• Title/Summary/Keyword: Li free anode

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A LiPF6-LiFSI Blended-Salt Electrolyte System for Improved Electrochemical Performance of Anode-Free Batteries

  • Choi, Haeyoung;Bae, YeoJi;Lee, Sang-Min;Ha, Yoon-Cheol;Shin, Heon-Cheol;Kim, Byung Gon
    • Journal of Electrochemical Science and Technology
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    • v.13 no.1
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    • pp.78-89
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    • 2022
  • ANODE-free Li-metal batteries (AFLMBs) operating with Li of cathode material have attracted enormous attention due to their exceptional energy density originating from anode-free structure in the confined cell volume. However, uncontrolled dendritic growth of lithium on a copper current collector can limit its practical application as it causes fatal issues for stable cycling such as dead Li formation, unstable solid electrolyte interphase, electrolyte exhaustion, and internal short-circuit. To overcome this limitation, here, we report a novel dual-salt electrolyte comprising of 0.2 M LiPF6 + 3.8 M lithium bis(fluorosulfonyl)imide in a carbonate/ester co-solvent with 5 wt% fluoroethylene carbonate, 2 wt% vinylene carbonate, and 0.2 wt% LiNO3 additives. Because the dual-salt electrolyte facilitates uniform/dense Li deposition on the current collector and can form robust/ionic conductive LiF-based SEI layer on the deposited Li, a Li/Li symmetrical cell exhibits improved cycling performance and low polarization for over 200 h operation. Furthermore, the anode-free LiFePO4/Cu cells in the carbonate electrolyte shows significantly enhanced cycling stability compared to the counterparts consisting of different salt ratios. This study shows an importance of electrolyte design guiding uniform Li deposition and forming stable SEI layer for AFLMBs.

Cycling Behavior of Binder-Free Graphite-Lithium Intercalation Anode In AICI3-EMIC-LiCI-SOCI2 Room-Temperature Molten Salt

  • Koura, Nobuyuki;Minami, Takuto;Etoh, Keiko;Idemoto, Yasushi;Matsumoto, Futoshi
    • Journal of the Korean Electrochemical Society
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    • v.5 no.4
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    • pp.178-182
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    • 2002
  • The electrochemical behavior of binder-free carbon anode, comprising of only artificial and natural graphite (AG and NG) particles, for intercalation and deintercalation of lithium ion $(Li^+)$ in aluminum chloride (AICI_3)-I-ethyl­3-methylimidazolium chloride (EMIC)-lithium chloride (LiCl)-thionyl chloride $(SOCI_2)$ room-temperature molten salt (RTMS) was studied. Binder-free carbon electrodes were fabricated using electrophoretic deposition (EPD) method. The binder-free carbon anodes provided a relatively flat charge and discharge potentials $(0\;to\;0.2V\;vs.\;Li/Li^+)$ and current capabilities $(250-340mAh{\cdot}g^{-1})$ for the intercalation and deintercalation of $Li^+$. Stability of the binder-free carbon anodes for intercalation and deintercalation of 50 cycles was confirmed.

Electrochemical Properties of Cu Current Collector with Li0.5La0.5TiO3 or Si Thin Film as a Li Free Anode (Li0.5La0.5TiO3와 Si박막을 갖는 구리 집전체의 Li free 음극으로써의 전기화학적 특성)

  • Lee Jae-Jun;Kim Soo-Ho;Lee Jong-Min;Yoon Young-Soo
    • Journal of the Korean Electrochemical Society
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    • v.9 no.1
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    • pp.34-39
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    • 2006
  • Electrochemical properties of Cu foil current collector with a $Li_{0.5}La_{0.5}TiO_3$ Cu a Si thin film deposited by r.f sputtering as an anode for Li free battery were evaluated. The Cu foil current collectors were lied in and out of plasma during sputtering process. The X-ray diffraction results indicated that the as-deposited Si and $Li_{0.5}La_{0.5}TiO_3$ thin films in and out of plasma did not show any crystalline difference. The $Li_{0.5}La_{0.5}TiO_3$ film in plasma and Si film out of plasma showed better cyclability since crystalline $Li_{0.5}La_{0.5}TiO_3$ has much higher ionic conductivity and crystalline Si film is much sensitive far volume change during charge-discharge process. These results suggested that the deposition of amorphous Si on Cu foil current collector is much better for fabrication of Li free battery and it can be useful for the unique battery with a cycling number constraint of below 10.

