Understanding the anisotropic strain effects on lithium diffusion in graphite anodes: A first-principles study

NASA Astrophysics Data System (ADS)

Ji, Xiang; Wang, Yang; Zhang, Junqian

2018-06-01

The lithium diffusion in graphite anode, which is the most widely used commercial electrode material today, affects the charge/discharge performance of lithium-ion batteries. In this study, the anisotropic strain effects on lithium diffusion in graphite anodes are systematically investigated using first-principles calculations based on density functional theory (DFT) with van der Waals corrections. It is found that the effects of external applied strains along various directions of LixC6 (i.e., perpendicular or parallel to the basal planes of the graphite host) on lithium diffusivity are different. Along the direction perpendicular to the graphite planes, the tensile strain facilitates in-plane Li diffusion by reducing the energy barrier, and the compressive strain hinders in-plane Li diffusion by raising the energy barrier. In contrast, the in-plane biaxial tensile strain (parallel to the graphite planes) hinders in-plane Li diffusion, and the in-plane biaxial compressive strain facilitates in-plane Li diffusion. Furthermore, both in-plane and transverse shear strains slightly influence Li diffusion in graphite anodes. A discussion is presented to explain the anisotropic strain dependence of lithium diffusion. This research provides data for the continuum modelling of the electrodes in the lithium-ion batteries.

Germanium and Tin Based Anode Materials for Lithium-Ion Batteries

NASA Astrophysics Data System (ADS)

Ji, Dongsheng

The discovery of safe anode materials with high energy density for lithium-ion batteries has always been a significant topic. Group IV elements have been under intensive study for their high capability of alloying with lithium. Batteries with graphite and tin based anode material have already been applied in cell phones and vehicles. In order to apply group IV elements, their dramatic volume change during lithiation and delithiation processes is the key point to work on. Reducing the particle size is the most common method to buffer the volume expansion. This strategy has been applied on both germanium and tin based materials. Germanium based anode material has been made by two different synthesis methods. The amorphous Ge-C-Ti composite material was made by ball milling method and performed much better than other germanium alloy including Ge-Mg, Ge-Fe and Ge-Fe.Germanium sphere nano particles with diameter of around 50 nm have been made by solution method. After ball milled with graphite, the resulted product performed stable capacity over 500 mAh˙g-1 for more than 20 cycles. Ball milled graphite in the composite plays an important role of buffering volume change and stabilizing germanium. Sn-Fe alloy is one of the feasible solutions to stabilize tin. Sn 2Fe-C composite has been made by ball milling method. After optimizations of the ratio of precursors, reaction time, milling balls and electrolyte additives, the electrochemistry performance was improved. The anode performed 420 mAh˙ -1 at 1.0 mA/cm2 and maintained its structure after cycling at 2.0 mA/cm2. At 0.3 mA/cm2 cycling rate, the anode performed 978 mAh/cm3 after 500 cycles, which still exceeds the theoretical capacity of graphite.

Physical, electrochemical, and thermal properties of granulated natural graphite as anodes for Li-ion batteries.

PubMed

Jo, Yong Nam; Park, Min-Sik; Kim, Jae-Hun; Kim, Young-Jun

2013-05-01

Two different types of granulated graphites were synthesized by blending and kneading of natural graphite with pitch followed by sintering methods. The electrochemical performances of granulated graphites were investigated as anode materials for use in Li-ion batteries. The blending type granulated graphite possesses a large amount of cavities and voids, while the kneading type granulated graphite has a relatively compact microstructure, which is responsible for a high tap density. Both granulated graphites show improved the initial coulombic efficiencies as a result of decrease of surface area by the granulations. In particular, the kneading type granulated graphite exhibits an excellent rate-capability without significant capacity loss. In addition, the thermal stabilities of both granulated graphites were also improved, which could be attributed to the decrease of active surface area due to pitch coating.

Controllable Self-Assembly of Micro-Nanostructured Si-Embedded Graphite/Graphene Composite Anode for High-Performance Li-Ion Batteries.

PubMed

Lin, Ning; Xu, Tianjun; Li, Tieqiang; Han, Ying; Qian, Yitai

2017-11-15

Si-containing graphite-based composites are considered as promising high-capacity anodes for lithium-ion batteries (LIBs). Here, a controllable and scalable self-assembly strategy is developed to produce micro-nanostructured graphite/Si/reduced graphene oxides composite (SGG). The self-assembly procedure is realized by the hydrogen bond interaction between acylamino-modified graphite and graphene oxides (GO); Si nanoparticles are in situ embedded between graphite and GO sheets uniformly. This architecture is able to overcome the incompatibility between Si nanoparticles and microsized graphite. Accordingly, the as-prepared SGG anode (Si 8 wt %) delivers a reversible Li-storage capacity of 572 mAh g -1 at 0.2 C, 502.2 mAh g -1 after 600 cycles at 0.8 C with a retention of 92%, and a capacity retention of 64% even at 10 C. The impressive electrochemical properties are ascribed to the stable architecture and three-dimensional conductive network constructed by graphite and graphene sheets, which can accommodate the huge volume change of Si, keep the conductive contact and structural integrity, and suppress side reactions with electrolyte. Additionally, the full-cell (LiFePO 4 cathode/SGG anode) delivers a specific capacity of 550 mAh g -1 with a working potential beyond 3.0 V.

Synthesis of Copper Oxide/Graphite Composite for High-Performance Rechargeable Battery Anode.

PubMed

Cho, Sanghun; Ahn, Yong-Keon; Yin, Zhenxing; You, Duck-Jae; Kim, Hyunjin; Piao, Yuanzhe; Yoo, Jeeyoung; Kim, Youn Sang

2017-08-25

A novel copper oxide/graphite composite (GCuO) anode with high capacity and long cycle stability is proposed. A simple, one-step synthesis method is used to prepare the GCuO, through heat treatment of the Cu ion complex and pristine graphite. The gases generated during thermal decomposition of the Cu ion complex (H 2 and CO 2 ) induce interlayer expansion of the graphite planes, which assists effective ion intercalation. Copper oxide is formed simultaneously as a high-capacity anode material through thermal reduction of the Cu ion complex. Material analyses reveal the formation of Cu oxide nanoparticles and the expansion of the gaps between the graphite layers from 0.34 to 0.40 nm, which is enough to alleviate layer stress for reversible ion intercalation for Li or Na batteries. The GCuO cell exhibits excellent Li-ion battery half-cell performance, with a capacity of 532 mAh g -1 at 0.2 C (C-rate) and capacity retention of 83 % after 250 cycles. Moreover, the LiFePO 4 /GCuO full cell is fabricated to verify the high performance of GCuO in practical applications. This cell has a capacity of 70 mAh g -1 and a coulombic efficiency of 99 %. The GCuO composite is therefore a promising candidate for use as an anode material in advanced Li- or Na-ion batteries. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

High performance Li-ion sulfur batteries enabled by intercalation chemistry.

PubMed

Lv, Dongping; Yan, Pengfei; Shao, Yuyan; Li, Qiuyan; Ferrara, Seth; Pan, Huilin; Graff, Gordon L; Polzin, Bryant; Wang, Chongmin; Zhang, Ji-Guang; Liu, Jun; Xiao, Jie

2015-09-11

The unstable interface of lithium metal in high energy density Li sulfur (Li-S) batteries raises concerns of poor cycling, low efficiency and safety issues, which may be addressed by using intercalation types of anode. Herein, a new prototype of Li-ion sulfur battery with high performance has been demonstrated by coupling a graphite anode with a sulfur cathode (2 mA h cm(-2)) after successfully addressing the interface issue of graphite in an ether based electrolyte.

Promising Cell Configuration for Next-Generation Energy Storage: Li2S/Graphite Battery Enabled by a Solvate Ionic Liquid Electrolyte.

PubMed

Li, Zhe; Zhang, Shiguo; Terada, Shoshi; Ma, Xiaofeng; Ikeda, Kohei; Kamei, Yutaro; Zhang, Ce; Dokko, Kaoru; Watanabe, Masayoshi

2016-06-29

Lithium-ion sulfur batteries with a [graphite|solvate ionic liquid electrolyte|lithium sulfide (Li2S)] structure are developed to realize high performance batteries without the issue of lithium anode. Li2S has recently emerged as a promising cathode material, due to its high theoretical specific capacity of 1166 mAh/g and its great potential in the development of lithium-ion sulfur batteries with a lithium-free anode such as graphite. Unfortunately, the electrochemical Li(+) intercalation/deintercalation in graphite is highly electrolyte-selective: whereas the process works well in the carbonate electrolytes inherited from Li-ion batteries, it cannot take place in the ether electrolytes commonly used for Li-S batteries, because the cointercalation of the solvent destroys the crystalline structure of graphite. Thus, only very few studies have focused on graphite-based Li-S full cells. In this work, simple graphite-based Li-S full cells were fabricated employing electrolytes beyond the conventional carbonates, in combination with highly loaded Li2S/graphene composite cathodes (Li2S loading: 2.2 mg/cm(2)). In particular, solvate ionic liquids can act as a single-phase electrolyte simultaneously compatible with both the Li2S cathode and the graphite anode and can further improve the battery performance by suppressing the shuttle effect. Consequently, these lithium-ion sulfur batteries show a stable and reversible charge-discharge behavior, along with a very high Coulombic efficiency.

Hierarchical silicon nanowires-carbon textiles matrix as a binder-free anode for high-performance advanced lithium-ion batteries

PubMed Central

Liu, Bin; Wang, Xianfu; Chen, Haitian; Wang, Zhuoran; Chen, Di; Cheng, Yi-Bing; Zhou, Chongwu; Shen, Guozhen

2013-01-01

Toward the increasing demands of portable energy storage and electric vehicle applications, the widely used graphite anodes with significant drawbacks become more and more unsuitable. Herein, we report a novel scaffold of hierarchical silicon nanowires-carbon textiles anodes fabricated via a facile method. Further, complete lithium-ion batteries based on Si and commercial LiCoO2 materials were assembled to investigate their corresponding across-the-aboard performances, demonstrating their enhanced specific capacity (2950 mAh g−1 at 0.2 C), good repeatability/rate capability (even >900 mAh g−1 at high rate of 5 C), long cycling life, and excellent stability in various external conditions (curvature, temperature, and humidity). Above results light the way to principally replacing graphite anodes with silicon-based electrodes which was confirmed to have better comprehensive performances. PMID:23572030

Microwave exfoliated graphene oxide/TiO{sub 2} nanowire hybrid for high performance lithium ion battery

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ishtiaque Shuvo, Mohammad Arif; Rodriguez, Gerardo; Karim, Hasanul

Lithium ion battery (LIB) is a key solution to the demand of ever-improving, high energy density, clean-alternative energy systems. In LIB, graphite is the most commonly used anode material; however, lithium-ion intercalation in graphite is limited, hindering the battery charge rate and capacity. To date, one of the approaches in LIB performance improvement is by using porous carbon (PC) to replace graphite as anode material. PC's pore structure facilitates ion transport and has been proven to be an excellent anode material candidate in high power density LIBs. In addition, to overcome the limited lithium-ion intercalation obstacle, nanostructured anode assembly hasmore » been extensively studied to increase the lithium-ion diffusion rate. Among these approaches, high specific surface area metal oxide nanowires connecting nanostructured carbon materials accumulation have shown promising results for enhanced lithium-ion intercalation. Herein, we demonstrate a hydrothermal approach of growing TiO{sub 2} nanowires (TON) on microwave exfoliated graphene oxide (MEGO) to further improve LIB performance over PC. This MEGO-TON hybrid not only uses the high surface area of MEGO but also increases the specific surface area for electrode–electrolyte interaction. Therefore, this new nanowire/MEGO hybrid anode material enhances both the specific capacity and charge–discharge rate. Scanning electron microscopy and X-ray diffraction were used for materials characterization. Battery analyzer was used for measuring the electrical performance of the battery. The testing results have shown that MEGO-TON hybrid provides up to 80% increment of specific capacity compared to PC anode.« less

Final Report: Novel ALD-Coated Nanoparticle Anodes for Enhanced Performance Lithium-Ion Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Groner, Markus

2009-04-16

The Phase I effort is described in detail in the Phase I report given below. The key accomplishments of the Phase I project were (1) the demonstration of high stability LiCoO2 cathodes using ALD-coated LiCoO2 particles, as well as on ALD-coated LiCoO2 electrodes and (2) the demonstration of high stability of graphite anodes using ALD-coated graphite electrodes.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jeong, Sookyung; Li, Xiaolin; Zheng, Jianming

With the ever increasing demands on Li-ion batteries with higher energy densities, alternative anode with higher reversible capacity is required to replace the conventional graphite anode. Here, we demonstrate a cost-effective hydrothermal-carbonization approach to prepare the hard carbon coated nano-Si/graphite (HC-nSi/G) composite as a high performance anode for Li-ion batteries. In this hierarchical structured composite, the hard carbon coating layer not only provides an efficient pathway for electron transfer, but also alleviates the volume variation of silicon during charge/discharge processes. The HC-nSi/G composite electrode shows excellent electrochemical performances including a high specific capacity of 878.6 mAh g-1 based on themore » total weight of composite, good rate performance and a decent cycling stability, which is promising for practical applications.« less

A high-performance ternary Si composite anode material with crystal graphite core and amorphous carbon shell

NASA Astrophysics Data System (ADS)

Sui, Dong; Xie, Yuqing; Zhao, Weimin; Zhang, Hongtao; Zhou, Ying; Qin, Xiting; Ma, Yanfeng; Yang, Yong; Chen, Yongsheng

2018-04-01

Si is a promising anode material for lithium-ion batteries, but suffers from sophisticated engineering structures and complex fabrication processes that pose challenges for commercial application. Herein, a ternary Si/graphite/pyrolytic carbon (SiGC) anode material with a structure of crystal core and amorphous shell using low-cost raw materials is developed. In this ternary SiGC composite, Si component exists as nanoparticles and is spread on the surface of the core graphite flakes while the sucrose-derived pyrolytic carbon further covers the graphite/Si components as the amorphous shell. With this structure, Si together with the graphite contributes to the high specific capacity of this Si ternary material. Also the graphite serves as the supporting and conducting matrix and the amorphous shell carbon could accommodate the volume change effect of Si, reinforces the integrity of the composite architecture, and prevents the graphite and Si from direct exposing to the electrolyte. The optimized ternary SiGC composite displays high reversible specific capacity of 818 mAh g-1 at 0.1 A g-1, initial Coulombic efficiency (CE) over 80%, and excellent cycling stability at 0.5 A g-1 with 83.6% capacity retention (∼610 mAh g-1) after 300 cycles.

Electrolyte volume effects on electrochemical performance and solid electrolyte interphase in Si-graphite/NMC lithium-ion pouch cells

DOE PAGES

An, Seong Jin; Li, Jianlin; Daniel, Claus; ...

2017-05-15

This study aims to explore the correlations between electrolyte volume, electrochemical performance, and properties of the solid electrolyte interphase in pouch cells with Si-graphite composite anodes. The electrolyte is 1.2 M LiPF 6 in ethylene carbonate:ethylmethyl carbonate with 10 wt.% fluoroethylene carbonate. Single layer pouch cells (100 mAh) were constructed with 15 wt.% Si-graphite/LiNi 0.5Mn 0.3CO 0.2O 2 electrodes. It is found that a minimum electrolyte volume factor of 3.1 times the total pore volume of cell components (cathode, anode, and separator) is needed for better cycling stability. Less electrolyte causes increases in ohmic and charge transfer resistances. Lithium dendritesmore » are observed when the electrolyte volume factor is low. The resistances from the anodes become significant as the cells are discharged. As a result, solid electrolyte interphase thickness grows as the electrolyte volume factor increases and is non-uniform after cycling.« less

The effects of anode material type on the optoelectronic properties of electroplated CdTe thin films and the implications for photovoltaic application

NASA Astrophysics Data System (ADS)

Echendu, O. K.; Dejene, B. F.; Dharmadasa, I. M.

2018-03-01

The effects of the type of anode material on the properties of electrodeposited CdTe thin films for photovoltaic application have been studied. Cathodic electrodeposition of two sets of CdTe thin films on glass/fluorine-doped tin oxide (FTO) was carried out in two-electrode configuration using graphite and platinum anodes. Optical absorption spectra of films grown with graphite anode displayed significant spread across the deposition potentials compared to those grown with platinum anode. Photoelectrochemical cell result shows that the CdTe grown with graphite anode became p-type after post-deposition annealing with prior CdCl2 treatment, as a result of carbon incorporation into the films, while those grown with platinum anode remained n-type after annealing. A review of recent photoluminescence characterization of some of these CdTe films reveals the persistence of a defect level at (0.97-0.99) eV below the conduction band in the bandgap of CdTe grown with graphite anode after annealing while films grown with platinum anode showed the absence of this defect level. This confirms the impact of carbon incorporation into CdTe. Solar cell made with CdTe grown with platinum anode produced better conversion efficiency compared to that made with CdTe grown using graphite anode, underlining the impact of anode type in electrodeposition.

High performance sulfur graphite full cell for next generation sulfur Li-ion battery

NASA Astrophysics Data System (ADS)

Wu, Yunwen; Momma, Toshiyuki; Yokoshima, Tokihiko; Nara, Hiroki; Osaka, Tetsuya

2018-06-01

Sulfur (S) Li-ion battery which use the metallic Li free anode is deemed as a promising solution to conquer the hazards originating from Li metal. However, stable cycling performance and low production price of the S Li-ion battery still remain challenging. Here, we propose a S-LixC full cell system by paring a S cathode and a pre-lithiated graphite anode which is cheap and commercially available. It shows stable cycling performance with a capacity around 1300 mAh (g-S)-1 at 0.2 C-rate and 1000 mAh (g-S)-1 at 0.5 C-rate. In addition, 0.1% per cycle capacity fading rate with a capacity retention of 880 mAh (g-S)-1 after 400 cycles at 0.2 C-rate has been achieved. The pre-formed solid electrolyte interphase (SEI) layer on the pre-lithaited graphite anode largely contributes to the high capacity performance. Notably, a 10-times-enlarged scale of S-LixC laminate type full cell has been assembled with high capacity performance (around 1000 mAh (g-S)-1) even after high rate cycling.

Macroporous graphitic carbon foam decorated with polydopamine as a high-performance anode for microbial fuel cell

NASA Astrophysics Data System (ADS)

Jiang, Hongmei; Yang, Lu; Deng, Wenfang; Tan, Yueming; Xie, Qingji

2017-09-01

Herein, a macroporous graphitic carbon foam (MGCF) electrode decorated with polydopamine (PDA) is used as a high-performance anode for microbial fuel cell (MFC) applications. The MGCF is facilely prepared by pyrolysis of a powder mixture comprising maltose, nickel nitrate, and ammonia chloride, without using solid porous template. The MGCF is coated with PDA by self-polymerization of dopamine in a basic solution. The MGCF can provide a large surface area for bacterial attachment, and PDA coated on the MGCF electrode can further promote bacterial adhesion resulting from the improved hydrophility, so the MGCF-PDA electrode as an anode in a MFC can show ultrahigh bacterial loading capacity. Moreover, the electrochemical oxidation of flavins at the MGCF-PDA electrode is greatly accelerated, so the extracellular electron transfer mediated by flavins is improved. As a result, the MFC equipped with a MGCF-PDA anode can show a maximum power density of 1735 mW cm-2, which is 6.7 times that of a MFC equipped with a commercial carbon felt anode, indicating a promising anode for MFC applications.

Combined carbon mesh and small graphite fiber brush anodes to enhance and stabilize power generation in microbial fuel cells treating domestic wastewater

NASA Astrophysics Data System (ADS)

Wu, Shijia; He, Weihua; Yang, Wulin; Ye, Yaoli; Huang, Xia; Logan, Bruce E.

2017-07-01

Microbial fuel cells (MFCs) need to have a compact architecture, but power generation using low strength domestic wastewater is unstable for closely-spaced electrode designs using thin anodes (flat mesh or small diameter graphite fiber brushes) due to oxygen crossover from the cathode. A composite anode configuration was developed to improve performance, by joining the mesh and brushes together, with the mesh used to block oxygen crossover to the brushes, and the brushes used to stabilize mesh potentials. In small, fed-batch MFCs (28 mL), the composite anode produced 20% higher power densities than MFCs using only brushes, and 150% power densities compared to carbon mesh anodes. In continuous flow tests at short hydraulic retention times (HRTs, 2 or 4 h) using larger MFCs (100 mL), composite anodes had stable performance, while brush anode MFCs exhibited power overshoot in polarization tests. Both configurations exhibited power overshoot at a longer HRT of 8 h due to lower effluent CODs. The use of composite anodes reduced biomass growth on the cathode (1.9 ± 0.2 mg) compared to only brushes (3.1 ± 0.3 mg), and increased coulombic efficiencies, demonstrating that they successfully reduced oxygen contamination of the anode and the bio-fouling of cathode.

From spent graphite to amorphous sp2+sp3 carbon-coated sp2 graphite for high-performance lithium ion batteries

NASA Astrophysics Data System (ADS)

Ma, Zhen; Zhuang, Yuchan; Deng, Yaoming; Song, Xiaona; Zuo, Xiaoxi; Xiao, Xin; Nan, Junmin

2018-02-01

Today, with the massive application of lithium ion batteries (LIBs) in the portable devices and electric vehicles, to supply the active materials with high-performances and then to recycle their wastes are two core issues for the development of LIBs. In this paper, the spent graphite (SG) in LIBs is used as raw materials to fabricate two comparative high-capacity graphite anode materials. Based on a microsurgery-like physical reconstruction, the reconstructed graphite (RG) with a sp2+sp3 carbon surface is prepared through a microwave exfoliation and subsequent spray drying process. In contrast, the neural-network-like amorphous sp2+sp3 carbon-coated graphite (AC@G) is synthesized using a self-reconfigurable chemical reaction strategy. Compared with SG and commercial graphite (CG), both RG and AC@G have enhanced specific capacities, from 311.2 mAh g-1 and 360.7 mAh g-1 to 409.7 mAh g-1 and 420.0 mAh g-1, at 0.1C after 100 cycles. In addition, they exhibit comparable cycling stability, rate capability, and voltage plateau with CG. Because the synthesis of RG and AC@G represents two typical physical and chemical methods for the recycling of SG, these results on the sp2+sp3 carbon layer coating bulk graphite also reveal an approach for the preparation of high-performance graphite anode materials derived from SG.

Intercalation of Li Ions into a Graphite Anode Material: Molecular Dynamics Simulations

NASA Astrophysics Data System (ADS)

Abou Hamad, Ibrahim; Novotny, Mark

2008-03-01

Large-scale molecular dynamics simulations of the anode half-cell of a lithium-ion battery are presented. The model system is composed of an anode represented by a stack of graphite sheets, an electrolyte of ethylene carbonate and propylene carbonate molecules, and lithium and hexafluorophosphate ions. The simulations are done in the NVT ensemble and at room temperature. One charging scheme explored is normal charging in which intercalation is enhanced by electric charges on the graphitic sheets. The second charging mechanism has an external applied oscillatory electric field of amplitude A and frequency f. The simulations were performed on 2.6 GHz Opteron processors, using 160 processors at a time. Our simulation results show an improvement in the intercalation time of the lithium ions for the second charging mechanism. The dependence of the intercalation time on A and f will be discussed.

Rice husk-originating silicon-graphite composites for advanced lithium ion battery anodes.

PubMed

Kim, Hye Jin; Choi, Jin Hyeok; Choi, Jang Wook

2017-01-01

Rice husk is produced in a massive amount worldwide as a byproduct of rice cultivation. Rice husk contains approximately 20 wt% of mesoporous SiO 2 . We produce mesoporous silicon (Si) by reducing the rice husk-originating SiO 2 using a magnesio-milling process. Taking advantage of meso-porosity and large available quantity, we apply rice husk-originating Si to lithium ion battery anodes in a composite form with commercial graphite. By varying the mass ratio between these two components, trade-off relation between specific capacity and cycle life was observed. A controllable pre-lithiation scheme was adopted to increase the initial Coulombic efficiency and energy density. The series of electrochemical results suggest that rice husk-originating Si-graphite composites are promising candidates for high capacity lithium ion battery anodes, with the prominent advantages in battery performance and scalability.

Direct methanol fuel cell with extended reaction zone anode: PtRu and PtRuMo supported on graphite felt

NASA Astrophysics Data System (ADS)

Bauer, Alex; Gyenge, Előd L.; Oloman, Colin W.

Pressed graphite felt (thickness ∼350 μm) with electrodeposited PtRu (43 g m -2, 1.4:1 atomic ratio) or PtRuMo (52 g m -2, 1:1:0.3 atomic ratio) nanoparticle catalysts was investigated as an anode for direct methanol fuel cells. At temperatures above 333 K the fuel cell performance of the PtRuMo catalyst was superior compared to PtRu. The power density was 2200 W m -2 with PtRuMo at 5500 A m -2 and 353 K while under the same conditions PtRu yielded 1925 W m -2. However, the degradation rate of the Mo containing catalyst formulation was higher. Compared to conventional gas diffusion electrodes with comparable PtRu catalyst composition and load, the graphite felt anodes gave higher power densities mainly due to the extended reaction zone for methanol oxidation.

High Voltage Li-Ion Battery Using Exfoliated Graphite/Graphene Nanosheets Anode.

PubMed

Agostini, Marco; Brutti, Sergio; Hassoun, Jusef

2016-05-04

The achievement of a new generation of lithium-ion battery, suitable for a continuously growing consumer electronic and sustainable electric vehicle markets, requires the development of new, low-cost, and highly performing materials. Herein, we propose a new and efficient lithium-ion battery obtained by coupling exfoliated graphite/graphene nanosheets (EGNs) anode and high-voltage, spinel-structure cathode. The anode shows a capacity exceeding by 40% that ascribed to commercial graphite in lithium half-cell, at very high C-rate, due to its particular structure and morphology as demonstrated by X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The Li-ion battery reveals excellent efficiency and cycle life, extending up to 150 cycles, as well as an estimated practical energy density of about 260 Wh kg(-1), that is, a value well exceeding the one associated with the present-state Li-ion battery.

Chemical Evolution in Silicon–Graphite Composite Anodes Investigated by Vibrational Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ruther, Rose E.; Hays, Kevin A.; An, Seong Jin

Silicon–graphite composites are under development for the next generation of high-capacity lithium-ion anodes, and vibrational spectroscopy is a powerful tool to identify the different mechanisms that contribute to performance loss. With alloy anodes, the underlying causes of cell failure are significantly different in half-cells with lithium metal counter electrodes compared to full cells with standard cathodes. However, most studies which take advantage of vibrational spectroscopy have only examined half-cells. In this work, a combination of FTIR and Raman spectroscopy describes several factors that lead to degradation in full pouch cells with LiNi 0.5Mn 0.3Co 0.2O 2 (NMC532) cathodes. The spectroscopicmore » signatures evolve after longer term cycling compared to the initial formation cycles. Several side-reactions that consume lithium ions have clear FTIR signatures, and comparison to a library of reference compounds facilitates identification. Raman microspectroscopy combined with mapping shows that the composite anodes are not homogeneous but segregate into graphite-rich and silicon-rich phases. Lithiation does not proceed uniformly either. A basis analysis of Raman maps identifies electrochemically inactive regions of the anodes. In conclusion, the spectroscopic results presented here emphasize the importance of improving electrode processing and SEI stability to enable practical composite anodes with high silicon loadings.« less

Chemical Evolution in Silicon–Graphite Composite Anodes Investigated by Vibrational Spectroscopy

DOE PAGES

Ruther, Rose E.; Hays, Kevin A.; An, Seong Jin; ...

2018-05-24

Silicon–graphite composites are under development for the next generation of high-capacity lithium-ion anodes, and vibrational spectroscopy is a powerful tool to identify the different mechanisms that contribute to performance loss. With alloy anodes, the underlying causes of cell failure are significantly different in half-cells with lithium metal counter electrodes compared to full cells with standard cathodes. However, most studies which take advantage of vibrational spectroscopy have only examined half-cells. In this work, a combination of FTIR and Raman spectroscopy describes several factors that lead to degradation in full pouch cells with LiNi 0.5Mn 0.3Co 0.2O 2 (NMC532) cathodes. The spectroscopicmore » signatures evolve after longer term cycling compared to the initial formation cycles. Several side-reactions that consume lithium ions have clear FTIR signatures, and comparison to a library of reference compounds facilitates identification. Raman microspectroscopy combined with mapping shows that the composite anodes are not homogeneous but segregate into graphite-rich and silicon-rich phases. Lithiation does not proceed uniformly either. A basis analysis of Raman maps identifies electrochemically inactive regions of the anodes. In conclusion, the spectroscopic results presented here emphasize the importance of improving electrode processing and SEI stability to enable practical composite anodes with high silicon loadings.« less

Synthesis and photocatalytic properties of graphitic carbon nitride nanofibers using porous anodic alumina templates

NASA Astrophysics Data System (ADS)

Suchitra, S. M.; Udayashankar, N. K.

2017-12-01

In the present study, we describe an effective method for the synthesis of Graphitic carbon nitride (GCN) nanostructures using porous anodic alumina (AAO) membrane as template by simple thermal condensation of cyanamide. Synthesized nanostructure was fully analysed by various techniques to detect its crystalline nature, morphology, luminescent properties followed by the evaluation of its photocatalytic activity in the degradation of Methylene blue dye. Structural analysis of synthesized GCNNF was systematically carried out using x-ray powder diffraction (XRD) and scanning electron microscope (SEM), and. The results confirmed the growth of GCN inside the nanochannels of anodic alumina templates. Luminescent properties of GCNNF were studied using photoluminescence (PL) spectroscopy. PL analysis showed the presence of a strong emission peak in the wavelength range of 350-600 nm in blue region. GCNNF displays higher photocatalytic performance in the photodegradation of methylene blue compare to the bulk GCN. Highlights 1. In the present paper, we report the synthesis of graphitic carbon nitride nanofibers (GCNNF) using porous anodic aluminium oxide membranes as templates through thermal condensation of cyanamide at 500 °C. 2. The synthesis of Graphitic carbon nitride nanofibers using porous andic alumina template is the efficient approach for increasing crystallinity and surface area. 3. The high surface area of graphitic carbon nitride nanofibers has a good impact on novel optical and photocatalytic properties of the bulkGCN. 4. AAO templating of GCN is one of the versatile method to produce tailorable GCN nanostructures with higher surface area and less number of structural defects. 5. Towards photocatalytic degradation of dyes, the tuning of physical properties is very essential thing hence we are succeeded in achieving better catalytic performance of GCN nanostructures by making use of AAO templates.

Phenol-degrading anode biofilm with high coulombic efficiency in graphite electrodes microbial fuel cell.

PubMed

Zhang, Dongdong; Li, Zhiling; Zhang, Chunfang; Zhou, Xue; Xiao, Zhixing; Awata, Takanori; Katayama, Arata

2017-03-01

A microbial fuel cell (MFC), with graphite electrodes as both the anode and cathode, was operated with a soil-free anaerobic consortium for phenol degradation. This phenol-degrading MFC showed high efficiency with a current density of 120 mA/m 2 and a coulombic efficiency of 22.7%, despite the lack of a platinum catalyst cathode and inoculation of sediment/soil. Removal of planktonic bacteria by renewing the anaerobic medium did not decrease the performance, suggesting that the phenol-degrading MFC was not maintained by the planktonic bacteria but by the microorganisms in the anode biofilm. Cyclic voltammetry analysis of the anode biofilm showed distinct oxidation and reduction peaks. Analysis of the microbial community structure of the anode biofilm and the planktonic bacteria based on 16S rRNA gene sequences suggested that Geobacter sp. was the phenol degrader in the anode biofilm and was responsible for current generation. Copyright © 2016 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

The Role of Cesium Cation in Controlling Interphasial Chemistry on Graphite Anode in Propylene Carbonate-Rich Electrolytes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xiang, Hongfa; Mei, Donghai; Yan, Pengfei

2015-09-10

Propylene carbonate (PC) is seldom used in lithium-ion batteries (LIBs) due to its sustained co-intercalation into graphene structure and the eventual graphite exfoliation, despite potential advantages it brings, such as wider liquid range and lower cost. Here we discover that cesium cation (Cs+), originally used to suppress dendrite growth of Li metal anode, directs the formation of solid electrolyte interphase (SEI) on graphitic anode in PC-rich electrolytes through preferential solvation. Effective suppression of PC-decomposition and graphite-exfoliation was achieved when the ratio of ethylene carbonate (EC)/PC in electrolytes was so adjusted that the reductive decomposition of Cs+-(EC)m (1≤m≤2) complex precedes thatmore » of Li+-(PC)n (3≤n≤5). The interphase directed by Cs+ is stable, ultrathin and compact, leading to significant improvements in LIB performances. In a broader context, the accurate tailoring of SEI chemical composition by introducing a new solvation center represents a fundamental breakthrough in manipulating interfacial reactions processes that once were elusive.« less

The optimization of CMC concentration as graphite binder on the anode of LiFePO4 battery

NASA Astrophysics Data System (ADS)

Hidayat, S.; Cahyono, T.; Mindara, J. Y.; Riveli, N.; Alamsyah, W.; Rahayu, I.

2017-05-01

Recently, the most dominating power supply on the mobile electronics market are rechargeable Lithium-ion batteries. This is because of a higher energy density and a longer lifetime compared to similar rechargeable battery systems. Graphite is commonly used as anode material in the Lithium-ion batteries, because of its excellent electrochemical characteristics and low cost fabrication. In this paper, we reported the optimization of the concentration of the CMC (carboxymethyl cellulose), that acts as the binder for graphite anode. Based on our experimental results, the best composition of graphite : C : CMC is 90 : 8 : 2 in weight %. Anode with such composition has, based on SEM measurement, a relatively good surface morphology, while it also has relatively high conductivity, about 2.68 S/cm. The result of cyclic voltammogram with a scan rate of 10 mV/s in the voltage range of 0 to 1 Volt, shows the peak of reduction voltage at 0.85 Volts and the peak voltage of oxidation is at -1.5 Volt. The performance of the battery system with LiFePO4 set as the cathode, shows that the working voltage is about 2.67 Volts at 1 mA current-loading, with the efficiency around 47%.

Pyrolytic Carbon Nanosheets for Ultrafast and Ultrastable Sodium-Ion Storage.

PubMed

Cho, Se Youn; Kang, Minjee; Choi, Jaewon; Lee, Min Eui; Yoon, Hyeon Ji; Kim, Hae Jin; Leal, Cecilia; Lee, Sungho; Jin, Hyoung-Joon; Yun, Young Soo

2018-04-01

Na-ion cointercalation in the graphite host structure in a glyme-based electrolyte represents a new possibility for using carbon-based materials (CMs) as anodes for Na-ion storage. However, local microstructures and nanoscale morphological features in CMs affect their electrochemical performances; they require intensive studies to achieve high levels of Na-ion storage performances. Here, pyrolytic carbon nanosheets (PCNs) composed of multitudinous graphitic nanocrystals are prepared from renewable bioresources by heating. In particular, PCN-2800 prepared by heating at 2800 °C has a distinctive sp 2 carbon bonding nature, crystalline domain size of ≈44.2 Å, and high electrical conductivity of ≈320 S cm -1 , presenting significantly high rate capability at 600 C (60 A g -1 ) and stable cycling behaviors over 40 000 cycles as an anode for Na-ion storage. The results of this study show the unusual graphitization behaviors of a char-type carbon precursor and exceptionally high rate and cycling performances of the resulting graphitic material, PCN-2800, even surpassing those of supercapacitors. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Germanium Nanowires-in-Graphite Tubes via Self-Catalyzed Synergetic Confined Growth and Shell-Splitting Enhanced Li-Storage Performance.

PubMed

Sun, Yong; Jin, Shuaixing; Yang, Guowei; Wang, Jing; Wang, Chengxin

2015-04-28

Despite the high theoretical capacity, pure Ge has various difficulties such as significant volume expansion and electron and Li(+) transfer problems, when applied as anode materials in lithium ion battery (LIB), for which the solution would finally rely on rational design like advanced structures and available hybrid. Here in this work, we report a one-step synthesis of Ge nanowires-in-graphite tubes (GNIGTs) with the liquid Ge/C synergetic confined growth method. The structure exhibits impressing LIB behavior in terms of both cyclic stability and rate performance. We found the semiclosed graphite shell with thickness of ∼50 layers experience an interesting splitting process that was driven by electrolyte diffusion, which occurs before the Ge-Li alloying plateau begins. Two types of different splitting mechanism addressed as "inside-out"/zipper effect and "outside-in" dominate this process, which are resulted from the SEI layer growing longitudinally along the Ge-graphite interface and the lateral diffusion of Li(+) across the shell, respectively. The former mechanism is the predominant way driving the initial shell to split, which behaves like a zipper with SEI layer as invisible puller. After repeated Li(+) insertion/exaction, the GNIGTs configuration is finally reconstructed by forming Ge nanowires-thin graphite strip hybrid, both of which are in close contact, resulting in enormous enchantment to the electrons/Li(+) transport. These features make the structures perform well as anode material in LIB. We believe both the progress in 1D assembly and the structure evolution of this Ge-C composite would contribute to the design of advanced LIB anode materials.

A Fluorinated Ether Electrolyte Enabled High Performance Prelithiated Graphite/Sulfur Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Shuru; Yu, Zhaoxin; Gordin, Mikhail L.

Lithium/sulfur (Li/S) batteries have attracted great attention as a promising energy storage technology, but so far their practical applications are greatly hindered by issues of polysulfide shuttling and unstable lithium/electrolyte interface. To address these issues, a feasible strategy is to construct a rechargeable prelithiated graphite/sulfur batteries. In this study, a fluorinated ether of bis(2,2,2-trifluoroethyl) ether (BTFE) was reported to blend with 1,3-dioxolane (DOL) for making a multifunctional electrolyte of 1.0 M LiTFSI DOL/BTFE (1:1, v/v) to enable high performance prelithiated graphite/S batteries. First, the electrolyte significantly reduces polysulfide solubility to suppress the deleterious polysulfide shuttling and thus improves capacity retentionmore » of sulfur cathodes. Second, thanks to the low viscosity and good wettability, the fluorinated electrolyte dramatically enhances the reaction kinetics and sulfur utilization of high-areal-loading sulfur cathodes. More importantly, this electrolyte forms a stable solid-electrolyte interphase (SEI) layer on graphite surface and thus enables remarkable cyclability of graphite anodes. Lastly, by coupling prelithiated graphite anodes with sulfur cathodes with high areal capacity of ~3 mAh cm -2, we demonstrate prelithiated graphite/sulfur batteries that show high sulfur-specific capacity of ~1000 mAh g -1 and an excellent capacity retention of >65% after 450 cycles at C/10.« less

A Fluorinated Ether Electrolyte Enabled High Performance Prelithiated Graphite/Sulfur Batteries

DOE PAGES

Chen, Shuru; Yu, Zhaoxin; Gordin, Mikhail L.; ...

2017-02-03

Lithium/sulfur (Li/S) batteries have attracted great attention as a promising energy storage technology, but so far their practical applications are greatly hindered by issues of polysulfide shuttling and unstable lithium/electrolyte interface. To address these issues, a feasible strategy is to construct a rechargeable prelithiated graphite/sulfur batteries. In this study, a fluorinated ether of bis(2,2,2-trifluoroethyl) ether (BTFE) was reported to blend with 1,3-dioxolane (DOL) for making a multifunctional electrolyte of 1.0 M LiTFSI DOL/BTFE (1:1, v/v) to enable high performance prelithiated graphite/S batteries. First, the electrolyte significantly reduces polysulfide solubility to suppress the deleterious polysulfide shuttling and thus improves capacity retentionmore » of sulfur cathodes. Second, thanks to the low viscosity and good wettability, the fluorinated electrolyte dramatically enhances the reaction kinetics and sulfur utilization of high-areal-loading sulfur cathodes. More importantly, this electrolyte forms a stable solid-electrolyte interphase (SEI) layer on graphite surface and thus enables remarkable cyclability of graphite anodes. Lastly, by coupling prelithiated graphite anodes with sulfur cathodes with high areal capacity of ~3 mAh cm -2, we demonstrate prelithiated graphite/sulfur batteries that show high sulfur-specific capacity of ~1000 mAh g -1 and an excellent capacity retention of >65% after 450 cycles at C/10.« less

Constructing a novel and safer energy storing system using a graphite cathode and a MoO 3 anode

NASA Astrophysics Data System (ADS)

Gunawardhana, Nanda; Park, Gum-Jae; Dimov, Nikolay; Thapa, Arjun Kumar; Nakamura, Hiroyoshi; Wang, Hongyu; Ishihara, Tatsumi; Yoshio, Masaki

A cell employing a graphite cathode and a molybdenum (VI) oxide (MoO 3) anode is investigated as a possible energy storage device. Graphite cathode allows raising the voltage well above the cathode materials of LIBs without causing safety issues. The bottom potential of this anode is 2.0 V vs. Li/Li +, which is well above the lithium plating potential. Pulse polarization experiment reveals that no lithium deposition occurs, which further enhances the safety of the graphite/MoO 3 full cell. Charge/discharge mechanism of this system results from intercalation and de-intercalation of the PF 6 - in the cathode (KS-6) and Li + in the anode (MoO 3). This mechanism is supported by in situ X-ray diffraction data of the graphite/MoO 3 cell recorded at various states of charge.

Understanding the crack formation of graphite particles in cycled commercial lithium-ion batteries by focused ion beam - scanning electron microscopy

NASA Astrophysics Data System (ADS)

Lin, Na; Jia, Zhe; Wang, Zhihui; Zhao, Hui; Ai, Guo; Song, Xiangyun; Bai, Ying; Battaglia, Vincent; Sun, Chengdong; Qiao, Juan; Wu, Kai; Liu, Gao

2017-10-01

The structure degradation of commercial Lithium-ion battery (LIB) graphite anodes with different cycling numbers and charge rates was investigated by focused ion beam (FIB) and scanning electron microscopy (SEM). The cross-section image of graphite anode by FIB milling shows that cracks, resulted in the volume expansion of graphite electrode during long-term cycling, were formed in parallel with the current collector. The crack occurs in the bulk of graphite particles near the lithium insertion surface, which might derive from the stress induced during lithiation and de-lithiation cycles. Subsequently, crack takes place along grain boundaries of the polycrystalline graphite, but only in the direction parallel with the current collector. Furthermore, fast charge graphite electrodes are more prone to form cracks since the tensile strength of graphite is more likely to be surpassed at higher charge rates. Therefore, for LIBs long-term or high charge rate applications, the tensile strength of graphite anode should be taken into account.

Functional interface of polymer modified graphite anode

NASA Astrophysics Data System (ADS)

Komaba, S.; Ozeki, T.; Okushi, K.

Graphite electrodes were modified by polyacrylic acid (PAA), polymethacrylic acid (PMA), and polyvinyl alcohol (PVA). Their electrochemical properties were examined in 1 mol dm -3 LiClO 4 ethylene carbonate:dimethyl carbonate (EC:DMC) and propylene carbonate (PC) solutions as an anode of lithium ion batteries. Generally, lithium ions hardly intercalate into graphite in the PC electrolyte due to a decomposition of the PC electrolyte at ca. 0.8 V vs. Li/Li +, and it results in the exfoliation of the graphene layers. However, the modified graphite electrodes with PAA, PMA, and PVA demonstrated the stable charge-discharge performance due to the reversible lithium intercalation not only in the EC:DMC but also in the PC electrolytes since the electrolyte decomposition and co-intercalation of solvent were successfully suppressed by the polymer modification. It is thought that these improvements were attributed to the interfacial function of the polymer layer on the graphite which interacted with the solvated lithium ions at the electrode interface.

High Energy, Long Cycle Life Lithium-ion Batteries for PHEV Application

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Donghai; Manthiram, Arumugam; Wang, Chao-Yang

High-loading and high quality PSU Si anode has been optimized and fabricated. The electrochemical performance has been utilized. The PSU Si-graphite anode exhibits the mass loading of 5.8 mg/cm2, charge capacity of 850 mAh/ g and good cycling performance. This optimized electrode has been used for full-cell fabrication. The performance enhancement of Ni-rich materials can be achieved by a diversity of strategies. Higher Mn content and a small amount of Al doping can improve the electrochemical performance by suppressing interfacial side reactions with electrolytes, thus greatly benefiting the cyclability of the samples. Also, surface coatings of Li-rich materials and AlFmore » 3 are able to improve the performance stability of Ni-rich cathodes. One kilogram of optimized concentration-gradient LiNi 0.76Co 0.10Mn 0.14O 2 (CG) with careful control of composition, morphology and electrochemical performance was delivered to our collaborators. The sample achieved an initial specific capacity close to 190 mA h g -1 at C/10 rate and 180 mA h g -1 at C/3 rate as well as good cyclability in pouch full cells with a 4.4 V upper cut-off voltage at room temperature. Electrolyte additive with Si-N skeleton forms a less resistant SEI on the surface of silicon anode (from PSU) as evidenced by the evolution of the impedance at various lithiation/de-lithiation stages and the cycling data The prelithiation result demonstrates a solution processing method to achieve large area, uniform SLMP coating on well-made anode surface for the prelithiation of lithium-ion batteries. The prelithiation effect with this method is applied both in graphite half cells, graphite/NMC full cells, SiO half cells, SiO/NMC full cells, Si-Graphite half cells and Si-Graphite/NMC full cells with improvements in cycle performance and higher first cycle coulombic efficiency than their corresponding cells without SLMP prelithiation. As to the full cell fabrication and test, full pouch cells with high capacity of 2.2 Ah and 1.2 Ah have been fabricated and delivered. The cells show great uniformity and good cycling performance. The prelithiation method effectively compensate the loss in the first cycle. The cell with high energy density and long-cycle life has been achieved.« less

Remarkable cycle-activated capacity increasing in onion-like carbon nanospheres as lithium battery anode material

NASA Astrophysics Data System (ADS)

Dong, Jiajun; Zhang, Tong; Zhang, Dong; Zhang, Weiwei; Zhang, Huafang; Liu, Ran; Yao, Mingguang; Liu, Bingbing

2017-01-01

Onion-like carbon nanospheres (OCNSs) with an average diameter of 43 nm were produced on a large scale via a combustion method and examined as an anode material for lithium ion batteries. The OCNSs exhibit a remarkable electrochemical cycling behavior and a capacity much higher than that of graphite. The capacity increases significantly with increasing charge-discharge cycles and reaches a value of 178% of the initial value (from 586 mA h g-1to 1045 mA h g-1) after 200 cycles. Further investigation provides unambiguous experimental evidence that such a remarkable capacity increase is related to the stable onion-like structure of the OCNSs and to the existence of large numbers of disordered/short graphitic fragments, which gradually provide more active sites for Li ion storage. The unique electrochemical performance of OCNSs provides a new way to design a high-performance anode material for rechargeable batteries.

Uneven biofilm and current distribution in three-dimensional macroporous anodes of bio-electrochemical systems composed of graphite electrode arrays.

PubMed

Li, Jun; Hu, Linbin; Zhang, Liang; Ye, Ding-Ding; Zhu, Xun; Liao, Qiang

2017-03-01

A 3-D macroporous anode was constructed using different numbers of graphite rod arrays in fixed-volume bio-electrochemical systems (BESs), and the current and biofilm distribution were investigated by dividing the 3-D anode into several subunits. In the fixed-volume chamber, current production was not significantly improved after the electrode number increased to 36. In the case of 100 electrodes, a significant uneven current distribution was found in the macroporous anode. This was attributed to a differential pH distribution, which resulted from proton accumulation inside the macroporous anode. The pH distribution influenced the biofilm development and led to an uneven biofilm distribution. With respect to current generation, the uneven distribution of both the pH and biofilm contributed to the uneven current distribution. The center had a low pH, which led to less biofilm and a lower contribution to the total current, limiting the performance of the BESs. Copyright © 2016 Elsevier Ltd. All rights reserved.

Conductive polymer binder for nano-silicon/graphite composite electrode in lithium-ion batteries towards a practical application

DOE PAGES

Zhao, Hui; Du, Allen; Ling, Min; ...

2016-05-10

The state-of-the-art graphite anode containing a small portion of silicon represents a promising way of applying high-capacity alloy anode in the next generation high energy density lithium-ion batteries. The conductive polymeric binders developed for Si anodes proved to be an effective binder for this graphite/nanoSi composite electrode. Without any acetylene black conductive additives in the electrode, a high areal capacity of above 2.5 mAh/cm 2 is achieved during long-term cycling over 100 cycles. Finally, this conductive polymer-enabled graphite/nanoSi composite electrode exhibits high specific capacity and high 1 st cycle efficiency, which is a significant progress toward commercial application of Simore » anodes.« less

Fundamental Investigation of Si Anode in Li-Ion Cells

NASA Technical Reports Server (NTRS)

Wu, James J.; Bennett, William R.

2012-01-01

Silicon is a promising and attractive anode material to replace graphite for high capacity lithium ion cells since its theoretical capacity is approximately 10 times of graphite and it is an abundant element on earth. However, there are challenges associated with using silicon as Li-ion anode due to the significant first cycle irreversible capacity loss and subsequent rapid capacity fade during cycling. In this paper, cyclic voltammetry and electrochemical impedance spectroscopy are used to build a fundamental understanding of silicon anodes. The results show that it is difficult to form the SEI film on the surface of Si anode during the first cycle, the lithium ion insertion and de-insertion kinetics for Si are sluggish, and the cell internal resistance changes with the state of lithiation after electrochemical cycling. These results are compared with those for extensively studied graphite anodes. The understanding gained from this study will help to design better Si anodes.

Shape Modification and Size Classification of Microcrystalline Graphite Powder as Anode Material for Lithium-Ion Batteries

NASA Astrophysics Data System (ADS)

Wang, Cong; Gai, Guosheng; Yang, Yufen

2018-03-01

Natural microcrystalline graphite (MCG) composed of many crystallites is a promising new anode material for lithium-ion batteries (LiBs) and has received considerable attention from researchers. MCG with narrow particle size distribution and high sphericity exhibits excellent electrochemical performance. A nonaddition process to prepare natural MCG as a high-performance LiB anode material is described. First, raw MCG was broken into smaller particles using a pulverization system. Then, the particles were modified into near-spherical shape using a particle shape modification system. Finally, the particle size distribution was narrowed using a centrifugal rotor classification system. The products with uniform hemispherical shape and narrow size distribution had mean particle size of approximately 9 μm, 10 μm, 15 μm, and 20 μm. Additionally, the innovative pilot experimental process increased the product yield of the raw material. Finally, the electrochemical performance of the prepared MCG was tested, revealing high reversible capacity and good cyclability.

Encapsulation of α-Fe2O3 nanoparticles in graphitic carbon microspheres as high-performance anode materials for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Zhang, Hongwei; Sun, Xiaoran; Huang, Xiaodan; Zhou, Liang

2015-02-01

A novel ``spray drying-carbonization-oxidation'' strategy has been developed for the fabrication of α-Fe2O3-graphitic carbon (α-Fe2O3@GC) composite microspheres, in which α-Fe2O3 nanoparticles with sizes of 30-50 nm are well-encapsulated by onion-like graphitic carbon shells with a thickness of 5-10 nm. In the constructed composite, the α-Fe2O3 nanoparticles act as the primary active material, providing a high capacity. Meanwhile, the graphitic carbon shells serve as the secondary active component, structural stabilizer, interfacial stabilizer, and electron-highway. As a result, the synthesized α-Fe2O3@GC nanocomposite exhibits a superior lithium-ion battery performance with a high reversible capacity (898 mA h g-1 at 400 mA g-1), outstanding rate capability, and excellent cycling stability. Our product, in terms of the facile and scalable preparation process and excellent electrochemical performance, demonstrates its great potential as a high-performance anode material for lithium-ion batteries.A novel ``spray drying-carbonization-oxidation'' strategy has been developed for the fabrication of α-Fe2O3-graphitic carbon (α-Fe2O3@GC) composite microspheres, in which α-Fe2O3 nanoparticles with sizes of 30-50 nm are well-encapsulated by onion-like graphitic carbon shells with a thickness of 5-10 nm. In the constructed composite, the α-Fe2O3 nanoparticles act as the primary active material, providing a high capacity. Meanwhile, the graphitic carbon shells serve as the secondary active component, structural stabilizer, interfacial stabilizer, and electron-highway. As a result, the synthesized α-Fe2O3@GC nanocomposite exhibits a superior lithium-ion battery performance with a high reversible capacity (898 mA h g-1 at 400 mA g-1), outstanding rate capability, and excellent cycling stability. Our product, in terms of the facile and scalable preparation process and excellent electrochemical performance, demonstrates its great potential as a high-performance anode material for lithium-ion batteries. Electronic supplementary information (ESI) available: XRD pattern, XPS spectrum, CV curves, TEM and SEM images, and table. See DOI: 10.1039/c4nr06771a

Optimization and Domestic Sourcing of Lithium Ion Battery Anode Materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wood, III, D. L.; Yoon, S.

2012-10-25

The purpose of this Cooperative Research and Development Agreement (CRADA) between ORNL and A123Systems, Inc. was to develop a low-temperature heat treatment process for natural graphite based anode materials for high-capacity and long-cycle-life lithium ion batteries. Three major problems currently plague state-of-the-art lithium ion battery anode materials. The first is the cost of the artificial graphite, which is heat-treated well in excess of 2000°C. Because of this high-temperature heat treatment, the anode active material significantly contributes to the cost of a lithium ion battery. The second problem is the limited specific capacity of state-of-the-art anodes based on artificial graphites, whichmore » is only about 200-350 mAh/g. This value needs to be increased to achieve high energy density when used with the low cell-voltage nanoparticle LiFePO4 cathode. Thirdly, the rate capability under cycling conditions of natural graphite based materials must be improved to match that of the nanoparticle LiFePO4. Natural graphite materials contain inherent crystallinity and lithium intercalation activity. They hold particular appeal, as they offer huge potential for industrial energy savings with the energy costs essentially subsidized by geological processes. Natural graphites have been heat-treated to a substantially lower temperature (as low as 1000-1500°C) and used as anode active materials to address the problems described above. Finally, corresponding graphitization and post-treatment processes were developed that are amenable to scaling to automotive quantities.« less

Silicon Based Anodes for Li-Ion Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Jiguang; Wang, Wei; Xiao, Jie

2012-06-15

Silicon is environmentally benign and ubiquitous. Because of its high specific capacity, it is considered one of the most promising candidates to replace the conventional graphite negative electrode used in today's Li ion batteries. Silicon has a theoretical specific capacity of nearly 4200 mAh/g (Li21Si5), which is 10 times larger than the specific capacity of graphite (LiC6, 372 mAh/g). However, the high capacity of silicon is associated with huge volume changes (more than 300 percent) when alloyed with lithium, which can cause severe cracking and pulverization of the electrode and lead to significant capacity loss. Significant scientific research has beenmore » conducted to circumvent the deterioration of silicon based anode materials during cycling. Various strategies, such as reduction of particle size, generation of active/inactive composites, fabrication of silicon based thin films, use of alternative binders, and the synthesis of 1-D silicon nanostructures have been implemented by a number of research groups. Fundamental mechanistic research has also been performed to better understand the electrochemical lithiation and delithiation process during cycling in terms of crystal structure, phase transitions, morphological changes, and reaction kinetics. Although efforts to date have not attained a commercially viable Si anode, further development is expected to produce anodes with three to five times the capacity of graphite. In this chapter, an overview of research on silicon based anodes used for lithium-ion battery applications will be presented. The overview covers electrochemical alloying of the silicon with lithium, mechanisms responsible for capacity fade, and methodologies adapted to overcome capacity degradation observed during cycling. The recent development of silicon nanowires and nanoparticles with significantly improved electrochemical performance will also be discussed relative to the mechanistic understanding. Finally, future directions on the development of silicon based anodes will be considered.« less

Graphite anode surface modification with controlled reduction of specific aryl diazonium salts for improved microbial fuel cells power output.

PubMed

Picot, Matthieu; Lapinsonnière, Laure; Rothballer, Michael; Barrière, Frédéric

2011-10-15

Graphite electrodes were modified with reduction of aryl diazonium salts and implemented as anodes in microbial fuel cells. First, reduction of 4-aminophenyl diazonium is considered using increased coulombic charge density from 16.5 to 200 mC/cm(2). This procedure introduced aryl amine functionalities at the surface which are neutral at neutral pH. These electrodes were implemented as anodes in "H" type microbial fuel cells inoculated with waste water, acetate as the substrate and using ferricyanide reduction at the cathode and a 1000 Ω external resistance. When the microbial anode had developed, the performances of the microbial fuel cells were measured under acetate saturation conditions and compared with those of control microbial fuel cells having an unmodified graphite anode. We found that the maximum power density of microbial fuel cell first increased as a function of the extent of modification, reaching an optimum after which it decreased for higher degree of surface modification, becoming even less performing than the control microbial fuel cell. Then, the effect of the introduction of charged groups at the surface was investigated at a low degree of surface modification. It was found that negatively charged groups at the surface (carboxylate) decreased microbial fuel cell power output while the introduction of positively charged groups doubled the power output. Scanning electron microscopy revealed that the microbial anode modified with positively charged groups was covered by a dense and homogeneous biofilm. Fluorescence in situ hybridization analyses showed that this biofilm consisted to a large extent of bacteria from the known electroactive Geobacter genus. In summary, the extent of modification of the anode was found to be critical for the microbial fuel cell performance. The nature of the chemical group introduced at the electrode surface was also found to significantly affect the performance of the microbial fuel cells. The method used for modification is easy to control and can be optimized and implemented for many carbon materials currently used in microbial fuel cells and other bioelectrochemical systems. Copyright © 2011 Elsevier B.V. All rights reserved.

Theoretical Limits of Energy Density in Silicon-Carbon Composite Anode Based Lithium Ion Batteries.

PubMed

Dash, Ranjan; Pannala, Sreekanth

2016-06-17

Silicon (Si) is under consideration as a potential next-generation anode material for the lithium ion battery (LIB). Experimental reports of up to 40% increase in energy density of Si anode based LIBs (Si-LIBs) have been reported in literature. However, this increase in energy density is achieved when the Si-LIB is allowed to swell (volumetrically expand) more than graphite based LIB (graphite-LIB) and beyond practical limits. The volume expansion of LIB electrodes should be negligible for applications such as automotive or mobile devices. We determine the theoretical bounds of Si composition in a Si-carbon composite (SCC) based anode to maximize the volumetric energy density of a LIB by constraining the external dimensions of the anode during charging. The porosity of the SCC anode is adjusted to accommodate the volume expansion during lithiation. The calculated threshold value of Si was then used to determine the possible volumetric energy densities of LIBs with SCC anode (SCC-LIBs) and the potential improvement over graphite-LIBs. The level of improvement in volumetric and gravimetric energy density of SCC-LIBs with constrained volume is predicted to be less than 10% to ensure the battery has similar power characteristics of graphite-LIBs.

Single-Wall Carbon Nanotube Production by the Arc Process: A Parametric Study

NASA Technical Reports Server (NTRS)

Scott, Carl D.; Gorelik, Olga; Proft, William J.

2000-01-01

Single wall carbon nanotubes are produced using the arc discharge process. Graphite anodes are filled with a mixture of nickel and yttrium metallic powders, then vaporized by creating a high current arc. By varying the current, gap distance, and ambient pressure it is shown that the best yield of single wall carbon nanotubes is obtained within a narrow range of conditions. The relative yield and purity of the product are indicated semi-quantitatively from scanning electric microscopy (SEM) and thermogravimetric analysis (TGA). Two types of anodes have been investigated. The first is hollow and filled with a powder mixture of graphite, nickel and yttrium. The second is filled with a paste made of a mixture of metal nitrates, graphite powder and carbon adhesive, then reduced in an argon atmosphere at high temperature. Product purity and yield will be compared for the two types of anodes. The graphite in the anodes may have hydrogen attached in the pores. To remove this impurity anodes have been baked up to 1400 - 1500 C. The effect of baking the anodes on impurities in the product will be given.

Understanding the crack formation of graphite particles in cycled commercial lithium-ion batteries by focused ion beam - scanning electron microscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Na; Jia, Zhe; Wang, Zhihui

Here in this paper, the structure degradation of commercial Lithium-ion battery (LIB) graphite anodes with different cycling numbers and charge rates was investigated by focused ion beam (FIB) and scanning electron microscopy (SEM). The cross-section image of graphite anode by FIB milling shows that cracks, resulted in the volume expansion of graphite electrode during long-term cycling, were formed in parallel with the current collector. The crack occurs in the bulk of graphite particles near the lithium insertion surface, which might derive from the stress induced during lithiation and de-lithiation cycles. Subsequently, crack takes place along grain boundaries of the polycrystallinemore » graphite, but only in the direction parallel with the current collector. Furthermore, fast charge graphite electrodes are more prone to form cracks since the tensile strength of graphite is more likely to be surpassed at higher charge rates. Therefore, for LIBs long-term or high charge rate applications, the tensile strength of graphite anode should be taken into account.« less

Understanding the crack formation of graphite particles in cycled commercial lithium-ion batteries by focused ion beam - scanning electron microscopy

DOE PAGES

Lin, Na; Jia, Zhe; Wang, Zhihui; ...

2017-10-01

Here in this paper, the structure degradation of commercial Lithium-ion battery (LIB) graphite anodes with different cycling numbers and charge rates was investigated by focused ion beam (FIB) and scanning electron microscopy (SEM). The cross-section image of graphite anode by FIB milling shows that cracks, resulted in the volume expansion of graphite electrode during long-term cycling, were formed in parallel with the current collector. The crack occurs in the bulk of graphite particles near the lithium insertion surface, which might derive from the stress induced during lithiation and de-lithiation cycles. Subsequently, crack takes place along grain boundaries of the polycrystallinemore » graphite, but only in the direction parallel with the current collector. Furthermore, fast charge graphite electrodes are more prone to form cracks since the tensile strength of graphite is more likely to be surpassed at higher charge rates. Therefore, for LIBs long-term or high charge rate applications, the tensile strength of graphite anode should be taken into account.« less

High-pressure-assisted design of porous topological semimetal carbon for Li-ion battery anode with high-rate performance

NASA Astrophysics Data System (ADS)

Liu, Junyi; Wang, Shuo; Qie, Yu; Zhang, Cunzhi; Sun, Qiang

2018-02-01

It has been a great challenge to develop a high-rate anode material with high-capacity, fast Li-ions diffusion and long cycling life going beyond the commercially used graphite in Li-ion battery. Here for the first time we propose a strategy combined high-pressure synthesis method with the global structure search to find a topological semimetal porous carbon as the desired anode. Our crystal-structure searching shows that we can obtain the ground state of an orthorhombic phase Li C6 with regular pores at 30 GPa, and when the Li atoms are removed, the resulting carbon structure is the recently predicted interlocked graphene network (IGN) that is a topological semimetal with an intrinsic high electronic conductivity. Based on the state-of-the-art first-principles calculations, we further find that the Li-ion migration energy barrier in the IGN is extremely low and the estimated diffusion coefficient can reach a magnitude of 10-4c m2/s at both low and high Li concentrations, which is three orders of magnitude larger than that of graphite anode. Moreover, the volume changes during the Li insertion and deinsertion are smaller than 3.2 % , while the theoretical specific capacity is the same as that of graphite anode. Our studies not only suggest a practical way of synthesizing the topological semimetal carbon but also propose a new anode material for Li-ion battery.

Selecting the Best Graphite for Long-Life, High-Energy Li-Ion Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mao, Chengyu; Wood, Marissa; David, Lamuel Abraham

Here, most lithium-ion batteries still rely on intercalation-type graphite materials for anodes, so it is important to consider their role in full cells for applications in electric vehicles. Here, we systematically evaluate the chemical and physical properties of six commercially-available natural and synthetic graphites to establish which factors have the greatest impact on the cycling stability of full cells with nickel-rich LiNi0.8Mn0.1Co0.1O2 (NMC811) cathodes. Electrochemical data and post-mortem characterization explain the origin of capacity fade. The NMC811 cathode shows large irreversible capacity loss and impedance growth, accounting for much of full cell degradation. However, six graphite anodes demonstrate significant differencesmore » with respect to structural change, surface area, impedance growth, and SEI chemistry, which impact overall capacity retention. We found long cycle life correlated most strongly with stable graphite crystallite size. In addition, graphites with lower surface area generally had higher coulombic efficiencies during formation cycles, which led to more stable long-term cycling. The best graphite screened here enables a capacity retention around 90% in full pouch cells over extensive long-term cycling compared to only 82% for cells with the lowest performing graphite. The results show that optimal graphite selection improves cycling stability of high energy lithium-ion cells.« less

Selecting the Best Graphite for Long-Life, High-Energy Li-Ion Batteries

DOE PAGES

Mao, Chengyu; Wood, Marissa; David, Lamuel Abraham; ...

2018-06-16

Here, most lithium-ion batteries still rely on intercalation-type graphite materials for anodes, so it is important to consider their role in full cells for applications in electric vehicles. Here, we systematically evaluate the chemical and physical properties of six commercially-available natural and synthetic graphites to establish which factors have the greatest impact on the cycling stability of full cells with nickel-rich LiNi0.8Mn0.1Co0.1O2 (NMC811) cathodes. Electrochemical data and post-mortem characterization explain the origin of capacity fade. The NMC811 cathode shows large irreversible capacity loss and impedance growth, accounting for much of full cell degradation. However, six graphite anodes demonstrate significant differencesmore » with respect to structural change, surface area, impedance growth, and SEI chemistry, which impact overall capacity retention. We found long cycle life correlated most strongly with stable graphite crystallite size. In addition, graphites with lower surface area generally had higher coulombic efficiencies during formation cycles, which led to more stable long-term cycling. The best graphite screened here enables a capacity retention around 90% in full pouch cells over extensive long-term cycling compared to only 82% for cells with the lowest performing graphite. The results show that optimal graphite selection improves cycling stability of high energy lithium-ion cells.« less

Electrowinning process with electrode compartment to avoid contamination of electrolyte

DOEpatents

Poa, Davis S.; Pierce, R. Dean; Mulcahey, Thomas P.; Johnson, Gerald K.

1993-01-01

An electrolytic process and apparatus for reducing calcium oxide in a molten electrolyte of CaCl.sub.2 -CaF.sub.2 with a graphite anode in which particles or other contamination from the anode is restricted by the use of a porous barrier in the form of a basket surrounding the anode which may be removed from the electrolyte to burn the graphite particles, and wherein the calcium oxide feed is introduced to the anode compartment to increase the oxygen ion concentration at the anode.

Theoretical Limits of Energy Density in Silicon-Carbon Composite Anode Based Lithium Ion Batteries

PubMed Central

Dash, Ranjan; Pannala, Sreekanth

2016-01-01

Silicon (Si) is under consideration as a potential next-generation anode material for the lithium ion battery (LIB). Experimental reports of up to 40% increase in energy density of Si anode based LIBs (Si-LIBs) have been reported in literature. However, this increase in energy density is achieved when the Si-LIB is allowed to swell (volumetrically expand) more than graphite based LIB (graphite-LIB) and beyond practical limits. The volume expansion of LIB electrodes should be negligible for applications such as automotive or mobile devices. We determine the theoretical bounds of Si composition in a Si–carbon composite (SCC) based anode to maximize the volumetric energy density of a LIB by constraining the external dimensions of the anode during charging. The porosity of the SCC anode is adjusted to accommodate the volume expansion during lithiation. The calculated threshold value of Si was then used to determine the possible volumetric energy densities of LIBs with SCC anode (SCC-LIBs) and the potential improvement over graphite-LIBs. The level of improvement in volumetric and gravimetric energy density of SCC-LIBs with constrained volume is predicted to be less than 10% to ensure the battery has similar power characteristics of graphite-LIBs. PMID:27311811

Formation of novel hydrogel bio-anode by immobilization of biocatalyst in alginate/polyaniline/titanium-dioxide/graphite composites and its electrical performance.

PubMed

Szöllősi, Attila; Hoschke, Ágoston; Rezessy-Szabó, Judit M; Bujna, Erika; Kun, Szilárd; Nguyen, Quang D

2017-05-01

A new bio-anode containing gel-entrapped bacteria in alginate/polyaniline/TiO 2 /graphite composites was constructed and electrically investigated. Alginate as dopant and template as well as entrapped gel was used for immobilization of microorganism cells. Increase of polyaniline concentration resulted an increase in the conductivity in gels. Addition of 0.01 and 0.02 g/mL polyaniline caused 6-fold and 10-fold higher conductivity, respectively. Furthermore, addition of 0.05 g/mL graphite powder caused 10-fold higher conductivity and 4-fold higher power density, respectively. The combination of polyaniline and graphite resulted 105-fold higher conductivity and 7-fold higher power-density output. Optimized concentrations of polyaniline and graphite powder were determined to be 0.02 g/mL and 0.05 g/mL, respectively. Modified hydrogel anode was successfully used in microbial fuel cell systems both in semi- and continuous operations modes. In semi-continuous mode, about 7.88 W/m 3 power density was obtained after 13 h of fermentation. The glucose consumption rate was calculated to be about 7 mg glucose/h/1.2·10 7  CFU immobilized cells. Similar power density was observed in the continuous operation mode of the microbial fuel cell, and it was operated stably for more than 7 days. Our results are very promising for development of an improved microbial fuel cell with new type of bio-anode that have higher power density and can operate for long term. Copyright © 2017 Elsevier Ltd. All rights reserved.

Open circuit versus closed circuit enrichment of anodic biofilms in MFC: effect on performance and anodic communities.

PubMed

Larrosa-Guerrero, Amor; Scott, Keith; Katuri, Krishna P; Godinez, Carlos; Head, Ian M; Curtis, Thomas

2010-08-01

The influence of various carbon anodes; graphite, sponge, paper, cloth, felt, fiber, foam and reticulated vitreous carbon (RVC); on microbial fuel cell (MFC) performance is reported. The feed was brewery wastewater diluted in domestic wastewater. Biofilms were grown at open circuit or under an external load. Microbial diversity was analysed as a function of current and anode material. The bacterial community formed at open circuit was influenced by the anode material. However at closed circuit its role in determining the bacterial consortia formed was less important than the passage of current. The rate and extent of organic matter removal were similar for all materials: over 95% under closed circuit. The biofilm in MFCs working at open circuit and in the control reactors, increased COD removal by up to a factor of nine compared with that for baseline reactors. The average voltage output was 0.6 V at closed circuit, with an external resistor of 300 kOmega and 0.75 V at open circuit for all materials except RVC. The poor performance of this material might be related to the surface area available and concentration polarizations caused by the morphology of the material and the structure of the biofilm. Peak power varied from 1.3 mW m(-2) for RVC to 568 mW m(-2) for graphite with biofilm grown at closed circuit.

Electric treatment for hydrophilic ink deinking.

PubMed

Du, Xiaotang; Hsieh, Jeffery S

2017-09-01

Hydrophilic inks have been widely used due to higher printing speed, competitive cost and being healthy non-organic solvents. However, they cause problems in both product quality and process runnability due to their hydrophilic surface wettability, strong negative surface charge and sub-micron size. Electric treatment was shown to be able to increase the ink sizes from 60 nm to 700 nm through electrocoagulation and electrophoresis. In addition, electric treatment assisted flotation could reduce effective residual ink concentration (ERIC) by 90 ppm, compared with only 20 ppm by traditional flotation. Furthermore, the effect of electric treatment alone on ink separation was investigated by two anode materials, graphite and stainless steel. Both of them could remove hydrophilic inks with less than 1% yield loss via electroflotation and electrophoresis. But graphite is a better material as the anode because graphite reduced ERIC by an additional 100 ppm. The yield loss of flotation following electric treatment was also lower by 17% if graphite was the anode material. The difference between the two electrode materials resulted from electrocoagulation and ink redeposition during electric treatment. An electric pretreatment-flotation-hyperwashing process was conducted to understand the deinking performance in conditions similar to a paper mill, and the ERIC was reduced from 950 ppm to less than 400 ppm.

Electrochemical deposition of honeycomb magnetite on partially exfoliated graphite as anode for capacitive applications

NASA Astrophysics Data System (ADS)

Sun, Zhen; Cai, Xiang; Song, Yu; Liu, Xiao-Xia

2017-08-01

Research on anode materials with high capacitive performance is lagging behind that of cathode materials, which has severely hindered the development of high-efficient energy storage devices. Compared with other anode materials, Fe3O4 exhibits highly desirable advantages due to its low cost, high theoretical capacity and preferable electronic conductivity of ∼102 S cm-1. Herein, hierarchical honeycomb Fe3O4 is integrated on functionalized exfoliated graphite through electrochemical deposition and the following chemical conversion. The hierarchical honeycomb Fe3O4 is constructed by the oxide nanorods, which are assembled by a number of nanoparticles. This unique porous structure not only ensures fast ion diffusion in the electrode, but also provides large amount of active sites for electrochemical reactions. The exfoliated graphene atop the graphite base can act as 3D conductive scaffold to facilitate the electron transport of the electrode. Therefore, FEG/Fe3O4 exhibits large specific capacitances of 327 F g-1@1 A g-1 and 275 F g-1@10 A g-1. Good cycling stability is also achieved due to the flexibility of the graphene substrate. The assembled asymmetric device using FEG/Fe3O4 as anode can deliver a high energy density of 54 Wh kg-1.

Anode macrostructures influence electricity generation in microbial fuel cells for wastewater treatment.

PubMed

Ishii, Yoshikazu; Miyahara, Morio; Watanabe, Kazuya

2017-01-01

Microbial fuel cells (MFCs) are devices that exploit microbes for generating electricity from organic substrates, including waste biomass and wastewater pollutants. MFCs have the potential to treat wastewater and simultaneously generate electricity. The present study examined how anode macrostructure influences wastewater treatment, electricity generation and microbial communities in MFCs. Cassette-electrode MFCs were equipped with graphite-felt anodes with three different macrostructures, flat-plate (FP), vertical-fin (VF), and horizontal-fin (HF) structures (these were composed of a same amount of graphite felt), and were continuously supplied with artificial wastewater containing starch as the major organic constituent. Polarization analyses revealed that MFCs equipped with VF and HF anodes generated 33% and 21% higher volumetric power densities, respectively, than that of MFCs equipped with FP anodes. Organics were also more efficiently removed from wastewater in MFCs with VF and HF anodes compared to reactors containing FP anodes. In addition, pyrosequencing of PCR-amplified 16S rRNA gene fragments from microbial samples collected from the anodes showed that the presence of fins also affected the bacterial compositions in anode biofilms. Taken together, the findings presented here suggest that the modification of anodes with fins improves organics removal and electricity generation in MFCs. The optimization of anode macrostructure therefore appears to be a promising strategy for improving MFC performance without additional material costs. Copyright © 2016 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

Structural changes in a commercial lithium-ion battery during electrochemical cycling: An in situ neutron diffraction study

NASA Astrophysics Data System (ADS)

Sharma, Neeraj; Peterson, Vanessa K.; Elcombe, Margaret M.; Avdeev, Maxim; Studer, Andrew J.; Blagojevic, Ned; Yusoff, Rozila; Kamarulzaman, Norlida

The structural response to electrochemical cycling of the components within a commercial Li-ion battery (LiCoO 2 cathode, graphite anode) is shown through in situ neutron diffraction. Lithuim insertion and extraction is observed in both the cathode and anode. In particular, reversible Li incorporation into both layered and spinel-type LiCoO 2 phases that comprise the cathode is shown and each of these components features several phase transitions attributed to Li content and correlated with the state-of-charge of the battery. At the anode, a constant cell voltage correlates with a stable lithiated graphite phase. Transformation to de-lithiated graphite at the discharged state is characterised by a sharp decrease in both structural cell parameters and cell voltage. In the charged state, a two-phase region exists and is composed of the lithiated graphite phase and about 64% LiC 6. It is postulated that trapping Li in the solid|electrolyte interface layer results in minimal structural changes to the lithiated graphite anode across the constant cell voltage regions of the electrochemical cycle.

