed only a 70.3% retention. The results of this study are expected to be relevant to future analyses of the deterioration characteristics of the negative electrode and battery deterioration mechanisms, and are also expected to provide basic data for advanced battery design.

• 한국전기화학회:학술대회논문집
• /
• 2000.04a
• /
• pp.47-47
• /
• 2000

• Journal of the Korean Electrochemical Society
• /
• v.13 no.1
• /
• pp.19-33
• /
• 2010

The surface film, which is formed on graphite negative electrodes during the initial charging, is a key component in lithium secondary batteries. The battery reactions are strongly affected by the nature of the surface film. It is thus very important to understand the physicochemical properties of the surface film. On the other hand, the surface film formation is a very complicated interfacial phenomenon occurring at the graphite/electrolyte interface. In studies on electrode surfaces in lithium secondary batteries, in-situ experimental techniques are very important because the surface film is highly reactive and unstable in the air. In this respect electrochemical atomic force microscopy (ECAFM) is a useful tool for direct visualizing electrode/solution interfaces at which various electrochemical reactions occur under potential control. In the present review, mechanism of surface film formation and its correlation with electrolyte are summarized on the basis of in-situ ECAFM studies for understanding of the nature of the surface film on graphite negative electrodes.

• Applied Chemistry for Engineering
• /
• v.9 no.7
• /
• pp.1065-1069
• /
• 1998

This study was investigated to improve peformance of carbon negative electrode for lithium ion secondary battery. The carbon electrode was prepared by mixing with graphitic carbon material, natural graphite, and nongraphitic carbon material, petroleum cokes, which was heat-treated at $700^{\circ}C$ for l hour. Its electrochemical and charge-discharge characteristics were tested according to mixing ratio of different two types of carbon material. The carbon electrode prepared with various mixing ratio showed both charateristcs of two different types of carbon materials and the best characteristics as carbon electrode was demonstrated at mixing ratio of 1:1.

• Transactions of the Korean hydrogen and new energy society
• /
• v.24 no.2
• /
• pp.179-185
• /
• 2013

The behavior of surface film formation was greatly dependent on the speed of potential cycling. In $LiClO_4$ / EC + DEC, cyclic voltammetry results showed that the peaks originated from surface film formation on graphite electrode at the high charge-discharge rate was shifted to the lower potentials as the charge-discharge rate decrease. This indicates that surface films with different morphology and thickness were formed by different charge-discharge rate. Transmission electron microscopy (TEM) results indicated that the properties such as thickness and morphology of the surface film were greatly affected by the charge-discharge rate. Electrochemical impedance spectroscopy (EIS) showed that the resistance of surface film was affected by the speed of potential cycling. In addition, the charge transfer resistance was also dependent on the charge-discharge rate indicating that the charge transfer reaction was affected by the nature of surface film. TEM and EIS results suggested that the chemical property as well as the physical property of the surface film was affected by the charge-discharge rate.

• Journal of the Korean Electrochemical Society
• /
• v.15 no.1
• /
• pp.19-26
• /
• 2012

SEI (solid electrolyte interphase) layers are generated on a graphite negative electrode from three different electrolytes and low-temperature ($-30^{\circ}C$) charge/discharge performance of the graphite electrode is examined. The electrolytes are prepared by adding 2 wt% of vinylene carbonate (VC) and fluoroethylene carbonate (FEC) into a standard electrolyte solution. The charge-discharge capacity of graphite electrode shows the following decreasing order; FEC-added one>standard>VC-added one. The polarization during a constant-current charging shows the reverse order. These observations illustrate that the SEI film resistance and charge transfer resistance differ according to the used additives. This feature has been confirmed by analyzing the chemical composition and thickness of three SEI layers. The SEI layer generated from the standard electrolyte is composed of polymeric carbon-oxygen species and the decomposition products ($Li_xPF_yO_z$) of lithium salt. The VC-derived surface film shows the largest resistance value even if the salt decomposition is not severe due to the presence of dense film comprising C-O species. The FEC-derived SEI layer shows the lowest resistance value as the C-O species are less populated and salt decomposition is not serious. In short, the FEC-added electrolyte generates the SEI layer of the smallest resistance to give the best low-temperature performance for the graphite negative electrode.

