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.

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.

Alloy-Based Anode Materials toward Advanced Sodium-Ion Batteries.

PubMed

Lao, Mengmeng; Zhang, Yu; Luo, Wenbin; Yan, Qingyu; Sun, Wenping; Dou, Shi Xue

2017-12-01

Sodium-ion batteries (SIBs) are considered as promising alternatives to lithium-ion batteries owing to the abundant sodium resources. However, the limited energy density, moderate cycling life, and immature manufacture technology of SIBs are the major challenges hindering their practical application. Recently, numerous efforts are devoted to developing novel electrode materials with high specific capacities and long durability. In comparison with carbonaceous materials (e.g., hard carbon), partial Group IVA and VA elements, such as Sn, Sb, and P, possess high theoretical specific capacities for sodium storage based on the alloying reaction mechanism, demonstrating great potential for high-energy SIBs. In this review, the recent research progress of alloy-type anodes and their compounds for sodium storage is summarized. Specific efforts to enhance the electrochemical performance of the alloy-based anode materials are discussed, and the challenges and perspectives regarding these anode materials are proposed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A facile synthesis of zinc oxide/multiwalled carbon nanotube nanocomposite lithium ion battery anodes by sol-gel method

NASA Astrophysics Data System (ADS)

Köse, Hilal; Karaal, Şeyma; Aydın, Ali Osman; Akbulut, Hatem

2015-11-01

Free standing zinc oxide (ZnO) and multiwalled carbon nanotube (MWCNT) nanocomposite materials are prepared by a sol gel technique giving a new high capacity anode material for lithium ion batteries. Free-standing ZnO/MWCNT nanocomposite anodes with two different chelating agent additives, triethanolamine (TEA) and glycerin (GLY), yield different electrochemical performances. Field emission gun scanning electron microscopy (FEG-SEM), energy dispersive X-ray spectrometer (EDS), high resolution transmission electron microscopy (HRTEM) and X-ray diffraction (XRD) analyses reveal the produced anode electrodes exhibit a unique structure of ZnO coating on the MWCNT surfaces. Li-ion cell assembly using a ZnO/MWCNT/GLY free-standing anode and Li metal cathode possesses the best discharge capacity, remaining as high as 460 mAh g-1 after 100 cycles. This core-shell structured anode can offer increased energy storage and performance over conventional anodes in Li-ion batteries.

Nanostructured silicon anodes for lithium ion rechargeable batteries.

PubMed

Teki, Ranganath; Datta, Moni K; Krishnan, Rahul; Parker, Thomas C; Lu, Toh-Ming; Kumta, Prashant N; Koratkar, Nikhil

2009-10-01

Rechargeable lithium ion batteries are integral to today's information-rich, mobile society. Currently they are one of the most popular types of battery used in portable electronics because of their high energy density and flexible design. Despite their increasing use at the present time, there is great continued commercial interest in developing new and improved electrode materials for lithium ion batteries that would lead to dramatically higher energy capacity and longer cycle life. Silicon is one of the most promising anode materials because it has the highest known theoretical charge capacity and is the second most abundant element on earth. However, silicon anodes have limited applications because of the huge volume change associated with the insertion and extraction of lithium. This causes cracking and pulverization of the anode, which leads to a loss of electrical contact and eventual fading of capacity. Nanostructured silicon anodes, as compared to the previously tested silicon film anodes, can help overcome the above issues. As arrays of silicon nanowires or nanorods, which help accommodate the volume changes, or as nanoscale compliant layers, which increase the stress resilience of silicon films, nanoengineered silicon anodes show potential to enable a new generation of lithium ion batteries with significantly higher reversible charge capacity and longer cycle life.

Porous nitrogen-doped carbon microspheres as anode materials for lithium ion batteries.

PubMed

Chen, Taiqiang; Pan, Likun; Loh, T A J; Chua, D H C; Yao, Yefeng; Chen, Qun; Li, Dongsheng; Qin, Wei; Sun, Zhuo

2014-10-28

Nitrogen-doped carbon microspheres (NCSs) were fabricated via a simple, fast and energy-saving microwave-assisted method followed by thermal treatment under an ammonia atmosphere. NCSs thermally treated at different temperatures were investigated as anode materials for lithium ion batteries (LIBs). The results show that NCSs treated at 900 °C exhibit a maximum reversible capacity of 816 mA h g(-1) at a current density of 50 mA g(-1) and preserve a capacity of 660 mA h g(-1) after 50 cycles, and even at a high current density of 1000 mA g(-1), a capacity of 255 mA h g(-1) is maintained. The excellent electrochemical performance of NCSs is due to their porous structure and nitrogen-doping. The present NCSs should be promising low-cost anode materials with a high capacity and good cycle stability for LIBs.

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.

High rate, long cycle life battery electrode materials with an open framework structure

DOEpatents

Wessells, Colin; Huggins, Robert; Cui, Yi; Pasta, Mauro

2015-02-10

A battery includes a cathode, an anode, and an aqueous electrolyte disposed between the cathode and the anode and including a cation A. At least one of the cathode and the anode includes an electrode material having an open framework crystal structure into which the cation A is reversibly inserted during operation of the battery. The battery has a reference specific capacity when cycled at a reference rate, and at least 75% of the reference specific capacity is retained when the battery is cycled at 10 times the reference rate.

Final Scientific/Technical Report for Low Cost, High Capacity Non- Intercalation Chemistry Automotive Cells

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

Berdichevsky, Gene

Commercial Li-ion batteries typically use Ni- and Co-based intercalation cathodes. As the demand for improved performance from batteries increases, these cathode materials will no longer be able to provide the desired energy storage characteristics since they are currently approaching their theoretical limits. Conversion cathode materials are prime candidates for improvement of Li-ion batteries. On both a volumetric and gravimetric basis they have higher theoretical capacity than intercalation cathode materials. Metal fluoride (MFx) cathodes offer higher specific energy density and dramatically higher volumetric energy density. Challenges associated with metal fluoride cathodes were addressed through nanostructured material design and synthesis. A majormore » goal of this project was to develop and demonstrate Li-ion cells based on Si-comprising anodes and metal fluoride (MFx) comprising cathodes. Pairing the high-capacity MFx cathode with a high-capacity anode, such as an alloying Si anode, allows for the highest possible energy density on a cell level. After facing and overcoming multiple material synthesis and electrochemical instability challenges, we succeeded in fabrication of MFx half cells with cycle stability in excess of 500 cycles (to 20% or smaller degradation) and full cells with MFx-based cathodes and Si-based anodes with cycle stability in excess of 200 cycles (to 20% or smaller degradation).« less

Nanowire Heterostructures Comprising Germanium Stems and Silicon Branches as High-Capacity Li-Ion Anodes with Tunable Rate Capability.

PubMed

Kennedy, Tadhg; Bezuidenhout, Michael; Palaniappan, Kumaranand; Stokes, Killian; Brandon, Michael; Ryan, Kevin M

2015-07-28

Here we report the rational design of a high-capacity Li-ion anode material comprising Ge nanowires with Si branches. The unique structure provides an electrode material with tunable properties, allowing the performance to be tailored for either high capacity or high rate capability by controlling the mass ratio of Si to Ge. The binder free Si-Ge branched nanowire heterostructures are grown directly from the current collector and exhibit high capacities of up to ∼1800 mAh/g. Rate capability testing revealed that increasing the Ge content within the material boosted the performance of the anode at fast cycling rates, whereas a higher Si content was optimal at slower rates of charge and discharge. Using ex-situ electron microscopy, Raman spectroscopy and energy dispersive X-ray spectroscopy mapping, the composition of the material is shown to be transient in nature, transforming from a heterostructure to a Si-Ge alloy as a consequence of repeated lithiation and delithiation.

Elaborate strategy for preparing Li4Ti5O12-based anode materials with significantly improved lithium storage: TiO2 nanodots in-situ decoration and hierarchical structure construction

NASA Astrophysics Data System (ADS)

Xu, Hui; Tian, Qinghua; Huang, Jun; Bao, Dongmei; Zhang, Zhengxi; Yang, Li

2017-11-01

Spinel Li4Ti5O12 (LTO) has attracted extensive attention as potential anode materials for power lithium-ion batteries due to its outstanding structural stability and remarkable safety. However, it's practical application yet be limited by such disadvantages of dissatisfied specific capacity, poor electron conductivity and low lithium-ion diffusion coefficient. Thus, design and preparation of LTO anodes with desirable performance is still a challenge. Herein, we have successfully and greatly improved the performance of LTO anodes, in terms of rate capability, life and specific capacity in particular via dot-to-face anatase TiO2in-situ decoration and hierarchical structure construction under a facile approach (directly using the tetrabutyl titanate as titanium source instead of specially prepared titanium oxide precursors). The as-prepared LTO-based anode (denoted as T-LTO) delivers an ultra-high reversible specific capacity of 196.5 mAh g-1 after 300 cycles at 20 mA g-1, and superior rate performance and even ultra-long life of more than 145.8 mAh g-1 at 28.5C between 1.0 and 3.0 V. The achieved outstanding electrochemical performance largely surpasses that of reportedly state-of-the-art LTO-based anode materials. This work may open up a broader vision into developing advanced LTO-based anode materials for lithium-ion batteries.

Multidimensional Germanium-Based Materials as Anodes for Lithium-Ion Batteries.

PubMed

Qin, Jinwen; Cao, Minhua

2016-04-20

Metallic germanium is an ideal anode for lithium-ion batteries (LIBs), owing to its high theoretical capacity (1624 mA h g(-1) ) and low operating voltage. Herein, we highlight recent advances in the development of Ge-based anodes in LIBs, although improvements in their coulombic efficiency (CE), capacity retention, and rate performance are still required. One of the major concerns facing the development of Ge anodes is the controlled formation of microstructures. In this Focus Review, we summarize Ge-based materials with different structural dimensions, that is, zero-dimensional (0D), one-dimensional (1D), two-dimensional (2D), three-dimensional (3D), and even monolithic and macroscale structures. Moreover, the design of Ge-based oxide materials, as an effective route for achieving higher Li-storage capacities and cycling performance, is also discussed. Finally, we briefly summarize new types of Ge-based materials, such as ternary germanium oxides, germanium sulfides, and germanium phosphides, and predict that they will bring about a reformation in the field of LIBs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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.

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.

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

Mathematical modeling of a primary zinc/air battery

NASA Technical Reports Server (NTRS)

Mao, Z.; White, R. E.

1992-01-01

The mathematical model developed by Sunu and Bennion has been extended to include the separator, precipitation of both solid ZnO and K2Zn(OH)4, and the air electrode, and has been used to investigate the behavior of a primary Zn-Air battery with respect to battery design features. Predictions obtained from the model indicate that anode material utilization is predominantly limited by depletion of the concentration of hydroxide ions. The effect of electrode thickness on anode material utilization is insignificant, whereas material loading per unit volume has a great effect on anode material utilization; a higher loading lowers both the anode material utilization and delivered capacity. Use of a thick separator will increase the anode material utilization, but may reduce the cell voltage.

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

High-Capacity and Long-Cycle Life Aqueous Rechargeable Lithium-Ion Battery with the FePO4 Anode.

PubMed

Wang, Yuesheng; Yang, Shi-Ze; You, Ya; Feng, Zimin; Zhu, Wen; Gariépy, Vincent; Xia, Jiexiang; Commarieu, Basile; Darwiche, Ali; Guerfi, Abdelbast; Zaghib, Karim

2018-02-28

Aqueous lithium-ion batteries are emerging as strong candidates for a great variety of energy storage applications because of their low cost, high-rate capability, and high safety. Exciting progress has been made in the search for anode materials with high capacity, low toxicity, and high conductivity; yet, most of the anode materials, because of their low equilibrium voltages, facilitate hydrogen evolution. Here, we show the application of olivine FePO 4 and amorphous FePO 4 ·2H 2 O as anode materials for aqueous lithium-ion batteries. Their capacities reached 163 and 82 mA h/g at a current rate of 0.2 C, respectively. The full cell with an amorphous FePO 4 ·2H 2 O anode maintained 92% capacity after 500 cycles at a current rate of 0.2 C. The acidic aqueous electrolyte in the full cells prevented cathodic oxygen evolution, while the higher equilibrium voltage of FePO 4 avoided hydrogen evolution as well, making them highly stable. A combination of in situ X-ray diffraction analyses and computational studies revealed that olivine FePO 4 still has the biphase reaction in the aqueous electrolyte and that the intercalation pathways in FePO 4 ·2H 2 O form a 2-D mesh. The low cost, high safety, and outstanding electrochemical performance make the full cells with olivine or amorphous hydrated FePO 4 anodes commercially viable configurations for aqueous lithium-ion batteries.

Yolk-shell structured Sb@C anodes for high energy Na-ion batteries

DOE PAGES

Song, Junhua; Yan, Pengfei; Luo, Langli; ...

2017-09-04

Despite great advances in sodium-ion battery developments, the search for high energy and stable anode materials remains a challenge. Alloy or conversion-typed anode materials are attractive candidates of high specific capacity and low voltage potential, yet their applications are hampered by the large volume expansion and hence poor electrochemical reversibility and fast capacity fade. Here in this paper, we use antimony (Sb) as an example to demonstrate the use of yolk-shell structured anodes for high energy Na-ion batteries. The Sb@C yolk-shell structure prepared by controlled reduction and selective removal of Sb 2O 3 from carbon coated Sb 2O 3 nanoparticlesmore » can accommodate the Sb swelling upon sodiation and improve the structural/electrical integrity against pulverization. It delivers a high specific capacity of ~ 554 mAh g -1, good rate capability (315 mhA g-1 at 10 C rate) and long cyclability (92% capacity retention over 200 cycles). Full-cells of O3-Na 0.9[Cu0.22Fe 0.30Mn 0.48]O 2 cathodes and Sb@C-hard carbon composite anodes demonstrate a high specific energy of ~ 130 Wh kg-1 (based on the total mass of cathode and anode) in the voltage range of 2.0–4.0 V, ~ 1.5 times energy of full-cells with similar design using hard carbon anodes.« less

Yolk-shell structured Sb@C anodes for high energy Na-ion batteries

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

Song, Junhua; Yan, Pengfei; Luo, Langli

Despite great advances in sodium-ion battery developments, the search for high energy and stable anode materials remains a challenge. Alloy or conversion-typed anode materials are attractive candidates of high specific capacity and low voltage potential, yet their applications are hampered by the large volume expansion and hence poor electrochemical reversibility and fast capacity fade. Here, we use antimony (Sb) as an example to demonstrate the use of yolk-shell structured anodes for high energy Na-ion batteries. The Sb@C yolk-shell structure prepared by controlled reduction and selective removal of Sb2O3 from carbon coated Sb2O3 nanoparticles can accommodate the Sb swelling upon sodiationmore » and improve the structural/electrical integrity against pulverization. It delivers a high specific capacity of ~554 mAh•g-1, good rate capability (315 mhA•g-1 at 10C rate) and long cyclability (92% capacity retention over 200 cycles). Full-cells of O3-Na0.9[Cu0.22Fe0.30Mn0.48]O2 cathodes and Sb@C-hard carbon composite anodes demonstrate a high specific energy of ~130 Wh•kg-1 (based on the total mass of cathode and anode) in the voltage range of 2.0-4.0 V, ~1.5 times energy of full-cells with similar design using hard carbon anodes.« less

Yolk-shell structured Sb@C anodes for high energy Na-ion batteries

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

Song, Junhua; Yan, Pengfei; Luo, Langli

Despite great advances in sodium-ion battery developments, the search for high energy and stable anode materials remains a challenge. Alloy or conversion-typed anode materials are attractive candidates of high specific capacity and low voltage potential, yet their applications are hampered by the large volume expansion and hence poor electrochemical reversibility and fast capacity fade. Here in this paper, we use antimony (Sb) as an example to demonstrate the use of yolk-shell structured anodes for high energy Na-ion batteries. The Sb@C yolk-shell structure prepared by controlled reduction and selective removal of Sb 2O 3 from carbon coated Sb 2O 3 nanoparticlesmore » can accommodate the Sb swelling upon sodiation and improve the structural/electrical integrity against pulverization. It delivers a high specific capacity of ~ 554 mAh g -1, good rate capability (315 mhA g-1 at 10 C rate) and long cyclability (92% capacity retention over 200 cycles). Full-cells of O3-Na 0.9[Cu0.22Fe 0.30Mn 0.48]O 2 cathodes and Sb@C-hard carbon composite anodes demonstrate a high specific energy of ~ 130 Wh kg-1 (based on the total mass of cathode and anode) in the voltage range of 2.0–4.0 V, ~ 1.5 times energy of full-cells with similar design using hard carbon anodes.« less

Monodispersed Carbon-Coated Cubic NiP2 Nanoparticles Anchored on Carbon Nanotubes as Ultra-Long-Life Anodes for Reversible Lithium Storage.