Tris(trimethylsilyl) Phosphite as an Efficient Electrolyte Additive To Improve the Surface Stability of Graphite Anodes.

PubMed

Yim, Taeeun; Han, Young-Kyu

2017-09-27

Tris(trimethylsilyl) phosphite (TMSP) has received considerable attention as a functional additive for various cathode materials in lithium-ion batteries, but the effect of TMSP on the surface stability of a graphite anode has not been studied. Herein, we demonstrate that TMSP serves as an effective solid electrolyte interphase (SEI)-forming additive for graphite anodes in lithium-ion batteries (LIBs). TMSP forms SEI layers by chemical reactions between TMSP and a reductively decomposed ethylene carbonate (EC) anion, which is strikingly different from the widely known mechanism of the SEI-forming additives. TMSP is stable under cathodic polarization, but it reacts chemically with radical anion intermediates derived from the electrochemical reduction of the carbonate solvents to generate a stable SEI layer. These TMSP-derived SEI layers improve the interfacial stability of the graphite anode, resulting in a retention of 96.8% and a high Coulombic efficiency of 95.2%. We suggest the use of TMSP as a functional additive that effectively stabilizes solid electrolyte interfaces of both the anode and cathode in lithium-ion batteries.

Preparation of RuO2-TiO2/Nano-graphite composite anode for electrochemical degradation of ceftriaxone sodium.

PubMed

Li, Dong; Guo, Xiaolei; Song, Haoran; Sun, Tianyi; Wan, Jiafeng

2018-06-05

Graphite-like material is widely used for preparing various electrodes for wastewater treatment. To enhance the electrochemical degradation efficiency of Nano-graphite (Nano-G) anode, RuO 2 -TiO 2 /Nano-G composite anode was prepared through the sol-gel method and hot-press technology. RuO 2 -TiO 2 /Nano-G composite was characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy and N 2 adsorption-desorption. Results showed that RuO 2 , TiO 2 and Nano-G were composited successfully, and RuO 2 and TiO 2 nanoparticles were distributed uniformly on the surface of Nano-G sheet. Specific surface area of RuO 2 -TiO 2 /Nano-G composite was higher than that of TiO 2 /Nano-G composite and Nano-G. Electrochemical performances of RuO 2 -TiO 2 /Nano-G anode were investigated by cyclic voltammetry, electrochemical impedance spectroscopy. RuO 2 -TiO 2 /Nano-G anode was applied to electrochemical degradation of ceftriaxone. The generation of hydroxyl radical (OH) was measured. Results demonstrated that RuO 2 -TiO 2 /Nano-G anode displayed enhanced electrochemical degradation efficiency towards ceftriaxone and yield of OH, which is derived from the synergetic effect between RuO 2 , TiO 2 and Nano-G, which enhance the specific surface area, improve the electrochemical oxidation activity and lower the charge transfer resistance. Besides, the possible degradation intermediates and pathways of ceftriaxone sodium were identified. This study may provide a viable and promising prospect for RuO 2 -TiO 2 /Nano-G anode towards effective electrochemical degradation of antibiotics from wastewater. Copyright © 2018 Elsevier B.V. All rights reserved.

Forming gas treatment of lithium ion battery anode graphite powders

DOEpatents

Contescu, Cristian Ion; Gallego, Nidia C; Howe, Jane Y; Meyer, III, Harry M; Payzant, Edward Andrew; Wood, III, David L; Yoon, Sang Young

2014-09-16

The invention provides a method of making a battery anode in which a quantity of graphite powder is provided. The temperature of the graphite powder is raised from a starting temperature to a first temperature between 1000 and 2000.degree. C. during a first heating period. The graphite powder is then cooled to a final temperature during a cool down period. The graphite powder is contacted with a forming gas during at least one of the first heating period and the cool down period. The forming gas includes H.sub.2 and an inert gas.

Formation of NiFe2O4/Expanded Graphite Nanocomposites with Superior Lithium Storage Properties

NASA Astrophysics Data System (ADS)

Xiao, Yinglin; Zai, Jiantao; Tian, Bingbing; Qian, Xuefeng

2017-07-01

A NiFe2O4/expanded graphite (NiFe2O4/EG) nanocomposite was prepared via a simple and inexpensive synthesis method. Its lithium storage properties were studied with the goal of applying it as an anode in a lithium-ion battery. The obtained nanocomposite exhibited a good cycle performance, with a capacity of 601 mAh g-1 at a current of 1 A g-1 after 800 cycles. This good performance may be attributed to the enhanced electrical conductivity and layered structure of the EG. Its high mechanical strength could postpone the disintegration of the nanocomposite structure, efficiently accommodate volume changes in the NiFe2O4-based anodes, and alleviate aggregation of NiFe2O4 nanoparticles.

Nickel-Tin Electrode Materials for Nonaqueous Li-Ion Cells

NASA Technical Reports Server (NTRS)

Ehrlich, Grant M.; Durand, Christopher

2005-01-01

Experimental materials made from mixtures of nickel and tin powders have shown promise for use as the negative electrodes of rechargeable lithium-ion electrochemical power cells. During charging (or discharging) of a lithium-ion cell, lithium ions are absorbed into (or desorbed from, respectively) the negative electrode, typically through an intercalation or alloying process. The negative electrodes (for this purpose, designated as anodes) in state-of-the-art Li-ion cells are made of graphite, in which intercalation occurs. Alternatively, the anodes can be made from metals, in which alloying can occur. For reasons having to do with the electrochemical potential of intercalated lithium, metallic anode materials (especially materials containing tin) are regarded as safer than graphite ones; in addition, such metallic anode materials have been investigated in the hope of obtaining reversible charge/discharge capacities greater than those of graphite anodes. However, until now, each of the tin-containing metallic anode formulations tested has been found to be inadequate in some respect.

Electrolysis of metal oxides in MgCl2 based molten salts with an inert graphite anode.

PubMed

Yuan, Yating; Li, Wei; Chen, Hualin; Wang, Zhiyong; Jin, Xianbo; Chen, George Z

2016-08-15

Electrolysis of solid metal oxides has been demonstrated in MgCl2-NaCl-KCl melt at 700 °C taking the electrolysis of Ta2O5 as an example. Both the cathodic and anodic processes have been investigated using cyclic voltammetry, and potentiostatic and constant voltage electrolysis, with the cathodic products analysed by XRD and SEM and the anodic products by GC. Fast electrolysis of Ta2O5 against a graphite anode has been realized at a cell voltage of 2 V, or a total overpotential of about 400 mV. The energy consumption was about 1 kW h kgTa(-1) with a nearly 100% Ta recovery. The cathodic product was nanometer Ta powder with sizes of about 50 nm. The main anodic product was Cl2 gas, together with about 1 mol% O2 gas and trace amounts of CO. The graphite anode was found to be an excellent inert anode. These results promise an environmentally-friendly and energy efficient method for metal extraction by electrolysis of metal oxides in MgCl2 based molten salts.

The state of understanding of the lithium-ion-battery graphite solid electrolyte interphase (SEI) and its relationship to formation cycling

DOE PAGES

An, Seong Jin; Li, Jianlin; Daniel, Claus; ...

2016-04-09

An in-depth review is presented on the science of lithium-ion battery (LIB) solid electrolyte interphase (SEI) formation on the graphite anode, including structure, morphology, chemical composition, electrochemistry, formation mechanism, and LIB formation cycling. During initial operation of LIBs, the SEI layer forms on the graphite surfaces, the most commonly used anode material, due to side reactions with the electrolyte solvent/salt at low electro-reduction potentials. It is accepted that the SEI layer is essential to the long-term performance of LIBs, and it also has an impact on its initial capacity loss, self-discharge characteristics, cycle life, rate capability, and safety. While themore » presence of the anode SEI layer is vital, it is difficult to control its formation and growth, as the chemical composition, morphology, and stability depend on several factors. These factors include the type of graphite, electrolyte composition, electrochemical conditions, and cell temperature. Thus, SEI layer formation and electrochemical stability over long-term operation should be a primary topic of future investigation in the development of LIB technology. We review the progression of knowledge gained about the anode SEI, from its discovery in 1979 to the current state of understanding, and covers its formation process, differences in the chemical and structural makeup when cell materials and components are varied, methods of characterization, and associated reactions with the liquid electrolyte phase. It also discusses the relationship of the SEI layer to the LIB formation step, which involves both electrolyte wetting and subsequent slow charge-discharge cycles to grow the SEI.« less

Scalable Preparation of Ternary Hierarchical Silicon Oxide-Nickel-Graphite Composites for Lithium-Ion Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang , Jing; Bao, Wurigumula; Ma, Lu

2015-11-09

Silicon monoxide is a promising anode candidate because of its high theoretical capacity and good cycle performance. To solve the problems associated with this material, including large volume changes during charge-discharge processes, we report a ternary hierarchical silicon oxide–nickel–graphite composite prepared by a facile two-step ball-milling method. The composite consists of nano-Si dispersed silicon oxides embedded in nano-Ni/graphite matrices (Si@SiOx/Ni/graphite). In the composite, crystalline nano-Si particles are generated by the mechanochemical reduction of SiO by ball milling with Ni. These nano-Si dispersed oxides have abundant electrochemical activity and can provide high Li-ion storage capacity. Furthermore, the milled nano-Ni/graphite matrices stickmore » well to active materials and interconnect to form a crosslinked framework, which functions as an electrical highway and a mechanical backbone so that all silicon oxide particles become electrochemically active. Owing to these advanced structural and electrochemical characteristics, the composite enhances the utilization efficiency of SiO, accommodates its large volume expansion upon cycling, and has good ionic and electronic conductivity. The composite electrodes thus exhibit substantial improvements in electrochemical performance. This ternary hierarchical Si@SiOx/Ni/graphite composite is a promising candidate anode material for high-energy lithium-ion batteries. Additionally, the mechanochemical ball-milling method is low cost and easy to reproduce, indicating potential for the commercial production of the composite materials.« less

Scalable Preparation of Ternary Hierarchical Silicon Oxide-Nickel-Graphite Composites for Lithium-Ion Batteries.

PubMed

Wang, Jing; Bao, Wurigumula; Ma, Lu; Tan, Guoqiang; Su, Yuefeng; Chen, Shi; Wu, Feng; Lu, Jun; Amine, Khalil

2015-12-07

Silicon monoxide is a promising anode candidate because of its high theoretical capacity and good cycle performance. To solve the problems associated with this material, including large volume changes during charge-discharge processes, we report a ternary hierarchical silicon oxide-nickel-graphite composite prepared by a facile two-step ball-milling method. The composite consists of nano-Si dispersed silicon oxides embedded in nano-Ni/graphite matrices (Si@SiOx /Ni/graphite). In the composite, crystalline nano-Si particles are generated by the mechanochemical reduction of SiO by ball milling with Ni. These nano-Si dispersed oxides have abundant electrochemical activity and can provide high Li-ion storage capacity. Furthermore, the milled nano-Ni/graphite matrices stick well to active materials and interconnect to form a crosslinked framework, which functions as an electrical highway and a mechanical backbone so that all silicon oxide particles become electrochemically active. Owing to these advanced structural and electrochemical characteristics, the composite enhances the utilization efficiency of SiO, accommodates its large volume expansion upon cycling, and has good ionic and electronic conductivity. The composite electrodes thus exhibit substantial improvements in electrochemical performance. This ternary hierarchical Si@SiOx /Ni/graphite composite is a promising candidate anode material for high-energy lithium-ion batteries. Additionally, the mechanochemical ball-milling method is low cost and easy to reproduce, indicating potential for the commercial production of the composite materials. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effective regeneration of anode material recycled from scrapped Li-ion batteries

NASA Astrophysics Data System (ADS)

Zhang, Jin; Li, Xuelei; Song, Dawei; Miao, Yanli; Song, Jishun; Zhang, Lianqi

2018-06-01

Recycling high-valuable metal elements (such as Li, Ni, Co, Al and Cu elements) from scrapped lithium ion batteries can bring significant economic benefits. However, recycling and reusing anode material has not yet attracted wide attention up to now, due to the lower added-value than the above valuable metal materials and the difficulties in regenerating process. In this paper, a novel regeneration process with significant green advance is proposed to regenerate anode material recycled from scrapped Li-ion batteries for the first time. After regenerated, most acetylene black (AB) and all the styrene butadiene rubber (SBR), carboxymethylcellulose sodium (CMC) in recycled anode material are removed, and the surface of anode material is coated with pyrolytic carbon from phenolic resin again. Finally, the regenerated anode material (graphite with coating layer, residual AB and a little CMC pyrolysis product) is obtained. As expected, all the technical indexs of regenerated anode material exceed that of a midrange graphite with the same type, and partial technical indexs are even closed to that of the unused graphite. The results indicate the effective regeneration of anode material recycled from scrapped Li-ion batteries is really achieved.

A sodium-ion battery exploiting layered oxide cathode, graphite anode and glyme-based electrolyte

NASA Astrophysics Data System (ADS)

Hasa, Ivana; Dou, Xinwei; Buchholz, Daniel; Shao-Horn, Yang; Hassoun, Jusef; Passerini, Stefano; Scrosati, Bruno

2016-04-01

Room-temperature rechargeable sodium-ion batteries (SIBs), in view of the large availability and low cost of sodium raw materials, represent an important class of electrochemical systems suitable for application in large-scale energy storage. In this work, we report a novel, high power SIB formed by coupling the layered P2-Na0.7CoO2 cathode with the graphite anode in an optimized ether-based electrolyte. The study firstly addresses the electrochemical optimization of the two electrode materials and then the realization and characterization of the novel SIB based on their combination. The cell represents an original sodium rocking chair battery obtained combining the intercalation/de-intercalation processes of sodium within the cathode and anode layers. We show herein that this battery, favored by suitable electrode/electrolyte combination, offers unique performance in terms of cycle life, efficiency and, especially, power capability.

The Role of Electrolyte Upon the SEI Formation Characteristics and Low Temperature Performance of Lithium-Ion Cells With Graphite Anodes

NASA Technical Reports Server (NTRS)

Smart, M. C.; Ratnakumar, B. V.; Greenbaum, S.; Surampudi, S.

2000-01-01

Quarternary lithium-ion battery electrolyte solutions containing ester co-solvents in mixtures of carbonates have been demonstrated to have high conductivity at low temperatures (< -20C). However, in some cases the presence of such co-solvents does not directly translate into improved low temperature cell performance, presumably due to the formation of ionically resistive surface films on carbonaceous anodes. In order to understand this behavior, a number of lithium-graphite cells have been studied containing electrolytes with various ester co-solvents, including methyl acetate (MA), ethyl acetate (EA), ethyl propionate (EP), and ethyl butyrate (EB). The charge/discharge characterization of these cells indicates that the higher molecular weight esters result in electrolytes which possess superior low temperature performance in contrast to the lower molecular weight ester-containing solutions, even though these solutions display lower conductivity values.

Battery Electrode Materials with High Cycle Lifetimes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Prof. Brent Fultz

2001-06-29

In an effort to understand the capacity fade of nickel-metal hydride (Ni-MH) batteries, we performed a systematic study of the effects of solute additions on the cycle life of metal hydride electrodes. We also performed a series of measurements on hydrogen absorption capacities of novel carbon and graphite-based materials including graphite nanofibers and single-walled carbon nanotubes. Towards the end of this project we turned our attention to work on Li-ion cells with a focus on anode materials.

Applications of Carbon Nanotubes for Lithium Ion Battery Anodes

PubMed Central

Xiong, Zhili; Yun, Young Soo; Jin, Hyoung-Joon

2013-01-01

Carbon nanotubes (CNTs) have displayed great potential as anode materials for lithium ion batteries (LIBs) due to their unique structural, mechanical, and electrical properties. The measured reversible lithium ion capacities of CNT-based anodes are considerably improved compared to the conventional graphite-based anodes. Additionally, the opened structure and enriched chirality of CNTs can help to improve the capacity and electrical transport in CNT-based LIBs. Therefore, the modification of CNTs and design of CNT structure provide strategies for improving the performance of CNT-based anodes. CNTs could also be assembled into free-standing electrodes without any binder or current collector, which will lead to increased specific energy density for the overall battery design. In this review, we discuss the mechanism of lithium ion intercalation and diffusion in CNTs, and the influence of different structures and morphologies on their performance as anode materials for LIBs. PMID:28809361

Bacterial Community Analysis, New Exoelectrogen Isolation and Enhanced Performance of Microbial Electrochemical Systems Using Nano-Decorated Anodes

NASA Astrophysics Data System (ADS)

Xu, Shoutao

Microbial electrochemical systems (MESs) have attracted much research attention in recent years due to their promising applications in renewable energy generation, bioremediation, and wastewater treatment. In a MES, microorganisms interact with electrodes via electrons, catalyzing oxidation and reduction reactions at the anode and the cathode. The bacterial community of a high power mixed consortium MESs (maximum power density is 6.5W/m2) was analyzed by using denature gradient gel electrophoresis (DGGE) and 16S DNA clone library methods. The bacterial DGGE profiles were relatively complex (more than 10 bands) but only three brightly dominant bands in DGGE results. These results indicated there are three dominant bacterial species in mixed consortium MFCs. The 16S DNA clone library method results revealed that the predominant bacterial species in mixed culture is Geobacter sp (66%), Arcobacter sp and Citrobacter sp. These three bacterial species reached to 88% of total bacterial species. This result is consistent with the DGGE result which showed that three bright bands represented three dominant bacterial species. Exoelectrogenic bacterial strain SX-1 was isolated from a mediator-less microbial fuel cell by conventional plating techniques with ferric citrate as electron acceptor under anaerobic conditions. Phylogenetic analysis of the 16S rDNA sequence revealed that it was related to the members of Citrobacter genus with Citrobacter sp. sdy-48 being the most closely related species. The bacterial strain SX-1 produced electricity from citrate, acetate, glucose, sucrose, glycerol, and lactose in MFCs with the highest current density of 205 mA/m2 generated from citrate. Cyclic voltammetry analysis indicated that membrane associated proteins may play an important role in facilitating electron transfer from the bacteria to the electrode. This is the first study that demonstrates that Citrobacter species can transfer electrons to extracellular electron acceptors. Citrobacter strain SX-1 is capable of generating electricity from a wide range of substrates in MFCs. This finding increases the known diversity of power generating exoelectrogens and provids a new strain to explore the mechanisms of extracellular electron transfer from bacteria to electrode. The wide range of substrate utilization by SX-1 increases the application potential of MFCs in renewable energy generation and waste treatment. Anode properties are critical for the performance of microbial electrolysis cells (MECs). Inexpensive Fe nanoparticle modified graphite disks were used as anodes to preliminarily investigate the effects of nanoparticles on the performance of Shewanella oneidensis MR-1 in MECs. Results demonstrated that average current densities produced with Fe nanoparticle decorated anodes were up to 5.9-fold higher than plain graphite anodes. Whole genome microarray analysis of the gene expression showed that genes encoding biofilm formation were significantly up-regulated as a response to nanoparticle decorated anodes. Increased expression of genes related to nanowires, flavins and c-type cytochromes indicate that enhanced mechanisms of electron transfer to the anode may also have contributed to the observed increases in current density. The majority of the remaining differentially expressed genes were associated with electron transport and anaerobic metabolism demonstrating a systemic response to increased power loads. The carbon nanotube (CNT) is another form of nano materials. Carbon nanotube (CNT) modified graphite disks were used as anodes to investigate the effects of nanostructures on the performance S. oneidensis MR-1 in microbial electrolysis cells (MECs). The current densities produced with CNT decorated anodes were up to 5.6-fold higher than plain graphite anodes. Global transcriptome analysis showed that cytochrome c genes associated with extracellular electron transfer are up-expressed by CNT decorated anodes, which is the leading factor to contribute current increase in CNT decorated anode MECs. The up regulated genes encoded to flavin also contribute to current enhancement in CNT decorated anode MECs.

Correlation of Electrolyte Volume and Electrochemical Performance in Lithium-Ion Pouch Cells with Graphite Anodes and NMC532 Cathodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

An, Seong Jin; Li, Jianlin; Mohanty, Debasish

2017-01-01

The work herein reports on studies aimed at exploring the correlation between electrolyte volume and electrochemical performance of full cell, pouch-cells consisting of graphite/ Li 1.02Ni 0.50Mn 0.29Co 0.19O 2 (NMC-532) as the electrodes and 1.2 M LiPF6 in ethylene carbonate:ethylmethyl carbonate (EC:EMC) as the electrolyte. It is demonstrated that a minimum electrolyte volume factor of 1.9 times the total pore volume of cell components (cathode, anode, and separator) is needed for long-term cyclability and low impedance. Less electrolyte results in an increase of the measured ohmic resistances. Increased resistance ratios for charge transfer and passivation layers at cathode, relativemore » to initial values, were 1.5–2.0 after 100 cycles. At the cathode, the resistance from charge transfer was 2–3 times higher than for passivation layers. Differential voltage analysis showed that anodes were less delithiated after discharging as the cells were cycled.« less

Correlation of Electrolyte Volume and Electrochemical Performance in Lithium-Ion Pouch Cells with Graphite Anodes and NMC532 Cathodes

DOE PAGES

An, Seong Jin; Li, Jianlin; Mohanty, Debasish; ...

2017-04-07

The work herein reports on studies aimed at exploring the correlation between electrolyte volume and electrochemical performance of full cell, pouch-cells consisting of graphite/ Li 1.02Ni 0.50Mn 0.29Co 0.19O 2 (NMC-532) as the electrodes and 1.2 M LiPF 6 in ethylene carbonate:ethylmethyl carbonate (EC:EMC) as the electrolyte. In addition, it is demonstrated that a minimum electrolyte volume factor of 1.9 times the total pore volume of cell components (cathode, anode, and separator) is needed for long-term cyclability and low impedance. Less electrolyte results in an increase of the measured Ohmic resistances. Increased resistance ratios for charge transfer and passivation layersmore » at cathode, relative to initial values, were 1.5 2.0 after 100 cycles. At the cathode, the resistance from charge transfer was 2-3 times higher than for passivation layers. Lastly, differential voltage analysis showed that anodes were less delithiated after discharging as the cells were cycled.« less

N-type nano-silicon powders with ultra-low electrical resistivity as anode materials in lithium ion batteries

NASA Astrophysics Data System (ADS)

Yue, Zhihao; Zhou, Lang; Jin, Chenxin; Xu, Guojun; Liu, Liekai; Tang, Hao; Li, Xiaomin; Sun, Fugen; Huang, Haibin; Yuan, Jiren

2017-06-01

N-type silicon wafers with electrical resistivity of 0.001 Ω cm were ball-milled to powders and part of them was further mechanically crushed by sand-milling to smaller particles of nano-size. Both the sand-milled and ball-milled silicon powders were, respectively, mixed with graphite powder (silicon:graphite = 5:95, weight ratio) as anode materials for lithium ion batteries. Electrochemical measurements, including cycle and rate tests, present that anode using sand-milled silicon powder performed much better. The first discharge capacity of sand-milled silicon anode is 549.7 mAh/g and it is still up to 420.4 mAh/g after 100 cycles. Besides, the D50 of sand-milled silicon powder shows ten times smaller in particle size than that of ball-milled silicon powder, and they are 276 nm and 2.6 μm, respectively. In addition, there exist some amorphous silicon components in the sand-milled silicon powder excepting the multi-crystalline silicon, which is very different from the ball-milled silicon powder made up of multi-crystalline silicon only.

Development of an Acetate-Fed or Sugar-Fed Microbial Power Generator for Military Bases

DTIC Science & Technology

2011-01-01

quarter. We tested graphite and stainless steel as anode materials for ARB growth, showing the greater suitability of carbon fibers as anode material...microbial electrolysis cells (MECs) with graphite rods and stainless steel meshes as anodes to select the optimum material for use in MFC modules to...be tested in the future. We selected meshes made from 316-grade stainless steel for these initial studies. We conducted several trials with the MECs

Dendrite-free Li metal anode enabled by a 3D free-standing lithiophilic nitrogen-enriched carbon sponge

NASA Astrophysics Data System (ADS)

Hou, Guangmei; Ren, Xiaohua; Ma, Xiaoxin; Zhang, Le; Zhai, Wei; Ai, Qing; Xu, Xiaoyan; Zhang, Lin; Si, Pengchao; Feng, Jinkui; Ding, Fei; Ci, Lijie

2018-05-01

Lithium metal is considered as the ultimate anode material for high-energy Li battery systems. However, the commercial application of lithium anode is impeded by issues with safety and low coulombic efficiency induced by Li dendrite growth. Herein, a free-standing three-dimensional nitrogen-enriched graphitic carbon sponge with a high nitrogen content is proposed as a multifunctional current collect for Lithium accommodation. The abundant lithiophilic N-containing functional groups are served as preferred nucleation sites to guide a uniform Li deposition. In addition, the nitrogen-enriched graphitic carbon sponge with a high specific surface area can effectively reduce the local current density. As a result of the synergistic effect, the nitrogen-enriched graphitic carbon sponge electrode realizes a long-term stable cycling without dendrites formation. Notably, the as-obtained composite electrode can deliver an ultra-high specific capacity of ∼3175 mA h g-1. The nitrogen-enriched graphitic carbon sponge might provide innovative insights to design a superior matrix for dendrite-free Li anode.

The Incorporation of Lithium Alloying Metals into Carbon Matrices for Lithium Ion Battery Anodes

NASA Astrophysics Data System (ADS)

Hays, Kevin A.

An increased interest in renewable energies and alternative fuels has led to recognition of the necessity of wide scale adoption of the electric vehicle. Automotive manufacturers have striven to produce an electric vehicle that can match the range of their petroleum-fueled counterparts. However, the state-of-the-art lithium ion batteries used to power the current offerings still do not come close to the necessary energy density. The energy and power densities of the lithium ion batteries must be increased significantly if they are going to make electric vehicles a viable option. The chemistry of the lithium ion battery, based on lithium cobalt oxide cathodes and graphite anodes, is limited by the amount of lithium the cathode can provide and the anode will accept. While these materials have proven themselves in portable electronics over the past two decades, plausible higher energy alternatives do exist. The focus is of this study is on anode materials that could achieve a capacity of more than 3 times greater than that of graphite anodes. The lithium alloying anode materials investigated and reported herein include tin, arsenic, and gallium arsenide. These metals were synthesized with nanoscale dimensions, improving their electrochemical and mechanical properties. Each exhibits their own benefits and challenges, but all display opportunities for incorporation in lithium ion batteries. Tin is incorporated in multilayer graphene nanoshells by introducing small amounts of metal in the core and, separately, on the outside of these spheres. Electrolyte decomposition on the anode limits cycle life of the tin cores, however, tin vii oxides introduced outside of the multilayer graphene nanoshells have greatly improved long term battery performance. Arsenic is a lithium alloying metal that has largely been ignored by the research community to date. One of the first long term battery performance tests of arsenic is reported in this thesis. Anodes were made from nanoscale arsenic particles that were synthesized on melt away carbon nanotubes by akalide reduction. The performance of these anodes proved sensitive to electrolyte composition, which was significantly improved by using fluorinated ethylene carbonate. Additionally, further gains in capacity retention can be made by limiting the loading voltage to 0.75 V vs lithium metal. The arsenic and melt away carbon nanotube composite was found to have excellent cycle life and capacity at high mass loading (80% arsenic) when the nanoparticles were directly synthesized on the melt away carbon nanotubes. Gallium arsenide is well known for its semiconducting properties, but its performance as in Li-ion battery anodes is first reported here. Gallium is a metal with a low melting point that has been touted as a possible self-healing material for lithium ion anodes. Alone, gallium proves to be unstable as a lithium ion battery anode, but when synthesized as gallium arsenide nanoparticles and mixed with melt away carbon nanotubes it can charge and discharge in a battery 100 times with approximately twice the capacity of graphite anodes. This first study of gallium arsenide shows dramatic cycle life improvements by using nanoscale rather that micron size gallium arsenide.

Study on preparation of SnO2-TiO2/Nano-graphite composite anode and electro-catalytic degradation of ceftriaxone sodium.

PubMed

Guo, Xiaolei; Wan, Jiafeng; Yu, Xiujuan; Lin, Yuhui

2016-12-01

In order to improve the electro-catalytic activity and catalytic reaction rate of graphite-like material, Tin dioxide-Titanium dioxide/Nano-graphite (SnO 2 -TiO 2 /Nano-G) composite was synthesized by a sol-gel method and SnO 2 -TiO 2 /Nano-G electrode was prepared in hot-press approach. The composite was characterized by X-ray photoelectron spectroscopy, fourier transform infrared, Raman, N 2 adsorption-desorption, scanning electrons microscopy, transmission electron microscopy and X-ray diffraction. The electrochemical performance of the SnO 2 -TiO 2 /Nano-G anode electrode was investigated via cyclic voltammetry and electrochemical impedance spectroscopy. The electro-catalytic performance was evaluated by the degradation of ceftriaxone sodium and the yield of ·OH radicals in the reaction system. The results demonstrated that TiO 2 , SnO 2 and Nano-G were composited successfully, and TiO 2 and SnO 2 particles dispersed on the surface and interlamination of the Nano-G uniformly. The specific surface area of SnO 2 modified anode was higher than that of TiO 2 /Nano-G anode and the degradation rate of ceftriaxone sodium within 120 min on SnO 2 -TiO 2 /Nano-G electrode was 98.7% at applied bias of 2.0 V. The highly efficient electro-chemical property of SnO 2 -TiO 2 /Nano-G electrode was attributed to the admirable conductive property of the Nano-G and SnO 2 -TiO 2 /Nano-G electrode. Moreover, the contribution of reactive species ·OH was detected, indicating the considerable electro-catalytic activity of SnO 2 -TiO 2 /Nano-G electrode. Copyright © 2016 Elsevier Ltd. All rights reserved.

Development of lithium powder based anode with conductive carbon materials for lithium batteries

NASA Astrophysics Data System (ADS)

Park, Man Su

Current lithium ion battery with a graphite anode shows stable cycle performance and safety. However, the lithium ion battery still has the limitation of having a low energy density caused by the application of lithium intercalated cathode and anode with low energy density. The combination of high capacity non-lithiated cathode such as sulfur and carbon and lithium metal anode has been researched for a long time to maximize battery's energy density. However, this cell design also has a lot of technical challenges to be solved. Among the challenges, lithium anode's problem related to lithium dendrite growth causing internal short and low cycling efficiency is very serious. Thus, extensive research on lithium metal anode has been performed to solve the lithium dendrite problem and a major part of the research has been focused on the control of the interface between lithium and electrolyte. However, research on lithium anode design itself has not been much conducted. In this research, innovative lithium anode design for less dendrite growth and higher cycling efficiency was suggested. Literature review for the lithium dendrite growth mechanism was conducted in Chapter 2 to develop electrode design concept and the importance of the current density on lithium dendrite growth was also found in the literatures. The preliminary test was conducted to verify the developed electrode concept by using lithium powder based anode (LIP) with conductive carbon materials and the results showed that lithium dendrite growth could be suppressed in this electrode design due to its increased electrochemical surface area and lithium deposition sites during lithium deposition. The electrode design suggested in Chapter 2 was extensively studied in Chapter 3 in terms of lithium dendrite growth morphology, lithium cycling efficiency and full cell cycling performance. This electrode concept was further developed to maximize the electrode's performance and safety in Chapter 4. In this new electrode design, electrically isolated super-p carbon agglomerates in the electrode were effectively reduced by adding conductive fillers such as graphite and further improvement in cycling performance and safety was also verified. The lithium powder based anode with conductive carbon materials is very useful concept as an alternative anode design instead of pure lithium metal anode for high energy density lithium batteries such as lithium-sulfur and lithium-air. As shown in Chapter 5, this electrode concept can be further developed and optimized through the application of new carbon materials and structure.

Expanded graphite embedded with aluminum nanoparticles as superior thermal conductivity anodes for high-performance lithium-ion batteries

PubMed Central

Zhao, Tingkai; She, Shengfei; Ji, Xianglin; Guo, Xinai; Jin, Wenbo; Zhu, Ruoxing; Dang, Alei; Li, Hao; Li, Tiehu; Wei, Bingqing

2016-01-01

The development of high capacity and long-life lithium-ion batteries is a long-term pursuing and under a close scrutiny. Most of the researches have been focused on exploring electrode materials and structures with high store capability of lithium ions and at the same time with a good electrical conductivity. Thermal conductivity of an electrode material will also have significant impacts on boosting battery capacity and prolonging battery lifetime, which is, however, underestimated. Here, we present the development of an expanded graphite embedded with Al metal nanoparticles (EG-MNPs-Al) synthesized by an oxidation-expansion process. The synthesized EG-MNPs-Al material exhibited a typical hierarchical structure with embedded Al metal nanoparticles into the interspaces of expanded graphite. The parallel thermal conductivity was up to 11.6 W·m−1·K−1 with a bulk density of 453 kg·m−3 at room temperature, a 150% improvement compared to expanded graphite (4.6 W·m−1·K−1) owing to the existence of Al metal nanoparticles. The first reversible capacity of EG-MNPs-Al as anode material for lithium ion battery was 480 mAh·g−1 at a current density of 100 mA·g−1, and retained 84% capacity after 300 cycles. The improved cycling stability and system security of lithium ion batteries is attributed to the excellent thermal conductivity of the EG-MNPs-Al anodes. PMID:27671848

Expanded graphite embedded with aluminum nanoparticles as superior thermal conductivity anodes for high-performance lithium-ion batteries.

PubMed

Zhao, Tingkai; She, Shengfei; Ji, Xianglin; Guo, Xinai; Jin, Wenbo; Zhu, Ruoxing; Dang, Alei; Li, Hao; Li, Tiehu; Wei, Bingqing

2016-09-27

The development of high capacity and long-life lithium-ion batteries is a long-term pursuing and under a close scrutiny. Most of the researches have been focused on exploring electrode materials and structures with high store capability of lithium ions and at the same time with a good electrical conductivity. Thermal conductivity of an electrode material will also have significant impacts on boosting battery capacity and prolonging battery lifetime, which is, however, underestimated. Here, we present the development of an expanded graphite embedded with Al metal nanoparticles (EG-MNPs-Al) synthesized by an oxidation-expansion process. The synthesized EG-MNPs-Al material exhibited a typical hierarchical structure with embedded Al metal nanoparticles into the interspaces of expanded graphite. The parallel thermal conductivity was up to 11.6 W·m -1 ·K -1 with a bulk density of 453 kg·m -3 at room temperature, a 150% improvement compared to expanded graphite (4.6 W·m -1 ·K -1 ) owing to the existence of Al metal nanoparticles. The first reversible capacity of EG-MNPs-Al as anode material for lithium ion battery was 480 mAh·g -1 at a current density of 100 mA·g -1 , and retained 84% capacity after 300 cycles. The improved cycling stability and system security of lithium ion batteries is attributed to the excellent thermal conductivity of the EG-MNPs-Al anodes.

A contrastive study of three graphite anodes in the piperidinium based electrolytes for lithium ion batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jiang, Xiao-Tao; Wang, Chen-Yi; Gao, Kun, E-mail: gaokun0451@163.com

Graphical abstract: The fitting results of R{sub sei} and R{sub ct} of three graphite/Li cells. Besides three graphite/Li cells show the similar R{sub sei}, the NG198/Li cell demonstrates a higher R{sub ct} value in all test temperatures. Especially, the R{sub ct} at 333 K is even up to 355.8 Ω cm{sup 2}. Obviously, the narrow distribution of edge plane for NG198 caused this result, and then greatly restricts its cell capacity. By contrast, CMB with bigger specific surface area and more Li{sup +} insertion points shows lower resistance at room temperature, which should help to improve its capacity. - Highlights:more » • SEI film is closely related to graphite structures and formation temperature. • The graphite with bigger surface area and more Li{sup +} insertion points behaves better. • The graphite with narrow edge plane is uncompetitive for ionic liquid electrolyte. - Abstract: The electrochemical behaviors of natural graphite (NG198), artificial graphite (AG360) and carbon microbeads (CMB) in an ionic liquid based electrolyte are investigated by cyclic voltammetry (CV). The surface and structure of three graphite materials are characterized by scanning electron microscope (SEM) and X-ray diffraction (XRD) before and after cycling. It is found that solid electrolyte interface (SEI) is closely related to graphite structure. Benefiting from larger specific surface area and more dispersed Li{sup +} insertion points, CMB shows a better Li{sup +} insertion/de-insertion behavior than NG198 and AG360. Furthermore, electrochemical impedance spectra (EIS) prove that the SEI of different graphite electrodes has different intrinsic resistance and Li{sup +} penetrability. By comparison, CMB behaves better cell performances than AG360, while the narrow edge plane makes NG198 uncompetitive as a potential anode for the ionic liquids (ILs)-type Li-ion battery.« less

The Role of Electrolyte Upon the SEI Formation Characteristics and Low Temperature Performance of Lithium-Ion Cells With Graphite Anodes

NASA Technical Reports Server (NTRS)

Smart, M.; Ratnakumar, B.; Greenbaum, S.; Surampudi, S.

1998-01-01

Quarternary lithium-ion battery electrolyte solutions containing ester co-solvents in mixtures of carbonates have been demonstrated to have high conductivity at low temperatures (<-20 degrees Celcius).

Post-mortem analysis on LiFePO4|Graphite cells describing the evolution & composition of covering layer on anode and their impact on cell performance

NASA Astrophysics Data System (ADS)

Lewerenz, Meinert; Warnecke, Alexander; Sauer, Dirk Uwe

2017-11-01

During cyclic aging of lithium-ion batteries the formation of a μm-thick covering layer on top of the anode facing the separator is found on top of the anode. In this work several post-mortem analyses of cyclic aged cylindrical LFP|Graphite cells are evaluated to give a detailed characterization of the covering layer and to find possible causes for the evolution of such a layer. The analyses of the layer with different methods return that it consists to high percentage of plated active lithium, deposited Fe and products of a solid electrolyte interphase (SEI). The deposition is located mainly in the center of the cell symmetrical to the coating direction. The origin of these depositions is assumed in locally overcharged particles, Fe deposition or inhomogeneous distribution of capacity density. As a secondary effect the deposition on one side increases the thickness locally; thereafter a pressure-induced overcharging due to charge agglomeration of the back side of the anode occurs. Finally a compact and dense covering layer in a late state of aging leads to deactivation of the covered parts of the anode and cathode due to suppressed lithium-ion conductivity. This leads to increasing slope of capacity fade and increase of internal resistance.

Quantifying microstructural dynamics and electrochemical activity of graphite and silicon-graphite lithium ion battery anodes

NASA Astrophysics Data System (ADS)

Pietsch, Patrick; Westhoff, Daniel; Feinauer, Julian; Eller, Jens; Marone, Federica; Stampanoni, Marco; Schmidt, Volker; Wood, Vanessa

2016-09-01

Despite numerous studies presenting advances in tomographic imaging and analysis of lithium ion batteries, graphite-based anodes have received little attention. Weak X-ray attenuation of graphite and, as a result, poor contrast between graphite and the other carbon-based components in an electrode pore space renders data analysis challenging. Here we demonstrate operando tomography of weakly attenuating electrodes during electrochemical (de)lithiation. We use propagation-based phase contrast tomography to facilitate the differentiation between weakly attenuating materials and apply digital volume correlation to capture the dynamics of the electrodes during operation. After validating that we can quantify the local electrochemical activity and microstructural changes throughout graphite electrodes, we apply our technique to graphite-silicon composite electrodes. We show that microstructural changes that occur during (de)lithiation of a pure graphite electrode are of the same order of magnitude as spatial inhomogeneities within it, while strain in composite electrodes is locally pronounced and introduces significant microstructural changes.

Thermal abuse performance of high-power 18650 Li-ion cells

NASA Astrophysics Data System (ADS)

Roth, E. P.; Doughty, D. H.

High-power 18650 Li-ion cells have been developed for hybrid electric vehicle applications as part of the DOE Advanced Technology Development (ATD) program. The thermal abuse response of two advanced chemistries (Gen1 and Gen2) were measured and compared with commercial Sony 18650 cells. Gen1 cells consisted of an MCMB graphite based anode and a LiNi 0.85Co 0.15O 2 cathode material while the Gen2 cells consisted of a MAG10 anode graphite and a LiNi 0.80Co 0.15 Al 0.05O 2 cathode. Accelerating rate calorimetry (ARC) and differential scanning calorimetry (DSC) were used to measure the thermal response and properties of the cells and cell materials up to 400 °C. The MCMB graphite was found to result in increased thermal stability of the cells due to more effective solid electrolyte interface (SEI) formation. The Al stabilized cathodes were seen to have higher peak reaction temperatures that also gave improved cell thermal response. The effects of accelerated aging on cell properties were also determined. Aging resulted in improved cell thermal stability with the anodes showing a rapid reduction in exothermic reactions while the cathodes only showed reduced reactions after more extended aging.

Catalytic membranes for fuel cells

DOEpatents

Liu, Di-Jia [Naperville, IL; Yang, Junbing [Bolingbrook, IL; Wang, Xiaoping [Naperville, IL

2011-04-19

A fuel cell of the present invention comprises a cathode and an anode, one or both of the anode and the cathode including a catalyst comprising a bundle of longitudinally aligned graphitic carbon nanotubes including a catalytically active transition metal incorporated longitudinally and atomically distributed throughout the graphitic carbon walls of said nanotubes. The nanotubes also include nitrogen atoms and/or ions chemically bonded to the graphitic carbon and to the transition metal. Preferably, the transition metal comprises at least one metal selected from the group consisting of Fe, Co, Ni, Mn, and Cr.

Ab initio molecular dynamics simulations of the initial stages of solid-electrolyte interphase formation on lithium ion battery graphitic anodes.

PubMed

Leung, Kevin; Budzien, Joanne L

2010-07-07

The decomposition of ethylene carbonate (EC) during the initial growth of solid-electrolyte interphase (SEI) films at the solvent-graphitic anode interface is critical to lithium ion battery operations. Ab initio molecular dynamics simulations of explicit liquid EC/graphite interfaces are conducted to study these electrochemical reactions. We show that carbon edge terminations are crucial at this stage, and that achievable experimental conditions can lead to surprisingly fast EC breakdown mechanisms, yielding decomposition products seen in experiments but not previously predicted.

High performance 1.2 Ah Si-alloy/Graphite|LiNi0.5Mn0.3Co0.2O2 prototype Li-ion battery

NASA Astrophysics Data System (ADS)

Marinaro, Mario; Yoon, Dong-hwan; Gabrielli, Giulio; Stegmaier, Petra; Figgemeier, Egbert; Spurk, Paul C.; Nelis, Daniël; Schmidt, Gregory; Chauveau, Jerome; Axmann, Peter; Wohlfahrt-Mehrens, Margret

2017-07-01

The study reports on realization and electrochemical testing of prototype Si-alloy/Graphite|LiNi0.5Mn0.3Co0.2O2 batteries. Water soluble polyacrylic acid (PAA), used as the only binder at the anode side, demonstrates excellent dispersant and binding properties. Sedimentation tests and rheological measurements show remarkable stability and mostly a thinning behavior of the non-Newtonian type of slurry. The cathode is processed in N-Methylpyrrolidone based slurry using polyvinylidene fluoride (PVDF) as the binding agent. The electronic conductivities of the manufactured Si-alloy/Graphite and LiNi0.5Mn0.3Co0.2O2 electrodes are evaluated. Furthermore, the cathode and anode electrochemical behavior is initially studied in half-cells, and subsequently in full Li-ion stacked prototype soft pouch-cells (1.22 Ah). It is demonstrated that the manufactured prototype cells can sustain about 290 charge/discharge galvanostatic cycles before the retained capacity drops below 80%. Cell aging is monitored using Electrochemical Impedance Spectroscopy (EIS), whereas post-mortem SEM analysis of electrodes cross-section is used to shed light on the causes of performance degradation of the cells.

Performance evaluation of GDC-SrMoO4-YSZ SOFCs prepared with different pore formers

NASA Astrophysics Data System (ADS)

Hongxin, You; Lian, Peng; Xiaojuan, Wang; Cong, Zhao; Yajun, Guan; Tao, Yu; Lijun, Xu; Abuliti

2018-04-01

The paper aims to evaluate the performance of anodes prepared with different pore formers. Anodic precursor material SrMoO4 was prepared by hard template method. Gd0.2Ce0.8O1.9 (GDC) was introduced to the precursor to prepare composite anode material GDC-SrMoO4-YSZ by wet impregnation method. Cotton-fibers, graphite powder, flour and activated carbon fibers (ACF) were added as pore formers to the anode to prepare the corresponding solid oxide fuel cell (SOFC), respectively. The electrical performance testing was conducted under the methane environment at 800°C. The result showed that the single cell with 5wt% cotton-fibers as anode pore-former performed best with the maximum power density (464.49 mW.cm2). The cross section samples of the test cells indicated that the anode was left with a plenty of continuous long channels because of the burning of cotton-fibers. Thus, the influence of the amount of cotton-fibers (2wt%, 4wt%, 5wt%, 7wt%, 10wt%) of the anode on the performance of SOFC was tested and further analyzed by the scanning electron microscope (SEM). It was indicated that the optimum adding amount of cotton-fibers was 5wt%.

Relationships between structure and activity of carbon as a multifunctional support for electrocatalysts.

PubMed

Stevanović, Sanja I; Panić, Vladimir V; Dekanski, Aleksandar B; Tripković, Amalija V; Jovanović, Vladislava M

2012-07-14

We report on new insights into the relationships between structure and activity of glassy carbon (GC), as a model material for electrocatalyst support, during its anodization in acid solution. Our investigation strongly confirms the role of CFGs in promotion of Pt activity by the "spill-over" effect related to CO(ads) for methanol electrooxidation (MEO) on a carbon-supported Pt catalyst. Combined analysis of voltammetric and impedance behaviour as well as changes in GC surface morphology induced by intensification of anodizing conditions reveal an intrinsic influence of the carbon functionalization and the structure of a graphene oxide (GO) layer on the electrical and electrocatalytic properties of activated GC. Although GO continuously grows during anodization, it structurally changes from being a graphite inter-layer within graphite ribbons toward a continuous GO surface layer that deteriorates the native structure of GC. As a consequence of the increased distance between GO-spaced graphite layers, the GC conductivity decreases until the case of profound GO exfoliation under drastic anodizing conditions. This exposes the native, yet abundantly functionalized, GC texture. While GC capacitance continuously increases with intensification of anodizing conditions, the surface nano-roughness and GO resistance reach the highest values at modest anodizing conditions, and then decrease upon drastic anodization due to the onset of GO exfoliation. We found for the first time that the activity of a GC-supported Pt catalyst in MEO, as one of the promising half-reactions in polymer electrolyte fuel cells, strictly follows the changes in GC nano-roughness and GO-induced GC resistance. The highest GC/Pt MEO activity is reached when optimal distance between graphite layers and optimal degree of GC functionalization bring the highest amount of CFGs into intimate contact with the Pt surface. This confirms the promoting role of CFGs in MEO catalysis.

Si-FeSi2/C nanocomposite anode materials produced by two-stage high-energy mechanical milling

NASA Astrophysics Data System (ADS)

Yang, Yun Mo; Loka, Chadrasekhar; Kim, Dong Phil; Joo, Sin Yong; Moon, Sung Whan; Choi, Yi Sik; Park, Jung Han; Lee, Kee-Sun

2017-05-01

High capacity retention Silicon-based nanocomposite anode materials have been extensively explored for use in lithium-ion rechargeable batteries. Here we report the preparation of Si-FeSi2/C nanocomposite through scalable a two-stage high-energy mechanical milling process, in which nano-scale Si-FeSi2 powders are besieged by the carbon (graphite/amorphous phase) layer; and investigation of their structure, morphology and electrochemical performance. Raman analysis revealed that the carbon layer structure comprised of graphitic and amorphous phase rather than a single amorphous phase. Anodes fabricated with the Si-FeSi2/C showed excellent electrochemical behavior such as a first discharge capacity of 1082 mAh g-1 and a high capacity retention until the 30th cycle. A remarkable coulombic efficiency of 99.5% was achieved within a few cycles. Differential capacity plots of the Si-FeSi2/C anodes revealed a stable lithium reaction with Si for lithiation/delithiation. The enhanced electrochemical properties of the Si-FeSi2/C nanocomposite are mainly attributed to the nano-size Si and stable solid electrolyte interface formation and highly conductive path driven by the carbon layer.

Understanding capacity fade in silicon based electrodes for lithium-ion batteries using three electrode cells and upper cut-off voltage studies

NASA Astrophysics Data System (ADS)

Beattie, Shane D.; Loveridge, M. J.; Lain, Michael J.; Ferrari, Stefania; Polzin, Bryant J.; Bhagat, Rohit; Dashwood, Richard

2016-01-01

Commercial Li-ion batteries are typically cycled between 3.0 and 4.2 V. These voltages limits are chosen based on the characteristics of the cathode (e.g. lithium cobalt oxide) and anode (e.g. graphite). When alternative anode/cathode chemistries are studied the same cut-off voltages are often, mistakenly, used. Silicon (Si) based anodes are widely studied as a high capacity alternative to graphite for Lithium-ion batteries. When silicon-based anodes are paired with high capacity cathodes (e.g. Lithium Nickel Cobalt Aluminium Oxide; NCA) the cell typically suffers from rapid capacity fade. The purpose of this communication is to understand how the choice of upper cut-off voltage affects cell performance in Si/NCA cells. A careful study of three-electrode cell data will show that capacity fade in Si/NCA cells is due to an ever-evolving silicon voltage profile that pushes the upper voltage at the cathode to >4.4 V (vs. Li/Li+). This behaviour initially improves cycle efficiency, due to liberation of new lithium, but ultimately reduces cycling efficiency, resulting in rapid capacity fade.

Multiscale Engineered Si/SiO x Nanocomposite Electrodes for Lithium-Ion Batteries Using Layer-by-Layer Spray Deposition.

PubMed

Huang, Chun; Kim, Ayoung; Chung, Dong Jae; Park, Eunjun; Young, Neil P; Jurkschat, Kerstin; Kim, Hansu; Grant, Patrick S

2018-05-09

Si-based high-capacity materials have gained much attention as an alternative to graphite in Li-ion battery anodes. Although Si additions to graphite anodes are now commercialized, the fraction of Si that can be usefully exploited is restricted due to its poor cyclability arising from the large volume changes during charge/discharge. Si/SiO x nanocomposites have also shown promising behavior, such as better capacity retention than Si alone because the amorphous SiO x helps to accommodate the volume changes of the Si. Here, we demonstrate a new electrode architecture for further advancing the performance of Si/SiO x nanocomposite anodes using a scalable layer-by-layer atomization spray deposition technique. We show that particulate C interlayers between the current collector and the Si/SiO x layer and between the separator and the Si/SiO x layer improved electrical contact and reduced irreversible pulverization of the Si/SiO x significantly. Overall, the multiscale approach based on microstructuring at the electrode level combined with nanoengineering at the material level improved the capacity, rate capability, and cycling stability compared to that of an anode comprising a random mixture of the same materials.

Nanoporous Tin with a Granular Hierarchical Ligament Morphology as a Highly Stable Li-Ion Battery Anode

DOE PAGES

Cook, John B.; Detsi, Eric; Liu, Yijin; ...

2016-12-07

Next generation Li-ion batteries will require negative electrode materials with energy densities many-fold higher than that found in the graphitic carbon currently used in commercial Li-ion batteries. While various nanostructured alloying-type anode materials may satisfy that requirement, such materials do not always exhibit long cycle lifetimes and/or their processing routes are not always suitable for large-scale synthesis. Here, we report on a high-performance anode material for next generation Li-ion batteries made of nanoporous Sn powders with hierarchical ligament morphology. This material system combines both long cycle lifetimes (more than 72% capacity retention after 350 cycles), high capacity (693 mAh/g, nearlymore » twice that of commercial graphitic carbon), good charging/discharging capabilities (545 mAh/g at 1 A/g, 1.5C), and a scalable processing route that involves selective alloy corrosion. The good cycling performance of this system is attributed to its nanoporous architecture and its unique hierarchical ligament morphology, which accommodates the large volume changes taking place during lithiation, as confirmed by synchrotron-based ex-situ X-ray 3D tomography analysis. In conclusion, our findings are an important step for the development of high-performance Li-ion batteries.« less

Sinusoidal current and stress evolutions in lithium-ion batteries

NASA Astrophysics Data System (ADS)

Yang, Xiao-Guang; Bauer, Christoph; Wang, Chao-Yang

2016-09-01

Mechanical breakdown of graphite materials due to diffusion-induced stress (DIS) is a key aging mechanism of lithium-ion batteries. In this work, electrochemical-thermal coupled model along with a DIS model is developed to study the DIS distribution across the anode thickness. Special attention is paid to the evolution behavior of surface tangential stress (STS) in the discharge process for graphite at different locations of the anode. For the first time, we report that the evolution of STS, as well as local current, at all locations of the anode, evolve like sinusoidal waves in the discharge process with several crests and troughs. The staging behavior of graphite active material, in particular the sharp change of open-circuit potential (OCP) of graphite in the region between two plateaus, is found to be the root cause for the sinusoidal patterns of current and stress evolution. Furthermore, the effects of various parameters, such as starting state of charge, discharge C-rate and electrode thickness on the current and stress evolutions are investigated.

The spectral emissivity of the anode of a carbon arc.

PubMed

Schurer, K

1968-03-01

Data in the literature on the spectral emissivity of carbon and graphite show a great divergence, ranging from 0.75 to 0.99 in the visible region. A new determination has been undertaken at a number of wavelengths using an integrating sphere and modulated light. Emissivities ranging from 0.99 in the visible to 0.96 at 0.28 micro and 1.7 micro have been found for several different graphite anodes; the values for lampblack anodes are about 0.005 lower. There is a good agreement with the highest values thus far published. Most of the literature data on the spectral radiance of the anode are consistent with the emissivities found by the present author.

Chromic acid anodizing of aluminum foil

NASA Technical Reports Server (NTRS)

Dursch, H.

1988-01-01

The success of the Space Station graphite/epoxy truss structure depends on its ability to endure long-term exposure to the LEO environment, primarily the effects of atomic oxygen and the temperture cycling resulting from the 94 minute orbit. This report describes the development and evaluation of chromic acid anodized (CAA) aluminum foil as protective coatings for these composite tubes. Included are: development of solar absorptance and thermal emittance properties required of Al foil and development of CAA parameters to achieve these optical properties; developing techniques to CAA 25 ft lengths of Al foil; developing bonding processes for wrapping the Al foil to graphite/epoxy tubes; and atomic oxygen testing of the CAA Al foil. Two specifications were developed and are included in the report: Chromic Acid Anodizing of Aluminum Foil Process Specification and Bonding of Anodized Aluminum Foil to Graphite/Epoxy Tubes. Results show that CAA Al foil provides and excellent protective and thermal control coating for the Space Station truss structure.

Recycled tire crumb rubber anodes for sustainable power production in microbial fuel cells

NASA Astrophysics Data System (ADS)

Wang, Heming; Davidson, Matthew; Zuo, Yi; Ren, Zhiyong

One of the greatest challenges facing microbial fuel cells (MFCs) in large scale applications is the high cost of electrode material. We demonstrate here that recycled tire crumb rubber coated with graphite paint can be used instead of fine carbon materials as the MFC anode. The tire particles showed satisfactory conductivity after 2-4 layers of coating. The specific surface area of the coated rubber was over an order of magnitude greater than similar sized graphite granules. Power production in single chamber tire-anode air-cathode MFCs reached a maximum power density of 421 mW m -2, with a coulombic efficiency (CE) of 25.1%. The control graphite granule MFC achieved higher power density (528 mW m -2) but lower CE (15.6%). The light weight of tire particle could reduce clogging and maintenance cost but posts challenges in conductive connection. The use of recycled material as the MFC anodes brings a new perspective to MFC design and application and carries significant economic and environmental benefit potentials.

Carbon materials derived from waste tires as high-performance anodes in microbial fuel cells.

PubMed

Chen, Wei; Feng, Huajun; Shen, Dongsheng; Jia, Yufeng; Li, Na; Ying, Xianbin; Chen, Ting; Zhou, Yuyang; Guo, Jiayun; Zhou, Mengjiao

2018-03-15

In this study, carbonized waste tires were directly used as a high-performance anode material in microbial fuel cells (MFCs). The effect of the pyrolysis temperature used for waste tire carbonization on the current output performance was investigated to determine the optimal pyrolysis temperature. Thermal gravimetric analysis/differential scanning calorimetry showed that tire carbonization started at 200°C and ended at about 500°C; the weight loss was about 64%. When used in an MFC, the electrode obtained from waste tires carbonized at 800°C gave a current density of 23.1±1.4Am -2 , which is much higher than that achieved with traditional graphite felt anodes (5.5±0.1Am -2 ). The results of this study will be useful in optimizing the design of carbonized waste tire anodes for enhancing MFC performances and will alleviate the environmental problems caused by waste tires. Copyright © 2017 Elsevier B.V. All rights reserved.

Preliminary Development of Electrodes for an Electric-Arc Wind Tunnel

NASA Technical Reports Server (NTRS)

Shepard, Charles E.; Boldman, Donald R.

1959-01-01

Two electrode configurations were tested in an electric-arc wind tunnel at the NASA Lewis Research Center. The results indicated approximately the same heat-loss rate per unit of arc power input for each of the configurations. Measured heat-loss rates were on the order of 40 percent of the arc power input. Nearly all this loss occurred at the anode. The power input and arc current limitations of the electrodes appear to be the critical design factors. Up to now, the maximum power to the stream has been 115 kilowatts with a cooled tungsten cathode and a cooled cylindrical anode incorporating a magnetic field. The maximum power input to this anode could not be established with the cooled tungsten cathode because cathode failures occurred at a gross power level of approximately 175 kilowatts. It was necessary to use a graphite cathode to seek the limitation of the anode. The results indicated that the anode limitation was primarily a function of arc current rather than power input. The anode was successfully operated at a power of 340 kilowatts at 1730 amperes; however, the anode failed with a power input of 324 kilowatts and a current of 2140 amperes. The magnetic flux density at the time of failure was 0.32 weber per square meter, or 3200 gauss. The graphite cathode was used only to establish the anode limitation; further investigation of graphite cathodes was discontinued because of the large amount of stream contamination associated with this type of electrode.

Degradation Mechanisms of Electrochemically Cycled Graphite Anodes in Lithium-ion Cells

NASA Astrophysics Data System (ADS)

Bhattacharya, Sandeep

This research is aimed at developing advanced characterization methods for studying the surface and subsurface damage in Li-ion battery anodes made of polycrystalline graphite and identifying the degradation mechanisms that cause loss of electrochemical capacity. Understanding microstructural aspects of the graphite electrode degradation mechanisms during charging and discharging of Li-ion batteries is of key importance in order to design durable anodes with high capacity. An in-situ system was constructed using an electrochemical cell with an observation window, a large depth-of-field digital microscope and a micro-Raman spectrometer. It was revealed that electrode damage by removal of the surface graphite fragments of 5-10 mum size is the most intense during the first cycle that led to a drastic capacity drop. Once a solid electrolyte interphase (SEI) layer covered the electrode surface, the rate of graphite particle loss decreased. Yet, a gradual loss of capacity continued by the formation of interlayer cracks adjacent to SEI/graphite interfaces. Deposition of co-intercalation compounds, LiC6, Li2CO3 and Li2O, near the crack tips caused partial closure of propagating graphite cracks during cycling and reduced the crack growth rate. Bridging of crack faces by delaminated graphite layers also retarded crack propagation. The microstructure of the SEI layer, formed by electrochemical reduction of the ethylene carbonate based electrolyte, consisted of ˜5-20 nm sized crystalline domains (containing Li2CO3, Li2O 2 and nano-sized graphite fragments) dispersed in an amorphous matrix. During the SEI formation, two regimes of Li-ion diffusion were identified at the electrode/electrolyte interface depending on the applied voltage scan rate (dV/dt). A low Li-ion diffusion coefficient ( DLi+) at dV/dt < 0.05 mVs-1 produced a tubular SEI that uniformly covered the graphite surface and prevented damage at 25°C. At 60°C, a high D Li+ formed a Li2CO3-enriched SEI and ensued a 28% increase in the battery capacity at 25°C. On correlating the microscopic information to the electrochemical performance, novel Li2CO3-coated electrodes were fabricated that were durable. The SEI formed on pre-treated electrodes reduced the strain in the graphite lattice from 0.4% (for uncoated electrodes) to 0.1%, facilitated Li-ion diffusion and hence improved the capacity retention of Li-ion batteries during long-term cycling.

Homogeneity of lithium distribution in cylinder-type Li-ion batteries

PubMed Central

Senyshyn, A.; Mühlbauer, M. J.; Dolotko, O.; Hofmann, M.; Ehrenberg, H.

2015-01-01

Spatially-resolved neutron powder diffraction with a gauge volume of 2 × 2 × 20 mm3 has been applied as an in situ method to probe the lithium concentration in the graphite anode of different Li-ion cells of 18650-type in charged state. Structural studies performed in combination with electrochemical measurements and X-ray computed tomography under real cell operating conditions unambiguously revealed non-homogeneity of the lithium distribution in the graphite anode. Deviations from a homogeneous behaviour have been found in both radial and axial directions of 18650-type cells and were discussed in the frame of cell geometry and electrical connection of electrodes, which might play a crucial role in the homogeneity of the lithium distribution in the active materials within each electrode. PMID:26681110

Three-dimensional anode engineering for the direct methanol fuel cell

NASA Astrophysics Data System (ADS)

Bauer, A.; Oloman, C. W.; Gyenge, E. L.

Catalyzed graphite felt three-dimensional anodes were investigated in direct methanol fuel cells (DMFCs) operated with sulfuric acid supporting electrolyte. With a conventional serpentine channel flow field the preferred anode thickness was 100 μm, while a novel flow-by anode showed the best performance with a thickness of 200-300 μm. The effects of altering the methanol concentration, anolyte flow rate and operating temperature on the fuel cell superficial power density were studied by full (2 3 + 1) factorial experiments on a cell with anode area of 5 cm 2 and excess oxidant O 2 at 200 kPa(abs). For operation in the flow-by mode with 2 M methanol at 2 cm 3 min -1 and 353 K the peak power density was 2380 W m -2 with a PtRuMo anode catalyst, while a PtRu catalyst yielded 2240 W m -2 under the same conditions.

Single chamber microbial fuel cell with spiral anode for dairy wastewater treatment.

PubMed

Mardanpour, Mohammad Mahdi; Nasr Esfahany, Mohsen; Behzad, Tayebeh; Sedaqatvand, Ramin

2012-01-01

This study reports on the fabrication of a novel annular single chamber microbial fuel cell (ASCMFC) with spiral anode. The stainless steel mesh anode with graphite coating was used as anode. Dairy wastewater, containing complex organic matter, was used as substrate. ASCMFC had been operated for 450 h and results indicated a high open circuit voltage (about 810 mV) compared with previously published results. The maximum power density of 20.2 W/m(3) obtained in this study is significantly greater than the power densities reported in previous studies. Besides, a maximum coulombic efficiency of 26.87% with 91% COD removal was achieved. Good bacterial adhesion on the spiral anode is clearly shown in SEM micrographs. High power density and a successful performance in wastewater treatment in ASCMFC suggest it as a promising alternative to conventional MFCs for power generation and wastewater treatment. ASCMFC performance as a power generator was characterized based on polarization behavior and cell potentials. Copyright © 2012 Elsevier B.V. All rights reserved.

Tin-based anode materials with well-designed architectures for next-generation lithium-ion batteries

NASA Astrophysics Data System (ADS)

Liu, Lehao; Xie, Fan; Lyu, Jing; Zhao, Tingkai; Li, Tiehu; Choi, Bong Gill

2016-07-01

Tin (Sn) has long been considered to be a promising replacement anode material for graphite in next-generation lithium-ion batteries (LIBs), because of its attractive comprehensive advantages of high gravimetric/volumetric capacities, environmental benignity, low cost, high safety, etc. However, Sn-based anodes suffer from severe capacity fading resulting mainly from their large volume expansions/contractions during lithiation/delithiation and subsequent pulverization, coalescence, delamination from current collectors, and poor Li+/electron transport. To circumvent these issues, a number of extraordinary architectures from nanostructures to anchored, layered/sandwich, core-shell, porous and even integrated structures have been exquisitely constructed to enhance the cycling performance. To cater for the rapid development of Sn-based anodes, we summarize the advances made in structural design principles, fabrication methods, morphological features and battery performance with focus on material structures. In addition, we identify the associated challenges and problems presented by recently-developed anodes and offer suggestions and perspectives for facilitating their practical implementations in next-generation LIBs.

High Temperature Carbonized Grass as a High Performance Sodium Ion Battery Anode.

PubMed

Zhang, Fang; Yao, Yonggang; Wan, Jiayu; Henderson, Doug; Zhang, Xiaogang; Hu, Liangbing

2017-01-11

Hard carbon is currently considered the most promising anode candidate for room temperature sodium ion batteries because of its relatively high capacity, low cost, and good scalability. In this work, switchgrass as a biomass example was carbonized under an ultrahigh temperature, 2050 °C, induced by Joule heating to create hard carbon anodes for sodium ion batteries. Switchgrass derived carbon materials intrinsically inherit its three-dimensional porous hierarchical architecture, with an average interlayer spacing of 0.376 nm. The larger interlayer spacing than that of graphite allows for the significant Na ion storage performance. Compared to the sample carbonized under 1000 °C, switchgrass derived carbon at 2050 °C induced an improved initial Coulombic efficiency. Additionally, excellent rate capability and superior cycling performance are demonstrated for the switchgrass derived carbon due to the unique high temperature treatment.

Boosting the power performance of multilayer graphene as lithium-ion battery anode via unconventional doping with in-situ formed Fe nanoparticles

PubMed Central

Raccichini, Rinaldo; Varzi, Alberto; Chakravadhanula, Venkata Sai Kiran; Kübel, Christian; Passerini, Stefano

2016-01-01

Graphene is extensively investigated and promoted as a viable replacement for graphite, the state-of-the-art material for lithium-ion battery (LIB) anodes, although no clear evidence is available about improvements in terms of cycling stability, delithiation voltage and volumetric capacity. Here we report the microwave-assisted synthesis of a novel graphene-based material in ionic liquid (i.e., carved multilayer graphene with nested Fe3O4 nanoparticles), together with its extensive characterization via several physical and chemical techniques. When such a composite material is used as LIB anode, the carved paths traced by the Fe3O4 nanoparticles, and the unconverted metallic iron formed in-situ upon the 1st lithiation, result in enhanced rate capability and, especially at high specific currents (i.e., 5 A g−1), remarkable cycling stability (99% of specific capacity retention after 180 cycles), low average delithiation voltage (0.244 V) and a substantially increased volumetric capacity with respect to commercial graphite (58.8 Ah L−1 vs. 9.6 Ah L−1). PMID:27026069

Gas Evolution in Operating Lithium-Ion Batteries Studied In Situ by Neutron Imaging

PubMed Central

Michalak, Barbara; Sommer, Heino; Mannes, David; Kaestner, Anders; Brezesinski, Torsten; Janek, Jürgen

2015-01-01

Gas generation as a result of electrolyte decomposition is one of the major issues of high-performance rechargeable batteries. Here, we report the direct observation of gassing in operating lithium-ion batteries using neutron imaging. This technique can be used to obtain qualitative as well as quantitative information by applying a new analysis approach. Special emphasis is placed on high voltage LiNi0.5Mn1.5O4/graphite pouch cells. Continuous gassing due to oxidation and reduction of electrolyte solvents is observed. To separate gas evolution reactions occurring on the anode from those associated with the cathode interface and to gain more insight into the gassing behavior of LiNi0.5Mn1.5O4/graphite cells, neutron experiments were also conducted systematically on other cathode/anode combinations, including LiFePO4/graphite, LiNi0.5Mn1.5O4/Li4Ti5O12 and LiFePO4/Li4Ti5O12. In addition, the data were supported by gas pressure measurements. The results suggest that metal dissolution in the electrolyte and decomposition products resulting from the high potentials adversely affect the gas generation, particularly in the first charge cycle (i.e., during graphite solid-electrolyte interface layer formation). PMID:26496823

Si@SiOx/Graphene nanosheet anode materials for lithium-ion batteries synthesized by ball milling process

NASA Astrophysics Data System (ADS)

Tie, Xiaoyong; Han, Qianyan; Liang, Chunyan; Li, Bo; Zai, Jiantao; Qian, Xuefeng

2017-12-01

Si@SiOx/Graphene nanosheet (GNS) nanocomposites as high performance anode materials for lithium-ion batteries are synthesized by mechanically blending the mixture of expanded graphite with Si nanoparticles, and characterized by X-ray diffraction, Raman spectrum, field emission scanning electron microscopy and transmission electron microscopy. During the ball milling process, the size of Si nanoparticles will decrease, and the layer of expanded graphite can be peeled off to thin multilayers. Electrochemical performances reveal that the obtained Si@SiOx/GNS nanocomposites exhibit improved cycling stability, high reversible lithium storage capacity and superior rate capability, e.g. the discharge capacity is kept as high as 1055 mAh g-1 within 50 cycles at a current density of 200 mA g-1, retaining 63.6% of the initial value. The high performance of the obtained nanocomposites can be ascribed to GNS prepared through heat-treat and ball-milling methods, the decrease in the size of Si nanoparticles and SiOx layer on Si surface, which enhance the interactions between Si and GNS.

Sensitive Voltammetric Determination of Natural Flavonoid Quercetin on a Disposable Graphite Lead

PubMed Central

Vu, Dai Long; Žabčíková, Simona; Ertek, Bensu; Dilgin, Yusuf

2015-01-01

Summary In this paper, a pencil graphite electrode was pretreated using chronoamperometry technique in phosphate buffer solution (pH=7.0) for sensitive determination of quercetin. Oxidation of quercetin was investigated using pretreated pencil graphite electrode and anodic stripping differential pulse voltammetry. Under optimal conditions, the anodic current of quercetin exhibited linear response to its concentration in the range from 0.001 to 1.5 µmol/L with the limit of detection of 0.3·10–3 µmol/L. The proposed method was successfully applied for the determination of quercetin in cranberry and blackcurrant juices with recovery rate from 93.2 to 94.7%. Solid-phase extraction was found to be necessary prior to voltammetric determination of quercetin in fruit juice samples using pretreated pencil graphite electrode. PMID:27904372

RECOVERY OF VALUABLE MATERIAL FROM GRAPHITE BODIES

DOEpatents

Fromm, L.W. Jr.

1959-09-01

An electrolytic process for recovering uranium from a graphite fuel element is described. The uraniumcontaining graphite body is disposed as the anode of a cell containing a nitric acid electrolyte and a 5 amp/cm/sup 2/ current passed to induce a progressive disintegration of the graphite body. The dissolved uranium is quickly and easily separated from the resulting graphite particles by simple mechanical means, such as centrifugation, filtration, and decontamination.

Dissecting anode swelling in commercial lithium-ion batteries

NASA Astrophysics Data System (ADS)

Zhang, Ningxin; Tang, Huaqiong

2012-11-01

An innovative method is applied to investigate anode swelling during electrochemical processes in commercial lithium-ion batteries. Cathode surface is partially covered with a piece of paste to block the transportation of lithium ion from active material during charging/discharging, and the corresponding part on the anode film shows no formation of Li-graphite compounds during different electrochemical processes, which is confirmed by XRD analysis. The increases of anode thickness within and outside lithiated zone are measured, and defined as electrochemical swelling and physical swelling respectively. The microscopic lattice expansion of graphite due to lithiation process correlates to mesoscopic electrochemical swelling synchronically, while physical swelling tends to decrease steadily with time. The relationship among the microscopic stress due to lithium-ion intercalation, the mesoscopic stress resulting in anode swelling, and the macroscopic rippling of pouch cell after a large number of cycle test, is analyzed and correlated in terms of stress evolution across different scales, and suggestions for solving anode swelling are provided.

Novel Non-Carbonate Based Electrolytes for Silicon Anodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Ye; Yang, Johnny; Cheng, Gang

2016-09-09

Substantial improvement in the energy density of rechargeable lithium batteries is required to meet the future needs for electric and plug-in electric vehicles (EV and PHEV). Present day lithium ion battery technology is based on shuttling lithium between graphitic carbon and inorganic oxides. Non-graphitic anodes, such as silicon can provide significant improvements in energy density but are currently limited in cycle life due to reactivity with the electrolyte. Wildcat/3M proposes the development of non-carbonate electrolyte formulations tailored for silicon alloy anodes. Combining these electrolytes with 3M’s anode and an NMC cathode will enable up to a 20% increase in themore » volumetric cell energy density, while still meeting the PHEV/EV cell level cycle/calendar life goals.« less

Investigation of Metal Oxide/Carbon Nano Material as Anode for High Capacity Lithium-ion Cells

NASA Technical Reports Server (NTRS)

Wu, James Jianjun; Hong, Haiping

2014-01-01

NASA is developing high specific energy and high specific capacity lithium-ion battery (LIB) technology for future NASA missions. Current state-of-art LIBs have issues in terms of safety and thermal stability, and are reaching limits in specific energy capability based on the electrochemical materials selected. For example, the graphite anode has a limited capability to store Li since the theoretical capacity of graphite is 372 mAh/g. To achieve higher specific capacity and energy density, and to improve safety for current LIBs, alternative advanced anode, cathode, and electrolyte materials are pursued under the NASA Advanced Space Power System Project. In this study, the nanostructed metal oxide, such as Fe2O3 on carbon nanotubes (CNT) composite as an LIB anode has been investigated.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Travis, Jonathan; Orendorff, Christopher J.