Electrorefining of CuZr Alloy Using Ba2ZrF8-LiF Electrolyte

  • Lee, Seong Hun;Choi, Jeong Hun;Yoo, Bung Uk;Lee, Jong Hyeon
    • Korean Journal of Materials Research
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    • v.27 no.12
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    • pp.672-678
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    • 2017
  • In the production of zirconium cladding tube, a pickling acid solution is used to remove surface contaminants, which generates tons of pickling acid waste. The waste pickling solution is a valuable resource of Hf-free Zr. Many studies have investigated separating the Hf-free Zr source from the waste pickling acid. The results showed that $Ba_2ZrF_8$ precipitates prepared from the waste pickling acid were useful as an electrolyte for the electrorefining of Zr in molten salt. In the present work, electrorefining was performed in a $Ba_2ZrF_8-LiF$ binary electrolyte to recover Zr from a Hf-free CuZr ingot anode prepared by electroreduction. Before electrorefining, two pretreatments are performed. First, electrolyte melting was carried out to determine the eutectic temperature, and second, the electrolyte was treated to eliminate impurities, mainly hydride. After electrorefining, the cathode deposits were analyzed by $O_2$ gas analyzer and SEM-EDX to explore the possibility of recovering nuclear-grade Zr metal. Moreover, the anode was analyzed by SEM-EDX to determine the Zr dissolution depth.

Li-free Thin-Film Batteries with Structural Configuration of Pt/LiCoO2/LiPON/Cu and Pt/LiCoO2/LiPON/LiCoO2/Cu (Pt/LiCoO2/LiPON/Cu와 Pt/LiCoO2/LiPON/LiCoO2/Cu 구조를 갖는 Li-free 박막전지)

  • Shin, Min-Seon;Kim, Tae-Yeon;Lee, Sung-Man
    • Journal of the Korean institute of surface engineering
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    • v.51 no.4
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    • pp.243-248
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    • 2018
  • All solid state thin film batteries with two types of cell structure, Pt / $LiCoO_2$ / LiPON / Cu and Pt / $LiCoO_2$ / LiPON / $LiCoO_2$ / Cu, are prepared and their electrochemical performances are investigated to evaluate the effect of $LiCoO_2$ interlayer at the interface of LiPON / Cu. The crystallinity of the deposited $LiCoO_2$ thin films is confirmed by XRD and Raman analysis. The crystalline $LiCoO_2$ cathode thin film is obtained and $LiCoO_2$ as the interlayer appears to be amorphous. The surface morphology of Cu current collector after cycling of the batteries is observed by AFM. The presence of a 10 nm-thick layer of $LiCoO_2$ at the interface of LiPON / Cu enhances the interfacial adhesion and reduces the interfacial resistance. As a result, Li plating / stripping at the interface of LiPON / Cu during charge/discharge reaction takes place more uniformly on Cu current collector, while without the interlayer of $LiCoO_2$ at the interface of LiPON / Cu, the Li plating / stripping is localized on current collector. The thin film batteries with the interlayer of $LiCoO_2$ at the interface of LiPON / Cu exhibits enhanced initial coulombic efficiency, reversible capacity and cycling stability. The thickness of the anode current collector Cu also appears to be crucial for electrochemical performances of all solid state thin film batteries.

UV-cured Polymer Solid Electrolyte Reinforced using a Ceramic-Polymer Composite Layer for Stable Solid-State Li Metal Batteries

  • Hye Min Choi;Su Jin Jun;Jinhong Lee;Myung-Hyun Ryu;Hyeyoung Shin;Kyu-Nam Jung
    • Journal of Electrochemical Science and Technology
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    • v.14 no.1
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    • pp.85-95
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    • 2023
  • In recent years, solid-state Li metal batteries (SSLBs) have attracted significant attention as the next-generation batteries with high energy and power densities. However, uncontrolled dendrite growth and the resulting pulverization of Li during repeated plating/stripping processes must be addressed for practical applications. Herein, we report a plastic-crystal-based polymer/ceramic composite solid electrolyte (PCCE) to resolve these issues. To fabricate the one-side ceramic-incorporated PCCE (CI-PCCE) film, a mixed precursor solution comprising plastic-crystal-based polymer (succinonitrile, SN) with garnet-structured ceramic (Li7La3Zr2O12, LLZO) particles was infused into a thin cellulose membrane, which was used as a mechanical framework, and subsequently solidified by using UV-irradiation. The CI-PCCE exhibited good flexibility and a high room-temperature ionic conductivity of over 10-3 S cm-1. The Li symmetric cell assembled with CI-PCCE provided enhanced durability against Li dendrite penetration through the solid electrolyte (SE) layer than those with LLZO-free PCCEs and exhibited long-term cycling stability (over 200 h) for Li plating/stripping. The enhanced Li+ transference number and lower interfacial resistance of CI-PCCE indicate that the ceramic-polymer composite layer in contact with the Li anode enabled the uniform distribution of Li+ flux at the interface between the Li metal and CI-PCCE, thereby promoting uniform Li plating/stripping. Consequently, the Li//LiFePO4 (LFP) full cell constructed with CI-PCCE demonstrated superior rate capability (~120 mAh g-1 at 2 C) and stable cycle performance (80% after 100 cycles) than those with ceramic-free PCCE.