PubMed

Lou, Peili; Cui, Zhonghui; Jia, Zhiqing; Sun, Jiyang; Tan, Yingbin; Guo, Xiangxin

2017-04-25

In search of new electrode materials for lithium-ion batteries, metal phosphides that exhibit desirable properties such as high theoretical capacity, moderate discharge plateau, and relatively low polarization recently have attracted a great deal of attention as anode materials. However, the large volume changes and thus resulting collapse of electrode structure during long-term cycling are still challenges for metal-phosphide-based anodes. Here we report an electrode design strategy to solve these problems. The key to this strategy is to confine the electroactive nanoparticles into flexible conductive hosts (like carbon materials) and meanwhile maintain a monodispersed nature of the electroactive particles within the hosts. Monodispersed carbon-coated cubic NiP 2 nanoparticles anchored on carbon nanotubes (NiP 2 @C-CNTs) as a proof-of-concept were designed and synthesized. Excellent cyclability (more than 1000 cycles) and capacity retention (high capacities of 816 mAh g -1 after 1200 cycles at 1300 mA g -1 and 654.5 mAh g -1 after 1500 cycles at 5000 mA g -1 ) are characterized, which is among the best performance of the NiP 2 anodes and even most of the phosphide-based anodes reported so far. The impressive performance is attributed to the superior structure stability and the enhanced reaction kinetics incurred by our design. Furthermore, a full cell consisting of a NiP 2 @C-CNTs anode and a LiFePO 4 cathode is investigated. It delivers an average discharge capacity of 827 mAh g -1 based on the mass of the NiP 2 anode and exhibits a capacity retention of 80.7% over 200 cycles, with an average output of ∼2.32 V. As a proof-of-concept, these results demonstrate the effectiveness of our strategy on improving the electrode performance. We believe that this strategy for construction of high-performance anodes can be extended to other phase-transformation-type materials, which suffer a large volume change upon lithium insertion/extraction.

Innovation Meets Performance Demands of Advanced Lithium-ion Batteries

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

Advancements in high capacity and low density battery technologies have led to a growing need for battery materials with greater charge capacity and therefore stability. NREL's developments in ALD and molecular layer MLD allow for thin film coatings to battery composite electrodes, which can improve battery lifespan, high charge capacity, and stability. Silicon, one of the best high-energy anode materials for Li-ion batteries, can experience capacity fade from volumetric expansion. Using MLD to examine how surface modification could stabilize silicon anode material in Li-ion batteries, researchers discovered a new reaction precursor that leads to a flexible surface coating that accommodatesmore » volumetric expansion of silicon electrodes.« less

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

Additive-free thick graphene film as an anode material for flexible lithium-ion batteries

NASA Astrophysics Data System (ADS)

Rana, Kuldeep; Kim, Seong Dae; Ahn, Jong-Hyun

2015-04-01

This work demonstrates a simple route to develop mechanically flexible electrodes for Li-ion batteries (LIBs) that are usable as lightweight effective conducting networks for both cathodes and anodes. Removing electrochemically dead elements, such as binders, conducting agents and metallic current collectors, from the battery components will allow remarkable progress in this area. To investigate the feasibility of using thick, additive-free graphene films as anodes for flexible LIBs, we have synthesized and tested thick, additive-free, freestanding graphene films as anodes, first in a coin cell and further in a flexible full cell. As an anode material in a half cell, it showed a discharge capacity of about 350 mA h g-1 and maintained nearly this capacity over 50 cycles at various current rates. This film was also tested as an anode material in a full cell with a LiCoO2 cathode and showed good electrochemical performance. Because the graphene-based flexible film showed good performance in half- and full coin cells, we used this film as a flexible anode for flexible LIBs. No conducting agent or binder was used in the anode side, which helped in realizing the flexible LIBs. Using this, we demonstrate a thin, lightweight and flexible lithium ion battery with good electrochemical performance in both its flat and bent states.This work demonstrates a simple route to develop mechanically flexible electrodes for Li-ion batteries (LIBs) that are usable as lightweight effective conducting networks for both cathodes and anodes. Removing electrochemically dead elements, such as binders, conducting agents and metallic current collectors, from the battery components will allow remarkable progress in this area. To investigate the feasibility of using thick, additive-free graphene films as anodes for flexible LIBs, we have synthesized and tested thick, additive-free, freestanding graphene films as anodes, first in a coin cell and further in a flexible full cell. As an anode material in a half cell, it showed a discharge capacity of about 350 mA h g-1 and maintained nearly this capacity over 50 cycles at various current rates. This film was also tested as an anode material in a full cell with a LiCoO2 cathode and showed good electrochemical performance. Because the graphene-based flexible film showed good performance in half- and full coin cells, we used this film as a flexible anode for flexible LIBs. No conducting agent or binder was used in the anode side, which helped in realizing the flexible LIBs. Using this, we demonstrate a thin, lightweight and flexible lithium ion battery with good electrochemical performance in both its flat and bent states. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr06082b

Three-dimensionally interconnected Si frameworks derived from natural halloysite clay: a high-capacity anode material for lithium-ion batteries.

PubMed

Wan, Hao; Xiong, Hao; Liu, Xiaohe; Chen, Gen; Zhang, Ning; Wang, Haidong; Ma, Renzhi; Qiu, Guanzhou

2018-05-23

On account of its high theoretical capacity, silicon (Si) has been regarded as a promising anode material for Li-ion batteries. Extracting Si content from earth-abundant and low-cost aluminosilicate minerals, rather than from artificial silica (SiO2) precursors, is a more favorable and practical method for the large-scale application of Si anodes. In this work, three-dimensionally interconnected (3D-interconnected) Si frameworks with a branch diameter of ∼15 nm are prepared by the reduction of amorphous SiO2 nanotubes derived from natural halloysite clay. Benefiting from their nanostructure, the as-prepared 3D-interconnected Si frameworks yield high reversible capacities of 2.54 A h g-1 at 0.1 A g-1 after 50 cycles, 1.87 A h g-1 at 0.5 A g-1 after 200 cycles, and 0.97 A h g-1 at 2 A g-1 after a long-term charge-discharge process of 500 cycles, remarkably outperforming the commercial Si material. Further, when the as-prepared Si frameworks and commercial LiCoO2 cathodes are paired in full cells, a high anode capacity of 0.98 A h g-1 is achieved after 100 cycles of rapid charge/discharge at 2 A g-1. This work provides a new strategy for the synthesis of high-capacity Si anodes derived from natural aluminosilicate clay.

Development of high-energy silicon-based anode materials for lithium-ion storage

NASA Astrophysics Data System (ADS)

Yi, Ran

The emerging markets of electric vehicles (EV) and hybrid electric vehicles (HEV) generate a tremendous demand for low-cost lithium-ion batteries (LIBs) with high energy and power densities, and long cycling life. The development of such LIBs requires development of low cost, high-energy-density cathode and anode materials. Conventional anode materials in commercial LIBs are primarily synthetic graphite-based materials with a capacity of ˜370 mAh/g. Improvements in anode performance, particularly in anode capacity, are essential to achieving high energy densities in LIBs for EV and HEV applications. This dissertation focuses on development of micro-sized silicon-carbon (Si-C) composites as anode materials for high energy and power densities LIBs. First, a new, low-cost, large-scale approach was developed to prepare a micro-sized Si-C composite with excellent performance as an anode material for LIBs. The composite shows a reversible capacity of 1459 mAh/g after 200 cycles at 1 A/g (97.8% capacity retention) and excellent high rate performance of 700 mAh/g at 12.8 A/g, and also has a high tap density of 0.78 g/cm3. The structure of the composite, micro-sized as a whole, features the interconnected nanoscale size of the Si building blocks and the uniform carbon filling, which enables the maximum utilization of silicon even when the micro-sized particles break into small pieces upon cycling. To understand the effects of key parameters in designing the micro-sized Si-C composites on their electrochemical performance and explore how to optimize them, the influence of Si nanoscale building block size and carbon coating on the electrochemical performance of the micro-sized Si-C composites were investigated. It has been found that the critical Si building block size is 15 nm, which enables a high capacity without compromising the cycling stability, and that carbon coating at higher temperature improves the 1st cycle coulombic efficiency (CE) and the rate capability. Corresponding reasons underneath electrochemical performance have been revealed by various characterizations. Combining both optimized Si building block size and carbon coating temperature, the resultant composite can sustain 600 cycles at 1.2 A/g with a fixed lithiation capacity of 1200 mAh/g, the best cycling performance with such a high capacity for micro-sized Si-based anodes. To further improve the the rate capability of Si-based anode materials, an effecitive method of facile boron doping was demonstrated. Boron-doped Si-C composite can deliver a high capacity of 575 mAh/g at 6.4 A/g without addition of any conductive additives, 80% higher than that of undoped composite. Compared to the obvious capacity fading of undoped Si-C composite, boron-doped Si-C composite maintains its capacity well upon long cycling at a high current density. Electrochemical impedance spectroscopy (EIS) measurement shows boron-doped Si-C composite has lower charge transfer resistance, which helps improve its rate capability. A novel micro-sized graphene/Si-C composite (G/Si-C) was then developed to translate the performance of such micro-sized Si-C composites from the material level to the electrode level aiming to achieve high areal capacities (mAh/cm2) besides gravimetric capacities (mAh/g). Owing to dual conductive networks both within single particles formed by carbon and between different particles formed by graphene, low electrical resistance can be maintained at high mass loading, which enables a high degree of material utilization. Areal capacity thus increases almost linearly with mass loading. As a result, G/Si-C exhibits a high areal capacity of 3.2 mAh/cm2 after 100 cycles with high coulombic efficiency (average 99.51% from 2nd to 100th cycle), comparable to that of commercial anodes. Finally, a micro-sized Si-based material (B-Si/SiO2/C) featuring high rate performance was developed via a facile route without use of toxic hydrofluoric acid. A Li-ion hybrid battery constructed of such a Si-based anode and a porous carbon cathode was demonstrated with both high power and energy densities. Boron-doping is employed to improve the rate capability of B-Si/SiO2/C. At a high current density of 6.4 A/g, B-Si/SiO 2/C delivers a capacity of 685 mAh/g, 2.4 times that of the undoped Si/SiO2/C. Benefiting from the high rate performance along with low working voltage, high capacity and good cycling stability of B-Si/SiO 2/C, the hybrid battery exhibits a high energy density of 128 Wh/kg at 1229 W/kg. Even when power density increases to the level of a conventional supercapacitor (9704 W/kg), 89 Wh/kg can be obtained, the highest values of any hybrid battery to date. Long cycling life (capacity retention of 70% after 6000 cycles) and low self-discharge rate (voltage retention of 82% after 50 hours) are also achieved.

Carbon-Confined SnO2-Electrodeposited Porous Carbon Nanofiber Composite as High-Capacity Sodium-Ion Battery Anode Material.

PubMed

Dirican, Mahmut; Lu, Yao; Ge, Yeqian; Yildiz, Ozkan; Zhang, Xiangwu

2015-08-26

Sodium resources are inexpensive and abundant, and hence, sodium-ion batteries are promising alternative to lithium-ion batteries. However, lower energy density and poor cycling stability of current sodium-ion batteries prevent their practical implementation for future smart power grid and stationary storage applications. Tin oxides (SnO2) can be potentially used as a high-capacity anode material for future sodium-ion batteries, and they have the advantages of high sodium storage capacity, high abundance, and low toxicity. However, SnO2-based anodes still cannot be used in practical sodium-ion batteries because they experience large volume changes during repetitive charge and discharge cycles. Such large volume changes lead to severe pulverization of the active material and loss of electrical contact between the SnO2 and carbon conductor, which in turn result in rapid capacity loss during cycling. Here, we introduce a new amorphous carbon-coated SnO2-electrodeposited porous carbon nanofiber (PCNF@SnO2@C) composite that not only has high sodium storage capability, but also maintains its structural integrity while ongoing repetitive cycles. Electrochemical results revealed that this SnO2-containing nanofiber composite anode had excellent electrochemical performance including high-capacity (374 mAh g(-1)), good capacity retention (82.7%), and large Coulombic efficiency (98.9% after 100th cycle).

Rechargeable Zinc Alkaline Anodes for Long-Cycle Energy Storage

DOE PAGES

Turney, Damon E.; Gallaway, Joshua W.; Yadav, Gautam G.; ...

2017-05-03

Zinc alkaline anodes command significant share of consumer battery markets and are a key technology for the emerging grid-scale battery market. Improved understanding of this electrode is required for long-cycle deployments at kWh and MWh scale due to strict requirements on performance, cost, and safety. For this article, we give a modern literature survey of zinc alkaline anodes with levelized performance metrics and also present an experimental assessment of leading formulations. Long-cycle materials characterization, performance metrics, and failure analysis are reported for over 25 unique anode formulations with up to 1500 cycles and ~1.5 years of shelf life per test.more » Statistical repeatability of these measurements is made for a baseline design (fewest additives) via 15 duplicates. Baseline design capacity density is 38 mAh per mL of anode volume, and lifetime throughput is 72 Ah per mL of anode volume. We then report identical measurements for anodes with improved material properties via additives and other perturbations, some of which achieve capacity density over 192 mAh per mL of anode volume and lifetime throughput of 190 Ah per mL of anode volume. Novel in operando X-ray microscopy of a cycling zinc paste anode reveals the formation of a nanoscale zinc material that cycles electrochemically and replaces the original anode structure over long-cycle life. Ex situ elemental mapping and other materials characterization suggest that the key physical processes are hydrogen evolution reaction (HER), growth of zinc oxide nanoscale material, concentration deficits of OH – and ZnOH 4 2–, and electrodeposition of Zn growths outside and through separator membranes.« less

Rechargeable Zinc Alkaline Anodes for Long-Cycle Energy Storage

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

Turney, Damon E.; Gallaway, Joshua W.; Yadav, Gautam G.