This work investigated the effects of Al 2O 3 ALD coatings on the performance and thermal abuse tolerance of graphite based anodes and Li(NixMnyCoz)O2 (NMC) based cathodes. It was found that 5 cycles of Al 2O 3 ALD on the graphite anode increased the onset temperature of thermal runaway by approximately 20 °C and drastically reduced the anode’s contribution to the overall amount of heat released during thermal runaway. Although Al 2O 3 ALD improves the cycling stability of NMC based cathodes, the thermal abuse tolerance was not greatly improved. A series of conductive aluminum oxide/carbon composites were created andmore » characterized as potential thicker protective coatings for use on NMC based cathode materials. A series of electrodes were coated with manganese monoxide ALD to test the efficacy of an oxygen scavenging coating on NMC based cathodes.« less

Electrolytic exfoliation of graphite in water with multifunctional electrolytes: en route towards high quality, oxide-free graphene flakes.

PubMed

Munuera, J M; Paredes, J I; Villar-Rodil, S; Ayán-Varela, M; Martínez-Alonso, A; Tascón, J M D

2016-02-07

Electrolytic--usually referred to as electrochemical--exfoliation of graphite in water under anodic potential holds enormous promise as a simple, green and high-yield method for the mass production of graphene, but currently suffers from several drawbacks that hinder its widespread adoption, one of the most critical being the oxidation and subsequent structural degradation of the carbon lattice that is usually associated with such a production process. To overcome this and other limitations, we introduce and implement the concept of multifunctional electrolytes. The latter are amphiphilic anions (mostly polyaromatic hydrocarbons appended with sulfonate groups) that play different relevant roles as (1) an intercalating electrolyte to trigger exfoliation of graphite into graphene flakes, (2) a dispersant to afford stable aqueous colloidal suspensions of the flakes suitable for further use, (3) a sacrificial agent to prevent graphene oxidation during exfoliation and (4) a linker to promote nanoparticle anchoring on the graphene flakes, yielding functional hybrids. The implementation of this strategy with some selected amphiphiles even furnishes anodically exfoliated graphenes of a quality similar to that of flakes produced by direct, ultrasound- or shear-induced exfoliation of graphite in the liquid phase (i.e., almost oxide- and defect-free). These high quality materials were used for the preparation of catalytically efficient graphene-Pt nanoparticle hybrids, as demonstrated by model reactions (reduction of nitroarenes). The multifunctional performance of these electrolytes is also discussed and rationalized, and a mechanistic picture of their oxidation-preventing ability is proposed. Overall, the present results open the prospect of anodic exfoliation as a competitive method for the production of very high quality graphene flakes.

Phosphomolybdic acid immobilized on graphite as an environmental photoelectrocatalyst.

PubMed

Aber, Soheil; Yaghoubi, Zeynab; Zarei, Mahmoud

2016-10-01

A new phosphomolybdic acid (PMA)/Graphite surface was prepared based on electrostatic interactions between phosphomolybdic acid and graphite surface. The PMA/Graphite was characterized by cyclic voltammetry (CV) analysis and scanning electron microscope (SEM). SEM images showed that the phosphomolybdic acid particles were well stabilized on the graphite surface and they were evidenced the size of particles (approximately 10 nm). The CV results not only showed that the modified surface has good electrochemical activity toward the removal of the dyestuff, but also exhibits long term stability. The PMA/Graphite was used as a photoanode for decolorization of Reactive Yellow 39 by photoelectrocatalytic system under UV irradiation. The effects of parameters such as the amount of phosphomolybdic acid used in preparation of PMA/Graphite surface, applied potential on anode electrode and solution pH were studied by response surface methodology. The optimum conditions were obtained as follows: dye solution pH 3, 1.5 g of immobilized PMA on graphite surface and applied potential on anode electrode 1 V. Under optimum conditions after 90 min of reaction time, the decolorization efficiency was 95%. Copyright © 2016 Elsevier Ltd. All rights reserved.

Development of Ambient Temperature Lithium-Ion Cells

NASA Technical Reports Server (NTRS)

Huang, C. K.; Ratnakumar, B. V.; Surampudi, S.; Halpert, G.

1994-01-01

Four types of materials have been evaluated as anodes for Li-ion cell fabrication. Among the materials evaluated, graphite and magnasium silicide were identified to be suitable candidate anode materials.

Li-Ion polymer cells thermal property changes as a function of cycle-life

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maleki, Hossein; Wang, Hsin; Porter, Wallace D

2014-01-01

The impact of elevated temperature chargeedischarge cycling on thermal conductivity (K-value) of Lithium Ion Polymer (LIP) cells of various chemistries from three different manufacturers was investigated. These included high voltage (Graphite/LiCoO2:3.0e4.35 V), wide voltage (Si:C/LiCoO2:2.7e4.35 V) and conventional (Graphite/LiCoO2:3.0e4.2 V) chemistries. Investigation results show limited variability within the in-plane and through-plane K-values for the fresh cells with graphite-based anodes from all three suppliers. After 500 cycles at 45 C, in-plane and through-plane K-values of the high voltage cells reduced less vs. those for the wide voltage cells. Such results suggest that high temperature cycling could have a greater impact onmore » thermal properties of Si:C cells than on the LIP cells with graphite (Gr) anode cells we tested. This difference is due to the excess swelling of Si:C-anode based cells vs. Gr-anode cells during cycling, especially at elevated temperatures. Thermal modeling is used to evaluate the impact of K-value changes, due to cycles at 45 C, on the cells internal heat propagation under internal short circuit condition that leads to localized meltdown of the separator.« less

Exploiting Anti-T-shaped Graphene Architecture to Form Low Tortuosity, Sieve-like Interfaces for High-Performance Anodes for Li-Based Cells

PubMed Central

2017-01-01

Graphitic carbon anodes have long been used in Li ion batteries due to their combination of attractive properties, such as low cost, high gravimetric energy density, and good rate capability. However, one significant challenge is controlling, and optimizing, the nature and formation of the solid electrolyte interphase (SEI). Here it is demonstrated that carbon coating via chemical vapor deposition (CVD) facilitates high electrochemical performance of carbon anodes. We examine and characterize the substrate/vertical graphene interface (multilayer graphene nanowalls coated onto carbon paper via plasma enhanced CVD), revealing that these low-tortuosity and high-selection graphene nanowalls act as fast Li ion transport channels. Moreover, we determine that the hitherto neglected parallel layer acts as a protective surface at the interface, enhancing the anode performance. In summary, these findings not only clarify the synergistic role of the parallel functional interface when combined with vertical graphene nanowalls but also have facilitated the development of design principles for future high rate, high performance batteries. PMID:29392179

Poly(isobutylene-alt-maleic anhydride) binders containing lithium for high-performance Li-ion batteries

NASA Astrophysics Data System (ADS)

Ku, Jun-Hwan; Hwang, Seung-Sik; Ham, Dong-Jin; Song, Min-Sang; Shon, Jeong-Kuk; Ji, Sang-Min; Choi, Jae-Man; Doo, Seok-Gwang

2015-08-01

Anode materials including graphite are known to be thermodynamically unstable toward organic solvents and salts and become covered by a passivating film (Solid electrolyte interphase, SEI) which retards the kinetics because of the high electronic resistivity. To achieve high performance in lithium ion batteries (LIBs), the SEIs are required to be mechanically stable during repeated cycling and possess highly ion-conductive. In this work, we have investigated an artificial pre-SEI on graphite electrode using a polymer binder containing lithium (i.e., a Li-copolymer of isobutylene and maleic anhydride, Li-PIMA) and its effect on the anode performances. During charging, the polymer binder with the functional group (-COOLi) acts as a SEI component, reducing the electrolyte decomposition and providing a stable passivating layer for the favorable penetration of lithium ions. Hence, by using the binder containing lithium, we have been able to obtain the first Coulombic efficiency of 84.2% (compared to 77.2% obtained using polyvinylidene fluoride as the binder) and a capacity retention of 99% after 100 cycles. The results of our study demonstrate that binder containing lithium we have used is a favorable candidate for the development of high-performance LIBs.

Low-cost carbon-silicon nanocomposite anodes for lithium ion batteries.

PubMed

Badi, Nacer; Erra, Abhinay Reddy; Hernandez, Francisco C Robles; Okonkwo, Anderson O; Hobosyan, Mkhitar; Martirosyan, Karen S

2014-01-01

The specific energy of the existing lithium ion battery cells is limited because intercalation electrodes made of activated carbon (AC) materials have limited lithium ion storage capacities. Carbon nanotubes, graphene, and carbon nanofibers are the most sought alternatives to replace AC materials but their synthesis cost makes them highly prohibitive. Silicon has recently emerged as a strong candidate to replace existing graphite anodes due to its inherently large specific capacity and low working potential. However, pure silicon electrodes have shown poor mechanical integrity due to the dramatic expansion of the material during battery operation. This results in high irreversible capacity and short cycle life. We report on the synthesis and use of carbon and hybrid carbon-silicon nanostructures made by a simplified thermo-mechanical milling process to produce low-cost high-energy lithium ion battery anodes. Our work is based on an abundant, cost-effective, and easy-to-launch source of carbon soot having amorphous nature in combination with scrap silicon with crystalline nature. The carbon soot is transformed in situ into graphene and graphitic carbon during mechanical milling leading to superior elastic properties. Micro-Raman mapping shows a well-dispersed microstructure for both carbon and silicon. The fabricated composites are used for battery anodes, and the results are compared with commercial anodes from MTI Corporation. The anodes are integrated in batteries and tested; the results are compared to those seen in commercial batteries. For quick laboratory assessment, all electrochemical cells were fabricated under available environment conditions and they were tested at room temperature. Initial electrochemical analysis results on specific capacity, efficiency, and cyclability in comparison to currently available AC counterpart are promising to advance cost-effective commercial lithium ion battery technology. The electrochemical performance observed for carbon soot material is very interesting given the fact that its production cost is away cheaper than activated carbon. The cost of activated carbon is about $15/kg whereas the cost to manufacture carbon soot as a by-product from large-scale milling of abundant graphite is about $1/kg. Additionally, here, we propose a method that is environmentally friendly with strong potential for industrialization.

Low-cost carbon-silicon nanocomposite anodes for lithium ion batteries

PubMed Central

2014-01-01

The specific energy of the existing lithium ion battery cells is limited because intercalation electrodes made of activated carbon (AC) materials have limited lithium ion storage capacities. Carbon nanotubes, graphene, and carbon nanofibers are the most sought alternatives to replace AC materials but their synthesis cost makes them highly prohibitive. Silicon has recently emerged as a strong candidate to replace existing graphite anodes due to its inherently large specific capacity and low working potential. However, pure silicon electrodes have shown poor mechanical integrity due to the dramatic expansion of the material during battery operation. This results in high irreversible capacity and short cycle life. We report on the synthesis and use of carbon and hybrid carbon-silicon nanostructures made by a simplified thermo-mechanical milling process to produce low-cost high-energy lithium ion battery anodes. Our work is based on an abundant, cost-effective, and easy-to-launch source of carbon soot having amorphous nature in combination with scrap silicon with crystalline nature. The carbon soot is transformed in situ into graphene and graphitic carbon during mechanical milling leading to superior elastic properties. Micro-Raman mapping shows a well-dispersed microstructure for both carbon and silicon. The fabricated composites are used for battery anodes, and the results are compared with commercial anodes from MTI Corporation. The anodes are integrated in batteries and tested; the results are compared to those seen in commercial batteries. For quick laboratory assessment, all electrochemical cells were fabricated under available environment conditions and they were tested at room temperature. Initial electrochemical analysis results on specific capacity, efficiency, and cyclability in comparison to currently available AC counterpart are promising to advance cost-effective commercial lithium ion battery technology. The electrochemical performance observed for carbon soot material is very interesting given the fact that its production cost is away cheaper than activated carbon. The cost of activated carbon is about $15/kg whereas the cost to manufacture carbon soot as a by-product from large-scale milling of abundant graphite is about $1/kg. Additionally, here, we propose a method that is environmentally friendly with strong potential for industrialization. PMID:25114651

Capacitance‐Assisted Sustainable Electrochemical Carbon Dioxide Mineralisation

PubMed Central

Lamb, Katie J.; Dowsett, Mark R.; Chatzipanagis, Konstantinos; Scullion, Zhan Wei; Kröger, Roland; Lee, James D.

2017-01-01

Abstract An electrochemical cell comprising a novel dual‐component graphite and Earth‐crust abundant metal anode, a hydrogen producing cathode and an aqueous sodium chloride electrolyte was constructed and used for carbon dioxide mineralisation. Under an atmosphere of 5 % carbon dioxide in nitrogen, the cell exhibited both capacitive and oxidative electrochemistry at the anode. The graphite acted as a supercapacitive reagent concentrator, pumping carbon dioxide into aqueous solution as hydrogen carbonate. Simultaneous oxidation of the anodic metal generated cations, which reacted with the hydrogen carbonate to give mineralised carbon dioxide. Whilst conventional electrochemical carbon dioxide reduction requires hydrogen, this cell generates hydrogen at the cathode. Carbon capture can be achieved in a highly sustainable manner using scrap metal within the anode, seawater as the electrolyte, an industrially relevant gas stream and a solar panel as an effective zero‐carbon energy source. PMID:29171724

Investigation of the electrochemically active surface area and lithium diffusion in graphite anodes by a novel OsO4 staining method

NASA Astrophysics Data System (ADS)

Pfaffmann, Lukas; Birkenmaier, Claudia; Müller, Marcus; Bauer, Werner; Mitsch, Tim; Feinauer, Julian; Krämer, Yvonne; Scheiba, Frieder; Hintennach, Andreas; Schleid, Thomas; Schmidt, Volker; Ehrenberg, Helmut

2016-03-01

Negative electrodes of lithium-ion batteries generally consist of graphite-based active materials. In order to realize batteries with a high current density and therefore accelerated charging processes, the intercalation of lithium and the diffusion processes of these carbonaceous materials must be understood. In this paper, we visualized the electrochemical active surface area for three different anode materials using a novel OsO4 staining method in combination with scanning electron microscopy techniques. The diffusion behavior of these three anode materials is investigated by potentiostatic intermittent titration technique measurements. From those we determine the diffusion coefficient with and without consideration of the electrochemical active surface area.

Spontaneous modification of graphite anode by anthraquinone-2-sulfonic acid for microbial fuel cells.

PubMed

Tang, Xinhua; Li, Haoran; Du, Zhuwei; Ng, How Yong

2014-07-01

In this study, anthraquinone-2-sulfonic acid (AQS), an electron transfer mediator, was immobilized onto graphite felt surface via spontaneous reduction of the in situ generated AQS diazonium cations. Cyclic voltammetry (CV) and energy dispersive spectrometry (EDS) characterizations of AQS modified graphite demonstrated that AQS was covalently grafted onto the graphite surface. The modified graphite, with a surface AQS concentration of 5.37 ± 1.15 × 10(-9)mol/cm(2), exhibited good electrochemical activity and high stability. The midpoint potential of the modified graphite was about -0.248 V (vs. normal hydrogen electrode, NHE), indicating that electrons could be easily transferred from NADH in bacteria to the electrode. AQS modified anode in MFCs increased the maximum power density from 967 ± 33 mW/m(2) to 1872 ± 42 mW/m(2). These results demonstrated that covalently modified AQS functioned as an electron transfer mediator to facilitate extracellular electron transfer from bacteria to electrode and significantly enhanced the power production in MFCs. Copyright © 2014 Elsevier Ltd. All rights reserved.

Mechanistic elucidation of thermal runaway in potassium-ion batteries

NASA Astrophysics Data System (ADS)

Adams, Ryan A.; Varma, Arvind; Pol, Vilas G.

2018-01-01

For the first time, thermal runaway of charged graphite anodes for K-ion batteries is investigated, using differential scanning calorimetry (DSC) to probe the exothermic degradation reactions. Investigated parameters such as state of charge, cycle number, surface area, and binder demonstrate strong influences on the DSC profiles. Thermal runaway initiates at 100 °C owing to KxC8 - electrolyte reactions, but the K-ion graphite anode evolves significantly less heat as compared to the analogous Li-ion system (395 J g-1 vs. 1048 J g-1). The large volumetric expansion of graphite during potassiation cracks the SEI layer, enabling contact and reaction of KC8 - electrolyte, which diminishes with cycle number due to continuous SEI growth. High surface area graphite decreases the total heat generation, owing to thermal stability of the K-ion SEI layer. These findings illustrate the dynamic nature of K-ion thermal runaway and its many contrasts with the Li-ion graphite system, permitting possible engineering solutions for safer batteries.

Silicon hollow sphere anode with enhanced cycling stability by a template-free method

NASA Astrophysics Data System (ADS)

Chen, Song; Chen, Zhuo; Luo, Yunjun; Xia, Min; Cao, Chuanbao

2017-04-01

Silicon is a promising alternative anode material since it has a ten times higher theoretical specific capacity than that of a traditional graphite anode. However, the poor cycling stability due to the huge volume change of Si during charge/discharge processes has seriously hampered its widespread application. To address this challenge, we design a silicon hollow sphere nanostructure by selective etching and a subsequent magnesiothermic reduction. The Si hollow spheres exhibit enhanced electrochemical properties compared to the commercial Si nanoparticles. The initial discharge and charge capacities of the Si hollow sphere anode are 2215.8 mAh g-1 and 1615.1 mAh g-1 with a high initial coulombic efficiency (72%) at a current density of 200 mA g-1, respectively. In particular, the reversible capacity is 1534.5 mAh g-1 with a remarkable 88% capacity retention against the second cycle after 100 cycles, over four times the theoretical capacity of the traditional graphite electrode. Therefore, our work demonstrates the considerable potential of silicon structures for displacing commercial graphite, and might open up new opportunities to rationally design various nanostructured materials for lithium ion batteries.

Colloidal Synthesis of Silicon-Carbon Composite Material for Lithium-Ion Batteries.

PubMed

Su, Haiping; Barragan, Alejandro A; Geng, Linxiao; Long, Donghui; Ling, Licheng; Bozhilov, Krassimir N; Mangolini, Lorenzo; Guo, Juchen

2017-08-28

We report colloidal routes to synthesize silicon@carbon composites for the first time. Surface-functionalized Si nanoparticles (SiNPs) dissolved in styrene and hexadecane are used as the dispersed phase in oil-in-water emulsions, from which yolk-shell and dual-shell hollow SiNPs@C composites are produced via polymerization and subsequent carbonization. As anode materials for Li-ion batteries, the SiNPs@C composites demonstrate excellent cycling stability and rate performance, which is ascribed to the uniform distribution of SiNPs within the carbon hosts. The Li-ion anodes composed of 46 wt % of dual-shell SiNPs@C, 46 wt % of graphite, 5 wt % of acetylene black, and 3 wt % of carboxymethyl cellulose with an areal loading higher than 3 mg cm -2 achieve an overall specific capacity higher than 600 mAh g -1 , which is an improvement of more than 100 % compared to the pure graphite anode. These new colloidal routes present a promising general method to produce viable Si-C composites for Li-ion batteries. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Single-Wall Carbon Nanotube Anodes for Lithium Cells

NASA Technical Reports Server (NTRS)

Hepp, Aloysius F.; Raffaelle, Ryne; Gennett, Tom; Kumta, Prashant; Maranchi, Jeff; Heben, Mike

2006-01-01

In recent experiments, highly purified batches of single-wall carbon nanotubes (SWCNTs) have shown promise as superior alternatives to the graphitic carbon-black anode materials heretofore used in rechargeable thin-film lithium power cells. The basic idea underlying the experiments is that relative to a given mass of graphitic carbon-black anode material, an equal mass of SWCNTs can be expected to have greater lithium-storage and charge/discharge capacities. The reason for this expectation is that whereas the microstructure and nanostructure of a graphitic carbon black is such as to make most of the interior of the material inaccessible for intercalation of lithium, a batch of SWCNTs can be made to have a much more open microstructure and nanostructure, such that most of the interior of the material is accessible for intercalation of lithium. Moreover, the greater accessibility of SWCNT structures can be expected to translate to greater mobilities for ion-exchange processes and, hence, an ability to sustain greater charge and discharge current densities.

Development of Electroactive and Anaerobic Ammonium-Oxidizing (Anammox) Biofilms from Digestate in Microbial Fuel Cells.

PubMed

Di Domenico, Enea Gino; Petroni, Gianluca; Mancini, Daniele; Geri, Alberto; Di Palma, Luca; Ascenzioni, Fiorentina

2015-01-01

Microbial Fuel cells (MFCs) have been proposed for nutrient removal and energy recovery from different wastes. In this study the anaerobic digestate was used to feed H-type MFC reactors, one with a graphite anode preconditioned with Geobacter sulfurreducens and the other with an unconditioned graphite anode. The data demonstrate that the digestate acts as a carbon source, and even in the absence of anode preconditioning, electroactive bacteria colonise the anodic chamber, producing a maximum power density of 172.2 mW/m(2). The carbon content was also reduced by up to 60%, while anaerobic ammonium oxidation (anammox) bacteria, which were found in the anodic compartment of the reactors, contributed to nitrogen removal from the digestate. Overall, these results demonstrate that MFCs can be used to recover anammox bacteria from natural sources, and it may represent a promising bioremediation unit in anaerobic digestor plants for the simultaneous nitrogen removal and electricity generation using digestate as substrate.

Development of Electroactive and Anaerobic Ammonium-Oxidizing (Anammox) Biofilms from Digestate in Microbial Fuel Cells

PubMed Central

Petroni, Gianluca; Mancini, Daniele; Geri, Alberto; Palma, Luca Di

2015-01-01

Microbial Fuel cells (MFCs) have been proposed for nutrient removal and energy recovery from different wastes. In this study the anaerobic digestate was used to feed H-type MFC reactors, one with a graphite anode preconditioned with Geobacter sulfurreducens and the other with an unconditioned graphite anode. The data demonstrate that the digestate acts as a carbon source, and even in the absence of anode preconditioning, electroactive bacteria colonise the anodic chamber, producing a maximum power density of 172.2 mW/m2. The carbon content was also reduced by up to 60%, while anaerobic ammonium oxidation (anammox) bacteria, which were found in the anodic compartment of the reactors, contributed to nitrogen removal from the digestate. Overall, these results demonstrate that MFCs can be used to recover anammox bacteria from natural sources, and it may represent a promising bioremediation unit in anaerobic digestor plants for the simultaneous nitrogen removal and electricity generation using digestate as substrate. PMID:26273609

Proposal of simple and novel method of capacity fading analysis using pseudo-reference electrode in lithium ion cells: Application to solvent-free lithium ion polymer batteries

NASA Astrophysics Data System (ADS)

Shono, Kumi; Kobayashi, Takeshi; Tabuchi, Masato; Ohno, Yasutaka; Miyashiro, Hajime; Kobayashi, Yo

2014-02-01

We propose a simple procedure for introducing a pseudo-reference electrode (PRE) to lithium ion batteries using isometric lithium metal placed between the cathode and anode, and we successfully obtained the cathode and anode voltage profiles, individual interfacial impedances, and the misalignment of the operation range between the cathode and anode after cycle operation. The proposed procedure is applicable to lithium ion battery systems using a solid electrolyte to prepare two cells with a lithium counter electrode. We determined the capacity decrease of a solvent-free lithium ion polymer battery consisting of a LiNi1/3Mn1/3Co1/3O2 (NMC), a polyether-based solid polymer electrolyte (SPE), and a graphite (Gr) with the proposed PRE over 1000 cycles. The capacity retention of the [Gr|SPE|NMC] cell reached 50% at the 1000th cycle upon the optimization of cell preparation, and we found that the main factor of the capacity decrease was the continuous irreversible loss of active lithium at the graphite anode, not the oxidation of the SPE. Our findings suggest that we should reconsider combining a polyether-based SPE with a conventionally used 4 V class cathode and a graphite anode to develop an innovative, safe, and low-cost battery for the expected large lithium ion battery systems for stationary use.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cook, John B.; Detsi, Eric; Liu, Yijin

Next generation Li-ion batteries will require negative electrode materials with energy densities many-fold higher than that found in the graphitic carbon currently used in commercial Li-ion batteries. While various nanostructured alloying-type anode materials may satisfy that requirement, such materials do not always exhibit long cycle lifetimes and/or their processing routes are not always suitable for large-scale synthesis. Here, we report on a high-performance anode material for next generation Li-ion batteries made of nanoporous Sn powders with hierarchical ligament morphology. This material system combines both long cycle lifetimes (more than 72% capacity retention after 350 cycles), high capacity (693 mAh/g, nearlymore » twice that of commercial graphitic carbon), good charging/discharging capabilities (545 mAh/g at 1 A/g, 1.5C), and a scalable processing route that involves selective alloy corrosion. The good cycling performance of this system is attributed to its nanoporous architecture and its unique hierarchical ligament morphology, which accommodates the large volume changes taking place during lithiation, as confirmed by synchrotron-based ex-situ X-ray 3D tomography analysis. In conclusion, our findings are an important step for the development of high-performance Li-ion batteries.« less

Self-Passivating Lithium/Solid Electrolyte/Iodine Cells

NASA Technical Reports Server (NTRS)

Bugga, Ratnakumar; Whitcare, Jay; Narayanan, Sekharipuram; West, William

2006-01-01

Robust lithium/solid electrolyte/iodine electrochemical cells that offer significant advantages over commercial lithium/ iodine cells have been developed. At room temperature, these cells can be discharged at current densities 10 to 30 times those of commercial lithium/iodine cells. Moreover, from room temperature up to 80 C, the maximum discharge-current densities of these cells exceed those of all other solid-electrolyte-based cells. A cell of this type includes a metallic lithium anode in contact with a commercial flexible solid electrolyte film that, in turn, is in contact with an iodine/ graphite cathode. The solid electrolyte (the chemical composition of which has not been reported) offers the high ionic conductivity needed for high cell performance. However, the solid electrolyte exhibits an undesirable chemical reactivity to lithium that, if not mitigated, would render the solid electrolyte unsuitable for use in a lithium cell. In this cell, such mitigation is affected by the formation of a thin passivating layer of lithium iodide at the anode/electrolyte interface. Test cells of this type were fabricated from iodine/graphite cathode pellets, free-standing solid-electrolyte films, and lithium-foil anodes. The cathode mixtures were made by grinding together blends of nominally 10 weight percent graphite and 90 weight percent iodine. The cathode mixtures were then pressed into pellets at 36 kpsi (248 MPa) and inserted into coin-shaped stainless-steel cell cases that were coated with graphite paste to minimize corrosion. The solid-electrolyte film material was stamped to form circular pieces to fit in the coin cell cases, inserted in the cases, and pressed against the cathode pellets with polyethylene gaskets. Lithium-foil anodes were placed directly onto the electrolyte films. The layers described thus far were pressed and held together by stainless- steel shims, wave springs, and coin cell caps. The assembled cells were then crimped to form hermetic seals. It was found that the solid electrolyte films became discolored within seconds after they were placed in contact with the cathodes - a result of facile diffusion of iodine through the solid electrolyte material (see figure).

Electro-catalytic degradation of sulfisoxazole by using graphene anode.

PubMed

Wang, Yanyan; Liu, Shuan; Li, Ruiping; Huang, Yingping; Chen, Chuncheng

2016-05-01

Graphite and graphene electrodes were prepared by using pure graphite as precursor. The electrode materials were characterized by a scanning electron microscope (SEM), X-ray diffraction (XRD) and cyclic voltammetry (CV) measurements. The electro-catalytic activity for degradation of sulfisoxazole (SIZ) was investigated by using prepared graphene or graphite anode. The results showed that the degradation of SIZ was much more rapid on the graphene than that on the graphite electrode. Moreover, the graphene electrode exhibited good stability and recyclability. The analysis on the intermediate products and the measurement of active species during the SIZ degradation demonstrated that indirect oxidation is the dominant mechanism, involving the electro-catalytic generation of OH and O2(-) as the main active oxygen species. This study implies that graphene is a promising potential electrode material for long-term application to electro-catalytic degradation of organic pollutants. Copyright © 2015. Published by Elsevier B.V.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Danial, Wan Hazman, E-mail: hazmandanial@gmail.com; Majid, Zaiton Abdul, E-mail: zaiton@kimia.fs.utm.my; Aziz, Madzlan

The present work reports the synthesis and characterization of graphene via electrochemical exfoliation of graphite rod using two-electrode system assisted by Sodium Dodecyl Sulphate (SDS) as a surfactant. The electrochemical process was carried out with sequence of intercalation of SDS onto the graphite anode followed by exfoliation of the SDS-intercalated graphite electrode when the anode was treated as cathode. The effect of intercalation potential from 5 V to 9 V and concentration of the SDS surfactant of 0.1 M and 0.01 M were investigated. UV-vis Spectroscopic analysis indicated an increase in the graphene production with higher intercalation potential. Transmission Electron Microscopy (TEM)more » analysis showed a well-ordered hexagonal lattice of graphene image and indicated an angle of 60° between two zigzag directions within the honeycomb crystal lattice. Raman spectroscopy analysis shows the graphitic information effects after the exfoliation process.« less

The Anode Challenge for Lithium-Ion Batteries: A Mechanochemically Synthesized Sn-Fe-C Composite Anode Surpasses Graphitic Carbon

DOE PAGES

Dong, Zhixin; Zhang, Ruibo; Ji, Dongsheng; ...

2016-02-04

Carbon-based anodes are the key limiting factor in increasing the volumetric capacity of lithium-ion batteries. Tin-based composites are one alternative approach. Nanosized Sn–Fe–C anode materials are mechanochemically synthesized by reducing SnO with Ti in the presence of carbon. The optimum synthesis conditions are found to be 1:0.25:10 for initial ratio of SnO, Ti, and graphite with a total grinding time of 8 h. This optimized composite shows excellent extended cycling at the C/10 rate, delivering a first charge capacity as high as 740 mAh g –1 and 60% of which still remained after 170 cycles. The calculated volumetric capacity significantlymore » exceeds that of carbon. In conclusion, it also exhibits excellent rate capability, delivering volumetric capacity higher than 1.6 Ah cc –1 over 140 cycles at the 1 C rate.« less

Capacitance-Assisted Sustainable Electrochemical Carbon Dioxide Mineralisation.

PubMed

Lamb, Katie J; Dowsett, Mark R; Chatzipanagis, Konstantinos; Scullion, Zhan Wei; Kröger, Roland; Lee, James D; Aguiar, Pedro M; North, Michael; Parkin, Alison

2018-01-10

An electrochemical cell comprising a novel dual-component graphite and Earth-crust abundant metal anode, a hydrogen producing cathode and an aqueous sodium chloride electrolyte was constructed and used for carbon dioxide mineralisation. Under an atmosphere of 5 % carbon dioxide in nitrogen, the cell exhibited both capacitive and oxidative electrochemistry at the anode. The graphite acted as a supercapacitive reagent concentrator, pumping carbon dioxide into aqueous solution as hydrogen carbonate. Simultaneous oxidation of the anodic metal generated cations, which reacted with the hydrogen carbonate to give mineralised carbon dioxide. Whilst conventional electrochemical carbon dioxide reduction requires hydrogen, this cell generates hydrogen at the cathode. Carbon capture can be achieved in a highly sustainable manner using scrap metal within the anode, seawater as the electrolyte, an industrially relevant gas stream and a solar panel as an effective zero-carbon energy source. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Atmospheric pressure arc discharge with ablating graphite anode

NASA Astrophysics Data System (ADS)

Nemchinsky, V. A.; Raitses, Y.

2015-06-01

The anodic carbon arc discharge is used to produce carbon nanoparticles. Recent experiments with the carbon arc at atmospheric pressure helium demonstrated the enhanced ablation rate for narrow graphite anodes resulting in high deposition rates of carbonaceous products on the copper cathode (Fetterman et al 2008 Carbon 46 1322-6). The proposed model explains these results with interconnected steady-state models of the cathode and the anode processes. When considering cathode functioning, the model predicts circulation of the particles in the near-cathode region: evaporation of the cathode material, ionization of evaporated atoms and molecules in the near-cathode plasma, return of the resulting ions to the cathode, surface recombination of ions and electrons followed again by cathode evaporation etc. In the case of the low anode ablation rate, the ion acceleration in the cathode sheath provides the major cathode heating mechanism. In the case of an intensive anode ablation, an additional cathode heating is due to latent fusion heat of the atomic species evaporated from the anode and depositing at the cathode. Using the experimental arc voltage as the only input discharge parameter, the model allows us to calculate the anode ablation rate. A comparison of the results of calculations with the available experimental data shows reasonable agreement.

Facile and cost effective synthesis of mesoporous spinel NiCo2O4 as an anode for high lithium storage capacity

NASA Astrophysics Data System (ADS)

Jadhav, Harsharaj S.; Kalubarme, Ramchandra S.; Park, Choong-Nyeon; Kim, Jaekook; Park, Chan-Jin

2014-08-01

To fulfill the high power and high energy density demands for Li-ion batteries (LIBs) new anode materials need to be explored to replace conventional graphite. Herein, we report the urea assisted facile co-precipitation synthesis of spinel NiCo2O4 and its application as an anode material for LIBs. The synthesized NiCo2O4 exhibited an urchin-like microstructure and polycrystalline and mesoporous nature. In addition, the mesoporous NiCo2O4 electrode exhibited an initial discharge capacity of 1095 mA h g-1 and maintained a reversible capacity of 1000 mA h g-1 for 400 cycles at 0.5 C-rate. The reversible capacity of NiCo2O4 could still be maintained at 718 mA h g-1, even at 10 C. The mesoporous NiCo2O4 exhibits great potential as an anode material for LIBs with the advantages of unique performance and facile preparation.To fulfill the high power and high energy density demands for Li-ion batteries (LIBs) new anode materials need to be explored to replace conventional graphite. Herein, we report the urea assisted facile co-precipitation synthesis of spinel NiCo2O4 and its application as an anode material for LIBs. The synthesized NiCo2O4 exhibited an urchin-like microstructure and polycrystalline and mesoporous nature. In addition, the mesoporous NiCo2O4 electrode exhibited an initial discharge capacity of 1095 mA h g-1 and maintained a reversible capacity of 1000 mA h g-1 for 400 cycles at 0.5 C-rate. The reversible capacity of NiCo2O4 could still be maintained at 718 mA h g-1, even at 10 C. The mesoporous NiCo2O4 exhibits great potential as an anode material for LIBs with the advantages of unique performance and facile preparation. Electronic supplementary information (ESI) available: Experimental details and additional experimental results. See DOI: 10.1039/c4nr02183e

Bacterial cellulose-polyaniline nano-biocomposite: A porous media hydrogel bioanode enhancing the performance of microbial fuel cell

NASA Astrophysics Data System (ADS)

Mashkour, Mehrdad; Rahimnejad, Mostafa; Mashkour, Mahdi

2016-09-01

Microbial fuel cells (MFCs) are one of the possible renewable energy supplies which microorganisms play an active role in bio-oxidize reactions of a substrate such as glucose. Electrode materials and surface modifications are highly effective tools in enhancing MFCs' Performance. In this study, new composite anodes are fabricated. Bacterial cellulose (BC) is used as continuous phase and polyaniline (PANI) as dispersed one which is synthesized by in situ chemical oxidative polymerization on BC's fibers. With hydrogel nature of BC as a novel feature and polyaniline conductivity there meet the favorable conditions to obtain an active microbial biofilm on anode surface. Maximum power density of 117.76 mW/m2 in current density of 617 mA/m2 is achieved for BC/PANI anode. The amounts demonstrate a considerable enhancement compared with graphite plate (1 mW/m2 and 10 mA/m2).

Web-structured graphitic carbon fiber felt as an interlayer for rechargeable lithium-sulfur batteries with highly improved cycling performance

NASA Astrophysics Data System (ADS)

Lee, Dong Kyu; Ahn, Chi Won; Jeon, Hwan-Jin

2017-08-01

Graphitic carbon fiber felt (GCFF) with a crystalline graphitic carbon structure was facilely prepared by a combination of electrospinning and graphitization (2800 °C heat treatment) and was used as an interlayer between the cathode and separator in Li-S batteries. This GCFF interlayer trapped the polysulfides on the cathode side and increased the utilization of sulfur by suppressing the shuttle phenomenon. Also, the GCFF was shown to be able to act as an upper current collector to reduce the charge-transfer resistance owing to the high crystallinity of the graphitic carbon fibers. The sulfur cathode with the GCFF interlayer showed a high specific initial discharge capacity of 1280.14 mAh g-1 and excellent cycling stability (1004.62 mAh g-1 after 100 cycles) at 0.2 C. Also, an image of the glass fiber (GF) separator on the anode side confirmed the presence of an SEI after 200 cycles, which apparently resulted from stable Li deposition on the Li metal because of the low or medium concentration of sulfur in the electrolyte solution. Our observations should contribute to elucidating the key features of complex three-dimensional carbon fabrics with crystalline graphitic structures that allow them, when inserted as interlayers, to markedly improve the performance of rechargeable batteries.

Enhanced Stability of PtRu Supported on N-Doped Carbon for the Anode of a DMFC

DTIC Science & Technology

2012-09-18

nitrogen functionalities are most likely limited to pyrrolic , N-C=O and amine groups. In the case of PtRu/C (N- doped), the ion implantation introduces...suggesting the presence of graphitic, quaternary, pyridinic, C-N=O, pyrrolic , amine and nitrile groups.32,46 Initial DMFC performance and electrochemical

Advancing Lithium Metal Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Bin; Zhang, Ji-Guang; Xu, Wu

Considering the unsatisfied energy density of traditional graphite anode-based lithium (Li)-ion batteries, any alterative high capacity anodes will be highly expected to be practically applied in future high energy battery systems. Li metal is regarded as one of the most promising anodes due to its ultrahigh capacity (3860 mAh g-1), the lowest standard negative electrochemical potential (-3.040 V) and the very low gravimetric density (0.534 g cm-3). However, dendrite growth and high reactivity of Li metal result in low cycling efficiency and severe safety concerns. The revival of research and development on Li metal anode in recent years has broughtmore » new in-depth understandings and key experimental achievements regarding Li metal protection and enhanced performances of Li-metal batteries. In this perspective article, we first concisely review the recent discoveries and then offer possible research directions for further development of Li metal batteries.« less

A nanoporous metal recuperated MnO2 anode for lithium ion batteries.

PubMed

Guo, Xianwei; Han, Jiuhui; Zhang, Ling; Liu, Pan; Hirata, Akihiko; Chen, Luyang; Fujita, Takeshi; Chen, Mingwei

2015-10-07

Lithium-ion batteries (LIBs) have been intensively studied to meet the increased demands for the high energy density of portable electronics and electric vehicles. The low specific capacity of the conventional graphite based anodes is one of the key factors that limit the capacity of LIBs. Transition metal oxides, such as NiO, MnO2 and Fe3O4, are known to be promising anode materials that are expected to improve the specific capacities of LIBs for several times. However, the poor electrical conductivity of these oxides significantly restricts the lithium ion storage and charge/discharge rate. Here we report that dealloyed nanoporous metals can realize the intrinsic lithium storage performance of the oxides by forming oxide/metal composites. Without any organic binder, conductive additive and additional current collector, the hybrid electrodes can be directly used as anodes and show highly reversible specific capacity with high-rate capability and long cyclic stability.

Unique Fe2P Nanoparticles Enveloped in Sandwichlike Graphited Carbon Sheets as Excellent Hydrogen Evolution Reaction Catalyst and Lithium-Ion Battery Anode.

PubMed

Zhang, Yan; Zhang, Huijuan; Feng, Yangyang; Liu, Li; Wang, Yu

2015-12-09

The novel Fe2P nanoparticles encapsulated in sandwichlike graphited carbon envelope nanocomposite (Fe2P/GCS) that can be first applied in hydrogen evolution reaction (HER) as well as lithium-ion batteries (LIBs) has been designed and fabricated. The unique sandwiched Fe2P/GCS is characterized with several prominent merits, including large specific surface area, nanoporous structure, excellent electronic conductivity, enhanced structural integrity and so on. All of these endow the Fe2P/GCS with brilliant electrochemical performance. When used as a HER electrocatalyst in acidic media, the harvested Fe2P/GCS demonstrates low onset overpotential and Tafel slope as well as particularly outstanding durability. Moreover, as an anode material for LIBs, the sandwiched Fe2P/GCS presents high specific capacity and excellent cyclability and rate capability. As a consequence, the acquired Fe2P/GCS is a promising material for energy applications, especially HER and LIBs.

SiLix-C Nanocomposites

NASA Technical Reports Server (NTRS)

Henry, Francois

2015-01-01

For this Phase II project, Superior Graphite Co., in collaboration with the Georgia Institute of Technology and Streamline Nanotechnologies, Inc., developed, explored the properties of, and demonstrated the enhanced capabilities of novel nanostructured SiLix-C anodes. These anodes can retain high capacity at a rapid 2-hour discharge rate and at 0 C when used in Li-ion batteries. In Phase I, these advanced anode materials had specific capacity in excess of 1,000 mAh/g, minimal irreversible capacity losses, and stable performance for 20 cycles at C/1. The goals in Phase II were to develop and apply a variety of novel nanomaterials, fine-tune the properties of composite particles at the nanoscale, optimize the composition of the anodes, and select appropriate binder and electrolytes. In order to achieve a breakthrough in power characteristics of Li-ion batteries, the team developed new nanostructured SiLix-C anode materials to offer up to 1,200 mAh/g at C/2 at 0 C.

Nitrogen-doped graphene by all-solid-state ball-milling graphite with urea as a high-power lithium ion battery anode

NASA Astrophysics Data System (ADS)

Liu, Chao; Liu, Xingang; Tan, Jiang; Wang, Qingfu; Wen, Hao; Zhang, Chuhong

2017-02-01

Nitrogen-doped graphene nanosheets (NGNS) are prepared by a novel mechanochemical method via all-solid-state ball-milling graphite with urea. The ball-milling process does not only successfully exfoliate the graphite into multi-layer (<10 layers) graphene nanosheets, but at the same time, enables the N element to be doped onto the graphene. Urea, acting as a new solid doping and assist-grinding agents, has the advantages of low cost and good water solubility that can simplify the fabrication process. The as-prepared NGNS are investigated in detail by XRD, SEM, HRTEM, TGA, XPS and Raman spectroscopy. The doping nitrogens are around 3.15% and dominated (>94%) by pyrindic-N and pyrrolic-N which facilitates the NGNS with enhanced electronic conductivity and Li-ion storage capability. For the first time, we demonstrate that the all-solid-state prepared NGNS exhibits, especially at high currents, enhanced cycling stability and rate capability as Lithium ion battery (LIB) anode active material when compared to pristine graphite and undoped graphene in half-cell configuration. The method presented in this article may provide a simple, clean, economical and scalable strategy for preparation of NGNS as a feasible and promising anode material for LIBs.

A novel self-powered and sensitive label-free DNA biosensor in microbial fuel cell.

PubMed

Asghary, Maryam; Raoof, Jahan Bakhsh; Rahimnejad, Mostafa; Ojani, Reza

2016-08-15

In this work, a novel self-powered, sensitive, low-cost, and label-free DNA biosensor is reported by applying a two-chambered microbial fuel cell (MFC) as a power supply. A graphite electrode and an Au nanoparticles modified graphite electrode (AuNP/graphite electrode) were used as anode and cathode in the MFC system, respectively. The active biocatalyst in the anodic chamber was a mixed culture of microorganisms. The sensing element of the biosensor was fabricated by the well-known Au-thiol binding the ssDNA probe on the surface of an AuNP/graphite cathode. Electrons produced by microorganisms were transported from the anode to the cathode through an external circuit, which could be detected by the terminal multi-meter detector. The difference between power densities of the ssDNA probe modified cathode in the absence and presence of complementary sequence served as the detection signal of the DNA hybridization with detection limit of 3.1nM. Thereafter, this biosensor was employed for diagnosis and determination of complementary sequence in a human serum sample. The hybridization specificity studies further revealed that the developed DNA biosensor could distinguish fully complementary sequences from one-base mismatched and non-complementary sequences. Copyright © 2016 Elsevier B.V. All rights reserved.

Graphene-Like-Graphite as Fast-Chargeable and High-Capacity Anode Materials for Lithium Ion Batteries.

PubMed

Cheng, Qian; Okamoto, Yasuharu; Tamura, Noriyuki; Tsuji, Masayoshi; Maruyama, Shunya; Matsuo, Yoshiaki

2017-11-01

Here we propose the use of a carbon material called graphene-like-graphite (GLG) as anode material of lithium ion batteries that delivers a high capacity of 608 mAh/g and provides superior rate capability. The morphology and crystal structure of GLG are quite similar to those of graphite, which is currently used as the anode material of lithium ion batteries. Therefore, it is expected to be used in the same manner of conventional graphite materials to fabricate the cells. Based on the data obtained from various spectroscopic techniques, we propose a structural GLG model in which nanopores and pairs of C-O-C units are introduced within the carbon layers stacked with three-dimensional regularity. Three types of highly ionic lithium ions are found in fully charged GLG and stored between its layers. The oxygen atoms introduced within the carbon layers seem to play an important role in accommodating a large amount of lithium ions in GLG. Moreover, the large increase in the interlayer spacing observed for fully charged GLG is ascribed to the migration of oxygen atoms within the carbon layer introduced in the state of C-O-C to the interlayer space maintaining one of the C-O bonds.

A general strategy toward graphitized carbon coating on iron oxides as advanced anodes for lithium-ion batteries.

PubMed

Ding, Chunyan; Zhou, Weiwei; Wang, Bin; Li, Xin; Wang, Dong; Zhang, Yong; Wen, Guangwu

2017-08-25

Integration of carbon materials with benign iron oxides is blazing a trail in constructing high-performance anodes for lithium-ion batteries (LIBs). In this paper, a unique general, simple, and controllable strategy is developed toward in situ uniform coating of iron oxide nanostructures with graphitized carbon (GrC) layers. The basic synthetic procedure only involves a simple dip-coating process for the loading of Ni-containing seeds and a subsequent Ni-catalyzed chemical vapor deposition (CVD) process for the growth of GrC layers. More importantly, the CVD treatment is conducted at a quite low temperature (450 °C) and with extremely facile liquid carbon sources consisting of ethylene glycol (EG) and ethanol (EA). The GrC content of the resulting hybrids can be controllably regulated by altering the amount of carbon sources. The electrochemical results reveal remarkable performance enhancements of iron oxide@GrC hybrids compared with pristine iron oxides in terms of high specific capacity, excellent rate and cycling performance. This can be attributed to the network-like GrC coating, which can improve not only the electronic conductivity but also the structural integrity of iron oxides. Moreover, the lithium storage performance of samples with different GrC contents is measured, manifesting that optimized electrochemical property can be achieved with appropriate carbon content. Additionally, the superiority of GrC coating is demonstrated by the advanced performance of iron oxide@GrC compared with its corresponding counterpart, i.e., iron oxides with amorphous carbon (AmC) coating. All these results indicate the as-proposed protocol of GrC coating may pave the way for iron oxides to be promising anodes for LIBs.

Kinetic experiments for evaluating the Nernst-Monod model for anode-respiring bacteria (ARB) in a biofilm anode.

PubMed

Torres, César I; Marcus, Andrew Kato; Parameswaran, Prathap; Rittmann, Bruce E

2008-09-01

Anode-respiring bacteria (ARB) are able to transfer electrons from reduced substrates to a solid electrode. Previously, we developed a biofilm model based on the Nernst-Monod equation to describe the anode potential losses of ARB that transfer electrons through a solid conductive matrix. In this work, we develop an experimental setup to demonstrate how well the Nernst-Monod equation is able to represent anode potential losses in an ARB biofilm. We performed low-scan cyclic voltammetry (LSCV) throughout the growth phase of an ARB biofilm on a graphite electrode growing on acetate in continuous mode. The (j)V response of 9 LSCVs corresponded well to the Nernst-Monod equation, and the half-saturation potential (E(KA)) was -0.425 +/- 0.002 V vs Ag/AgCl at 30 degrees C (-0.155 +/- 0.002 V vs SHE). Anode-potential losses from the potential of acetate reached approximately 0.225 V at current density saturation, and this loss was determined by our microbial community's E(KA) value. The LSCVs at high current densities showed no significant deviation from the Nernst-Monod ideal shape, indicating that the conductivity of the biofilm matrix (kappa(bio)) was high enough (> or = 0.5 mS/cm) that potential loss did not affect the performance of the biofilm anode. Our results confirm the applicability of the Nernst-Monod equation for a conductive biofilm anode and give insights of the processes that dominate anode potential losses in microbial fuel cells.

Glyoxalated polyacrylamide as a covalently attachable and rapidly cross-linkable binder for Si electrode in lithium ion batteries

NASA Astrophysics Data System (ADS)

Yoo, Jung-Keun; Jeon, Jaebeom; Kang, Kisuk; Jung, Yeon Sik

2017-03-01

Recently, investigation of Si-based anode materials for rechargeable battery applications garnered much interest due to its exceptionally high capacity. High-capacity Si anode ( 4,200 mAhg-1) is highly desirable for the replacement of conventional graphite anode (< 400 mAhg-1) for large-scale energy-storage applications such as in electric vehicles (EVs) and energy storage systems (ESSs) for renewable energy sources. However, Si-based anodes suffer from poor cycling stability due to their large volumetric changes during repeated Li insertion. Therefore, development of highly efficient binder materials that can suppress the volume change of Si is one of the most essential parts of improving the performance of batteries. We herein demonstrate highly cross-linked polymeric binder (glyoxalated polyacrylamide) with an enhanced mechanical property by applying wet-strengthening chemistry used in paper industry. We found that the degree of cross-linking can be systematically adjusted by controlling the acidity of the slurry and has a profound effect on the cell performance using Si anode. The enhanced cycle performance of Si nanoparticles obtained by treating the binder at pH 4 can be explained by its strong interaction between the binder and Si surface and current collector, and also rigidity of binder by cross-linking.

Shape Effect of Electrochemical Chloride Extraction in Structural Reinforced Concrete Elements Using a New Cement-Based Anodic System

PubMed Central

Carmona, Jesús; Climent, Miguel-Ángel; Antón, Carlos; de Vera, Guillem; Garcés, Pedro

2015-01-01

This article shows the research carried out by the authors focused on how the shape of structural reinforced concrete elements treated with electrochemical chloride extraction can affect the efficiency of this process. Assuming the current use of different anode systems, the present study considers the comparison of results between conventional anodes based on Ti-RuO2 wire mesh and a cement-based anodic system such as a paste of graphite-cement. Reinforced concrete elements of a meter length were molded to serve as laboratory specimens, to closely represent authentic structural supports, with circular and rectangular sections. Results confirm almost equal performances for both types of anode systems when electrochemical chloride extraction is applied to isotropic structural elements. In the case of anisotropic ones, such as rectangular sections with no uniformly distributed rebar, differences in electrical flow density were detected during the treatment. Those differences were more extreme for Ti-RuO2 mesh anode system. This particular shape effect is evidenced by obtaining the efficiencies of electrochemical chloride extraction in different points of specimens.

Size dependence effect of carbon-based anode material on intercalation characteristics of Li-ion battery

NASA Astrophysics Data System (ADS)

Anwar, Miftahul; Jupri, Dwi Rahmat; Saraswati, Teguh Endah

2017-01-01

This work aims to study the effect of the different size of Li-ion battery anode during charging state. Carbon-Based nanomaterial using arc-discharge in a liquid which is much simpler and cheaper compared to other techniques, i.e., CVD, laser vaporization, etc. The experiment was performed using intermediate DC power supply (1300 W) to produce an arc, and commercial graphite pencils (with 5 mm diameter) as negative and positive electrodes. Deionized water mixed with ethanol was used as a heat absorber. The result shows that arc discharge in deionized water could effectively produce carbon nanomaterial (i.e., nano-onions). In addition, finite element method-based simulation of the different intercalating process of Li-ion to the different shape of the anode, i.e., bulk semi-porous and porous anode materials for battery application is also presented. The results show that intercalation of Li ions depends on the anode structure due to the different potential density at anode region. This finding will provide support for design of Li-ion battery based on carbon nanomaterial

New Anode Material for Rechargeable Li-ION Cells

NASA Technical Reports Server (NTRS)

Huang, C. -K.; Smart, M.; Halpert, G.; Surampudi, S.; Wolfenstine, J.

1995-01-01

Carbon materials, such as graphite, cokes, pitch and PAN fibers, are being evaluated in lithium batteries as alternate anode materials with some degree of success. There is an effort to look for other non-carbon anode materials which have larger Li capacity, higher rate capability, smaller first charge capacity loss and better mechanical stability during cycling. A Li-Mg-Si material is evaluated.

The performance of 3-D graphite doped anodes in microbial electrolysis cells

NASA Astrophysics Data System (ADS)

Yasri, Nael G.; Nakhla, George

2017-02-01

This study investigated the use of granular activated carbon (GAC) as high surface area 3-dimensional (3-D) anode in MECs systems. The interfacial anodes' charge transfer resistance of the doped GAC did not impact the overall performance of MECs. Based on our finding, the 3-D anode packed with GAC-doped with nonconductive calcium sulfide (CaS) outperformed the more conductive iron (II) sulfide (FeS), magnetite (Fe3O4), or GAC without doping. The results showed higher current densities for 3-D CaS (40.1 A/m3), as compared with 3-D FeS (34.4 A/m3), 3-D Fe3O4 (29.8 A/m3), and 3-D GAC (23.1 A/m3). The higher current density in the 3-D CaS translated to higher coulombic efficiency (96.7%), hydrogen yield (3.6 mol H2/mol acetate), and attached biomass per anode mass (54.01 mg COD biomass/g GAC). Although the 3-D MEC achieved similar hydrogen yield, hydrogen recovery efficiency, and COD removal rate to a conventional sandwich type MEC, the current density, coulombic efficiency, and overall energy efficiency were higher.

Recent Studies on Metal Oxides as Anodes for Li-ION Batteries

NASA Astrophysics Data System (ADS)

Sharma, N.; Subba Rao, G. V.; Chowdari, B. V. R.

Commercial lithium ion batteries (LIB) use layer-type compounds as the electrode materials and Li-ion conducting liquid or polymeric gel as the electrolyte. The preferred cathode and anode are LiCoO2 and graphite respectively. Efforts to improve the performance as well as safety-in-operation of LIB led to the search for alternate electrode materials. As regards the anodes, metal-oxide systems received special attention: Tin (Sn) containing mixed oxides and various 3d- and 4d- transition metal (M) mixed oxides. The reversible capacities in these systems arise either from alloying/de-alloying, formation/decomposition of Li2O aided by the nanosize metal (M) particles/Li-M-O bronze or Li-intercalation/de-intercalation. A brief account of the recent studies is presented.

Direct electrochemical oxidation of ammonia on graphite as a treatment option for stored source-separated urine.

PubMed

Zöllig, Hanspeter; Fritzsche, Cristina; Morgenroth, Eberhard; Udert, Kai M

2015-02-01

Electrolysis can be a viable technology for ammonia removal from source-separated urine. Compared to biological nitrogen removal, electrolysis is more robust and is highly amenable to automation, which makes it especially attractive for on-site reactors. In electrolytic wastewater treatment, ammonia is usually removed by indirect oxidation through active chlorine which is produced in-situ at elevated anode potentials. However, the evolution of chlorine can lead to the formation of chlorate, perchlorate, chlorinated organic by-products and chloramines that are toxic. This study focuses on using direct ammonia oxidation on graphite at low anode potentials in order to overcome the formation of toxic by-products. With the aid of cyclic voltammetry, we demonstrated that graphite is active for direct ammonia oxidation without concomitant chlorine formation if the anode potential is between 1.1 and 1.6 V vs. SHE (standard hydrogen electrode). A comparison of potentiostatic bulk electrolysis experiments in synthetic stored urine with and without chloride confirmed that ammonia was removed exclusively by continuous direct oxidation. Direct oxidation required high pH values (pH > 9) because free ammonia was the actual reactant. In real stored urine (pH = 9.0), an ammonia removal rate of 2.9 ± 0.3 gN·m(-2)·d(-1) was achieved and the specific energy demand was 42 Wh·gN(-1) at an anode potential of 1.31 V vs. SHE. The measurements of chlorate and perchlorate as well as selected chlorinated organic by-products confirmed that no chlorinated by-products were formed in real urine. Electrode corrosion through graphite exfoliation was prevented and the surface was not poisoned by intermediate oxidation products. We conclude that direct ammonia oxidation on graphite electrodes is a treatment option for source-separated urine with three major advantages: The formation of chlorinated by-products is prevented, less energy is consumed than in indirect ammonia oxidation and readily available and cheap graphite can be used as the electrode material. Copyright © 2014 Elsevier Ltd. All rights reserved.

Electrochemically exfoliated graphene anodes with enhanced biocurrent production in single-chamber air-breathing microbial fuel cells.

PubMed

Najafabadi, Amin Taheri; Ng, Norvin; Gyenge, Előd

2016-07-15

Microbial fuel cells (MFCs) present promising options for environmentally sustainable power generation especially in conjunction with waste water treatment. However, major challenges remain including low power density, difficult scale-up, and durability of the cell components. This study reports enhanced biocurrent production in a membrane-free MFC, using graphene microsheets (GNs) as anode and MnOx catalyzed air cathode. The GNs are produced by ionic liquid assisted simultaneous anodic and cathodic electrochemical exfoliation of iso-molded graphite electrodes. The GNs produced by anodic exfoliation increase the MFC peak power density by over 300% compared to plain carbon cloth (i.e., 2.85Wm(-2) vs 0.66Wm(-2), respectively), and by 90% compared to conventional carbon black (i.e., Vulcan XC-72) anode. These results exceed previously reported power densities for graphene-containing MFC anodes. The fuel cell polarization results are corroborated by electrochemical impedance spectroscopy indicating three times lower charge transfer resistance for the GN anode. Material characterizations suggest that the best performing GN samples were of relatively smaller size (~500nm), with higher levels of ionic liquid induced surface functionalization during the electrochemical exfoliation process. Copyright © 2016 Elsevier B.V. All rights reserved.

Silicene Flowers: A Dual Stabilized Silicon Building Block for High-Performance Lithium Battery Anodes.

PubMed

Zhang, Xinghao; Qiu, Xiongying; Kong, Debin; Zhou, Lu; Li, Zihao; Li, Xianglong; Zhi, Linjie

2017-07-25

Nanostructuring is a transformative way to improve the structure stability of high capacity silicon for lithium batteries. Yet, the interface instability issue remains and even propagates in the existing nanostructured silicon building blocks. Here we demonstrate an intrinsically dual stabilized silicon building block, namely silicene flowers, to simultaneously address the structure and interface stability issues. These original Si building blocks as lithium battery anodes exhibit extraordinary combined performance including high gravimetric capacity (2000 mAh g -1 at 800 mA g -1 ), high volumetric capacity (1799 mAh cm -3 ), remarkable rate capability (950 mAh g -1 at 8 A g -1 ), and excellent cycling stability (1100 mA h g -1 at 2000 mA g -1 over 600 cycles). Paired with a conventional cathode, the fabricated full cells deliver extraordinarily high specific energy and energy density (543 Wh kg ca -1 and 1257 Wh L ca -1 , respectively) based on the cathode and anode, which are 152% and 239% of their commercial counterparts using graphite anodes. Coupled with a simple, cost-effective, scalable synthesis approach, this silicon building block offers a horizon for the development of high-performance batteries.

Real-time monitoring of subsurface microbial metabolism with graphite electrodes

DOE PAGES

Wardman, Colin; Nevin, Kelly P.; Lovley, Derek R.

2014-11-21

Monitoring in situ microbial activity in anoxic submerged soils and aquatic sediments can be labor intensive and technically difficult, especially in dynamic environments in which a record of changes in microbial activity over time is desired. Microbial fuel cell concepts have previously been adapted to detect changes in the availability of relatively high concentrations of organic compounds in waste water but, in most soils and sediments, rates of microbial activity are not linked to the concentrations of labile substrates, but rather to the turnover rates of the substrate pools with steady state concentrations in the nM-μ M range. In ordermore » to determine whether levels of current produced at a graphite anode would correspond to the rates of microbial metabolism in anoxic sediments, small graphite anodes were inserted in sediment cores and connected to graphite brush cathodes in the overlying water. Currents produced were compared with the rates of [2- 14C]-acetate metabolism. There was a direct correlation between current production and the rate that [2- 14C]-acetate was metabolized to 14CO 2 and 14CH 4 in sediments in which Fe(III) reduction, sulfate reduction, or methane production was the predominant terminal electron-accepting process. At comparable acetate turnover rates, currents were higher in the sediments in which sulfate-reduction or Fe(III) reduction predominated than in methanogenic sediments. This was attributed to reduced products (Fe(II), sulfide) produced at distance from the anode contributing to current production in addition to the current that was produced from microbial oxidation of organic substrates with electron transfer to the anode surface in all three sediment types. In conclusion, the results demonstrate that inexpensive graphite electrodes may provide a simple strategy for real-time monitoring of microbial activity in a diversity of anoxic soils and sediments.« less

Investigation of the characteristics of a stacked direct borohydride fuel cell for portable applications

NASA Astrophysics Data System (ADS)

Kim, Cheolhwan; Kim, Kyu-Jung; Ha, Man Yeong

To investigate the possibility of the portable application of a direct borohydride fuel cell (DBFC), weight reduction of the stack and high stacking of the cells are investigated for practical running conditions. For weight reduction, carbon graphite is adopted as the bipolar plate material even though it has disadvantages in tight stacking, which results in stacking loss from insufficient material strength. For high stacking, it is essential to have a uniform fuel distribution among cells and channels to maintain equal electric load on each cell. In particular, the design of the anode channel is important because active hydrogen generation causes non-uniformity in the fuel flow-field of the cells and channels. To reduce the disadvantages of stacking force margin and fuel maldistribution, an O-ring type-sealing system with an internal manifold and a parallel anode channel design is adopted, and the characteristics of a single and a five-cell fuel cell stack are analyzed. By adopting carbon graphite, the stack weight can be reduced by 4.2 times with 12% of performance degradation from the insufficient stacking force. When cells are stacked, the performance exceeds the single-cell performance because of the stack temperature increase from the reduction of the radiation area from the narrow stacking of cells.

Irreversible Capacities of Graphite in Low Temperature Electrolytes for Lithium-Ion Batteries

NASA Technical Reports Server (NTRS)

Ratnakumar, B.; Smart, M.; Surampudi, S.; Wang, Y.; Zhang, X.; Greenbaum, S.; Hightower, A.; Ahn, C.; Fultz, B.

1999-01-01

Carbonaceous anode materials in lithium ion rechargeable cells experience irreversible capacity, mainly due to a consumption of lithium in the formation of surface passive films. The stability and kinetics of lithium intercalation into the carbon anodes are dictated by these films.

Na-Ion Battery Anodes: Materials and Electrochemistry.

PubMed

Luo, Wei; Shen, Fei; Bommier, Clement; Zhu, Hongli; Ji, Xiulei; Hu, Liangbing

2016-02-16

The intermittent nature of renewable energy sources, such as solar and wind, calls for sustainable electrical energy storage (EES) technologies for stationary applications. Li will be simply too rare for Li-ion batteries (LIBs) to be used for large-scale storage purposes. In contrast, Na-ion batteries (NIBs) are highly promising to meet the demand of grid-level storage because Na is truly earth abundant and ubiquitous around the globe. Furthermore, NIBs share a similar rocking-chair operation mechanism with LIBs, which potentially provides high reversibility and long cycling life. It would be most efficient to transfer knowledge learned on LIBs during the last three decades to the development of NIBs. Following this logic, rapid progress has been made in NIB cathode materials, where layered metal oxides and polyanionic compounds exhibit encouraging results. On the anode side, pure graphite as the standard anode for LIBs can only form NaC64 in NIBs if solvent co-intercalation does not occur due to the unfavorable thermodynamics. In fact, it was the utilization of a carbon anode in LIBs that enabled the commercial successes. Anodes of metal-ion batteries determine key characteristics, such as safety and cycling life; thus, it is indispensable to identify suitable anode materials for NIBs. In this Account, we review recent development on anode materials for NIBs. Due to the limited space, we will mainly discuss carbon-based and alloy-based anodes and highlight progress made in our groups in this field. We first present what is known about the failure mechanism of graphite anode in NIBs. We then go on to discuss studies on hard carbon anodes, alloy-type anodes, and organic anodes. Especially, the multiple functions of natural cellulose that is used as a low-cost carbon precursor for mass production and as a soft substrate for tin anodes are highlighted. The strategies of minimizing the surface area of carbon anodes for improving the first-cycle Coulombic efficiency are also outlined, where graphene oxide was employed as dehydration agent and 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) was used to unzip wood fiber. Furthermore, surface modification by atomic layer deposition technology is introduced, where we discover that a thin layer of Al2O3 can function to encapsulate Sn nanoparticles, leading to a much enhanced cycling performance. We also highlight recent work about the phosphorene/graphene anode, which outperformed other anodes in terms of capacity. The aromatic organic anode is also studied as anode with very high initial sodiation capacity. Furthermore, electrochemical intercalation of Na ions into reduced graphene oxide is applied for fabricating transparent conductors, demonstrating the great feasibility of Na ion intercalation for optical applications.

SiC Nanofibers as Long-Life Lithium-Ion Battery Anode Materials.

PubMed

Sun, Xuejiao; Shao, Changzhen; Zhang, Feng; Li, Yi; Wu, Qi-Hui; Yang, Yonggang

2018-01-01

The development of high energy lithium-ion batteries (LIBs) has spurred the designing and production of novel anode materials to substitute currently commercial using graphitic materials. Herein, twisted SiC nanofibers toward LIBs anode materials, containing 92.5 wt% cubic β-SiC and 7.5 wt% amorphous C, were successfully synthesized from resin-silica composites. The electrochemical measurements showed that the SiC-based electrode delivered a stable reversible capacity of 254.5 mAh g -1 after 250 cycles at a current density of 0.1 A g -1 . It is interesting that a high discharge capacity of 540.1 mAh g -1 was achieved after 500 cycles at an even higher current density of 0.3 A g -1 , which is higher than the theoretical capacity of graphite. The results imply that SiC nanomaterials are potential anode candidate for LIBs with high stability due to their high structure stability as supported with the transmission electron microscopy images.

Alkaline fuel cells for the regenerative fuel cell energy storage system

NASA Technical Reports Server (NTRS)

Martin, R. E.

1983-01-01

The development of the alkaline Regenerative Fuel Cell System, whose fuel cell module would be a derivative of the 12-kW fuel cell power plant currently being produced for the Space Shuttle Orbiter, is reviewed. Long-term endurance testing of full-size fuel cell modules has demonstrated: (1) the extended endurance capability of potassium titanate matrix cells, (2) the long-term performance stability of the anode catalyst, and (3) the suitability of a lightweight graphite structure for use at the anode. These approaches, developed in the NASA-sponsored fuel cell technology advancement program, would also reduce cell weight by nearly one half.

Synthesis and characterization of lithium ion nanobatteries and lithium battery nanoelectrode arrays

NASA Astrophysics Data System (ADS)

Vullum, Fride

2005-07-01

Arrays of individual nanobatteries were constructed by confining V 2O5 ambigel and a PEO wax electrolyte containing lithium triflate in the porous structure of an alumina membrane. The pores had an average diameter of 200 nm. Cyclic voltammetry data indicated that this configuration could be described by a nanoelectrode array model. A.C. impedance data of the macro cell coupled with a lithium anode showed that there was little or no unstable passivation behavior of the lithium anode in contact with the PEO wax electrolyte. This was attributed to a self-assembled hydrocarbon layer that formed at the surface of the wax preventing the lithium metal from chemically reacting with oxygen atoms in the PEO backbone. Individual nanobatteries were characterized by charge/discharge analysis. Electrical contact with individual nanocathodes was achieved using the cantilever tip of an atomic force microscope. Of the three different anode materials that were investigated SnO2 seemed to perform better than either graphite or lithium metal. This was attributed to SnO2 being able to accept more lithium ions into its structure than graphite. The favorable capacity values compared to the lithium anode batteries were attributed to better contact between the electrolyte and the anode. Average volumetric capacities for the SnO2 system were found to be around 45 muAh/cm2mum, which compare favorably to similar systems reported in literature. These nanobatteries also exhibited capacitor-like behavior, having capacitances around 300-400 F/g, which is in the range of what is expected for a supercapacitor. An electrochemical cell combining battery-like and capacitor-like behavior is a very promising power supply for applications such as electric vehicle propulsion systems.

Activated graphene as a cathode material for Li-ion hybrid supercapacitors.

PubMed

Stoller, Meryl D; Murali, Shanthi; Quarles, Neil; Zhu, Yanwu; Potts, Jeffrey R; Zhu, Xianjun; Ha, Hyung-Wook; Ruoff, Rodney S

2012-03-14

Chemically activated graphene ('activated microwave expanded graphite oxide', a-MEGO) was used as a cathode material for Li-ion hybrid supercapacitors. The performance of a-MEGO was first verified with Li-ion electrolyte in a symmetrical supercapacitor cell. Hybrid supercapacitors were then constructed with a-MEGO as the cathode and with either graphite or Li(4)Ti(5)O(12) (LTO) for the anode materials. The results show that the activated graphene material works well in a symmetrical cell with the Li-ion electrolyte with specific capacitances as high as 182 F g(-1). In a full a-MEGO/graphite hybrid cell, specific capacitances as high as 266 F g(-1) for the active materials at operating potentials of 4 V yielded gravimetric energy densities for a packaged cell of 53.2 W h kg(-1).

Performance evaluation of tubular fuel cells fuelled by pulverized graphite

NASA Astrophysics Data System (ADS)

Kim, Jong-Pil; Lim, Ho; Jeon, Chung-Hwan; Chang, Young-June; Koh, Kwang-Nak; Choi, Soon-Mok; Song, Ju-Hun

A fuel cell fuelled by carbonaceous graphite is proposed. The tubular fuel cell, with the carbon in a fixed-bed form on the anode side, is employed to convert directly the chemical energy of carbon into electricity. Surface platinum electrodes are coated on the cell electrolyte, which is a yttria-stabilized zirconia (YSZ) tube of 1.5 mm thickness. The effect of using different sizes of graphite powder (in the range 0-180 μm) as fuel is analyzed. Power density and actual open-circuit voltage (OCV) values are measured as the temperature is varied from 0 to 950 °C. The cell provides a maximum power density of 16.8 mW cm -2 and an OCV of 1.115 V at the highest temperature condition (950 °C) tested in this study.

Fire-extinguishing organic electrolytes for safe batteries

NASA Astrophysics Data System (ADS)

Wang, Jianhui; Yamada, Yuki; Sodeyama, Keitaro; Watanabe, Eriko; Takada, Koji; Tateyama, Yoshitaka; Yamada, Atsuo

2018-01-01

Severe safety concerns are impeding the large-scale employment of lithium/sodium batteries. Conventional electrolytes are highly flammable and volatile, which may cause catastrophic fires or explosions. Efforts to introduce flame-retardant solvents into the electrolytes have generally resulted in compromised battery performance because those solvents do not suitably passivate carbonaceous anodes. Here we report a salt-concentrated electrolyte design to resolve this dilemma via the spontaneous formation of a robust inorganic passivation film on the anode. We demonstrate that a concentrated electrolyte using a salt and a popular flame-retardant solvent (trimethyl phosphate), without any additives or soft binders, allows stable charge-discharge cycling of both hard-carbon and graphite anodes for more than 1,000 cycles (over one year) with negligible degradation; this performance is comparable or superior to that of conventional flammable carbonate electrolytes. The unusual passivation character of the concentrated electrolyte coupled with its fire-extinguishing property contributes to developing safe and long-lasting batteries, unlocking the limit toward development of much higher energy-density batteries.

Rice husks as a sustainable source of nanostructured silicon for high performance Li-ion battery anodes

PubMed Central

Liu, Nian; Huo, Kaifu; McDowell, Matthew T.; Zhao, Jie; Cui, Yi

2013-01-01

The recovery of useful materials from earth-abundant substances is of strategic importance for industrial processes. Despite the fact that Si is the second most abundant element in the Earth's crust, processes to form Si nanomaterials is usually complex, costly and energy-intensive. Here we show that pure Si nanoparticles (SiNPs) can be derived directly from rice husks (RHs), an abundant agricultural byproduct produced at a rate of 1.2 × 108 tons/year, with a conversion yield as high as 5% by mass. And owing to their small size (10–40 nm) and porous nature, these recovered SiNPs exhibits high performance as Li-ion battery anodes, with high reversible capacity (2,790 mA h g−1, seven times greater than graphite anodes) and long cycle life (86% capacity retention over 300 cycles). Using RHs as the raw material source, overall energy-efficient, green, and large scale synthesis of low-cost and functional Si nanomaterials is possible. PMID:23715238

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yen, Hung-Ju; Tsai, Hsinhan; Zhou, Ming

In this paper, functionalized 3D nanographenes with controlled electronic properties have been synthesized through a multistep organic synthesis method and are further used as promising anode materials for lithium-ion batteries, exhibiting a much increased capacity (up to 950 mAh g -1), three times higher than that of the graphite anode (372 mAh g -1).

Porous carbon-coated graphite electrodes for energy production from salinity gradient using reverse electrodialysis

NASA Astrophysics Data System (ADS)

Lee, Su-Yoon; Jeong, Ye-Jin; Chae, So-Ryong; Yeon, Kyeong-Ho; Lee, Yunkyu; Kim, Chan-Soo; Jeong, Nam-Jo; Park, Jin-Soo

2016-04-01

Performance of graphite foil electrodes coated by porous carbon black (i.e., Vulcan) was investigated in comparison with metal electrodes for reverse electrodialysis (RED) application. The electrode slurry that was used for fabrication of the porous carbon-coated graphite foil is composed of 7.2 wt% of carbon black (Vulcan X-72), 0.8 wt% of a polymer binder (polyvinylidene fluoride, PVdF), and 92.0 wt% of a mixing solvent (dimethylacetamide, DMAc). Cyclic voltammograms of both the porous carbon (i.e., Vulcan)-coated graphite foil electrode and the graphite foil electrode without Vulcan showed good reversibility in the hexacyanoferrate(III) (i.e., Fe(CN)63-) and hexacyanoferrate(II) (i.e., Fe(CN)64-) redox couple and 1 M Na2SO4 at room temperature. However, anodic and cathodic current of the Vulcan-coated graphite foil electrode was much higher than those of the graphite foil electrode. Using a bench-scale RED stack, the current-voltage polarization curve of the Vulcan-coated graphite electrode was compared to that of metal electrodes such as iridium (Ir) and platinum (Pt). From the results, it was confirmed that resistance of four different electrodes increased with the following order: the Vulcan-coated graphite foil

Conductive Polymer Binder-Enabled SiO–Sn xCo yC z Anode for High-Energy Lithium-Ion Batteries

DOE PAGES

Zhao, Hui; Fu, Yanbao; Ling, Min; ...

