• Applied Chemistry for Engineering
• /
• v.26 no.6
• /
• pp.674-680
• /
• 2015

A solvent-soluble polyimide (PI) polymeric binder was synthesized by a two-step reaction for silicon (Si) anodes for lithium-ion batteries. Polyamic acid was first prepared through ring opening between two monomers, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (BCDA) and 4,4-oxydianiline (ODA), followed by condensation reaction. Using the synthesized PI polymeric binder (molecular weight = ~10,945), the coating slurry was then prepared and Si anode was fabricated. For the control system, Si anode based on polyvinylidene fluoride (PVDF, molecular weight = ~350,000) having the same constituent ratio was prepared. During precycling, PI polymeric binder revealed much improved discharge capacity ($2,167mAh\;g^{-1}$) compared to that of using PVDF polymeric binder ($1,740mAh\;g^{-1}$), while the Coulombic efficiency of two systems were similar. PI polymeric binder improved the cycle retention ability during cycles compared to that of using PVDF, which is attributed to an improved adhesion property inside Si anode diminishing the dimensional stress during Si volume changes. The adhesion property of each polymeric binder in Si anode was confirmed by surface and interfacial cutting analysis system (SAICAS) (Si anode based on PI polymeric binder = $0.217kN\;m^{-1}$ and Si anode based on PVDF polymeric binder = $0.185kN\;m^{-1}$).

• Journal of the Korean Electrochemical Society
• /
• v.15 no.3
• /
• pp.154-159
• /
• 2012

Structural volume change occurring on the Si-based anode battery materials during alloying/dealloying with lithium is noticed to be a major drawback responsible for a limited cycle life. Silicon monoxide has been reported to show relatively improved cycling performance compared to Si-containing materials for rechargeable lithium batteries, due to the structural buffering role of in-situ formed $Li_2O$ and lithium silicate during the reaction of silicon monoxide and lithium. Here we report improved cycling ability of interfacially stabilized Si-$SiO_2$-graphite composite anode using silane-based electrolyte additive for rechargeable lithium batteries, which includes low cost silicon dioxide for structural stabilization and graphite for enhanced conductivity.

• Korean Chemical Engineering Research
• /
• v.54 no.4
• /
• pp.459-464
• /
• 2016

In this study, the electrochemical characteristics of porous silicon/carbon composite anode were investigated to improve the cycle stability and rate performance in lithium ion batteries. In this study, the effect of TEOS and $NH_3$ concentration, mixing speed and temperature on particle size of nano silica was investigated using $St{\ddot{o}}ber$ method. Nano porous Si/C composites were prepared by the fabrication processes including the synthesis of nano $SiO_2$, magnesiothermic reduction of nano $SiO_2$ to obtain nano porous Si by HCl etching, and carbonization of phenolic resin. Also the electrochemical performances of nano porous Si/C composites as the anode were performed by constant current charge/discharge test, cyclic voltammetry and impedance tests in the electrolyte of $LiPF_6$ dissolved inorganic solvents (EC:DMC:EMC=1:1:1vol%). It is found that the coin cell using nano porous Si/C composite has the capacity of 2,006 mAh/g and the capacity retention ratio was 55.4% after 40 cycle.

• Journal of the Korean Electrochemical Society
• /
• v.17 no.2
• /
• pp.79-85
• /
• 2014

Silicon (Si) has been investigated as promising negative-electrode (anode) materials because its theoretical specific capacity of 4200 mAh/g for $Li_{4.4}Si$ is far higher than that of carbonaceous anodes in current commercial products. However, in practice, the application of Si to Li-ion batteries is still quite challenging because Si suffers from severe volume expansion and contraction and lead to a continuous solid electrolyte interphase (SEI)-filming process by cracking of Si. This process consumes the limited $Li^+$ source, builds up thick and unstable SEI layer on the Si active materials, and will eventually disable the cell. Since unstable SEI reduces electrochemical performance and thermal stability of the Si anode, the surface chemistry of the anode should be modified by using a functional additive. It is found that lithium bis(oxalato)borate (LiBOB) as an additive effectively protected the Si anode surface, improved capacity retention when stored at $60^{\circ}C$, and alleviated exothermic thermal reactions of fully lithiated Si anode.

• 한국전기화학회:학술대회논문집
• /
• 2002.10a
• /
• pp.60-60
• /
• 2002

• 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.