• Transactions of the Korean hydrogen and new energy society
• /
• v.22 no.5
• /
• pp.592-598
• /
• 2011

Electrode of solid oxide fuel cell must have sufficient porosity to allow gas transport to the interface with electrolyte effectively but high porosity has a negative impact on structural stability in electrode support. Thus, the upper limit of porosity is based on consideration of mechanical strength of electrode. In this study, the effect of microstructure of Ni-YSZ anode supported SOFC on the mechanical and electrical property was investigated. LSCF composite cathode and 8YSZ electrolyte were used. The porosity of the anode was modified by the amount of graphite powder and added graphite contents were 24, 18, 12 vol%, respectively. The higher the porosity, the better the electrical performance, $P_{max}$. While the flexural strength decreased with increasing the amount of graphite. But the rate of increase in electrical performance and the rate of decrease in mechanical strength were not directly proportional to amount of graphite. The optimum graphite content incorporating both electrical and mechanical performance was 18 vol%.

• Journal of the Korean Electrochemical Society
• /
• v.18 no.3
• /
• pp.130-135
• /
• 2015

The rate capability and low-temperature characteristics of graphite electrode are investigated after surface treatment with copper phthalocyanine (CuPc) or phthalocyanine (Pc). Uniform coating layers comprising amorphous carbon or copper are generated after the treatment. The rate performance of graphite electrodes is enhanced by the surface treatment, which is more prominent with CuPc. The resistance of the graphite electrode estimated from electrochemical impedance spectroscopy and pulse resistance measurement is the smallest for the CuPc-treated graphite. It is likely that the amorphous carbon layer formed by the decomposition of Pc facilitates $Li^+$ diffusion and the metallic copper derived from CuPc improves the electrical conductivity of the graphite electrode.

• Journal of the Korean Electrochemical Society
• /
• v.22 no.4
• /
• pp.155-163
• /
• 2019

Mixture electrodes of a graphite having a good cycle performance and a silicon monoxide (SiO) having a high capacity are fabricated and their cycle performances are evaluated as negative electrodes for lithium-ion batteries. The electrode prepared by mixing the natural graphite and carbon-coated SiO in a mass ratio of 9:1 shows a reversible capacity of $480mAh\;g^{-1}$, 33% higher than that of graphite. However, the capacity deteriorates continuously upon cycling due to the volume change of silicon monoxide. In this study, the factors that can improve the cycle performance have been discussed through the change in the configurations of the electrode and the electrolyte. The electrode using the carboxymethyl cellulose (CMC) binder shows the best cycle performance compared to the conventional binders. The electrode sing the CMC and styrene-butadiene rubber (SBR) binder not only has almost the similar cycle characteristics with the electrode using the CMC binder but also has the better rate capability. When the fluoroethylene carbonate (FEC) is used as an electrolyte additive, the cycle life is improved. However, the electrolyte with 5 wt% of FEC is appropriate because the rate capability decreases when the content of FEC is increased to 10 wt%. In addition, when the mass loading of the electrode is lowered, the cycle performance is greatly improved. Also, enhanced cycle performance is achieved using the roughened Cu current collector polished by abrasive paper.

• Journal of the Korean Magnetic Resonance Society
• /
• v.3 no.2
• /
• pp.90-99
• /
• 1999

Doping of boron atoms in graphite has been well known method to increase the discharge capacity as the negative electrode material for lithium secondary battery. Herein, the boron-doped graphites are prepared by mixing 1, 2.5, 5, and 7 wt. % of boron carbide in carbon during the graphitizing process. The structural states of boron in boron-doped graphites are investigated by solid-state 11B NMR spectroscopy. The resonance lines for substitutional boron atoms are identified as the second order quadrupolar powder pattern with the quardrupole coupling constant, QCC = 3.36(2) MHz. The quantitative analysis of 11B NMR spectra with boron-doped graphite has also been performed via simulation.