Zinc alkaline anodes command significant share of consumer battery markets and are a key technology for the emerging grid-scale battery market. Improved understanding of this electrode is required for long-cycle deployments at kWh and MWh scale due to strict requirements on performance, cost, and safety. For this article, we give a modern literature survey of zinc alkaline anodes with levelized performance metrics and also present an experimental assessment of leading formulations. Long-cycle materials characterization, performance metrics, and failure analysis are reported for over 25 unique anode formulations with up to 1500 cycles and ~1.5 years of shelf life per test.more » Statistical repeatability of these measurements is made for a baseline design (fewest additives) via 15 duplicates. Baseline design capacity density is 38 mAh per mL of anode volume, and lifetime throughput is 72 Ah per mL of anode volume. We then report identical measurements for anodes with improved material properties via additives and other perturbations, some of which achieve capacity density over 192 mAh per mL of anode volume and lifetime throughput of 190 Ah per mL of anode volume. Novel in operando X-ray microscopy of a cycling zinc paste anode reveals the formation of a nanoscale zinc material that cycles electrochemically and replaces the original anode structure over long-cycle life. Ex situ elemental mapping and other materials characterization suggest that the key physical processes are hydrogen evolution reaction (HER), growth of zinc oxide nanoscale material, concentration deficits of OH – and ZnOH 4 2–, and electrodeposition of Zn growths outside and through separator membranes.« less

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.

Disordered anodes for Ni-metal rechargeable battery

DOEpatents

Young, Kwo-hsiung; Wang, Lixin; Mays, William C.

2016-11-22

An electrochemical cell is provided that includes a structurally and compositionally disordered electrochemically active alloy material as an anode active material with unexpected capacity against a nickel hydroxide based cathode active material. The disordered metal hydroxide alloy includes three or more transition metal elements and is formed in such a way so as to produce the necessary disorder in the overall system. When an anode active material includes nickel as a predominant, the resulting cells represent the first demonstration of a functional Ni/Ni cell.

Nitrogen doped graphene - Silver nanowire hybrids: An excellent anode material for lithium ion batteries

NASA Astrophysics Data System (ADS)

Nair, Anju K.; Elizabeth, Indu; S, Gopukumar; Thomas, Sabu; M. S, Kala; Kalarikkal, Nandakumar

2018-01-01

We present an in-situ polyol assisted synthesis approach for the preparation of silver nanowires (AgNW) over the nitrogen doped graphene (NG) sheets and has been tested as a viable LIBs anode material for the first time. The use of NG serves as nucleation sites, thereby facilitating the growth of AgNWs. The specific material design of the as-prepared NG-AgNW hybrids involves some advantages, including a continuous AgNW-graphene conducting network. Since AgNWs are electrically conductive, it provides an electrical contact with NG sheets which can effectively help the charge transport process and limit the variations in volume during the lithiation/de-lithiation processes. Apart from this, the insertion of metallic Ag nanowires into a percolated NG network increases the interlayer distance of NG sheets and prevent its restacking. Moreover, the more porous nature of the hybrid structure accommodating the large volume changes of AgNWs. As an anode material for LIBs, the NG-AgNW hybrid displays a remarkable initial discharge capacity of 1215 mAh g-1 and attains a stable capacity of 724 mAh g-1 at a current density of 100 mA g-1 after 50 cycles. The electrode exhibits a stable reversible capacity of 714, 634, 550 and 464 mA h g-1 at 0.1, 0.2, 0.5, 1 Ag-1 respectively. The reversible capacity (710 mAh g-1) at 0.1 Ag-1 is recovered after the cycling at various current densities confirming outstanding rate performance of the material. In addition, the coulombic efficiency, the NG-AgNW anode retains nearly 99% after the second cycle, further indicating its excellent reversibility. The hybrid material exhibits better cycling stability, greater rate capability, capacity retention and superior reversible capacity than that of bare AgNW and NG sheets. Our smart design will pave way for the development of efficient electrode materials for high capacity and long cycle life LIBs.

Tunneled Mesoporous Carbon Nanofibers with Embedded ZnO Nanoparticles for Ultrafast Lithium Storage.

PubMed

An, Geon-Hyoung; Lee, Do-Young; Ahn, Hyo-Jin

2017-04-12

Carbon and metal oxide composites have received considerable attention as anode materials for Li-ion batteries (LIBs) owing to their excellent cycling stability and high specific capacity based on the chemical and physical stability of carbon and the high theoretical specific capacity of metal oxides. However, efforts to obtain ultrafast cycling stability in carbon and metal oxide composites at high current density for practical applications still face important challenges because of the longer Li-ion diffusion pathway, which leads to poor ultrafast performance during cycling. Here, tunneled mesoporous carbon nanofibers with embedded ZnO nanoparticles (TMCNF/ZnO) are synthesized by electrospinning, carbonization, and postcalcination. The optimized TMCNF/ZnO shows improved electrochemical performance, delivering outstanding ultrafast cycling stability, indicating a higher specific capacity than previously reported ZnO-based anode materials in LIBs. Therefore, the unique architecture of TMCNF/ZnO has potential for use as an anode material in ultrafast LIBs.

Nanoscale Engineering of Heterostructured Anode Materials for Boosting Lithium-Ion Storage.

PubMed

Chen, Gen; Yan, Litao; Luo, Hongmei; Guo, Shaojun

2016-09-01

Rechargeable lithium-ion batteries (LIBs), as one of the most important electrochemical energy-storage devices, currently provide the dominant power source for a range of devices, including portable electronic devices and electric vehicles, due to their high energy and power densities. The interest in exploring new electrode materials for LIBs has been drastically increasing due to the surging demands for clean energy. However, the challenging issues essential to the development of electrode materials are their low lithium capacity, poor rate ability, and low cycling stability, which strongly limit their practical applications. Recent remarkable advances in material science and nanotechnology enable rational design of heterostructured nanomaterials with optimized composition and fine nanostructure, providing new opportunities for enhancing electrochemical performance. Here, the progress as to how to design new types of heterostructured anode materials for enhancing LIBs is reviewed, in the terms of capacity, rate ability, and cycling stability: i) carbon-nanomaterials-supported heterostructured anode materials; ii) conducting-polymer-coated electrode materials; iii) inorganic transition-metal compounds with core@shell structures; and iv) combined strategies to novel heterostructures. By applying different strategies, nanoscale heterostructured anode materials with reduced size, large surfaces area, enhanced electronic conductivity, structural stability, and fast electron and ion transport, are explored for boosting LIBs in terms of high capacity, long cycling lifespan, and high rate durability. Finally, the challenges and perspectives of future materials design for high-performance LIB anodes are considered. The strategies discussed here not only provide promising electrode materials for energy storage, but also offer opportunities in being extended for making a variety of novel heterostructured nanomaterials for practical renewable energy applications. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhanced lithium ion battery cycling of silicon nanowire anodes by template growth to eliminate silicon underlayer islands.

PubMed

Cho, Jeong-Hyun; Picraux, S Tom

2013-01-01

It is well-known that one-dimensional nanostructures reduce pulverization of silicon (Si)-based anode materials during Li ion cycling because they allow lateral relaxation. However, even with improved designs, Si nanowire-based structures still exhibit limited cycling stability for extended numbers of cycles, with the specific capacity retention with cycling not showing significant improvements over commercial carbon-based anode materials. We have found that one important reason for the lack of long cycling stability can be the presence of milli- and microscale Si islands which typically form under nanowire arrays during their growth. Stress buildup in these Si island underlayers with cycling results in cracking, and the loss of specific capacity for Si nanowire anodes, due to progressive loss of contact with current collectors. We show that the formation of these parasitic Si islands for Si nanowires grown directly on metal current collectors can be avoided by growth through anodized aluminum oxide templates containing a high density of sub-100 nm nanopores. Using this template approach we demonstrate significantly enhanced cycling stability for Si nanowire-based lithium-ion battery anodes, with retentions of more than ~1000 mA·h/g discharge capacity over 1100 cycles.

Penta-graphene: A Promising Anode Material as the Li/Na-Ion Battery with Both Extremely High Theoretical Capacity and Fast Charge/Discharge Rate.

PubMed

Xiao, Bo; Li, Yan-Chun; Yu, Xue-Fang; Cheng, Jian-Bo

2016-12-28

Recently, a new two-dimensional (2D) carbon allotrope named penta-graphene was theoretically proposed ( Zhang , S. ; et al. Proc. Natl. Acad. Sci. U.S.A. 2015 , 112 , 2372 ) and has been predicted to be the promising candidate for broad applications due to its intriguing properties. In this work, by using first-principles simulation, we have further extended the potential application of penta-graphene as the anode material for a Li/Na-ion battery. Our results show that the theoretical capacity of Li/Na ions on penta-graphene reaches up to 1489 mAh·g -1 , which is much higher than that of most of the previously reported 2D anode materials. Meanwhile, the calculated low open-circuit voltages (from 0.24 to 0.60 V), in combination with the low diffusion barriers (≤0.33 eV) and the high electronic conductivity during the whole Li/Na ions intercalation processes, further show the advantages of penta-graphene as the anode material. Particularly, molecular dynamics simulation (300 K) reveals that Li ion could freely diffuse on the surface of penta-graphene, and thus the ultrafast Li ion diffusivity is expected. Superior performance of penta-graphene is further confirmed by comparing with the other 2D anode materials. The light weight and unique atomic arrangement (with isotropic furrow paths on the surface) of penta-graphene are found to be mainly responsible for the high Li/Na ions storage capacity and fast diffusivity. In this regard, except penta-graphene, many other recently proposed 2D metal-free materials with pentagonal Cairo-tiled structures may be the potential candidates as the Li/Na-ion battery anodes.

Large-Area Carbon Nanosheets Doped with Phosphorus: A High-Performance Anode Material for Sodium-Ion Batteries.

PubMed

Hou, Hongshuai; Shao, Lidong; Zhang, Yan; Zou, Guoqiang; Chen, Jun; Ji, Xiaobo

2017-01-01

Large-area phosphorus-doped carbon nanosheets (P-CNSs) are first obtained from carbon dots (CDs) through self-assembly driving from thermal treatment with Na catalysis. This is the first time to realize the conversion from 0D CDs to 2D nanosheets doped with phosphorus. The sodium storage behavior of phosphorus-doped carbon material is also investigated for the first time. As anode material for sodium-ion batteries (SIBs), P-CNSs exhibit superb performances for electrochemical storage of sodium. When cycled at 0.1 A g -1 , the P-CNSs electrode delivers a high reversible capacity of 328 mAh g -1 , even at a high current density of 20 A g -1 , a considerable capacity of 108 mAh g -1 can still be maintained. Besides, this material also shows excellent cycling stability, at a current density of 5 A g -1 , the reversible capacity can still reach 149 mAh g -1 after 5000 cycles. This work will provide significant value for the development of both carbon materials and SIBs anode materials.

Facile synthesis of one-dimensional hollow Sb2O3@TiO2 composites as anode materials for lithium ion batteries

NASA Astrophysics Data System (ADS)

Wang, Zhaomin; Cheng, Yong; Li, Qian; Chang, Limin; Wang, Limin

2018-06-01

Metallic Sb is deemed as a promising anode material for lithium ion batteries (LIBs) due to its flat voltage platform and high security. Nevertheless, the limited capacity restricts its large-scale application. Therefore, a simple and effective method to explore novel antimony trioxide with high capacity used as anode material for LIBs is imperative. In this work, we report a facile and efficient strategy to fabricate 1D hollow Sb2O3@TiO2 composites by using the Kirkendall effect. When used as an anode material for LIBs, the optimal Sb2O3@TiO2 composite displays a high reversible discharge capacity of 593 mAh g-1 at a current density of 100 mA g-1 after 100 cycles and a relatively superior discharge capacity of 439 mAh g-1 at a current density of 500 mA g-1 even after 600 cycles. In addition, a reversible discharge capacity of 334 mAh g-1 can also be obtained even at a current density of 2000 mA g-1. The excellent cycling stability and rate performance of the Sb2O3@TiO2 composite can be attributed to the synergistic effect of TiO2 shell and hollow structure of Sb2O3, both of which can effectively buffer the volume expansion and maintain the integrity of the electrode during the repeated charge-discharge cycles.

The design of a Li-ion full cell battery using a nano silicon and nano multi-layer graphene composite anode

NASA Astrophysics Data System (ADS)

Eom, KwangSup; Joshi, Tapesh; Bordes, Arnaud; Do, Inhwan; Fuller, Thomas F.

2014-03-01

In this study, a Si-graphene composite, which is composed of nano Si particles and nano-sized multi-layer graphene particles, and micro-sized multi-layer graphene plate conductor, was used as the anode for Li-ion battery. The Si-graphene electrode showed the high capacity and stable cyclability at charge/discharge rate of C/2 in half cell tests. Nickel cobalt aluminum material (NCA) was used as a cathode in the full cell to evaluate the practicality of the new Si-graphene material. Although the Si-graphene anode has more capacity than the NCA cathode in this designed full cell, the Si-graphene anode had a greater effect on the full-cell performance due to its large initial irreversible capacity loss and continuous SEI formation during cycling. When fluoro-ethylene carbonate was added to the electrolyte, the cyclability of the full cell was much improved due to less SEI formation, which was confirmed by the decreases in the 1st irreversible capacity loss, overpotential for the 1st lithiation, and the resistance of the SEI.

Carbon/tin oxide composite electrodes for improved lithium-ion batteries

DOE PAGES

Li, Yunchao; Levine, Alan M.; Zhang, Jinshui; ...