• Journal of the Korean institute of surface engineering
• /
• v.56 no.1
• /
• pp.62-68
• /
• 2023

Silicon (Si) is considered as a promising substitute for the conventional graphite due to its high theoretical specific capacity (3579 mAh/g, Li₁₅Si₄) and proper working voltage (~0.3V vs Li⁺/Li). However, the large volume change of Si during (de)lithiation brings about severe degradation of battery performances, rendering it difficult to be applied in the practical battery directly. As a one feasible candidate of industrial Si anode, silicon monoxide (SiO_x) demonstrates great electrochemical stability with its specialized strategy, downsized Si nanocrystallites surrounded by Li⁺ inactive buffer phase (Li₂O and Li₄SiO₄). Nevertheless, SiO_x inherently has the initial irreversible capacity and poor electrical conductivity. To overcome those issues, conformal carbon coating has been performed on SiO_x utilizing ethylbenzene as the carbon precursor of chemical vapor deposition (CVD). Through various characterizations, it is confirmed that the carbon is homogeneously coated on the surface of SiO_x. Accordingly, the carbon-coated SiOx from CVD using ethylbenzene demonstrates 73% of the first cycle efficiency and great cycle life (88.1% capacity retention at 50th cycle). This work provides a promising synthetic route of the uniform and scalable carbon coating on Si anode for high-energy density.

• Journal of the Korean Ceramic Society
• /
• v.50 no.6
• /
• pp.480-484
• /
• 2013

Since SiOC was introduced as an anode material for lithium ion batteries, it has been studied with different chemical compositions and microstructures using various silicon based inorganic polymers. Poly(phenyl carbosilane) is a SiOC precursor with a high carbon supply in the form of the phenyl unit, and it has been investigated for film applications. Unlike any other siloxane-based polymers, oxygen atoms must be utilized in an oxidation process, and the amount of oxygen is controllable. In this study, SiOC anodes were prepared using poly(phenyl carbosilane) with different heat treatment conditions, and their electrochemical properties as an anode material for lithium ion batteries were studied. In detail, cyclic voltammetry and charge-discharge cycling behavior were evaluated using a half-cell. A SiOC anode which was prepared under a heat treatment condition at $1200^{\circ}C$ after an oxidation step showed stable cyclic performance with a reversible capacity of 360 mAh/g.

• Journal of Electrochemical Science and Technology
• /
• v.13 no.2
• /
• pp.269-278
• /
• 2022

Utilization of high-voltage electrolyte additive(s) at a small fraction is a cost-effective strategy for a good solid electrolyte interphase (SEI) formation and performance improvement of a lithium-rich layered oxide-based high-energy lithium-ion cell by avoiding the occurrence of metal-dissolution that is one of the failure modes. To mitigate metal-dissolution, we explored fluorinated dual-additives of fluoroethylene carbonate (FEC) and di(2,2,2-trifluoroethyl)carbonate (DFDEC) for building-up of a good SEI in a 4.7 V full-cell that consists of high-capacity silicon-graphite composite (15 wt% Si/C/CF/C-graphite) anode and Li_1.13Mn_0.463Ni_0.203Co_0.203O₂ (LMNC) cathode. The full-cell including optimum fractions of dual-additives shows increased capacity to 228 mAhg^-1 at 0.2C and improved performance from the one in the base electrolyte. Surface analysis results find that the SEI stabilization of LMNC cathode induced by dual-additives leads to a suppression of soluble Mn²⁺-O formation at cathode surface, mitigating metal-dissolution event and crack formation as well as structural degradation. The SEI and structure of Si/C/CF/C-graphite anode is also stabilized by the effects of dual-additives, contributing to performance improvement. The data give insight into a basic understanding of cathode-electrolyte and anode-electrolyte interfacial processes and cathode-anode interaction that are critical factors affecting full-cell performance.

• Journal of Electrochemical Science and Technology
• /
• v.15 no.2
• /
• pp.291-298
• /
• 2024

Due to its high theoretical capacity, Silicon (Si) has shown great potential as an anode material for lithium-ion batteries (LIBs). However, the large volume change of Si during cycling leads to poor cycling stability and low Coulombic efficiency. In this study, we synthesized Si/Carbon C45:Graphene composites using a ball-milling method with a fixed Si content (20%) and investigated the influence of the C45/Gr ratio on the electrochemical performance of the composites. The results showed that carbon C45 networks can provide good conductivity, but tend to break at Si locations, resulting in poor conductivity. However, the addition of graphene helps to reconnect the broken C45 networks, improving the conductivity of the composite. Moreover, the C45 can also act as a protective coating around Si particles, reducing the volume expansion of Si during charging/discharging cycles. The Si/C45:Gr (70:10 wt%) composite exhibits improved electrochemical performance with high capacity (~1660 mAh g^-1 at 0.1 C) and cycling stability (~1370 mAh g^-1 after 100 cycles). This work highlights the effective role of carbon C45 and graphene in Si/C composites for enhancing the performance of Si-based anode materials for LIBs.