2016-05-10

In this paper, a SiOSnCoC composite anode is assembled using a conductive polymer binder for the application in next-generation high energy density lithium-ion batteries. A specific capacity of 700 mAh/g is achieved at a 1C (900 mA/g) rate. A high active material loading anode with an areal capacity of 3.5 mAh/cm 2 is demonstrated by mixing SiOSnCoC with graphite. To compensate for the lithium loss in the first cycle, stabilized lithium metal powder (SLMP) is used for prelithiation; when paired with a commercial cathode, a stable full cell cycling performance with a 86% first cycle efficiency is realized. Finally, bymore » achieving these important metrics toward a practical application, this conductive polymer binder/SiOSnCoC anode system presents great promise to enable the next generation of high-energy lithium-ion batteries.« less

Effect of mass and charge transport speed and direction in porous anodes on microbial electrolysis cell performance.

PubMed

Sleutels, Tom H J A; Hamelers, Hubertus V M; Buisman, Cees J N

2011-01-01

The use of porous electrodes like graphite felt as anode material has the potential of achieving high volumetric current densities. High volumetric current densities, however, may also lead to mass transport limitations within these porous materials. Therefore, in this study we investigated the mass and charge transport limitations by increasing the speed of the forced flow and changing the flow direction through the porous anode. Increase of the flow speed led to a decrease in current density when the flow was directed towards the membrane caused by an increase in anode resistance. Current density increased at higher flow speed when the flow was directed away from the membrane. This was caused by a decrease in transport resistance of ions through the membrane which increased the buffering effect of the system. Furthermore, the increase in flow speed led to an increase of the coulombic efficiency by 306%. Copyright © 2010 Elsevier Ltd. All rights reserved.

Silicon algae with carbon topping as thin-film anodes for lithium-ion microbatteries by a two-step facile method

NASA Astrophysics Data System (ADS)

Biserni, E.; Xie, M.; Brescia, R.; Scarpellini, A.; Hashempour, M.; Movahed, P.; George, S. M.; Bestetti, M.; Li Bassi, A.; Bruno, P.

2015-01-01

Silicon-based electrodes for Li-ion batteries (LIB) attract much attention because of their high theoretical capacity. However, their large volume change during lithiation results in poor cycling due to mechanical cracking. Moreover, silicon can hardly form a stable solid electrolyte interphase (SEI) layer with common electrolytes. We present a safe, innovative strategy to prepare nanostructured silicon-carbon anodes in a two-step process. The nanoporosity of Si films accommodates the volume expansion while a disordered graphitic C layer on top promotes the formation of a stable SEI. This approach shows its promises: carbon-coated porous silicon anodes perform in a very stable way, reaching the areal capacity of ∼175 μAh cm-2, and showing no decay for at least 1000 cycles. With requiring only a two-step deposition process at moderate temperatures, this novel very simple cell concept introduces a promising way to possibly viable up-scaled production of next-generation nanostructured Si anodes for lithium-ion microbatteries.

High-temperature solid electrolyte interphases (SEI) in graphite electrodes

NASA Astrophysics Data System (ADS)

Rodrigues, Marco-Tulio F.; Sayed, Farheen N.; Gullapalli, Hemtej; Ajayan, Pulickel M.

2018-03-01

Thermal fragility of the solid electrolyte interphase (SEI) is a major source of performance decay in graphite anodes, and efforts to overcome the issues offered by extreme environments to Li-ion batteries have had limited success. Here, we demonstrate that the SEI can be extensively reinforced by carrying the formation cycles at elevated temperatures. Under these conditions, decomposition of the ionic liquid present in the electrolyte favored the formation of a thicker and more protective layer. Cells in which the solid electrolyte interphase was cast at 90 °C were significantly less prone to self-discharge when exposed to high temperature, with no obvious damages to the formed SEI. This additional resilience was accomplished at the expense of rate capability, as charge transfer became growingly inefficient in these systems. At slower rates, however, cells that underwent SEI formation at 90 °C presented superior performances, as a result of improved Li+ transport through the SEI, and optimal wetting of graphite by the electrolyte. This work analyzes different graphite hosts and ionic liquids, showing that this effect is more pervasive than anticipated, and offering the unique perspective that, for certain systems, temperature can actually be an asset for passivation.

Development of Lithium Dimethyl Phosphate as an Electrolyte Additive for Lithium Ion Batteries

DOE PAGES

Milien, Mickdy S.; Tottempudi, Usha; Son, Miyoung; ...

2016-04-27

The novel electrolyte additive lithium dimethyl phosphate (LiDMP) has been synthesized and characterized. Incorporation of LiDMP (0.1% wt) into LiPF 6 in ethylene carbonate (EC) / ethyl methyl carbonate (EMC) (3:7 wt) results in improved rate performance and reduced impedance for graphite / LiNi 1/3Mn 1/3Co 1/3O 2 cells. Ex-situ surface analysis of the electrodes suggests that incorporation of LiDMP results in a modification of the solid electrolyte interphase (SEI) on the anode. A decrease in the concentration of lithium alkyl carbonates and an increase in the concentration of lithium fluoro phosphates are observed. The change in the anode SEImore » structure is responsible for the increased rate performance and decreased cell impedance.« less

Purification process of natural graphite as anode for Li-ion batteries: chemical versus thermal

NASA Astrophysics Data System (ADS)

Zaghib, K.; Song, X.; Guerfi, A.; Rioux, R.; Kinoshita, K.

The intercalation of Li ions in natural graphite that was purified by chemical and thermal processes was investigated. A new chemical process was developed that involved a mixed aqueous solution containing 30% H 2SO 4 and 30% NH xF y heated to 90 °C. The results of this process are compared to those obtained by heating the natural graphite from 1500 to 2400 °C in an inert environment (thermal process). The first-cycle coulombic efficiency of the purified natural graphite obtained by the chemical process is 91 and 84% after the thermal process at 2400 °C. Grinding the natural graphite before or after purification had no significant effect on electrochemical performance at low currents. However, grinding to a very small particle size before purification permitted optimization of the size distribution of the particles, which gives rise to a more homogenous electrode. The impurities in the graphite play a role as microabrasion agents during grinding which enhances its hardness and improves its mechanical properties. Grinding also modifies the particle morphology from a 2- to a 3-D structure (similar in shape to a potato). This potato-shaped natural graphite shows high reversible capacity at high current densities (about 90% at 1 C rate). Our analysis suggests that thermal processing is considerably more expensive than the chemical process to obtain purified natural graphite.

Carbon with Expanded and Well-Developed Graphene Planes Derived Directly from Condensed Lignin as a High-Performance Anode for Sodium-Ion Batteries.

PubMed

Yoon, Dohyeon; Hwang, Jieun; Chang, Wonyoung; Kim, Jaehoon

2018-01-10

In this study, we demonstrate that lignin, which constitutes 30-40 wt % of the terrestrial lignocellulosic biomass and is produced from second generation biofuel plants as a cheap byproduct, is an excellent precursor material for sodium-ion battery (NIB) anodes. Because it is rich in aromatic monomers that are highly cross-linked by ether and condensed bonds, the lignin material carbonized at 1300 °C (C-1300) in this study has small graphitic domains with well-developed graphene layers, a large interlayer spacing (0.403 nm), and a high micropore surface area (207.5 m 2 g -1 ). When tested as an anode in an NIB, C-1300 exhibited an initial Coulombic efficiency of 68% and a high reversible capacity of 297 mA h g -1 at 50 mA g -1 after 50 cycles. The high capacity of 199 mA h g -1 at less than 0.1 V with a flat voltage profile and an extremely low charge-discharge voltage hysteresis (<0.03 V) make C-1300 a promising energy-dense electrode material. In addition, C-1300 exhibited an excellent high-rate performance of 116 mA h g -1 at 2.5 A g -1 and showed stable cycling retention (0.2% capacity decay per cycle after 500 cycles). By comparing the properties of the lignin-derived carbon with oak sawdust-derived and sugar-derived carbons and a low-temperature carbonized sample (900 °C), the reasons for the excellent performance of C-1300 were determined to result from facilitated Na + -ion transport to the graphitic layer and the microporous regions that penetrate through the less defective and enlarged interlayer spacings.

Lithium storage in structurally tunable carbon anode derived from sustainable source

DOE PAGES

Lim, Daw Gen; Kim, Kyungho; Razdan, Mayuri; ...

2017-09-01

Here, a meticulous solid state chemistry approach has been developed for the synthesis of carbon anode from a sustainable source. The reaction mechanism of carbon formation during pyrolysis of sustainable feed-stock was studied in situ by employing Raman microspectroscopy. No Raman spectral changes observed below 160°C (thermally stable precursor) followed by color change, however above 280°C characteristic D and G bands of graphitic carbon are recorded. Derived carbon particles exhibited high specific surface area with low structural ordering (active carbons) to low specific surface area with high graphitic ordering as a function of increasing reaction temperature. Carbons synthesized at 600°Cmore » demonstrated enhanced reversible lithiation capacity (390 mAh g -1), high charge-discharge rate capability, and stable cycle life. On the contrary, carbons synthesized at higher temperatures (>1200°C) produced more graphite-like structure yielding longer specific capacity retention with lower reversible capacity.« less

How to get between the sheets: a review of recent works on the electrochemical exfoliation of graphene materials from bulk graphite

NASA Astrophysics Data System (ADS)

Abdelkader, A. M.; Cooper, A. J.; Dryfe, R. A. W.; Kinloch, I. A.

2015-04-01

Since the beginning of the `graphene era' post-2004, there has been significant interest in developing a high purity, high yield, and scalable fabrication route toward graphene materials for both primary research purposes and industrial production. One suitable approach to graphene production lies in the realm of electrochemical exfoliation, in which a potential difference is applied between a graphite anode/cathode in the presence of an electrolyte-containing medium. Herein we review various works on the electrochemical fabrication of graphene materials specifically through the use of electrochemical intercalation and exfoliation of a graphite source electrode, focusing on the quality and purity of products formed. We categorise the most significant works in terms of anodic and cathodic control, highlighting the merits of the respective approaches, as well as indicating the challenges associated with both procedures.

Molten Salt Electrolytically Produced Carbon/Tin Nanomaterial as the Anode in a Lithium Ion Battery

NASA Astrophysics Data System (ADS)

Das Gupta, Rajshekar; Schwandt, Carsten; Fray, Derek J.

2017-03-01

A carbon/tin nanomaterial, consisting of predominantly Sn-filled carbon nanotubes and nanoparticles, is prepared by molten salt electrochemistry, using electrodes of graphite and an electrolyte of LiCl salt containing a small admixture of SnCl2. The C/Sn hybrid material generated is incorporated into the active anode material of a lithium ion battery and tested with regard to storage capacity and cycling behavior. The results demonstrate that the C/Sn material has favorable properties, in terms of energy density and in particular long-term stability, that exceed those of the individual components alone. The initial irreversible capacity of the material is somewhat larger than that of conventional battery graphite which is due to its unique nanostructure. Overall the results would indicate the suitability of this material for use in the anodes of lithium ion batteries with high rate capability.

Development of Carbon Anode for Rechargeable Lithium Cells

NASA Technical Reports Server (NTRS)

Huang, C. -K.; Surampudi, S.; Halpert, G.

1994-01-01

Conventionally, rechargeable lithium cells employ a pure lithium anode. To overcome problems associated with the pure lithium electrode, it has been proposed to replace the conventional electrode with an alternative material having a greater stability with respect to the cell electrolytes. For this reason, several graphitic and coke based carbonaceous materials were evaluated as candidate anode materials...In this paper, we summarize the results of the studies on Li-ion cell development.

Development of Nitrogen Sensor for Determination of PN(2) in Body Tissues.

DTIC Science & Technology

1982-07-01

3) The progress of the reduction reaction (1) was followed by voltammetry. A single anodic potential sweep , starting from the open circuit...Graphite Electrode The progressive attachment of [Ru(NH3 ) 5 H2 0] +2 to PVP-coated graphite electrodes was observed by cyclic voltametry as an

Metallic Sn‐Based Anode Materials: Application in High‐Performance Lithium‐Ion and Sodium‐Ion Batteries

PubMed Central

Ying, Hangjun

2017-01-01

Abstract With the fast‐growing demand for green and safe energy sources, rechargeable ion batteries have gradually occupied the major current market of energy storage devices due to their advantages of high capacities, long cycling life, superior rate ability, and so on. Metallic Sn‐based anodes are perceived as one of the most promising alternatives to the conventional graphite anode and have attracted great attention due to the high theoretical capacities of Sn in both lithium‐ion batteries (LIBs) (994 mA h g−1) and sodium‐ion batteries (847 mA h g−1). Though Sony has used Sn–Co–C nanocomposites as its commercial LIB anodes, to develop even better batteries using metallic Sn‐based anodes there are still two main obstacles that must be overcome: poor cycling stability and low coulombic efficiency. In this review, the latest and most outstanding developments in metallic Sn‐based anodes for LIBs and SIBs are summarized. And it covers the modification strategies including size control, alloying, and structure design to effectually improve the electrochemical properties. The superiorities and limitations are analyzed and discussed, aiming to provide an in‐depth understanding of the theoretical works and practical developments of metallic Sn‐based anode materials. PMID:29201624

Metallic Sn-Based Anode Materials: Application in High-Performance Lithium-Ion and Sodium-Ion Batteries.

PubMed

Ying, Hangjun; Han, Wei-Qiang

2017-11-01

With the fast-growing demand for green and safe energy sources, rechargeable ion batteries have gradually occupied the major current market of energy storage devices due to their advantages of high capacities, long cycling life, superior rate ability, and so on. Metallic Sn-based anodes are perceived as one of the most promising alternatives to the conventional graphite anode and have attracted great attention due to the high theoretical capacities of Sn in both lithium-ion batteries (LIBs) (994 mA h g -1 ) and sodium-ion batteries (847 mA h g -1 ). Though Sony has used Sn-Co-C nanocomposites as its commercial LIB anodes, to develop even better batteries using metallic Sn-based anodes there are still two main obstacles that must be overcome: poor cycling stability and low coulombic efficiency. In this review, the latest and most outstanding developments in metallic Sn-based anodes for LIBs and SIBs are summarized. And it covers the modification strategies including size control, alloying, and structure design to effectually improve the electrochemical properties. The superiorities and limitations are analyzed and discussed, aiming to provide an in-depth understanding of the theoretical works and practical developments of metallic Sn-based anode materials.

High-performance lithium-ion batteries with 1.5 μm thin copper nanowire foil as a current collector

NASA Astrophysics Data System (ADS)

Chu, Hsun-Chen; Tuan, Hsing-Yu

2017-04-01

Cu Foil, a thin sheet of Cu, is the common anode current collector in commercial lithium ion batteries (LIBs) which accounts for ∼ 10 wt% of the total cell weight. However, thickness reduction of LIB-based Cu foils below 6 μm has been limited by the incapability of conventional rolling annealing or electrodeposition process. We here report a new type of Cu foil, so called Cu nanowire foil (CuNW foil), for use as an LIB anode current collector. We fabricate Cu NW foils by rolling press Cu nanowire fabric to reduce the thickness down to ∼1.5 μm with an areal weight down to ∼1.2 mg cm-2 and a density approximately 96% to that of bulk Cu. The rough surface and porous structure of CuNW foil enable better wetting and adhering properties of graphite slurry on foil. In full cell examination, a cell of a areal capacity of 3 mAh cm-2 exhibits 83.6% capacity retention for 600 cycles at 0.6 C that meets the standard specification of most commercial LIBs. As a proof-of-concept of demonstration, we fabricate a 700 mA pouch-type battery implemented with graphite-Cu NWs foil anodes to serve as energy supply to operate electronic devices.

Enhanced ablation of small anodes in a carbon nanotube arc discharge

NASA Astrophysics Data System (ADS)

Raitses, Yevgeny; Fetterman, Abraham; Keidar, Michael

2008-11-01

An atmospheric pressure helium arc discharge is used for carbon nanotube synthesis. The arc discharge operates in an anodic mode with the ablating anode made from a graphite material. For such conditions, models predict the electron-repelling (negative) anode sheath. In the present experiments, the anode ablation rate is investigated as a function of the anode diameter. It is found that anomalously high ablation occurs for small anode diameters (< 0.4 cm). This result is explained by the formation of an electron-attracting (positive) anode sheath leading to increased power losses on small anodes as compared to larger anodes [1]. The suggested mechanism for the positive anode sheath formation is plasma convergence. The increased ablation rate due to this positive sheath could imply a greater yield of carbon nanotube production. [1] A. J. Fetterman, Y. Raitses and M. Keidar, Carbon (2008).

A long life 4 V class lithium-ion polymer battery with liquid-free polymer electrolyte

NASA Astrophysics Data System (ADS)

Kobayashi, Yo; Shono, Kumi; Kobayashi, Takeshi; Ohno, Yasutaka; Tabuchi, Masato; Oka, Yoshihiro; Nakamura, Tatsuya; Miyashiro, Hajime

2017-02-01

Ether-based solid polymer electrolyte (SPE) is one of the most well-known lithium ion conductors. Unlike the other inorganic electrolytes, SPE exhibits advantages of flexibility and large-area production, enabling low cost production of large size batteries. However, because the ether group is oxidized at 4 V versus Li/Li+ cathode, and due to its high irreversibility with the carbon anode, ether-based SPE was believed to be inapplicable to 4 V class lithium-ion batteries with carbon anode. Here we report a remarkably stable SPE in combination with a 4 V class cathode and carbon anode achieved by the proper design at the interface. The introduced boron-based lithium salt prohibits further oxidation of SPE at the cathode interface. The surface modification of graphite by the annealing of polyvinyl chloride mostly prohibits the continuous consumption of lithium at the graphite anode. Using above interface design, we achieved 60% capacity retention after 5400 cycles. The proposed battery provides a possible approach for realizing flammable electrolyte-free lithium-ion batteries, which achieve innovative safety improvements of large format battery systems for stationary use.

Inert gas rejection device for zinc-halogen battery systems

DOEpatents

Hammond, Michael J.; Arendell, Mark W.

1981-01-01

An electrolytic cell for separating chlorine gas from other (foreign) gases, having an anode, a cathode assembly, an aqueous electrolyte, a housing, and a constant voltage power supply. The cathode assembly is generally comprised of a dense graphite electrode having a winding channel formed in the face opposing the anode, a gas impermeable (but liquid permeable) membrane sealed into the side of the cathode electrode over the channel, and a packing of graphite particles contained in the channel of the cathode electrode. The housing separates and parallelly aligns the anode and cathode assembly, and provides a hermetic seal for the cell. In operation, a stream of chlorine and foreign gases enters the cell at the beginning of the cathode electrode channel. The chlorine gas is dissolved into the electrolyte and electrochemically reduced into chloride ions. The chloride ions disfuse through the gas impermeable membrane, and are electrochemically oxidized at the anode into purified chlorine gas. The foreign gases do not participate in the above electrochemical reactions, and are vented from the cell at the end of the cathode electrode channel.

Carbon treated commercial aluminium alloys as anodes for aluminium-air batteries in sodium chloride electrolyte

NASA Astrophysics Data System (ADS)

Pino, M.; Herranz, D.; Chacón, J.; Fatás, E.; Ocón, P.

2016-09-01

An easy treatment based in carbon layer deposition into aluminium alloys is presented to enhance the performance of Al-air primary batteries with neutral pH electrolyte. The jellification of aluminate in the anode surface is described and avoided by the carbon covering. Treated commercial Al alloys namely Al1085 and Al7475 are tested as anodes achieving specific capacities above 1.2 Ah g-1vs 0.5 Ah g-1 without carbon covering. The influence of the binder proportion in the treatment as well as different carbonaceous materials, Carbon Black, Graphene and Pyrolytic Graphite are evaluated as candidates for the covering. Current densities of 1-10 mA cm-2 are measured and the influence of the alloy explored. A final battery design of 4 cells in series is presented for discharges with a voltage plateau of 2 V and 1 Wh g-1 energy density.

Hard-Soft Composite Carbon as a Long-Cycling and High-Rate Anode for Potassium-Ion Batteries

DOE PAGES

Jian, Zelang; Hwang, Sooyeon; Li, Zhifei; ...

2017-05-05

There exist tremendous needs for sustainable storage solutions for intermittent renewable energy sources, such as solar and wind energy. Thus, systems based on Earth-abundant elements deserve much attention. Potassium-ion batteries represent a promising candidate because of the abundance of potassium resources. As for the choices of anodes, graphite exhibits encouraging potassium-ion storage properties; however, it suffers limited rate capability and poor cycling stability. Here in this paper, nongraphitic carbons as K-ion anodes with sodium carboxymethyl cellulose as the binder are systematically investigated. Compared to hard carbon and soft carbon, a hard–soft composite carbon with 20 wt% soft carbon distributed inmore » the matrix phase of hard carbon microspheres exhibits highly amenable performance: high capacity, high rate capability, and very stable long-term cycling. In contrast, pure hard carbon suffers limited rate capability, while the capacity of pure soft carbon fades more rapidly.« less

One-step electrolytic preparation of Si-Fe alloys as anodes for lithium ion batteries

NASA Astrophysics Data System (ADS)

Wang, Hailong; Sun, Diankun; Song, Qiqi; Xie, Wenqi; Jiang, Xu; Zhang, Bo

2016-06-01

One-step electrolytic formation of uniform crystalline Si-Fe alloy particles was successfully demonstrated in direct electro-reduction of solid mixed oxides of SiO2 and Fe2O3 in molten CaCl2 at 900∘C. Upon constant voltage electrolysis of solid mixed oxides at 2.8V between solid oxide cathode and graphite anode for 5h, electrolytic Si-Fe with the same Si/Fe stoichimetry of the precursory oxides was generated. The firstly generated Fe could function as depolarizers to enhance reduction rate of SiO2, resulting in the enhanced reduction kinetics to the electrolysis of individual SiO2. When evaluated as anode for lithium ion batteries, the prepared SiFe electrode showed a reversible lithium storage capacity as high as 470mAh g-1 after 100 cycles at 200mA g-1, promising application in high-performance lithium ion batteries.

Hard-Soft Composite Carbon as a Long-Cycling and High-Rate Anode for Potassium-Ion Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jian, Zelang; Hwang, Sooyeon; Li, Zhifei

There exist tremendous needs for sustainable storage solutions for intermittent renewable energy sources, such as solar and wind energy. Thus, systems based on Earth-abundant elements deserve much attention. Potassium-ion batteries represent a promising candidate because of the abundance of potassium resources. As for the choices of anodes, graphite exhibits encouraging potassium-ion storage properties; however, it suffers limited rate capability and poor cycling stability. Here in this paper, nongraphitic carbons as K-ion anodes with sodium carboxymethyl cellulose as the binder are systematically investigated. Compared to hard carbon and soft carbon, a hard–soft composite carbon with 20 wt% soft carbon distributed inmore » the matrix phase of hard carbon microspheres exhibits highly amenable performance: high capacity, high rate capability, and very stable long-term cycling. In contrast, pure hard carbon suffers limited rate capability, while the capacity of pure soft carbon fades more rapidly.« less

Corrosion of graphite composites in phosphoric acid fuel cells

NASA Technical Reports Server (NTRS)

Christner, L. G.; Dhar, H. P.; Farooque, M.; Kush, A. K.

1986-01-01

Polymers, polymer-graphite composites and different carbon materials are being considered for many of the fuel cell stack components. Exposure to concentrated phosphoric acid in the fuel cell environment and to high anodic potential results in corrosion. Relative corrosion rates of these materials, failure modes, plausible mechanisms of corrosion and methods for improvement of these materials are investigated.

Full scale phosphoric acid fuel cell stack technology development

NASA Technical Reports Server (NTRS)

Christner, L.; Faroque, M.

1984-01-01

The technology development for phosphoric acid fuel cells is summarized. The preparation, heat treatment, and characterization of carbon composites used as bipolar separator plates are described. Characterization included resistivity, porosity, and electrochemical corrosion. High density glassy carbon/graphite composites performed well in long-term fuel cell endurance tests. Platinum alloy cathode catalysts and low-loaded platinum electrodes were evaluated in 25 sq cm cells. Although the alloys displayed an initial improvement, some of this improvement diminished after a few thousand hours of testing. Low platinum loading (0.12 mg/sq cm anodes and 0.3 mg/sq cm cathodes) performed nearly as well as twice this loading. A selectively wetproofed anode backing paper was tested in a 5 by 15 inch three-cell stack. This material may provide for acid volume expansion, acid storage, and acid lateral distribution.

Electrocatalytic properties of N-doped graphite felt in electro-Fenton process and degradation mechanism of levofloxacin.

PubMed

Liu, Xiaocheng; Yang, Danxing; Zhou, Yaoyu; Zhang, Jiachao; Luo, Lin; Meng, Sijun; Chen, Song; Tan, Mengjiao; Li, Zhicheng; Tang, Lin

2017-09-01

The degradation of antibiotic levofloxacin was investigated by dimensionally stable anode as well as modified cathode using low-cost chemical reagents of hydrazine hydrate and ethanol for electro-Fenton in an undivided cell at pH 3.0 under room temperature. Comparison of unmodified and modified cathode was performed. The apparent rate constant of levofloxacin decay was found to be 0.2883 min -1 for graphite felt-10 with the best performance at 200 mA, which is lower than graphite felt at 400 mA. The optimum modified cathode showed a significant improvement of complete mineralization of levofloxacin, reaching a 92% TOC removal at 200 mA for 480 min higher than unmodified one at twice the current. Surface physicochemical properties and morphology were investigated by scanning electron microscope, contact angle and X-ray photoelectron spectroscopy. The electrochemical characterization of hydrogen evolution reaction was adopted to clarify a possible pathway for the higher mineralization of levofloxacin, indicating a potential pilot-scale study to the pollution with the similar structure. Copyright © 2017 Elsevier Ltd. All rights reserved.

Anode materials for electrochemical waste destruction

NASA Technical Reports Server (NTRS)

Molton, Peter M.; Clarke, Clayton

1990-01-01

Electrochemical Oxidation (ECO) offers promise as a low-temperature, atmospheric pressure method for safe destruction of hazardous organic chemical wastes in water. Anode materials tend to suffer corrosion in the intensely oxidizing environment of the ECO cell. There is a need for cheaper, more resistant materials. In this experiment, a system is described for testing anode materials, with examples of several common anodes such as stainless steel, graphite, and platinized titanium. The ECO system is simple and safe to operate and the experiment can easily be expanded in scope to study the effects of different solutions, temperatures, and organic materials.

Improved Direct Methanol Fuel Cell Stack

DOEpatents

Wilson, Mahlon S.; Ramsey, John C.

2005-03-08

A stack of direct methanol fuel cells exhibiting a circular footprint. A cathode and anode manifold, tie-bolt penetrations and tie-bolts are located within the circular footprint. Each fuel cell uses two graphite-based plates. One plate includes a cathode active area that is defined by serpentine channels connecting the inlet and outlet cathode manifold. The other plate includes an anode active area defined by serpentine channels connecting the inlet and outlet of the anode manifold, where the serpentine channels of the anode are orthogonal to the serpentine channels of the cathode. Located between the two plates is the fuel cell active region.

Natural gas anodes for aluminium electrolysis in molten fluorides.

PubMed

Haarberg, Geir Martin; Khalaghi, Babak; Mokkelbost, Tommy

2016-08-15

Industrial primary production of aluminium has been developed and improved over more than 100 years. The molten salt electrolysis process is still suffering from low energy efficiency and considerable emissions of greenhouse gases (CO2 and PFC). A new concept has been suggested where methane is supplied through the anode so that the CO2 emissions may be reduced significantly, the PFC emissions may be eliminated and the energy consumption may decrease significantly. Porous carbon anodes made from different graphite grades were studied in controlled laboratory experiments. The anode potential, the anode carbon consumption and the level of HF gas above the electrolyte were measured during electrolysis. In some cases it was found that the methane oxidation was effectively participating in the anode process.

Thermal investigation of an electrical high-current arc with porous gas-cooled anode

NASA Technical Reports Server (NTRS)

Eckert, E. R. G.; Schoeck, P. A.; Winter, E. R. F.

1984-01-01

The following guantities were measured on a high-intensity electric arc with tungsten cathode and transpiration-cooled graphite anode burning in argon: electric current and voltage, cooling gas flow rate (argon), surface temperature of the anode and of the anode holder, and temperature profile in three cross-sections of the arc are column. The last mentioned values were obtained from spectroscopic photographs. From the measured quantities, the following values were calculated: the heat flux into the anode surface, the heat loss of the anode by radiation and conduction, and the heat which was regeneratively transported by the cooling gas back into the arc space. Heat balances for the anode were also obtained. The anode losses (which are approximately 80% of the total arc power for free burning arcs) were reduced by transpiration cooling to 20%. The physical processes of the energy transfer from the arc to the anode are discussed qualitatively.

Analysis of a Li-Ion Nanobattery with Graphite Anode Using Molecular Dynamics Simulations

DOE PAGES

Ponce, Victor; Galvez-Aranda, Diego E.; Seminario, Jorge M.

2017-05-19

In this work, molecular dynamics simulations were performed of the initial charging of a Li-ion nanobattery with a graphite anode and lithium hexaflourphosphate (LiPF 6) salt dissolved in ethylene carbonate (CO 3C 2H 4) solvent as the electrolyte solution. The charging was achieved through the application of external electric fields simulating voltage sources. A variety of force fields were combined to simulate the materials of the nanobattery, including the solid electrolyte interphase, metal collectors, and insulator cover. Some of the force field parameters were estimated using ab initio methods and others were taken from the literature. We studied the behaviormore » of Li-ions traveling from cathode to anode through electrolyte solutions of concentrations 1.15 and 3.36 M. Time-dependent variables such as energy, temperature, volume, polarization, and mean square displacement are reported; a few of these variables, as well as others such as current, resistance, current density, conductivity, and resistivity are reported as a function of the external field and charging voltage. A solid electrolyte interphase (SEI) layer was also added to the model to study the mechanism behind the diffusion of the Li-ions through the SEI. As the battery is charged, the depletion of Li atoms in the cathode and their accumulation in the anode follow a linear increase of the polarizability in the solvent, until reaching a saturation point after which the charging of the battery stops, i.e., the energy provided by the external source decays to very low levels. Lastly, the nanobattery model containing the most common materials of a commercial lithium-ion battery is very useful to determine atomistic information that is difficult or too expensive to obtain experimentally; available data shows consistency with our results.« less

Carbon foam anode modified by urea and its higher electrochemical performance in marine benthic microbial fuel cell

NASA Astrophysics Data System (ADS)

Fu, Yubin; Lu, Zhikai; Zai, Xuerong; Wang, Jian

2015-08-01

Electrode materials have an important effect on the property of microbial fuel cell (MFC). Carbon foam is utilized as an anode and further modified by urea to improve its performance in marine benthic microbial fuel cell (BMFC) with higher voltage and output power. The electrochemical properties of plain carbon foam (PC) and urea-modified carbon foam (UC) are measured respectively. Results show that the UC obtains better wettability after its modification and higher anti-polarization ability than the PC. A novel phenomenon has been found that the electrical potential of the modified UC anode is nearly 100 mV lower than that of the PC, reaching -570 ±10 mV ( vs. SCE), and that it also has a much higher electron transfer kinetic activity, reaching 9399.4 mW m-2, which is 566.2-fold higher than that from plain graphite anode (PG). The fuel cell containing the UC anode has the maximum power density (256.0 mW m-2) among the three different BMFCs. Urea would enhance the bacteria biofilm formation with a more diverse microbial community and maintain more electrons, leading to a lower anodic redox potential and higher power output. The paper primarily analyzes why the electrical potential of the modified anode becomes much lower than that of others after urea modification. These results can be utilized to construct a novel BMFC with higher output power and to design the conditioner of voltage booster with a higher conversion ratio. Finally, the carbon foam with a bigger pore size would be a potential anodic material in conventional MFC.

Green synthesis of boron doped graphene and its application as high performance anode material in Li ion battery

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sahoo, Madhumita; Sreena, K.P.; Vinayan, B.P.

2015-01-15

Graphical abstract: Boron doped graphene (B-G), synthesized by simple hydrogen induced reduction technique using boric acid as boron precursor, have more uneven surface as a result of smaller bonding distance of boron compared to carbon, showed high capacity and high rate capability compared to pristine graphene as an anode material for Li ion battery application. - Abstract: The present work demonstrates a facile route for the large-scale, catalyst free, and green synthesis approach of boron doped graphene (B-G) and its use as high performance anode material for Li ion battery (LIB) application. Boron atoms were doped into graphene framework withmore » an atomic percentage of 5.93% via hydrogen induced thermal reduction technique using graphite oxide and boric acid as precursors. Various characterization techniques were used to confirm the boron doping in graphene sheets. B-G as anode material shows a discharge capacity of 548 mAh g{sup −1} at 100 mA g{sup −1} after 30th cycles. At high current density value of 1 A g{sup −1}, B-G as anode material enhances the specific capacity by about 1.7 times compared to pristine graphene. The present study shows a simplistic way of boron doping in graphene leading to an enhanced Li ion adsorption due to the change in electronic states.« less

Potassium-Based Dual Ion Battery with Dual-Graphite Electrode.

PubMed

Fan, Ling; Liu, Qian; Chen, Suhua; Lin, Kairui; Xu, Zhi; Lu, Bingan

2017-08-01

A potassium ion battery has potential applications for large scale electric energy storage systems due to the abundance and low cost of potassium resources. Dual graphite batteries, with graphite as both anode and cathode, eliminate the use of transition metal compounds and greatly lower the overall cost. Herein, combining the merits of the potassium ion battery and dual graphite battery, a potassium-based dual ion battery with dual-graphite electrode is developed. It delivers a reversible capacity of 62 mA h g -1 and medium discharge voltage of ≈3.96 V. The intercalation/deintercalation mechanism of K + and PF 6 - into/from graphite is proposed and discussed in detail, with various characterizations to support. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

CuC1 thermochemical cycle for hydrogen production

DOEpatents

Fan, Qinbai [Chicago, IL; Liu, Renxuan [Chicago, IL

2012-01-03

An electrochemical cell for producing copper having a dense graphite anode electrode and a dense graphite cathode electrode disposed in a CuCl solution. An anion exchange membrane made of poly(ethylene vinyl alcohol) and polyethylenimine cross-linked with a cross-linking agent selected from the group consisting of acetone, formaldehyde, glyoxal, glutaraldehyde, and mixtures thereof is disposed between the two electrodes.

Inspection of anode and field wires for the COMPASS drift chamber, DC5, with Environmental Scanning Electron Microscope

NASA Astrophysics Data System (ADS)

Cyuzuzo, Sonia

2014-09-01

The COMPASS experiment at CERN uses a secondary pion beam from the Super Proton Synchrotron (SPS) at CERN to explore the spin structure of nucleons. A new drift chamber, DC5, will be integrated into the COMPASS spectrometer to replace an aging straw tube detector. DC5 will detect muon pairs from Drell-Yan scattering of a pion-beam off a transversely polarized proton target. This data will be used to determine the correlation between transverse proton spin and the intrinsic transverse momentum of up-quarks inside the proton, the Sivers effect. DC5 is a large area planar drift chamber with 8 layers of anode-frames made of G10 fiberglass-epoxy. The G10 frames support printed circuit boards for soldering 20 μm diameter anode and 100 μm diameter field wires. The anode planes are sandwiched by 13 graphite coated Mylar cathode planes. To ensure a well-functioning of DC5, the wires were carefully tested. An optical inspection and a spectral analysis was performed with an Environmental Scanning Electron Microscope (ESEM) to verify the composition and dimensions and the integrity of the gold plating on the surface of these wires. The spectra of the wires were studied at 10 and 30 keV. The COMPASS experiment at CERN uses a secondary pion beam from the Super Proton Synchrotron (SPS) at CERN to explore the spin structure of nucleons. A new drift chamber, DC5, will be integrated into the COMPASS spectrometer to replace an aging straw tube detector. DC5 will detect muon pairs from Drell-Yan scattering of a pion-beam off a transversely polarized proton target. This data will be used to determine the correlation between transverse proton spin and the intrinsic transverse momentum of up-quarks inside the proton, the Sivers effect. DC5 is a large area planar drift chamber with 8 layers of anode-frames made of G10 fiberglass-epoxy. The G10 frames support printed circuit boards for soldering 20 μm diameter anode and 100 μm diameter field wires. The anode planes are sandwiched by 13 graphite coated Mylar cathode planes. To ensure a well-functioning of DC5, the wires were carefully tested. An optical inspection and a spectral analysis was performed with an Environmental Scanning Electron Microscope (ESEM) to verify the composition and dimensions and the integrity of the gold plating on the surface of these wires. The spectra of the wires were studied at 10 and 30 keV. Acknowledging NSF and UIUC.

Graphene oxide and H2 production from bioelectrochemical graphite oxidation.

PubMed

Lu, Lu; Zeng, Cuiping; Wang, Luda; Yin, Xiaobo; Jin, Song; Lu, Anhuai; Jason Ren, Zhiyong

2015-11-17

Graphene oxide (GO) is an emerging material for energy and environmental applications, but it has been primarily produced using chemical processes involving high energy consumption and hazardous chemicals. In this study, we reported a new bioelectrochemical method to produce GO from graphite under ambient conditions without chemical amendments, value-added organic compounds and high rate H2 were also produced. Compared with abiotic electrochemical electrolysis control, the microbial assisted graphite oxidation produced high rate of graphite oxide and graphene oxide (BEGO) sheets, CO2, and current at lower applied voltage. The resultant electrons are transferred to a biocathode, where H2 and organic compounds are produced by microbial reduction of protons and CO2, respectively, a process known as microbial electrosynthesis (MES). Pseudomonas is the dominant population on the anode, while abundant anaerobic solvent-producing bacteria Clostridium carboxidivorans is likely responsible for electrosynthesis on the cathode. Oxygen production through water electrolysis was not detected on the anode due to the presence of facultative and aerobic bacteria as O2 sinkers. This new method provides a sustainable route for producing graphene materials and renewable H2 at low cost, and it may stimulate a new area of research in MES.

Graphene oxide and H2 production from bioelectrochemical graphite oxidation

PubMed Central

Lu, Lu; Zeng, Cuiping; Wang, Luda; Yin, Xiaobo; Jin, Song; Lu, Anhuai; Jason Ren, Zhiyong

2015-01-01

Graphene oxide (GO) is an emerging material for energy and environmental applications, but it has been primarily produced using chemical processes involving high energy consumption and hazardous chemicals. In this study, we reported a new bioelectrochemical method to produce GO from graphite under ambient conditions without chemical amendments, value-added organic compounds and high rate H2 were also produced. Compared with abiotic electrochemical electrolysis control, the microbial assisted graphite oxidation produced high rate of graphite oxide and graphene oxide (BEGO) sheets, CO2, and current at lower applied voltage. The resultant electrons are transferred to a biocathode, where H2 and organic compounds are produced by microbial reduction of protons and CO2, respectively, a process known as microbial electrosynthesis (MES). Pseudomonas is the dominant population on the anode, while abundant anaerobic solvent-producing bacteria Clostridium carboxidivorans is likely responsible for electrosynthesis on the cathode. Oxygen production through water electrolysis was not detected on the anode due to the presence of facultative and aerobic bacteria as O2 sinkers. This new method provides a sustainable route for producing graphene materials and renewable H2 at low cost, and it may stimulate a new area of research in MES. PMID:26573014

A "Sticky" Mucin-Inspired DNA-Polysaccharide Binder for Silicon and Silicon-Graphite Blended Anodes in Lithium-Ion Batteries.

PubMed

Kim, Sunjin; Jeong, You Kyeong; Wang, Younseon; Lee, Haeshin; Choi, Jang Wook

2018-05-14

New binder concepts have lately demonstrated improvements in the cycle life of high-capacity silicon anodes. Those binder designs adopt adhesive functional groups to enhance affinity with silicon particles and 3D network conformation to secure electrode integrity. However, homogeneous distribution of silicon particles in the presence of a substantial volumetric content of carbonaceous components (i.e., conductive agent, graphite, etc.) is still difficult to achieve while the binder maintains its desired 3D network. Inspired by mucin, the amphiphilic macromolecular lubricant, secreted on the hydrophobic surface of gastrointestine to interface aqueous serous fluid, here, a renatured DNA-alginate amphiphilic binder for silicon and silicon-graphite blended electrodes is reported. Mimicking mucin's structure comprised of a hydrophobic protein backbone and hydrophilic oligosaccharide branches, the renatured DNA-alginate binder offers amphiphilicity from both components, along with a 3D fractal network structure. The DNA-alginate binder facilitates homogeneous distribution of electrode components in the electrode as well as its enhanced adhesion onto a current collector, leading to improved cyclability in both silicon and silicon-graphite blended electrodes. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Flavins contained in yeast extract are exploited for anodic electron transfer by Lactococcus lactis.

PubMed

Masuda, Masaki; Freguia, Stefano; Wang, Yung-Fu; Tsujimura, Seiya; Kano, Kenji

2010-06-01

Cyclic voltammograms of yeast extract-containing medium exhibit a clear redox peak around -0.4V vs. Ag|AgCl. Fermentative bacterium Lactococcus lactis was hereby shown to exploit this redox compound for extracellular electron transfer towards a graphite anode using glucose as an electron donor. High performance liquid chromatography revealed that this may be a flavin-type compound. The ability of L. lactis to exploit exogenous flavins for anodic glucose oxidation was confirmed by tests where flavin-type compounds were supplied to the bacterium in well defined media. Based on its mid-point potential, riboflavin can be regarded as a near-optimal mediator for microbially catalyzed anodic electron transfer. Riboflavin derivative flavin mononucleotide (FMN) was also exploited by L. lactis as a redox shuttle, unlike flavin adenine dinucleotide (FAD), possibly due to the absence of a specific transporter for the latter. The use of yeast extract in microbial fuel cell media is herein discouraged based on the related unwanted artificial addition of redox mediators which may distort experimental results. Copyright 2009 Elsevier B.V. All rights reserved.

Leaching lithium from the anode electrode materials of spent lithium-ion batteries by hydrochloric acid (HCl).

PubMed

Guo, Yang; Li, Feng; Zhu, Haochen; Li, Guangming; Huang, Juwen; He, Wenzhi

2016-05-01

Spent lithium-ion batteries (LIBs) are considered as an important secondary resource for its high contents of valuable components, such as lithium and cobalt. Currently, studies mainly focus on the recycling of cathode electrodes. There are few studies concentrating on the recovery of anode electrodes. In this work, based on the analysis result of high amount of lithium contained in the anode electrode, the acid leaching process was applied to recycle lithium from anode electrodes of spent LIBs. Hydrochloric acid was introduced as leaching reagent, and hydrogen peroxide as reducing agent. Within the range of experiment performed, hydrogen peroxide was found to have little effect on lithium leaching process. The highest leaching recovery of 99.4wt% Li was obtained at leaching temperature of 80°C, 3M hydrochloric acid and S/L ratio of 1:50g/ml for 90min. The graphite configuration with a better crystal structure obtained after the leaching process can also be recycled. Copyright © 2015 Elsevier Ltd. All rights reserved.

Computational Evaluation of Amorphous Carbon Coating for Durable Silicon Anodes for Lithium-Ion Batteries

PubMed Central

Hwang, Jeongwoon; Ihm, Jisoon; Lee, Kwang-Ryeol; Kim, Seungchul

2015-01-01

We investigate the structural, mechanical, and electronic properties of graphite-like amorphous carbon coating on bulky silicon to examine whether it can improve the durability of the silicon anodes of lithium-ion batteries using molecular dynamics simulations and ab-initio electronic structure calculations. Structural models of carbon coating are constructed using molecular dynamics simulations of atomic carbon deposition with low incident energies (1–16 eV). As the incident energy decreases, the ratio of sp2 carbons increases, that of sp3 decreases, and the carbon films become more porous. The films prepared with very low incident energy contain lithium-ion conducting channels. Also, those films are electrically conductive to supplement the poor conductivity of silicon and can restore their structure after large deformation to accommodate the volume change during the operations. As a result of this study, we suggest that graphite-like porous carbon coating on silicon will extend the lifetime of the silicon anodes of lithium-ion batteries. PMID:28347087

Adsorption and Formation of Small Na Clusters on Pristine and Double-Vacancy Graphene for Anodes of Na-Ion Batteries.

PubMed

Liang, Zhicong; Fan, Xiaofeng; Zheng, Weitao; Singh, David J

2017-05-24

Layered carbon is a likely anode material for Na-ion batteries (NIBs). Graphitic carbon has a low capacity of approximately 35 (mA h)/g due to the formation of NaC 64 . Using first-principles methods including van der Waals interactions, we analyze the adsorption of Na ions and clusters on graphene in the context of anodes. The interaction between Na ions and graphene is found to be weak. Small Na clusters are not stable on the surface of pristine graphene in the electrochemical environment of NIBs. However, we find that Na ions and clusters can be stored effectively on defected graphene that has double vacancies. In addition, the adsorption energy of small Na clusters near a double vacancy is found to decrease with increasing cluster size. With high concentrations of vacancies the capacity of Na on defective graphene is found to be as much as 10-30 times higher than that of graphitic carbon.

Computational Evaluation of Amorphous Carbon Coating for Durable Silicon Anodes for Lithium-Ion Batteries.

PubMed

Hwang, Jeongwoon; Ihm, Jisoon; Lee, Kwang-Ryeol; Kim, Seungchul

2015-10-13

We investigate the structural, mechanical, and electronic properties of graphite-like amorphous carbon coating on bulky silicon to examine whether it can improve the durability of the silicon anodes of lithium-ion batteries using molecular dynamics simulations and ab-initio electronic structure calculations. Structural models of carbon coating are constructed using molecular dynamics simulations of atomic carbon deposition with low incident energies (1-16 eV). As the incident energy decreases, the ratio of sp ² carbons increases, that of sp ³ decreases, and the carbon films become more porous. The films prepared with very low incident energy contain lithium-ion conducting channels. Also, those films are electrically conductive to supplement the poor conductivity of silicon and can restore their structure after large deformation to accommodate the volume change during the operations. As a result of this study, we suggest that graphite-like porous carbon coating on silicon will extend the lifetime of the silicon anodes of lithium-ion batteries.

Calendar aging of a graphite/LiFePO4 cell

NASA Astrophysics Data System (ADS)

Kassem, M.; Bernard, J.; Revel, R.; Pélissier, S.; Duclaud, F.; Delacourt, C.

2012-06-01

Graphite/LFP commercial cells are stored under 3 different conditions of temperature (30 °C, 45 °C, and 60 °C) and SOC (30%, 65%, and 100%) during up to 8 months. Several non-destructive electrochemical tests are performed at different storage times in order to understand calendar aging phenomena. After storage, all the cells except those stored at 30 °C exhibited capacity fade. The extent of capacity fade strongly increases with storage temperature and to a lesser extent with the state of charge. From in-depth data analysis, cyclable lithium loss was identified as the main source of capacity fade. This loss arises from side reactions taking place at the anode, e.g. solvent decomposition leading to the growth of the solid electrolyte interphase. However, the existence of reversible capacity loss also suggests the presence of side reactions occurring at the cathode, which are less prominent than those at the anode. The analyses do not show any evidence about active-material loss in the electrodes. The cells do not suffer substantial change in internal resistance. According to EIS analysis, the overall impedance increase is 70% or less.

Carbon-Encapsulated Co3O4 Nanoparticles as Anode Materials with Super Lithium Storage Performance

NASA Astrophysics Data System (ADS)

Leng, Xuning; Wei, Sufeng; Jiang, Zhonghao; Lian, Jianshe; Wang, Guoyong; Jiang, Qing

2015-11-01

A high-performance anode material for lithium storage was successfully synthesized by glucose as carbon source and cobalt nitrate as Co3O4 precursor with the assistance of sodium chloride surface as a template to reduce the carbon sheet thickness. Ultrafine Co3O4 nanoparticles were homogeneously embedded in ultrathin porous graphitic carbon in this material. The carbon sheets, which have large specific surface area, high electronic conductivity, and outstanding mechanical flexibility, are very effective to keep the stability of Co3O4 nanoparticales which has a large capacity. As a consequence, a very high reversible capacity of up to 1413 mA h g-1 at a current density of 0.1 A g-1 after 100 cycles, a high rate capability (845, 560, 461 and 345 mA h g-1 at 5, 10, 15 and 20 C, respectively, 1 C = 1 A g-1), and a superior cycling performance at an ultrahigh rate (760 mA h g-1 at 5 C after 1000 cycles) are achieved by this lithium-ion-battery anode material.

Interdigitated Eutectic Alloy Foil Anodes for Rechargeable Batteries

DOE PAGES

Kreder, III, Karl J.; Heligman, Brian T.; Manthiram, Arumugam

2017-09-19

An interdigitated eutectic alloy (IdEA) foil is presented as a framework for the development of alloy anodes with a capacity that is significantly higher than that of the traditional graphite/copper assembly. In conclusion, it is a simple, low-cost approach that can be applied to a broad range of alloy systems with various working ions such as Li, Na, or Mg.

Evaluation of selected thermal control coatings for long-life space structures

NASA Technical Reports Server (NTRS)

Teichman, Louis A.; Slemp, Wayne S.; Witte, William G., Jr.

1992-01-01

Graphite-reinforced resin matrix composites are being considered for spacecraft structural applications because of their light weight, high stiffness, and lower thermal expansion. Thin protective coatings with stable optical properties and the proper ratio of solar absorption (alpha sub s) to thermal emittance (epsilon) minimize orbital thermal extremes and protect these materials against space environment degradation. Sputtered coatings applied directly to graphite/epoxy composite surfaces and anodized coatings applied to thin aluminum foil were studied for use both as an atomic oxygen barrier and as thermal control coatings. Additional effort was made to develop nickel-based coatings which could be applied directly to composites. These coating systems were selected because their inherent tenacity made them potentially more reliable than commercial white paints for long-life space missions. Results indicate that anodized aluminum foil coatings are suitable for tubular and flat composite structures on large platforms in low Earth orbit. Anodized foil provides protection against some elements of the natural space environment (atomic oxygen, ultraviolet, and particulate radiation) and offers a broad range of tailored alpha sub s/epsilon. The foil is readily available and can be produced in large quantities, while the anodizing process is a routine commercial technique.

Binders and Hosts for High-Capacity Lithium-ion Battery Anodes

NASA Astrophysics Data System (ADS)

Dufficy, Martin Kyle

Lithium-ion batteries (LIBs) are universal electrochemical energy storage devices that have revolutionized our mobile society. Nonetheless, societal and technological advances drive consumer demand for LIBs with enhanced electrochemical performance, such as higher charge capacity and longer life, compared to conventional LIBs. One method to enhance LIB performance is to replace graphite, the industry standard anode since commercialization of LIBs in 1991, with high-charge capacity materials. Implementing high-capacity anode materials such as tin, silicon, and manganese vanadates, to LIBs presents challenges; Li-insertion is destructive to anode framework, and increasing capacity increases structural strains that pulverize anode materials and results in a short-cycle life. This thesis reports on various methods to extended the cycle life of high-capacity materials. Most of the work is conducted on nano-sized anode materials to reduce Li and electron transport pathway length (facilitating charge-transfer) and reduce strains from volume expansions (preserving anode structure). The first method involves encapsulating tin particles into a graphene-containing carbon nanofiber (CNF) matrix. The composite-CNF matrix houses tin particles to assume strains from tin-volume expansions and produces favorable surface-electrolyte chemistries for stable charge-discharge cycling. Before tin addition, graphene-containing CNFs are produced and assessed as anode materials for LIBs. Graphene addition to CNFs improves electronic and mechanical properties of CNFs. Furthermore, the 2-D nature of graphene provides Li-binding sites to enhance composite-CNF both first-cycle and high-rate capacities > 150% when compared to CNFs in the absence of graphene. With addition of Sn, we vary loadings and thermal production temperature to elucidate structure-composition relationships of tin and graphene-containing CNF electrodes that lead to increased capacity retention. Of note, electrodes containing ≤ 20 wt% tin result in small tin (metallic and tin oxide) particles (≤ 15 nm) within the composite-CNF matrix, which yield long cycle-lives; large reversible capacities of ˜ 600 mAh g-1 are observed at 0.2-C rates, while capacities of ˜ 400 mAh g-1 (double the capacity of CNFs) are observed after hundreds of cycles at 2-C rates. The second method comprises an approach to enhance the cycle life of silicon anodes. Many researchers believe that Si is the future anode material of LIBs, and Si is capable of providing a much needed boost in overall cell performance. Silicon has the highest known charge capacity at ˜ 3579 mAh g-1, nearly an order of magnitude larger than graphite (372 mAh g-1). In attempt to realize the entire capacity of Si anodes, we use binding agents to prolong cycle life. Binding agents enhance capacity retention via favorable interactions with cell components such as active materials and electrolytes. In this study, we introduce galactomannans (specifically, guar) as viable, inexpensive, biopolymer binders for Si electrodes. In attempt to elucidate the role of the binder in Si electrodes, we study guar-electrode and -electrolyte interactions that lead to electrochemical performance enhancements. We recognize that there are deficiencies in guar-silicon systems, which we address in our following approach. Notably, we develop a guar-derived binder to increase the strength and conductivity of Si-based electrodes by crosslinking guar and carbon black dispersions. The crosslinked binders, in effect, enhance electrode adhesion and hinder electrode cracking by self-healing. This study monitors gelation via rheological methods and assesses effects of crosslinking density on physical and electrochemical properties. Lastly, we consider a vacancy-induced manganese vanadate as high-capacity, high-power anodes for LIBs. Rather than assessing nanoparticles, we tailored molecular structure to enhance electrochemical performances. X-ray diffraction studies enable us to suggest a Li-insertion mechanism, where Li travels through large channels created by defects in the crystal structure. The ensuing manganese vanadate structure produces a stable framework that results in stable cycling of hundreds of cycles.

Tailored Recovery of Carbons from Waste Tires for Enhanced Performance as Anodes in Lithium-ion Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Naskar, Amit K; Bi,; Saha, Dipendu

2014-01-01

Morphologically tailored pyrolysis-recovered carbon black is utilized in lithium-ion batteries as a potential solution for adding value to waste tire-rubber-derived materials. Micronized tire rubber was digested in a hot oleum bath to yield a sulfonated rubber slurry that was then filtered, washed, and compressed into a solid cake. Carbon was recovered from the modified rubber cake by pyrolysis in a nitrogen atmosphere. The chemical pretreatment of rubber produced a carbon monolith with higher yield than that from the control (a fluffy tire-rubber-derived carbon black). The carbon monolith showed a very small volume fraction of pores of widths 3 4 nm,more » reduced specific surface area, and an ordered assembly of graphitic domains. Electrochemical studies on the recovered-carbon-based anode revealed an improved Li-ion battery performance with higher reversible capacity than that of commercial carbon materials. Anodes made with a sulfonated tire-rubber-derived carbon and a control tire-rubber-derived carbon, respectively, exhibited an initial coulombic efficiency of 80% and 45%, respectively. The reversible capacity of the cell with the sulfonated carbon as anode was 400 mAh/g after 100 cycles, with nearly 100% coulombic efficiency. Our success in producing higher performance carbon material from waste tire rubber for potential use in energy storage applications adds a new avenue to tire rubber recycling.« less

Ferric chloride-graphite intercalation compounds as anode materials for Li-ion batteries.

PubMed

Wang, Lili; Zhu, Yongchun; Guo, Cong; Zhu, Xiaobo; Liang, Jianwen; Qian, Yitai

2014-01-01

Ferric chloride-graphite intercalation compounds (FeCl3 -GICs) with stage 1 and stage 2 structures were synthesized by reacting FeCl3 and expanded graphite (EG) in air in a stainless-steel autoclave. As rechargeable Li-ion batteries, these FeCl3 -GICs exhibit high capacity, excellent cycling stability, and superior rate capability, which could be attributed to their unique intercalation features. This work may enable new possibilities for the fabrication of Li-ion batteries. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Unstable behavior of anodic arc discharge for synthesis of nanomaterials

DOE PAGES

Gershman, Sophia; Raitses, Yevgeny

2016-07-27

A short carbon arc operating with a high ablation rate of the graphite anode exhibits a combined motion of the arc and the arc attachment to the anode. A characteristic time scale of this motion is in a 10 -3 sec range. The arc exhibits a negative differential resistance before the arc motion occurs. Thermal processes in the arc plasma region interacting with the ablating anode are considered as possible causes of this unstable arc behavior. It is also hypothesized that the arc motion could potentially cause mixing of the various nanoparticles synthesized in the arc in the high ablationmore » regime.« less

Unstable behavior of anodic arc discharge for synthesis of nanomaterials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gershman, Sophia; Raitses, Yevgeny

A short carbon arc operating with a high ablation rate of the graphite anode exhibits a combined motion of the arc and the arc attachment to the anode. A characteristic time scale of this motion is in a 10 -3 sec range. The arc exhibits a negative differential resistance before the arc motion occurs. Thermal processes in the arc plasma region interacting with the ablating anode are considered as possible causes of this unstable arc behavior. It is also hypothesized that the arc motion could potentially cause mixing of the various nanoparticles synthesized in the arc in the high ablationmore » regime.« less

Co3O4 nanocrystals with exposed low-surface-energy planes anchored on chemically integrated graphitic carbon nitride-modified nitrogen-doped graphene: A high-performance anode material for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Zhang, Wenyao; Fu, Yongsheng; Wang, Xin

2018-05-01

A facile strategy to synthesize a composite composed of cubic Co3O4 nanocrystals anchored on chemically integrated g-C3N4-modified N-graphene (CN-NG) as an advanced anode material for high-performance lithium-ion batteries is reported. It is found that the morphology of the Co3O4 nanocrystals contains blunt-edge nanocubes with well-demarcated boundaries and numerous exposed low-index (1 1 1) crystallographic facets. These planes can be directly involved in the electrochemical reactions, providing rapid Li-ion transport channels for charging and discharging and thus enhancing the round-trip diffusion efficiency. On the other hand, the CN-NG support displays unusual textural features, such as superior structural stability, accessible active sites, and good electrical conductivity. The experimental results reveal that the chemical and electronic coupling of graphitic carbon nitride and nitrogen-doped graphene synergistically facilitate the anchoring of Co3O4 nanocrystals and prevents their migration. The resulting Co3O4/CN-NG composite exhibits a high specific reversible capacity of up to 1096 mAh g-1 with excellent cycling stability and rate capability. We believe that such a hybrid carbon support could open a new path for applications in electrocatalysis, sensors, supercapacitors, etc., in the near future.

Note: Arc discharge plasma source with plane segmented LaB{sub 6} cathode

DOE Office of Scientific and Technical Information (OSTI.GOV)

Akhmetov, T. D., E-mail: t.d.akhmetov@inp.nsk.su; Davydenko, V. I.; Ivanov, A. A.

2016-05-15

A plane cathode composed of close-packed hexagonal LaB{sub 6} (lanthanum hexaboride) segments is described. The 6 cm diameter circular cathode is heated by radiation from a graphite foil flat spiral. The cathode along with a hollow copper anode is used for the arc discharge plasma production in a newly developed linear plasma device. A separately powered coil located around the anode is used to change the magnetic field strength and geometry in the anode region. Different discharge regimes were realized using this coil.

Negative ion generator

DOEpatents

Stinnett, R.W.

1984-05-08

A negative ion generator is formed from a magnetically insulated transmission line having a coating of graphite on the cathode for producing negative ions and a plurality of apertures on the opposed anode for the release of negative ions. Magnetic insulation keeps electrons from flowing from the cathode to the anode. A transverse magnetic field removes electrons which do escape through the apertures from the trajectory of the negative ions. 8 figs.

Negative ion generator

DOEpatents

Stinnett, Regan W.

1984-01-01

A negative ion generator is formed from a magnetically insulated transmission line having a coating of graphite on the cathode for producing negative ions and a plurality of apertures on the opposed anode for the release of negative ions. Magnetic insulation keeps electrons from flowing from the cathode to the anode. A transverse magnetic field removes electrons which do escape through the apertures from the trajectory of the negative ions.

Structurally Defined 3D Nanographene Assemblies via Bottom-Up Chemical Synthesis for Highly Efficient Lithium Storage

DOE PAGES

Yen, Hung-Ju; Tsai, Hsinhan; Zhou, Ming; ...

2016-10-10

In this paper, functionalized 3D nanographenes with controlled electronic properties have been synthesized through a multistep organic synthesis method and are further used as promising anode materials for lithium-ion batteries, exhibiting a much increased capacity (up to 950 mAh g -1), three times higher than that of the graphite anode (372 mAh g -1).

Facile synthesis of tin dioxide-based high performance anodes for lithium ion batteries assisted by graphene gel

NASA Astrophysics Data System (ADS)

Wan, Yuanxin; Sha, Ye; Luo, Shaochuan; Deng, Weijia; Wang, Xiaoliang; Xue, Gi; Zhou, Dongshan

2015-11-01

Tin dioxide (SnO2) is an attractive material for anodes in energy storage devices, because it has four times the theoretical capacity of the prevalent anode material (graphite). The main obstacle hampers SnO2 from practical application is the pulverization problem caused by drastic volume change (∼300%) during lithium-ion insertion or extraction, which would lead to the loss of electrical conductivity, unstable solid-electrolyte interphase (SEI) formation and consequently severe capacity fading in the cycling. Here, we anchored the SnO2 nanocrystals into three dimensional graphene gel network to tackle this problem. As a result of the three dimensional (3-D) architecture, the huge volume change during cycling was tolerated by the large free space in this 3-D construction, resulting in a high capacity of 1090 mAh g-1 even after 200 cycles. What's more, at a higher current density 5 A g-1, a reversible capacity of about 491 mAh g-1 was achieved with this electrode.

Apparatus for producing diamond-like carbon flakes

NASA Technical Reports Server (NTRS)

Banks, Bruce A. (Inventor)

1986-01-01

A vacuum arc from a spot at the face of a graphite cathode to a graphite anode produces a beam of carbon ions and atoms. A carbon coating from this beam is deposited on an ion beam sputtered target to produce diamond-like carbon flakes. A graphite tube encloses the cathode, and electrical isolation is provided by an insulating sleeve. The tube forces the vacuum arc spot to be confined to the surface on the outermost end of the cathode. Without the tube the arc spot will wander to the side of the cathode. This spot movement results in low rates of carbon deposition, and the properties of the deposited flakes are more graphite-like than diamond-like.

Interpenetrated Networks between Graphitic Carbon Infilling and Ultrafine TiO2 Nanocrystals with Patterned Macroporous Structure for High-Performance Lithium Ion Batteries.

PubMed

Zheng, Wenji; Yan, Zhijun; Dai, Yan; Du, Naixu; Jiang, Xiaobin; Dai, Hailing; Li, Xiangcun; He, Gaohong

2017-06-21

Interpenetrated networks between graphitic carbon infilling and ultrafine TiO 2 nanocrystals with patterned macropores (100-200 nm) were successfully synthesized. Polypyrrole layer was conformably coated on the primary TiO 2 nanoparticles (∼8 nm) by a photosensitive reaction and was then transformed into carbon infilling in the interparticle mesopores of the TiO 2 nanoparticles. Compared to the carbon/graphene supported TiO 2 nanoparticles or carbon coated TiO 2 nanostructures, the carbon infilling would provide a conductive medium and buffer layer for volume expansion of the encapsulated TiO 2 nanoparticles, thus enhancing conductivity and cycle stability of the C-TiO 2 anode materials for lithium ion batteries (LIBs). In addition, the macropores with diameters of 100-200 nm in the C-TiO 2 anode and the mesopores in carbon infilling could improve electrolyte transportation in the electrodes and shorten the lithium ion diffusion length. The C-TiO 2 electrode can provide a large capacity of 192.8 mA h g -1 after 100 cycles at 200 mA g -1 , which is higher than those of the pure macroporous TiO 2 electrode (144.8 mA h g -1 ), C-TiO 2 composite electrode without macroporous structure (128 mA h g -1 ), and most of the TiO 2 based electrodes in the literature. Importantly, the C-TiO 2 electrode exhibits a high rate performance and still delivers a high capacity of ∼140 mA h g -1 after 1000 cycles at 1000 mA g -1 (∼5.88 C), suggesting good lithium storage properties of the macroporous C-TiO 2 composites with high capacity, cycle stability, and rate capability. This work would be instructive for designing hierarchical porous TiO 2 based anodes for high-performance LIBs.

Co-solvents with high coulombic efficiency in propylene carbonate based electrolytes

DOEpatents

Liu, Gao; Zhao, Hui; Park, Sang-Jae

2017-06-27

A homologous series of cyclic carbonate or propylene carbonate (PC) analogue solvents with increasing length of linear alkyl substitutes were synthesized and used as co-solvents with PC for graphite based lithium ion half cells. A graphite anode reaches a capacity around 310 mAh/g in PC and its analogue co-solvents with 99.95% Coulombic efficiency. Cyclic carbonate co-solvents with longer alkyl chains are able to prevent exfoliation of graphite when used as co-solvents with PC. The cyclic carbonate co-solvents of PC compete for solvation of Li ion with PC solvent, delaying PC co-intercalation. Reduction products of PC on graphite surfaces via single-electron path form a stable Solid Electrolyte Interphase (SEI), which allows the reversible cycling of graphite.

Hierarchical Porous Intercalation-Type V2 O3 as High-Performance Anode Materials for Li-Ion Batteries.

PubMed

Liu, Pengcheng; Zhu, Kongjun; Xu, Yuan; Bian, Kan; Wang, Jing; Tai, Guo'an; Gao, Yanfeng; Luo, Hongjie; Lu, Li; Liu, Jinsong

2017-06-01

As intercalation-type anode materials for Li-ion batteries (LIBs), the commercially used graphite and Li 4 Ti 5 O 12 exhibit good cycling and rate properties, but their theoretical specific capacities are too low to meet the ever-growing demands of high-energy applications such as electric vehicles. Therefore, the development of new intercalation-type anode materials with larger capacity is very desirable. Herein, we design and synthesize novel 3 D hierarchical porous V 2 O 3 @C micro/nanostructures consisting of crumpled nanosheets, through self-reduction under annealing from the structurally similar VO 2 (B)@C precursors without the addition of any other reducing reagent or gas. Excitingly, it is found for the first time through ex situ XRD technology that V 2 O 3 is a new, promising intercalation-type anode material for LIBs with a high capacity. V 2 O 3 @C micro/nanostructures can deliver a large capacity of 732 mAh g -1 without capacity loss at 100 mA g -1 even after 136 cycles, as well as exhibiting excellent cycling and rate performances. The application of V 2 O 3 for Na-ion batteries (NIBs) is elaborated for the first time, and excitingly, it is found that V 2 O 3 @C micro/nanostructures may be promising anode materials for NIBs. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of Olive-Like Nitrogen-Doped Carbon with Embedded Ge Nanoparticles for Ultrahigh Stable Lithium Battery Anodes.

PubMed

Ma, Xiaomei; Zhou, Yongning; Chen, Min; Wu, Limin

2017-05-01

The development of environment-friendly and high-performance carbon materials for energy applications has remained a great challenge. Here, a novel and facile method for synthesis of olive-like nitrogen-doped carbon embedded with germanium (Ge) nanoparticles using widespread and nontoxic dopamine as carbon and nitrogen precursors is demonstrated, especially by understanding the tendency of pure GeO 2 nanoparticles forming ellipsoidal aggregation, and the chelating reaction of the catechol structure in dopamine with metal ions. The as-synthesized Ge/N-C composites show an olive-like porous carbon structure with a loading weight of as high as 68.5% Ge nanoparticles. A lithium ion battery using Ge/N-C as the anode shows 1042 mAh g -1 charge capacity after 2000 cycles (125 d) charge/discharge at C/2 (1C = 1600 mA g -1 ) with a capacity maintaining efficiency of 99.6%, significantly exceeding those of the previously reported Ge/C-based anode materials. This prominent cyclic charge/discharge performance of the Ge/N-C anode is attributed to the well-dispersed Ge nanoparticles in graphitic N-doped carbon matrix, which facilitates high rates (0.5-15 C) of charge/discharge and increases the anode structure integrity. The synthesis strategy presented here may be a very promising approach to prepare a series of active nanoparticle-carbon hybrid materials with nitrogen doping for more and important applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Recent Progress in Graphite Intercalation Compounds for Rechargeable Metal (Li, Na, K, Al)-Ion Batteries.

PubMed

Xu, Jiantie; Dou, Yuhai; Wei, Zengxi; Ma, Jianmin; Deng, Yonghong; Li, Yutao; Liu, Huakun; Dou, Shixue

2017-10-01

Lithium-ion batteries (LIBs) with higher energy density are very necessary to meet the increasing demand for devices with better performance. With the commercial success of lithiated graphite, other graphite intercalation compounds (GICs) have also been intensively reported, not only for LIBs, but also for other metal (Na, K, Al) ion batteries. In this Progress Report, we briefly review the application of GICs as anodes and cathodes in metal (Li, Na, K, Al) ion batteries. After a brief introduction on the development history of GICs, the electrochemistry of cationic GICs and anionic GICs is summarized. We further briefly summarize the use of cationic GICs and anionic GICs in alkali ion batteries and the use of anionic GICs in aluminium-ion batteries. Finally, we reach some conclusions on the drawbacks, major progress, emerging challenges, and some perspectives on the development of GICs for metal (Li, Na, K, Al) ion batteries. Further development of GICs for metal (Li, Na, K, Al) ion batteries is not only a strong supplement to the commercialized success of lithiated-graphite for LIBs, but also an effective strategy to develop diverse high-energy batteries for stationary energy storage in the future.

Recent Progress in Graphite Intercalation Compounds for Rechargeable Metal (Li, Na, K, Al)‐Ion Batteries

PubMed Central

Xu, Jiantie; Dou, Yuhai; Wei, Zengxi; Li, Yutao; Liu, Huakun; Dou, Shixue

2017-01-01

Abstract Lithium‐ion batteries (LIBs) with higher energy density are very necessary to meet the increasing demand for devices with better performance. With the commercial success of lithiated graphite, other graphite intercalation compounds (GICs) have also been intensively reported, not only for LIBs, but also for other metal (Na, K, Al) ion batteries. In this Progress Report, we briefly review the application of GICs as anodes and cathodes in metal (Li, Na, K, Al) ion batteries. After a brief introduction on the development history of GICs, the electrochemistry of cationic GICs and anionic GICs is summarized. We further briefly summarize the use of cationic GICs and anionic GICs in alkali ion batteries and the use of anionic GICs in aluminium‐ion batteries. Finally, we reach some conclusions on the drawbacks, major progress, emerging challenges, and some perspectives on the development of GICs for metal (Li, Na, K, Al) ion batteries. Further development of GICs for metal (Li, Na, K, Al) ion batteries is not only a strong supplement to the commercialized success of lithiated‐graphite for LIBs, but also an effective strategy to develop diverse high‐energy batteries for stationary energy storage in the future. PMID:29051856

Capacity fade in high energy silicon-graphite electrodes for lithium-ion batteries

DOE PAGES

Dose, W. M.; Piernas-Munoz, M. J.; Maroni, V. A.; ...

2018-02-09

A silicon-graphite blended anode is paired with a high capacity LiFePO 4 reference/counter electrode to track irreversibility and lithium inventory. The LiFePO 4 electrode provides a reliable, flat potential for dQ dV -1 analysis of Li xSi and Li xC electrochemical reactions. We can relate this electrochemistry to the morphological and physical changes taking place.

Capacity fade in high energy silicon-graphite electrodes for lithium-ion batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dose, W. M.; Piernas-Munoz, M. J.; Maroni, V. A.

A silicon-graphite blended anode is paired with a high capacity LiFePO 4 reference/counter electrode to track irreversibility and lithium inventory. The LiFePO 4 electrode provides a reliable, flat potential for dQ dV -1 analysis of Li xSi and Li xC electrochemical reactions. We can relate this electrochemistry to the morphological and physical changes taking place.

Improved anode materials for lithium-ion batteries comprise non-covalently bonded graphene and silicon nanoparticles

NASA Astrophysics Data System (ADS)

Ye, Yun-Sheng; Xie, Xiao-Lin; Rick, John; Chang, Feng-Chih; Hwang, Bing-Joe

2014-02-01

Si, when compared to conventional graphite, offers an order-of-magnitude improvement as a high capacity anode material for Li-ion batteries. Despite significant advances in nanostructured Si-based anodes, the formation of stable Si anodes remains a challenge, due to the significant volume changes that occur during lithiation and delithiation. Si/graphene composites, with graphene sheets and Si nanoparticles bound in a dispersion obtained by a self-assembly technique using non-covalent electrostatic attraction (following thermal processing to remove residual organic material) are used to prepare Si-based anodes for use in Li-ion batteries. A mesoporous structure, obtained by further thermal processing is able to accommodate large Si nanoparticle volume changes during cycling, thereby facilitating Li-ion diffusion within the electrode. Morphological analysis showed that Si nanoparticles are homogeneously distributed on the graphene sheets, which is thought to account for the excellent electrochemical performance of the resulting Si/graphene composite. A composite containing Si 67.3 wt% exhibits a greatly improved capacity and cycling stability in comparison with bare Si in combination with the thermal reduction of a simple mixture of graphene oxide and Si nanoparticles without electrostatic attraction (Si content = 64.6 wt%; capacity of 512 mAh g-1 in 40th cycle).

Analysis of carbon fiber brush loading in anodes on startup and performance of microbial fuel cells

NASA Astrophysics Data System (ADS)

Hutchinson, Adam J.; Tokash, Justin C.; Logan, Bruce E.

Flat carbon anodes placed near a cathode in a microbial fuel cell (MFC) are adversely affected by oxygen crossover, but graphite fiber brush anodes placed near the cathode produce high power densities. The impact of the brush size and electrode spacing was examined by varying the distance of the brush end from the cathode and solution conductivity in multiple MFCs. The startup time was increased from 8 ± 1 days with full brushes (all buffer concentrations) to 13 days (50 mM), 14 days (25 mM) and 21 days (8 mM) when 75% of the brush anode was removed. When MFCs were all first acclimated with a full brush, up to 65% of the brush material could be removed without appreciably altering maximum power. Electrochemical impedance spectroscopy (EIS) showed that the main source of internal resistance (IR) was diffusion resistance, which together with solution resistance reached 100 Ω. The IR using EIS compared well with that obtained using the polarization data slope method, indicating no major components of IR were missed. These results show that using full brush anodes avoids adverse effects of oxygen crossover during startup, although brushes are much larger than needed to sustain high power.

Using live algae at the anode of a microbial fuel cell to generate electricity.