2018-05-17

Tin and tin oxide-based electrodes are promising high-capacity anodes for lithium-ion batteries. However, poor capacity retention is the major issue with these materials due to the large volumetric expansion that occurs when lithium is alloyed with tin during lithiation and delithiation process. Here, a method to prepare a low-cost, scalable carbon and tin(II) oxide composite anode is reported. The composite material was prepared by ball milling of carbon recovered from used tire powders with 25 wt% tin(II) oxide to form lithium-ion battery anode. With the impact of energy from the ball milling, tin oxide powders were uniformly distributed inside themore » pores of waste-tire-derived carbon. During lithiation and delithiation, the carbon matrix can effectively absorb the volume expansion caused by tin, thereby minimizing pulverization and capacity fade of the electrodes. In conclusion, the as-synthesized anode yielded a capacity of 690 mAh g –1 after 300 cycles at a current density of 40 mA g –1 with a stable battery performance.« less

Carbon/tin oxide composite electrodes for improved lithium-ion batteries

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

Li, Yunchao; Levine, Alan M.; Zhang, Jinshui

Tin and tin oxide-based electrodes are promising high-capacity anodes for lithium-ion batteries. However, poor capacity retention is the major issue with these materials due to the large volumetric expansion that occurs when lithium is alloyed with tin during lithiation and delithiation process. Here, a method to prepare a low-cost, scalable carbon and tin(II) oxide composite anode is reported. The composite material was prepared by ball milling of carbon recovered from used tire powders with 25 wt% tin(II) oxide to form lithium-ion battery anode. With the impact of energy from the ball milling, tin oxide powders were uniformly distributed inside themore » pores of waste-tire-derived carbon. During lithiation and delithiation, the carbon matrix can effectively absorb the volume expansion caused by tin, thereby minimizing pulverization and capacity fade of the electrodes. In conclusion, the as-synthesized anode yielded a capacity of 690 mAh g –1 after 300 cycles at a current density of 40 mA g –1 with a stable battery performance.« less

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.

In situ preparation of Fe3O4 in a carbon hybrid of graphene nanoscrolls and carbon nanotubes as high performance anode material for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Liu, Yuewen; Hassan Siddique, Ahmad; Huang, Heran; Fang, Qile; Deng, Wei; Zhou, Xufeng; Lu, Huanming; Liu, Zhaoping

2017-11-01

A new conductive carbon hybrid combining both reduced graphene nanoscrolls and carbon nanotubes (rGNSs-CNTs) is prepared, and used to host Fe3O4 nanoparticles through an in situ synthesis method. As an anode material for LIBs, the obtained Fe3O4@rGNSs-CNTs shows good electrochemical performance. At a current density of 0.1 A g-1, the anode material shows a high reversible capacity of 1232.9 mAh g-1 after 100 cycles. Even at a current density of 1 A g-1, it still achieves a high reversible capacity of 812.3 mAh g-1 after 200 cycles. Comparing with bare Fe3O4 and Fe3O4/rGO composite anode materials without nanoscroll structure, Fe3O4@rGNSs-CNTs shows much better rate capability with a reversible capacity of 605.0 and 500.0 mAh g-1 at 3 and 5 A g-1, respectively. The excellent electrochemical performance of the Fe3O4@rGNSs-CNTs anode material can be ascribed to the hybrid structure of rGNSs-CNTs, and their strong interaction with Fe3O4 nanoparticles, which on one hand provides more pathways for lithium ions and electrons, on the other hand effectively relieves the volume change of Fe3O4 during the charge-discharge process.

Ionic liquid-assisted solvothermal synthesis of hollow Mn2O3 anode and LiMn2O4 cathode materials for Li-ion batteries

NASA Astrophysics Data System (ADS)

He, Xin; Wang, Jun; Jia, Haiping; Kloepsch, Richard; Liu, Haidong; Beltrop, Kolja; Li, Jie

2015-10-01

Mn-based Mn2O3 anode and LiMn2O4 cathode materials are prepared by a solvothermal method combined with post annealing process. Environmentally friendly ionic liquid 1-Butyl-3-methylimidazolium tetrafluoroborate as both structure-directing agent and fluorine source is used to prepare hollow polyhedron MnF2 precursor. Both target materials Mn2O3 anode and LiMn2O4 cathode have the morphology of the MnF2 precursor. The Mn2O3 anode using carboxymethyl cellulose as binder could deliver slight better electrochemical performance than the one using poly (vinyldifluoride) as binder. The former has an initial charge capacity of 800 mAh g-1 at a current density of 101.8 mA g-1, and exhibits no obvious capacity decay for 150 cycles at 101.8 mA g-1. The LiMn2O4 cathode material prepared with molten salt assistant could display much better electrochemical performance than the one prepared without molten salt assistance. In particular, it has an initial discharge capacity of 117.5 mAh g-1 at a current density of 0.5C and good rate capability. In the field of lithium ion batteries, both the Mn2O3 anode and LiMn2O4 cathode materials could exhibit enhanced electrochemical performance due to the well formed morphology based on the ionic liquid-assisted solvothermal method.

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).

Ultra-thick, Low-Tortuosity, and Mesoporous Wood Carbon Anode for High-Performance Sodium-Ion Batteries

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

Shen, Fei; Luo, Wei; Dai, Jiaqi

Sodium-ion batteries (SIBs) have attracted extensive interest in the past few years because of the low cost and abundance of sodium resources and hence the potential for grid scale energy storage. Developing low cost electrode materials, particularly anode materials, is the key for further promoting the application of SIBs. Here, we for the first time report a self-standing porous carbon anode directly from natural wood for SIBs, which processes following advantages: (i) ultra-thick carbon anode with a high areal capacity, for example a capacity of 13.6 mAh cm-2 was delivered when the thickness reached 0.85 mm; (ii) low tortuosity, wheremore » numerous inherited aligned channels in the wood carbon provide a rapid ion transport path; (iii) porous nature enables a fast ion transfer between the carbon electrode and the electrolyte; (iv) 100% utilization of the wood carbon that conductive additives, binders, and current-collectors are not needed; v) when coupling a Na3V2(PO4)3 cathode with the wood carbon anode, a high capacity of 80 mAh g-1 was obtained at 0.5 C rate (base on cathode) and excellent cycling stability of 300 cycles was also achieved, which demonstrated the promising performance of earth-abundant wood derived carbon material.« less

Centrifugally-spun carbon microfibers and porous carbon microfibers as anode materials for sodium-ion batteries

NASA Astrophysics Data System (ADS)

Dirican, Mahmut; Zhang, Xiangwu

2016-09-01

Natural abundance and low cost of sodium resources bring forward the sodium-ion batteries as a promising alternative to widely-used lithium-ion batteries. However, insufficient energy density and low cycling stability of current sodium-ion batteries hinder their practical use for next-generation smart power grid and stationary storage applications. Electrospun carbon microfibers have recently been introduced as a high-performance anode material for sodium-ion batteries. However, electrospinning is not feasible for mass production of carbon microfibers due to its complex processing condition, low production rate and high cost. Herein, we report centrifugal spinning, a high-rate and low-cost microfiber production method, as an alternative approach to electrospinning for carbon microfiber production and introduce centrifugally-spun carbon microfibers (CMFs) and porous carbon microfibers (PCMFs) as anode materials for sodium-ion batteries. Electrochemical performance results indicated that the highly porous nature of centrifugally-spun PCMFs led to increased Na+ storage capacity and improved cycling stability. The reversible capacity of centrifugally-spun PCMF anodes at the 200th cycle was 242 mAh g-1, which was much higher than that of centrifugally-spun CMFs (143 mAh g-1). The capacity retention and coulombic efficiency of the centrifugally-spun PCMF anodes were 89.0% and 99.9%, respectively, even at the 200th cycle.

Hybrid lithium-ion capacitor with LiFePO4/AC composite cathode - Long term cycle life study, rate effect and charge sharing analysis

NASA Astrophysics Data System (ADS)

Shellikeri, A.; Yturriaga, S.; Zheng, J. S.; Cao, W.; Hagen, M.; Read, J. A.; Jow, T. R.; Zheng, J. P.

2018-07-01

Energy storage devices, which can combine the advantages of lithium-ion battery with that of electric double layer capacitor, are of prime interest. Recently, composite cathodes, which combine a battery material with capacitor material, have shown promise in enhancing life cycle and energy/power performances. Lithium-ion capacitor (LIC), with unique charge storage mechanism of combining a pre-lithiated battery anode with a capacitor cathode, is one such device which has the potential to synergistically incorporate the composite cathode to enhance capacity and cycle life. We report here a hybrid LIC consisting of a lithium iron phosphate (LiFePO4-LFP)/Activated Carbon composite cathode in combination with a hard carbon anode, by integrating the cycle life and capacity enhancing strategies of a dry method of electrode fabrication, anode pre-lithiation and a 3:1 anode to cathode capacity ratio, demonstrating a long cycle life, while elaborating on the charge sharing between the faradaic and non-faradaic mechanism in the battery and capacitor materials, respectively in the composite cathode. An excellent cell capacity retention of 94% (1000 cycles at 1C) and 92% (100,000 cycles at 60C) were demonstrated, while retaining 78% (over 6000 cycles at 2.7C) and 67% (over 70,000 cycles at 43C) of the LFP capacity in the composite cathode.

Development of Novel Metal Hydride-Carbon Nanomaterial Based Nanocomposites as Anode Electrode Materials for Lithium Ion Battery

DTIC Science & Technology

2014-06-30

The aim of this study is to develop metal hydride-carbon nanomaterial based nanocomposites as anode electrode materials for high capacity lithium ion battery and...henceforth to develop high energy density, and good cyclic stability lithium ion battery .

Fundamental Investigation of Silicon Anode in Lithium-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 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. Understanding solid electrolyte interphase (SEI) formation along with the lithium ion insertion/de-insertion kinetics in silicon anodes will provide greater insight into overcoming these issues, thereby lead to better cycle performance. 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 a 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, and the combination of cyclic voltammetry with impedance spectroscopy provides a useful tool to evaluate the effectiveness of the design modifications on the Si anode performance.

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.

Superior lithium electroactive mesoporous Si@carbon core-shell nanowires for lithium battery anode material.

PubMed

Kim, Hyesun; Cho, Jaephil

2008-11-01

Mesoporous Si@carbon core-shell nanowires with a diameter of approximately 6.5 nm were prepared for a lithium battery anode material using a SBA-15 template. As-synthesized nanowires demonstrated excellent first charge capacity of 3163 mA h/g with a Coulombic efficiency of 86% at a rate of 0.2 C (600 mA/g) between 1.5 and 0 V in coin-type half-cells. Moreover, the capacity retention after 80 cycles was 87% and the rate capability at 2 C (6000 mA/g) was 78% the capacity at 0.2 C.

Facile synthesis of nanostructured TiNb2O7 anode materials with superior performance for high-rate lithium ion batteries.

PubMed

Lou, Shuaifeng; Ma, Yulin; Cheng, Xinqun; Gao, Jinlong; Gao, Yunzhi; Zuo, Pengjian; Du, Chunyu; Yin, Geping

2015-12-18

One-dimensional nanostructured TiNb2O7 was prepared by a simple solution-based process and subsequent thermal annealing. The obtained anode materials exhibited excellent electrochemical performance with superior reversible capacity, rate capability and cyclic stability.

Conductive Polymeric Binder for Lithium-Ion Battery Anode

NASA Astrophysics Data System (ADS)

Gao, Tianxiang

Tin (Sn) has a high-specific capacity (993 mAhg-1) as an anode material for Li-ion batteries. To overcome the poor cycling performance issue caused by its large volume expansion and pulverization during the charging and discharging process, many researchers put efforts into it. Most of the strategies are through nanostructured material design and introducing conductive polymer binders that serve as matrix of the active material in anode. This thesis aims for developing a novel method for preparing the anode to improve the capacity retention rate. This would require the anode to have high electrical conductivity, high ionic conductivity, and good mechanical properties, especially elasticity. Here the incorporation of a conducting polymer and a conductive hydrogel in Sn-based anodes using a one-step electrochemical deposition via a 3-electrode cell method is reported: the Sn particles and conductive component can be electrochemically synthesized and simultaneously deposited into a hybrid thin film onto the working electrode directly forming the anode. A well-defined three dimensional network structure consisting of Sn nanoparticles coated by conducting polymers is achieved. Such a conductive polymer-hydrogel network has multiple advantageous features: meshporous polymeric structure can offer the pathway for lithium ion transfer between the anode and electrolyte; the continuous electrically conductive polypyrrole network, with the electrostatic interaction with elastic, porous hydrogel, poly (2-acrylamido-2-methyl-1-propanesulfonic acid-co-acrylonitrile) (PAMPS) as both the crosslinker and doping anion for polypyrrole (PPy) can decrease the volume expansion by creating porous scaffold and softening the system itself. Furthermore, by increasing the amount of PAMPS and creating an interval can improve the cycling performance, resulting in improved capacity retention about 80% after 20 cycles, compared with only 54% of that of the control sample without PAMPS. The cycle is performed under current of 0.1 C.

Energy Storage Materials from Nature through Nanotechnology: A Sustainable Route from Reed Plants to a Silicon Anode for Lithium-Ion Batteries.

PubMed

Liu, Jun; Kopold, Peter; van Aken, Peter A; Maier, Joachim; Yu, Yan

2015-08-10

Silicon is an attractive anode material in energy storage devices, as it has a ten times higher theoretical capacity than its state-of-art carbonaceous counterpart. However, the common process to synthesize silicon nanostructured electrodes is complex, costly, and energy-intensive. Three-dimensional (3D) porous silicon-based anode materials have been fabricated from natural reed leaves by calcination and magnesiothermic reduction. This sustainable and highly abundant silica source allows for facile production of 3D porous silicon with very good electrochemical performance. The obtained silicon anode retains the 3D hierarchical architecture of the reed leaf. Impurity leaching and gas release during the fabrication process leads to an interconnected porosity and the reductive treatment to an inside carbon coating. Such anodes show a remarkable Li-ion storage performance: even after 4000 cycles and at a rate of 10 C, a specific capacity of 420 mA h g(-1) is achieved. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fabrication of bristlegrass-like VO2 (B)-ZnO heteroarchitectures as anode materials for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Ma, Yining; Li, Wenjing; Ji, Shidong; Zhou, Huaijuan; Li, Rong; Li, Ning; Yao, Heliang; Cao, Xun; Jin, Ping

2017-08-01

Three-dimensional bristlegrass-like hierarchical VO2 (B)-ZnO heteroarchitectures with ZnO nanorods grown radially on VO2 (B) nanorods were successfully fabricated via a simple two-step synthesized method. When applied as an anode material for lithium-ion batteries, the VO2 (B)-ZnO hybrid electrode exhibited high reversible capacity and excellent recyclability, which could be originated from the unique hierarchical structure of the bristlegrass. After 80 cycles, the nanocomposite still maintained a higher reversible capacity of 329.4 mA h g-1 at a current density of 50 mA g-1. Therefore, the particular architecture of VO2 (B)-ZnO nanocomposite can be a promising candidate as the anode material in lithium-ion batteries.

High capacity and stable all-solid-state Li ion battery using SnO2-embedded nanoporous carbon.

PubMed

Notohara, Hiroo; Urita, Koki; Yamamura, Hideyuki; Moriguchi, Isamu

2018-06-08

Extensive research efforts are devoted to development of high performance all-solid-state lithium ion batteries owing to their potential in not only improving safety but also achieving high stability and high capacity. However, conventional approaches based on a fabrication of highly dense electrode and solid electrolyte layers and their close contact interface is not always applicable to high capacity alloy- and/or conversion-based active materials such as SnO 2 accompanied with large volume change in charging-discharging. The present work demonstrates that SnO 2 -embedded nanoporous carbons without solid electrolyte inside the nanopores are a promising candidate for high capacity and stable anode material of all-solid-state battery, in which the volume change reactions are restricted in the nanopores to keep the constant electrode volume. A prototype all-solid-state full cell consisting of the SnO 2 -based anode and a LiNi 1/3 Co 1 / 3 Mn 1/3 O 2 -based cathode shows a good performance of 2040 Wh/kg at 268.6 W/kg based on the anode material weight.