Electrochemical Properties of Additive-Free Nanostructured Cobalt Oxide (CoO) Lithium Ion Battery Electrode (첨가제 없이 제작된 나노구조 코발트 산화물 리튬이온 배터리 전극의 전기 화학적 특성)

  • Kim, Juyun;Park, Byoungnam
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.31 no.5
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    • pp.335-340
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    • 2018
  • Transition metal oxide materials have attracted widespread attention as Li-ion battery electrode materials owing to their high theoretical capacity and good Li storage capability, in addition to various nanostructured materials. Here, we fabricated a CoO Li-ion battery in which Co nanoparticles (NPs) are deposited into a current collector through electrophoretic deposition (EPD) without binding and conductive agents, enabling us to focus on the intrinsic electrochemical properties of CoO during the conversion reaction. Through optimized Co NP synthesis and electrophoretic deposition (EPD), CoO Li-ion battery with 630 mAh/g was fabricated with high cycle stability, which can potentially be used as a test platform for a fundamental understanding of conversion reaction.

Binder-free Sn/Graphene Nanocomposites Prepared by Electrophoretic Deposition for Anode Materials in Lithium Ion Batteries

  • Bae, Eun Gyoung;Hwang, Yun-Hwa;Pyo, Myoungho
    • Bulletin of the Korean Chemical Society
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    • v.34 no.4
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    • pp.1199-1204
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    • 2013
  • Nanocomposites consisting of Sn nanoparticles and graphene oxide (GO) were electrophoretically deposited onto Cu current collectors that was used for anodes in Li ion batteries (LIBs). In order to optimize the electrochemical performance of nanocomposites as an anode material by controlling the oxygen functionality, the GO was subjected to $O_3$ treatment prior to electrophoretic deposition (EPD). During thermal reduction of the GO in the nanocomposites, the Sn nanoparticles were reduced in size, along with the formation of SnO and/or $SnO_2$ at a small fraction, relying on the oxygen functionalities of the GO. The variation in the duration of time for the $O_3$ irradiation resulted in a small change in total oxygen content, but in a significantly different fraction of each functional group in the GO, which influenced the Sn nanoparticle size and the amount of SnO (and/or $SnO_2$). As a result, the EPD films prepared with the GO that possessed the least amount of carboxylic groups (made by treating GO in an $O_3$ environment for 3 h) showed the best performance, when compared with the nanocomposites composed of untreated GO or GO that was $O_3$-treated for a duration of less than 3 h.

The Corrosion Behavior of Li/K Carbonate Melts with CaCO3 Additives on Separator Plate in the Molten Carbonate Fuel Cell in the Anode Environments

  • Cho, Kyehyun;Lee, Chul-Hwan;Sung, Zu-Hwan
    • Corrosion Science and Technology
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    • v.5 no.4
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    • pp.129-136
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    • 2006
  • High temperature corrosion behavior of AISI-type 316L stainless steel for the MCFC(molten carbonate fuel cell) bipolar application was studied by immersion test and penetration attack method in anode environment ($650^{\circ}C$, $Li_2CO_3/K_2CO_3=62/38$ mol%, $H_2/CO_2=80/20$ vol%) without or with different $CaCO_3$ content. Not only immersion test method but also morphological observation of samples in the carbonate melts are adopted as experimental methods. With aid of the morphological observation of cross section of samples immersed in a carbonate melt was possible to obtain penetration attack. The concentration effect of $CaCO_3$ inhibitor was investigated in order to verify the optimum concentration for practical application in MCFC stack operation. The corrosion rate in the presence of $CaCO_3$ was proven to be decreased as a function of $CaCO_3$ concentration. The corrosion rate in the presence of $CaCO_3$ was measured with a value of 6.9 mpy which is 2.4 times lower than that of inhibitor-free electrolyte. The cross section microscopy revealed that the internal penetration by oxidation in molten carbonate is very severe. In this case, the attack was occurred not only dissolution loss in the electrolyte by corrosion reaction but also weight gain through oxide layer by internal penetration.

Integrated Thyristor Switch Structures for Capacitor Discharge Application

  • Kim, Eun-Dong;Zhang, Chang-Li;Kim, Sang-Cheol;Baek, Do-Hyun
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2001.05b
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    • pp.22-25
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    • 2001
  • A thyristor switch circuit for capacitor discharge application, of which the equivalent circuit includes a resistor between cathode and gate of a reverse-conducting thyristor and an avalanche diode anti-parallel between its anode and gate to set thyristor tum-on voltage, is monolithically integrated by planar process with AVE double-implantation method. To ensure a lower breakdown voltage of the avalanche diode for thyristor tum-on than the break-over voltage of the thyristor, $p^+$ wells on thyristor p base layer are made by boron implantation/drive-in for a steeper doping profile with higher concentrations while rest p layers of thyristor and free-wheeling diode parts are formed with Al implantation/drive-in for a doping profile of lower steepness. The free-wheeling diode part is isolated from the thyristor part by formation of separated p-well emitter for suppressing commutation between them, which is achieved during the formation of thyristor p-base layer.

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