PubMed

Xu, Chang; Poon, Karen; Choi, Martin M F; Wang, Ruihua

2015-10-01

Live green microalgae Chlorella pyrenoidosa was introduced in the anode of a microbial fuel cell (MFC) to act as an electron donor. By controlling the oxygen content, light intensity, and algal cell density at the anode, microalgae would generate electricity without requiring externally added substrates. Two models of algal microbial fuel cells (MFCs) were constructed with graphite/carbon electrodes and no mediator. Model 1 algal MFC has live microalgae grown at the anode and potassium ferricyanide at the cathode, while model 2 algal MFC had live microalgae in both the anode and cathode in different growth conditions. Results indicated that a higher current produced in model 1 algal MFC was obtained at low light intensity of 2500 lx and algal cell density of 5 × 10(6) cells/ml, in which high algal density would limit the electricity generation, probably by increasing oxygen level and mass transfer problem. The maximum power density per unit anode volume obtained in model 1 algal MFC was relatively high at 6030 mW/m(2), while the maximum power density at 30.15 mW/m(2) was comparable with that of previous reported bacteria-driven MFC with graphite/carbon electrodes. A much smaller power density at 2.5 mW/m(2) was observed in model 2 algal MFC. Increasing the algal cell permeability by 4-nitroaniline would increase the open circuit voltage, while the mitochondrial acting and proton leak promoting agents resveratrol and 2,4-dinitrophenol would increase the electric current production in algal MFC.

Structural and thermal stabilities of layered Li(Ni 1/3Co 1/3Mn 1/3)O 2 materials in 18650 high power batteries

NASA Astrophysics Data System (ADS)

He, Yan-Bing; Ning, Feng; Yang, Quan-Hong; Song, Quan-Sheng; Li, Baohua; Su, Fangyuan; Du, Hongda; Tang, Zhi-Yuan; Kang, Feiyu

The structural and thermal stabilities of the layered Li(Ni 1/3Co 1/3Mn 1/3)O 2 cathode materials under high rate cycling and abusive conditions are investigated using the commercial 18650 Li(Ni 1/3Co 1/3Mn 1/3)O 2/graphite high power batteries. The Li(Ni 1/3Co 1/3Mn 1/3)O 2 materials maintain their layered structure even when the power batteries are subjected to 200 cycles with 10 C discharge rate at temperatures of 25 and 50 °C, whereas their microstructure undergoes obvious distortion, which leads to the relatively poor cycling performance of power batteries at high charge/discharge rates and working temperature. Under abusive conditions, the increase in the battery temperature during overcharge is attributed to both the reactions of electrolyte solvents with overcharged graphite anode and Li(Ni 1/3Co 1/3Mn 1/3)O 2 cathode and the Joule heat that results from the great increase in the total resistance (R cell) of batteries. The reactions of fully charged Li(Ni 1/3Co 1/3Mn 1/3)O 2 cathodes and graphite anodes with electrolyte cannot be activated during short current test in the fully charged batteries. However, these reactions occur at around 140 °C in the fully charged batteries during oven test, which is much lower than the temperature of about 240 °C required for the reactions outside batteries.

The Role of Dissolved Gas in Ionic Liquid Electrolytes for Secondary Lithium Metal Batteries

DTIC Science & Technology

2013-01-07

devices use lithium-ion batteries comprised of a graphite anode and metal oxide cathode . Lithium, being the third-lightest element, is already synonymous...support shuttling lithium ions (battery cycling) such as the separator, electrolyte, and cathode and anode superstructures contribute most of the...ability of electro-deposit lithium non-dendritically. When lithium is electrodeposited , as during battery charging, it tends to form needle-like

New insights into pre-lithiation kinetics of graphite anodes via nuclear magnetic resonance spectroscopy

NASA Astrophysics Data System (ADS)

Holtstiege, Florian; Schmuch, Richard; Winter, Martin; Brunklaus, Gunther; Placke, Tobias

2018-02-01

Pre-lithiation of anode materials can be an effective method to compensate active lithium loss which mainly occurs in the first few cycles of a lithium ion battery (LIB), due to electrolyte decomposition and solid electrolyte interphase (SEI) formation at the surface of the anode. There are many different pre-lithiation methods, whereas pre-lithiation using metallic lithium constitutes the most convenient and widely utilized lab procedure in literature. In this work, for the first time, solid state nuclear magnetic resonance spectroscopy (NMR) is applied to monitor the reaction kinetics of the pre-lithiation process of graphite with lithium. Based on static 7Li NMR, we can directly observe both the dissolution of lithium metal and parallel formation of LiCx species in the obtained NMR spectra with time. It is also shown that the degree of pre-lithiation as well as distribution of lithium metal on the electrode surface have a strong impact on the reaction kinetics of the pre-lithiation process and on the remaining amount of lithium metal. Overall, our findings are highly important for further optimization of pre-lithiation methods for LIB anode materials, both in terms of optimized pre-lithiation time and appropriate amounts of lithium metal.

Fabrication of Ti substrate grain dependent C/TiO2 composites through carbothermal treatment of anodic TiO2.

PubMed

Rüdiger, Celine; Favaro, Marco; Valero-Vidal, Carlos; Calvillo, Laura; Bozzolo, Nathalie; Jacomet, Suzanne; Hejny, Clivia; Gregoratti, Luca; Amati, Matteo; Agnoli, Stefano; Granozzi, Gaetano; Kunze-Liebhäuser, Julia

2016-04-07

Composite materials of titania and graphitic carbon, and their optimized synthesis are highly interesting for application in sustainable energy conversion and storage. We report on planar C/TiO2 composite films that are prepared on a polycrystalline titanium substrate by carbothermal treatment of compact anodic TiO2 with acetylene. This thin film material allows for the study of functional properties of C/TiO2 as a function of chemical composition and structure. The chemical and structural properties of the composite on top of individual Ti substrate grains are examined by scanning photoelectron microscopy and micro-Raman spectroscopy. Through comparison of these data with electron backscatter diffraction, it is found that the amount of generated carbon and the grade of anodic film crystallinity correlate with the crystallographic orientation of the Ti substrate grains. On top of Ti grains with ∼(0001) orientations the anodic TiO2 exhibits the highest grade of crystallinity, and the composite contains the highest fraction of graphitic carbon compared to Ti grains with other orientations. This indirect effect of the Ti substrate grain orientation yields new insights into the activity of TiO2 towards the decomposition of carbon precursors.

Cycling capacity recovery effect: A coulombic efficiency and post-mortem study

NASA Astrophysics Data System (ADS)

Wilhelm, Jörn; Seidlmayer, Stefan; Keil, Peter; Schuster, Jörg; Kriele, Armin; Gilles, Ralph; Jossen, Andreas

2017-10-01

The analysis of lithium-ion battery aging relies on correct differentiation between irreversible and reversible capacity changes. Anode overhang regions have been observed to influence Coulombic Efficiency (CE) measurements through lithium diffusion into and out of these areas, complicating precise capacity determination. This work presents an analysis of the extent of graphite anode overhang lithiation after calendar storage by means of local X-ray diffraction (XRD), CE measurements, and color change analysis. We found LiC12 lithiation of the anode overhang area after 20 month storage at 40 °C at high state of charge (SoC) and partial lithiation (LiC18) at medium SoC storage at 40 °C and 25 °C. Graphite color changes in the overhang areas are observed and consistent with the state of lithiation measured by XRD. Coulombic efficiencies greater than unity and increasing capacity during 1200 h of cycling are detected for high SoC storage cells. The capacity difference between high and low storage SoC batteries decreases by up to 40 mAh (3.6% of nominal capacity) after cycling compared to tests directly after storage. Consequently, the size of the anode overhang areas as well as the battery storage temperature and duration need to be considered in CE analysis and state of health assessment.

Enhancing substrate utilization and power production of a microbial fuel cell with nitrogen-doped carbon aerogel as cathode catalyst.

PubMed

Tardy, Gábor Márk; Lóránt, Bálint; Lóka, Máté; Nagy, Balázs; László, Krisztina

2017-07-01

Catalytic efficiency of a nitrogen-doped, mesoporous carbon aerogel cathode catalyst was investigated in a two-chambered microbial fuel cell (MFC) applying graphite felt as base material for cathode and anode, utilizing peptone as carbon source. This mesoporous carbon aerogel containing catalyst layer on the cathode increased the maximum power density normalized to the anode volume to 2.7 times higher compared to the maximum power density obtained applying graphite felt cathode without the catalyst layer. At high (2 and 3) cathode/anode volume ratios, maximum power density exceeded 40 W m -3 . At the same time, current density and specific substrate utilization rate increased by 58% resulting in 31.9 A m -3 and 18.8 g COD m -3  h -1 , respectively (normalized to anode volume). Besides the increase of the power and the rate of biodegradation, the investigated catalyst decreased the internal resistance from the range of 450-600 to 350-370 Ω. Although Pt/C catalyst proved to be more efficient, a considerable decrease in the material costs might be achieved by substituting it with nitrogen-doped carbon aerogel in MFCs. Such cathode still displays enhanced catalytic effect.

Bacteria-Affinity 3D Macroporous Graphene/MWCNTs/Fe3O4 Foams for High-Performance Microbial Fuel Cells.

PubMed

Song, Rong-Bin; Zhao, Cui-E; Jiang, Li-Ping; Abdel-Halim, Essam Sayed; Zhang, Jian-Rong; Zhu, Jun-Jie

2016-06-29

Promoting the performance of microbial fuel cells (MFCs) relies heavily on the structure design and composition tailoring of electrode materials. In this work, three-dimensional (3D) macroporous graphene foams incorporated with intercalated spacer of multiwalled carbon nanotubes (MWCNTs) and bacterial anchor of Fe3O4 nanospheres (named as G/MWCNTs/Fe3O4 foams) were first synthesized and used as anodes for Shewanella-inoculated microbial fuel cells (MFCs). Thanks to the macroporous structure of 3D graphene foams, the expanded electrode surface by MWCNTs spacing, as well as the high affinity of Fe3O4 nanospheres toward Shewanella oneidensis MR-1, the anode exhibited high bacterial loading capability. In addition to spacing graphene nanosheets for accommodating bacterial cells, MWCNTs paved a smoother way for electron transport in the electrode substrate of MFCs. Meanwhile, the embedded bioaffinity Fe3O4 nanospheres capable of preserving the bacterial metabolic activity provided guarantee for the long-term durability of the MFCs. With these merits, the constructed MFC possessed significantly higher power output and stronger stability than that with conventional graphite rod anode.

Electrospun core-shell fibers for robust silicon nanoparticle-based lithium ion battery anodes.

PubMed

Hwang, Tae Hoon; Lee, Yong Min; Kong, Byung-Seon; Seo, Jin-Seok; Choi, Jang Wook

2012-02-08

Because of its unprecedented theoretical capacity near 4000 mAh/g, which is approximately 10-fold larger compared to those of the current commercial graphite anodes, silicon has been the most promising anode for lithium ion batteries, particularly targeting large-scale energy storage applications including electrical vehicles and utility grids. Nevertheless, Si suffers from its short cycle life as well as the limitation for scalable electrode fabrication. Herein, we develop an electrospinning process to produce core-shell fiber electrodes using a dual nozzle in a scalable manner. In the core-shell fibers, commercially available nanoparticles in the core are wrapped by the carbon shell. The unique core-shell structure resolves various issues of Si anode operations, such as pulverization, vulnerable contacts between Si and carbon conductors, and an unstable sold-electrolyte interphase, thereby exhibiting outstanding cell performance: a gravimetric capacity as high as 1384 mAh/g, a 5 min discharging rate capability while retaining 721 mAh/g, and cycle life of 300 cycles with almost no capacity loss. The electrospun core-shell one-dimensional fibers suggest a new design principle for robust and scalable lithium battery electrodes suffering from volume expansion. © 2011 American Chemical Society

How much does size really matter? Exploring the limits of graphene as Li ion battery anode material

NASA Astrophysics Data System (ADS)

Sun, H.; Varzi, A.; Pellegrini, V.; Dinh, D. A.; Raccichini, R.; Del Rio-Castillo, A. E.; Prato, M.; Colombo, M.; Cingolani, R.; Scrosati, B.; Passerini, S.; Bonaccorso, F.

2017-02-01

We unravel the role of flake dimensionality on the lithiation/de-lithiation processes and electrochemical performance of anodes based on few-(FLG) and multi-layer graphene (MLG) flakes prepared by liquid phase exfoliation (LPE) of pristine graphite. The flakes are sorted by lateral size (from 380 to 75 nm) and thickness from 20 (MLG) to 2 nm (FLG) exploiting a sedimentation-based separation in centrifugal field and, finally, deposited onto Cu disks for the realization of four binder-free anodes. The electrochemical results show that decreasing lateral size and thickness leads to an increase of the initial specific capacity from ≈590 to ≈1270mAhg-1. However, an increasing irreversible capacity is also associated to the reduction of flakes' size. We find, in addition, that the preferential Li ions storage by adsorption rather than intercalation in small lateral size (<100 nm) FLG flakes has a detrimental effect on the average de-lithiation voltage, resulting on low voltage efficiency of these anodes. We believe that the results reported in this work, provide the guidelines for the practical exploitation of graphene-based electrodes.

Homogeneous growth of TiO2-based nanotubes on nitrogen-doped reduced graphene oxide and its enhanced performance as a Li-ion battery anode.

PubMed

Mehraeen, Shayan; Taşdemir, Adnan; Gürsel, Selmiye Alkan; Yürüm, Alp

2018-06-22

The pursuit of a promising replacement candidate for graphite as a Li-ion battery anode, which can satisfy both engineering criteria and market needs has been the target of researchers for more than two decades. In this work, we have investigated the synergistic effect of nitrogen-doped reduced graphene oxide (NrGO) and nanotubular TiO 2 to achieve high rate capabilities with high discharge capacities through a simple, one-step and scalable method. First, nanotubes of hydrogen titanate were hydrothermally grown on the surface of NrGO sheets, and then converted to a mixed phase of TiO 2 -B and anatase (TB) by thermal annealing. Specific surface area, thermal gravimetric, structural and morphological characterizations were performed on the synthesized product. Electrochemical properties were investigated by cyclic voltammetry and cyclic charge/discharge tests. The prepared anode showed high discharge capacity of 150 mAh g -1 at 1 C current rate after 50 cycles. The promising capacity of synthesized NrGO-TB was attributed to the unique and novel microstructure of NrGO-TB in which long nanotubes of TiO 2 have been grown on the surface of NrGO sheets. Such architecture synergistically reduces the solid-state diffusion distance of Li + and increases the electronic conductivity of the anode.

Homogeneous growth of TiO2-based nanotubes on nitrogen-doped reduced graphene oxide and its enhanced performance as a Li-ion battery anode

NASA Astrophysics Data System (ADS)

Mehraeen, Shayan; Taşdemir, Adnan; Alkan Gürsel, Selmiye; Yürüm, Alp

2018-06-01

The pursuit of a promising replacement candidate for graphite as a Li-ion battery anode, which can satisfy both engineering criteria and market needs has been the target of researchers for more than two decades. In this work, we have investigated the synergistic effect of nitrogen-doped reduced graphene oxide (NrGO) and nanotubular TiO2 to achieve high rate capabilities with high discharge capacities through a simple, one-step and scalable method. First, nanotubes of hydrogen titanate were hydrothermally grown on the surface of NrGO sheets, and then converted to a mixed phase of TiO2-B and anatase (TB) by thermal annealing. Specific surface area, thermal gravimetric, structural and morphological characterizations were performed on the synthesized product. Electrochemical properties were investigated by cyclic voltammetry and cyclic charge/discharge tests. The prepared anode showed high discharge capacity of 150 mAh g‑1 at 1 C current rate after 50 cycles. The promising capacity of synthesized NrGO-TB was attributed to the unique and novel microstructure of NrGO-TB in which long nanotubes of TiO2 have been grown on the surface of NrGO sheets. Such architecture synergistically reduces the solid-state diffusion distance of Li+ and increases the electronic conductivity of the anode.

Carbon dioxide as a green carbon source for the synthesis of carbon cages encapsulating porous silicon as high performance lithium-ion battery anodes.

PubMed

Zhang, Yaguang; Du, Ning; Chen, Yifan; Lin, Yangfan; Jiang, Jinwei; He, Yuanhong; Lei, Yu; Yang, Deren

2018-03-28

Si/C composite is one of the most promising candidate materials for next-generation lithium-ion battery anodes. Herein, we demonstrate the novel structure of carbon cages encapsulating porous Si synthesized by the reaction between magnesium silicide (Mg 2 Si) and carbon dioxide (CO 2 ) and subsequent acid washing. Benefitting from the in situ deposition through magnesiothermic reduction of CO 2 , the carbon cage seals the inner Si completely and shows higher graphitization than that obtained from the decomposition of acetylene. After removing MgO, pores are created, which can accommodate the volume change of the Si anode during the charge/discharge process. As the anode material for lithium-ion batteries, the porous Si/C electrode shows a charge capacity of ∼1124 mA h g -1 after 100 cycles with 86.4% capacity retention at the current density of 0.4 A g -1 . When the current density increases to 1.6 and 3.2 A g -1 , the capacity can still be maintained at ∼860 and ∼460 mA h g -1 , respectively. The prominent cycling and rate performance is contributed by the built-in space for Si expansion, static carbon cages that prevent penetration of electrolyte and stabilize the solid electrolyte interface (SEI) outside, and fast charge transport by the novel structure.

Electrochemical performance of Fe3O4 micro flower as anode for lithium ion batteries

NASA Astrophysics Data System (ADS)

Noerochim, Lukman; Anggara, Dika; Susanti, Diah; Subhan, Achmad; Sudaryanto

2018-04-01

Graphite is generally employed in commercial lithium ion batteries which has a specific capacity of 372 mAh/g. In this study, graphite is replaced with carbon-coated magnetite (Fe3O4/C) which has large theoretical specific capacity of 926 mAh/g, environmental friendly, and low cost production. The synthesis of Fe3O4/C is carried out by hydrothermal method with reacting FeCl3 and hexamethylenetetramine (HMT) at temperature variation of 160, 170 and 180°C. The following process is heated by calcination at temperature variations 450, 500 and 550°C. XRD and SEM results show that the as-prepared Fe3O4/C powder has a single phase of Fe3O4 and morphology micro-flowers like with size between 700 nm - 3 µm. CV test results show redox reaction occurs in the voltage range between 0.21-0.85 V and 1.68-1.81 V. The highest specific discharge capacity is obtained 644 mAh/g for specimen with temperature hydrothermal of 170°C and temperature calcination of 550°C. This result shows that Fe3O4/C has a high potential as anode material for lithium ion battery.

Fe{sub 2}O{sub 3} nanowires on HOPG as precursor of new carbon-based anode for high-capacity lithium ion batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Angelucci, Marco; Frau, Eleonora; Betti, Maria Grazia

Iron Oxides nanostructures are very promising systems for new generation of anode material for Lithium-Ion batteries because of their high capacity associated to their surface area. A core-level photoemission study of Fe{sub 2}O{sub 3} nanowires deposited on highly-oriented pyrolitic graphite (HOPG) under Li exposure is presented. The Fe-2p, Fe-3p, and Li-1s core-level lineshape evolution upon Li exposure in ultra-high-vacuum conditions clearly brings to light the Fe ion reduction from fully trivalent to prevalently divalent at saturation. Furthermore, the graphite substrate allows allocation of a large amount of Li ions surrounding the iron-oxide nanowires, opening a new scenario towards the usemore » of graphene for improving the ionic charge exchange.« less

Electrochemical characterisation of CaCl2 deficient LiCl-KCl-CaCl2 eutectic melt and electro-deoxidation of solid UO2

NASA Astrophysics Data System (ADS)

Sri Maha Vishnu, D.; Sanil, N.; Mohandas, K. S.; Nagarajan, K.

2016-03-01

The CaCl2 deficient ternary eutectic melt LiCl-KCl-CaCl2 (50.5: 44.2: 5.3 mol %) was electrochemically characterised by cyclic voltammetry and polarization techniques in the context of its probable use as the electrolyte in the electrochemical reduction of solid UO2 to uranium metal. Tungsten (cathodic polarization) and graphite (anodic polarization) working electrodes were used in these studies carried out in the temperature range 623 K-923 K. The cathodic limit of the melt was observed to be set by the deposition of Ca2+ ions followed by Li+ ions on the tungsten electrode and the anodic limit by oxidation of chloride ions on the graphite electrode (chlorine evolution). The difference between the onset potential of deposition of Ca2+ and Li+ was found to be 0.241 V at a scan rate of 20 mV/s at 623 K and the difference decreased with increase in temperature and vanished at 923 K. Polarization measurements with stainless steel (SS) cathode and graphite anode at 673 K showed the possibility of low-energy reactions occurring on the UO2 electrode in the melt. UO2 pellets were cathodically polarized at 3.9 V for 25 h to test the feasibility of electro-reduction to uranium in the melt. The surface of the pellets was found reduced to U metal.

Improving the Performance at Elevated Temperature of High Voltage Graphite/LiNi 0.5Mn 1.5O 4 Cells with Added Lithium Catechol Dimethyl Borate

DOE PAGES

Dong, Yingnan; Demeaux, Julien; Zhang, Yuzi; ...

2016-12-13

Performance of LiNi 0.5Mn 1.5O 4/graphite cells cycled to 4.8 V at 55°C with the 1.2 M LiPF 6 in EC/EMC (3/7, STD electrolyte) with and without added lithium catechol dimethyl borate (LiCDMB) has been investigated. The incorporation of 0.5 wt% LiCDMB to the STD electrolyte results in an improved capacity retention and coulombic efficiency upon cycling at 55°C. Ex-situ analysis of the electrode surfaces via a combination of SEM, TEM, and XPS reveals that oxidation of LiCDMB at high potential results in the deposition of a passivation layer on the electrode surface, preventing transition metal ion dissolution from themore » cathode and subsequent deposition on the anode. NMR investigations of the bulk electrolyte stored at 85°C reveals that added LiCDMB prevents the thermal decomposition of LiPF 6.« less

Improving the Performance at Elevated Temperature of High Voltage Graphite/LiNi 0.5Mn 1.5O 4 Cells with Added Lithium Catechol Dimethyl Borate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dong, Yingnan; Demeaux, Julien; Zhang, Yuzi

Performance of LiNi 0.5Mn 1.5O 4/graphite cells cycled to 4.8 V at 55°C with the 1.2 M LiPF 6 in EC/EMC (3/7, STD electrolyte) with and without added lithium catechol dimethyl borate (LiCDMB) has been investigated. The incorporation of 0.5 wt% LiCDMB to the STD electrolyte results in an improved capacity retention and coulombic efficiency upon cycling at 55°C. Ex-situ analysis of the electrode surfaces via a combination of SEM, TEM, and XPS reveals that oxidation of LiCDMB at high potential results in the deposition of a passivation layer on the electrode surface, preventing transition metal ion dissolution from themore » cathode and subsequent deposition on the anode. NMR investigations of the bulk electrolyte stored at 85°C reveals that added LiCDMB prevents the thermal decomposition of LiPF 6.« less

Electrostatic spray deposition of porous Fe 2O 3 thin films as anode material with improved electrochemical performance for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Wang, L.; Xu, H. W.; Chen, P. C.; Zhang, D. W.; Ding, C. X.; Chen, C. H.

Iron oxide materials are attractive anode materials for lithium-ion batteries for their high capacity and low cost compared with graphite and most of other transition metal oxides. Porous carbon-free α-Fe 2O 3 films with two types of pore size distribution were prepared by electrostatic spray deposition, and they were characterized by X-ray diffraction, scanning electron microscopy and X-ray absorption near-edge spectroscopy. The 200 °C-deposited thin film exhibits a high reversible capacity of up to 1080 mAh g -1, while the initial capacity loss is at a remarkable low level (19.8%). Besides, the energy efficiency and energy specific average potential (E av) of the Fe 2O 3 films during charge/discharge process were also investigated. The results indicate that the porous α-Fe 2O 3 films have significantly higher energy density than Li 4Ti 5O 12 while it has a similar E av of about 1.5 V. Due to the porous structure that can buffer the volume changes during lithium intercalation/de-intercalation, the films exhibit stable cycling performance. As a potential anode material for high performance lithium-ion batteries that can be applied on electric vehicle and energy storage, rate capability and electrochemical performance under high-low temperatures were also investigated.

Advanced electrolyte/additive for lithium-ion batteries with silicon anode

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Shuo; He, Meinan; Su, Chi-Cheung

State-of-the-art lithium-ion batteries (LIBs) are based on a lithium transition metal oxide cathode, a graphite anode and a nonaqueous carbonate electrolyte. To further increase the energy and power density of LIBs, silicon anodes have been intensively explored due to their high theoretical capacity, low operation potential, and low cost. However, the main challenges for Si anode are the large volume change during lithiation/delithiation process and the instability of the solid-electrolyte-interphase associated with this process. Recently, significant progress has been achieved via advanced material fabrication technologies and rational electrolyte design in terms of improving the Coulombic efficiency and capacity retention. Inmore » this paper, new developments in advanced electrolyte and additive for LIBs with Si anode were systematically reviewed, and perspectives over future research were suggested.« less

Anodic Stripping Voltammetry with Pencil Graphite Electrode for Determination of Chromium (III)

NASA Astrophysics Data System (ADS)

Wyantuti, S.; Hafidza, R. A.; Ishmayana, S.; Hartati, Y. W.

2017-02-01

Chromium is required as micronutrient that has roles in insulin metabolism and blood glucose level regulation. Chromium (III) deficiency can cause hyperglycemia and glycosuria. However, a high amount of chromium in body can cause allergic reaction, organ damage, and even death because of its toxicity. Chromium is commonly used in steel industries. Simultaneously with the development of industry, the waste disposal that can endanger environment also increased. Therefore, a sensitive and specific analysis method for chromium detection is required. Stripping voltammetry is one of the voltammetric methods that is commonly used for heavy metal analysis due to the very low limit of detection (sub ppb). The present study was conducted to develop an analysis method for chromium (III) determination using pencil graphite electrode. Quantitative determination was performed for chromium (III) which measured at -0.8 to +1.0 V with deposition time for 60 s and 50 mV/s scan rate. Stripping voltammetric analysis of chromium (III) using pencil graphite electrode gave linear range at 12.5 to 75 ppm with limit of detection of 0.31 ppm.

Modeling studies of electrolyte flow and bubble behavior in advanced Hall cells

NASA Astrophysics Data System (ADS)

Shekhar, R.; Evans, J. W.

Much research was performed in recent years by corporations and university/government labs on materials for use in advanced Hall-Heroult cells. Attention has focussed on materials for use as wettable cathodes and inert anodes and much was achieved in terms of material development. Comparatively less attention was devoted to how these materials might be incorporated in new or existing cells, i.e., to how the cells should be designed and redesigned, to take full advantage of these materials. The effort, supported by the U.S. Department of Energy, to address this issue, is described. The primary objectives are cell design where electrolyte flow can be managed to promote both the removal of the anode gas bubbles and the convection of dissolved alumina in the inter-electrode region, under conditions where the anode-cathode distance is small. The principal experimental tool was a water model consisting of a large tank in which simulated anodes can be suspended in either the horizontal or vertical configurations. Gas generation was by forcing compressed air through porous graphite and the fine bubbles characteristic of inert anodes were produced by adding butanol to the water. Velocities were measured using a laser Doppler velocimeter. Velocity measurements with two different anode designs (one that is flat and the other that has grooves) are presented. The results show that the electrode configuration has a significant effect on the fluid flow pattern in the inter-electrode region. Furthermore, it is shown that rapid fluid flow is obtained when the cell is operated with a submerged anode.

Mixed Electronic and Ionic Conductor-Coated Cathode Material for High-Voltage Lithium Ion Battery.

PubMed

Shim, Jae-Hyun; Han, Jung-Min; Lee, Joon-Hyung; Lee, Sanghun

2016-05-18

A lithium ionic conductor, Li1.3Al0.3Ti1.7(PO4)3 (LATP), is introduced as a coating material on the surface of Mg-doped LiCoO2 to improve electrochemical performances for high-voltage (4.5 V) lithium ion batteries. Structure, morphology, elemental distribution, and electrical properties of the materials are thoroughly characterized by SEM, TEM, EELS, EDS, and C-AFM. The coating layer is electrically conductive with the aid of Mg ions which are used as a dopant for the active materials; therefore, this mixed electronic ionic conductor strongly enhances the electrochemical performances of initial capacity, cycling property, and rate capability. The LATP coating layer also demonstrates very promising applicability for 4.4 V prismatic full cells with graphite anode, which correspond to the 4.5 V half-cells with lithium anode. The 2900 mA h full cells show 85% of capacity retention after 500 cycles and more than 60% after 700 cycles.

Pillared graphite anodes for reversible sodiation.

PubMed

Zhang, Hanyang; Li, Zhifei; Xu, Wei; Chen, Yicong; Ji, Xiulei; Lerner, Michael M

2018-08-10

There has been a major effort recently to develop new rechargeable sodium-ion electrodes. In lithium ion batteries, LiC 6 forms from graphite and desolvated Li cations during the first charge. With sodium ions, graphite only shows a significant capacity when Na + intercalates as a solvated complex, resulting in ternary graphite intercalation compounds (GICs). Although this chemistry has been shown to be highly reversible and to support high rates in small test cells, these GICs can require >250% volume expansion and contraction during cycling. Here we demonstrate the first example of GICs that reversibly sodiate/desodiate without any significant volume change. These pillared GICs are obtained by electrochemical reduction of graphite in an ether/amine co-solvent electrolyte. The initial gallery expansion, 0.36 nm, is less than half of that in diglyme-based systems, and shows a similar capacity. Thermal analyses suggest the pillaring phenomenon arises from stronger co-intercalate interactions in the GIC galleries.

A simple synthesis of MnN0.43@C nanocomposite: characterization and application as battery material

NASA Astrophysics Data System (ADS)

Milke, Bettina; Wall, Clemens; Metzke, Sarah; Clavel, Guylhaine; Fichtner, Maximilian; Giordano, Cristina

2014-12-01

In the search of new materials for advanced batteries, manganese nitride is an appealing choice. However, in order to fully explore its potentiality, a suitable synthesis is the first mandatory step. In this contribution, nanosized manganese nitride covered by a graphitic shell has been prepared by a simple sol-gel-based process. Since graphite has a high thermal and chemical stability, it acts as stabilizing agent for the MnN0.43 nanoparticles. As a consequence, the particles do not oxidize for instance during the handling of the material and can be stored in air without special precautions. Furthermore, the graphitic shell makes the material more interesting for electrochemical applications, because graphite provides on the one hand an electrical conductivity, which is necessary for the function of active materials, and on the other hand also contributes to the Li storage capacity. The as-prepared nanocomposite was tested as anode material versus lithium metal as counter electrode, showing excellent cyclic stability, 230 mAh/g of capacity, and coulombic efficiencies close to 100 %. Since MnN0.43 possesses a theoretical capacity higher than commercial graphite and exhibits less polarization than several previously reported metal nitrides, it represents an attractive candidate as alternative/novel anode material. The method presented herein offers a simple route to prepare MnN0.43 nanoparticles encapsulated in carbon. The formation mechanism has been investigated, and the detailed characterization of the material before and after battery test (via XRD, HR-TEM, SAED, EELS) is discussed in the text.

Differential voltage analysis as a tool for analyzing inhomogeneous aging: A case study for LiFePO4|Graphite cylindrical cells

NASA Astrophysics Data System (ADS)

Lewerenz, Meinert; Marongiu, Andrea; Warnecke, Alexander; Sauer, Dirk Uwe

2017-11-01

In this work the differential voltage analysis (DVA) is evaluated for LiFePO4|Graphite cylindrical cells aged in calendaric and cyclic tests. The homogeneity of the active lithium distribution and the loss of anode active material (LAAM) are measured by the characteristic shape and peaks of the DVA. The results from this analysis exhibit an increasing homogeneity of the lithium-ion distribution during aging for all cells subjected to calendaric aging. At 60 °C, LAAM is found additionally and can be associated with the deposition of dissolved Fe from the cathode on the anode, where it finally leads to the clogging of pores. For cells aged under cyclic conditions, several phenomena are correlated to degradation, such as loss of active lithium and local LAAM for 100% DOD. Moreover, the deactivation of certain parts of anode and cathode due to a lithium-impermeable covering layer on top of the anode is observed for some cells. While the 100% DOD cycling is featured by a continuous LAAM, the LAAM due to deactivation by a covering layer of both electrodes starts suddenly. The homogeneity of the active lithium distribution within the cycled cells is successively reduced with deposited passivation layers and with LAAM that is lost locally at positions with lower external pressure on the electrode.

Hierarchical MoS2 tubular structures internally wired by carbon nanotubes as a highly stable anode material for lithium-ion batteries

PubMed Central

Chen, Yu Ming; Yu, Xin Yao; Li, Zhen; Paik, Ungyu; Lou, Xiong Wen (David)

2016-01-01

Molybdenum disulfide (MoS2), a typical two-dimensional material, is a promising anode material for lithium-ion batteries because it has three times the theoretical capacity of graphite. The main challenges associated with MoS2 anodes are the structural degradation and the low rate capability caused by the low intrinsic electric conductivity and large strain upon cycling. Here, we design hierarchical MoS2 tubular structures internally wired by carbon nanotubes (CNTs) to tackle these problems. These porous MoS2 tubular structures are constructed from building blocks of ultrathin nanosheets, which are believed to benefit the electrochemical reactions. Benefiting from the unique structural and compositional characteristics, these CNT-wired MoS2 tubular structures deliver a very high specific capacity of ~1320 mAh g−1 at a current density of 0.1 A g−1, exceptional rate capability, and an ultralong cycle life of up to 1000 cycles. This work may inspire new ideas for constructing high-performance electrodes for electrochemical energy storage. PMID:27453938

Reversible calcium alloying enables a practical room-temperature rechargeable calcium-ion battery with a high discharge voltage

NASA Astrophysics Data System (ADS)

Wang, Meng; Jiang, Chunlei; Zhang, Songquan; Song, Xiaohe; Tang, Yongbing; Cheng, Hui-Ming

2018-06-01

Calcium-ion batteries (CIBs) are attractive candidates for energy storage because Ca2+ has low polarization and a reduction potential (-2.87 V versus standard hydrogen electrode, SHE) close to that of Li+ (-3.04 V versus SHE), promising a wide voltage window for a full battery. However, their development is limited by difficulties such as the lack of proper cathode/anode materials for reversible Ca2+ intercalation/de-intercalation, low working voltages (<2 V), low cycling stability, and especially poor room-temperature performance. Here, we report a CIB that can work stably at room temperature in a new cell configuration using graphite as the cathode and tin foils as the anode as well as the current collector. This CIB operates on a highly reversible electrochemical reaction that combines hexafluorophosphate intercalation/de-intercalation at the cathode and a Ca-involved alloying/de-alloying reaction at the anode. An optimized CIB exhibits a working voltage of up to 4.45 V with capacity retention of 95% after 350 cycles.

DOE Office of Scientific and Technical Information (OSTI.GOV)

An, Seong Jin; Li, Jianlin; Daniel, Claus

Simple three-electrode pouch cells which can be used in distinguishing the voltage and resistance in individual electrodes of lithium ion batteries have been designed. Baseline (1 mm-staggered alignment, cathode away from a reference electrode) and aligned electrodes to a reference electrode located outside of the anode and cathode were studied to see alignment effects on resistance analysis. Cells composed of A12 graphite anodes, LiNi 0.5Mn 0.3Co 0.2O 2 (NMC 532 or NCM 523) cathodes, lithium foil references, microporous tri-layer membranes, and electrolytes, were cycled with cathode cutoff voltages between 3.0 V and 4.3 V for formation cycles or 4.6 Vmore » for C-rate performance testing. By applying a hybrid pulse power characterization (HPPC) technique to the cells, resistances of the baseline cells contributed by the anode and cathode were found to be different from those of the aligned cells, although overall resistances were close to ones from aligned cells. As a result, resistances obtained via electrochemical impedance spectroscopy (EIS) and 2D simulation were also compared with those obtained from HPPC.« less

High Voltage TAL Erosion Characterization

NASA Technical Reports Server (NTRS)

Jacobson, David T.

2003-01-01

Extended operation of a D-80 anode layer thruster at high voltage was investigated. The thruster was operated for 1200 hours at 700 Volts and 4 Amperes. Laser profilometry was employed to quantify the erosion of the thruster's graphite guard rings and electrodes at 0, 300, 600, 900, and 1200 hours. Thruster performance and electrical characteristics were monitored over the duration of the investigation. The guard rings exhibited asymmetric erosion that was greatest in the region of the cathode. Erosion of the guard rings exposed the magnet poles between 600 to 900 hours of operation.

Influence of porewidening duration on the template assisted growth of graphitic carbon nitride nanostructures

NASA Astrophysics Data System (ADS)

Suchitra, S. M.; Udayashankar, N. K.

2018-01-01

Porous anodic aluminium oxide (AAO) membranes with a highly ordered pore arrangement are typically used as ideal templates for the synthesis of numerous nanostructured materials. Highly ordered templates gained significant attraction due to the fact that they are readily fabricated through self-organised simple anodization process. In this paper, the effect of different pore-widening treatments on the quality of the pores of the AAO templates prepared with different electrolytes were inspected. Results confirmed that, without altering the interpore distance different pore dimensions and diameters of the AAO templates can be easily achieved by chemical pore widening process at room temperature. Also, graphitic carbon nitride nanorods of different dimension have been fabricated from AAO template after porewidening process. These nanostructures are widely used in case of metal free visible light driven photo catalysis, photo degradation of organic pollutants, photo electric conversion and water splitting applications.

Synthesis of carbon nanotubes by arc discharge in open air.

PubMed

Paladugu, Mohan Chand; Maneesh, K; Nair, P Kesavan; Haridoss, Prathap

2005-05-01

In this work Carbon nanotubes have been synthesized by arc discharge in open air. A TIG welding ac/dc inverter was used as the power source for arc discharge. During each run of the arc discharge based synthesis, the anode was a low purity (approximately 85% C by weight) graphite rod. The effect of varying the atmosphere on the yield of soot of the carbon nanotube containing carbon soot has been studied. Various soots were produced, purified by oxidation and characterized to confirm formation of carbon nanotubes and their relative quality, using transmission electron microscopy, Raman spectroscopy, and XRD. It was found that the yield of soot formed on the cathode is higher when synthesis is carried out in open air than when carried out in a flowing argon atmosphere. When synthesized in open air, using a 7.2-mm-diameter graphite rod as anode, the yield of soot was around 50% by weight of the graphite consumed. Current and voltage for arcing were at identical starting values in all the experiments. This modified method does not require a controlled atmosphere as in the case of a conventional arc discharge method of synthesis and hence the cost of production may be reduced.

Enhancing biodegradation and energy generation via roughened surface graphite electrode in microbial desalination cell.

PubMed

Ebrahimi, Atieh; Yousefi Kebria, Daryoush; Najafpour Darzi, Ghasem

2017-09-01

The microbial desalination cell (MDC) is known as a newly developed technology for water and wastewater treatment. In this study, desalination rate, organic matter removal and energy production in the reactors with and without desalination function were compared. Herein, a new design of plain graphite called roughened surface graphite (RSG) was used as the anode electrode in both microbial fuel cell (MFC) and MDC reactors for the first time. Among the three type of anode electrodes investigated in this study, RSG electrode produced the highest power density and salt removal rate of 10.81 W/m 3 and 77.6%, respectively. Such a power density was 2.33 times higher than the MFC reactor due to the junction potential effect. In addition, adding the desalination function to the MFC reactor enhanced columbic efficiency from 21.8 to 31.4%. These results provided a proof-of-concept that the use of MDC instead of MFC would improve wastewater treatment efficiency and power generation, with an added benefit of water desalination. Furthermore, RSG can successfully be employed in an MDC or MFC, enhancing the bio-electricity generation and salt removal.

Atomic Layer Deposition of Metal Oxides on sp2-Graphitic Carbon Substrates

DTIC Science & Technology

2014-03-31

supercapacitors . The research explored the ALD nucleation procedure based on NO2 and TMA. Al2O3 ALD films resulting from the nucleation procedure were...TiO2 and ZnO were used for electrodes for Li ion batteries and pseudocapacitance supercapacitors . 15. SUBJECT TERMS F-16 Aircraft, High Power...sp2 Graphitic Carbon Substrates 11 4.4.1 TiO2 ALD as Anode Material for Li Ion Batteries 11 4.4.2 TiO2 ALD for Pseudocapacitance Supercapacitors

Effect of entropy change of lithium intercalation in cathodes and anodes on Li-ion battery thermal management

NASA Astrophysics Data System (ADS)

Viswanathan, Vilayanur V.; Choi, Daiwon; Wang, Donghai; Xu, Wu; Towne, Silas; Williford, Ralph E.; Zhang, Ji-Guang; Liu, Jun; Yang, Zhenguo

The entropy changes (Δ S) in various cathode and anode materials, as well as in complete Li-ion batteries, were measured using an electrochemical thermodynamic measurement system (ETMS). LiCoO 2 has a much larger entropy change than electrodes based on LiNi xCo yMn zO 2 and LiFePO 4, while lithium titanate based anodes have lower entropy change compared to graphite anodes. The reversible heat generation rate was found to be a significant portion of the total heat generation rate. The appropriate combinations of cathode and anode were investigated to minimize reversible heat generation rate across the 0-100% state of charge (SOC) range. In addition to screening for battery electrode materials with low reversible heat, the techniques described in this paper can be a useful engineering tool for battery thermal management in stationary and transportation applications.

Failure Analysis of Batteries Using Synchrotron-based Hard X-ray Microtomography

PubMed Central

Harry, Katherine J.; Parkinson, Dilworth Y.; Balsara, Nitash P.

2015-01-01

Imaging morphological changes that occur during the lifetime of rechargeable batteries is necessary to understand how these devices fail. Since the advent of lithium-ion batteries, researchers have known that the lithium metal anode has the highest theoretical energy density of any anode material. However, rechargeable batteries containing a lithium metal anode are not widely used in consumer products because the growth of lithium dendrites from the anode upon charging of the battery causes premature cell failure by short circuit. Lithium dendrites can also form in commercial lithium-ion batteries with graphite anodes if they are improperly charged. We demonstrate that lithium dendrite growth can be studied using synchrotron-based hard X-ray microtomography. This non-destructive imaging technique allows researchers to study the growth of lithium dendrites, in addition to other morphological changes inside batteries, and subsequently develop methods to extend battery life. PMID:26382323

Graphite fiber brush anodes for increased power production in air-cathode microbial fuel cells.

PubMed

Logan, Bruce; Cheng, Shaoan; Watson, Valerie; Estadt, Garett

2007-05-01

To efficiently generate electricity using bacteria in microbial fuel cells (MFCs), highly conductive noncorrosive materials are needed that have a high specific surface area (surface area per volume) and an open structure to avoid biofouling. Graphite brush anodes, consisting of graphite fibers wound around a conductive, but noncorrosive metal core, were examined for power production in cube (C-MFC) and bottle (B-MFC) air-cathode MFCs. Power production in C-MFCs containing brush electrodes at 9600 m2/m3 reactor volume reached a maximum power density of 2400 mW/m2 (normalized to the cathode projected surface area), or 73 W/m3 based on liquid volume, with a maximum Coulombic efficiency (CE) of 60%. This power density, normalized by cathode projected area, is the highest value yet achieved by an air-cathode system. The increased power resulted from a reduction in internal resistance from 31 to 8 Q. Brush electrodes (4200 m2/m3) were also tested in B-MFCs, consisting of a laboratory media bottle modified to have a single side arm with a cathode clamped to its end. B-MFCs inoculated with wastewater produced up to 1430 mW/m2 (2.3 W/m3, CE = 23%) with brush electrodes, versus 600 mW/m2 with a plain carbon paper electrode. These findings show that brush anodes that have high surface areas and a porous structure can produce high power densities, and therefore have qualities that make them ideal for scaling up MFC systems.

Regular Arrays of Germanium Nanoparticles Assisted by Thermoset Polymer Composites for High Capacity Lithium Ion Battery

NASA Astrophysics Data System (ADS)

Jo, Gyuha; Park, Moon Jeong

2012-02-01

In recent years Li-batteries have attracted significant interests for a variety of applications such as portable electronics and electric vehicle (EV) batteries due to their high energy densities. Key challenges in advancing the technology lie in specific energy density, the long term cycle properties, and durability at elevated temperature. In present study, we were motivated to prepare high capacity Li-battery by creating regular arrays of germanium nanoparticles (GeNPs, 1600 mAh/g) to replace commercial graphite anode (370 mAh/g). Thermoset polymers were employed to prepare GeNPs/polymer composites with tunable NP loadings and spacings, followed by carbonization process to prepare GeNPs/carbon composite anode material. Due to the large volume change of GeNPs with charge/discharge cycles, the regular arrays of GeNPs are turned out to be a crucial parameter in obtaining enhanced cyclability. The GeNPs/carbon anode materials were cycle tested in a half cell configuration using Lithium foil as a counter electrode and lithium salt doped PS-PEO block copolymers as electrolytes. High capacity and rate capability were achieved, which demonstrate the role of nano-sized and regularly-arrayed anode active materials in obtaining the improved battery performance.

A Novel Approach to Synthesize Micrometer-Sized Porous Silicon as a High Performance Anode for Lithium-Ion Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jia, Haiping; Zheng, Jianming; Song, Junhua

Porous structured silicon (p-Si) has been recognized as one of the most promising anodes for Li-ion batteries. However, many available methods to synthesize p-Si are difficult to scale up due to their high production cost. Here we introduce a new approach to obtain spherical micrometer-sized silicon with unique porous structure by using a microemulsion of the cost-effective of silica nanoparticles and magnesiothermic reduction method. The spherical micron-sized p-Si particles prepared by this approach consist of highly aligned nano-sized silicon and exhibit a tap density close to that of bulk Si particles. They have demonstrated significantly improved electrochemical stability compared tomore » nano-Si. Well controlled void space and a highly graphitic carbon coating on the p-Si particles enable good stability of the structure and low overall resistance, thus resulting in a Si-based anode with high capacity (~1467 mAh g –1 at 1 C), enhanced cycle life (370 cycles with 83% capacity retention), and high rate capability (~650 mAh g –1 at 5 C). Furthermore, this approach may also be generalized to prepare other hierarchical structured high capacity anode materials for constructing high energy density lithium ion batteries.« less

TiO2 Nanostructures as Anode Materials for Li/Na-ion Batteries.

PubMed

Vazquez-Santos, Maria B; Tartaj, Pedro; Morales, Enrique; Amarilla, Jose Manuel

2018-03-14

Here we summarize some results on the use of TiO 2 nanostructures as anode materials for more efficient Li-ion (LIBs) and Na-ion (NIBs) batteries. LIBs are the leader to power portable electronic devices, and represent in the short-term the most adequate technology to power electrical vehicles, while NIBs hold promise for large storage of energy generated from renewable sources. Specifically, TiO 2 an abundant, low cost, chemically stable and environmentally safe oxide represents in LIBs an alternative to graphite for applications in which safety is mandatory. For NIBs, TiO 2 anodes (or more precisely negative electrodes) work at low voltage, assuring acceptable energy density values. Finally, assembling different TiO 2 polymorphs in the form of nanostructures decreases diffusion distances, increases the number of contacts and offering additional sites for Na + storage, helping to improve power efficiency. More specifically, in this contribution we highlighted our work on TiO 2 anatase mesocrystals of colloidal size. These sophisticate materials; showing excellent textural properties, have remarkable electrochemical performance as anodes for Li/Na-ion batteries, with conventional alkyl carbonates electrolytes and safe electrolytes based on ionic liquids. © 2018 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Layered oxides-LiNi1/3Co1/3Mn1/3O2 as anode electrode for symmetric rechargeable lithium-ion batteries

NASA Astrophysics Data System (ADS)

Wang, Yuesheng; Feng, Zimin; Yang, Shi-Ze; Gagnon, Catherine; Gariépy, Vincent; Laul, Dharminder; Zhu, Wen; Veillette, René; Trudeau, Michel L.; Guerfi, Abdelbast; Zaghib, Karim

2018-02-01

High-performance and long-cycling rechargeable lithium-ion batteries have been in steadily increasing demand for the past decades. Nevertheless, the two dominant anodes at the moment, graphite and L4T5O12, suffer from a safety issue of lithium plating (operating voltage at ∼ 0.1 V vs. Li+/Li) and low capacity (175 mAh/g), respectively. Here, we report LiNi1/3Co1/3Mn1/3O2 as an alternative anode material which has a working voltage of ∼1.1 V and a capacity as high as 330 mAh/g at the current rate of C/15. Symmetric cells with both electrodes containing LiNi1/3Co1/3Mn1/3O2 can deliver average discharge voltage of 2.2 V. In-situ XRD, HRTEM and first principles calculations indicate that the reaction mechanism of a LiNi1/3Co1/3Mn1/3O2 anode is comprised mainly of conversion. Both the fundamental understanding and practical demonstrations suggest that LiNi1/3Co1/3Mn1/3O2 is a promising negative electrode material for lithium-ion batteries.

Developing High-Performance Lithium Metal Anode in Liquid Electrolytes: Challenges and Progress.

PubMed

Li, Sa; Jiang, Mengwen; Xie, Yong; Xu, Hui; Jia, Junyao; Li, Ju

2018-04-01

Lithium metal anodes are potentially key for next-generation energy-dense batteries because of the extremely high capacity and the ultralow redox potential. However, notorious safety concerns of Li metal in liquid electrolytes have significantly retarded its commercialization: on one hand, lithium metal morphological instabilities (LMI) can cause cell shorting and even explosion; on the other hand, breaking of the grown Li arms induces the so-called "dead Li"; furthermore, the continuous consumption of the liquid electrolyte and cycleable lithium also shortens cell life. The research community has been seeking new strategies to protect Li metal anodes and significant progress has been made in the last decade. Here, an overview of the fundamental understandings of solid electrolyte interphase (SEI) formation, conceptual models, and advanced real-time characterizations of LMI are presented. Instructed by the conceptual models, strategies including increasing the donatable fluorine concentration (DFC) in liquid to enrich LiF component in SEI, increasing salt concentration (ionic strength) and sacrificial electrolyte additives, building artificial SEI to boost self-healing of natural SEI, and 3D electrode frameworks to reduce current density and delay Sand's extinction are summarized. Practical challenges in competing with graphite and silicon anodes are outlined. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Novel Approach to Synthesize Micrometer-Sized Porous Silicon as a High Performance Anode for Lithium-Ion Batteries

DOE PAGES

Jia, Haiping; Zheng, Jianming; Song, Junhua; ...

2018-05-21

Porous structured silicon (p-Si) has been recognized as one of the most promising anodes for Li-ion batteries. However, many available methods to synthesize p-Si are difficult to scale up due to their high production cost. Here we introduce a new approach to obtain spherical micrometer-sized silicon with unique porous structure by using a microemulsion of the cost-effective of silica nanoparticles and magnesiothermic reduction method. The spherical micron-sized p-Si particles prepared by this approach consist of highly aligned nano-sized silicon and exhibit a tap density close to that of bulk Si particles. They have demonstrated significantly improved electrochemical stability compared tomore » nano-Si. Well controlled void space and a highly graphitic carbon coating on the p-Si particles enable good stability of the structure and low overall resistance, thus resulting in a Si-based anode with high capacity (~1467 mAh g –1 at 1 C), enhanced cycle life (370 cycles with 83% capacity retention), and high rate capability (~650 mAh g –1 at 5 C). Furthermore, this approach may also be generalized to prepare other hierarchical structured high capacity anode materials for constructing high energy density lithium ion batteries.« less

Cathodic and anodic biofilms in Single Chamber Microbial Fuel Cells.

PubMed

Cristiani, P; Carvalho, M L; Guerrini, E; Daghio, M; Santoro, C; Li, B

2013-08-01

The oxygen reduction due to microaerophilic biofilms grown on graphite cathodes (biocathodes) in Single Chamber Microbial Fuel Cells (SCMFCs) is proved and analysed in this paper. Pt-free cathode performances are compared with those of different platinum-loaded cathodes, before and after the biofilm growth. Membraneless SCMFCs were operating in batch-mode, filled with wastewater. A substrate (fuel) of sodium acetate (0.03 M) was periodically added and the experiment lasted more than six months. A maximum of power densities, up to 0.5 W m(-2), were reached when biofilms developed on the electrodes and the cathodic potential decreased (open circuit potential of 50-200 mV vs. SHE). The power output was almost constant with an acetate concentration of 0.01-0.05 M and it fell down when the pH of the media exceeded 9.5, independently of the Pt-free/Pt-loading at the cathodes. Current densities varied in the range of 1-5 Am(-2) (cathode area of 5 cm(2)). Quasi-stationary polarization curves performed with a three-electrode configuration on cathodic and anodic electrodes showed that the anodic overpotential, more than the cathodic one, may limit the current density in the SCMFCs for a long-term operation. Copyright © 2012 Elsevier B.V. All rights reserved.

Where is the lithium? Quantitative determination of the lithium distribution in lithium ion battery cells: Investigations on the influence of the temperature, the C-rate and the cell type

NASA Astrophysics Data System (ADS)

Vortmann-Westhoven, Britta; Winter, Martin; Nowak, Sascha

2017-04-01

With lithium being the capacity determining species in lithium-ion battery (LIB) cells, the local quantification is of enormous importance for understanding of the cell performance. The investigation of the lithium distribution in LIB full cells is performed with two different cell types, T-cells of the Swagelok® type and pouch bag cells with lithium nickel cobalt manganese oxide and mesocarbon microbead graphite as the active materials as well as a lithium hexafluorophosphate based organic carbonate solvent electrolyte. The lithium content of/at the individual components of the cells is analyzed for different states of charge (SOCs) by inductively coupled plasma-optical emission spectrometry (ICP-OES) and the lithium distribution as well as the loss of active lithium within the cells is calculated after cycling. With increasing the SOC, the lithium contents decrease in the cathodes and simultaneously increase in the anodes. The temperature increase shows a clear shift of the lithium content in the direction of the anode for the T-cells. The comparison of the C-rate influence shows that the lower the C-rate, the more the lithium content on the electrodes is shifted into the direction of the anode.

Silicon as a potential anode material for Li-ion batteries: where size, geometry and structure matter.

PubMed

Ashuri, Maziar; He, Qianran; Shaw, Leon L

2016-01-07

Silicon has attracted huge attention in the last decade because it has a theoretical capacity ∼10 times that of graphite. However, the practical application of Si is hindered by three major challenges: large volume expansion during cycling (∼300%), low electrical conductivity, and instability of the SEI layer caused by repeated volume changes of the Si material. Significant research efforts have been devoted to addressing these challenges, and significant breakthroughs have been made particularly in the last two years (2014 and 2015). In this review, we have focused on the principles of Si material design, novel synthesis methods to achieve such structural designs, and the synthesis-structure-performance relationships to enhance the properties of Si anodes. To provide a systematic overview of the Si material design strategies, we have grouped the design strategies into several categories: (i) particle-based structures (containing nanoparticles, solid core-shell structures, hollow core-shell structures, and yolk-shell structures), (ii) porous Si designs, (iii) nanowires, nanotubes and nanofibers, (iv) Si-based composites, and (v) unusual designs. Finally, our personal perspectives on outlook are offered with an aim to stimulate further discussion and ideas on the rational design of durable and high performance Si anodes for the next generation Li-ion batteries in the near future.

Applications of Graphene-Modified Electrodes in Microbial Fuel Cells

PubMed Central

Yu, Fei; Wang, Chengxian; Ma, Jie

2016-01-01

Graphene-modified materials have captured increasing attention for energy applications due to their superior physical and chemical properties, which can significantly enhance the electricity generation performance of microbial fuel cells (MFC). In this review, several typical synthesis methods of graphene-modified electrodes, such as graphite oxide reduction methods, self-assembly methods, and chemical vapor deposition, are summarized. According to the different functions of the graphene-modified materials in the MFC anode and cathode chambers, a series of design concepts for MFC electrodes are assembled, e.g., enhancing the biocompatibility and improving the extracellular electron transfer efficiency for anode electrodes and increasing the active sites and strengthening the reduction pathway for cathode electrodes. In spite of the challenges of MFC electrodes, graphene-modified electrodes are promising for MFC development to address the reduction in efficiency brought about by organic waste by converting it into electrical energy. PMID:28773929

Highly Conductive In-SnO2/RGO Nano-Heterostructures with Improved Lithium-Ion Battery Performance

NASA Astrophysics Data System (ADS)

Liu, Ying; Palmieri, Alessandro; He, Junkai; Meng, Yongtao; Beauregard, Nicole; Suib, Steven L.; Mustain, William E.

2016-05-01

The increasing demand of emerging technologies for high energy density electrochemical storage has led many researchers to look for alternative anode materials to graphite. The most promising conversion and alloying materials do not yet possess acceptable cycle life or rate capability. In this work, we use tin oxide, SnO2, as a representative anode material to explore the influence of graphene incorporation and In-doping to increase the electronic conductivity and concomitantly improve capacity retention and cycle life. It was found that the incorporation of In into SnO2 reduces the charge transfer resistance during cycling, prolonging life. It is also hypothesized that the increased conductivity allows the tin oxide conversion and alloying reactions to both be reversible, leading to very high capacity near 1200 mAh/g. Finally, the electrodes show excellent rate capability with a capacity of over 200 mAh/g at 10C.

Characterization of microbial current production as a function of microbe-electrode-interaction.

PubMed

Dolch, Kerstin; Danzer, Joana; Kabbeck, Tobias; Bierer, Benedikt; Erben, Johannes; Förster, Andreas H; Maisch, Jan; Nick, Peter; Kerzenmacher, Sven; Gescher, Johannes

2014-04-01

Microbe-electrode-interactions are keys for microbial fuel cell technology. Nevertheless, standard measurement routines to analyze the interplay of microbial physiology and material characteristics have not been introduced yet. In this study, graphite anodes with varying surface properties were evaluated using pure cultures of Shewanella oneidensis and Geobacter sulfurreducens, as well as defined and undefined mixed cultures. The evaluation routine consisted of a galvanostatic period, a current sweep and an evaluation of population density. The results show that surface area correlates only to a certain extent with population density and anode performance. Furthermore, the study highlights a strain-specific microbe-electrode-interaction, which is affected by the introduction of another microorganism. Moreover, evidence is provided for the possibility of translating results from pure culture to undefined mixed species experiments. This is the first study on microbe-electrode-interaction that systematically integrates and compares electrochemical and biological data. Copyright © 2014 Elsevier Ltd. All rights reserved.

Electrochemical and thermal studies of lithium ion batteries

NASA Astrophysics Data System (ADS)

Lu, Wenquan

The structural, electrochemical, and thermal characteristics of carbonaceous anodes and LiNi0.8Co0.2O2 cathode in Li-ion cells were investigated using various electrochemical and calorimetric techniques. The electrode-electrolyte interface was investigated for various carbonaceous materials such as graphite with different shapes, surface modified graphite with copper, and novel carbon material derived from sepiolite template. The structural and morphological properties were determined using XRD, TGA, SEM, BET techniques. The electrochemical characteristics were studied using conventional electrochemical techniques such as galvanostatic charge/discharge cycling, cyclic voltammetry, and impedance (AC and DC) methods. It was observed that the electrochemical active surface area instead of the BET area plays a critical role in the irreversible capacity loss associated with the carbonaceous anodes. It was also found that the exfoliation of carbon anodes especially in PC based electrolyte could be significantly reduced by protective copper coating of the natural graphite. LiNi0.8Co0.2O2 cathode material was found to possess high energy density and excellent cycling characteristics. The structural and electrochemical properties of LiNi0.8Co 0.2O2 synthesized by sol-gel and solid-state methods were studied. Results of the AC impedance spectroscopy carried out on LiNi 0.8Co0.2O2 cathodes revealed that the charge transfer resistance is a function of the state of charge. The solid state Li + diffusion was calculated to be around 10-13 cm2/s in the oxide particle by Warburg impedance method. In addition, the cell fabricated with LiNi0.8Co0.2O 2 cathode showed excellent energy and power performance under static and dynamic load conditions that prevail in Electric and Hybrid Vehicles. Thermal properties of the LiNi0.8Co0.2O2 cathode, carbonaceous anodes, and Li-ion cells fabricated with these electrodes were also investigated using isothermal microcalorimetry (IMC), differential scanning calorimetry (DSC) and accelerated rate calorimetry (ARC). Isothermal micro-calorimeter was used to investigate the thermal behavior of the Li-ion cell and its electrodes. The overall heat changes during charge-discharge processes were explained in terms of the irreversible (resistive) and reversible (entropic) heats. It was observed that the reversible heat strongly depends on the structural or phase change occurring in the electrodes during Li-ion insertion and extraction reactions. It was also found that the contribution of the reversible heat to the overall cell heat generation rate was significant only at low cycling rates.

Enhanced lithium storage in Fe2O3-SnO2-C nanocomposite anode with a breathable structure

NASA Astrophysics Data System (ADS)

Rahman, Md Mokhlesur; Glushenkov, Alexey M.; Ramireddy, Thrinathreddy; Tao, Tao; Chen, Ying

2013-05-01

A novel nanocomposite architecture of a Fe2O3-SnO2-C anode, based on clusters of Fe2O3 and SnO2 nanoparticles dispersed along the conductive chains of Super P Li™ carbon black (Timcal Ltd.), is presented as a breathable structure in this paper for lithium-ion batteries. The synthesis of the nanocomposite is achieved by combining a molten salt precipitation process and a ball milling method for the first time. The crystalline structure, morphology, and electrochemical characterization of the synthesised product are investigated systematically. Electrochemical results demonstrate that the reversible capacity of the composite anode is 1110 mA h g-1 at a current rate of 158 mA g-1 with only 31% of initial irreversible capacity in the first cycle. A high reversible capacity of 502 mA h g-1 (higher than the theoretical capacity of graphite, ~372 mA h g-1) can be obtained at a high current rate of 3950 mA g-1. The electrochemical performance is compared favourably with those of Fe2O3-SnO2 and Fe2O3-SnO2-C composite anodes for lithium-ion batteries reported in the literature. This work reports a promising method for the design and preparation of nanocomposite electrodes for lithium-ion batteries.A novel nanocomposite architecture of a Fe2O3-SnO2-C anode, based on clusters of Fe2O3 and SnO2 nanoparticles dispersed along the conductive chains of Super P Li™ carbon black (Timcal Ltd.), is presented as a breathable structure in this paper for lithium-ion batteries. The synthesis of the nanocomposite is achieved by combining a molten salt precipitation process and a ball milling method for the first time. The crystalline structure, morphology, and electrochemical characterization of the synthesised product are investigated systematically. Electrochemical results demonstrate that the reversible capacity of the composite anode is 1110 mA h g-1 at a current rate of 158 mA g-1 with only 31% of initial irreversible capacity in the first cycle. A high reversible capacity of 502 mA h g-1 (higher than the theoretical capacity of graphite, ~372 mA h g-1) can be obtained at a high current rate of 3950 mA g-1. The electrochemical performance is compared favourably with those of Fe2O3-SnO2 and Fe2O3-SnO2-C composite anodes for lithium-ion batteries reported in the literature. This work reports a promising method for the design and preparation of nanocomposite electrodes for lithium-ion batteries. Electronic supplementary information (ESI) available: Electrochemical Impedance Spectroscopy (EIS). See DOI: 10.1039/c3nr00690e

Systematic aging of commercial LiFePO4|Graphite cylindrical cells including a theory explaining rise of capacity during aging

NASA Astrophysics Data System (ADS)

Lewerenz, Meinert; Münnix, Jens; Schmalstieg, Johannes; Käbitz, Stefan; Knips, Marcus; Sauer, Dirk Uwe

2017-03-01

The contribution introduces a new theory explaining the capacity increase that is often observed in early stages of life of lithium-ion batteries. This reversible and SOC-depending capacity rise is explained by the passive electrode effect in this work. The theory assumes a slow, compensating flow of active lithium between the passive and the active part of the anode, where the passive part represents the geometric excess anode with respect to the cathode. The theory is validated using a systematic test of 50 cylindrical 8 Ah LiFePO4|Graphite battery cells analyzed during cyclic and calendaric aging. The cyclic aging has been performed symmetrically at 40 °C cell temperature, varying current rates and DODs. The calendar aging is executed at three temperatures and up to four SOCs. The aging is dominated by capacity fade while the increase of internal resistance is hardly influenced. Surprisingly shallow cycling between 45 and 55% SOC shows stronger aging than aging at higher DOD and tests at 4 C exhibit less aging than aging at lower C-rates. Aging mechanisms at 60 °C seem to deviate from those at 40 °C or lower. The data of this aging matrix is used for further destructive and non-destructive characterization in future contributions.

Development and Testing of High Surface Area Iridium Anodes for Molten Oxide Electrolysis

NASA Technical Reports Server (NTRS)

Shchetkovskiy, Anatoliy; McKechnie, Timothy; Sadoway, Donald R.; Paramore, James; Melendez, Orlando; Curreri, Peter A.

2010-01-01

Processing of lunar regolith into oxygen for habitat and propulsion is needed to support future space missions. Direct electrochemical reduction of molten regolith is an attractive method of processing, because no additional chemical reagents are needed. The electrochemical processing of molten oxides requires high surface area, inert anodes. Such electrodes need to be structurally robust at elevated temperatures (1400-1600?C), be resistant to thermal shock, have good electrical conductivity, be resistant to attack by molten oxide (silicate), be electrochemically stable and support high current density. Iridium with its high melting point, good oxidation resistance, superior high temperature strength and ductility is the most promising candidate for anodes in high temperature electrochemical processes. Several innovative concepts for manufacturing such anodes by electrodeposition of iridium from molten salt electrolyte (EL-Form? process) were evaluated. Iridium electrodeposition to form of complex shape components and coating was investigated. Iridium coated graphite, porous iridium structure and solid iridium anodes were fabricated. Testing of electroformed iridium anodes shows no visible degradation. The result of development, manufacturing and testing of high surface, inert iridium anodes will be presented.

Development and Testing of High Surface Area Iridium Anodes for Molten Oxide Electrolysis

NASA Technical Reports Server (NTRS)

Shchetkovskiy, Anatoliy; McKechnie, Timothy; Sadoway, Donald R.; Paramore, James; Melendez, Orlando; Curreri, Peter A.

2010-01-01

Processing of lunar regolith into oxygen for habitat and propulsion is needed to support future space missions. Direct electrochemical reduction of molten regolith is an attractive method of processing, because no additional chemical reagents are needed. The electrochemical processing of molten oxides requires high surface area, inert anodes. Such electrodes need to be structurally robust at elevated temperatures (1400-1600 C), be resistant to thermal shock, have good electrical conductivity, be resistant to attack by molten oxide (silicate), be electrochemically stable and support high current density. Iridium with its high melting point, good oxidation resistance, superior high temperature strength and ductility is the most promising candidate for anodes in high temperature electrochemical processes. Several innovative concepts for manufacturing such anodes by electrodeposition of iridium from molten salt electrolyte (EL-Form process) were evaluated. Iridium electrodeposition to form of complex shape components and coating was investigated. Iridium coated graphite, porous iridium structure and solid iridium anodes were fabricated. Testing of electroformed iridium anodes shows no visible degradation. The result of development, manufacturing and testing of high surface, inert iridium anodes will be presented.

Carbon nanosheet frameworks derived from peat moss as high performance sodium ion battery anodes.

PubMed

Ding, Jia; Wang, Huanlei; Li, Zhi; Kohandehghan, Alireza; Cui, Kai; Xu, Zhanwei; Zahiri, Beniamin; Tan, Xuehai; Lotfabad, Elmira Memarzadeh; Olsen, Brian C; Mitlin, David

2013-12-23

We demonstrate that peat moss, a wild plant that covers 3% of the earth's surface, serves as an ideal precursor to create sodium ion battery (NIB) anodes with some of the most attractive electrochemical properties ever reported for carbonaceous materials. By inheriting the unique cellular structure of peat moss leaves, the resultant materials are composed of three-dimensional macroporous interconnected networks of carbon nanosheets (as thin as 60 nm). The peat moss tissue is highly cross-linked, being rich in lignin and hemicellulose, suppressing the nucleation of equilibrium graphite even at 1100 °C. Rather, the carbons form highly ordered pseudographitic arrays with substantially larger intergraphene spacing (0.388 nm) than graphite (c/2 = 0.3354 nm). XRD analysis demonstrates that this allows for significant Na intercalation to occur even below 0.2 V vs Na/Na(+). By also incorporating a mild (300 °C) air activation step, we introduce hierarchical micro- and mesoporosity that tremendously improves the high rate performance through facile electrolyte access and further reduced Na ion diffusion distances. The optimized structures (carbonization at 1100 °C + activation) result in a stable cycling capacity of 298 mAh g(-1) (after 10 cycles, 50 mA g(-1)), with ∼150 mAh g(-1) of charge accumulating between 0.1 and 0.001 V with negligible voltage hysteresis in that region, nearly 100% cycling Coulombic efficiency, and superb cycling retention and high rate capacity (255 mAh g(-1) at the 210th cycle, stable capacity of 203 mAh g(-1) at 500 mA g(-1)).

The Weinstein conjecture with multiplicities on spherizations

NASA Astrophysics Data System (ADS)

Hertzberg, Benjamin J.

2011-07-01

Si-based anodes have recently received considerable attention for use in Li-ion batteries, due to their extremely high specific capacity---an order of magnitude beyond that offered by conventional graphite anode materials. However, during the lithiation process, Si-based anodes undergo extreme increases in volume, potentially by more than 300 %. The stresses produced within the electrode by these volume changes can damage the electrode binder, the active Si particles and the solid electrolyte interphase (SEI), causing the electrode to rapidly fail and lose capacity. These problems can be overcome by producing new anode materials incorporating both Si and C, which may offer a favorable combination of the best properties of both materials, and which can be designed with internal porosity, thereby buffering the high strains produced during battery charge and discharge with minimal overall volume changes. However, in order to develop useful anode materials, we must gain a thorough understanding of the structural, microstructural and chemical changes occurring within the electrode during the lithiation and delithiation process, and we must develop new processes for synthesizing composite anode particles which can survive the extreme strains produced during lithium intercalation of Si and exhibit no volume changes in spite of the volume changes in Si. In this work we have developed several novel synthesis processes for producing internally porous Si-C nanocomposite anode materials for Li-ion batteries. These nanocomposites possess excellent specific capacity, Coulombic efficiency, cycle lifetime, and rate capability. We have also investigated the influence of a range of different parameters on the electrochemical performance of these materials, including pore size and shape, carbon and silicon film thickness and microstructure, and binder chemistry.

Chemical passivation as a method of improving the electrochemical corrosion resistance of Co-Cr-based dental alloy.

PubMed

Rylska, Dorota; Sokołowski, Grzegorz; Sokołowski, Jerzy; Łukomska-Szymańska, Monika

2017-01-01

The purpose of the study was to evaluate corrosion resistance of Wirobond C® alloy after chemical passivation treatment. The alloy surface undergone chemical passivation treatment in four different media. Corrosion studies were carried out by means of electrochemical methods in saline solution. Corrosion effects were determined using SEM. The greatest increase in the alloy polarization resistance was observed for passive layer produced in Na2SO4 solution with graphite. The same layer caused the highest increase in corrosion current. Generally speaking, the alloy passivation in Na2SO4 solution with graphite caused a substantial improvement of the corrosion resistance. The sample after passivation in Na2SO4 solution without graphite, contrary to others, lost its protective properties along with successive anodic polarization cycles. The alloy passivation in Na3PO4 solution with graphite was the only one that caused a decrease in the alloy corrosion properties. The SEM studies of all samples after chemical passivation revealed no pit corrosion - in contrast to the sample without any modification. Every successive polarization cycle in anodic direction of pure Wirobond C® alloy enhances corrosion resistance shifting corrosion potential in the positive direction and decreasing corrosion current value. The chemical passivation in solutions with low pH values decreases susceptibility to electrochemical corrosion of Co-Cr dental alloy. The best protection against corrosion was obtained after chemical passivation of Wirobond C® in Na2SO4 solution with graphite. Passivation with Na2SO4 in solution of high pH does not cause an increase in corrosion resistance of WIROBOND C. Passivation process increases alloy resistance to pit corrosion.

Natural graphite demand and supply - Implications for electric vehicle battery requirements

USGS Publications Warehouse

Olson, Donald W.; Virta, Robert L.; Mahdavi, Mahbood; Sangine, Elizabeth S.; Fortier, Steven M.

2016-01-01

Electric vehicles have been promoted to reduce greenhouse gas emissions and lessen U.S. dependence on petroleum for transportation. Growth in U.S. sales of electric vehicles has been hindered by technical difficulties and the high cost of the lithium-ion batteries used to power many electric vehicles (more than 50% of the vehicle cost). Groundbreaking has begun for a lithium-ion battery factory in Nevada that, at capacity, could manufacture enough batteries to power 500,000 electric vehicles of various types and provide economies of scale to reduce the cost of batteries. Currently, primary synthetic graphite derived from petroleum coke is used in the anode of most lithium-ion batteries. An alternate may be the use of natural flake graphite, which would result in estimated graphite cost reductions of more than US$400 per vehicle at 2013 prices. Most natural flake graphite is sourced from China, the world's leading graphite producer. Sourcing natural flake graphite from deposits in North America could reduce raw material transportation costs and, given China's growing internal demand for flake graphite for its industries and ongoing environmental, labor, and mining issues, may ensure a more reliable and environmentally conscious supply of graphite. North America has flake graphite resources, and Canada is currently a producer, but most new mining projects in the United States require more than 10 yr to reach production, and demand could exceed supplies of flake graphite. Natural flake graphite may serve only to supplement synthetic graphite, at least for the short-term outlook.

Sacrificing power for more cost-effective treatment: A techno-economic approach for engineering microbial fuel cells.

PubMed

Stoll, Zachary A; Ma, Zhaokun; Trivedi, Christopher B; Spear, John R; Xu, Pei

2016-10-01

Microbial fuel cells (MFCs) are a promising energy-positive wastewater treatment technology, however, the system's cost-effectiveness has been overlooked. In this study, two new anode materials - hard felt (HF) and carbon foam (CF) - were evaluated against the standard graphite brush (GB) to determine if using inexpensive materials with less than ideal properties can achieve more cost-effective treatment than high-cost, high-performing materials. Using domestic wastewater as the substrate, power densities for the GB, HF and CF-MFCs were 393, 339 and 291 mW m(-2) normalized by cathodic surface area, respectively. Higher power densities correlated with larger anodic surface areas and anodic current densities but not with electrical conductivity. Cyclic voltammetry revealed that redox systems used for extracellular electron transport in the GB, HF and CF-MFCs were similar (-0.143 ± 0.046, -0.158 ± 0.004 and -0.100 ± 0.014 V vs. Ag/AgCl) and that the electrochemical kinetics of the MFCs showed no correlation with their respective electrical conductivity. 16S rRNA sequencing showed the GB, HF and CF microbial community compositions were not statistically different while organic removal rates were nearly identical for all MFCs. The HF-MFC generated a power output to electrode cost (W $(-1)) 1.9 times greater than the GB-MFC, despite producing 14% less power and 15% less anodic current, while having 2.6 times less anodic surface area, 2.1 times larger charge transfer resistance and an electrical conductivity three orders of magnitude lower. The results demonstrate that inexpensive materials are capable of achieving more cost-effective treatment than high-performing materials despite generating lower power when treating real wastewater. Copyright © 2016 Elsevier Ltd. All rights reserved.