Three-Dimensional SnS Decorated Carbon Nano-Networks as Anode Materials for Lithium and Sodium Ion Batteries.

PubMed

Zhou, Yanli; Wang, Qi; Zhu, Xiaotao; Jiang, Fuyi

2018-02-28

The three-dimensional (3D) SnS decorated carbon nano-networks (SnS@C) were synthesized via a facile two-step method of freeze-drying combined with post-heat treatment. The lithium and sodium storage performances of above composites acting as anode materials were investigated. As anode materials for lithium ion batteries, a high reversible capacity of 780 mAh·g -1 for SnS@C composites can be obtained at 100 mA·g -1 after 100 cycles. Even cycled at a high current density of 2 A·g -1 , the reversible capacity of this composite can be maintained at 610 mAh·g -1 after 1000 cycles. The initial charge capacity for sodium ion batteries can reach 333 mAh·g -1 , and it retains a reversible capacity of 186 mAh·g -1 at 100 mA·g -1 after 100 cycles. The good lithium or sodium storage performances are likely attributed to the synergistic effects of the conductive carbon nano-networks and small SnS nanoparticles.

Hard Carbon Originated from Polyvinyl Chloride Nanofibers As High-Performance Anode Material for Na-Ion Battery

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

Bai, Ying; Wang, Zhen; Wu, Chuan

2015-02-27

Two types of hard carbon materials were synthesized through direct pyrolysis of commercial polyvinyl chloride (PVC) particles and pyrolysis of PVC nanofibers at 600-800 degrees C, respectively, where the nanofibers were prepared by an electrospinning PVC precursors method. These as-prepared hard carbon samples were used as anode materials for Na-ion batteries. The hard carbon obtained from PVC nanofibers achieved a high reversible capacity of 271 mAh/g and an initial Coulombic efficiency of 69.9%, which were much superior to the one from commercial PVC, namely, a reversible capacity of 206 mAh/g and an initial Coulombic efficiency of 60.9%. In addition, themore » hard carbon originated from the PVC nanofibers exhibited good cycling stability and rate performance: the initial discharge capacities were 389, 228, 194, 178, 147 mAh/g at the current density of 12, 24, 60, 120, and 240 mA/g, respectively, retaining 211 mAh/g after 150 cycles. Such excellent cycle performance, high reversible capacity, and good rate capability enabled this hard carbon to be a promising candidate as anode material for Na-ion battery application.« less

Hard carbon originated from polyvinyl chloride nanofibers as high-performance anode material for Na-ion battery.

PubMed

Bai, Ying; Wang, Zhen; Wu, Chuan; Xu, Rui; Wu, Feng; Liu, Yuanchang; Li, Hui; Li, Yu; Lu, Jun; Amine, Khalil

2015-03-11

Two types of hard carbon materials were synthesized through direct pyrolysis of commercial polyvinyl chloride (PVC) particles and pyrolysis of PVC nanofibers at 600-800 °C, respectively, where the nanofibers were prepared by an electrospinning PVC precursors method. These as-prepared hard carbon samples were used as anode materials for Na-ion batteries. The hard carbon obtained from PVC nanofibers achieved a high reversible capacity of 271 mAh/g and an initial Coulombic efficiency of 69.9%, which were much superior to the one from commercial PVC, namely, a reversible capacity of 206 mAh/g and an initial Coulombic efficiency of 60.9%. In addition, the hard carbon originated from the PVC nanofibers exhibited good cycling stability and rate performance: the initial discharge capacities were 389, 228, 194, 178, 147 mAh/g at the current density of 12, 24, 60, 120, and 240 mA/g, respectively, retaining 211 mAh/g after 150 cycles. Such excellent cycle performance, high reversible capacity, and good rate capability enabled this hard carbon to be a promising candidate as anode material for Na-ion battery application.

MoTe2, A novel anode material for sodium ion battery

NASA Astrophysics Data System (ADS)

Panda, Manas Ranjan; Anish Raj, K.; Bao, Qiaoliang; Mitra, Sagar

2018-04-01

2D layered transition metal dichalcogenides are considered as a potential anode for sodium-ion batteries due to their high specific capacity, structural stability and its well-developed two-dimensional layers. 2D layered structure Molybdenum ditelluride (MoTe2) provides a superior Na-ion storage properties in sodium ion battery due to its comparative more interlayer spacing (0.699 nm). In the current study MoTe2 polycrystalline powder sample has been prepared by solid state reaction process, the structural and morphological studies have been carried out by XRD, FE-SEM and EDS etc. XRD study revealsthe well crystalline structure of the material having hexagonal structure. FE-SEM and EDS studies depict the uniformflakes like structure of the material. When it is tested as sodium-ion battery anode by applying a potential window 0.1-2.5 V, the material demonstrates a high capacity and high power performances. The as prepared MoTe2 shows an initial discharge capacity of 376 mA h g-1 and a corresponding discharge capacity of 303 mA h g-1 after the 50th cycle at a current density of 500 mA g-1.

Additive-free thick graphene film as an anode material for flexible lithium-ion batteries.

PubMed

Rana, Kuldeep; Kim, Seong Dae; Ahn, Jong-Hyun

2015-04-28

This work demonstrates a simple route to develop mechanically flexible electrodes for Li-ion batteries (LIBs) that are usable as lightweight effective conducting networks for both cathodes and anodes. Removing electrochemically dead elements, such as binders, conducting agents and metallic current collectors, from the battery components will allow remarkable progress in this area. To investigate the feasibility of using thick, additive-free graphene films as anodes for flexible LIBs, we have synthesized and tested thick, additive-free, freestanding graphene films as anodes, first in a coin cell and further in a flexible full cell. As an anode material in a half cell, it showed a discharge capacity of about 350 mA h g(-1) and maintained nearly this capacity over 50 cycles at various current rates. This film was also tested as an anode material in a full cell with a LiCoO2 cathode and showed good electrochemical performance. Because the graphene-based flexible film showed good performance in half- and full coin cells, we used this film as a flexible anode for flexible LIBs. No conducting agent or binder was used in the anode side, which helped in realizing the flexible LIBs. Using this, we demonstrate a thin, lightweight and flexible lithium ion battery with good electrochemical performance in both its flat and bent states.

A pomegranate-inspired nanoscale design for large-volume-change lithium battery anodes

NASA Astrophysics Data System (ADS)

Liu, Nian; Lu, Zhenda; Zhao, Jie; McDowell, Matthew T.; Lee, Hyun-Wook; Zhao, Wenting; Cui, Yi

2014-03-01

Silicon is an attractive material for anodes in energy storage devices, because it has ten times the theoretical capacity of its state-of-the-art carbonaceous counterpart. Silicon anodes can be used both in traditional lithium-ion batteries and in more recent Li-O2 and Li-S batteries as a replacement for the dendrite-forming lithium metal anodes. The main challenges associated with silicon anodes are structural degradation and instability of the solid-electrolyte interphase caused by the large volume change (~300%) during cycling, the occurrence of side reactions with the electrolyte, and the low volumetric capacity when the material size is reduced to a nanometre scale. Here, we propose a hierarchical structured silicon anode that tackles all three of these problems. Our design is inspired by the structure of a pomegranate, where single silicon nanoparticles are encapsulated by a conductive carbon layer that leaves enough room for expansion and contraction following lithiation and delithiation. An ensemble of these hybrid nanoparticles is then encapsulated by a thicker carbon layer in micrometre-size pouches to act as an electrolyte barrier. As a result of this hierarchical arrangement, the solid-electrolyte interphase remains stable and spatially confined, resulting in superior cyclability (97% capacity retention after 1,000 cycles). In addition, the microstructures lower the electrode-electrolyte contact area, resulting in high Coulombic efficiency (99.87%) and volumetric capacity (1,270 mAh cm-3), and the cycling remains stable even when the areal capacity is increased to the level of commercial lithium-ion batteries (3.7 mAh cm-2).

In situ X-ray diffraction characterization of NiSe2 as a promising anode material for sodium ion batteries

NASA Astrophysics Data System (ADS)

Ou, Xing; Li, Jiao; Zheng, Fenghua; Wu, Peng; Pan, Qichang; Xiong, Xunhui; Yang, Chenghao; Liu, Meilin

2017-03-01

Reduced graphene oxide (rGO) homogenously wrapped nickel diselenide (NiSe2/rGO) hybrid has been prepared by a facile one-spot hydrothermal method. When investigated as anode material for sodium ion batteries (SIBs), NiSe2/rGO hybrid delivers a high reversible capacity (433 mAh g-1 at 100 mA g-1), superior rate performance (406, 386, 366, 347 and 318 mAh g-1 at 200, 500, 1000, 2000 and 5000 mA g-1, respectively) and excellent cycling stability (a capacity retention of 346 mAh g-1 after 1000 cycles at 1000 mA g-1) within the 0.4-3.0 V voltage range. In situ XRD analysis and ex situ SEM/TEM measurement reveal that the high capacity of NiSe2/rGO is originated from the combined Na+ intercalation and conversion reactions. These results validate the impact of voltage range on electrochemical property, providing a new route to rationalize the limiting factors that affect the performance of NiSe2 anode material. The facile synthesis and superior electrochemical performance of the NiSe2/rGO hybrid render it a promising anode material for SIBs.

Carbon-Coated Honeycomb Ni-Mn-Co-O Inverse Opal: A High Capacity Ternary Transition Metal Oxide Anode for Li-ion Batteries

PubMed Central

McNulty, David; Geaney, Hugh; O’Dwyer, Colm

2017-01-01

We present the formation of a carbon-coated honeycomb ternary Ni-Mn-Co-O inverse opal as a conversion mode anode material for Li-ion battery applications. In order to obtain high capacity via conversion mode reactions, a single phase crystalline honeycombed IO structure of Ni-Mn-Co-O material was first formed. This Ni-Mn-Co-O IO converts via reversible redox reactions and Li2O formation to a 3D structured matrix assembly of nanoparticles of three (MnO, CoO and NiO) oxides, that facilitates efficient reactions with Li. A carbon coating maintains the structure without clogging the open-worked IO pore morphology for electrolyte penetration and mass transport of products during cycling. The highly porous IO was compared in a Li-ion half-cell to nanoparticles of the same material and showed significant improvement in specific capacity and capacity retention. Further optimization of the system was investigated by incorporating a vinylene carbonate additive into the electrolyte solution which boosted performance, offering promising high-rate performance and good capacity retention over extended cycling. The analysis confirms the possibility of creating a ternary transition metal oxide material with binder free accessible open-worked structure to allow three conversion mode oxides to efficiently cycle as an anode material for Li-ion battery applications. PMID:28186183

Carbon-Coated Honeycomb Ni-Mn-Co-O Inverse Opal: A High Capacity Ternary Transition Metal Oxide Anode for Li-ion Batteries.

PubMed

McNulty, David; Geaney, Hugh; O'Dwyer, Colm

2017-02-10

We present the formation of a carbon-coated honeycomb ternary Ni-Mn-Co-O inverse opal as a conversion mode anode material for Li-ion battery applications. In order to obtain high capacity via conversion mode reactions, a single phase crystalline honeycombed IO structure of Ni-Mn-Co-O material was first formed. This Ni-Mn-Co-O IO converts via reversible redox reactions and Li 2 O formation to a 3D structured matrix assembly of nanoparticles of three (MnO, CoO and NiO) oxides, that facilitates efficient reactions with Li. A carbon coating maintains the structure without clogging the open-worked IO pore morphology for electrolyte penetration and mass transport of products during cycling. The highly porous IO was compared in a Li-ion half-cell to nanoparticles of the same material and showed significant improvement in specific capacity and capacity retention. Further optimization of the system was investigated by incorporating a vinylene carbonate additive into the electrolyte solution which boosted performance, offering promising high-rate performance and good capacity retention over extended cycling. The analysis confirms the possibility of creating a ternary transition metal oxide material with binder free accessible open-worked structure to allow three conversion mode oxides to efficiently cycle as an anode material for Li-ion battery applications.

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.

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.

Highly stable carbon coated Mg2Si intermetallic nanoparticles for lithium-ion battery anode

NASA Astrophysics Data System (ADS)

Tamirat, Andebet Gedamu; Hou, Mengyan; Liu, Yao; Bin, Duan; Sun, Yunhe; Fan, Long; Wang, Yonggang; Xia, Yongyao

2018-04-01

Silicon is an ideal candidate anode material for Li-ion batteries (LIBs). However, it suffers from rapid capacity fading due to large volume expansion upon lithium insertion. Herein, we design and fabricate highly stable carbon coated porous Mg2Si intermetallic anode material using facile mechano-thermal technique followed by carbon coating using thermal vapour deposition (TVD), toluene as carbon source. The electrode exhibits an excellent first reversible capacity of 726 mAh g-1 at a rate of 100 mA g-1. More importantly, the electrode demonstrates high rate capability (380 mAh g-1 at high rate of 2 A g-1) as well as high cycle stability, with capacity retentions of 65% over 500 cycles. These improvements are attributable to both Mg supporting medium and the uniform carbon coating, which can effectively increase the conductivity and electronic contact of the active material and protects large volume alterations during the electrochemical cycling process.

CROSS-DISCIPLINARY PHYSICS AND RELATED AREAS OF SCIENCE AND TECHNOLOGY: Electrochemical properties of SnO2 nanorods as anode materials in lithium-ion battery

NASA Astrophysics Data System (ADS)

Shi, Song-Lin; Liu, Yong-Gang; Zhang, Jing-Yuan; Wang, Tai-Hong

2009-10-01

Well-dispersed SnO2 nanorods with diameter of 4-15 nm and length of 100-200 nm are synthesised through a hydrothermal route and their potential as anode materials in lithium-ion batteries is investigated. The observed initial discharge capacity is as high as 1778 mA·h/g, much higher than the theoretical value of the bulk SnO2 (1494 mA·h/g). During the following 15 cycles, the reversible capacity decreases from 929 to 576 mA·h/g with a fading rate of 3.5% per cycle. The fading mechanism is discussed. Serious capacity fading can be avoided by reducing the cycling voltages from 0.05-3.0 to 0.4-1.2 V. At the end, SnO2 nanorods with much smaller size are synthesized and their performance as anode materials is studied. The size effect on the electrochemical properties is briefly discussed.

Well-ordered mesoporous Fe2O3/C composites as high performance anode materials for sodium-ion batteries.

