Lithium ion batteries have been extensively used in portable electronic devices due to their high energy density and long cycle life. Recently, lithium ion batteries are required to run conditions that drive up to 1.5C, 2.0C, or higher in order to produce quick charge secondary cells, but the life degradation and safety concerns and rising. In other words, as the number of repetitions of the charge and discharge increases, the binding between the active materials and the ionic conductors becomes loose, and the contact resistance between the particles increases, and due to the increased resistance of the electrode, the battery performance is degraded, and during the life cycle degradation of cathode and anode materials occurs, and it is directly linked to life and safety issues. This study aims to improve the quick charge performance by improving the lithium ion material.
리튬이온 이차전지는 리튬이온이 이동하면서 전기화학적 충방전사이클을 완성하는 에너지변환장치를 의미한다. 리튬이온 이차전지는 높은 에너지밀도와 낮은 자가방전률, 상대적으로 긴 수명주기 등 다양한 장점을 갖는다. 최근 전기차 수 요증가는 고용량 리튬이온 이차전지 개발을 촉진하고 있으나 음극에서의 dendrite 형성으로 인한 전기적 단락 현상과 전지 폭 발 문제와 같은 심각한 안전문제를 야기한다. 또한, 리튬이온 이차전지 구동시 상승된 온도에서 폴리올레핀계열(예 : 폴리에 틸렌과 폴리프로필렌) 격리막의 열수축 문제가 발생한다. 이와 같이 낮은 열 안정성은 리튬이온 이차전지의 성능과 수명의 감소로 이어진다. 본 연구에서는 폴리올레핀계열 함침격리막 제조를 위한 중요한 소재로서 술폰화 폴리아릴렌에테르술폰 랜 덤 공중합체를 사용하였으며, 제조된 격리막을 이용하여 dendrite 형성과 관련된 금속이온 흡착 능력과 리튬이온전도성, 열적 내구성이 평가되었다.
Two different types of graphite, such as flake graphite (FG) and spherical graphite (SG), were used as anode materials for a lithium-ion secondary battery in order to investigate their electrochemical performance. The FG particles were prepared by pulverizing natural graphite with a planetary mill. The SG particles were treated by immersing them in acid solutions or mixing them with various carbon additives. With a longer milling time, the particle size of the FG decreased. Since smaller particles allow more exposure of the edge planes toward the electrolyte, it could be possible for the FG anodes with longer milling time to deliver high reversible capacity; however, their initial efficiency was found to have decreased. The initial efficiency of SG anodes with acid treatments was about 90%, showing an over 20% higher value than that of FG anodes. With acid treatment, the discharge rate capability and the initial efficiency improved slightly. The electrochemical properties of the SG anodes improved slightly with carbon additives such as acetylene black (AB), Super P, Ketjen black, and carbon nanotubes. Furthermore, the cyclability was much improved due to the effect of the conductive bridge made by carbon additives such as AB and Super P.
Carbon/silicon composites were synthesized by mixing silicon powders with petroleum pitch and subsequent heat-treatment. The resultant composites were composed of carbon and nano-size crystalline silicon identified by XRD and EDX. FIB images and SEM images were taken respectively to detect the existence of silicon impregnated in carbon and the distribution of silicon on the carbon surface. The obtained carbon/silicon materials were assembled as half cell anodes for lithium ion secondary battery and their electrochemical properties were tested. The pitch/silicon composite (3 : 1 wt. ratio) heat treated at 1000℃ and mixed with 55.5 wt.% of graphite showed relatively good electrochemical properties such as the initial efficiency of 78%, the initial discharge capacity of 605 mAh/g, and the discharge capacity of 500 mAh/g after 20 cycles.
The properties and electrochemical characteristics of anode material using pitch-coated graphite residue compounds by heat-treatment at 600℃ for 1 hour were investigated. The distance of layers of pitch-coated graphite residual compounds was 3.3539 a, which was as same as that of graphite. Its electrochemical and charge discharge characteristics were tested according to different four types of carbon material, natural graphite, pitch-coated graphite, amorphous graphite and pitch-coated graphite residual compounds, respectively. So it was shown the best charge-discharge characteristics in all of the samples. For the electrochemical and charge-discharge characteristics, although pitch-coated graphite residual compounds had different carbon contents 70% and 80%, these two samples were shown good electrochemical and charge-discharge characteristics.
The natural graphite particles A and heat-treated graphite particles B at 1800 ℃ after pitch-coating were used as the anode base materials for lithium ion secondary battery. In order to improve the performance of anode materials, the base anode materials were treated with various acids. With the acid treatments of 62% HNO3 and 95% H2SO4 aqueous solution, the specific surface area and electrical conductivity of base anode materials were increased, and the initial charge-discharge capacity and cycle performance were improved due to the elimination of structural defects.
In order to improve the lithium ion battery's performance, the carbon nanofibers were introduced to the anode electrode fabricated with natural graphite particles. The influence of structural adjustment of the particles by the introduction method of carbon nanofibers and the content of carbon nanofibers on the electrical property and charge/discharge characteristics of the electrode were investigated. The electrode fabricated with the mixture of 10 wt% of carbon nanofibers grown separately and 90 wt% of graphite particles showed an excellent discharge capacity of 400 mAh/g and the improved cycle performance. The improved performance could be explained by that the carbon nanofibers shortened and uniformly distributed on the surface of graphite particles by ball milling increased the stability for the intercalation/deintercalation of lithium ion and increased the electrical conductivity due to the closed packing between graphite particles.
휴대용 정보 통신기기의 소형 경량화에 적합한 고용량 전지인 리튬이온 이차전지에 응용되는 미세다공성 고분자 격리막에 관한 특성을 검토하였다. 격리막으로서 요구되어지는 항목은 전지 성능에도 관련되며, 안전에도 관련된 것들 이어서, 전지의 부재로서 상당히 중요한 부분을 차지하고 있다. 철재는 폴리에틸렌(PE) 등과 같은 폴리올레핀 소재를 연신하여 제조한 미세다공성 격리막이 주로 채용되고 있으며, 다양한 shut-down온도에 적용 가능하고, wettability가 향상된 미세다공성 격리막으로서, 불소계 고분자의 적용 및 폴리올레핀계 소재의 표면개질 등에 관한 연구가 지속되고 있다.