Formation and Inhibition of Metallic Lithium Microstructures in Lithium Batteries Driven by Chemical Crossover

DOE PAGES

Li, Wangda; Kim, Un-Hyuck; Dolocan, Andrei; ...

2017-05-14

The formation of metallic lithium microstructures in the form of dendrites or mosses at the surface of anode electrodes (e.g., lithium metal, graphite, and silicon) leads to rapid capacity fade and poses grave safety risks in rechargeable lithium batteries. In this work, we present here a direct, relative quantitative analysis of lithium deposition on graphite anodes in pouch cells under normal operating conditions, paired with a model cathode material, the layered nickel-rich oxide LiNi 0.61Co 0.12Mn 0.27O 2, over the course of 3000 charge-discharge cycles. Secondary-ion mass spectrometry chemically dissects the solid-electrolyte interphase (SEI) on extensively cycled graphite with virtuallymore » atomic depth resolution and reveals substantial growth of Li-metal deposits. With the absence of apparent kinetic (e.g., fast charging) or stoichiometric restraints (e.g., overcharge) during cycling, we show lithium deposition on graphite is triggered by certain transition-metal ions (manganese in particular) dissolved from the cathode in a disrupted SEI. This insidious effect is found to initiate at a very early stage of cell operation (<200 cycles) and can be effectively inhibited by substituting a small amount of aluminum (~1 mol %) in the cathode, resulting in much reduced transition-metal dissolution and drastically improved cyclability. In conclusion, our results may also be applicable to studying the unstable electrodeposition of lithium on other substrates, including Li metal.« less

Formation and Inhibition of Metallic Lithium Microstructures in Lithium Batteries Driven by Chemical Crossover

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Wangda; Kim, Un-Hyuck; Dolocan, Andrei

The formation of metallic lithium microstructures in the form of dendrites or mosses at the surface of anode electrodes (e.g., lithium metal, graphite, and silicon) leads to rapid capacity fade and poses grave safety risks in rechargeable lithium batteries. In this work, we present here a direct, relative quantitative analysis of lithium deposition on graphite anodes in pouch cells under normal operating conditions, paired with a model cathode material, the layered nickel-rich oxide LiNi 0.61Co 0.12Mn 0.27O 2, over the course of 3000 charge-discharge cycles. Secondary-ion mass spectrometry chemically dissects the solid-electrolyte interphase (SEI) on extensively cycled graphite with virtuallymore » atomic depth resolution and reveals substantial growth of Li-metal deposits. With the absence of apparent kinetic (e.g., fast charging) or stoichiometric restraints (e.g., overcharge) during cycling, we show lithium deposition on graphite is triggered by certain transition-metal ions (manganese in particular) dissolved from the cathode in a disrupted SEI. This insidious effect is found to initiate at a very early stage of cell operation (<200 cycles) and can be effectively inhibited by substituting a small amount of aluminum (~1 mol %) in the cathode, resulting in much reduced transition-metal dissolution and drastically improved cyclability. In conclusion, our results may also be applicable to studying the unstable electrodeposition of lithium on other substrates, including Li metal.« less

Effect of Binder Architecture on the Performance of Silicon/Graphite Composite Anodes for Lithium Ion Batteries

DOE PAGES

Cao, Peng-Fei; Naguib, Michael; Du, Zhijia; ...

2018-01-04

Although significant progress has been made in improving cycling performance of silicon-based electrodes, few studies have been performed on the architecture effect on polymer binder performance for lithium-ion batteries. A systematic study on the relationship between polymer architectures and binder performance is especially useful in designing synthetic polymer binders. In this paper, a graft block copolymer with readily tunable architecture parameters is synthesized and tested as the polymer binder for the high-mass loading silicon (15 wt %)/graphite (73 wt %) composite electrode (active materials >2.5 mg/cm 2). With the same chemical composition and functional group ratio, the graft block copolymermore » reveals improved cycling performance in both capacity retention (495 mAh/g vs 356 mAh/g at 100th cycle) and Coulombic efficiency (90.3% vs 88.1% at first cycle) than the physical mixing of glycol chitosan (GC) and lithium polyacrylate (LiPAA). Galvanostatic results also demonstrate the significant impacts of different architecture parameters of graft copolymers, including grafting density and side chain length, on their ultimate binder performance. Finally, by simply changing the side chain length of GC-g-LiPAA, the retaining delithiation capacity after 100 cycles varies from 347 mAh/g to 495 mAh/g.« less

Effect of Binder Architecture on the Performance of Silicon/Graphite Composite Anodes for Lithium Ion Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cao, Peng-Fei; Naguib, Michael; Du, Zhijia

Although significant progress has been made in improving cycling performance of silicon-based electrodes, few studies have been performed on the architecture effect on polymer binder performance for lithium-ion batteries. A systematic study on the relationship between polymer architectures and binder performance is especially useful in designing synthetic polymer binders. In this paper, a graft block copolymer with readily tunable architecture parameters is synthesized and tested as the polymer binder for the high-mass loading silicon (15 wt %)/graphite (73 wt %) composite electrode (active materials >2.5 mg/cm 2). With the same chemical composition and functional group ratio, the graft block copolymermore » reveals improved cycling performance in both capacity retention (495 mAh/g vs 356 mAh/g at 100th cycle) and Coulombic efficiency (90.3% vs 88.1% at first cycle) than the physical mixing of glycol chitosan (GC) and lithium polyacrylate (LiPAA). Galvanostatic results also demonstrate the significant impacts of different architecture parameters of graft copolymers, including grafting density and side chain length, on their ultimate binder performance. Finally, by simply changing the side chain length of GC-g-LiPAA, the retaining delithiation capacity after 100 cycles varies from 347 mAh/g to 495 mAh/g.« less

Evaluation of ion release, cytotoxicity, and platelet adhesion of electrochemical anodized 316 L stainless steel cardiovascular stents.

PubMed

Díaz, M; Sevilla, P; Galán, A M; Escolar, G; Engel, E; Gil, F J

2008-11-01

316L Stainless steel is one of the most used metallic material in orthopedical prosthesis, osteosinthesis plates, and cardiovascular stents. One of the main problems this material presents is the nickel and chromium release, specially the Ni ion release that provokes allergy in a high number of patients. Recently, experimental applications in vitro and in vivo seem to indicate that the thickness of the nature oxide of the stainless steel results in very strong reinforcement of the biological response and reduce the ion release due to the thicker surface oxide. It is possible to grow the natural chromium oxide layer by electrolytic method such anodization. In this study, two main anodization methods to grow chromium oxide on the 316L stainless steel have been evaluated. Nickel and Chromium ions release in human blood at 37 degrees C were detected at times of 1, 6, 11, and 15 days by means of atomic absorption in a graphite furnace (GAAF). Moreover, cytocompatibility tests were carried out. Perfusion experiments were performed to evaluate morphometrically platelet interaction with the material and to explore the potential thrombogenicity. The results showed a good cytocompatibility between the material and the osteoblast-like cells. However, these anodization methods released between 2 and 10 times more nickel and chromium than the original stainless steel, depending on the method used. Besides, anodized samples shown an increase of the percentage of surface covered by platelets. Consequently, the anodization methods studied do not improve the long-term behavior of the stainless steel for its application as cardiovascular stents.

Advanced rechargeable aluminium ion battery with a high-quality natural graphite cathode

PubMed Central

Wang, Di-Yan; Wei, Chuan-Yu; Lin, Meng-Chang; Pan, Chun-Jern; Chou, Hung-Lung; Chen, Hsin-An; Gong, Ming; Wu, Yingpeng; Yuan, Chunze; Angell, Michael; Hsieh, Yu-Ju; Chen, Yu-Hsun; Wen, Cheng-Yen; Chen, Chun-Wei; Hwang, Bing-Joe; Chen, Chia-Chun; Dai, Hongjie

2017-01-01

Recently, interest in aluminium ion batteries with aluminium anodes, graphite cathodes and ionic liquid electrolytes has increased; however, much remains to be done to increase the cathode capacity and to understand details of the anion–graphite intercalation mechanism. Here, an aluminium ion battery cell made using pristine natural graphite flakes achieves a specific capacity of ∼110 mAh g−1 with Coulombic efficiency ∼98%, at a current density of 99 mA g−1 (0.9 C) with clear discharge voltage plateaus (2.25–2.0 V and 1.9–1.5 V). The cell has a capacity of 60 mAh g−1 at 6 C, over 6,000 cycles with Coulombic efficiency ∼ 99%. Raman spectroscopy shows two different intercalation processes involving chloroaluminate anions at the two discharging plateaus, while C–Cl bonding on the surface, or edges of natural graphite, is found using X-ray absorption spectroscopy. Finally, theoretical calculations are employed to investigate the intercalation behaviour of choloraluminate anions in the graphite electrode. PMID:28194027

Advanced rechargeable aluminium ion battery with a high-quality natural graphite cathode

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Di-Yan; Wei, Chuan-Yu; Lin, Meng-Chang

There has been some interest in aluminium ion batteries with aluminium anodes, graphite cathodes and ionic liquid electrolytes has increased; however, much remains to be done to increase the cathode capacity and to understand details of the anion–graphite intercalation mechanism. An aluminium ion battery cell made using pristine natural graphite flakes achieves a specific capacity of B110 mAhg -1 with Coulombic efficiency B98%, at a current density of 99mAg -1 (0.9 C) with clear discharge voltage plateaus (2.25–2.0 V and 1.9–1.5 V). The cell has a capacity of 60mAhg -1 at 6 C, over 6,000 cycles with Coulombic efficiency Bmore » 99%. Raman spectroscopy shows two different intercalation processes involving chloroaluminate anions at the two discharging plateaus, while C–Cl bonding on the surface, or edges of natural graphite, is found using X-ray absorption spectroscopy. Lastly, theoretical calculations are employed to investigate the intercalation behaviour of choloraluminate anions in the graphite electrode.« less

Advanced rechargeable aluminium ion battery with a high-quality natural graphite cathode

DOE PAGES

Wang, Di-Yan; Wei, Chuan-Yu; Lin, Meng-Chang; ...

2017-02-13

There has been some interest in aluminium ion batteries with aluminium anodes, graphite cathodes and ionic liquid electrolytes has increased; however, much remains to be done to increase the cathode capacity and to understand details of the anion–graphite intercalation mechanism. An aluminium ion battery cell made using pristine natural graphite flakes achieves a specific capacity of B110 mAhg -1 with Coulombic efficiency B98%, at a current density of 99mAg -1 (0.9 C) with clear discharge voltage plateaus (2.25–2.0 V and 1.9–1.5 V). The cell has a capacity of 60mAhg -1 at 6 C, over 6,000 cycles with Coulombic efficiency Bmore » 99%. Raman spectroscopy shows two different intercalation processes involving chloroaluminate anions at the two discharging plateaus, while C–Cl bonding on the surface, or edges of natural graphite, is found using X-ray absorption spectroscopy. Lastly, theoretical calculations are employed to investigate the intercalation behaviour of choloraluminate anions in the graphite electrode.« less

Caramel popcorn shaped silicon particle with carbon coating as a high performance anode material for Li-ion batteries.

PubMed

He, Meinan; Sa, Qina; Liu, Gao; Wang, Yan

2013-11-13

Silicon is a very promising anode material for lithium ion batteries. It has a 4200 mAh/g theoretical capacity, which is ten times higher than that of commercial graphite anodes. However, when lithium ions diffuse to Si anodes, the volume of Si will expand to almost 400% of its initial size and lead to the crack of Si. Such a huge volume change and crack cause significant capacity loss. Meanwhile, with the crack of Si particles, the conductivity between the electrode and the current collector drops. Moreover, the solid electrolyte interphase (SEI), which is generated during the cycling, reduces the discharge capacity. These issues must be addressed for widespread application of this material. In this work, caramel popcorn shaped porous silicon particles with carbon coating are fabricated by a set of simple chemical methods as active anode material. Si particles are etched to form a porous structure. The pores in Si provide space for the volume expansion and liquid electrolyte diffusion. A layer of amorphous carbon is formed inside the pores, which gives an excellent isolation between the Si particle and electrolyte, so that the formation of the SEI layer is stabilized. Meanwhile, this novel structure enhances the mechanical properties of the Si particles, and the crack phenomenon caused by the volume change is significantly restrained. Therefore, an excellent cycle life under a high rate for the novel Si electrode is achieved.

Mode Transitions in Hall Effect Thrusters

DTIC Science & Technology

2013-07-01

Al2O3), silicon carbide ( SiC ) and graphite (C). The significant differences being ion bombardment sputter yield and secondary electron emission...channel cross-section is radially symmetric about ( mirrored above and below) discharge channel centerline from the anode to the exit plane, whereas

Electrospun N-doped Hierarchical Porous Carbon Nanofiber with Improved Graphitization Degree for High Performance Lithium Ion Capacitor.

PubMed

Li, Baohua; Shi, Ruiying; Han, Cuiping; Xu, Xiaofu; Qing, Xianying; Xu, Lei; Li, Hongfei; Li, Junqin; Wong, Ching-Ping

2018-05-14

Lithium ion capacitor (LIC) has been regarded as a promising device to combine the merits of lithium ion batteries and supercapacitors, which can meet the requirements for both high energy and power density. The development of advanced electrode is the key. Herein, we demonstrate the bottom-up synthesis of activated carbon nanofiber (a-PANF) with hierarchical porous structure and high graphitization degree. Electrospinning is employed to prepare interconnected fiber network with macropores and ferric acetylacetonate is introduced as both mesopore creating agent and graphitic catalyst to increase the graphitization degree. Furthermore, chemical activation enlarges the specific surface area by producing rich micropores. Half cell evaluation of the as-prepared a-PANF displays a discharge capacity of 80 mAh g-1 at 0.1 A g-1 within 2~4.5 V and no capacity fading after 1000 cycles at 2 A g-1, which is significantly higher than conventional activated carbon. Furthermore, the as-assembled LIC with a-PANF cathode and Fe3O4 anode achieves a superior energy density of 124.6 Wh kg-1 at a specific power of 93.8 W kg-1, and remains 103.7 Wh kg-1 at 4687.5 W kg-1, demonstrating the promising application of a-PANF as potential electrode candidates for efficient energy storage systems. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemical fabrication of capacitors

DOEpatents

Mansour, Azzam N.; Melendres, Carlos A.

1999-01-01

A film of nickel oxide is anodically deposited on a graphite sheet held in osition on an electrochemical cell during application of a positive electrode voltage to the graphite sheet while exposed to an electrolytic nickel oxide solution within a volumetrically variable chamber of the cell. An angularly orientated x-ray beam is admitted into the cell for transmission through the deposited nickel oxide film in order to obtain structural information while the film is subject to electrochemical and in-situ x-ray spectroscopy from which optimum film thickness, may be determined by comparative analysis for capacitor fabrication purposes.

In Situ Activation of Nitrogen-Doped Graphene Anchored on Graphite Foam for a High-Capacity Anode.

PubMed

Ji, Junyi; Liu, Jilei; Lai, Linfei; Zhao, Xin; Zhen, Yongda; Lin, Jianyi; Zhu, Yanwu; Ji, Hengxing; Zhang, Li Li; Ruoff, Rodney S

2015-08-25

We report the fabrication of a three-dimensional free-standing nitrogen-doped porous graphene/graphite foam by in situ activation of nitrogen-doped graphene on highly conductive graphite foam (GF). After in situ activation, intimate "sheet contact" was observed between the graphene sheets and the GF. The sheet contact produced by in situ activation is found to be superior to the "point contact" obtained by the traditional drop-casting method and facilitates electron transfer. Due to the intimate contact as well as the use of an ultralight GF current collector, the composite electrode delivers a gravimetric capacity of 642 mAh g(-1) and a volumetric capacity of 602 mAh cm(-3) with respect to the whole electrode mass and volume (including the active materials and the GF current collector). When normalized based on the mass of the active material, the composite electrode delivers a high specific capacity of up to 1687 mAh g(-1), which is superior to that of most graphene-based electrodes. Also, after ∼90 s charging, the anode delivers a capacity of about 100 mAh g(-1) (with respect to the total mass of the electrode), indicating its potential use in high-rate lithium-ion batteries.

Effect of anode polarization on biofilm formation and electron transfer in Shewanella oneidensis/graphite felt microbial fuel cells.

PubMed

Pinto, David; Coradin, Thibaud; Laberty-Robert, Christel

2018-04-01

In microbial fuel cells, electricity generation is assumed by bacterial degradation of low-grade organics generating electrons that are transferred to an electrode. The nature and efficiency of the electron transfer from the bacteria to the electrodes are determined by several chemical, physical and biological parameters. Specifically, the application of a specific potential at the bioanode has been shown to stimulate the formation of an electro-active biofilm, but the underlying mechanisms remain poorly understood. In this study, we have investigated the effect of an applied potential on the formation and electroactivity of biofilms established by Shewanella oneidensis bacteria on graphite felt electrodes in single- and double-chamber reactor configurations in oxic conditions. Using amperometry, cyclic voltammetry, and OCP/Power/Polarization curves techniques, we showed that a potential ranging between -0.3V and +0.5V (vs. Ag/AgCl/KCl sat.) and its converse application to a couple of electrodes leads to different electrochemical behaviors, anodic currents and biofilm architectures. For example, when the bacteria were confined in the anodic compartment of a double-chamber cell, a negative applied potential (-0.3V) at the bioanode favors a mediated electron transfer correlated with the progressive formation of a biofilm that fills the felt porosity and bridges the graphite fibers. In contrast, a positive applied potential (+0.3V) at the bioanode stimulates a direct electron transfer resulting in the fast-bacterial colonization of the fibers only. These results provide significant insight for the understanding of the complex bacteria-electrode interactions in microbial fuel cells. Copyright © 2017 Elsevier B.V. All rights reserved.

Organic anodes and sulfur/selenium cathodes for advanced Li and Na batteries

NASA Astrophysics Data System (ADS)

Luo, Chao

To address energy crisis and environmental pollution induced by fossil fuels, there is an urgent demand to develop sustainable, renewable, environmental benign, low cost and high capacity energy storage devices to power electric vehicles and enhance clean energy approaches such as solar energy, wind energy and hydroenergy. However, the commercial Li-ion batteries cannot satisfy the critical requirements for next generation rechargeable batteries. The commercial electrode materials (graphite anode and LiCoO 2 cathode) are unsustainable, unrenewable and environmental harmful. Organic materials derived from biomasses are promising candidates for next generation rechargeable battery anodes due to their sustainability, renewability, environmental benignity and low cost. Driven by the high potential of organic materials for next generation batteries, I initiated a new research direction on exploring advanced organic compounds for Li-ion and Na-ion battery anodes. In my work, I employed croconic acid disodium salt and 2,5-Dihydroxy-1,4-benzoquinone disodium salt as models to investigate the effects of size and carbon coating on electrochemical performance for Li-ion and Na-ion batteries. The results demonstrate that the minimization of organic particle size into nano-scale and wrapping organic materials with graphene oxide can remarkably enhance the rate capability and cycling stability of organic anodes in both Li-ion and Na-ion batteries. To match with organic anodes, high capacity sulfur and selenium cathodes were also investigated. However, sulfur and selenium cathodes suffer from low electrical conductivity and shuttle reaction, which result in capacity fading and poor lifetime. To circumvent the drawbacks of sulfur and selenium, carbon matrixes such as mesoporous carbon, carbonized polyacrylonitrile and carbonized perylene-3, 4, 9, 10-tetracarboxylic dianhydride are employed to encapsulate sulfur, selenium and selenium sulfide. The resulting composites exhibit exceptional electrochemical performance owing to the high conductivity of carbon and effective restriction of polysulfides and polyselenides in carbon matrix, which avoids shuttle reaction.

Hybrid-PIC Simulation of Backsputtered Carbon Transport in the Near-Field Plume of a Hall Thruster

NASA Technical Reports Server (NTRS)

Choi, Maria; Yim, John T.; Williams, George J.; Herman, Daniel A.; Gilland, James H.

2017-01-01

Magnetic shielding has eliminated boron nitride erosion as the life limiting mechanism in a Hall thruster but has resulted in erosion of the front magnetic field pole pieces. Recent experiments show that the erosion of graphite pole covers, which are added to protect the magnetic field pole pieces, causes carbon to redeposit on other surfaces, such as boron nitride discharge channel and cathode keeper surfaces. As a part of the risk-reduction activities for AEPS thruster development, this study models transport of backsputtered carbon from the graphite front pole covers and vacuum facility walls. Fluxes, energy distributions, and redeposition rates of backsputtered carbon on the anode, discharge channel, and graphite cathode keeper surfaces are predicted.

Electrochemical behaviour of vanadium(V)/vanadium(IV) redox couple at graphite electrodes

NASA Astrophysics Data System (ADS)

Zhong, S.; Skyllas-Kazacos, M.

The electrochemical behaviour of the V(V)/V(IV) couple has been studied at a graphite disc electrode in sulfuric acid using both cyclic and rotating-disc voltammetry. The results from the latter technique have revealed that the cathodic and anodic characteristics of this redox couple are quite different. The diffusion coefficient for V(IV), 2.14×10-6 cm2 s-1, is independent of the vanadium concentration. For V(IV) oxidation, the electrode kinetic parameters i0 and α have values of 2.47×10-4 A cm-2 and 0.71, respectively. The exchange current density, i0, for the V(V)/V(IV) reaction has been obtained at both graphite felt and reticulated vitreous carbon electrodes.

Intense Electrochemical Oxidation on Graphitized Carbon Electrodes in the Presence of Ozone

NASA Astrophysics Data System (ADS)

Klochikhin, V. L.; Potapova, G. F.; Putilov, A. V.

2018-06-01

A new intense oxidation process for water treatment in which oxidation with ozone is coupled to electrochemical processes is described, and the results from its application to water purification are presented along with the discussion of its practical implementation. The use of graphitized carbon materials for this process is explained and tested experimentally. The use of glassy carbon for the anode enables us to achieve very high (up to 25 vol %) concentrations of ozone in the generated ozone-oxygen mixture. The material used for the cathode—graphitized carbon cloth (GCC) reinforced with Ni allows different electrocatalytic processes to proceed on its developed surface, and combines the high sorption capacity of this cathode and potentialcontrolled selectivity of cathodic electrochemical processes.

Self-Activating, Capacitive Anion Intercalation Enables High-Power Graphite Cathodes.

PubMed

Wang, Gang; Yu, Minghao; Wang, Jungang; Li, Debao; Tan, Deming; Löffler, Markus; Zhuang, Xiaodong; Müllen, Klaus; Feng, Xinliang

2018-05-01

Developing high-power cathodes is crucial to construct next-generation quick-charge batteries for electric transportation and grid applications. However, this mainly relies on nanoengineering strategies at the expense of low scalability and high battery cost. Another option is provided herein to build high-power cathodes by exploiting inexpensive bulk graphite as the active electrode material, where anion intercalation is involved. With the assistance of a strong alginate binder, the disintegration problem of graphite cathodes due to the large volume variation of >130% is well suppressed, making it possible to investigate the intrinsic electrochemical behavior and to elucidate the charge storage kinetics of graphite cathodes. Ultrahigh power capability up to 42.9 kW kg -1 at the energy density of >300 Wh kg -1 (based on graphite mass) and long cycling life over 10 000 cycles are achieved, much higher than those of conventional cathode materials for Li-ion batteries. A self-activating and capacitive anion intercalation into graphite is discovered for the first time, making graphite a new intrinsic intercalation-pseudocapacitance cathode material. The finding highlights the kinetical difference of anion intercalation (as cathode) from cation intercalation (as anode) into graphitic carbon materials, and new high-power energy storage devices will be inspired. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Corrosion Behavior of an Abradable Seal Coating System

NASA Astrophysics Data System (ADS)

Zhang, Feng; Xu, Cunguan; Lan, Hao; Huang, Chuanbing; Zhou, Yang; Du, Lingzhong; Zhang, Weigang

2014-08-01

A novel NiTi/BN composite abradable coating and two traditional Ni/C and Ni/BN coatings were manufactured with NiAl as the bond layer using thermal spray technology and their corrosion behaviors were investigated. In salt spray corrosion testing of the Ni/BN coating, defective sites of the metal matrix were corroded preferentially. Simulated occlusion experiments and electrochemical tests indicated that migration of ions resulted in pH decrease and Cl- enrichment in defects, and a more aggressive electrolyte led to a decrease of the corrosion potential of the metal inside defects but an increase of the corrosion current density, representing an autocatalytic corrosion process. Moreover, galvanic corrosion between the top and bond coatings of the abradable system was studied via the electrochemical technique. The results showed that, for the NiTi/BN, Ni/BN, and Ni/graphite coatings with a NiAl bond coating, current flow was generated between the anode and cathode. The NiTi/BN coating acted as the cathode due to its passivation, while the Ni/BN and Ni/graphite coatings acted as the anode because of their lower corrosion potential compared with the NiAl coating. The anode suffered serious corrosion damage due to galvanic corrosion, while the cathode corroded only slightly.

Highly uniform Co9S8 nanoparticles grown on graphene nanosheets as advanced anode materials for improved Li-storage performance

NASA Astrophysics Data System (ADS)

Liu, Shumin; Wang, Jinxian; Wang, Jianwei; Zhang, Feifei; Wang, Limin

2016-12-01

A Co9S8/GNS (graphene nanosheets) nanocomposites has been synthesized via a facile solvothermal approach followed by thermal treatment in nitrogen at 500 °C using graphite oxide sheets, CoCl2·6H2O and thiourea as the starting materials. Highly uniform Co9S8 nanoparticles with a size of about 80-90 nm are evenly grafted on the surface of GNS, forming a unique Co9S8/GNS hybrid nanostructure. When evaluated as anode materials for lithium ion batteries, impressive electrochemical performances of the as-prepared nanocomposites are achieved compared to that of pure bulk Co9S8, with an high reversible capacity of 1480 mAh g-1. Moreover, the as-synthesized nanocomposites present excellent cycling durability and high-rate capability. The improvement in the electrochemical properties could be attributed to the well-designed structure of the Co9S8/GNS nanocomposite which possesses large number of accessible active sites for lithium-ion insertion, fast ion diffusion rate and good electronic conductivity.

Pyrolytic carbon-coated stainless steel felt as a high-performance anode for bioelectrochemical systems.

PubMed

Guo, Kun; Hidalgo, Diana; Tommasi, Tonia; Rabaey, Korneel

2016-07-01

Scale up of bioelectrochemical systems (BESs) requires highly conductive, biocompatible and stable electrodes. Here we present pyrolytic carbon-coated stainless steel felt (C-SS felt) as a high-performance and scalable anode. The electrode is created by generating a carbon layer on stainless steel felt (SS felt) via a multi-step deposition process involving α-d-glucose impregnation, caramelization, and pyrolysis. Physicochemical characterizations of the surface elucidate that a thin (20±5μm) and homogenous layer of polycrystalline graphitic carbon was obtained on SS felt surface after modification. The carbon coating significantly increases the biocompatibility, enabling robust electroactive biofilm formation. The C-SS felt electrodes reach current densities (jmax) of 3.65±0.14mA/cm(2) within 7days of operation, which is 11 times higher than plain SS felt electrodes (0.30±0.04mA/cm(2)). The excellent biocompatibility, high specific surface area, high conductivity, good mechanical strength, and low cost make C-SS felt a promising electrode for BESs. Copyright © 2016 Elsevier Ltd. All rights reserved.

All 2D materials as electrodes for high power hybrid energy storage applications

NASA Astrophysics Data System (ADS)

Kato, Keiko; Sayed, Farheen N.; Babu, Ganguli; Ajayan, Pulickel M.

2018-04-01

Achieving both high energy and power densities from energy storage devices is a core strategy to meet the increasing demands of high performance portable electronics and electric transportation systems. Li-ion capacitor is a promising hybrid technology that strategically exploits high energy density from a Li-ion battery electrode and high power density from a supercapacitor electrode. However, the performance and safety of hybrid devices are still major concerns due to the use of graphite anodes which form passivation layers with organic electrolytes at lower potentials. Here, we explore 2D nanosheets as both anode and cathode electrodes to build a high power system without compromising energy density. Owing to the high electrical conductivity and multivalent redox activity at higher potentials, the Li-ion intercalation electrode is capable of maintaining large energy density at higher current rates with less safety risk than conventional systems. Hybrid devices consisting of all in all 2D electrodes deliver energy density as high as 121 Wh g-1 (at 240 W kg-1) and retains 29 Wh g-1 at high power density of 3600 W kg-1.

Mesoporous wormholelike carbon with controllable nanostructure for lithium ion batteries application

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Xiaoqing, E-mail: yxq-886@163.com; Li, Xinxi; Li, Zhenghui

2015-06-15

Highlights: • Wormholelike carbon (WMC) with controllable nanostructure is prepared by sol–gel method. • The reversible capacity of WMC is much higher than that of many other reported nanocarbons. • The effect of pore diameter on Li storage capacity is investigated. - Abstract: A class of mesoporous wormholelike carbon (WMC) with controllable nanostructure was prepared by sol–gel method and then used as the anode material of lithium-ion batteries. Based on the experimental results, it is found that the nanostructure of the as-prepared WMC plays an important role in the electrochemical performances. A suitable mesopore size is necessary for a highmore » performance carbon-based anode material since it can not only guarantee effective mass transport channels but also provide large surface area. As a result, F30 with a mesopore size of 4.4 nm coupled with high surface area of 1077 m{sup 2} g{sup −1} shows a reversible capacity of 630 mAh g{sup −1}, much higher than commercial graphite and many other reported nanocarbons.« less

Designed synergetic effect of electrolyte additives to improve interfacial chemistry of MCMB electrode in propylene carbonate-based electrolyte for enhanced low and room temperature performance.

PubMed

Wotango, Aselefech Sorsa; Su, Wei-Nien; Haregewoin, Atetegeb Meazah; Chen, Hung-Ming; Cheng, Ju-Hsiang; Lin, Ming-Hsien; Wang, Chia-Hsin; Hwang, Bing-Joe

2018-05-09

The performance of lithium ion batteries rapidly falls at lower temperatures due to decreasing conductivity of electrolytes and Solid Electrolyte Interphase (SEI) on graphite anode. Hence, it limits the practical use of lithium ion batteries at sub-zero temperatures and also affects the development of lithium ion batteries for widespread applications. The SEI formed on the graphite surface is very influential in determining the performance of the battery. Herein, a new electrolyte additive, 4-Chloromethyl-1,3,2-dioxathiolane-2-oxide (CMDO), is prepared to improve the properties of commonly used electrolyte constituents - ethylene carbonate (EC), and fluoroethylene carbonate (FEC). The formation of an efficient passivation layer in propylene carbonate (PC) -based electrolyte for MCMB electrode was investigated. The addition of CMDO resulted in a much less irreversible capacity loss and induces thin SEI formation. However, the combination of the three additives played a key role to enhance reversible capacity of MCMB electrode at lower or ambient temperature. The electrochemical measurement analysis showed that the SEI formed from a mixture of the three additives gave better intercalation-deintercalation of lithium ions.

ELECTROCHEMICAL DECHLORINATION OF TRICHLOROETHYLENE USING GRANULAR-GRAPHITE ELECTRODES: IDENTIFICATION AND QUANTIFICATION OF DECHLORINATION PRODUCTS

EPA Science Inventory

Electrochemical degradation (ECD) utilizes high redox potential at the anode and low redox potential at the cathode to oxidize and/or reduce organic and inorganic contaminants. ECD of Trichloroethylene (TCE), although theoretically possible, has not been experimentally proven. Th...

Vacuum Plasma Spray Forming of Tungsten Lorentz Force Accelerator Components

NASA Technical Reports Server (NTRS)

Zimmerman, Frank R.

2001-01-01

The Vacuum Plasma Spray (VPS) Laboratory at NASA's Marshall Space Flight Center has developed and demonstrated a fabrication technique using the VPS process to form anode sections for a Lorentz force accelerator from tungsten. Lorentz force accelerators are an attractive form of electric propulsion that provides continuous, high-efficiency propulsion at useful power levels for such applications as orbit transfers or deep space missions. The VPS process is used to deposit refractory metals such as tungsten onto a graphite mandrel of the desired shape. Because tungsten is reactive at high temperatures, it is thermally sprayed in an inert environment where the plasma gun melts and accelerates the metal powder onto the mandrel. A three-axis robot inside the chamber controls the motion of the plasma spray torch. A graphite mandrel acts as a male mold, forming the required contour and dimensions of the inside surface of the anode. This paper describes the processing techniques, design considerations, and process development associated with the VPS forming of the Lorentz force accelerator.

Effect of overcharge on Li(Ni0.5Mn0.3Co0.2)O2/Graphite lithium ion cells with poly(vinylidene fluoride) binder. I - Microstructural changes in the anode

NASA Astrophysics Data System (ADS)

Dietz Rago, Nancy; Bareño, Javier; Li, Jianlin; Du, Zhijia; Wood, David L.; Steele, Leigh Anna; Lamb, Joshua; Spangler, Scott; Grosso, Christopher; Fenton, Kyle; Bloom, Ira

2018-05-01

Cells based on NMC/graphite, containing poly(vinylidene difluoride) (PVDF) binders in the positive and negative electrodes, were systematically overcharged to 100, 120, 140, 160, 180, and 250% state-of-charge (SOC). At 250% SOC the cell vented. Scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) of the anodes showed several state-of-overcharge-dependent trends. Starting at 120% SOC, dendrites appeared and increased in concentration as the SOC increased. Dendrite morphology appeared to be dependent on whether the active material was on the "dull" or "shiny" side of the copper collector. Significantly more delamination of the active material from the collector was seen on the "shiny" side of the collector particularly at 180 and 250% SOC. Transition metals were detected at 120% SOC and increased in concentration as the SOC increased. There was considerable spatial heterogeneity in the microstructures across each laminate with several regions displaying complex layered structures.

Design and Demonstration of Three-Electrode Pouch Cells for Lithium-Ion Batteries

DOE PAGES

An, Seong Jin; Li, Jianlin; Daniel, Claus; ...

2017-06-14

Simple three-electrode pouch cells which can be used in distinguishing the voltage and resistance in individual electrodes of lithium ion batteries have been designed. Baseline (1 mm-staggered alignment, cathode away from a reference electrode) and aligned electrodes to a reference electrode located outside of the anode and cathode were studied to see alignment effects on resistance analysis. Cells composed of A12 graphite anodes, LiNi 0.5Mn 0.3Co 0.2O 2 (NMC 532 or NCM 523) cathodes, lithium foil references, microporous tri-layer membranes, and electrolytes, were cycled with cathode cutoff voltages between 3.0 V and 4.3 V for formation cycles or 4.6 Vmore » for C-rate performance testing. By applying a hybrid pulse power characterization (HPPC) technique to the cells, resistances of the baseline cells contributed by the anode and cathode were found to be different from those of the aligned cells, although overall resistances were close to ones from aligned cells. As a result, resistances obtained via electrochemical impedance spectroscopy (EIS) and 2D simulation were also compared with those obtained from HPPC.« less

Research on low-temperature anodic bonding using induction heating

NASA Astrophysics Data System (ADS)

Chen, Mingxiang; Yi, Xinjian; Yuan, Liulin; Liu, Sheng

2006-04-01

This paper presents a new low temperature silicon-glass anodic bonding process using induction heating. Anodic bonding between silicon and glass (Pyrex 7740) has been achieved at temperature below 300 °C and almost bubble-free interfaces have been obtained. A 1KW 400KHz power supply is used to induce heat in graphite susceptors (simultaneously as the high-voltage electrodes of anodic bonding), which conduct heat to the bonding pair and permanently join the pair in 5 minutes. The results of pull tests indicate a bonding strength of above 5.0MPa for induction heating, which is greater than the strength for resistive heating at the same temperature. The fracture mainly occurs across the interface or inside the glass other than in the interface when the bonding temperature is over 200 °C Finally, the interfaces are examined and analyzed by scanning electron microscopy (SEM) and the bonding mechanisms are discussed.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tan, Guoqiang; Bao, Wurigumula; Yuan, Yifei

To spread lithium ion batteries into large-scale energy storage technologies, high ener-gy/power densities and long cycling life of carbon-based anodes must be achieved. This re-quires revolutionary design of the anode’s architectures that can facilitate the fast electronic and ionic transport, as well as accommodate the electrode structural instability. Here we re-port a thin-film electrode design and demonstrate its use in flexible, and large-area carbon-based anode assemblies. The fabrication of electrodes is realized by sputtering a graphite tar-get in the high-purity nitrogen atmosphere, then highly-defect nitrogen-doped carbon nano-fibers are deposited vertically onto copper substrates with a thin film configuration. The high-ly-defectmore » nitrogen-doping enhances the lithium storage and transport, the orientation grown mechanism improves the charge transfer, and the compact configuration makes the high tap density possible. As a result, the thin films exhibit high specific capacities of ~ 500 mAh g-1, namely a volume capacity of ~ 100 mAh cm-3. They also exhibit stable cycle performance (400 mAh g-1 after 200 cycles) and good rate capability (450 mAh g-1 at 1 A g-1 rate). This work opens up a new carbon-based anode design by using sputtering technology for effec-tively incorporating high content nitrogen into carbon matrices. Such electrode architecture significantly improves the electrochemical performance of carbon-based materials.« less

A Tunable Molten-Salt Route for Scalable Synthesis of Ultrathin Amorphous Carbon Nanosheets as High-Performance Anode Materials for Lithium-Ion Batteries.

PubMed

Wang, Yixian; Tian, Wei; Wang, Luhai; Zhang, Haoran; Liu, Jialiang; Peng, Tingyue; Pan, Lei; Wang, Xiaobo; Wu, Mingbo

2018-02-14

Amorphous carbon is regarded as a promising alternative to commercial graphite as the lithium-ion battery anode due to its capability to reversibly store more lithium ions. However, the structural disorder with a large number of defects can lead to low electrical conductivity of the amorphous carbon, thus limiting its application for high power output. Herein, ultrathin amorphous carbon nanosheets were prepared from petroleum asphalt through tuning the carbonization temperature in a molten-salt medium. The amorphous nanostructure with expanded carbon interlayer spacing can provide substantial active sites for lithium storage, while the two-dimensional (2D) morphology can facilitate fast electrical conductivity. As a result, the electrodes deliver a high reversible capacity, outstanding rate capability, and superior cycling performance (579 and 396 mAh g -1 at 2 and 5 A g -1 after 900 cycles). Furthermore, full cells consisting of the carbon anodes coupled with LiMn 2 O 4 cathodes exhibit high specific capacity (608 mAh g -1 at 50 mA g -1 ) and impressive cycling stability with slow capacity loss (0.16% per cycle at 200 mA g -1 ). The present study not only paves the way for industrial-scale synthesis of advanced carbon materials for lithium-ion batteries but also deepens the fundamental understanding of the intrinsic mechanism of the molten-salt method.

Nitrogen-Doped Hollow Carbon Nanospheres for High-Performance Li-Ion Batteries.

PubMed

Yang, Yufen; Jin, Song; Zhang, Zhen; Du, Zhenzhen; Liu, Huarong; Yang, Jia; Xu, Hangxun; Ji, Hengxing

2017-04-26

N-doped carbon materials is of particular attraction for anodes of lithium-ion batteries (LIBs) because of their high surface areas, superior electrical conductivity, and excellent mechanical strength, which can store energy by adsorption/desorption of Li + at the interfaces between the electrolyte and electrode. By directly carbonization of zeolitic imidazolate framework-8 nanospheres synthesized by an emulsion-based interfacial reaction, we obtained N-doped hollow carbon nanospheres with tunable shell thickness (20 nm to solid sphere) and different N dopant concentrations (3.9 to 21.7 at %). The optimized anode material possessed a shell thickness of 20 nm and contained 16.6 at % N dopants that were predominately pyridinic and pyrrolic. The anode delivered a specific capacity of 2053 mA h g -1 at 100 mA g -1 and 879 mA h g -1 at 5 A g -1 for 1000 cycles, implying a superior cycling stability. The improved electrochemical performance can be ascribed to (1) the Li + adsorption dominated energy storage mechanism prevents the volume change of the electrode materials, (2) the hollow nanostructure assembled by the nanometer-sized primary particles prevents the agglomeration of the nanoparticles and favors for Li + diffusion, (3) the optimized N dopant concentration and configuration facilitate the adsorption of Li + ; and (4) the graphitic carbon nanostructure ensures a good electrical conductivity.

Oligo(ethylene glycol)-functionalized disiloxanes as electrolytes for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Zhang, Zhengcheng; Dong, Jian; West, Robert; Amine, Khalil

Functionalized disiloxane compounds were synthesized by attaching oligo(ethylene glycol) chains, -(CH 2CH 2O)- n, n = 2-7, via hydrosilation, dehydrocoupling, and nucleophilic substitution reactions and were examined as non-aqueous electrolyte solvents in lithium-ion cells. The compounds were fully characterized by 1H, 13C, and 29Si nuclear magnetic resonance (NMR) spectroscopy. Upon doping with lithium bis(oxalato)borate (LiBOB) or LiPF 6, the disiloxane electrolytes showed conductivities up to 6.2 × 10 -4 S cm -1 at room temperature. The thermal behavior of the electrolytes was studied by differential scanning calorimetry, which revealed very low glass transition temperatures before and after LiBOB doping and much higher thermal stability compared to organic carbonate electrolytes. Cyclic voltammetry measurements showed that disiloxane-based electrolytes with 0.8 M LiBOB salt concentration are stable to 4.7 V. The LiBOB/disiloxane combinations were found to be good electrolytes for lithium-ion cells; unlike LiPF 6, LiBOB can provide a good passivation film on the graphite anode. The LiPF 6/disiloxane electrolyte was enabled in lithium-ion cells by adding 1 wt% vinyl ethylene carbonate (VEC). Full cell performance tests with LiNi 0.80Co 0.15Al 0.05O 2 as the cathode and mesocarbon microbead (MCMB) graphite as the anode show stable cyclability. The results demonstrate that disiloxane-based electrolytes have considerable potential as electrolytes for use in lithium-ion batteries.

Enhanced generation of hydroxyl radicals on well-crystallized molybdenum trioxide/nano-graphite anode with sesame cake-like structure for degradation of bio-refractory antibiotic.

PubMed

Tang, Bo; Du, Jiannan; Feng, Qingmao; Zhang, Jiaqi; Wu, Dan; Jiang, Xiankai; Dai, Ying; Zou, Jinlong

2018-05-01

Anodic electro-catalysis oxidation is a highly effective way to solve the pollution problem of antibiotics in wastewater and receiving water bodies. In this study, for the first time, molybdenum trioxide/Nano-graphite (MoO 3 /Nano-G) composites are synthesized as anodic catalysts by a surfactant-assisted solvothermal method followed by low-temperature calcination. The effects of the proportion of MoO 3 to Nano-G (10, 30 and 50%) on the properties of composites are investigated through structural characterizations and electrochemical measurements. Results indicate that MoO 3 (30)/Nano-G electrode displays the electro-catalysis degradation efficiency of 99.9% towards ceftazidime, which is much higher than those of Nano-G (46.7%) and dimensionally stable anode (69.2%). The degradation mechanism for ceftazidime is studied by investigating the yields and kinds of active species. Results show that all of the OH, O 2- and H 2 O 2 are responsible for the electro-catalytic degradation process, and the produced OH radicals are the major active species for ceftazidime degradation. The synergistic effects between MoO 3 and Nano-G greatly contribute to the activation of H 2 O molecules to produce OH, meanwhile the special sesame cake-like structure facilitates to the exposure of contaminants to OH on active sites to enhance the degradation efficiency. These results suggest that MoO 3 /Nano-G electrodes can be considered as the promising catalysts for treating bio-refractory organic wastewater. Copyright © 2018 Elsevier Inc. All rights reserved.

4-Vinyl-1,3-Dioxolane-2-One as an Additive for Li-Ion Cells

NASA Technical Reports Server (NTRS)

Smart, Marshall; Bugga, Ratnakumar

2006-01-01

Electrolyte additive 4-vinyl-1,3-dioxolane-2-one has been found to be promising for rechargeable lithium-ion electrochemical cells. This and other additives, along with advanced electrolytes comprising solutions of LiPF6 in various mixtures of carbonate solvents, have been investigated in a continuing effort to improve the performances of rechargeable lithium-ion electrochemical cells, especially at low temperatures. In contrast to work by other researchers who have investigated the use of this additive to improve the high-temperature resilience of Li-ion cells, the current work involves the incorporation of 4-vinyl-1,3-dioxolane-2-one into quaternary carbonate electrolyte mixtures, previously optimized for low-temperature applications, resulting in improved low-temperature performance. The benefit afforded by 4-vinyl-1,3- dioxolane-2-one can be better understood in the light of relevant information from a number of prior NASA Tech Briefs articles about electrolytes and additives for such cells. To recapitulate: The loss of performance with decreasing temperature is attributable largely to a decrease of ionic conductivity and the increase in viscosity of the electrolyte. What is needed to extend the lower limit of operating temperature is a stable electrolyte solution with relatively small lowtemperature viscosity, a large electric permittivity, adequate coordination behavior, and appropriate ranges of solubilities of liquid and salt constituents. Whether the anode is made of graphitic or non-graphitic carbon, a film on the surface of the anode acts as a solid/electrolyte interface (SEI), the nature of which is critical to low-temperature performance. Desirably, the surface film should exert a chemically protective (passivating) effect on both the anode and the electrolyte, yet should remain conductive to lithium ions to facilitate intercalation and de-intercalation of the ions into and out of the carbon during discharging and charging, respectively. The additives investigated previously include alkyl pyrocarbonates. Those additives help to improve low-temperature performances by giving rise to the formation of SEIs having desired properties. The formation of the SEIs is believed to be facilitated by products (e.g., CO2) of the decomposition of these additives. These decomposition products are believed to react to form Li2CO3-based films on the carbon electrodes. The present additive, 4-vinyl-1,3-dioxolane-2-one, also helps to improve lowtemperature performance by contributing to the formation of SEIs having desired properties, but probably in a different manner: It is believed that, as part of the decomposition process, the compound polymerizes on the surfaces of carbon electrodes.

Elimination of a pollution associated with chromic acid during the electro-deposition of Cr(III) using appropriate anodic and membrane materials in a double film bath.

PubMed

Jiang, Xiaojun; Chen, Wenchao; Xu, Hongbo

2009-01-01

A method using trivalent chromium has been used to replace hexavalent chromium for the electro-deposition of chromium. Using a tri-chamber bath system various anodic materials and membranes were evaluated to minimize the production of environmentally and health damaging chromic acid. By measuring the absorbance of Cr(VI) at 640 nm, the results indicate that the use of a titanium plated ruthenium (Ti-Ru) anode produces the least amount of chromic acid byproduct compared to lead-gold alloy and graphite anodes. The concentration of Cr(VI) in the immediate vicinity of the Ti-Ru anode decreased from 0.389 mg/L to 0 during a 40-min deposition period. The use of a Nafion(TM) quaternary cation exchange membrane portioning the buffer and anode selectively prevented Cr(III) from entering the anode compartment whilst allowing the migration of H(+) to maintain overall voltaic continuity. It has been demonstrated that the use of a Ti-Ru anode with a Nafion(TM) membrane can eliminate the production of chromic acid associated with the electro-deposition of chromium plate thereby preventing its health damaging exposure to plant operators and preventing discharge of Cr(VI) into the environment. Addition of a surfactant improved current efficiency by 34.7%.

Effect of Copper and Silicon on Al-5%Zn Alloy as a Candidate Low Voltage Sacrificial Anode

NASA Astrophysics Data System (ADS)

Pratesa, Yudha; Ferdian, Deni; Togina, Inez

2017-05-01

One common method used for corrosion protection is a sacrificial anode. Sacrificial anodes that usually employed in the marine environment are an aluminum alloy sacrificial anode, especially Al-Zn-In. However, the electronegativity of these alloys can cause corrosion overprotection and stress cracking (SCC) on a high-strength steel. Therefore, there is a development of the sacrificial anode aluminum low voltage to reduce the risk of overprotection. The addition of alloying elements such as Cu, Si, and Ge will minimize the possibility of overprotection. This study was conducted to analyze the effect of silicon and copper addition in Al-5Zn. The experiment started from casting the sacrificial anode aluminum uses electrical resistance furnace in a graphite crucible in 800°C. The results alloy was analyzed using Optical emission spectroscopy (OES), Differential scanning calorimetry, electrochemical impedance spectroscopy, and metallography. Aluminum alloy with the addition of a copper alloy is the most suitable and efficient to serve as a low-voltage sacrificial anode aluminum. Charge transfer resistivity of copper is smaller than silicon which indicates that the charge transfer between the metal and the electrolyte is easier t to occur. Also, the current potential values in coupling with steel are also in the criteria range of low-voltage aluminum sacrificial anodes.

Porous carbon derived from disposable shaddock peel as an excellent catalyst toward VO2+/VO2+ couple for vanadium redox battery

NASA Astrophysics Data System (ADS)

Liu, J.; Wang, Z. A.; Wu, X. W.; Yuan, X. H.; Hu, J. P.; Zhou, Q. M.; Liu, Z. H.; Wu, Y. P.

2015-12-01

Functional porous carbon (PC) derived from bio-friendly shaddock peel has been firstly explored as catalyst for vanadium redox flow battery (VRB). The prepared PC is micro-mesoporous with high BET surface area of 882.7 m2 g-1, has some surface oxygen-containing functional groups, and is doped with N and P heteroatoms. These three factors greatly favor the electrochemical reactions of VO2+/VO2+ on the PC modified glass carbon (PC-GC). Compared with the naked GC and graphite modified GC, the PC-GC presents a lower peak separation (66 mV), higher anodic current density (17.1 mA cm-2) and cathodic current density (15.0 mA cm-2). The VRB using PC modified graphite felt (GF) as positive electrode demonstrates an enhanced voltage efficiency of 82.7% at the current density of 60 mA cm-2, and a better rate performance than that from the virginal GF.

Enabling LiTFSI-based electrolytes for safer lithium-ion batteries by using linear fluorinated carbonates as (Co)solvent.

PubMed

Kalhoff, Julian; Bresser, Dominic; Bolloli, Marco; Alloin, Fannie; Sanchez, Jean-Yves; Passerini, Stefano

2014-10-01

In this Full Paper we show that the use of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) as conducting salt in commercial lithium-ion batteries is made possible by introducing fluorinated linear carbonates as electrolyte (co)solvents. Electrolyte compositions based on LiTFSI and fluorinated carbonates were characterized regarding their ionic conductivity and electrochemical stability towards oxidation and with respect to their ability to form a protective film of aluminum fluoride on the aluminum surface. Moreover, the investigation of the electrochemical performance of standard lithium-ion anodes (graphite) and cathodes (Li[Ni1/3 Mn1/3 Co1/3 ]O2 , NMC) in half-cell configuration showed stable cycle life and good rate capability. Finally, an NMC/graphite full-cell confirmed the suitability of such electrolyte compositions for practical lithium-ion cells, thus enabling the complete replacement of LiPF6 and allowing the realization of substantially safer lithium-ion batteries. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of the cathode material on the removal of nitrates by electrolysis in non-chloride media.

PubMed

Lacasa, Engracia; Cañizares, Pablo; Llanos, Javier; Rodrigo, Manuel A

2012-04-30

In this work, the effect of the cathode material (conductive diamond, stainless steel, silicon carbide, graphite or lead) and the current density (150-1400 A m(-2)) on the removal of nitrates from aqueous solutions is studied by electrolysis in non-divided electrochemical cells equipped with conductive diamond anodes, using sodium sulphate as the electrolyte. The results show that the cathode material very strongly influences both the process performance and the product distribution. The main products obtained are gaseous nitrogen (NO, N(2)O and NO(2)) and ammonium ions. Nitrate removal follows first order kinetics, which indicates that the electrolysis process is controlled by mass transfer. Furthermore, the stainless steel and graphite cathodes show a great selectivity towards the production of ammonium ions, whereas the silicon carbide cathode leads to the highest formation of gaseous nitrogen, which production is promoted at low current densities. Copyright © 2012 Elsevier B.V. All rights reserved.

Microbial community structure elucidates performance of Glyceria maxima plant microbial fuel cell.

PubMed

Timmers, Ruud A; Rothballer, Michael; Strik, David P B T B; Engel, Marion; Schulz, Stephan; Schloter, Michael; Hartmann, Anton; Hamelers, Bert; Buisman, Cees

2012-04-01

The plant microbial fuel cell (PMFC) is a technology in which living plant roots provide electron donor, via rhizodeposition, to a mixed microbial community to generate electricity in a microbial fuel cell. Analysis and localisation of the microbial community is necessary for gaining insight into the competition for electron donor in a PMFC. This paper characterises the anode-rhizosphere bacterial community of a Glyceria maxima (reed mannagrass) PMFC. Electrochemically active bacteria (EAB) were located on the root surfaces, but they were more abundant colonising the graphite granular electrode. Anaerobic cellulolytic bacteria dominated the area where most of the EAB were found, indicating that the current was probably generated via the hydrolysis of cellulose. Due to the presence of oxygen and nitrate, short-chain fatty acid-utilising denitrifiers were the major competitors for the electron donor. Acetate-utilising methanogens played a minor role in the competition for electron donor, probably due to the availability of graphite granules as electron acceptors.

Effects of atmospheric air plasma treatment of graphite and carbon felt electrodes on the anodic current from Shewanella attached cells.

PubMed

Epifanio, Monica; Inguva, Saikumar; Kitching, Michael; Mosnier, Jean-Paul; Marsili, Enrico

2015-12-01

The attachment of electrochemically active microorganisms (EAM) on an electrode is determined by both the chemistry and topography of the electrode surface. Pre-treatment of the electrode surface by atmospheric air plasma introduces hydrophilic functional groups, thereby increasing cell attachment and electroactivity in short-term experiments. In this study, we use graphite and carbon felt electrodes to grow the model EAM Shewanella loihica PV-4 at oxidative potential (0.2 V vs. Ag/AgCl). Cell attachment and electroactivity are measured through electrodynamic methods. Atmospheric air plasma pre-treatment increases cell attachment and current output at graphite electrodes by 25%, while it improves the electroactivity of the carbon felt electrodes by 450%. Air plasma pre-treatment decreased the coulombic efficiency on both carbon felt and graphite electrodes by 60% and 80%, respectively. Microbially produced flavins adsorb preferentially at the graphite electrode, and air plasma pre-treatment results in lower flavin adsorption at both graphite and carbon felt electrodes. Results show that air plasma pre-treatment is a feasible option to increase current output in bioelectrochemical systems. Copyright © 2015 Elsevier B.V. All rights reserved.

Hybrid-Particle-In-Cell Simulation of Backsputtered Carbon Transport in the Near-Field Plume of a Hall Thruster

NASA Technical Reports Server (NTRS)

Choi, Maria; Yim, John T.; Williams, George J.; Herman, Daniel A.; Gilland, James H.

2018-01-01

Magnetic shielding has eliminated boron nitride erosion as the life limiting mechanism in a Hall thruster but has resulted in erosion of the front magnetic field pole pieces. Recent experiments show that the erosion of graphite pole covers, which are added to protect the magnetic field pole pieces, causes carbon to redeposit on other surfaces, such as boron nitride discharge channel and cathode keeper surfaces. As a part of the risk-reduction activities for Advanced Electric Propulsion System thruster development, this study models transport of backsputtered carbon from the graphite front pole covers and vacuum facility walls. Fluxes, energy distributions, and redeposition rates of backsputtered carbon on the anode, discharge channel, and graphite cathode keeper surfaces are predicted.

Development of Microbial and Enzymatic Fuel Cells for Bio-Inspired Power Sources

DTIC Science & Technology

2009-03-01

that of the oxidation of NADH as possible.[30] A variety of organic mediators have been studied for the anode, including phenazines ,[38] dyes,[39,40...glucose-6-phosphate dehydrogenase on the rotating graphite disc electrode modified with phenazine methosulfate. Enzyme Microb. Technol. 1993, 15 (6), 525

Ion sputter textured graphite electrode plates

NASA Technical Reports Server (NTRS)

Curren, A. N.; Forman, R.; Sovey, J. S.; Wintucky, E. G. (Inventor)

1983-01-01

A specially textured surface of pyrolytic graphite exhibits extremely low yields of secondary electrons and reduced numbers of reflected primary electrons after impingement of high energy primary electrons. Electrode plates of this material are used in multistage depressed collectors. An ion flux having an energy between 500 iV and 1000 iV and a current density between 1.0 mA/sq cm and 6.0 mA/sq cm produces surface roughening or texturing which is in the form of needles or spires. Such textured surfaces are especially useful as anode collector plates in high tube devices.

Addition of acetate improves stability of power generation using microbial fuel cells treating domestic wastewater.

PubMed

Stager, Jennifer L; Zhang, Xiaoyuan; Logan, Bruce E

2017-12-01

Power generation using microbial fuel cells (MFCs) must provide stable, continuous conversion of organic matter in wastewaters into electricity. However, when relatively small diameter (0.8cm) graphite fiber brush anodes were placed close to the cathodes in MFCs, power generation was unstable during treatment of low strength domestic wastewater. One reactor produced 149mW/m 2 before power generation failed, while the other reactor produced 257mW/m 2 , with both reactors exhibiting severe power overshoot in polarization tests. Using separators or activated carbon cathodes did not result in stable operation as the reactors continued to exhibit power overshoot based on polarization tests. However, adding acetate (1g/L) to the wastewater produced stable performance during fed batch and continuous flow operation, and there was no power overshoot in polarization tests. These results highlight the importance of wastewater strength and brush anode size for producing stable and continuous power in compact MFCs. Copyright © 2017 Elsevier B.V. All rights reserved.

Targeted synthesis of novel hierarchical sandwiched NiO/C arrays as high-efficiency lithium ion batteries anode

NASA Astrophysics Data System (ADS)

Feng, Yangyang; Zhang, Huijuan; Li, Wenxiang; Fang, Ling; Wang, Yu

2016-01-01

In this contribution, the novel 2D sandwich-like NiO/C arrays on Ti foil are successfully designed and fabricated for the first time via simple and controllable hydrothermal process. In this strategy, we use green glucose as carbon source and ultrathin Ni(OH)2 nanosheet arrays as precursor for NiO nanoparticles and sacrificial templates for coupled graphitized carbon layers. This advanced sandwiched composite can not only provide large surface area for numerous active sites and continuous contact between active materials and electrolyte, but also protect the active nanoparticles from aggregation, pulverization and peeling off from conductive substrates. Furthermore, the porous structure derived from lots of substances loss under high-temperature calcinations can effectively buffer possible volume expansion and facilitate ion transfer. In this article, sandwiched NiO/C arrays, utilized as anode for LIBs, demonstrated high specific capacity (∼1458 mAh g-1 at 500 mA g-1) and excellent rate performance and cyclablity (∼95.7% retention after 300 cycles).

Direct fabrication of 3D graphene on nanoporous anodic alumina by plasma-enhanced chemical vapor deposition

PubMed Central

Zhan, Hualin; Garrett, David J.; Apollo, Nicholas V.; Ganesan, Kumaravelu; Lau, Desmond; Prawer, Steven; Cervenka, Jiri

2016-01-01

High surface area electrode materials are of interest for a wide range of potential applications such as super-capacitors and electrochemical cells. This paper describes a fabrication method of three-dimensional (3D) graphene conformally coated on nanoporous insulating substrate with uniform nanopore size. 3D graphene films were formed by controlled graphitization of diamond-like amorphous carbon precursor films, deposited by plasma-enhanced chemical vapour deposition (PECVD). Plasma-assisted graphitization was found to produce better quality graphene than a simple thermal graphitization process. The resulting 3D graphene/amorphous carbon/alumina structure has a very high surface area, good electrical conductivity and exhibits excellent chemically stability, providing a good material platform for electrochemical applications. Consequently very large electrochemical capacitance values, as high as 2.1 mF for a sample of 10 mm3, were achieved. The electrochemical capacitance of the material exhibits a dependence on bias voltage, a phenomenon observed by other groups when studying graphene quantum capacitance. The plasma-assisted graphitization, which dominates the graphitization process, is analyzed and discussed in detail. PMID:26805546

Direct fabrication of 3D graphene on nanoporous anodic alumina by plasma-enhanced chemical vapor deposition.

PubMed

Zhan, Hualin; Garrett, David J; Apollo, Nicholas V; Ganesan, Kumaravelu; Lau, Desmond; Prawer, Steven; Cervenka, Jiri

2016-01-25

High surface area electrode materials are of interest for a wide range of potential applications such as super-capacitors and electrochemical cells. This paper describes a fabrication method of three-dimensional (3D) graphene conformally coated on nanoporous insulating substrate with uniform nanopore size. 3D graphene films were formed by controlled graphitization of diamond-like amorphous carbon precursor films, deposited by plasma-enhanced chemical vapour deposition (PECVD). Plasma-assisted graphitization was found to produce better quality graphene than a simple thermal graphitization process. The resulting 3D graphene/amorphous carbon/alumina structure has a very high surface area, good electrical conductivity and exhibits excellent chemically stability, providing a good material platform for electrochemical applications. Consequently very large electrochemical capacitance values, as high as 2.1 mF for a sample of 10 mm(3), were achieved. The electrochemical capacitance of the material exhibits a dependence on bias voltage, a phenomenon observed by other groups when studying graphene quantum capacitance. The plasma-assisted graphitization, which dominates the graphitization process, is analyzed and discussed in detail.

Effect of Vinylene Carbonate and Fluoroethylene Carbonate on SEI Formation on Graphitic Anodes in Li-Ion Batteries

DOE PAGES

Nie, Mengyun; Demeaux, Julien; Young, Benjamin T.; ...

2015-07-23

Binder free (BF) graphite electrodes were utilized to investigate the effect of electrolyte additives fluoroethylene carbonate (FEC) and vinylene carbonate (VC) on the structure of the solid electrolyte interface (SEI). The structure of the SEI has been investigated via ex-situ surface analysis including X-ray Photoelectron spectroscopy (XPS), Hard XPS (HAXPES), Infrared spectroscopy (IR) and transmission electron microscopy (TEM). The components of the SEI have been further investigated via nuclear magnetic resonance (NMR) spectroscopy of D2O extractions. The SEI generated on the BF-graphite anode with a standard electrolyte (1.2 M LiPF6 in ethylene carbonate (EC) / ethyl methyl carbonate (EMC), 3/7more » (v/v)) is composed primarily of lithium alkyl carbonates (LAC) and LiF. Incorporation of VC (3% wt) results in the generation of a thinner SEI composed of Li2CO3, poly(VC), LAC, and LiF. Incorporation of VC inhibits the generation of LAC and LiF. Incorporation of FEC (3% wt) also results in the generation of a thinner SEI composed of Li2CO3, poly(FEC), LAC, and LiF. The concentration of poly(FEC) is lower than the concentration of poly(VC) and the generation of LAC is inhibited in the presence of FEC. The SEI appears to be a homogeneous film for all electrolytes investigated.« less

Perfluoroalkyl-substituted ethylene carbonates: Novel electrolyte additives for high-voltage lithium-ion batteries

NASA Astrophysics Data System (ADS)

Zhu, Ye; Casselman, Matthew D.; Li, Yan; Wei, Alexander; Abraham, Daniel P.

2014-01-01

A new family of polyfluoroalkyl-substituted ethylene carbonates is synthesized and tested as additives in lithium-ion cells containing EC:EMC + LiPF6-based electrolyte. The influence of these compounds is investigated in Li1.2Ni0.15Mn0.55Co0.1O2//graphite cells via a combination of galvanostatic cycling and electrochemical impedance spectroscopy (EIS) tests. Among the four additives studied in this work (4-(trifluoromethyl)-1,3-dioxolan-2-one (TFM-EC), 4-(perfluorobutyl)-1,3-dioxolan-2-one (PFB-EC), 4-(perfluorohexyl)-1,3-dioxolan-2-one (PFH-EC), and 4-(perfluorooctyl)-1,3-dioxolan-2-one (PFO-EC)), small amounts (0.5 wt%) of PFO-EC is found to be most effective in lessening cell performance degradation during extended cycling. Linear sweep voltammetry (LSV), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy are used to further characterize the effects of PFO-EC on the positive and negative electrodes. LSV data from the electrolyte, and XPS analyses of electrodes harvested after cycling, suggest that PFO-EC is oxidized on the cathode forming surface films that slow electrode/cell impedance rise. Differential capacity (dQ/dV) plots from graphite//Li cells suggest that PFO-EC is involved in solid electrolyte interphase (SEI) formation. Raman data from anodes after cycling suggest that structural disordering of graphite is reduced by the addition of PFO-EC, which may explain the improved cell capacity retention.

Oxygen-consuming chlor alkali cell configured to minimize peroxide formation

DOEpatents

Chlistunoff, Jerzy B [Los Alamos, NM; Lipp, Ludwig [Brookfield, CT; Gottesfeld, Shimshon [Niskayuna, NY

2006-08-01

Oxygen-consuming zero gap chlor-alkali cell was configured to minimize peroxide formation. The cell included an ion-exchange membrane that divided the cell into an anode chamber including an anode and a cathode chamber including an oxygen gas diffusion cathode. The cathode included a single-piece of electrically conducting graphitized carbon cloth. Catalyst and polytetrafluoroethylene were attached to only one side of the cloth. When the cathode was positioned against the cation exchange membrane with the catalyst side away from the membrane, electrolysis of sodium chloride to chlorine and caustic (sodium hydroxide) proceeded with minimal peroxide formation.

Embedded Si/Graphene Composite Fabricated by Magnesium-Thermal Reduction as Anode Material for Lithium-Ion Batteries

NASA Astrophysics Data System (ADS)

Zhu, Jiangliu; Ren, Yurong; Yang, Bo; Chen, Wenkai; Ding, Jianning

2017-12-01

Embedded Si/graphene composite was fabricated by a novel method, which was in situ generated SiO2 particles on graphene sheets followed by magnesium-thermal reduction. The tetraethyl orthosilicate (TEOS) and flake graphite was used as original materials. On the one hand, the unique structure of as-obtained composite accommodated the large volume change to some extent. Simultaneously, it enhanced electronic conductivity during Li-ion insertion/extraction. The MR-Si/G composite is used as the anode material for lithium ion batteries, which shows high reversible capacity and ascendant cycling stability reach to 950 mAh·g-1 at a current density of 50 mA·g-1 after 60 cycles. These may be conducive to the further advancement of Si-based composite anode design.

Preparation of Advanced Carbon Anode Materials from Mesocarbon Microbeads for Use in High C-Rate Lithium Ion Batteries

PubMed Central

Fang, Ming-Dar; Ho, Tsung-Han; Yen, Jui-Pin; Lin, Yu-Run; Hong, Jin-Long; Wu, She-Huang; Jow, Jiin-Jiang

2015-01-01

Mesophase soft carbon (MSC) and mesophase graphite (SMG), for use in comparative studies of high C-rate Lithium Ion Battery (LIB) anodes, were made by heating mesocarbon microbeads (MCMB) at 1300 °C and 3000 °C; respectively. The crystalline structures and morphologies of the MSC, SMG, and commercial hard carbon (HC) were investigated by X-ray diffraction, transmission electron microscopy, scanning electron microscopy, and Raman spectroscopy. Additionally, their electrochemical properties, when used as anode materials in LIBs, were also investigated. The results show that MSC has a superior charging rate capability compared to SMG and HC. This is attributed to MSC having a more extensive interlayer spacing than SMG, and a greater number of favorably-oriented pathways when compared to HC.

High specific power, direct methanol fuel cell stack

DOEpatents

Ramsey, John C [Los Alamos, NM; Wilson, Mahlon S [Los Alamos, NM

2007-05-08

The present invention is a fuel cell stack including at least one direct methanol fuel cell. A cathode manifold is used to convey ambient air to each fuel cell, and an anode manifold is used to convey liquid methanol fuel to each fuel cell. Tie-bolt penetrations and tie-bolts are spaced evenly around the perimeter to hold the fuel cell stack together. Each fuel cell uses two graphite-based plates. One plate includes a cathode active area that is defined by serpentine channels connecting the inlet manifold with an integral flow restrictor to the outlet manifold. The other plate includes an anode active area defined by serpentine channels connecting the inlet and outlet of the anode manifold. Located between the two plates is the fuel cell active region.

Graphite|LiFePO4 lithium-ion battery working at the heat engine coolant temperature

NASA Astrophysics Data System (ADS)

Lewandowski, Andrzej; Kurc, Beata; Swiderska-Mocek, Agnieszka; Kusa, Natalia

2014-11-01

Electrochemical properties of the graphite anode and the LiFePO4 cathode, working together with the 1 M LiPF6 in TMS (sulpholane) at 90 °C have been studied. The general aim of the investigation was to demonstrate a potential application for a Li-ion cell working in the cooling system of a car heat engine (90 °C). Electrodes were characterized with the use of electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM) as well as galvanostatic charging/discharging tests. SEM images of both electrodes after charging/discharging processes were covered with a film (electrochemical SEI formation). The charge transfer resistance at 90 °C, Rct, of the C6Li|Li+ anode and the LiFePO4 cathode was 24 Ω and 110 Ω, respectively. Reversible capacity of the LiC6 anode after 10-20 cycles, at a low current rate was close to the theoretical value of 370 mAh g-1 however an increasing current rate decreased to ca. 200 mAh g-1 (for 1C). The reversibility of the process was close to 95%. The capacity of the LiFePO4 cathode was ca. 150 mAh g-1, almost independent of the current rate and close to the theoretical value of 170 mAh g-1.

Plant and microorganisms support media for electricity generation in biological fuel cells with living hydrophytes.

PubMed

Salinas-Juárez, María Guadalupe; Roquero, Pedro; Durán-Domínguez-de-Bazúa, María Del Carmen

2016-12-01

Plant support media may impact power output in a biological fuel cell with living plants, due to the physical and biochemical processes that take place in it. A material for support medium should provide the suitable conditions for the robust microbial growth and its metabolic activity, degrading organic matter and other substances; and, transferring electrons to the anode. To consider the implementation of this type of bio-electrochemical systems in constructed wetlands, this study analyzes the electrochemical behavior of biological fuel cells with the vegetal species Phragmites australis, by using two different support media: graphite granules and a volcanic slag, commonly known as tezontle (stone as light as hair, from the Aztec or Nahuatl language). Derived from the results, both, graphite and tezontle have the potential to be used as support medium for plants and microorganisms supporting a maximum power of 26.78mW/m(2) in graphite reactors. These reactors worked under mixed control: with ohmic and kinetic resistances of the same order of magnitude. Tezontle reactors operated under kinetic control with a high activation resistance supplying 9.73mW/m(2). These performances could be improved with stronger bacterial populations in the reactor, to ensure the rapid depletion of substrate. Copyright © 2016 Elsevier B.V. All rights reserved.

A novel bio-electrochemical system with sand/activated carbon separator, Al anode and bio-anode integrated micro-electrolysis/electro-flocculation cost effectively treated high load wastewater with energy recovery.

PubMed

Gao, Changfei; Liu, Lifen; Yang, Fenglin

2018-02-01

A novel bio-electrochemical system (BES) was developed by integrating micro-electrolysis/electro-flocculation from attaching a sacrificing Al anode to the bio-anode, it effectively treated high load wastewater with energy recovery (maximum power density of 365.1 mW/m 3 and a maximum cell voltage of 0.97 V), and achieving high removals of COD (>99.4%), NH 4 + -N (>98.7%) and TP (>98.6%). The anode chamber contains microbes, activated carbon (AC)/graphite granules and Al anode. It was separated from the cathode chamber containing bifunctional catalytic and filtration membrane cathode (loaded with Fe/Mn/C/F/O catalyst) by a multi-medium chamber (MMC) filled with manganese sand and activated carbon granules, which replaced expensive PEM and reduced cost. An air contact oxidation bed for aeration was still adopted before liquid entering the cathode chamber. micro-electrolysis/electro-flocculation helps in achieving high removal efficiencies and contributes to membrane fouling migration. The increase of activated carbon in the separator MMC increased power generation and reduced system electric resistance. Copyright © 2017 Elsevier Ltd. All rights reserved.

Operando NMR and XRD study of chemically synthesized LiCx oxidation in a dry room environment

DOE PAGES

Sacci, Robert L.; Gill, Lance W.; Hagaman, Edward W.; ...

2015-04-07

We test the stability of pre-lithiated graphite anodes for Li-ion batteries in a dry room battery processing room. The reaction between LiCx and laboratory air was followed using operando NMR and x-ray diffraction as these methods are sensitive to change in Li stoichiometry in graphite. There is minimal reactivity between LiC 6 and N 2, CO 2 or O 2; however, LiC 6 reacts with moisture to form lithium (hydr)oxide. The reaction rate follows zero-order kinetics with respects to intercalated lithium suggesting that lithium transport through the graphite is fast. The reaction mechanism occurs by sequential formation of higher stagesmore » LiC 12, then LiC 18, and then LiC 24 as the hydrolysis proceeds to the formation of Li xOH y and graphite end products. Slowing down the formation rate of the Li xOH y passivation layer stabilizes of the higher stages.« less

Electrochemical Exfoliation of Graphite in Aqueous Sodium Halide Electrolytes toward Low Oxygen Content Graphene for Energy and Environmental Applications.

PubMed

Munuera, J M; Paredes, J I; Enterría, M; Pagán, A; Villar-Rodil, S; Pereira, M F R; Martins, J I; Figueiredo, J L; Cenis, J L; Martínez-Alonso, A; Tascón, J M D

2017-07-19

Graphene and graphene-based materials have shown great promise in many technological applications, but their large-scale production and processing by simple and cost-effective means still constitute significant issues in the path of their widespread implementation. Here, we investigate a straightforward method for the preparation of a ready-to-use and low oxygen content graphene material that is based on electrochemical (anodic) delamination of graphite in aqueous medium with sodium halides as the electrolyte. Contrary to previous conflicting reports on the ability of halide anions to act as efficient exfoliating electrolytes in electrochemical graphene exfoliation, we show that proper choice of both graphite electrode (e.g., graphite foil) and sodium halide concentration readily leads to the generation of large quantities of single-/few-layer graphene nanosheets possessing a degree of oxidation (O/C ratio down to ∼0.06) lower than that typical of anodically exfoliated graphenes obtained with commonly used electrolytes. The halide anions are thought to play a role in mitigating the oxidation of the graphene lattice during exfoliation, which is also discussed and rationalized. The as-exfoliated graphene materials exhibited a three-dimensional morphology that was suitable for their practical use without the need to resort to any kind of postproduction processing. When tested as dye adsorbents, they outperformed many previously reported graphene-based materials (e.g., they adsorbed ∼920 mg g -1 for methyl orange) and were useful sorbents for oils and nonpolar organic solvents. Supercapacitor cells assembled directly from the as-exfoliated products delivered energy and power density values (up to 15.3 Wh kg -1 and 3220 W kg -1 , respectively) competitive with those of many other graphene-based devices but with the additional advantage of extreme simplicity of preparation.