PubMed

Li, Mei; Ma, Chao; Zhu, Qian-Cheng; Xu, Shu-Mao; Wei, Xiao; Wu, Yong-Min; Tang, Wei-Ping; Wang, Kai-Xue; Chen, Jie-Sheng

2017-04-11

Sodium-ion batteries have attracted considerable attention in recent years. In order to promote the practical application of sodium-ion batteries, the electrochemical performances, such as specific capacity, reversibility, and rate capability of the anode materials, should be further improved. In this work, a Fe 2 O 3 /C composite with a well-ordered mesoporous structure is prepared via a facile co-impregnation method by using mesoporous silica SBA-15 as a hard template. When used as an anode material for sodium-ion batteries, the well-ordered mesoporous structure ensures fast mass transport kinetics. The presence of nano-sized Fe 2 O 3 particles confined within the carbon walls significantly enhances the specific capacity of the composite. The carbon walls in the composite act not only as an active material contributing to the specific capacity, but also as a conductive matrix improving the cycling stability of Fe 2 O 3 nanoparticles. As a result, the well-ordered mesoporous Fe 2 O 3 /C composite exhibits high specific capacity, excellent cycleability, and high rate capability. It is proposed that this simple co-impregnation method is applicable for the preparation of well-ordered mesoporous transition oxide/carbon composite electrode materials for high performance sodium-ion and lithium-ion batteries.

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.

Crack-resistant polyimide coating for high-capacity battery anodes

NASA Astrophysics Data System (ADS)

Li, Yingshun; Wang, Shuo; Lee, Pui-Kit; He, Jieqing; Yu, Denis Y. W.

2017-10-01

Electrode cracking is a serious problem that hinders the application of many next-generation high-capacity anode materials for lithium-ion batteries. Even though nano-sizing the material can reduce fracturing of individual particles, capacity fading is still observed due to large volume change and loss of contact in the electrode during lithium insertion and extraction. In this study, we design a crack-resistant high-modulus polyimide coating with high compressive strength which can hold multiple particles together during charge and discharge to maintain contact. The effectiveness of the coating is demonstrated on tin dioxide, a high-capacity large-volume-change material that undergoes both alloy and conversion reactions. The polyimide coating improves capacity retention of SnO2 from 80% to 100% after 80 cycles at 250 mA g-1. Stable capacity of 585 mAh g-1 can be obtained even at 500 mA g-1 after 300 cycles. Scanning electron microscopy and in-situ dilatometry confirm that electrode cracking is suppressed and thickness change is reduced with the coating. In addition, the chemically-stable polyimide film can separate the surface from direct contact with electrolyte, improving coulombic efficiency to ∼100%. We expect the novel strategy of suppressing electrode degradation with a crack-resistant coating can also be used for other alloy and conversion-based anodes.

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

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.

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.

Bismuth Nanoparticles Embedded in Carbon Spheres as Anode Materials for Sodium/Lithium-Ion Batteries.

PubMed

Yang, Fuhua; Yu, Fan; Zhang, Zhian; Zhang, Kai; Lai, Yanqing; Li, Jie

2016-02-12

Sodium-ion batteries (SIBs) are regarded as an attractive alternative to lithium-ion batteries (LIBs) for large-scale commercial applications, because of the abundant terrestrial reserves of sodium. Exporting suitable anode materials is the key to the development of SIBs and LIBs. In this contribution, we report on the fabrication of Bi@C microspheres using aerosol spray pyrolysis technique. When used as SIBs anode materials, the Bi@C microsphere delivered a high capacity of 123.5 mAh g(-1) after 100 cycles at 100 mA g(-1) . The rate performance is also impressive (specific capacities of 299, 252, 192, 141, and 90 mAh g(-1) are obtained under current densities of 0.1, 0.2, 0.5, 1, and 2 A g(-1) , respectively). Furthermore, the Bi@C microsphere also proved to be suitable LIB anode materials. The excellent electrochemical performance for both SIBs and LIBs can attributed to the Bi@C microsphere structure with Bi nanoparticles uniformly dispersed in carbon spheres. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Recycled diesel carbon nanoparticles for nanostructured battery anodes

NASA Astrophysics Data System (ADS)

Chen, Yuming; Liu, Chang; Sun, Xiaoxuan; Ye, Han; Cheung, Chunshun; Zhou, Limin

2015-02-01

Considerable attention has been devoted to using rational nanostructure design to address critical carbonaceous anode material issues for next-generation lithium-ion batteries (LIBs). However, the fabrication of nanostructured carbonaceous anode materials often involves complex processes and expensive starting materials. Diesel engine is an important source of nanostructured carbon particles with diameters ranging 20 nm-60 nm suspended in air, resulting in a serious scourge of global climate and a series of diseases such as lung cancer, asthma, and cardiovascular disease. Here, we show that diesel carbon nanoparticles collected from diesel engines can be chemically activated to create a porous structure. The resulting nanostructured carbon electrodes have a high specific capacity of 936 mAh g-1 after 40 cycles at 0.05 A/g, and excellent cycle stability while retaining a capacity of ∼210 mAh g-1 after 1200 cycles at 5 A/g. As recycled diesel carbon nanoparticles are readily available due to the several billion tons of diesel fuel consumed every year by diesel engines, their use represents an exciting source for nanostructured carbonaceous anode materials for high-performance LIBs and improves our environment and health.

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.

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

Polymer-pyrolysis assisted synthesis of vanadium trioxide and carbon nanocomposites as high performance anode materials for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Dong, Yucheng; Ma, Ruguang; Hu, Mingjun; Cheng, Hua; Lee, Jong-Min; Li, Yang Yang; Zapien, Juan Antonio

2014-09-01

We present a simple polymer-pyrolysis assisted method to prepare vanadium trioxide and carbon nanocomposites as an advanced anode material for lithium-ion batteries. The as-prepared material deliver a superior battery performance with highly retained capacity of ∼780 mAh g-1 over 100 cycles at a current density of 200 mA g-1, showing excellent cyclic stability, and good rate capability. The improved electrochemical performance of vanadium trioxide and carbon nanocomposites electrode makes it promising as a suitable anode material for practical battery applications.

Free-standing hierarchically sandwich-type tungsten disulfide nanotubes/graphene anode for lithium-ion batteries.

PubMed

Chen, Renjie; Zhao, Teng; Wu, Weiping; Wu, Feng; Li, Li; Qian, Ji; Xu, Rui; Wu, Huiming; Albishri, Hassan M; Al-Bogami, A S; El-Hady, Deia Abd; Lu, Jun; Amine, Khalil

2014-10-08

Transition metal dichalcogenides (TMD), analogue of graphene, could form various dimensionalities. Similar to carbon, one-dimensional (1D) nanotube of TMD materials has wide application in hydrogen storage, Li-ion batteries, and supercapacitors due to their unique structure and properties. Here we demonstrate the feasibility of tungsten disulfide nanotubes (WS2-NTs)/graphene (GS) sandwich-type architecture as anode for lithium-ion batteries for the first time. The graphene-based hierarchical architecture plays vital roles in achieving fast electron/ion transfer, thus leading to good electrochemical performance. When evaluated as anode, WS2-NTs/GS hybrid could maintain a capacity of 318.6 mA/g over 500 cycles at a current density of 1A/g. Besides, the hybrid anode does not require any additional polymetric binder, conductive additives, or a separate metal current-collector. The relatively high density of this hybrid is beneficial for high capacity per unit volume. Those characteristics make it a potential anode material for light and high-performance lithium-ion batteries.

Zn-Ge-Sb glass composite mixed with Ba2+ ions: a high capacity anode material for Na-ion batteries

NASA Astrophysics Data System (ADS)

Ravuri, Balaji Rao; Gandi, Suman; Chinta, Srinivasa Rao

2018-06-01

(100-x)(0.7[0.625ZnO-0.375GeO2]-0.3Sb2O3)-xBaO (x = 0, 2, 4 and 6 mol%, labeled as ZGSB x ) glass anode samples are synthesized using a high-energy ball-milling method and employed as anode material for Na-ion batteries. The results on microstructures (XRD, SEM) and electrochemical properties (constant current charge/discharge tests, CV and EIS) indicated that the optimum concentration of Ba2+ ions in the Zn-Ge-Sb glass anode network exhibits the pillaring effect, which would lead to increased electrical conductivity, minimize the volume changes, cracks and voids to boost up electrochemical performance. The ZGSB4 glass anode sample exhibits good capacity retention even after 20 cycles with 95% coulombic efficiency, which is a significant trend for a successful anode network. Electrochemical performance is considerably enhanced by reducing the cut-off voltage from 2 to 1.25 V due to the disassembly of amorphous intermediate domains, optimum volume changes and increased electrical conductivity in this ZGSB x glass network.

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.

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.

Nanosheets of earth-abundant jarosite as novel anodes for high-rate and long-life lithium-ion batteries.

PubMed

Ding, Yuan-Li; Wen, Yuren; Chen, Chia-Chin; van Aken, Peter A; Maier, Joachim; Yu, Yan

2015-05-20

Nanosheets of earth-abundant jarosite were fabricated via a facile template-engaged redox coprecipitation strategy at room temperature and employed as novel anode materials for lithium-ion batteries (LIBs) for the first time. These 2D materials exhibit high capacities, excellent rate capability, and prolonged cycling performance. As for KFe3(SO4)2(OH)6 jarosite nanosheets (KNSs), the reversible capacities of above 1300 mAh g(-1) at 100 mA g(-1) and 620 mAh g(-1) after 4000 cycles at a very high current density of 10 A g(-1) were achieved, respectively. Moreover, the resulting 2D nanomaterials retain good structural integrity upon cycling. These results reveal great potential of jarosite nanosheets as low-cost and high-performance anode materials for next-generation LIBs.

Si/Ti2O3/Reduced Graphene Oxide Nanocomposite Anodes for Lithium-Ion Batteries with Highly Enhanced Cyclic Stability.

PubMed

Park, A Reum; Son, Dae-Yong; Kim, Jung Sub; Lee, Jun Young; Park, Nam-Gyu; Park, Juhyun; Lee, Joong Kee; Yoo, Pil J

2015-08-26

Silicon (Si) has attracted tremendous attention as a high-capacity anode material for next generation Li-ion batteries (LIBs); unfortunately, it suffers from poor cyclic stability due to excessive volume expansion and reduced electrical conductivity after repeated cycles. To circumvent these issues, we propose that Si can be complexed with electrically conductive Ti2O3 to significantly enhance the reversible capacity and cyclic stability of Si-based anodes. We prepared a ternary nanocomposite of Si/Ti2O3/reduced graphene oxide (rGO) using mechanical blending and subsequent thermal reduction of the Si, TiO2 nanoparticles, and rGO nanosheets. As a result, the obtained ternary nanocomposite exhibited a specific capacity of 985 mAh/g and a Coulombic efficiency of 98.4% after 100 cycles at a current density of 100 mA/g. Furthermore, these ternary nanocomposite anodes exhibited outstanding rate capability characteristics, even with an increased current density of 10 A/g. This excellent electrochemical performance can be ascribed to the improved electron and ion transport provided by the Ti2O3 phase within the Si domains and the structurally reinforced conductive framework comprised of the rGO nanosheets. Therefore, it is expected that our approach can also be applied to other anode materials to enable large reversible capacity, excellent cyclic stability, and good rate capability for high-performance LIBs.

In Situ Activation of 3D Porous Bi/Carbon Architectures: Toward High-Energy and Stable Nickel-Bismuth Batteries.

PubMed

Zeng, Yinxiang; Lin, Ziqi; Wang, Zifan; Wu, Mingmei; Tong, Yexiang; Lu, Xihong

2018-05-01

To achieve high-energy and stable aqueous rechargeable batteries, state-of-the art of anode materials are needed. Bismuth (Bi) has recently emerged as an attractive anode material due to its highly reversible redox reaction and suitable negative operating working window. However, the capacity and durability of currently reported Bi anodes are still far from satisfactory. Here, an in situ activation strategy is reported to prepare a 3D porous high-density Bi nanoparticles/carbon architecture (P-Bi-C) as an efficient anode for nickel-bismuth batteries. Taking advantages of the fast channels for charge transfer and ion diffusion, enhanced wettability, and accessible surface area, the highly loaded P-Bi-C electrode delivers a remarkable capacity of 2.11 mA h cm -2 as well as high rate capability (1.19 mA h cm -2 at 120 mA cm -2 ). To highlight, a robust aqueous rechargeable Ni//Bi battery based on the P-Bi-C anode is first constructed, achieving decent capacity (141 mA h g -1 ), impressive durability (94% capacity retention after 5000 cycles), and admirable energy density (16.9 mW h cm -3 ). This work paves the way for designing superfast nickel-bismuth batteries with high energy and long-life and may inspire new development for aqueous rechargeable batteries. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Commercial expanded graphite as a low-cost, long-cycling life anode for potassium-ion batteries with conventional carbonate electrolyte

NASA Astrophysics Data System (ADS)

An, Yongling; Fei, Huifang; Zeng, Guifang; Ci, Lijie; Xi, Baojuan; Xiong, Shenglin; Feng, Jinkui

2018-02-01

Design and synthesis of capable anode materials that can store the large size K+ is the key of development for potassium-ion batteries. The low-cost and commercial expanded graphite with large particles is a graphite-derived material with good conductivity and enlarged interlayer spaces to boost the potassium ion diffusion coefficient during charge/discharge process. Thus, we achieve excellent anode performance for potassium-ion batteries based on an expanded graphite. It can deliver a capacity of 263 mAh g-1 at the rate of 10 mA g-1 and the reversible capacity remains almost unchanged after 500 cycles at a high rate of 200 mA g-1 with a coulombic efficiency of around 100%. The potassium storage mechanism is investigated by the ex situ XRD technique. This excellent potassium storage performance will make the expanded graphite promising anode candidate for potassium ion batteries.

Carbon coated SnO2 nanoparticles anchored on CNT as a superior anode material for lithium-ion batteries.

PubMed

Ma, Chunrong; Zhang, Weimin; He, Yu-Shi; Gong, Qiang; Che, Haiying; Ma, Zi-Feng

2016-02-21

Hierarchically structured carbon coated SnO2 nanoparticles well-anchored on the surface of a CNT (C-SnO2/CNT) material were synthesized by a facile hydrothermal process and subsequent carbonization. The as-obtained C-SnO2/CNT hybrid, when applied as an anode material for lithium ion batteries (LIBs), showed a high reversible capacity up to 1572 mA h g(-1) at 200 mA g(-1) with a superior rate capability (685 mA h g(-1) at 4000 mA g(-1)). Even after 100 charge/discharge cycles at 1000 mA g(-1), a specific capacity of 1100 mA h g(-1) can still be maintained. Such impressive electrochemical performance can be mainly attributed to the hierarchical sandwiched structure and strong synergistic effects of the ultrafine SnO2 nanoparticles and the carbon coating, and thus presents this material a promising anode material for LIBs.