Surface characteristics of spacecraft components affect the aggregation of microorganisms and may lead to different survival rates of bacteria on Mars landers.

PubMed

Schuerger, Andrew C; Richards, Jeffrey T; Hintze, Paul E; Kern, Roger G

2005-08-01

Layers of dormant endospores of Bacillus subtilis HA101 were applied to eight different spacecraft materials and exposed to martian conditions of low pressure (8.5 mbar), low temperature (-10 degrees C), and high CO(2) gas composition and irradiated with a Mars-normal ultraviolet (UV-visible- near-infrared spectrum. Bacterial layers were exposed to either 1 min or 1 h of Mars-normal UV irradiation, which simulated clear-sky conditions on equatorial Mars (0.1 tau). When exposed to 1 min of Mars UV irradiation, the numbers of viable endospores of B. subtilis were reduced three to four orders of magnitude for two brands of aluminum (Al), stainless steel, chemfilm-treated Al, clear-anodized Al, and black-anodized Al coupons. In contrast, bacterial survival was reduced only one to two orders of magnitude for endospores on the non-metal materials astroquartz and graphite composite when bacterial endospores were exposed to 1 min of Mars UV irradiation. When bacterial monolayers were exposed to 1 h of Mars UV irradiation, no viable bacteria were recovered from the six metal coupons listed above. In contrast, bacterial survival was reduced only two to three orders of magnitude for spore layers on astroquartz and graphite composite exposed to 1 h of Mars UV irradiation. Scanning electron microscopy images of the bacterial monolayers on all eight spacecraft materials revealed that endospores of B. subtilis formed large aggregates of multilayered spores on astroquartz and graphite composite, but not on the other six spacecraft materials. It is likely that the formation of multilayered aggregates of endospores on astroquartz and graphite composite is responsible for the enhanced survival of bacterial cells on these materials.

Surface characteristics of spacecraft components affect the aggregation of microorganisms and may lead to different survival rates of bacteria on Mars landers

NASA Technical Reports Server (NTRS)

Schuerger, Andrew C.; Richards, Jeffrey T.; Hintze, Paul E.; Kern, Roger G.

2005-01-01

Layers of dormant endospores of Bacillus subtilis HA101 were applied to eight different spacecraft materials and exposed to martian conditions of low pressure (8.5 mbar), low temperature (-10 degrees C), and high CO(2) gas composition and irradiated with a Mars-normal ultraviolet (UV-visible- near-infrared spectrum. Bacterial layers were exposed to either 1 min or 1 h of Mars-normal UV irradiation, which simulated clear-sky conditions on equatorial Mars (0.1 tau). When exposed to 1 min of Mars UV irradiation, the numbers of viable endospores of B. subtilis were reduced three to four orders of magnitude for two brands of aluminum (Al), stainless steel, chemfilm-treated Al, clear-anodized Al, and black-anodized Al coupons. In contrast, bacterial survival was reduced only one to two orders of magnitude for endospores on the non-metal materials astroquartz and graphite composite when bacterial endospores were exposed to 1 min of Mars UV irradiation. When bacterial monolayers were exposed to 1 h of Mars UV irradiation, no viable bacteria were recovered from the six metal coupons listed above. In contrast, bacterial survival was reduced only two to three orders of magnitude for spore layers on astroquartz and graphite composite exposed to 1 h of Mars UV irradiation. Scanning electron microscopy images of the bacterial monolayers on all eight spacecraft materials revealed that endospores of B. subtilis formed large aggregates of multilayered spores on astroquartz and graphite composite, but not on the other six spacecraft materials. It is likely that the formation of multilayered aggregates of endospores on astroquartz and graphite composite is responsible for the enhanced survival of bacterial cells on these materials.

Intercalation of Lithium in Pitch-Based Graphitized Carbon Fibers Chemically Modified by Fluorine: Soft Carbon With or Without an Oxide Surface

NASA Technical Reports Server (NTRS)

Hung, Ching-Chen; Prisko, Aniko

1999-01-01

The effects of carbon structure and surface oxygen on the carbon's performance as the anode in lithium-ion battery were studied. Two carbon materials were used for the electrochemical tests: soft carbon made from defluorination of graphite fluoride, and the carbon precursor from which the graphite fluoride was made. In this research the precursor was graphitized carbon fiber P-100. It was first fluorinated to form CF(0.68), then defluorinated slowly at 350 to 450 C in bromoform, and finally heated in 1000 C nitrogen before exposed to room temperature air, producing disordered soft carbon having basic surface oxides. This process caused very little carbon loss. The electrochemical test involved cycles of lithium intercalation and deintercalation using C/saturated LiI-50/50 (vol %) EC and DMC/Li half cell. The cycling test had four major results. (1) The presence of a basic oxide surface may prevent solvent from entering the carbon structure and therefore prolong the carbon's cycle life for lithium intercalation-deintercalation. (2) The disordered soft carbon can store lithium through two different mechanisms. One of them is lithium intercalation. which gives the disordered carbon an electrochemical behavior similar to its more ordered graphitic precursor. The other is unknown in its chemistry, but is responsible for the high-N,oltage portion (less than 0.3V) of the charge-discharge curve. (3) Under certain conditions, the disordered carbon can store more lithium than its precursor. (4) These sample and its precursor can intercalate at 200 mA/g. and deintercalate at a rate of 2000 mA/g without significant capacity loss.

Enhanced performance of spherical natural graphite coated by Li4Ti5O12 as anode for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Lu, Mi; Tian, Yanyan; Zheng, Xiaodong; Gao, Jun; Huang, Bing

2012-12-01

The natural graphite (NG) is coated with Li4Ti5O12 (LTO) and the composite shows a markedly enhanced rate performance due to the decrease of charge transfer resistance after LTO coating. The specific capacity of the NG charge-discharged at 2 C is increased by 60.3% (128.7 vs. 80.3 mAh g-1) by coating it with 1 wt.% of Li4Ti5O12 (LTO). The comparison of the NG and that coated with 1 wt.% LTO at 0.1 C shows that the initial reversible capacity is increased from 318.1 mAh g-1 to 357.5 mAh g-1 after coating, while the total irreversible capacity loss after 50 cycles is decreased from 122.8 mAh g-1 to 103.9 mAh g-1. The composite improves the energy and power densities, safety, cycle life and lowers the price of the lithium-ion battery while avoiding the gas-swelling of full battery caused by Ti4+ because the final coating material is the lithiated LTO (Li7Ti5O12 or Li9Ti5O12).

Efficient reduced graphene oxide grafted porous Fe3O4 composite as a high performance anode material for Li-ion batteries.

PubMed

Bhuvaneswari, Subramani; Pratheeksha, Parakandy Muzhikara; Anandan, Srinivasan; Rangappa, Dinesh; Gopalan, Raghavan; Rao, Tata Narasinga

2014-03-21

Here, we report facile fabrication of Fe3O4-reduced graphene oxide (Fe3O4-RGO) composite by a novel approach, i.e., microwave assisted combustion synthesis of porous Fe3O4 particles followed by decoration of Fe3O4 by RGO. The characterization studies of Fe3O4-RGO composite demonstrate formation of face centered cubic hexagonal crystalline Fe3O4, and homogeneous grafting of Fe3O4 particles by RGO. The nitrogen adsorption-desorption isotherm shows presence of a porous structure with a surface area and a pore volume of 81.67 m(2) g(-1), and 0.106 cm(3) g(-1) respectively. Raman spectroscopic studies of Fe3O4-RGO composite confirm the existence of graphitic carbon. Electrochemical studies reveal that the composite exhibits high reversible Li-ion storage capacity with enhanced cycle life and high coulombic efficiency. The Fe3O4-RGO composite showed a reversible capacity ∼612, 543, and ∼446 mA h g(-1) at current rates of 1 C, 3 C and 5 C, respectively, with a coulombic efficiency of 98% after 50 cycles, which is higher than graphite, and Fe3O4-carbon composite. The cyclic voltammetry experiment reveals the irreversible and reversible Li-ion storage in Fe3O4-RGO composite during the starting and subsequent cycles. The results emphasize the importance of our strategy which exhibited promising electrochemical performance in terms of high capacity retention and good cycling stability. The synergistic properties, (i) improved ionic diffusion by porous Fe3O4 particles with a high surface area and pore volume, and (ii) increased electronic conductivity by RGO grafting attributed to the excellent electrochemical performance of Fe3O4, which make this material attractive to use as anode materials for lithium ion storage.

Micro-size spherical TiO2(B) secondary particles as anode materials for high-power and long-life lithium-ion batteries

NASA Astrophysics Data System (ADS)

Takami, Norio; Harada, Yasuhiro; Iwasaki, Takuya; Hoshina, Keigo; Yoshida, Yorikazu

2015-01-01

Electrochemical properties of micro-size spherical TiO2(B) secondary particles have been investigated in order to develop TiO2(B) anodes for lithium-ion batteries with high-power and long-life performance. The spherical TiO2(B) electrodes with a small amount of a carbon conductor additive had a high electrode density of 2.2 g cm-3 and a volumetric reversible capacity of 475 mAh cm-3 comparable to that of graphite electrodes. Compared with nano-size needle-like TiO2(B) electrodes, the spherical TiO2(B) electrodes exhibited higher-rate discharge capability and longer-cycle life performance. The impedance of the TiO2(B)/electrolyte interface model indicated that the charge transfer resistance Rc and the passivating film resistance Rf of the spherical TiO2(B) were much smaller than those of the needle-like one. The high-rate discharge and the long-cycle performance of the spherical TiO2(B) electrode are attributed to the superior electronic connective property and Rc and Rf values smaller than those of the needle-like one. Lithium-ion cells using the spherical TiO2(B) anodes and LiNi0.8Co0.1Mn0.1O2 cathode with a capacity of 2.8 Ah exhibited a high energy density of 100 Wh kg-1, a high output power density of 1800 W kg-1 for 10 s pulse, and a long cycle life of more than 3000 cycles.

A novel high energy density rechargeable lithium/air battery.

PubMed

Zhang, Tao; Imanishi, Nobuyuki; Shimonishi, Yuta; Hirano, Atsushi; Takeda, Yasuo; Yamamoto, Osamu; Sammes, Nigel

2010-03-14

A novel rechargeable lithium/air battery was fabricated, which consisted of a water-stable multilayer Li-metal anode, acetic acid-water electrolyte, and a fuel-cell analogous air-diffusion cathode and possessed a high energy density of 779 W h kg(-1), twice that of the conventional graphite/LiCoO(2) cell.

A Bio-Inspired, Heavy-Metal-Free, Dual-Electrolyte Liquid Battery towards Sustainable Energy Storage.

PubMed

Ding, Yu; Yu, Guihua

2016-04-04

Wide-scale exploitation of renewable energy requires low-cost efficient energy storage devices. The use of metal-free, inexpensive redox-active organic materials represents a promising direction for environmental-friendly, cost-effective sustainable energy storage. To this end, a liquid battery is designed using hydroquinone (H2BQ) aqueous solution as catholyte and graphite in aprotic electrolyte as anode. The working potential can reach 3.4 V, with specific capacity of 395 mA h g(-1) and stable capacity retention about 99.7% per cycle. Such high potential and capacity is achieved using only C, H and O atoms as building blocks for redox species, and the replacement of Li metal with graphite anode can circumvent potential safety issues. As H2BQ can be extracted from biomass directly and its redox reaction mimics the bio-electrochemical process of quinones in nature, using such a bio-inspired organic compound in batteries enables access to greener and more sustainable energy-storage technology. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of overcharge on Li(Ni 0.5Mn 0.3Co 0.2)O 2/Graphite lithium ion cells with poly(vinylidene fluoride) binder. I - Microstructural changes in the anode

DOE PAGES

Dietz Rago, Nancy; Bareno, Javier; Li, Jianlin; ...

2018-03-17

Cells based on NMC/graphite, containing poly(vinylidene difluoride) (PVDF) binders in the positive and negative electrodes, were systematically overcharged to 100, 120, 140, 160, 180, and 250% state-of-charge (SOC). At 250% SOC the cell vented. Scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) of the anodes showed several state-of-overcharge-dependent trends. Starting at 120% SOC, dendrites appeared and increased in concentration as the SOC increased. Dendrite morphology appeared to be dependent on whether the active material was on the “dull” or “shiny” side of the copper collector. Significantly more delamination of the active material from the collector was seen on themore » “shiny” side of the collector particularly at 180 and 250% SOC. Transition metals were detected at 120% SOC and increased in concentration as the SOC increased. Finally, there was considerable spatial heterogeneity in the microstructures across each laminate with several regions displaying complex layered structures.« less

Vacuum Plasma Spray Forming of Tungsten Lorentz Force Accelerator Components

NASA Technical Reports Server (NTRS)

Zimmerman, Frank R.

2004-01-01

The Vacuum Plasma Spray (VPS) Laboratory at NASA's Marshall Space Flight Center, working with the Jet Propulsion Laboratory, has developed and demonstrated a fabrication technique using the VPS process to form anode and cathode sections for a Lorentz force accelerator made from tungsten. Lorentz force accelerators are an attractive form of electric propulsion that provides continuous, high-efficiency propulsion at useful power levels for such applications as orbit transfers or deep space missions. The VPS process is used to deposit refractory metals such as tungsten onto a graphite mandrel of the desired shape. Because tungsten is reactive at high temperatures, it is thermally sprayed in an inert environment where the plasma gun melts and deposits the molten metal powder onto a mandrel. A three-axis robot inside the chamber controls the motion of the plasma spray torch. A graphite mandrel acts as a male mold, forming the required contour and dimensions for the inside surface of the anode or cathode of the accelerator. This paper describes the processing techniques, design considerations, and process development associated with the VPS forming of Lorentz force accelerator components.

Effect of overcharge on Li(Ni 0.5Mn 0.3Co 0.2)O 2/Graphite lithium ion cells with poly(vinylidene fluoride) binder. I - Microstructural changes in the anode

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dietz Rago, Nancy; Bareno, Javier; Li, Jianlin

Cells based on NMC/graphite, containing poly(vinylidene difluoride) (PVDF) binders in the positive and negative electrodes, were systematically overcharged to 100, 120, 140, 160, 180, and 250% state-of-charge (SOC). At 250% SOC the cell vented. Scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) of the anodes showed several state-of-overcharge-dependent trends. Starting at 120% SOC, dendrites appeared and increased in concentration as the SOC increased. Dendrite morphology appeared to be dependent on whether the active material was on the “dull” or “shiny” side of the copper collector. Significantly more delamination of the active material from the collector was seen on themore » “shiny” side of the collector particularly at 180 and 250% SOC. Transition metals were detected at 120% SOC and increased in concentration as the SOC increased. Finally, there was considerable spatial heterogeneity in the microstructures across each laminate with several regions displaying complex layered structures.« less

A Lithium-ion Battery Using Partially Lithiated Graphite Anode and Amphi-redox LiMn2O4 Cathode.

PubMed

Jeon, Yuju; Noh, Hyun Kuk; Song, Hyun-Kon

2017-11-01

Delithiation followed by lithiation of Li + -occupied (n-type) tetrahedral sites of cubic LiMn 2 O 4 spinel (LMO) at ~4 [Formula: see text] (delivering ~100 mAh g LMO -1 ) has been used for energy storage by lithium ion batteries (LIBs). In this work, we utilized unoccupied (p-type) octahedral sites of LMO available for lithiation at ~3 [Formula: see text] (delivering additional ~100 mAh g LMO -1 ) that have never been used for LIBs in full-cell configuration. The whole capacity of amphi-redox LMO, including both oxidizable n-type and reducible p-type redox sites, at ~200 mAh g LMO -1 was realized by using the reactions both at 4 [Formula: see text] and 3 [Formula: see text]. Durable reversibility of the 3 V reaction was achieved by graphene-wrapping LMO nanoparticles (LMO@Gn). Prelithiated graphite (Li n C 6 , n < 1) was used as anodes to lithiate the unoccupied octahedral sites of LMO for the 3 V reaction.

Mesoporous Silicon Hollow Nanocubes Derived from Metal-Organic Framework Template for Advanced Lithium-Ion Battery Anode.

PubMed

Yoon, Taeseung; Bok, Taesoo; Kim, Chulhyun; Na, Younghoon; Park, Soojin; Kim, Kwang S

2017-05-23

Controlling the morphology of nanostructured silicon is critical to improving the structural stability and electrochemical performance in lithium-ion batteries. The use of removable or sacrificial templates is an effective and easy route to synthesize hollow materials. Herein, we demonstrate the synthesis of mesoporous silicon hollow nanocubes (m-Si HCs) derived from a metal-organic framework (MOF) as an anode material with outstanding electrochemical properties. The m-Si HC architecture with the mesoporous external shell (∼15 nm) and internal void (∼60 nm) can effectively accommodate volume variations and relieve diffusion-induced stress/strain during repeated cycling. In addition, this cube architecture provides a high electrolyte contact area because of the exposed active site, which can promote the transportation of Li ions. The well-designed m-Si HC with carbon coating delivers a high reversible capacity of 1728 mAhg -1 with an initial Coulombic efficiency of 80.1% after the first cycle and an excellent rate capability of >1050 mAhg -1 even at a 15 C-rate. In particular, the m-Si HC anode effectively suppresses electrode swelling to ∼47% after 100 cycles and exhibits outstanding cycle stability of 850 mAhg -1 after 800 cycles at a 1 C-rate. Moreover, a full cell (2.9 mAhcm -2 ) comprising a m-Si HC-graphite anode and LiCoO 2 cathode exhibits remarkable cycle retention of 72% after 100 cycles at a 0.2 C-rate.

The Impact of Li Grain Size on Coulombic Efficiency in Li Batteries.

PubMed

Mehdi, B Layla; Stevens, Andrew; Qian, Jiangfeng; Park, Chiwoo; Xu, Wu; Henderson, Wesley A; Zhang, Ji-Guang; Mueller, Karl T; Browning, Nigel D

2016-10-05

One of the most promising means to increase the energy density of state-of-the-art lithium Li-ion batteries is to replace the graphite anode with a Li metal anode. While the direct use of Li metal may be highly advantageous, at present its practical application is limited by issues related to dendrite growth and low Coulombic efficiency, CE. Here operando electrochemical scanning transmission electron microscopy (STEM) is used to directly image the deposition/stripping of Li at the anode-electrolyte interface in a Li-based battery. A non-aqueous electrolyte containing small amounts of H 2 O as an additive results in remarkably different deposition/stripping properties as compared to the "dry" electrolyte when operated under identical electrochemical conditions. The electrolyte with the additive deposits more Li during the first cycle, with the grain sizes of the Li deposits being significantly larger and more variable. The stripping of the Li upon discharge is also more complete, i.e., there is a higher cycling CE. This suggests that larger grain sizes are indicative of better performance by leading to more uniform Li deposition and an overall decrease in the formation of Li dendrites and side reactions with electrolyte components, thus potentially paving the way for the direct use of Li metal in battery technologies.

The Impact of Li Grain Size on Coulombic Efficiency in Li Batteries

PubMed Central

Mehdi, B. Layla; Stevens, Andrew; Qian, Jiangfeng; Park, Chiwoo; Xu, Wu; Henderson, Wesley A.; Zhang, Ji-Guang; Mueller, Karl T.; Browning, Nigel D.

2016-01-01

One of the most promising means to increase the energy density of state-of-the-art lithium Li-ion batteries is to replace the graphite anode with a Li metal anode. While the direct use of Li metal may be highly advantageous, at present its practical application is limited by issues related to dendrite growth and low Coulombic efficiency, CE. Here operando electrochemical scanning transmission electron microscopy (STEM) is used to directly image the deposition/stripping of Li at the anode-electrolyte interface in a Li-based battery. A non-aqueous electrolyte containing small amounts of H2O as an additive results in remarkably different deposition/stripping properties as compared to the “dry” electrolyte when operated under identical electrochemical conditions. The electrolyte with the additive deposits more Li during the first cycle, with the grain sizes of the Li deposits being significantly larger and more variable. The stripping of the Li upon discharge is also more complete, i.e., there is a higher cycling CE. This suggests that larger grain sizes are indicative of better performance by leading to more uniform Li deposition and an overall decrease in the formation of Li dendrites and side reactions with electrolyte components, thus potentially paving the way for the direct use of Li metal in battery technologies. PMID:27703188

The effect of chemical vapor deposition temperature on the performance of binder-free sewage sludge-derived anodes in microbial fuel cells.

PubMed

Feng, Huajun; Jia, Yufeng; Shen, Dongsheng; Zhou, Yuyang; Chen, Ting; Chen, Wei; Ge, Zhipeng; Zheng, Shuting; Wang, Meizhen

2018-04-13

Conversion of sewage sludge (SS) into value-added material has garnered increasing attention due to its potential applications. In this study, we propose a new application of the sewage sludge-derived carbon (SSC) as an electrode without binder in microbial fuel cells (MFCs). SS was firstly converted into SSC monoliths by methane chemical vapor method at different temperature (600, 800, 1000 or 1200°C). Scanning electron microscopy images showed that carbon micro-wires were present on the surfaces of the samples prepared at 1000 and 1200°C. The results showed that it was beneficial for converting sludge into a highly conductive electrode and increasing carbon content of the electrode at higher temperatures, thereby improving the current generation. The conductivity results show that a higher temperature favors the conversion of sludge into a highly conductive electrode. The MFC using an SSC anode processed at 1200°C generated the maximum power density of 2228mWm -2 and the maximum current density of 14.2Am -2 . This value was 5 times greater than that generated by an MFC equipped with a graphite anode. These results present a promising means of converting SS into electrode materials. Copyright © 2018 Elsevier B.V. All rights reserved.

Fabrication, Optimization and Characterization of Natural Dye Sensitized Solar Cell

PubMed Central

Ghann, William; Kang, Hyeonggon; Sheikh, Tajbik; Yadav, Sunil; Chavez-Gil, Tulio; Nesbitt, Fred; Uddin, Jamal

2017-01-01

The dyes extracted from pomegranate and berry fruits were successfully used in the fabrication of natural dye sensitized solar cells (NDSSC). The morphology, porosity, surface roughness, thickness, absorption and emission characteristics of the pomegranate dye sensitized photo-anode were studied using various analytical techniques including FESEM, EDS, TEM, AFM, FTIR, Raman, Fluorescence and Absorption Spectroscopy. Pomegranate dye extract has been shown to contain anthocyanin which is an excellent light harvesting pigment needed for the generation of charge carriers for the production of electricity. The solar cell’s photovoltic performance in terms of efficiency, voltage, and current was tested with a standard illumination of air-mass 1.5 global (AM 1.5 G) having an irradiance of 100 mW/cm2. After optimization of the photo-anode and counter electrode, a photoelectric conversion efficiency (η) of 2%, an open-circuit voltage (Voc) of 0.39 mV, and a short-circuit current density (Isc) of 12.2 mA/cm2 were obtained. Impedance determination showed a relatively low charge-transfer resistance (17.44 Ω) and a long lifetime, signifying a reduction in recombination losses. The relatively enhanced efficiency is attributable in part to the use of a highly concentrated pomegranate dye, graphite counter electrode and TiCl4 treatment of the photo-anode. PMID:28128369

Fabrication, Optimization and Characterization of Natural Dye Sensitized Solar Cell

NASA Astrophysics Data System (ADS)

Ghann, William; Kang, Hyeonggon; Sheikh, Tajbik; Yadav, Sunil; Chavez-Gil, Tulio; Nesbitt, Fred; Uddin, Jamal

2017-01-01

The dyes extracted from pomegranate and berry fruits were successfully used in the fabrication of natural dye sensitized solar cells (NDSSC). The morphology, porosity, surface roughness, thickness, absorption and emission characteristics of the pomegranate dye sensitized photo-anode were studied using various analytical techniques including FESEM, EDS, TEM, AFM, FTIR, Raman, Fluorescence and Absorption Spectroscopy. Pomegranate dye extract has been shown to contain anthocyanin which is an excellent light harvesting pigment needed for the generation of charge carriers for the production of electricity. The solar cell’s photovoltic performance in terms of efficiency, voltage, and current was tested with a standard illumination of air-mass 1.5 global (AM 1.5 G) having an irradiance of 100 mW/cm2. After optimization of the photo-anode and counter electrode, a photoelectric conversion efficiency (η) of 2%, an open-circuit voltage (Voc) of 0.39 mV, and a short-circuit current density (Isc) of 12.2 mA/cm2 were obtained. Impedance determination showed a relatively low charge-transfer resistance (17.44 Ω) and a long lifetime, signifying a reduction in recombination losses. The relatively enhanced efficiency is attributable in part to the use of a highly concentrated pomegranate dye, graphite counter electrode and TiCl4 treatment of the photo-anode.

Conductive Polymer Binder for High-Tap-Density Nanosilicon Material for Lithium-Ion Battery Negative Electrode Application.

PubMed

Zhao, Hui; Wei, Yang; Qiao, Ruimin; Zhu, Chenhui; Zheng, Ziyan; Ling, Min; Jia, Zhe; Bai, Ying; Fu, Yanbao; Lei, Jinglei; Song, Xiangyun; Battaglia, Vincent S; Yang, Wanli; Messersmith, Phillip B; Liu, Gao

2015-12-09

High-tap-density silicon nanomaterials are highly desirable as anodes for lithium ion batteries, due to their small surface area and minimum first-cycle loss. However, this material poses formidable challenges to polymeric binder design. Binders adhere on to the small surface area to sustain the drastic volume changes during cycling; also the low porosities and small pore size resulting from this material are detrimental to lithium ion transport. This study introduces a new binder, poly(1-pyrenemethyl methacrylate-co-methacrylic acid) (PPyMAA), for a high-tap-density nanosilicon electrode cycled in a stable manner with a first cycle efficiency of 82%-a value that is further improved to 87% when combined with graphite material. Incorporating the MAA acid functionalities does not change the lowest unoccupied molecular orbital (LUMO) features or lower the adhesion performance of the PPy homopolymer. Our single-molecule force microscopy measurement of PPyMAA reveals similar adhesion strength between polymer binder and anode surface when compared with conventional polymer such as homopolyacrylic acid (PAA), while being electronically conductive. The combined conductivity and adhesion afforded by the MAA and pyrene copolymer results in good cycling performance for the high-tap-density Si electrode.

Solid phase microbial fuel cell (SMFC) for harnessing bioelectricity from composite food waste fermentation: influence of electrode assembly and buffering capacity.

PubMed

Mohan, S Venkata; Chandrasekhar, K

2011-07-01

Solid phase microbial fuel cells (SMFC; graphite electrodes; open-air cathode) were designed to evaluate the potential of bioelectricity production by stabilizing composite canteen based food waste. The performance was evaluated with three variable electrode-membrane assemblies. Experimental data depicted feasibility of bioelectricity generation from solid state fermentation of food waste. Distance between the electrodes and presence of proton exchange membrane (PEM) showed significant influence on the power yields. SMFC-B (anode placed 5 cm from cathode-PEM) depicted good power output (463 mV; 170.81 mW/m(2)) followed by SMFC-C (anode placed 5 cm from cathode; without PEM; 398 mV; 53.41 mW/m(2)). SMFC-A (PEM sandwiched between electrodes) recorded lowest performance (258 mV; 41.8 mW/m(2)). Sodium carbonate amendment documented marked improvement in power yields due to improvement in the system buffering capacity. SMFCs operation also documented good substrate degradation (COD, 76%) along with bio-ethanol production. The operation of SMFC mimicked solid-sate fermentation which might lead to sustainable solid waste management practices. Copyright © 2011 Elsevier Ltd. All rights reserved.

Building one-dimensional oxide nanostructure arrays on conductive metal substrates for lithium-ion battery anodes.

PubMed

Jiang, Jian; Li, Yuanyuan; Liu, Jinping; Huang, Xintang

2011-01-01

Lithium ion battery (LIB) is potentially one of the most attractive energy storage devices. To meet the demands of future high-power and high-energy density requirements in both thin-film microbatteries and conventional batteries, it is challenging to explore novel nanostructured anode materials instead of conventional graphite. Compared to traditional electrodes based on nanostructure powder paste, directly grown ordered nanostructure array electrodes not only simplify the electrode processing, but also offer remarkable advantages such as fast electron transport/collection and ion diffusion, sufficient electrochemical reaction of individual nanostructures, enhanced material-electrolyte contact area and facile accommodation of the strains caused by lithium intercalation and de-intercalation. This article provides a brief overview of the present status in the area of LIB anodes based on one-dimensional nanostructure arrays growing directly on conductive inert metal substrates, with particular attention to metal oxides synthesized by an anodized alumina membrane (AAM)-free solution-based or hydrothermal methods. Both the scientific developments and the techniques and challenges are critically analyzed.

Building one-dimensional oxidenanostructure arrays on conductive metal substrates for lithium-ion battery anodes

NASA Astrophysics Data System (ADS)

Jiang, Jian; Li, Yuanyuan; Liu, Jinping; Huang, Xintang

2011-01-01

Lithium ion battery (LIB) is potentially one of the most attractive energy storage devices. To meet the demands of future high-power and high-energy density requirements in both thin-film microbatteries and conventional batteries, it is challenging to explore novel nanostructured anode materials instead of conventional graphite. Compared to traditional electrodes based on nanostructure powder paste, directly grown ordered nanostructure array electrodes not only simplify the electrode processing, but also offer remarkable advantages such as fast electron transport/collection and ion diffusion, sufficient electrochemical reaction of individual nanostructures, enhanced material-electrolyte contact area and facile accommodation of the strains caused by lithium intercalation and de-intercalation. This article provides a brief overview of the present status in the area of LIB anodes based on one-dimensional nanostructure arrays growing directly on conductive inert metal substrates, with particular attention to metal oxides synthesized by an anodized aluminamembrane (AAM)-free solution-based or hydrothermal methods. Both the scientific developments and the techniques and challenges are critically analyzed.

Three-dimensionally scaffolded Co3O4 nanosheet anodes with high rate performance

NASA Astrophysics Data System (ADS)

Liu, Jinyun; Kelly, Sean J.; Epstein, Eric S.; Pan, Zeng; Huang, Xingjiu; Liu, Jinhuai; Braun, Paul V.

2015-12-01

Advances in secondary batteries are required for realization of many technologies. In particular, there remains a need for stable higher energy batteries. Here we suggest a new anode concept consisting of an ultrathin Co3O4 nanosheet-coated Ni inverse opal which provides high charge-discharge rate performance using a material system with potential for high energy densities. Via a hydrothermal process, about 4 nm thick Co3O4 nanosheets were grown throughout a three-dimensional Ni scaffold. This architecture provides efficient pathways for both lithium and electron transfer, enabling high charge-discharge rate performance. The scaffold also accommodates volume changes during cycling, which serves to reduce capacity fade. Because the scaffold has a low electrical resistance, and is three-dimensionally porous, it enables most of the electrochemically active nanomaterials to take part in lithiation-delithiation reactions, resulting in a near-theoretical capacity. On a Co3O4 basis, the Ni@Co3O4 electrode possesses a capacity of about 726 mAh g-1 at a current density of 500 mA g-1 after 50 cycles, which is about twice the theoretical capacity of graphite. The capacity is 487 mAh g-1, even at a current density of 1786 mA g-1.

A-few-second synthesis of silicon nanoparticles by gas-evaporation and their self-supporting electrodes based on carbon nanotube matrix for lithium secondary battery anodes

NASA Astrophysics Data System (ADS)

Kowase, Takayuki; Hori, Keisuke; Hasegawa, Kei; Momma, Toshiyuki; Noda, Suguru

2017-09-01

Rapid gas-evaporation method is proposed and developed, which yields Si nanoparticles (SiNPs) in a few seconds at high yields of 20%-60% from inexpensive and safe bulk Si. Such rapid process is realized by heating the Si source to a temperature ≥2000 °C, much higher than the melting point of Si (1414 °C). The size of SiNPs is controlled at tens to hundreds nanometers simply by the Ar gas pressure during the evaporation process. Self-supporting films are fabricated simply by co-dispersion and filtration of the SiNPs and carbon nanotubes (CNTs) without using binders nor metal foils. The half-cell tests showed the improved performances of the SiNP-CNT composite films as anode when coated with graphitic carbon layer. Their performances are evaluated with various SiNP sizes and Si/CNT ratios systematically. The SiNP-CNT film with a Si/CNT mass ratio of 4 realizes the balanced film-based capacities of 618 mAh/gfilm, 230 mAh/cm3, and 0.644 mAh/cm2 with a moderate Si-based performance of 863 mAh/gSi at the 100th cycle.

Silver/iron oxide/graphitic carbon composites as bacteriostatic catalysts for enhancing oxygen reduction in microbial fuel cells

NASA Astrophysics Data System (ADS)

Ma, Ming; You, Shijie; Gong, Xiaobo; Dai, Ying; Zou, Jinlong; Fu, Honggang

2015-06-01

Biofilms from anode heterotrophic bacteria are inevitably formed over cathodic catalytic sites, limiting the performances of single-chamber microbial fuel cells (MFCs). Graphitic carbon (GC) - based nano silver/iron oxide (AgNPs/Fe3O4/GC) composites are prepared from waste pomelo skin and used as antibacterial oxygen reduction catalysts for MFCs. AgNPs and Fe3O4 are introduced in situ into the composites by one-step carbothermal reduction, enhancing their conductivity and catalytic activity. To investigate the effects of Fe species on the antibacterial and catalytic properties, AgNPs/Fe3O4/GC is washed with sulfuric acid (1 mol L-1) for 0.5 h, 1 h, and 5 h and marked as AgNPs/Fe3O4/GC-x (x = 0.5 h, 1 h and 5 h, respectively). A maximum power density of 1712 ± 35 mW m-2 is obtained by AgNPs/Fe3O4/GC-1 h, which declines by 4.12% after 17 cycles. Under catalysis of all AgNP-containing catalysts, oxygen reduction reaction (ORR) proceeds via the 4e- pathway, and no toxic effects to anode microorganisms result from inhibiting the cathodic biofilm overgrowth. With the exception of AgNPs/Fe3O4/GC-5 h, the AgNPs-containing composites exhibit remarkable power output and coulombic efficiency through lowering proton transfer resistance and air-cathode biofouling. This study provides a perspective for the practical application of MFCs using these efficient antibacterial ORR catalysts.

Embedded Si/Graphene Composite Fabricated by Magnesium-Thermal Reduction as Anode Material for Lithium-Ion Batteries.

PubMed

Zhu, Jiangliu; Ren, Yurong; Yang, Bo; Chen, Wenkai; Ding, Jianning

2017-12-16

Embedded Si/graphene composite was fabricated by a novel method, which was in situ generated SiO 2 particles on graphene sheets followed by magnesium-thermal reduction. The tetraethyl orthosilicate (TEOS) and flake graphite was used as original materials. On the one hand, the unique structure of as-obtained composite accommodated the large volume change to some extent. Simultaneously, it enhanced electronic conductivity during Li-ion insertion/extraction. The MR-Si/G composite is used as the anode material for lithium ion batteries, which shows high reversible capacity and ascendant cycling stability reach to 950 mAh·g -1 at a current density of 50 mA·g -1 after 60 cycles. These may be conducive to the further advancement of Si-based composite anode design.

Degradation of lithium ion batteries employing graphite negatives and nickel-cobalt-manganese oxide + spinel manganese oxide positives: Part 2, chemical-mechanical degradation model

NASA Astrophysics Data System (ADS)

Purewal, Justin; Wang, John; Graetz, Jason; Soukiazian, Souren; Tataria, Harshad; Verbrugge, Mark W.

2014-12-01

Capacity fade is reported for 1.5 Ah Li-ion batteries containing a mixture of Li-Ni-Co-Mn oxide (NCM) + Li-Mn oxide spinel (LMO) as positive electrode material and a graphite negative electrode. The batteries were cycled at a wide range of temperatures (10 °C-46 °C) and discharge currents (0.5C-6.5C). The measured capacity losses were fit to a simple physics-based model which calculates lithium inventory loss from two related mechanisms: (1) mechanical degradation at the graphite anode particle surface caused by diffusion-induced stresses (DIS) and (2) chemical degradation caused by lithium loss to continued growth of the solid-electrolyte interphase (SEI). These two mechanisms are coupled because lithium is consumed through SEI formation on newly exposed crack surfaces. The growth of crack surface area is modeled as a fatigue phenomenon due to the cyclic stresses generated by repeated lithium insertion and de-insertion of graphite particles. This coupled chemical-mechanical degradation model is consistent with the observed capacity loss features for the NCM + LMO/graphite cells.

Dehalogenation of iodinated X-ray contrast media in a bioelectrochemical system.

PubMed

Mu, Yang; Radjenovic, Jelena; Shen, Jinyou; Rozendal, René A; Rabaey, Korneel; Keller, Jürg

2011-01-15

Iodinated X-ray contrast media (ICM) are only to a limited extent removed from conventional wastewater treatment plants, due to their high recalcitrance. This work reports on the cathodic dehalogenation of the ICM iopromide in a bioelectrochemical system (BES), fed with acetate at the anode and iopromide at the cathode. When the granular graphite cathode potential was decreased from -500 to -850 mV vs standard hydrogen electrode (SHE), the iopromide removal and the iodide release rates increased from 0 to 4.62 ± 0.01 mmol m(-3) TCC d(-1) and 0 to 13.4 ± 0.16 mmol m(-3) TCC d(-1) (Total Cathodic Compartment, TCC) respectively. Correspondingly, the power consumption increased from 0.4 ± 1 to 20.5 ± 3.3 W m(-3) TCC. The Coulombic efficiency of the iopromide dehalogenation at the cathode was less than 1%, while the Coulombic efficiency of the acetate oxidation at the anode was lower than 50% at various granular graphite cathode potentials. The results suggest that iopromide could be completely dehalogenated in BESs when the granular graphite cathode potential was controlled at -800 mV vs SHE or lower. This finding was further confirmed using mass spectrometry to identify the dehalogenated intermediates and products of iopromide in BESs. Kinetic analysis indicates that iopromide dehalogenation in batch experiments can be described by a first-order model at various cathode potentials. This work demonstrates that the BESs have a potential for efficient dehalogenation of ICM from wastewater or environmental streams.

Microbial fuel cell characterisation and evaluation of Lysinibacillus macroides MFC02 electrigenic capability.

PubMed

Uma Vanitha, Murugan; Natarajan, Muthusamy; Sridhar, Harikrishnamoorthy; Umamaheswari, Sankaran

2017-05-01

Microbial fuel cell (MFC) is the most prominent research field due to its capability to generate electricity by utilizing the renewable sources. In the present study, Two MFC designs namely, H type-Microbial fuel cell (HT-MFC) and U type-Microbial fuel cell (UT-MFC) were constructed based on standardized H shaped anode and cathode compartment as well as U shaped anode and cathode compartments, respectively. In order to lower the cost for MFC construction, Pencil graphite lead was used as electrode and salt agar as Proton exchange membrane. Results inferred that newly constructed UT-MFC showed high electron production when compared to the HT-MFC. UT-MFC displayed an output of about 377 ± 18.85 mV (millivolts); whereas HT-MFC rendered only 237 ± 11.85 mV (millivolts) of power generation, which might be due to the low internal resistance. By increasing the number of cathode in UT-MFC, power production was increased upto 313 ± 15.65 mV in Open circuit voltage (OCV). Electrogenic bacteria namely, Lysinibacillus macroides (Acc. No. KX011879) rendered enriched power generation. The attachment of bacteria as a biofilm on pencil graphite lead was analyzed using fluorescent microscope and Scanning Electron Microscope (SEM). Based on our findings, it was observed that UT-MFC has a tendency to produce high electron generation using pencil graphite lead as the electrode material.

Investigating the Doping Mechanism of Pyrene Based Methacrylate Functional Conductive Binder in Silicon Anodes for Lithium-Ion Batteries

DOE PAGES

Ling, Min; Liu, Michael; Zheng, Tianyue; ...

2017-01-01

The doping mechanism of poly (1-pyrenemethyl methacrylate) (PPy) is investigated through electrochemical analytical and spectroscopic method. The performance of PPy as a Si materials binder is studied and compared with that of a commercial available lithium polyacrylate (PAALi) binder. The pyrene moiety consumes lithium ions according to the cyclic voltammogram (CV) measurement, as a doping to the PPy binder. Based on the lithium consumption, PPy based Si/graphite electrode doping is quantified at 1.1 electron/pyrene moiety. Lastly, the PPy binder based electrodes surface are uniform and crack free during lithiation/delithiation, which is revealed through Scanning electron microscope (SEM) imaging.

Pb2+ ions mobility perturbation by iron particles during electrokinetic remediation of contaminated soil.

PubMed

Zulfiqar, Waqas; Iqbal, Muhammad Asad; Butt, Mehwish Khalid

2017-02-01

Electrokinetic (EK) remediation is one of the most useful approaches for de-contamination of soils. However, it is unclear that how and when the electrokinetic remediation gives advantages over other remediation techniques in soil. This study was designed to find the influence of Fe 2+ particles on the mobility of Pb 2+ ions, during electrokinetic remediation, in soil contaminated purposely by lead nitrate Pb(NO 3 ) 2 . Two types of electrokinetic experiments were performed, by using iron and graphite electrodes. The Fe 2+ ions from the iron electrodes, produced due to acidic environment in anode compartment, affected the mobility of lead particles by precipitating as Fe(OH) 2 . Fe 2+ ions enhance the adsorption of lead ions in soil. The results show Fe 2+ ions of lower ionic conductivity decreased mobility of other particles in soil. Electrokinetic remediation for up to 120 h with iron electrodes is shown to be less effective for removal of lead. In contrast, graphite electrodes were 15 times more effective in lead removal from soil. Copyright © 2016 Elsevier Ltd. All rights reserved.

Importance of Electrode Material in the Electrochemical Treatment of Wastewater Containing Organic Pollutants

NASA Astrophysics Data System (ADS)

Panizza, Marco

Electrochemical oxidation is a promising method for the treatment of wastewaters containing organic compounds. As a general rule, the electrochemical incineration of organics at a given electrode can take place at satisfactory rates and without electrode deactivation only at high anodic potentials in the region of the water discharge due to the participation of the intermediates of oxygen evolution. The nature of the electrode material strongly influences both the selectivity and the efficiency of the process. In particular, anodes with low oxygen evolution overpotential (i.e., good catalysts for oxygen evolution reactions), such as graphite, IrO2, RuO2, and Pt only permit the partial oxidation of organics, while anodes with high oxygen evolution overpotential (i.e., anodes that are poor catalysts for oxygen evolution reactions), such as SnO2, PbO2, and boron-doped diamond (BDD) favor the complete oxidation of organics to CO2 and so are ideal electrodes for wastewater treatment.However, the application of SnO2 and PbO2 anodes may be limited by their short service life and the risk of lead contamination, while BDD electrodes exhibit good chemical and electrochemical stability, a long life, and a wide potential window for water discharge, and are thus promising anodes for industrial-scale wastewater treatment.

Porous Silicon as Anode Material for Lithium-Ion Batteries

NASA Astrophysics Data System (ADS)

Thakur, Madhuri; Pernites, Roderick; Sinsabaugh, Steve L.; Wong, Michael S.; Biswal, Sibani L.

Lithium-ion batteries are ubiquitous in our modern society, powering everything from cell phones, laptops, and power tools.They are also powering emerging applications such as electric vehicles and used for on-grid power stabilization. Lithium-ion batteries are a significant and growing part of this market due to their high specific energy. The worldwide market for lithium-ion batteries is projected to reach more than USD 9 billion by 2015. While lithium-ion batteries are often selected for their high specific energy, the market is demanding yet higher performance, usually in terms of energy stored per unit mass of battery. Many groups have recently turned their attention toward developing a silicon-based anode material to increase lithium-ion battery density. Silicon continues to draw great interest as an anode for lithium-ion batteries due to its large specific capacity as compared to the conventional graphite. Despite this exciting property, its practical use has been limited due to a large volume change associated with the insertion and extraction of lithium, which oftentimes leads to cracking and pulverization of the anode, limiting its cycle life. To overcome this problem, significant research has been focused toward developing various silicon nanostructures to accommodate the severe volume expansion and contraction. The structuring of the silicon often involves costly processing steps, limiting its application in price sensitive commercial lithium-ion batteries. To achieve commercial viability, work is being pursued on silicon battery anode structures and processes with a special emphasis on the cost and environment. In this review book chapter, we will summarize recent development of a cost-effective electrochemically etched porous silicon as an anode material for lithium-ion batteries. Briefly, the new approach involves creating hierarchical micron-and nanometer-sized pores on the surface of micron-sized silicon particulates, which are combined with an excellent conductor binder.

Interfacial Li-ion localization in hierarchical carbon anodes

DOE PAGES

McNutt, Nicholas W.; Rios, Orlando; Maroulas, Vasileios; ...

2016-10-24

An understanding of the nanoscale structure and energetics of carbon composites is critical for their applications in electric energy storage. Here, we study the properties of carbon anodes synthesized from low-cost renewable lignin biopolymers for use in energy storage applications such as Li-ion batteries. The anodes possess both nanoscale and mesoscale order, consisting of carbon nanocrystallites distributed within an amorphous carbon matrix. Molecular dynamics simulations of an experimentally validated model of the anode is used to elucidate the nature of Li-ion storage. We report the discovery of a novel mechanism of Li-ion storage, one in which Li+ is not intercalatedmore » between layers of carbon (as is the case in graphitic anodes), but rather is localized at the interface of crystalline carbon domains. In particular, the effects of Li-ion binding energy on the Li-Li, Li-H, and Li-C pair distribution functions are revealed, along with the effect on charge distribution. As a result, the atomic environments surrounding the Li-ions are grouped on the basis of ion energy and then convolved into archetypal structural motifs that reveal deep insight into the geometry of ion localization in disordered systems.« less

Vertical Graphene Growth on SiO Microparticles for Stable Lithium Ion Battery Anodes.

PubMed

Shi, Liurong; Pang, Chunlei; Chen, Shulin; Wang, Mingzhan; Wang, Kexin; Tan, Zhenjun; Gao, Peng; Ren, Jianguo; Huang, Youyuan; Peng, Hailin; Liu, Zhongfan

2017-06-14

Silicon-based materials are considered as strong candidates to next-generation lithium ion battery anodes because of their ultrahigh specific capacities. However, the pulverization and delamination of electrochemical active materials originated from the huge volume expansion (>300%) of silicon during the lithiation process results in rapid capacity fade, especially in high mass loading electrodes. Here we demonstrate that direct chemical vapor deposition (CVD) growth of vertical graphene nanosheets on commercial SiO microparticles can provide a stable conducting network via interconnected vertical graphene encapsulation during lithiation, thus remarkably improving the cycling stability in high mass loading SiO anodes. The vertical graphene encapsulated SiO (d-SiO@vG) anode exhibits a high capacity of 1600 mA h/g and a retention up to 93% after 100 cycles at a high areal mass loading of 1.5 mg/cm 2 . Furthermore, 5 wt % d-SiO@vG as additives increased the energy density of traditional graphite/NCA 18650 cell by ∼15%. We believe that the results strongly imply the important role of CVD-grown vertical graphene encapsulation in promoting the commercial application of silicon-based anodes.

Mechanical characterization and modeling for anodes and cathodes in lithium-ion batteries

NASA Astrophysics Data System (ADS)

Wang, Lubing; Yin, Sha; Zhang, Chao; Huan, Yong; Xu, Jun

2018-07-01

Mechanical properties of electrode materials have significant influence over electrochemical properties as well as mechanical integrity of lithium-ion battery cells. Here, anode and cathode in a commercially available 18650 NCA (Nickel Cobalt Aluminum Oxide)/graphite cell were comprehensively studied by tensile tests considering material anisotropy, SOC (state of charge), strain rate and electrolyte content. Results showed that the mechanical properties of both electrodes were highly dependent on strain rate and electrolyte content; however, anode was SOC dependent while cathode was not. Besides, coupled effects of strain rate and SOC of anodes were also discussed. SEM (scanning electron microscope) images of surfaces and cross-sections of electrodes showed the fracture morphology. In addition, mechanical behavior of Cu foil separated from anode with different SOC values were studied and compared. Finally, constitutive models of electrodes considering both strain rate and anisotropy effects were established. This study reveals the relationship between electrochemical dependent mechanical behavior of the electrodes. The established mechanical models of electrodes can be applied to the numerical computation of battery cells. Results are essential to predict the mechanical responses as well as the deformation of battery cell under various loading conditions, facilitating safer battery design and manufacturing.

Combinatorial electrochemical cell array for high throughput screening of micro-fuel-cells and metal/air batteries.

PubMed

Jiang, Rongzhong

2007-07-01

An electrochemical cell array was designed that contains a common air electrode and 16 microanodes for high throughput screening of both fuel cells (based on polymer electrolyte membrane) and metal/air batteries (based on liquid electrolyte). Electrode materials can easily be coated on the anodes of the electrochemical cell array and screened by switching a graphite probe from one cell to the others. The electrochemical cell array was used to study direct methanol fuel cells (DMFCs), including high throughput screening of electrode catalysts and determination of optimum operating conditions. For screening of DMFCs, there is about 6% relative standard deviation (percentage of standard deviation versus mean value) for discharge current from 10 to 20 mAcm(2). The electrochemical cell array was also used to study tin/air batteries. The effect of Cu content in the anode electrode on the discharge performance of the tin/air battery was investigated. The relative standard deviations for screening of metal/air battery (based on zinc/air) are 2.4%, 3.6%, and 5.1% for discharge current at 50, 100, and 150 mAcm(2), respectively.

Hydroxylamine hydrochloride: A novel anode material for high capacity lithium-ion batteries

NASA Astrophysics Data System (ADS)

Shao, Lianyi; Shu, Jie; Lao, Mengmeng; Lin, Xiaoting; Wu, Kaiqiang; Shui, Miao; Li, Peng; Long, Nengbing; Ren, Yuanlong

2014-12-01

H3NOHCl is used for the first time as anode material for lithium-ion batteries. Electrochemical results show that H3NOHCl with particle size of 4-12 μm can deliver an initial charge capacity of 1018.6 mAh g-1, which is much higher than commercial graphite. After 30 cycles, the reversible capacity can be kept at 676.1 mAh g-1 at 50 mA g-1. Up to 50 cycles, H3NOHCl still maintains a lithium storage capacity of 368.9 mAh g-1. Even cycled at 200 mA g-1, H3NOHCl can deliver a charge capacity of 715.7 mAh g-1. It suggests that H3NOHCl has high lithium storage capacity, excellent cycling stability and outstanding rate performance. Besides, the electrochemical reaction between H3NOHCl and Li is also investigated by various ex-situ techniques. It can be found that H3NOHCl irreversibly decomposes into Li3N and LiCl during the initial discharge process and LiNO2 can be formed after a reverse charge process.

Symposium on High Power, Ambient Temperature Lithium Batteries, 180th Meeting of the Electrochemical Society, Phoenix, AZ, Oct. 13-17, 1991, Proceedings

NASA Technical Reports Server (NTRS)

Clark, W. D. K. (Editor); Halpert, Gerald (Editor)

1992-01-01

Papers presented in these proceedings are on the state of the art in high-power lithium batteries, a design analysis of high-power Li-TiS2 battery, the performance and safety features of spiral wound lithium/thionyl chloride cells, the feasibility of a superhigh energy density battery of the Li/BrF3 electrochemical system, and an enhanced redox process of disulfide compounds and their application in high energy storage. Attention is also given to the structure and charge-discharge characteristics of mesophase-pitch based carbons, a study of carbons and graphites as anodes for lithium rechargeable cells, Li metal-free rechargeable Li(1+x)Mn2O4/carbon cells, and rechargeable lithium batteries using V6O13/V5O5 as the positive electrode material. Other papers discuss the electrochemical stability of organic electrolytes in contact with solid inorganic cathode materials, the electrochemical behavior of methyl formate solutions, and the interface between a solid polymer electrolyte and lithium anode.

Dry-air-stable lithium silicide-lithium oxide core-shell nanoparticles as high-capacity prelithiation reagents.

PubMed

Zhao, Jie; Lu, Zhenda; Liu, Nian; Lee, Hyun-Wook; McDowell, Matthew T; Cui, Yi

2014-10-03

Rapid progress has been made in realizing battery electrode materials with high capacity and long-term cyclability in the past decade. However, low first-cycle Coulombic efficiency as a result of the formation of a solid electrolyte interphase and Li trapping at the anodes, remains unresolved. Here we report LixSi-Li2O core-shell nanoparticles as an excellent prelithiation reagent with high specific capacity to compensate the first-cycle capacity loss. These nanoparticles are produced via a one-step thermal alloying process. LixSi-Li2O core-shell nanoparticles are processible in a slurry and exhibit high capacity under dry-air conditions with the protection of a Li2O passivation shell, indicating that these nanoparticles are potentially compatible with industrial battery fabrication processes. Both Si and graphite anodes are successfully prelithiated with these nanoparticles to achieve high first-cycle Coulombic efficiencies of 94% to >100%. The LixSi-Li2O core-shell nanoparticles enable the practical implementation of high-performance electrode materials in lithium-ion batteries.

Improving domestic wastewater treatment efficiency with constructed wetland microbial fuel cells: Influence of anode material and external resistance.

PubMed

Corbella, Clara; Puigagut, Jaume

2018-08-01

For the past few years, there has been an increasing interest in the operation of constructed wetlands as microbial fuel cells (CW-MFCs) for both the improvement of wastewater treatment efficiency and the production of energy. However, there is still scarce information on design and operation aspects to maximize CW-MFCs efficiency, especially for the treatment of real domestic wastewater. The aim of this study was to quantify the extent of treatment efficiency improvement carried out by membrane-less MFCs simulating a core of a shallow un-planted horizontal subsurface flow constructed wetland. The influence of the external resistance (50, 220, 402, 604 and 1000Ω) and the anode material (graphite and gravel) on treatment efficiency improvement were addressed. To this purpose, 6 lab-scale membrane-less MFCs were set-up and loaded in batch mode with domestic wastewater for 13weeks. Results showed that 220Ω was the best operation condition for maximising MFCs treatment efficiency, regardless the anode material employed. Gravel-based anode MFCs operated at closed circuit showed ca. 18%, 15%, 31% and 25% lower effluent concentration than unconnected MFCs to the COD, TOC, PO 4 -3 and NH 4 + -N, respectively. Main conclusion of the present work is that constructed wetlands operated as MFCs is a promising strategy to improve domestic wastewater treatment efficiency. However, further studies at pilot scale under more realistic conditions (such as planted systems operated under continuous mode) shall be performed to confirm the findings here reported. Copyright © 2018 Elsevier B.V. All rights reserved.

An Ultrahigh Capacity Graphite/Li 2S Battery with Holey-Li 2S Nanoarchitectures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ye, Fangmin; Noh, Hyungjun; Lee, Hongkyung

The pairing of high-capacity Li 2S cathode (1166 mAh g -1) and lithium-free anode (LFA) provides an unparalleled potential in developing safe and energy-dense next-generation secondary batteries. However, the low utilization of the Li 2S cathode and the lack of electrolytes compatible to both electrodes are impeding the development. Here, a novel graphite/Li 2S battery system, which features a self-assembled, holey-Li 2S nanoarchitecture and a stable solid electrolyte interface (SEI) on the graphite electrode, is reported. The holey structure on Li 2S is beneficial in decomposing Li 2S at the first charging process due to the enhanced Li ion extractionmore » and transfer from the Li 2S to the electrolyte. In addition, the concentrated dioxolane (DOL)-rich electrolyte designed lowers the irreversible capacity loss for SEI formation. By using the combined strategies, the graphite/holey-Li 2S battery delivers an ultrahigh discharge capacity of 810 mAh g -1 at 0.1 C (based on the mass of Li 2S) and of 714 mAh g -1 at 0.2 C. Moreover, it exhibits a reversible capacity of 300 mAh g -1 after a record lifecycle of 600 cycles at 1 C. These results suggest the great potential of the designed LFA/holey-Li 2S batteries for practical use.« less

An Ultrahigh Capacity Graphite/Li 2S Battery with Holey-Li 2S Nanoarchitectures

DOE PAGES

Ye, Fangmin; Noh, Hyungjun; Lee, Hongkyung; ...

2018-05-07

The pairing of high-capacity Li 2S cathode (1166 mAh g -1) and lithium-free anode (LFA) provides an unparalleled potential in developing safe and energy-dense next-generation secondary batteries. However, the low utilization of the Li 2S cathode and the lack of electrolytes compatible to both electrodes are impeding the development. Here, a novel graphite/Li 2S battery system, which features a self-assembled, holey-Li 2S nanoarchitecture and a stable solid electrolyte interface (SEI) on the graphite electrode, is reported. The holey structure on Li 2S is beneficial in decomposing Li 2S at the first charging process due to the enhanced Li ion extractionmore » and transfer from the Li 2S to the electrolyte. In addition, the concentrated dioxolane (DOL)-rich electrolyte designed lowers the irreversible capacity loss for SEI formation. By using the combined strategies, the graphite/holey-Li 2S battery delivers an ultrahigh discharge capacity of 810 mAh g -1 at 0.1 C (based on the mass of Li 2S) and of 714 mAh g -1 at 0.2 C. Moreover, it exhibits a reversible capacity of 300 mAh g -1 after a record lifecycle of 600 cycles at 1 C. These results suggest the great potential of the designed LFA/holey-Li 2S batteries for practical use.« less

Electrochemical and thermodynamic studies of the electrode materials for lithium ion batteries

NASA Astrophysics Data System (ADS)

Bang, Hyun Joo

A series of graphite samples were tested for their electrochemical performance as anode material for lithium ion cells. Specially treated natural graphite samples showed good reversible capacities and relatively small irreversible capacity losses. The good performance of these samples can be explained by the low surface area associated with the rounded edges and absence of exfoliation due to the presence of the rhombohedral phase and defects in the grain boundaries. Graphitized cokes showed larger irreversible capacity losses while mesophase carbons showed lower reversible capacity. The treated natural graphite samples, especially LBG25 were found to be high performance, low cost anode materials for the lithium ion cells. The electrochemical and thermal behaviors of the spinels---LiMn 2O4, LiCo1/6Mn11/6O4, LiFe 1/6Mn11/6O4, and LiNi1/6Mn11/6 O4 were studied using electrochemical and thermochemical techniques. The electrochemical techniques included cyclic voltammetry, charge/discharge cycling of 2016 coin cells and diffusion coefficient measurements using Galvanostatic Intermittent Titration Technique. Better capacity retention(GITT) was observed for the substituted spinels (0.11% loss/cycle for LiCo1/6Mn 11/6O4; 0.3% loss/cycle for LiFe1/6Mn11/6 O4; and 0.2% loss/cycle for LiNi1/6Mn11/6 O4) than for the lithium manganese dioxide spinel (1.6% loss/cycle for first 10 cycles, 0.9% loss/cycle for 33 cycles) during 33 cycles. The Differential Scanning Calorimetry (DSC) results showed that the cobalt substituted spinel has better thermal stability than the lithium manganese oxide and other substituted spinels. The thermal profile of LiMn2O4 and LiAl0.17 Mn1.83O3.97S0.03 was measured in an isothermal micro-calorimeter. The heat contributions are discussed in terms of reversible and irreversible heat generation, in combination with the entropy change directly obtained by the dE/dT measurements and the over-potential measurements. The endothermic and exothermic heat profiles observed during the charge and discharge processes are related to the Li insertion/extraction reaction in the spinel host structure for both materials. The reversible heat generation due to the lithium insertion/extraction reaction in the host electrode is estimated on the basis of the cell entropy change. The heat generation calculated from DeltaS and the open circuit potential results is consistent with the heat profile (exothermic/endothermic) generated during the charge/discharge process and with the magnitude of the heat generation from the experimental results obtained from the IMC at a slow charge/discharge rate. The irreversible heat generation dependence on the current rate is discussed at different discharge rates.

Silylated functionalized silicon-based composite as anode with excellent cyclic performance for lithium-ion battery

NASA Astrophysics Data System (ADS)

Li, Xiao; Tian, Xiaodong; Yang, Tao; Wang, Wei; Song, Yan; Guo, Quangui; Liu, Zhanjun

2018-05-01

Inferior cycling stability and rate performance respectively caused by rigorous volume change and poor electrical conductivity were the main challenge of state-of-the-art Silicon-based electrode. In this work, silylated functionalized exfoliated graphite oxide (EGO)/silicon@amorphous carbon (3-APTS-EGO/Si@C) was synthesized by adopting silane as intermediate to connect Si particles with EGO sheets followed by introduction of amorphous carbon. The result suggested that 3-Aminopropyltriethoxysilan connected the EGO sheets and Si nanoparticles via covalent bonds. Owing to the strong covalent interaction and the synergistic effect between the silicon, EGO sheets and amorphous carbon, 3-APTS-EGO/Si@C composite possessed a high capacity of 774 mAh g-1 even after 450 cycles at 0.4 A g-1 with the retention capacity of 97%. This work also provided an effective strategy to improve the long cycling life performance of Si-based electrode.

In-SITU, Time-resolved Raman Spectro-micro-topography of an Operating Lithium Ion Battery

NASA Technical Reports Server (NTRS)

Luo, Yu; Cai, Wen-Bin; Xing, Xue-Kun; Scherson, Daniel A.

2003-01-01

A Raman microscope has been coupled to a computer-controlled, two-dimensional linear translator attached to a custom-designed, sealed optical chamber to allow in situ acquisition of space-, and time-resolved spectra of an operating thin graphite/LiCoO2 Li-ion battery. This unique arrangement made it possible to collect continuously series of Raman spectra from a sharply defined edge of the battery exposing the anode (A), separator (S), and cathode (C), during charge and discharge, while the device was moved back and forth under the fixed focused laser beam along an axis normal to the layered A/S/C plane. Clear spectral evidence was obtained for changes in the amount of Li(+) within particles of graphite in the anode, and, to a lesser extent, of LiCoO2 in the cathode, during battery discharge both as a function of position and time. Analysis of time-resolved Raman spectro-micro-topography (SMT) measurements of the type described in this work are expected to open new prospects for assessing the validity of theoretical models aimed at simulating the flow of Li(+) within Li-ion batteries under operating conditions.

Facilitation of NADH Electrooxidation at Treated Carbon Nanotubes

PubMed Central

Wooten, Marilyn; Gorski, Waldemar

2010-01-01

The relationship between the state of the surface of carbon nanotubes (CNT) and their electrochemical activity was investigated using the enzyme cofactor dihydronicotinamide adenine dinucleotide (NADH) as a redox probe. The boiling of CNT in water, while nondestructive, activated them toward the oxidation of NADH as indicated by a shift in the anodic peak potential of NADH (ENADH) from 0.4 to 0.0 V. The shift in ENADH was due to the redox mediation of NADH oxidation by traces of quinone species that were formed on the surface of treated CNT. The harsher treatment that comprised of microwaving of CNT in concentrated nitric acid had a similar effect on the ENADH and, additionally, it increased the anodic peak current of NADH. The latter correlated with the formation of defects on the surface of acid-microwaved CNT as indicated by their Raman spectra. The increase in current was discussed considering a role of surface mediators on the buckled graphene sheets of acid-microwaved CNT. The other carbon allotropes including the edge plane pyrolytic graphite, graphite powder, and glassy carbon did not display a comparable activation toward the oxidation of NADH. PMID:20088562

A Universal Strategy for Hollow Metal Oxide Nanoparticles Encapsulated into B/N Co-Doped Graphitic Nanotubes as High-Performance Lithium-Ion Battery Anodes.

PubMed

Tabassum, Hassina; Zou, Ruqiang; Mahmood, Asif; Liang, Zibin; Wang, Qingfei; Zhang, Hao; Gao, Song; Qu, Chong; Guo, Wenhan; Guo, Shaojun

2018-02-01

Yolk-shell nanostructures have received great attention for boosting the performance of lithium-ion batteries because of their obvious advantages in solving the problems associated with large volume change, low conductivity, and short diffusion path for Li + ion transport. A universal strategy for making hollow transition metal oxide (TMO) nanoparticles (NPs) encapsulated into B, N co-doped graphitic nanotubes (TMO@BNG (TMO = CoO, Ni 2 O 3 , Mn 3 O 4 ) through combining pyrolysis with an oxidation method is reported herein. The as-made TMO@BNG exhibits the TMO-dependent lithium-ion storage ability, in which CoO@BNG nanotubes exhibit highest lithium-ion storage capacity of 1554 mA h g -1 at the current density of 96 mA g -1 , good rate ability (410 mA h g -1 at 1.75 A g -1 ), and high stability (almost 96% storage capacity retention after 480 cycles). The present work highlights the importance of introducing hollow TMO NPs with thin wall into BNG with large surface area for boosting LIBs in the terms of storage capacity, rate capability, and cycling stability. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Exploratory studies on some electrochemical cell systems

NASA Astrophysics Data System (ADS)

Chaudhuri, Srikumar; Guha, D.

Exploratory studies were conducted on cell systems with different metal anodes, and iodine and sulphur mixed with graphite powder in a polymer matrix as cathodes, using different electrolytes in non-aqueous and aqueous media as ionic charge carriers. The electrical conductance of the electrolyte solutions in aqueous and non-aqueous solvents, the open circuit voltage (OCV) and short circuit current (SCC) for the different cell systems were measured. To date, the non-aqueous solvents used in our studies were dimethylformamide, formamide, dioxan, and nitrobenzene, and the electrolytes used were potassium iodide, caustic potash, cetyltrimethylammonium bromide (CTAB), sodium lauryl sulphate (SLS) and calcium chloride. These electrolytes were used in both non-aqueous and aqueous media. In general, aqueous electrolyte solutions gave a better performance than non-aqueous electrolyte solutions. Of the aqueous electrolytes, the highest conductance was shown by potassium chloride solution in water (conductance=0.0334 mho). However, the best OCV and SCC were shown by aluminium as anode and iodine as cathode with a saturated solution of caustic potash in water. The OCV was 1.85 V and the SCC was 290 mA cm -2. The highest conductance among the non-aqueous systems was shown by caustic potash in formamide. (Conductance=0.013 mho.) The best OCV and SCC, however, were shown by a zinc anode and iodine cathode with saturated potassium chloride in formamide, having an OCV of 1.55 V and an SCC of 150 mA cm -2. Further studies are in progress to obtain detailed performance data and recharging characteristics of some of the more promising systems reported here.

Self-assembly synthesis of 3D graphene-encapsulated hierarchical Fe3O4 nano-flower architecture with high lithium storage capacity and excellent rate capability

NASA Astrophysics Data System (ADS)

Ma, Yating; Huang, Jian; Lin, Liang; Xie, Qingshui; Yan, Mengyu; Qu, Baihua; Wang, Laisen; Mai, Liqiang; Peng, Dong-Liang

2017-10-01

Graphene-encapsulated hierarchical metal oxides architectures can efficiently combine the merits of graphene and hierarchical metal oxides, which are deemed as the potential anode material candidates for the next-generation lithium-ion batteries due to the synergistic effect between them. Herein, a cationic surfactant induced self-assembly method is developed to construct 3D Fe3O4@reduction graphene oxide (H-Fe3O4@RGO) hybrid architecture in which hierarchical Fe3O4 nano-flowers (H-Fe3O4) are intimately encapsulated by 3D graphene network. Each H-Fe3O4 particle is constituted of rod-shaped skeletons surrounded by petal-like nano-flakes that are made up of enormous nanoparticles. When tested as the anode material in lithium-ion batteries, a high reversible capacity of 2270 mA h g-1 after 460 cycles is achieved under a current density of 0.5 A g-1. More impressively, even tested at a large current density of 10 A g-1, a decent reversible capacity of 490 mA h g-1 can be retained, which is still higher than the theoretical capacity of traditional graphite anode, demonstrating the remarkable lithium storage properties. The reasons for the excellent electrochemical performance of H-Fe3O4@RGO electrode have been discussed in detail.

Molten salt applications in materials processing

NASA Astrophysics Data System (ADS)

Mishra, Brajendra; Olson, David L.

2005-02-01

The science of molten salt electrochemistry for electrowinning of reactive metals, such as calcium, and its in situ application in pyro-reduction has been described. Calcium electrowinning has been performed in a 5 10 wt% calcium oxide calcium chloride molten salt by the electrolytic dissociation of calcium oxide. This electrolysis requires the use of a porous ceramic sheath around the anode to keep the cathodically deposited calcium and the anodic gases separate. Stainless steel cathode and graphite anode have been used in the temperature range of 850 950 °C. This salt mixture is produced as a result of the direct oxide reduction (DOR) of reactive metal oxides by calcium in a calcium chloride bath. The primary purpose of this process is to recover the expensive calcium reductant and to recycle calcium chloride. Experimental data have been included to justify the suitability as well as limitations of the electrowinning process. Transport of oxygen ions through the sheath is found to be the rate controlling step. Under the constraints of the reactor design, a calcium recovery rate of approx. 150 g/h was achieved. Feasibility of a process to produce metals by pyrometallurgical reduction, using the calcium reductant produced electrolytically within the same reactor, has been shown in a hybrid process. Several processes are currently under investigation to use this electrowon calcium for in situ reduction of metal oxides.

A highly stable (SnOx-Sn)@few layered graphene composite anode of sodium-ion batteries synthesized by oxygen plasma assisted milling

NASA Astrophysics Data System (ADS)

Cheng, Deliang; Liu, Jiangwen; Li, Xiang; Hu, Renzong; Zeng, Meiqing; Yang, Lichun; Zhu, Min

2017-05-01

The (SnOx-Sn)@few layered graphene ((SnOx-Sn)@FLG) composite has been synthesized by oxygen plasma-assisted milling. Owing to the synergistic effect of rapid plasma heating and ball mill grinding, SnOx (1 ≤ x ≤ 2) nanoparticles generated from the reaction of Sn with oxygen are tightly wrapped by FLG nanosheets which are simultaneously exfoliated from expanded graphite, forming secondary micro granules. Inside the granules, the small size of the SnOx nanoparticles enables the fast kinetics for Na+ transfer. The in-situ formed FLG and residual Sn nanoparticles improve the electrical conductivity of the composite, meanwhile alleviate the aggregation of SnOx nanoparticles and relieve the volume change during the cycling, which is beneficial for the cyclic stability for the Na+ storage. As an anode material for sodium-ion batteries, the (SnOx-Sn)@FLG composite exhibits a high reversible capacity of 448 mAh g-1 at a current density of 100 mA g-1 in the first cycle, with 82.6% capacity retention after 250 cycles. Even when the current density increases to 1000 mA g-1, this composite retains 316.5 mAh g-1 after 250 cycles. With superior Na+ storage stability, the (SnOx-Sn)@FLG composite can be a promising anode material for high performance sodium-ion batteries.

The Impact of Li Grain Size on Coulombic Efficiency in Li Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mehdi, B. Layla; Stevens, Andrew; Qian, Jiangfeng

One of the most promising means to increase the energy density of state-of-the-art lithium (Li)-ion batteries is to replace the graphite anode with a Li metal anode1, 2, 3. While the direct use of Li metal may be highly advantageous4,5, at present its practical application is limited by issues related to dendrite growth and low Coulombic efficiency (CE)6. Here operando electrochemical scanning transmission electron microscopy (STEM) is used to directly image the deposition/stripping of Li at the anode-electrolyte interface in a Li-based battery. A non-aqueous electrolyte containing small amounts of H2O as an additive results in remarkably different deposition/stripping propertiesmore » as compared to the "dry" electrolyte when operated under identical electrochemical conditions. The electrolyte with the additive deposits more Li during the first cycle, with the grain sizes of the Li deposits being significantly larger and more variable. The stripping of the Li upon discharge is also more complete, i.e., there is a higher cycling CE. This suggests that larger grain sizes are indicative of better performance by leading to more uniform Li deposition and an overall decrease in the formation of Li dendrites and side reactions with electrolyte components, thus potentially paving the way for the direct use of Li metal in battery technologies.« less

Lithium rich cathode/graphite anode combination for lithium ion cells with high tolerance to near zero volt storage

NASA Astrophysics Data System (ADS)

Crompton, K. R.; Staub, J. W.; Hladky, M. P.; Landi, B. J.

2017-03-01

Management of reversible lithium is an advantageous approach to design lithium ion cells that are tolerant to near zero volt (NZV) storage under fixed resistive load towards highly controllable, enhanced user-inactive safety. Presently, the first cycle loss from a high energy density Li-rich HE5050 cathode is used to provide excess reversible lithium when paired with an appropriately capacity matched mesocarbon microbead (MCMB) anode. Cells utilizing 1.2 M LiPF6 3:7 v/v ethylene carbonate:ethyl methyl carbonate electrolyte and a lithium reference were used for 3-electrode testing. After conditioning, a fixed resistive load was applied to 3-electrode cells for 72 or 168-h during which the anode potential and electrode asymptotic potential (EAP) remained less than the copper dissolution potential. After multiple storage cycles (room temperature or 40 °C), the NZV coulombic efficiency (cell reversibility) exceeded 97% and the discharge capacity retention was >98%. Conventional 2-electrode HE5050/MCMB pouch cells stored at NZV or open circuit for 3 days had nearly identical rate capability (up to 5C) and discharge performance stability (for 500 cycles under a 30% depth of discharge low-earth-orbit regime). Thus, lithium ion cells with appropriately capacity matched HE5050/MCMB electrodes have excellent tolerance to prolonged NZV storage, which can lead to enhanced user-inactive safety.

Microfabricated triggered vacuum switch

DOEpatents

Roesler, Alexander W [Tijeras, NM; Schare, Joshua M [Albuquerque, NM; Bunch, Kyle [Albuquerque, NM

2010-05-11

A microfabricated vacuum switch is disclosed which includes a substrate upon which an anode, cathode and trigger electrode are located. A cover is sealed over the substrate under vacuum to complete the vacuum switch. In some embodiments of the present invention, a metal cover can be used in place of the trigger electrode on the substrate. Materials used for the vacuum switch are compatible with high vacuum, relatively high temperature processing. These materials include molybdenum, niobium, copper, tungsten, aluminum and alloys thereof for the anode and cathode. Carbon in the form of graphitic carbon, a diamond-like material, or carbon nanotubes can be used in the trigger electrode. Channels can be optionally formed in the substrate to mitigate against surface breakdown.