Binary iron sulfides as anode materials for rechargeable batteries: Crystal structures, syntheses, and electrochemical performance

NASA Astrophysics Data System (ADS)

Xu, Qian-Ting; Li, Jia-Chuang; Xue, Huai-Guo; Guo, Sheng-Ping

2018-03-01

Effective utilization of energy requires the storage and conversion device with high ability. For well-developed lithium ion batteries (LIBs) and highly developing sodium ion batteries (SIBs), this ability especially denotes to high energy and power densities. It's believed that the capacity of a full cell is mainly contributed by anode materials. So, to develop inexpensive anode materials with high capacity are meaningful for various rechargeable batteries' better applications. Iron is a productive element in the crust, and its oxides, sulfides, fluorides, and oxygen acid salts are extensively investigated as electrode materials for batteries. In view of the importance of electrode materials containing iron, this review summarizes the recent achievements on various binary iron sulfides (FeS, FeS2, Fe3S4, and Fe7S8)-type electrodes for batteries. The contents are mainly focused on their crystal structures, synthetic methods, and electrochemical performance. Moreover, the challenges and some improvement strategies are also discussed.

One-pot hydrothermal synthesis of ZnS quantum dots/graphene hybrids as a dual anode for sodium ion and lithium ion batteries

NASA Astrophysics Data System (ADS)

Zhang, Rupeng; Wang, Yu; Jia, Mengqiu; Xu, Junjie; Pan, Erzhuang

2018-04-01

Committed to research high-performance sodium-ion batteries(SIBs) and lithium-ion batteries(LIBs) anode materials is attractive but challenging. Among the many promising anode materials, sulfides are considered as promising available anode material. In this paper, we successfully synthesized uniformly dispersed ZnS quantum dots (QDs) with sub-10-nm-scale on graphene nanosheets via a facile hydrothermal method. The prepared ZnS/graphene composites was studied as a dual anode for sodium-ion and lithium-ion batteries. Tested against SIBs, the nanocomposites exhibits an impressive specific capacity of 491 mAh/g at 100 mA/g after 100 cycles. Tested against LIBs, the nanocomposites delivers a superior specific capacity of 759 mAh/g at 100 mA/g after 100 cycles. This excellent performance is mainly due to the fact that graphene can improve the conductivity of the composites and effectively prevent the agglomeration and pulverization of ZnS quantum dots during cycling. Meanwhile, ZnS quantum dots with sub-10-nm-scale may also shorten diffuse path and reduce migration barrier, which is in favor of the full utilization of the active material and the improvement of the stability of the structure

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

Zhu, Yinhai; Xiang, Xiaoxia; Liu, Enhui, E-mail: liuenhui99@sina.com.cn

Highlights: ► Microporous carbon was prepared by chemical activation of phenol-melamine-formaldehyde resin. ► Activation leads to high surface area, well-developed micropores. ► Micropores lead to strong intercalation between carbon and lithium ion. ► Large surface area promotes to improve the lithium storage capacity. -- Abstract: Microporous carbon anode materials were prepared from phenol-melamine-formaldehyde resin by ZnCl{sub 2} and KOH activation. The physicochemical properties of the obtained carbon materials were characterized by scanning electron microscope, X-ray diffraction, Brunauer–Emmett–Teller, and elemental analysis. The electrochemical properties of the microporous carbon as anode materials in lithium ion secondary batteries were evaluated. At a currentmore » density of 100 mA g{sup −1}, the carbon without activation shows a first discharge capacity of 515 mAh g{sup −1}. After activation, the capacity improved obviously. The first discharge capacity of the carbon prepared by ZnCl{sub 2} and KOH activation was 1010 and 2085 mAh g{sup −1}, respectively. The reversible capacity of the carbon prepared by KOH activation was still as high as 717 mAh g{sup −1} after 20 cycles, which was much better than that activated by ZnCl{sub 2}. These results demonstrated that it may be a promising candidate as an anode material for lithium ion secondary batteries.« less

Spinel lithium titanate (Li4Ti5O12) as novel anode material for room-temperature sodium-ion battery

NASA Astrophysics Data System (ADS)

Zhao, Liang; Pan, Hui-Lin; Hu, Yong-Sheng; Li, Hong; Chen, Li-Quan

2012-02-01

This is the first time that a novel anode material, spinel Li4Ti5O12 which is well known as a “zero-strain" anode material for lithium storage, has been introduced for sodium-ion battery. The Li4Ti5O12 shows an average Na storage voltage of about 1.0 V and a reversible capacity of about 145 mAh/g, thereby making it a promising anode for sodium-ion battery. Ex-situ X-ray diffraction (XRD) is used to investigate the structure change in the Na insertion/deinsertion process. Based on this, a possible Na storage mechanism is proposed.

Facile Synthesis of Layer Structured GeP3/C with Stable Chemical Bonding for Enhanced Lithium-Ion Storage

NASA Astrophysics Data System (ADS)

Qi, Wen; Zhao, Haihua; Wu, Ying; Zeng, Hong; Tao, Tao; Chen, Chao; Kuang, Chunjiang; Zhou, Shaoxiong; Huang, Yunhui

2017-02-01

Recently, metal phosphides have been investigated as potential anode materials because of higher specific capacity compared with those of carbonaceous materials. However, the rapid capacity fade upon cycling leads to poor durability and short cycle life, which cannot meet the need of lithium-ion batteries with high energy density. Herein, we report a layer-structured GeP3/C nanocomposite anode material with high performance prepared by a facial and large-scale ball milling method via in-situ mechanical reaction. The P-O-C bonds are formed in the composite, leading to close contact between GeP3 and carbon. As a result, the GeP3/C anode displays excellent lithium storage performance with a high reversible capacity up to 1109 mA h g-1 after 130 cycles at a current density of 0.1 A g-1. Even at high current densities of 2 and 5 A g-1, the reversible capacities are still as high as 590 and 425 mA h g-1, respectively. This suggests that the GeP3/C composite is promising to achieve high-energy lithium-ion batteries and the mechanical milling is an efficient method to fabricate such composite electrode materials especially for large-scale application.

Controlled synthesis of MnOOH multilayer nanowires as anode materials for lithium-ion batteries

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

Wu, Yue; Yue, Kaiqiang; Wang, Yuanxin

MnOOH multilayer nanowires have been successfully synthesized by a hydrothermal method. It is found that the uniform multilayer structure of nanowires ran through the entire nanowire, which is formed via a layer by layer. The electrochemical properties of MnOOH multilayer nanowires as an anode material for Li-ion batteries (LIB) were investigated, and excellent capacity retention, superior cycling performance, and high rate capability were achieved. Specifically, the reversible capacity of MnOOH multilayer nanowires is 521 mAh/g after 500 cycles at 0.1 C, with excellent electrochemical stability. The multilayer nanowire electrodes exhibit short electron path lengths, high internal dislocation densities and largemore » surface to volume ratio, resulting in increased specific capacity, cycling stability and rate performance in the energy storage devices, which serves as an indication of their potential application in LIBs. - Highlights: •MnOOH multilayer nanowires were synthesized by a hydrothermal method. •The uniform multilayer structure of nanowires was formed via layer by layer. •The reversible capacity of product shows 521 mAh/g after 500 cycles at 0.1 C. •MnOOH multilayer nanowires showed higher property as anode material in LIB.« less

An Amorphous Carbon Nitride Composite Derived from ZIF-8 as Anode Material for Sodium-Ion Batteries.

PubMed

Fan, Jing-Min; Chen, Jia-Jia; Zhang, Qian; Chen, Bin-Bin; Zang, Jun; Zheng, Ming-Sen; Dong, Quan-Feng

2015-06-08

An composite comprising amorphous carbon nitride (ACN) and zinc oxide is derived from ZIF-8 by pyrolysis. The composite is a promising anode material for sodium-ion batteries. The nitrogen content of the ACN composite is as high as 20.4 %, and the bonding state of nitrogen is mostly pyridinic, as determined by X-ray photoelectron spectroscopy (XPS). The composite exhibits an excellent Na(+) storage performance with a reversible capacity of 430 mA h g(-1) and 146 mA h g(-1) at current densities of 83 mA g(-1) and 8.33 A g(-1) , respectively. A specific capacity of 175 mA h g(-1) was maintained after 2000 cycles at 1.67 A g(-1) , with only 0.016 % capacity degradation per cycle. Moreover, an accelerating rate calorimetry (ARC) test demonstrates the excellent thermal stability of the composite, with a low self heating rate and high onset temperature (210 °C). These results shows its promise as a candidate material for high-capacity, high-rate anodes for sodium-ion batteries. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemical characteristics of needle coke refined by molten caustic leaching as an anode material for a lithium-ion battery

NASA Astrophysics Data System (ADS)

Kang, Hyeong-Gon; Park, Jong-Kwang; Han, Byoung-Sung; Lee, Haeseong

Needle coke, the remaining material after refining petroleum, is used as an anode of a lithium-ion secondary battery. Sulfur is separated from the needle coke to below 0.1 wt.% using the molten caustic leaching (MCL) method developed at the Korea Institute of Energy Research. The needle coke with high-purity is carbonized at various temperatures, namely 0, 500, 700 and 900 °C. The coke treated at 700 °C gives a first and second discharge capacity of more than 560 and 460 mAh g -1, respectively, between 0 and 2.0 V. By contrast, the first and second discharge capacity of untreated coke is over 420 and 340 mAh g -1, respectively, between 0.05 and 2.0 V.The first discharge capacity of 560 mAh g -1 is beyond the theoretical maximum capacity of 372 mAh g -1 for LiC 6. Though the cycle efficiency is not consistent, the needle coke heat-treated at 700 °C persistently maintains an efficiency of over 90% until the 50th cycle, except on the first cycle. This study demonstrates that the needle coke with high-purity could be a good candidate for an anode material in fabricating high-capacity lithium-ion secondary batteries.

Hydrothermal vanadium manganese oxides: Anode and cathode materials for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Simões, Mário; Surace, Yuri; Yoon, Songhak; Battaglia, Corsin; Pokrant, Simone; Weidenkaff, Anke

2015-09-01

Vanadium manganese oxides with Mn content up to 33 at% were synthesized by a low temperature hydrothermal route allowing for the preparation of both anodic and cathodic materials for Li-ion batteries. Low amounts of manganese (below 13 at%) lead to the formation of elongated particles of layered hydrated vanadium oxides with manganese and water intercalated between the V2O5 slabs, while for higher Mn content of 33 at%, monoclinic MnV2O6 is formed. Former materials are suitable for high energy cathodes while the latter one is an anodic compound. The material containing 10 at% Mn has the composition Mn0.2V2O5·0.9H2O and shows the best cathodic activity with 20% capacity improvement over V2O5·0.5H2O. Lithiated MnV2O6 with Li5MnV2O6 composition prepared electrochemically was evaluated for the first time as anode in a full-cell against Mn0.2V2O5·0.9H2O cathode. An initial capacity ca. 300 A h kg-1 was measured with this battery corresponding to more than 500 Wh kg-1. These results confirm the prospect of using Li5MnV2O6 anodes in lithium-ion batteries as well as high-capacity layered hydrated vanadium oxides cathodes such as V2O5·0.5H2O and Mn0.2V2O5·0.9H2O.

Enhanced Electrochemical Performances of Bi2O3/rGO Nanocomposite via Chemical Bonding as Anode Materials for Lithium Ion Batteries.

PubMed

Deng, Zhuo; Liu, Tingting; Chen, Tao; Jiang, Jiaxiang; Yang, Wanli; Guo, Jun; Zhao, Jianqing; Wang, Haibo; Gao, Lijun

2017-04-12

Bismuth oxide/reduced graphene oxide (termed Bi 2 O 3 @rGO) nanocomposite has been facilely prepared by a solvothermal method via introducing chemical bonding that has been demonstrated by Raman and X-ray photoelectron spectroscopy spectra. Tremendous single-crystal Bi 2 O 3 nanoparticles with an average size of ∼5 nm are anchored and uniformly dispersed on rGO sheets. Such a nanostructure results in enhanced electrochemical reversibility and cycling stability of Bi 2 O 3 @rGO composite materials as anodes for lithium ion batteries in comparison with agglomerated bare Bi 2 O 3 nanoparticles. The Bi 2 O 3 @rGO anode material can deliver a high initial capacity of ∼900 mAh/g at 0.1C and shows excellent rate capability of ∼270 mAh/g at 10C rates (1C = 600 mA/g). After 100 electrochemical cycles at 1C, the Bi 2 O 3 @rGO anode material retains a capacity of 347.3 mAh/g with corresponding capacity retention of 79%, which is significantly better than that of bare Bi 2 O 3 material. The lithium ion diffusion coefficient during lithiation-delithiation of Bi 2 O 3 @rGO nanocomposite has been evaluated to be around ∼10 -15 -10 -16 cm 2 /S. This work demonstrates the effects of chemical bonding between Bi 2 O 3 nanoparticles and rGO substrate on enhanced electrochemical performances of Bi 2 O 3 @rGO nanocomposite, which can be used as a promising anode alterative for superior lithium ion batteries.

Surface modifications for carbon lithium intercalation anodes

DOEpatents

Tran, Tri D.; Kinoshita, Kimio

2000-01-01

A prefabricated carbon anode containing predetermined amounts of passivating film components is assembled into a lithium-ion rechargeable battery. The modified carbon anode enhances the reduction of the irreversible capacity loss during the first discharge of a cathode-loaded cell. The passivating film components, such as Li.sub.2 O and Li.sub.2 CO.sub.3, of a predetermined amount effective for optimal passivation of carbon, are incorporated into carbon anode materials to produce dry anodes that are essentially free of battery electrolyte prior to battery assembly.

High Areal Capacity Si/LiCoO 2 Batteries from Electrospun Composite Fiber Mats

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

Self, Ethan C.; Naguib, Michael; Ruther, Rose E.

Here, freestanding nanofiber mat Li-ion battery anodes containing Si nanoparticles, carbon black, and poly(acrylic acid) (Si/C/PAA) are prepared using electrospinning. The mats are compacted to a high fiber volume fraction (~0.85), and interfiber contacts are welded by exposing the mat to methanol vapor. A compacted+welded fiber mat anode containing 40 wt % Si exhibits high capacities of 1,484 mA h g -1 (3,500 mA h gmore » $$-1\\atop{Si}$$) at 0.1 C and 489 mAh g -1 at 1 C and good cycling stability (e.g., 73% capacity retention over 50 cycles). Post-mortem analysis of the fiber mats shows that the overall electrode structure is preserved during cycling. Whereas many nanostructured Si anodes are hindered by their low active material loadings and densities, thick, densely packed Si/C/PAA fiber mat anodes reported here have high areal and volumetric capacities (e.g., 4.5 mA h cm -2 and 750 mA h cm -3, respectively). A full cell containing an electrospun Si/C/PAA anode and electrospun LiCoO 2-based cathode has a high specific energy density of 270 Wh kg -1. The excellent performance of the electrospun Si/C/PAA fiber mat anodes is attributed to the: (i) PAA binder which interacts with the SiO x surface of Si nanoparticles and (ii) high material loading, high fiber volume fraction, and welded interfiber contacts of the electrospun mats« less

High Areal Capacity Si/LiCoO 2 Batteries from Electrospun Composite Fiber Mats

DOE PAGES

Self, Ethan C.; Naguib, Michael; Ruther, Rose E.; ...