Self-standing silicon-carbon nanotube/graphene by a scalable in situ approach from low-cost Al-Si alloy powder for lithium ion batteries

NASA Astrophysics Data System (ADS)

Cai, Hongyan; Han, Kai; Jiang, Heng; Wang, Jingwen; Liu, Hui

2017-10-01

Silicon/carbon (Si/C) composite shows great potential to replace graphite as lithium-ion battery (LIB) anode owing to its high theoretical capacity. Exploring low-cost scalable approach for synthesizing Si/C composites with excellent electrochemical performance is critical for practical application of Si/C anodes. In this study, we rationally applied a scalable in situ approach to produce Si-carbon nanotube (Si-CNT) composite via acid etching of commercial inexpensive micro-sized Al-Si alloy powder and CNT mixture. In the Si-CNT composite, ∼10 nm Si particles were uniformly deposited on the CNT surface. After combining with graphene sheets, a flexible self-standing Si-CNT/graphene paper was fabricated with three-dimensional (3D) sandwich-like structure. The in situ presence of CNT during acid-etching process shows remarkable two advantages: providing deposition sites for Si atoms to restrain agglomeration of Si nanoparticles after Al removal from Al-Si alloy powder, increasing the cross-layer conductivity of the paper anode to provide excellent conductive contact sites for each Si nanoparticles. When used as binder-free anode for LIBs without any further treatment, in situ addition of CNT especially plays important role to improve the initial electrochemical activity of Si nanoparticles synthesized from low-cost Al-Si alloy powder, thus resulting in about twice higher capacity than Si/G paper anode. The self-standing Si-CNT/graphene paper anode exhibited a high specific capacity of 1100 mAh g-1 even after 100 cycles at 200 mA g-1 current density with a Coulombic efficiency of >99%. It also showed remarkable rate capability improvement compared to Si/G paper without CNT. The present work demonstrates a low-cost scalable in situ approach from commercial micro-sized Al-Si alloy powder for Si-based composites with specific nanostructure. The Si-CNT/graphene paper is a promising anode candidate with high capacity and cycling stability for LIBs, especially for the flexible batteries application.

More About Arc-Welding Process for Making Carbon Nanotubes

NASA Technical Reports Server (NTRS)

Benavides, Jeanette M.; Leidecker, Henning

2005-01-01

High-quality batches of carbon nanotubes are produced at relatively low cost in a modified atmospheric-pressure electric-arc welding process that does not include the use of metal catalysts. What would normally be a welding rod and a weldment are replaced by an amorphous carbon anode rod and a wider, hollow graphite cathode rod. Both electrodes are water-cooled. The cathode is immersed in ice water to about 0.5 cm from the surface. The system is shielded from air by flowing helium during arcing. As the anode is consumed during arcing at 20 to 25 A, it is lowered to maintain it at an approximately constant distance above the cathode. The process causes carbon nanotubes to form on the lowest 5 cm of the anode. The arcing process is continued until the anode has been lowered to a specified height. The nanotube-containing material is then harvested. The additional information contained in the instant report consists mostly of illustrations of carbon nanotubes and a schematic diagram of the arc-welding setup, as modified for the production of carbon nanotubes.

Synthesis of TiO{sub 2} by electrochemical method from TiCl{sub 4} solution as anode material for lithium-ion batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nur, Adrian, E-mail: adriannur@staff.uns.ac.id; Purwanto, Agus; Jumari, Arif

Metal oxide combined with graphite becomes interesting composition. TiO{sub 2} is a good candidate for Li ion battery anode because of cost, availability of sufficient materials, and environmentally friendly. TiO{sub 2} gravimetric capacity varied within a fairly wide range. TiO{sub 2} crystals form highly depends on the synthesis method used. The electrochemical method is beginning to emerge as a valuable option for preparing TiO{sub 2} powders. Using the electrochemical method, the particle can easily be controlled by simply adjusting the imposed current or potential to the system. In this work, the effects of some key parameters of the electrosynthesis onmore » the formation of TiO{sub 2} have been investigated. The combination of graphite and TiO{sub 2} particle has also been studied for lithium-ion batteries. The homogeneous solution for the electrosynthesis of TiO{sub 2} powders was TiCl{sub 4} in ethanol solution. The electrolysis was carried out in an electrochemical cell consisting of two carbon electrodes with dimensions of (5 × 2) cm. The electrodes were set parallel with a distance of 2.6 cm between the electrodes and immersed in the electrolytic solution at a depth of 2 cm. The electrodes were connected to the positive and negative terminals of a DC power supply. The electrosynthesis was performed galvanostatically at 0.5 to 2.5 hours and voltages were varied from 8 to 12 V under constant stirring at room temperature. The resulted suspension was aged at 48 hrs, filtered, dried directly in an oven at 150°C for 2 hrs, washed 2 times, and dried again 60 °C for 6 hrs. The particle product has been used to lithium-ion battery as anode. Synthesis of TiO{sub 2} particle by electrochemical method at 10 V for 1 to 2.5 hrs resulted anatase and rutile phase.« less

Atomic and Molecular Layer Deposition for Enhanced Lithium Ion Battery Electrodes and Development of Conductive Metal Oxide/Carbon Composites

NASA Astrophysics Data System (ADS)

Travis, Jonathan

The performance and safety of lithium-ion batteries (LIBs) are dependent on interfacial processes at the positive and negative electrodes. For example, the surface layers that form on cathodes and anodes are known to affect the kinetics and capacity of LIBs. Interfacial reactions between the electrolyte and the electrodes are also known to initiate electrolyte combustion during thermal runaway events that compromise battery safety. Atomic layer deposition (ALD) and molecular layer deposition (MLD) are thin film deposition techniques based on sequential, self-limiting surface reactions. ALD and MLD can deposit ultrathin and conformal films on high aspect ratio and porous substrates such as composite particulate electrodes in lithium-ion batteries. The effects of electrode surface modification via ALD and MLD are studied using a variety of techniques. It was found that sub-nm thick coatings of Al2O 3 deposited via ALD have beneficial effects on the stability of LIB anodes and cathodes. These same Al2O3 ALD films were found to improve the safety of graphite based anodes through prevention of exothermic solid electrolyte interface (SEI) degradation at elevated temperatures. Ultrathin and conformal metal alkoxide polymer films known as "metalcones" were grown utilizing MLD techniques with trimethylaluminum (TMA) or titanium tetrachloride (TiCl4) and organic diols or triols, such as ethylene glycol (EG), glycerol (GL) or hydroquinone (HQ), as the reactants. Pyrolysis of these metalcone films under inert gas conditions led to the development of conductive metal oxide/carbon composites. The composites were found to contain sp2 carbon using micro-Raman spectroscopy in the pyrolyzed films with pyrolysis temperatures ≥ 600°C. Four point probe measurements demonstrated that the graphitic sp2 carbon domains in the metalcone films grown using GL and HQ led to significant conductivity. The pyrolysis of conformal MLD films to obtain conductive metal oxide/carbon composite films is presented as a method for enabling non-conductive, but possibly electrochemically active materials, to be used for electrochemical applications.

Effect of Acetylene Black Content to Half Cells Li-ion Battery Performance Based on Li4Ti5O12 using Li2CO3 as Lithium Ion Source with Hydrothermal Mechanochemical Process

NASA Astrophysics Data System (ADS)

Priyono, B.; Faizah; Syahrial, A. Z.; Subhan, A.

2017-07-01

Lithium titanate (Li4Ti5O12)/LTO is a promising candidate to be used as anode electrode in Li-ion battery, to replace graphite in Li-ion battery application. Crystal structure of lithium titanate/LTO is more stable or undergoes less strain than graphite during intercalation and de-intercalation process Li+ ions. However, although lithium titanate has good stability, the material has low electrical conductivity and lithium ion diffusion. The purpose of this research is to synthesis the spinel LTO using combinated hydrothermal and mechanochemical processes from xerogel TiO2. Then, to increase the conductivity, in the half-cell battery assembly process it was added acetylene black conductive (AB) additive with various from 10%, to 15% in wt. The LTO obtained were characterized using scanning electron microscope (SEM), X-Ray Diffraction (XRD) and Brunauer-Emmett-Teller (BET). The XRD showed a rutile as minor phase, while SEM showed homogeneous distribution of particle with an average particle size of 0.35 μm. The BET showed that the surface area of LTO formed is 2.26 m2/g. The assembled coin half cells used this Li4Ti5O12 as a cathode and lithium metal foil as the anode were tested using electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV) and charge discharge (CD). The conductivity value obtained from EIS corresponds to the contents of AB. Meanwhile, the CV and CD testing showed that higher percentage of AB causing the decrease of battery specific capacity. The highest specific capacity at the rate of 10C is obtained at the mixture of 10wt% AB with the value of 40.91 mAh/g.

In Situ Coating of Li[Ni0.33 Mn0.33 Co0.33 ]O2 Particles to Enable Aqueous Electrode Processing.

PubMed

Loeffler, Nicholas; Kim, Guk-Tae; Mueller, Franziska; Diemant, Thomas; Kim, Jae-Kwang; Behm, R Jürgen; Passerini, Stefano

2016-05-23

The aqueous processing of lithium-ion battery (LIB) electrodes has the potential to notably decrease the battery processing costs and paves the way for a sustainable and environmentally benign production (and recycling) of electrochemical energy storage devices. Although this concept has already been adopted for the industrial production of LIB graphite anodes, the performance decay of cathode electrodes based on transition metal oxides processed in aqueous environments is still an open issue. In this study, we show that the addition of small quantities of phosphoric acid into the cathodic slurry yields Li[Ni0.33 Mn0.33 Co0.33 ]O2 electrodes that have an outstanding electrochemical performance in lithium-ion cells. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Superhierarchical Cobalt-Embedded Nitrogen-Doped Porous Carbon Nanosheets as Two-in-One Hosts for High-Performance Lithium-Sulfur Batteries.

PubMed

Liu, Shaohong; Li, Jia; Yan, Xue; Su, Quanfei; Lu, Yuheng; Qiu, Jieshan; Wang, Zhiyu; Lin, Xidong; Huang, Junlong; Liu, Ruliang; Zheng, Bingna; Chen, Luyi; Fu, Ruowen; Wu, Dingcai

2018-03-01

Lithium-sulfur (Li-S) batteries, based on the redox reaction between elemental sulfur and lithium metal, have attracted great interest because of their inherently high theoretical energy density. However, the severe polysulfide shuttle effect and sluggish reaction kinetics in sulfur cathodes, as well as dendrite growth in lithium-metal anodes are great obstacles for their practical application. Herein, a two-in-one approach with superhierarchical cobalt-embedded nitrogen-doped porous carbon nanosheets (Co/N-PCNSs) as stable hosts for both elemental sulfur and metallic lithium to improve their performance simultaneously is reported. Experimental and theoretical results reveal that stable Co nanoparticles, elaborately encapsulated by N-doped graphitic carbon, can work synergistically with N heteroatoms to reserve the soluble polysulfides and promote the redox reaction kinetics of sulfur cathodes. Moreover, the high-surface-area pore structure and the Co-enhanced lithiophilic N heteroatoms in Co/N-PCNSs can regulate metallic lithium plating and successfully suppress lithium dendrite growth in the anodes. As a result, a full lithium-sulfur cell constructed with Co/N-PCNSs as two-in-one hosts demonstrates excellent capacity retention with stable Coulombic efficiency. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Conductive Polymer Binder for High-Tap-Density Nanosilicon Material for Lithium-Ion Battery Negative Electrode Application

DOE PAGES

Zhao, Hui; Wei, Yang; Qiao, Ruimin; ...

2015-11-24

High-tap-density silicon nanomaterials are highly desirable as anodes for lithium ion batteries, due to their small surface area and minimum first-cycle loss. However, this material poses formidable challenges to polymeric binder design. Binders adhere on to the small surface area to sustain the drastic volume changes during cycling; also the low porosities and small pore size resulting from this material are detrimental to lithium ion transport. This study introduces a new binder, poly(1-pyrenemethyl methacrylate-co-methacrylic acid) (PPyMAA), for a high-tap-density nanosilicon electrode cycled in a stable manner with a first cycle efficiency of 82%-a value that is further improved to 87%more » when combined with graphite material. Incorporating the MAA acid functionalities does not change the lowest unoccupied molecular orbital (LUMO) features or lower the adhesion performance of the PPy homopolymer. Our single-molecule force microscopy measurement of PPyMAA reveals similar adhesion strength between polymer binder and anode surface when compared with conventional polymer such as homopolyacrylic acid (PAA), while being electronically conductive. Finally, the combined conductivity and adhesion afforded by the MAA and pyrene copolymer results in good cycling performance for the high-tap-density Si electrode.« less

Carbon-Coated, Diatomite-Derived Nanosilicon as a High Rate Capable Li-ion Battery Anode.

PubMed

Campbell, Brennan; Ionescu, Robert; Tolchin, Maxwell; Ahmed, Kazi; Favors, Zachary; Bozhilov, Krassimir N; Ozkan, Cengiz S; Ozkan, Mihrimah

2016-10-07

Silicon is produced in a variety of ways as an ultra-high capacity lithium-ion battery (LIB) anode material. The traditional carbothermic reduction process required is expensive and energy-intensive; in this work, we use an efficient magnesiothermic reduction to convert the silica-based frustules within diatomaceous earth (diatomite, DE) to nanosilicon (nanoSi) for use as LIB anodes. Polyacrylic acid (PAA) was used as a binder for the DE-based nanoSi anodes for the first time, being attributed for the high silicon utilization under high current densities (up to 4C). The resulting nanoSi exhibited a high BET specific surface area of 162.6 cm 2 g -1 , compared to a value of 7.3 cm 2 g -1 for the original DE. DE contains SiO 2 architectures that make ideal bio-derived templates for nanoscaled silicon. The DE-based nanoSi anodes exhibit good cyclability, with a specific discharge capacity of 1102.1 mAh g -1 after 50 cycles at a C-rate of C/5 (0.7 A g Si -1 ) and high areal loading (2 mg cm -2 ). This work also demonstrates the fist rate capability testing for a DE-based Si anode; C-rates of C/30 - 4C were tested. At 4C (14.3 A g Si -1 ), the anode maintained a specific capacity of 654.3 mAh g -1 - nearly 2x higher than graphite's theoretical value (372 mAh g -1 ).

Toward better Li-ion batteries: hard x-ray photoelectron spectroscopy investigation of binder materials for Si-based anodes

NASA Astrophysics Data System (ADS)

Young, Benjamin; Heskett, David; Nguyen, Cao Cuong; Woicik, Joseph; Lucht, Brett

From portable electronics to space exploration, the desire for more capable rechargeable batteries is driving a search for high capacity anodes. There is much interest in incorporating silicon as a partial or full replacement for the current graphite material in the most popular batteries because it could potentially hold much more charge. There is a significant challenge, however, in that storing so much more lithium in either electrode as the battery is charged and discharged as this causes an accompanying increase in the physical size fluctuation of the electrodes. Specifically, in the anode where this investigation focuses, the active material may experience a 300% volume change between the charged and discharged state. This makes a long lifetime difficult to achieve because the passivation layer protecting the electrolyte material from decomposition is compromised upon each cycle. One approach to accommodating the large volumetric fluctuation without sacrificing lifetime is to find a better material to include in the anode substrate to act as a binder. Ideally, such a material would permit the anode to fluctuate without breaking. Polyvinylidene fluoride (PVdF) is not successful for silicon-based anodes and we present Hard X-ray photoelectron spectroscopy studies of batteries incorporating three alternatives. The alternative binders outperform the PVdF and we present possible explanations. DOE EPSCoR and RI College Faculty Research Fund.

Microsized Porous SiOx@C Composites Synthesized through Aluminothermic Reduction from Rice Husks and Used as Anode for Lithium-Ion Batteries.

PubMed

Cui, Jinlong; Cui, Yongfu; Li, Shaohui; Sun, Hongliang; Wen, Zhongsheng; Sun, Juncai

2016-11-09

Microsized porous SiO x @C composites used as anode for lithium-ion batteries (LIBs) are synthesized from rice husks (RHs) through low-temperature (700 °C) aluminothermic reduction. The resulting SiO x @C composite shows mesoporous irregular particle morphology with a high specific surface area of 597.06 m 2 /g under the optimized reduction time. This porous SiO x @C composite is constructed by SiO x nanoparticles uniformly dispersed in the C matrix. When tested as anode material for LIBs, it displays considerable specific capacity (1230 mAh/g at a current density of 0.1 A/g) and excellent cyclic stability with capacity fading of less than 0.5% after 200 cycles at 0.8 A/g. The dramatic volume change for the Si anode during lithium-ion (Li + ) insertion and extraction can be successfully buffered because of the formation of Li 2 O and Li 4 SiO 4 during initial lithiation process and carbon coating layer on the surface of SiO x . The porous structure could also mitigate the volume change and mechanical strains and shorten the Li + diffusion path length. These characteristics improve the cyclic stability of the electrode. This low-cost and environment-friendly SiO x @C composite anode material exhibits great potential as an alternative for traditional graphite anodes.

A structural study of solid electrolyte interface on negative electrode of lithium-Ion battery by electron microscopy.

PubMed

Matsushita, Tadashi; Watanabe, Jiro; Nakao, Tatsuya; Yamashita, Seiichi

2014-11-01

For the last decades, the performance of the lithium-ion battery (LIB) has been significantly improved and its applications have been expanding rapidly. However, its performance has yet to be enhanced.In the lithium-ion battery development, it is important to elucidate the electrode structure change in detail during the charge and discharge cycling. In particular, solid electrolyte interface (SEI) formed by decomposition of the electrolytes on the graphite negative electrode surface should play an important role for battery properties. Therefore, it is essential to control the structure and composition of SEI to improve the battery performance. Here, we conducted a scanning electron microscope (SEM) and transmission electron microscope (TEM) study to elucidate the structures of the SEI during the charge and discharge process using LiNi1/3Co1/3Mn1/3O2 [1] cathode and graphite anode. [2] Since SEI is a lithium-containing compound with high activity, it was observed without being exposed to the atmosphere. The electrodes including SEI were sampled after dismantling batteries with cutoff voltages of 3V and 4.2V for the charge process and 3V for the discharge process. Fig.1 shows SEM images of the graphite electrode surface during the charge and discharge process. The change of the SEI structure during the process was clearly observed. Further, TEM images showed that the SEI grew thicker during the charge process and becomes thinner when discharged. These results with regard to the reversible SEI structure could give a new insight for the battery development.jmicro;63/suppl_1/i21/DFU056F1F1DFU056F1Fig. 1.SEM images of the graphite electrode surface:(a) before charge process;(b) with charge-cutoff voltage of 3.0V; (c) with charge-cutoff voltage of 4.2V; (d) with discharge-cutoff voltage of 3.0V. © The Author 2014. Published by Oxford University Press on behalf of The Japanese Society of Microscopy. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Self-Organizing Batteries

DTIC Science & Technology

2005-12-16

of these principles to a lithium ion battery , resulting in the demonstration of the first self-organized rechargeable battery. These accomplishments...spherical graphite widely used as a lithium ion battery anode, was used as the high-index endmember and was attached to an AFM cantilever. Its...resulting junctions could be stable under electrochemical conditions typical of lithium ion battery systems. We used PEG + LiClO 4 as our model solid

Effect of anode material on the breakdown in low-pressure helium gas

NASA Astrophysics Data System (ADS)

Demidov, V. I.; Adams, S. F.; Kudryavtsev, A. A.; Kurlyandskaya, I. P.; Miles, J. A.; Tolson, B. A.

2017-10-01

The electric breakdown of gases is one of the fundamental phenomena of gas discharge physics. It has been studied for a long time but still attracts incessant interest of researchers. Besides the interesting physics, breakdown is important for many applications including development of reliable electric insulation in electric grids and the study of different aspects of gas discharge physics. In this work an experimental study of the electric breakdown in helium gas for the plane-parallel electrode configuration has been conducted using a copper cathode and a variety of anode materials: copper, aluminum, stainless steel, graphite, platinum-plated aluminum and gold-plated aluminum. According to the Paschen law for studied electrode configuration, the breakdown voltage is a function of the product of gas pressure and inter-electrode gap. The breakdown processes on the left, lower pressure side of the Paschen curve have been the subject of this investigation. For those pressures, the Paschen curve may become multi-valued, where any given pressure corresponds to three breakdown voltage values. It was experimentally demonstrated that the form of the Paschen curve might strongly depend on the material of the anode and the cleanness of the anode surface. A possible explanation for this phenomenon is that electrons streaming from the cathode are reflected by the surface of the anode.

Nanostructured ZnO-TiO2 thin film oxide as anode material in electrooxidation of organic pollutants. Application to the removal of dye Amido black 10B from water.

PubMed

El-Kacemi, Sana; Zazou, Hicham; Oturan, Nihal; Dietze, Matthias; Hamdani, Mohamed; Es-Souni, Mohammed; Oturan, Mehmet A

2017-01-01

Electrochemical oxidative degradation of diazo dye Amido black 10B (AB10B) as model pollutant in water has been studied using nanostructured ZnO-TiO 2 thin films deposited on graphite felt (GrF) substrate as anode. The influence of various operating parameters, namely the current intensity, the nature and concentration of catalyst, the nature of electrode materials (anode/cathode), and the adsorption of dye and ambient light were investigated. It was found that the oxidative degradation of AB10B followed pseudo first-order kinetics. The optimal operating conditions for the degradation of 0.12 mM (74 mg L -1 ) dye concentration and mineralization of its aqueous solution were determined as GrF-ZnO-TiO 2 thin film anode, 100 mA current intensity, and 0.1 mM Fe 2+ (catalyst) concentration. Under these operating conditions, discoloration of AB10B solution was reached at 60 min while 6 h treatment needed for a mineralization degree of 91 %. Therefore, this study confirmed that the electrochemical process is effective for the degradation of AB10B in water using nanostructured ZnO-TiO 2 thin film anodes.

Electrochemical Behavior of Sulfur in Aqueous Alkaline Solutions

NASA Astrophysics Data System (ADS)

Mamyrbekova, Aigul; Mamitova, A. D.; Mamyrbekova, Aizhan

2018-03-01

The kinetics and mechanism of the electrode oxidation-reduction of sulfur on an electrically conductive sulfur-graphite electrode in an alkaline solution was studied by the potentiodynamic method. To examine the mechanism of electrode processes occurring during AC polarization on a sulfur-graphite electrode, the cyclic polarization in both directions and anodic polarization curves were recorded. The kinetic parameters: charge transfer coefficients (α), diffusion coefficients ( D), heterogeneous rate constants of electrode process ( k s), and effective activation energies of the process ( E a) were calculated from the results of polarization measurements. An analysis of the results and calculated kinetic parameters of electrode processes showed that discharge ionization of sulfur in alkaline solutions occurs as a sequence of two stages and is a quasireversible process.

Method for fabricating carbon/lithium-ion electrode for rechargeable lithium cell

NASA Technical Reports Server (NTRS)

Attia, Alan I. (Inventor); Halpert, Gerald (Inventor); Huang, Chen-Kuo (Inventor); Surampudi, Subbarao (Inventor)

1995-01-01

The method includes steps for forming a carbon electrode composed of graphitic carbon particles adhered by an ethylene propylene diene monomer binder. An effective binder composition is disclosed for achieving a carbon electrode capable of subsequent intercalation by lithium ions. The method also includes steps for reacting the carbon electrode with lithium ions to incorporate lithium ions into graphitic carbon particles of the electrode. An electrical current is repeatedly applied to the carbon electrode to initially cause a surface reaction between the lithium ions and to the carbon and subsequently cause intercalation of the lithium ions into crystalline layers of the graphitic carbon particles. With repeated application of the electrical current, intercalation is achieved to near a theoretical maximum. Two differing multi-stage intercalation processes are disclosed. In the first, a fixed current is reapplied. In the second, a high current is initially applied, followed by a single subsequent lower current stage. Resulting carbon/lithium-ion electrodes are well suited for use as an anode in a reversible, ambient temperature, lithium cell.

Methanol metabolism and archaeal community changes in a bioelectrochemical anaerobic digestion sequencing batch reactor with copper-coated graphite cathode.

PubMed

Park, Jungyu; Lee, Beom; Shi, Peng; Kwon, Hyejeong; Jeong, Sang Mun; Jun, Hangbae

2018-07-01

In this study, the metabolism of methanol and changes in an archaeal community were examined in a bioelectrochemical anaerobic digestion sequencing batch reactor with a copper-coated graphite cathode (BEAD-SBR Cu ). Copper-coated graphite cathode produced methanol from food waste. The BEAD-SBR Cu showed higher methanol removal and methane production than those of the anaerobic digestion (AD)-SBR. The methane production and pH of the BEAD-SBR Cu were stable even under a high organic loading rate (OLR). The hydrogenotrophic methanogens increased from 32.2 to 60.0%, and the hydrogen-dependent methylotrophic methanogens increased from 19.5 to 37.7% in the bulk of BEAD-SBR Cu at high OLR. Where methanol was directly injected as a single substrate into the BEAD-SBR Cu , the main metabolism of methane production was hydrogenotrophic methanogenesis using carbon dioxide and hydrogen released by the oxidation of methanol on the anode through bioelectrochemical reactions. Copyright © 2018 Elsevier Ltd. All rights reserved.

Advanced cathode materials for high-power applications

NASA Astrophysics Data System (ADS)

Amine, K.; Liu, J.; Belharouak, I.; Kang, S.-H.; Bloom, I.; Vissers, D.; Henriksen, G.

In our efforts to develop low cost high-power Li-ion batteries with excellent safety, as well as long cycle and calendar life, lithium manganese oxide spinel and layered lithium nickel cobalt manganese oxide cathode materials were investigated. Our studies with the graphite/LiPF 6/spinel cells indicated a very significant degradation of capacity with cycling at 55 °C. This degradation was caused by the reduction of manganese ions on the graphite surface which resulted in a significant increase of the charge-transfer impedance at the anode/electrolyte interface. To improve the stability of the spinel, we investigated an alternative salt that would not generate HF acid that may attack the spinel. The alternative salt we selected for this work was lithium bisoxalatoborate, LiB(C 2O 4) 2 ("LiBoB"). In this case, the graphite/LiBoB/spinel Li-ion cells exhibited much improved cycle/calendar life at 55 °C and better abuse tolerance, as well as excellent power. A second system based on LiNi 1/3Co 1/3Mn 1/3O 2 layered material was also investigated and its performance was compared to commercial LiNi 0.8Co 0.15Al 0.05O 2. Cells based on LiNi 1/3Co 1/3Mn 1/3O 2 showed lower power fade and better thermal safety than the LiNi 0.8Co 0.15Al 0.05O 2-based commercial cells under similar test conditions. Li-ion cells based on the material with excess lithium (Li 1.1Ni 1/3Co 1/3Mn 1/3O 2) exhibited excellent power performance that exceeded the FreedomCAR requirements.

Aqueous Dispersions of Graphene from Electrochemically Exfoliated Graphite.

PubMed

Sevilla, Marta; Ferrero, Guillermo A; Fuertes, Antonio B

2016-11-21

A facile and environmentally friendly synthetic strategy for the production of stable and easily processable dispersions of graphene in water is presented. This strategy represents an alternative to classical chemical exfoliation methods (for example the Hummers method) that are more complex, harmful, and dangerous. The process is based on the electrochemical exfoliation of graphite and includes three simple steps: 1) the anodic exfoliation of graphite in (NH 4 ) 2 SO 4 , 2) sonication to separate the oxidized graphene sheets, and 3) reduction of oxidized graphene to graphene. The procedure makes it possible to convert around 30 wt % of the initial graphite into graphene with short processing times and high yields. The graphene sheets are well dispersed in water, have a carbon/oxygen atomic ratio of 11.7, a lateral size of about 0.5-1 μm, and contain only a few graphene layers, most of which are bilayer sheets. The processability of this type of aqueous dispersion has been demonstrated in the fabrication of macroscopic graphene structures, such as graphene aerogels and graphene films, which have been successfully employed as absorbents or as electrodes in supercapacitors, respectively. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Wide-Temperature Electrolytes for Lithium-Ion Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Qiuyan; Jiao, Shuhong; Luo, Langli

2017-05-26

Formulating electrolytes with solvents of low freezing points and high dielectric constants is a direct approach to extend the service temperature range of lithium (Li)-ion batteries (LIBs), for which propylene carbonate (PC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), methyl butyrate (MB) are excellent candidates. In this work, we report such low temperature electrolyte formulations by optimizing the content of ethylene carbonate (EC) in the EC-PC-EMC ternary solvent system with LiPF6 salt and CsPF6 additive. An extended service temperature range from 40°C to 60°C was obtained in LIBs with lithium nickel cobalt aluminum mixed oxide (LiNi0.80Co0.15Al0.05O2, NCA) as cathode andmore » graphite as anode. The discharge capacities at low temperatures and the cycle life at room and elevated temperatures were systematically investigated in association with the ionic conductivity and phase transition behaviors. The most promising electrolyte formulation was identified as 1.0 M LiPF6 in EC-PC-EMC (1:1:8 by wt.) with 0.05 M CsPF6, which was demonstrated in both coin cells of graphite||NCA and 1 Ah pouch cells of graphite||LiNi1/3Mn1/3Co1/3O2. This optimized electrolyte enables excellent wide-temperature performances, as evidenced by the 68% capacity retention at 40C and C/5 rate, and nearly identical stable cycle life at room and elevated temperatures up to 60C.« less

High Coulombic efficiency aluminum-ion battery using an AlCl3-urea ionic liquid analog electrolyte.

PubMed

Angell, Michael; Pan, Chun-Jern; Rong, Youmin; Yuan, Chunze; Lin, Meng-Chang; Hwang, Bing-Joe; Dai, Hongjie

2017-01-31

In recent years, impressive advances in harvesting renewable energy have led to a pressing demand for the complimentary energy storage technology. Here, a high Coulombic efficiency (∼99.7%) Al battery is developed using earth-abundant aluminum as the anode, graphite as the cathode, and a cheap ionic liquid analog electrolyte made from a mixture of AlCl 3 and urea in a 1.3:1 molar ratio. The battery displays discharge voltage plateaus around 1.9 and 1.5 V (average discharge = 1.73 V) and yielded a specific cathode capacity of ∼73 mAh g -1 at a current density of 100 mA g -1 (∼1.4 C). High Coulombic efficiency over a range of charge-discharge rates and stability over ∼150-200 cycles was easily demonstrated. In situ Raman spectroscopy clearly showed chloroaluminate anion intercalation/deintercalation of graphite (positive electrode) during charge-discharge and suggested the formation of a stage 2 graphite intercalation compound when fully charged. Raman spectroscopy and NMR suggested the existence of AlCl 4 - , Al 2 Cl 7 - anions and [AlCl 2 ·(urea) n ] + cations in the AlCl 3 /urea electrolyte when an excess of AlCl 3 was present. Aluminum deposition therefore proceeded through two pathways, one involving Al 2 Cl 7 - anions and the other involving [AlCl 2 ·(urea) n ] + cations. This battery is a promising prospect for a future high-performance, low-cost energy storage device.

Graphite from the University of Idaho Thermolyzed Asphalt Reaction (GUITAR): Fundamental Electrochemical Characterizations

NASA Astrophysics Data System (ADS)

Gyan, Isaiah Owusu

This dissertation details electrochemical characterization of GUITAR (Graphite from the University of Idaho Thermolyzed Asphalt Reaction), a new allotrope of carbon. Applications based on fundamental electrochemical properties of this material are also presented. The dissertation is presented in five chapters. Chapter one presents a summary of the discovery and physical characterizations of GUITAR and how its physical properties position it among carbon materials. In chapter two, fundamental electrochemical properties covering aqueous potential window and electron transfer kinetics with common dissolved redox couples are presented. This chapter highlights significant electrochemical differences between GUITAR and other sp2 carbon materials, notably, fast electron transfer across basal plane GUITAR, contrary to reports at basal planes of graphite and graphene electrodes. In chapter three, the concept of electron transfer facility is extended with biologically relevant molecules. GUITAR is shown to be suitable for biosensing with properties such as; facile electron transfer, low detection limit, high resistance to fouling and stability to anodic regeneration procedures. Chapter four presents further exploration of GUITAR's wide cathodic potential limits in other aqueous electrolytes and preliminary studies towards the exploitation of this property in the negative half of vanadium redox flow battery, where GUITAR-based electrodes are expected to increase coulombic efficiency and increase battery performance due to low hydrogen evolution. Chapter five concludes this dissertation with point-by-point presentation of significant discoveries that highlights GUITAR's uniqueness. This chapter also describes how the various fundamental electrochemical properties of GUITAR make it useful for various applications.

Bacterial Membrane Depolarization-Linked Fuel Cell Potential Burst as Signal for Selective Detection of Alcohol.

PubMed

Kaushik, Sharbani; Goswami, Pranab

2018-06-06

The biosensing application of microbial fuel cell (MFC) is hampered by its long response time, poor selectivity, and technical difficulty in developing portable devices. Herein, a novel signal form for rapid detection of ethanol was generated in a photosynthetic MFC (PMFC). First, a dual chambered (100 mL each) PMFC was fabricated by using cyanobacteria-based anode and abiotic cathode, and its performance was examined for detection of alcohols. A graphene-based nanobiocomposite matrix was layered over graphite anode to support cyanobacterial biofilm growth and to facilitate electron transfer. Injection of alcohols into the anodic chamber caused a transient potential burst of the PMFC within 60 s (load 1000 Ω), and the magnitude of potential could be correlated to the ethanol concentrations in the range 0.001-20% with a limit of detection (LOD) of 0.13% ( R 2 = 0.96). The device exhibited higher selectivity toward ethanol than methanol as discerned from the corresponding cell-alcohol interaction constant ( K i ) of 780 and 1250 mM. The concept was then translated to a paper-based PMFC (p-PMFC) (size ∼20 cm 2 ) wherein, the cells were merely immobilized over the anode. The device with a shelf life of ∼3 months detected ethanol within 10 s with a dynamic range of 0.005-10% and LOD of 0.02% ( R 2 = 0.99). The fast response time was attributed to the higher wettability of ethanol on the immobilized cell surface as validated by the contact angle data. Alcohols degraded the cell membrane on the order of ethanol > methanol, enhanced the redox current of the membrane-bound electron carrier proteins, and pushed the anodic band gap toward more negative value. The consequence was the potential burst, the magnitude of which was correlated to the ethanol concentrations. This novel approach has a great application potential for selective, sensitive, rapid, and portable detection of ethanol.

High performance nano-Ni/Graphite electrode for electro-oxidation in direct alkaline ethanol fuel cells

NASA Astrophysics Data System (ADS)

Soliman, Ahmed B.; Abdel-Samad, Hesham S.; Abdel Rehim, Sayed S.; Ahmed, Mohamed A.; Hassan, Hamdy H.

2016-09-01

Ni/Graphite electrocatalysts (Ni/G) are successfully prepared through electrodeposition of Ni from acidic (pH = 0.8) and feebly acidic (pH = 5.5) aqueous Ni (II) baths. The efficiencies of such electrodes are investigated as anodes for direct alkaline ethanol fuel cells through their ethanol electrooxidation cyclic voltammetric (CV) response in alkaline medium. A direct proportionality between the amount of the electrodeposited Ni and its CV response is found. The amounts of the deposited Ni from the two baths are recorded using the Electrochemical Quartz Crystal Microbalance (eQCM). The Ni/G electrodes prepared from the feebly acidic bath show a higher electrocatalytic response than those prepared from the acidic bath. Surface morphology of the Ni particles electrodeposited from feebly acidic bath appears in a nano-scale dimension. Various electrochemical experiments are conducted to confirm that the Ni/G ethanol electrooxidation CV response greatly depends on the pH rather than nickel ion concentration of the deposition bath. The eQCM technique is used to detect the crystalline phases of nickel as α-Ni(OH)2/γ-NiOOH and β-Ni(OH)2/β-NiOOH and their in-situ inter-transformations during the potentiodynamic polarization.

Scalable air cathode microbial fuel cells using glass fiber separators, plastic mesh supporters, and graphite fiber brush anodes.

PubMed

Zhang, Xiaoyuan; Cheng, Shaoan; Liang, Peng; Huang, Xia; Logan, Bruce E

2011-01-01

The combined use of brush anodes and glass fiber (GF1) separators, and plastic mesh supporters were used here for the first time to create a scalable microbial fuel cell architecture. Separators prevented short circuiting of closely-spaced electrodes, and cathode supporters were used to avoid water gaps between the separator and cathode that can reduce power production. The maximum power density with a separator and supporter and a single cathode was 75 ± 1 W/m(3). Removing the separator decreased power by 8%. Adding a second cathode increased power to 154 ± 1 W/m(3). Current was increased by connecting two MFCs connected in parallel. These results show that brush anodes, combined with a glass fiber separator and a plastic mesh supporter, produce a useful MFC architecture that is inherently scalable due to good insulation between the electrodes and a compact architecture. Copyright © 2010 Elsevier Ltd. All rights reserved.

A bio-anodic filter facilitated entrapment, decomposition and in situ oxidation of algal biomass in wastewater effluent.

PubMed

Mohammadi Khalfbadam, Hassan; Cheng, Ka Yu; Sarukkalige, Ranjan; Kaksonen, Anna H; Kayaalp, Ahmet S; Ginige, Maneesha P

2016-09-01

This study examined for the first time the use of bioelectrochemical systems (BES) to entrap, decompose and oxidise fresh algal biomass from an algae-laden effluent. The experimental process consisted of a photobioreactor for a continuous production of the algal-laden effluent, and a two-chamber BES equipped with anodic graphite granules and carbon-felt to physically remove and oxidise algal biomass from the influent. Results showed that the BES filter could retain ca. 90% of the suspended solids (SS) loaded. A coulombic efficiency (CE) of 36.6% (based on particulate chemical oxygen demand (PCOD) removed) was achieved, which was consistent with the highest CEs of BES studies (operated in microbial fuel cell mode (MFC)) that included additional pre-treatment steps for algae hydrolysis. Overall, this study suggests that a filter type BES anode can effectively entrap, decompose and in situ oxidise algae without the need for a separate pre-treatment step. Copyright © 2016 Elsevier Ltd. All rights reserved.

Chemical Passivation of Li(exp +)-Conducting Solid Electrolytes

NASA Technical Reports Server (NTRS)

West, William; Whitacre, Jay; Lim, James

2008-01-01

Plates of a solid electrolyte that exhibits high conductivity for positive lithium ions can now be passivated to prevent them from reacting with metallic lithium. Such passivation could enable the construction and operation of high-performance, long-life lithium-based rechargeable electrochemical cells containing metallic lithium anodes. The advantage of this approach, in comparison with a possible alternative approach utilizing lithium-ion graphitic anodes, is that metallic lithium anodes could afford significantly greater energy-storage densities. A major impediment to the development of such cells has been the fact that the available solid electrolytes having the requisite high Li(exp +)-ion conductivity are too highly chemically reactive with metallic lithium to be useful, while those solid electrolytes that do not react excessively with metallic lithium have conductivities too low to be useful. The present passivation method exploits the best features of both extremes of the solid-electrolyte spectrum. The basic idea is to coat a higher-conductivity, higher-reactivity solid electrolyte with a lower-conductivity, lower-reactivity solid electrolyte. One can then safely deposit metallic lithium in contact with the lower-reactivity solid electrolyte without incurring the undesired chemical reactions. The thickness of the lower-reactivity electrolyte must be great enough to afford the desired passivation but not so great as to contribute excessively to the electrical resistance of the cell. The feasibility of this method was demonstrated in experiments on plates of a commercial high-performance solid Li(exp +)- conducting electrolyte. Lithium phosphorous oxynitride (LiPON) was the solid electrolyte used for passivation. LiPON-coated solid-electrolyte plates were found to support electrochemical plating and stripping of Li metal. The electrical resistance contributed by the LiPON layers were found to be small relative to overall cell impedances.

Electrochemical Capacities of Commercially Available Structural Carbon Fibers, Fabrics, and Papers

DTIC Science & Technology

2008-09-01

Hollingsworth & Vose. A liquid electrolyte of ethylene carbonate: ethyl methyl carbonate (3:7 by weight) with 1.0 M lithium hexafluorophosphate (LiPF6) was...fiber pulp COTS commercial off-the-shelf Da dalton FE-SEM Field Emission Scanning Electron Microscope LiPF6 lithium hexafluorophosphate MWNT...material for anodes in modern technologies, particularly in lithium -ion batteries and electrochemical supercapacitors. Graphitic carbon allows for

Plastic-bonded electrodes for nickel-cadmium accumulators. IV - Some specific problems of the positive active layer

NASA Astrophysics Data System (ADS)

Micka, K.; Mrha, J.; Klapste, B.

1980-06-01

The active layer of plastic-bonded nickel oxide electrodes undergoes expansion during discharging and contraction during charging; the latter however does not fully compensate for the expansion. These volume changes can be made reversible by the action of an external pressure. The electro-chemical behavior of the conductive components, carbon black and graphite, shows more or less severe corrosion during anodic current loading.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shkrob, Ilya A.; Pupek, Krzysztof Z.; Gilbert, James A.

Lithium hexafluorophosphate (LiPF 6) is ubiquitous in commercial lithium-ion batteries, but it is hydrolytically unstable and corrosive on electrode surfaces. Using a more stable salt would confer multiple benefits for high-voltage operation, but many such electrolyte systems facilitate anodic dissolution and pitting corrosion of aluminum current collectors that negate their advantages. Lithium 2-trifluoromethyl-4,5-dicyanoimidazolide (LiTDI) is a new salt that was designed specifically for high-voltage cells. In this study we demonstrate that in carbonate electrolytes, LiTDI prevents anodic dissolution of Al current collectors, which places it into a select group of corrosion inhibitors. However, we also demonstrate that LiTDI becomes reducedmore » on lithiated graphite, undergoing sequential defluorination and yielding a thick and resistive solid-electrolyte interphase (SEI), which increases impedance and lowers electrode capacity. The mechanistic causes for this behavior are examined using computational chemistry methods in the light of recent spectroscopic studies. Here, we demonstrate that LiTDI reduction can be prevented by certain electrolyte additives, which include fluoroethylene carbonate, vinylene carbonate and lithium bis(oxalato)borate. This beneficial action is due to preferential reduction of these additives over LiTDI at a higher potential vs. Li/Li +, so the resulting SEI can prevent the direct reduction of LiTDI at lower potentials on the graphite electrode.« less

Dual-carbon enhanced silicon-based composite as superior anode material for lithium ion batteries

NASA Astrophysics Data System (ADS)

Wang, Jie; Liu, Dai-Huo; Wang, Ying-Ying; Hou, Bao-Hua; Zhang, Jing-Ping; Wang, Rong-Shun; Wu, Xing-Long

2016-03-01

Dual-carbon enhanced Si-based composite (Si/C/G) has been prepared via employing the widely distributed, low-cost and environmentally friendly Diatomite mineral as silicon raw material. The preparation processes are very simple, non-toxic and easy to scale up. Electrochemical tests as anode material for lithium ion batteries (LIBs) demonstrate that this Si/C/G composite exhibits much improved Li-storage properties in terms of superior high-rate capabilities and excellent cycle stability compared to the pristine Si material as well as both single-carbon modified composites. Specifically for the Si/C/G composite, it can still deliver a high specific capacity of about 470 mAh g-1 at an ultrahigh current density of 5 A g-1, and exhibit a high capacity of 938 mAh g-1 at 0.1 A g-1 with excellent capacity retention in the following 300 cycles. The significantly enhanced Li-storage properties should be attributed to the co-existence of both highly conductive graphite and amorphous carbon in the Si/C/G composite. While the former can enhance the electrical conductivity of the obtained composite, the latter acts as the adhesives to connect the porous Si particulates and conductive graphite flakes to form robust and stable conductive network.

Effect of overcharge on Li(Ni 0.5Mn 0.3Co 0.2)O 2 cathodes: NMP-soluble binder. II — Chemical changes in the anode

DOE PAGES

Bloom, Ira; Bareno, Javier; Dietz Rago, Nancy; ...

2018-02-13

For this study, cells based on nickel manganese cobalt oxide (NMC)/graphite electrodes, which contained polyvinylidene difluoride (PVDF) binders in the electrodes, were systematically charged to 100, 120, 140, 160, 180, and 250% state of charge (SOC). Characterization of the anodes by inductively-coupled-plasma mass spectrometry (ICP-MS), X-ray photoelectron spectroscopy (XPS), and high-performance liquid chromatography coupled with electrospray ionization mass spectrometry (HPLC-ESI-MS) showed several extent-of-overcharge-dependent trends. The concentrations (by wt) of nickel, manganese, and cobalt in the negative electrode increased with SOC, but the metals remained in the same ratio as that of the positive. Electrolyte reaction products, such as LiF:LiPO 3,more » increased with overcharge, as expected. Three organic products were found by HPLC-ESI-MS. From an analysis of the mass spectra, two of these compounds seem to be organophosphates, which were formed by the reaction of polymerized electrolyte decomposition products and PF 3 or O=PF 3. Their concentration tended to reach a constant ratio. The third was seen at 250% SOC only.« less

Facile one-pot synthesis of platinum nanoparticles decorated nitrogen-graphene with high electrocatalytic performance for oxygen reduction and anodic fuels oxidation

NASA Astrophysics Data System (ADS)

Navaee, Aso; Salimi, Abdollah; Soltanian, Saeid; Servati, Peyman

2015-03-01

Due to exceptional electronic properties of graphene (Gr) and nitrogen doped graphene (N-Gr), they are considered as superior supporting platforms for novel metal nanoparticle decorations. Here, we report, a novel one-step electrochemical method for synthesis of Nitrogen-doped graphene sheets uniformly decorated with platinum nanoparticles (Pt/N-Gr). A graphite rod and platinum wire are respectively used for graphene and platinum nanoparticles production. The potential is cycled from -3V to +3V in acetonitrile solution as a nitrogen dopant source. By increasing the number of cycles the nitrogen-doped graphene/platinum nanoparticles composite is generated. After heat-treating the composite is characterized with various techniques such as FTIR, Raman, XPS, SEM and TEM. The electrocatalytic activity of the prepared composite toward the reduction of O2 and the oxidation of usual anodic fuels such as methanol, ethanol, hydrazine and formic acid is investigated using cyclic voltammetry technique. In comparison to commercial platinum/carbon, the onset potentials and the current densities for both O2 reduction and fuels oxidation are remarkably improved. Furthermore, the modified electrode by this composite shows good long-term stability and poisoning tolerance.

Effect of overcharge on Li(Ni 0.5Mn 0.3Co 0.2)O 2 cathodes: NMP-soluble binder. II — Chemical changes in the anode

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bloom, Ira; Bareno, Javier; Dietz Rago, Nancy

For this study, cells based on nickel manganese cobalt oxide (NMC)/graphite electrodes, which contained polyvinylidene difluoride (PVDF) binders in the electrodes, were systematically charged to 100, 120, 140, 160, 180, and 250% state of charge (SOC). Characterization of the anodes by inductively-coupled-plasma mass spectrometry (ICP-MS), X-ray photoelectron spectroscopy (XPS), and high-performance liquid chromatography coupled with electrospray ionization mass spectrometry (HPLC-ESI-MS) showed several extent-of-overcharge-dependent trends. The concentrations (by wt) of nickel, manganese, and cobalt in the negative electrode increased with SOC, but the metals remained in the same ratio as that of the positive. Electrolyte reaction products, such as LiF:LiPO 3,more » increased with overcharge, as expected. Three organic products were found by HPLC-ESI-MS. From an analysis of the mass spectra, two of these compounds seem to be organophosphates, which were formed by the reaction of polymerized electrolyte decomposition products and PF 3 or O=PF 3. Their concentration tended to reach a constant ratio. The third was seen at 250% SOC only.« less

Effect of overcharge on Li(Ni0.5Mn0.3Co0.2)O2 cathodes: NMP-soluble binder. II - Chemical changes in the anode

NASA Astrophysics Data System (ADS)

Bloom, Ira; Bareño, Javier; Dietz Rago, Nancy; Dogan, Fulya; Graczyk, Donald G.; Tsai, Yifen; Naik, Seema R.; Han, Sang-Don; Lee, Eungje; Du, Zhijia; Sheng, Yangping; Li, Jianlin; Wood, David L.; Steele, Leigh Anna; Lamb, Joshua; Spangler, Scott; Grosso, Christopher; Fenton, Kyle

2018-05-01

Cells based on nickel manganese cobalt oxide (NMC)/graphite electrodes, which contained polyvinylidene difluoride (PVDF) binders in the electrodes, were systematically charged to 100, 120, 140, 160, 180, and 250% state of charge (SOC). Characterization of the anodes by inductively-coupled-plasma mass spectrometry (ICP-MS), X-ray photoelectron spectroscopy (XPS), and high-performance liquid chromatography coupled with electrospray ionization mass spectrometry (HPLC-ESI-MS) showed several extent-of-overcharge-dependent trends. The concentrations (by wt) of nickel, manganese, and cobalt in the negative electrode increased with SOC, but the metals remained in the same ratio as that of the positive. Electrolyte reaction products, such as LiF:LiPO3, increased with overcharge, as expected. Three organic products were found by HPLC-ESI-MS. From an analysis of the mass spectra, two of these compounds seem to be organophosphates, which were formed by the reaction of polymerized electrolyte decomposition products and PF3 or O=PF3. Their concentration tended to reach a constant ratio. The third was seen at 250% SOC only.

Manufacturing High-Quality Carbon Nanotubes at Lower Cost

NASA Technical Reports Server (NTRS)

Benavides, Jeanette M.; Lidecker, Henning

2004-01-01

A modified electric-arc welding process has been developed for manufacturing high-quality batches of carbon nanotubes at relatively low cost. Unlike in some other processes for making carbon nanotubes, metal catalysts are not used and, consequently, it is not necessary to perform extensive cleaning and purification. Also, unlike some other processes, this process is carried out at atmospheric pressure under a hood instead of in a closed, pressurized chamber; as a result, the present process can be implemented more easily. Although the present welding-based process includes an electric arc, it differs from a prior electric-arc nanotube-production process. The welding equipment used in this process includes an AC/DC welding power source with an integral helium-gas delivery system and circulating water for cooling an assembly that holds one of the welding electrodes (in this case, the anode). The cathode is a hollow carbon (optionally, graphite) rod having an outside diameter of 2 in. (approximately equal to 5.1 cm) and an inside diameter of 5/8 in. (approximately equal to 1.6 cm). The cathode is partly immersed in a water bath, such that it protrudes about 2 in. (about 5.1 cm) above the surface of the water. The bottom end of the cathode is held underwater by a clamp, to which is connected the grounding cable of the welding power source. The anode is a carbon rod 1/8 in. (approximately equal to 0.3 cm) in diameter. The assembly that holds the anode includes a thumbknob- driven mechanism for controlling the height of the anode. A small hood is placed over the anode to direct a flow of helium downward from the anode to the cathode during the welding process. A bell-shaped exhaust hood collects the helium and other gases from the process. During the process, as the anode is consumed, the height of the anode is adjusted to maintain an anode-to-cathode gap of 1 mm. The arc-welding process is continued until the upper end of the anode has been lowered to a specified height above the surface of the water bath. The process causes carbon nanotubes to form in the lowest 2.5 cm of the anode. It also causes a deposit reminiscent of a sandcastle to form on the cathode. The nanotube-containing material is harvested. The cathode and anode can then be cleaned (or the anode is replaced, if necessary) and the process repeated to produce more nanotubes. Tests have shown that the process results in approximately equal to 50-percent yield of carbon nanotubes (mostly of the single-wall type) of various sizes. Whereas the unit cost of purified single-wall carbon nanotubes produced by other process is about $1,000/g in the year 2000, it has been estimated that for the present process, the corresponding cost would be about $10/g.

Degradation pathway of malachite green in a novel dual-tank photoelectrochemical catalytic reactor.

PubMed

Diao, Zenghui; Li, Mingyu; Zeng, Fanyin; Song, Lin; Qiu, Rongliang

2013-09-15

A novel dual-tank photoelectrochemical catalytic reactor was designed to investigate the degradation pathway of malachite green. A thermally formed TiO₂/Ti thin film electrode was used as photoanode, graphite was used as cathode, and a saturated calomel electrode was employed as the reference electrode in the reactor. In the reactor, the anode and cathode tanks were connected by a cation exchange membrane. Results showed that the decolorization ratio of malachite green in the anode and cathode was 98.5 and 96.5% after 120 min, respectively. Malachite green in the two anode and cathode tanks was oxidized, achieving the bipolar double effect. Malachite green in both the anode and cathode tanks exhibited similar catalytic degradation pathways. The double bond of the malachite green molecule was attacked by strong oxidative hydroxyl radicals, after which the organic compound was degraded by the two pathways into 4,4-bis(dimethylamino) benzophenone, 4-(dimethylamino) benzophenone, 4-(dimethylamino) phenol, and other intermediate products. Eventually, malachite green was degraded into oxalic acid as a small molecular organic acid, which was degraded by processes such as demethylation, deamination, nitration, substitution, addition, and other reactions. Copyright © 2013 Elsevier B.V. All rights reserved.

Ab initio study of novel carbon nanofoam structure as an anode material for Li secondary battery

NASA Astrophysics Data System (ADS)

Park, Hanjin; Park, Sora; Kang, Seoung-Hun; Kwon, Young-Kyun

2014-03-01

Using ab inito density functional theory, we investigate the adsorption and diffusion properties of Li atoms on a new carbon nanostructure, which may be used as an anode of Li secondary battery. We focus on a special carbon nanofoam structure consisting of Schwarzite structures with negative Gaussian curvature as core parts, which are interconnected through (4,4) CNT segments. Considering the symmetry of the nanofoam structure, we find various Li adsorption sites exhibiting relatively large binding energies (>= 2 . 00 eV). Based on these adsorption sites, we identify several diffusion paths on the outside or inside surface of the nanofoam structure and examine the diffusion barriers along the paths. Our results show that Li atom can diffuse almost freely due to its low energy barriers on both outside and inside surfaces. Finally, we also evaluate the energy gain tendency and the volume expansion as well as the average binding energy while adding Li atoms to estimate the Li-capacity and recyclability of the system, which are important characterisitics for anode materials. We conclude that the carbon nanofoam structure would be better as an anode material than graphite in Li capacity and volume expansion.

Li-Ion Localization and Energetics as a Function of Anode Structure.

PubMed

McNutt, Nicholas W; McDonnell, Marshall; Rios, Orlando; Keffer, David J

2017-03-01

In this work, we study the effect of carbon composite anode structure on the localization and energetics of Li-ions. A computational molecular dynamics study is combined with experimental results from neutron scattering experiments to understand the effect of composite density, crystallite size, volume fraction of crystalline carbon, and ion loading on the nature of ion storage in novel, lignin-derived composite materials. In a recent work, we demonstrated that these carbon composites display a fundamentally different mechanism for Li-ion storage than traditional graphitic anodes. The edges of the crystalline and amorphous fragments of aromatic carbon that exist in these composites are terminated by hydrogen atoms, which play a crucial role in adsorption. In this work, we demonstrate how differences in composite structure due to changes in the processing conditions alter the type and extent of the interface between the amorphous and crystalline domains, thus impacting the nature of Li-ion storage. The effects of structural properties are evaluated using a suite of pair distribution functions as well as an original technique to extract archetypal structures, in the form of three-dimensional atomic density distributions, from highly disordered systems. The energetics of Li-ion binding are understood by relating changes in the energy and charge distributions to changes in structural properties. The distribution of Li-ion energies reveals that some structures lead to greater chemisorption, while others have greater physisorption. Carbon composites with a high volume fraction of small crystallites demonstrate the highest ion storage capacity because of the high interfacial area between the crystalline and amorphous domains. At these interfaces, stable H atoms, terminating the graphitic crystallites, provide favorable sites for reversible Li adsorption.

Study of Copper and Purine-Copper Complexes on Modified Carbon Electrodes by Cyclic and Elimination Voltammetry

PubMed Central

Trnkova, Libuse; Zerzankova, Lenka; Dycka, Filip; Mikelova, Radka; Jelen, Frantisek

2008-01-01

Using a paraffin impregnated graphite electrode (PIGE) and mercury-modified pyrolytic graphite electrode with basal orientation (Hg-PGEb) copper(II) and Cu(II)-DNA purine base solutions have been studied by cyclic (CV) and linear sweep voltammetry (LSV) in connection with elimination voltammetry with linear scan (EVLS). In chloride and bromide solutions (pH 6), the redox process of Cu(II) proceeded on PIGE with two cathodic and two anodic potentially separated signals. According to the elimination function E4, the first cathodic peak corresponds to the reduction Cu(II) + e- → Cu(I) with the possibility of fast disproportionation 2Cu(I) → Cu(II)+ Cu(0). The E4 of the second cathodic peak signalized an electrode process controlled by a surface reaction. The electrode system of Cu(II) on Hg-PGEb in borate buffer (pH 9.2) was characterized by one cathodic and one anodic peak. Anodic stripping voltammetry (ASV) on PIGE and cathodic stripping voltammetry (CSV) on Hg-PGEb were carried out at potentials where the reduction of copper ions took place and Cu(I)-purine complexes were formed. By using ASV and CSV in combination with EVLS, the sensitivity of Cu(I)-purine complex detection was enhanced relative to either ASV or CSV alone, resulting in higher peak currents of more than one order of magnitude. The statistical treatment of CE data was used to determine the reproducibility of measurements. Our results show that EVLS in connection with the stripping procedure is useful for both qualitative and quantitative microanalysis of purine derivatives and can also reveal details of studied electrode processes. PMID:27879715

Limitations of disordered carbons obtained from biomass as anodes for real lithium-ion batteries.

PubMed

Caballero, Alvaro; Hernán, Lourdes; Morales, Julián

2011-05-23

Two disordered microporous carbons were obtained from two different types of biomass residues: olive and cherry stones. The former (OS) was activated physically under steam while the latter (CS) chemically with an aqueous solution of ZnCl(2). Their structural and textural properties were studied by X-ray diffraction, scanning electron microscopy, and N(2) adsorption/desorption. Although the samples possess similar textural properties (BET surface areas, micropore surfaces and volumes), the CS carbon is more disordered than the OS carbon. Their electrochemical response in half-cells (CS[OS]/Li) is good; the values are comparable to those obtained from mesocarbon microbeads commonly used in commercial lithium-ion batteries, which consist of highly graphitized carbon. However, cells featuring the OS or CS carbon as anode and LiMn(2)O(4) as cathode perform poorly. Electrochemical activation of the electrodes against lithium metal, a recommended procedure for boosting the electrochemical properties of real lithium-ion batteries, improves cell performance (particularly with OS) but is ultimately ineffective: the delivered average capacity of the activated cell made from OS was less than half its theoretical value. The high irreversible capacity, high polarization between the charge and discharge curves, combined with the presence of various functional groups and the high disorder of the studied carbons which may facilitate side reactions such as electrolyte decomposition, results in a degraded cell performance. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High performance screen-printed electrodes prepared by a green solvent approach for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Gören, A.; Mendes, J.; Rodrigues, H. M.; Sousa, R. E.; Oliveira, J.; Hilliou, L.; Costa, C. M.; Silva, M. M.; Lanceros-Méndez, S.

2016-12-01

New inks based on lithium iron phosphate and graphite for cathode and anode, respectively, were developed for printable lithium-ion batteries using the "green solvent" N,N‧-dimethylpropyleneurea (DMPU) and poly(vinylidene fluoride), PVDF, as a binder. The results were compared with the ones from inks developed with the conventionally used solvent N-methyl-2-pyrrolidone, NMP. The rheological properties of the PVDF/DMPU binder solution shows a more pronounced shear thinning behavior than the PVDF/NMP solution. Cathode inks prepared with 2.25 mL and 2.50 mL of DMPU for 1 g of electrode mass show an apparent viscosity of 3 Pa s and 2 Pa s for a shear rate of 100 s-1, respectively, being therefore processable by screen-printing or doctor blade techniques. The electrodes prepared with DMPU and processed by screen-printing show a capacity of 52 mAh g-1 at 2C for the cathode and 349 mAh g-1 at C/5 for the anode, after 45 charge-discharge cycles. The electrochemical performance of both electrodes was evaluated in a full-cell and after 9 cycles, the discharge capacity value is 81 mAh g-1, showing a discharge capacity retention of 64%. The new inks presented in this work are thus suitable for the development of printed batteries and represent a step forward towards more environmental friendly processes.

Carbon deposition thresholds on nickel-based solid oxide fuel cell anodes I. Fuel utilization

NASA Astrophysics Data System (ADS)

Kuhn, J.; Kesler, O.

2015-03-01

In the first of a two part publication, the effect of fuel utilization (Uf) on carbon deposition rates in solid oxide fuel cell nickel-based anodes was studied. Representative 5-component CH4 reformate compositions (CH4, H2, CO, H2O, & CO2) were selected graphically by plotting the solutions to a system of mass-balance constraint equations. The centroid of the solution space was chosen to represent a typical anode gas mixture for each nominal Uf value. Selected 5-component and 3-component gas mixtures were then delivered to anode-supported cells for 10 h, followed by determination of the resulting deposited carbon mass. The empirical carbon deposition thresholds were affected by atomic carbon (C), hydrogen (H), and oxygen (O) fractions of the delivered gas mixtures and temperature. It was also found that CH4-rich gas mixtures caused irreversible damage, whereas atomically equivalent CO-rich compositions did not. The coking threshold predicted by thermodynamic equilibrium calculations employing graphite for the solid carbon phase agreed well with empirical thresholds at 700 °C (Uf ≈ 32%); however, at 600 °C, poor agreement was observed with the empirical threshold of ∼36%. Finally, cell operating temperatures correlated well with the difference in enthalpy between the supplied anode gas mixtures and their resulting thermodynamic equilibrium gas mixtures.

An extended life and performance test of a low-power arcjet

NASA Technical Reports Server (NTRS)

Curran, Francis M.; Haag, Thomas W.

1988-01-01

An automated, cyclic life test was performed to demonstrate the reliability and endurance of a low power dc cycle arcjet thruster. Over 1000 hr and 500 on-off cycles were accumulated which would represent the requirements for about 15 years of on-orbit lifetime. A hydrogen/nitrogen propellant mixture was used to simulate decomposed hydrazine propellant and the power level was nominally 1.2 kW after the burn-in period. The arcjet operated in a very repeatable fashion from cycle to cycle. The steady state voltage increased by approximately 6 V over the first 300 hr, and then by only 3 V through the remainder of the test. Thrust measurements taken before, during, and after the test verified that the thruster performed in a consistent fashion throughout the tests at a specific impulse of 450 to 460 sec. Post-test component evaluation revealed limited erosion on both the anode and cathode. Other thruster components, including graphite seals, appeared undamaged.

An antisymmetric cell structure for high-performance zinc bromine flow battery

NASA Astrophysics Data System (ADS)

Kim, Yongbeom; Jeon, Joonhyeon

2017-12-01

Zinc-bromine flow batteries (ZBBs) remain a problem of designing a cell with high coulombic efficiency and stability. This problem is caused intrinsically by different phase transition in each side of the half-cells during charge-discharge process. This paper describes a ZBB with an antisymmetric cell structure, which uses anode and cathode with different surface morphologies, for high-discharge capacity and reliability. The structure of the antisymmetric ZBB cell contains a carbon-surface electrode and a carbon-volume electrode in zinc and bromine half cells, respectively. To demonstrate the effectiveness of this proposed ZBB cell structure, Cyclic Voltammetry measurement is performed on a graphite foil and a carbon felt which are used as the surface and electrodes. Charge and discharge cyclic operations are also carried out with symmetric and antisymmetric ZBB cells combined with the two electrode types. Experimental results show that the arrangement of antisymmetric cell structure in ZBB provides a solution to the high performance and durability.

Electric field induced needle-pulsed arc discharge carbon nanotube production apparatus: circuitry and mechanical design.

PubMed

Kia, Kaveh Kazemi; Bonabi, Fahimeh

2012-12-01

A simple and low cost apparatus is reported to produce multiwall carbon nanotubes and carbon nano-onions by a low power short pulsed arc discharge reactor. The electric circuitry and the mechanical design details and a micro-filtering assembly are described. The pulsed-plasma is generated and applied between two graphite electrodes. The pulse width is 0.3 μs. A strong dc electric field is established along side the electrodes. The repetitive discharges occur in less than 1 mm distance between a sharp tip graphite rod as anode, and a tubular graphite as cathode. A hydrocarbon vapor, as carbon source, is introduced through the graphite nozzle in the cathode assembly. The pressure of the chamber is controlled by a vacuum pump. A magnetic field, perpendicular to the plasma path, is provided. The results show that the synergetic use of a pulsed-current and a dc power supply enables us to synthesize carbon nanoparticles with short pulsed plasma. The simplicity and inexpensiveness of this plan is noticeable. Pulsed nature of plasma provides some extra degrees of freedom that make the production more controllable. Effects of some design parameters such as electric field, pulse frequency, and cathode shape are discussed. The products are examined using scanning probe microscopy techniques.

Electric field induced needle-pulsed arc discharge carbon nanotube production apparatus: Circuitry and mechanical design

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kia, Kaveh Kazemi; Bonabi, Fahimeh

A simple and low cost apparatus is reported to produce multiwall carbon nanotubes and carbon nano-onions by a low power short pulsed arc discharge reactor. The electric circuitry and the mechanical design details and a micro-filtering assembly are described. The pulsed-plasma is generated and applied between two graphite electrodes. The pulse width is 0.3 {mu}s. A strong dc electric field is established along side the electrodes. The repetitive discharges occur in less than 1 mm distance between a sharp tip graphite rod as anode, and a tubular graphite as cathode. A hydrocarbon vapor, as carbon source, is introduced through themore » graphite nozzle in the cathode assembly. The pressure of the chamber is controlled by a vacuum pump. A magnetic field, perpendicular to the plasma path, is provided. The results show that the synergetic use of a pulsed-current and a dc power supply enables us to synthesize carbon nanoparticles with short pulsed plasma. The simplicity and inexpensiveness of this plan is noticeable. Pulsed nature of plasma provides some extra degrees of freedom that make the production more controllable. Effects of some design parameters such as electric field, pulse frequency, and cathode shape are discussed. The products are examined using scanning probe microscopy techniques.« less

Electric field induced needle-pulsed arc discharge carbon nanotube production apparatus: Circuitry and mechanical design

NASA Astrophysics Data System (ADS)

Kia, Kaveh Kazemi; Bonabi, Fahimeh

2012-12-01

A simple and low cost apparatus is reported to produce multiwall carbon nanotubes and carbon nano-onions by a low power short pulsed arc discharge reactor. The electric circuitry and the mechanical design details and a micro-filtering assembly are described. The pulsed-plasma is generated and applied between two graphite electrodes. The pulse width is 0.3 μs. A strong dc electric field is established along side the electrodes. The repetitive discharges occur in less than 1 mm distance between a sharp tip graphite rod as anode, and a tubular graphite as cathode. A hydrocarbon vapor, as carbon source, is introduced through the graphite nozzle in the cathode assembly. The pressure of the chamber is controlled by a vacuum pump. A magnetic field, perpendicular to the plasma path, is provided. The results show that the synergetic use of a pulsed-current and a dc power supply enables us to synthesize carbon nanoparticles with short pulsed plasma. The simplicity and inexpensiveness of this plan is noticeable. Pulsed nature of plasma provides some extra degrees of freedom that make the production more controllable. Effects of some design parameters such as electric field, pulse frequency, and cathode shape are discussed. The products are examined using scanning probe microscopy techniques.

Light-weight free-standing carbon nanotube-silicon films for anodes of lithium ion batteries.

PubMed

Cui, Li-Feng; Hu, Liangbing; Choi, Jang Wook; Cui, Yi

2010-07-27

Silicon is an attractive alloy-type anode material because of its highest known capacity (4200 mAh/g). However, lithium insertion into and extraction from silicon are accompanied by a huge volume change, up to 300%, which induces a strong strain on silicon and causes pulverization and rapid capacity fading due to the loss of the electrical contact between part of silicon and current collector. Si nanostructures such as nanowires, which are chemically and electrically bonded to the current collector, can overcome the pulverization problem, however, the heavy metal current collectors in these systems are larger in weight than Si active material. Herein we report a novel anode structure free of heavy metal current collectors by integrating a flexible, conductive carbon nanotube (CNT) network into a Si anode. The composite film is free-standing and has a structure similar to the steel bar reinforced concrete, where the infiltrated CNT network functions as both mechanical support and electrical conductor and Si as a high capacity anode material for Li-ion battery. Such free-standing film has a low sheet resistance of approximately 30 Ohm/sq. It shows a high specific charge storage capacity (approximately 2000 mAh/g) and a good cycling life, superior to pure sputtered-on silicon films with similar thicknesses. Scanning electron micrographs show that Si is still connected by the CNT network even when small breaking or cracks appear in the film after cycling. The film can also "ripple up" to release the strain of a large volume change during lithium intercalation. The conductive composite film can function as both anode active material and current collector. It offers approximately 10 times improvement in specific capacity compared with widely used graphite/copper anode sheets.

High Coulombic efficiency aluminum-ion battery using an AlCl3-urea ionic liquid analog electrolyte

PubMed Central

Angell, Michael; Pan, Chun-Jern; Rong, Youmin; Yuan, Chunze; Lin, Meng-Chang; Hwang, Bing-Joe; Dai, Hongjie

2017-01-01

In recent years, impressive advances in harvesting renewable energy have led to a pressing demand for the complimentary energy storage technology. Here, a high Coulombic efficiency (∼99.7%) Al battery is developed using earth-abundant aluminum as the anode, graphite as the cathode, and a cheap ionic liquid analog electrolyte made from a mixture of AlCl3 and urea in a 1.3:1 molar ratio. The battery displays discharge voltage plateaus around 1.9 and 1.5 V (average discharge = 1.73 V) and yielded a specific cathode capacity of ∼73 mAh g−1 at a current density of 100 mA g−1 (∼1.4 C). High Coulombic efficiency over a range of charge–discharge rates and stability over ∼150–200 cycles was easily demonstrated. In situ Raman spectroscopy clearly showed chloroaluminate anion intercalation/deintercalation of graphite (positive electrode) during charge–discharge and suggested the formation of a stage 2 graphite intercalation compound when fully charged. Raman spectroscopy and NMR suggested the existence of AlCl4−, Al2Cl7− anions and [AlCl2·(urea)n]+ cations in the AlCl3/urea electrolyte when an excess of AlCl3 was present. Aluminum deposition therefore proceeded through two pathways, one involving Al2Cl7− anions and the other involving [AlCl2·(urea)n]+ cations. This battery is a promising prospect for a future high-performance, low-cost energy storage device. PMID:28096353

Probing multiscale transport and inhomogeneity in a lithium-ion cells using in-situ neutron methods

DOE PAGES

Zhou, Hui; An, Ke; Allu, Srikanth; ...

2016-01-01

Here, we demonstrate for the first time the lithiation process in graphitic anodes using insitu neutron radiography in a pouch cell format. The neutron absorption contrast shows a direct correlation between degree of lithiation and the discharge voltage plateau. Furthermore, we provide a semi-quantitative comparison between the observed spatial variations of neutron attenuation line profile across the graphite electrode and the calculated lithium concentration profiles computed under similar electrochemical discharge conditions. In conjunction, in situ neutron diffraction of a similar pouch cell under identical test protocol was carried to obtain information about the local phase changes upon lithiation. Combined in-situmore » radiography and diffraction opens up a powerful nondestructive method to understand the multi-scale nature of lithium transport and degradation in practical lithium-ion cells.« less

Graphite nanocomposites sensor for multiplex detection of antioxidants in food.

PubMed

Ng, Khan Loon; Tan, Guan Huat; Khor, Sook Mei

2017-12-15

Butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), and tert-butylhydroquinone (TBHQ) are synthetic antioxidants used in the food industry. Herein, we describe the development of a novel graphite nanocomposite-based electrochemical sensor for the multiplex detection and measurement of BHA, BHT, and TBHQ levels in complex food samples using a linear sweep voltammetry technique. Moreover, our newly established analytical method exhibited good sensitivity, limit of detection, limit of quantitation, and selectivity. The accuracy and reliability of analytical results were challenged by method validation and comparison with the results of the liquid chromatography method, where a linear correlation of more than 0.99 was achieved. The addition of sodium dodecyl sulfate as supporting additive further enhanced the LSV response (anodic peak current, I pa ) of BHA and BHT by 2- and 20-times, respectively. Copyright © 2017 Elsevier Ltd. All rights reserved.

High-capacity nanostructured germanium-containing materials and lithium alloys thereof

DOEpatents

Graetz, Jason A.; Fultz, Brent T.; Ahn, Channing; Yazami, Rachid

2010-08-24

Electrodes comprising an alkali metal, for example, lithium, alloyed with nanostructured materials of formula Si.sub.zGe.sub.(z-1), where 0

Novel Epitaxy Between Oxides and Semiconductors - Growth and Interfacial Structures

DTIC Science & Technology

2007-05-16

observed to be impressively good. 15. SUBJECT TERMS Nanotechnology, Gallium Nitride 16. SECURITY CLASSIFICATION OF: 17. LIMITATION OF ABSTRACT Same as...with precursors or gases, a high-purity sapphire was employed in this work. E-beam evaporation was used due to the high melting point of sapphire, and...were carried out on a four-circle triple -axes diffractometer, using a 12 kW rotating anode Cu K-alpha source. A pair of graphite crystals is used to

Chemical stability of Lithium 2-trifluoromethyl-4,5-dicyanoimidazolide, an electrolyte salt for Li-ion cells

DOE PAGES

Shkrob, Ilya A.; Pupek, Krzysztof Z.; Gilbert, James A.; ...

2016-12-01

Lithium hexafluorophosphate (LiPF 6) is ubiquitous in commercial lithium-ion batteries, but it is hydrolytically unstable and corrosive on electrode surfaces. Using a more stable salt would confer multiple benefits for high-voltage operation, but many such electrolyte systems facilitate anodic dissolution and pitting corrosion of aluminum current collectors that negate their advantages. Lithium 2-trifluoromethyl-4,5-dicyanoimidazolide (LiTDI) is a new salt that was designed specifically for high-voltage cells. In this study we demonstrate that in carbonate electrolytes, LiTDI prevents anodic dissolution of Al current collectors, which places it into a select group of corrosion inhibitors. However, we also demonstrate that LiTDI becomes reducedmore » on lithiated graphite, undergoing sequential defluorination and yielding a thick and resistive solid-electrolyte interphase (SEI), which increases impedance and lowers electrode capacity. The mechanistic causes for this behavior are examined using computational chemistry methods in the light of recent spectroscopic studies. Here, we demonstrate that LiTDI reduction can be prevented by certain electrolyte additives, which include fluoroethylene carbonate, vinylene carbonate and lithium bis(oxalato)borate. This beneficial action is due to preferential reduction of these additives over LiTDI at a higher potential vs. Li/Li +, so the resulting SEI can prevent the direct reduction of LiTDI at lower potentials on the graphite electrode.« less