2017-03-24

Here, freestanding nanofiber mat Li-ion battery anodes containing Si nanoparticles, carbon black, and poly(acrylic acid) (Si/C/PAA) are prepared using electrospinning. The mats are compacted to a high fiber volume fraction (~0.85), and interfiber contacts are welded by exposing the mat to methanol vapor. A compacted+welded fiber mat anode containing 40 wt % Si exhibits high capacities of 1,484 mA h g -1 (3,500 mA h gmore » $$-1\\atop{Si}$$) at 0.1 C and 489 mAh g -1 at 1 C and good cycling stability (e.g., 73% capacity retention over 50 cycles). Post-mortem analysis of the fiber mats shows that the overall electrode structure is preserved during cycling. Whereas many nanostructured Si anodes are hindered by their low active material loadings and densities, thick, densely packed Si/C/PAA fiber mat anodes reported here have high areal and volumetric capacities (e.g., 4.5 mA h cm -2 and 750 mA h cm -3, respectively). A full cell containing an electrospun Si/C/PAA anode and electrospun LiCoO 2-based cathode has a high specific energy density of 270 Wh kg -1. The excellent performance of the electrospun Si/C/PAA fiber mat anodes is attributed to the: (i) PAA binder which interacts with the SiO x surface of Si nanoparticles and (ii) high material loading, high fiber volume fraction, and welded interfiber contacts of the electrospun mats« less

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.

Porous Hard Carbon Derived from Walnut Shell as an Anode Material for Sodium-Ion Batteries

NASA Astrophysics Data System (ADS)

Zhang, Sensen; Li, Ying; Li, Min

2018-02-01

Porous hard carbon with large interlayer distance was fabricated from walnut shells through a facile high-temperature pyrolysis process and investigated as an anode material for sodium-ion batteries (SIBs). The results show that the electrochemical performance is mainly dependent on the pyrolysis temperature. The porous hard carbon, which was carbonized at 1300°C, displays the highest reversible capacity of 230 mAh g-1 at 20 mA g-1 and an excellent cycling stability (96% capacity retained over 200 cycles). The promising electrochemical performances are attributed to the porous structure reducing distances for sodium ion diffusion and expanded interlayer spacing, which is beneficial for sodium reversible insertion/extraction. The excellent electrochemical performance as well as the low-cost and environmental friendliness demonstrates that walnut shell-derived porous hard carbon is a promising anode material candidate for SIBs.

Center-iodized graphene as an advanced anode material to significantly boost the performance of lithium-ion batteries.

PubMed

Chen, Jie; Xu, Mao-Wen; Wu, Jinggao; Li, Chang Ming

2018-05-17

Iodine edge-doped graphene can improve the capacity and stability of lithium-ion batteries (LIBs). Our theoretical calculations indicate that center-iodization can further significantly enhance the anode catalytic process. To experimentally prove the theoretical prediction, iodine-doped graphene materials were prepared by one-pot hydrothermal and ball-milling approaches to realize different doping-sites. Results show that the center-iodinated graphene (CIG) anode exhibits a remarkably high reversible capacity (1121 mA h g-1 after 180 cycles at 0.5 A g-1), long-cycle life (0.01% decay per cycle over 300 cycles at 1 A g-1) and high-rate capacity (374 mA h g-1 after 800 cycles at 8 A g-1), which greatly improves the performance of the edge-iodinated graphene anode and these results are in good agreement with the theoretical analysis. More importantly, the CIG anode also delivers a high-rate capacity and excellent cycling stability (279 mA h g-1 after 500 cycles at 10 A g-1) in full-cells. Both the theoretical analysis and experimental investigation reveal the enhancement mechanism, in which the center-iodization increases the surface charge for fast electron transfer rate, improves the conductivity for charge transport and rationalizes the pore structure for enhanced mass transport and ion insertion/desertion, thus resulting in a high rate capacity and long cycle life. This work not only discloses the critical role of catalytic sites including both amounts and site positions but also offers great potential for high-power rechargeable LIB applications.

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

Core-shell Si@TiO 2 nanosphere anode by atomic layer deposition for Li-ion batteries

DOE PAGES

Dai, Sheng

2016-01-28

Silicon (Si) is regarded as next-generation anode for high-energy lithium-ion batteries (LIBs) due to its high Li storage capacity (4200 mA h g -1). However, the mechanical degradation and resultant capacity fade critically hinder its practical application. In this regard, we demonstrate that nanocoating of Si spheres with a 3 nm titanium dioxide (TiO 2) layer via atomic layer deposition (ALD) can utmostly balance the high conductivity and the good structural stability to improve the cycling stability of Si core material. The resultant sample, Si@TiO 2-3 nm core–shell nanospheres, exhibits the best electrochemical performance of all with a highest initialmore » Coulombic efficiency and specific charge capacity retention after 50 cycles at 0.1C (82.39% and 1580.3 mA h g -1). In addition to making full advantage of the ALD technique, we believe that our strategy and comprehension in coating the electrode and the active material could provide a useful pathway towards enhancing Si anode material itself and community of LIBs.« less

Ternary tin-based chalcogenide nanoplates as a promising anode material for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Tang, Qiming; Su, Heng; Cui, Yanhui; Baker, Andrew P.; Liu, Yanchen; Lu, Juan; Song, Xiaona; Zhang, Huayu; Wu, Junwei; Yu, Haijun; Qu, Deyang

2018-03-01

As an advanced anode material for lithium-ion batteries, tin-chalcogenides receive substantial attention due to their high lithium-ion storage capacity. Here, tin chalcogenide (SnSe0.5S0.5) nanoplates are synthesized using a facile and quick polyol-method, followed by heating at different temperatures. Results show that the as-prepared of SnSe0.5S0.5 heated at temperature of 180 °C exhibits the best electrochemical performance with an outstanding discharge specific capacity of 1144 mA h g-1 at 0.1 A g-1 after 100 cycles and 682 mA h g-1 at 0.5 A g-1 after 200 cycles with a high coulombic efficiency (CE) of 98.7%. Even at a high current density of 5 A g-1, this anode material delivers a specific capacity of 473 mA h g-1. The high electrochemical performance of SnSe0.5S0.5 is shown by in-situ XRD analysis to originate from an enhanced Li+ intercalation and an alloy conversion process.

Hierarchical TiO2-B composed of nanosheets with exposed {010} facets as a high-performance anode for lithium ion batteries

NASA Astrophysics Data System (ADS)

Liu, Yubin; Chen, Wenqiang; Yang, Chengyu; Wei, Qiaohua; Wei, Mingdeng

2018-07-01

Facet engineering of electrode materials with a special facet provides a new strategy to enhance their electrochemical properties. In the present work, hierarchical TiO2-B composed of nanosheets with exposed {010} facets are successfully synthesized via a facial hydrothermal route. When used as an anode for lithium ion batteries, this material demonstrates high capacities, excellent rata capability and remarkable cycling performance. For instance, it displays a reversible capacity of 200.9 mA h g-1 after 200 cycles at a current density of 1.675 A g-1 (5 C). Furthermore, a full cell consisted of hierarchical TiO2-B composed of nanosheets with exposed {010} facets anode and LiFePO4 cathode exhibits a high capacity of 125.6 mA h g-1 after 1000 cycles at a current density of 2 A g-1. Such outstanding electrochemical properties of this material can be attributed to hierarchical structure and the presence of exposed {010} facets which provides favorable lithium transport channels.

Synthesis of Li2Ti3O7 Anode Materials by Ultrasonic Spray Pyrolysis and Their Electrochemical Properties

PubMed Central

Ogihara, Takashi; Kodera, Takayuki

2013-01-01

Ramsdellite-type lithium titanate (Li2Ti3O7) powders were synthesized by performing ultrasonic spray pyrolysis, and their chemical and physical properties were characterized by performing Scanning Electron Microscope (SEM), powder X-ray Diffraction (XRD), and Inductively Coupled Plasma (ICP) analyses. The as-prepared Li2Ti3O7 precursor powders had spherical morphologies with hollow microstructures, but an irregularly shaped morphology was obtained after calcination above 900 °C. The ramsdellite Li2Ti3O7 crystal phase was obtained after the calcination at 1100 °C under an argon/hydrogen atmosphere. The first rechargeable capacity of the Li2Ti3O7 anode material was 168 mAh/g at 0.1 C and 82 mAh/g at 20 C, and the discharge capacity retention ratio was 99% at 1 C after the 500th cycle. The cycle performance of the Li2Ti3O7 anode was also highly stable at 50 °C, demonstrating the superiority of Li2Ti3O7 anode materials reported previously. PMID:28809274

Self-assembly of novel hierarchical flowers-like Sn3O4 decorated on 2D graphene nanosheets hybrid as high-performance anode materials for LIBs

NASA Astrophysics Data System (ADS)

Chen, Xuefang; Huang, Ying; Li, Tianpeng; Wei, Chao; Yan, Jing; Feng, Xuansheng

2017-05-01

Novel hierarchical flower-like Sn3O4 assembled by thin Sn3O4 nanosheets, as a kind of mixed-valence tin oxide, decorated on two-dimensional graphene nanosheets has been synthesized via a hydrothermal route and a step solution deoxidization technique. More importantly, as the anode materials for lithium ion batteries, the flower-like Sn3O4/graphene composite has not been investigated in detail. Noticeably, the nanosheets stemming from flower-like Sn3O4 and graphene have been linked together to form a specials three dimensional structure, possessing high active surface area and large enough inner spaces, which is benefit to the diffusion of liquid electrolyte into the electrode materials. In addition, the special structure could provide sufficient free volume to buffer the volume expansion appeared in the process of discharging and charging. The as-prepared flowers-like Sn3O4/graphene displayed excellent electrochemical performance with high capacity and good cycling stability as anode materials for lithium ion batteries. The discharge capacity is 1727 mAh/g in the first cycle at the current density of 60 mA/g. The obtained reversible capacity is 631mAh/g with a coulomb efficiency of 97.04% after 50 cycles. With its better electrochemical properties, the as-prepared flowers-like Sn3O4/graphene has the potential to be the next generation materials as an environmentally benign, abundant, cheap anode materials for lithium ion batteries.

Novel strategy to improve the Li-storage performance of micro silicon anodes

NASA Astrophysics Data System (ADS)

Choi, Min-Jae; Xiao, Ying; Hwang, Jang-Yeon; Belharouak, Ilias; Sun, Yang-Kook

2017-04-01

Silicon (Si)-based materials have attracted significant research as an outstanding candidate for the anode material of lithium-ion batteries. However, the tremendous volume change and poor electron conductivity of bulk silicon result in inferior capacity retention and low Coulombic efficiency. Designing special Si with high energy density and good stability in a bulk electrode remains a significant challenge. In this work, we introduce an ingenious strategy to modify micro silicon by designing a porous structure, constructing nanoparticle blocks, and introducing carbon nanotubes as wedges. A disproportion reaction, coupled with a chemical etching process and a ball-milling reaction, are applied to generate the desired material. The as-prepared micro silicon material features porosity, small primary particles, and effective CNT-wedging, which combine to endow the resultant anode with a high reversible specific capacity of up to 2028.6 mAh g-1 after 100 cycles and excellent rate capability. The superior electrochemical performance is attributed to the unique architecture and optimized composition.

Aging behavior of lithium iron phosphate based 18650-type cells studied by in situ neutron diffraction

NASA Astrophysics Data System (ADS)

Paul, Neelima; Wandt, Johannes; Seidlmayer, Stefan; Schebesta, Sebastian; Mühlbauer, Martin J.; Dolotko, Oleksandr; Gasteiger, Hubert A.; Gilles, Ralph

2017-03-01

The aging behavior of commercially produced 18650-type Li-ion cells consisting of a lithium iron phosphate (LFP) based cathode and a graphite anode based on either mesocarbon microbeads (MCMB) or needle coke (NC) is studied by in situ neutron diffraction and standard electrochemical techniques. While the MCMB cells showed an excellent cycle life with only 8% relative capacity loss (i.e., referenced to the capacity after formation) after 4750 cycles and showed no capacity loss on storage for two years, the needle coke cells suffered a 23% relative capacity loss after cycling and a 11% loss after storage. Based on a combination of neutron diffraction and electrochemical characterization, it is shown that the entire capacity loss for both cell types is dominated by the loss of active lithium; no other aging mechanisms like structural degradation of anode or cathode active materials or deactivation of active material could be found, highlighting the high structural stability of the active material and the excellent quality of the investigated cells.

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.

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.

Pyrite (FeS2) nanocrystals as inexpensive high-performance lithium-ion cathode and sodium-ion anode materials

NASA Astrophysics Data System (ADS)

Walter, Marc; Zünd, Tanja; Kovalenko, Maksym V.

2015-05-01

In light of the impeding depletion of fossil fuels and necessity to lower carbon dioxide emissions, economically viable high-performance batteries are urgently needed for numerous applications ranging from electric cars to stationary large-scale electricity storage. Due to its low raw material cost, non-toxicity and potentially high charge-storage capacity pyrite (FeS2) is a highly promising material for such next-generation batteries. In this work we present the electrochemical performance of FeS2 nanocrystals (NCs) as lithium-ion and sodium-ion storage materials. First, we show that nanoscopic FeS2 is a promising lithium-ion cathode material, delivering a capacity of 715 mA h g-1 and average energy density of 1237 Wh kg-1 for 100 cycles, twice higher than for commonly used LiCoO2 cathodes. Then we demonstrate, for the first time, that FeS2 NCs can serve as highly reversible sodium-ion anode material with long cycling life. As sodium-ion anode material, FeS2 NCs provide capacities above 500 mA h g-1 for 400 cycles at a current rate of 1000 mA g-1. In all our tests and control experiments, the performance of chemically synthesized nanoscale FeS2 clearly surpasses bulk FeS2 as well as large number of other nanostructured metal sulfides.In light of the impeding depletion of fossil fuels and necessity to lower carbon dioxide emissions, economically viable high-performance batteries are urgently needed for numerous applications ranging from electric cars to stationary large-scale electricity storage. Due to its low raw material cost, non-toxicity and potentially high charge-storage capacity pyrite (FeS2) is a highly promising material for such next-generation batteries. In this work we present the electrochemical performance of FeS2 nanocrystals (NCs) as lithium-ion and sodium-ion storage materials. First, we show that nanoscopic FeS2 is a promising lithium-ion cathode material, delivering a capacity of 715 mA h g-1 and average energy density of 1237 Wh kg-1 for 100 cycles, twice higher than for commonly used LiCoO2 cathodes. Then we demonstrate, for the first time, that FeS2 NCs can serve as highly reversible sodium-ion anode material with long cycling life. As sodium-ion anode material, FeS2 NCs provide capacities above 500 mA h g-1 for 400 cycles at a current rate of 1000 mA g-1. In all our tests and control experiments, the performance of chemically synthesized nanoscale FeS2 clearly surpasses bulk FeS2 as well as large number of other nanostructured metal sulfides. Electronic supplementary information (ESI) available: Materials and methods, additional structural and electrochemical characterization. See DOI: 10.1039/c5nr00398a

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.

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

Sn4+x P3 @ amorphous Sn-P composites as anodes for sodium-ion batteries with low cost, high capacity, long life, and superior rate capability.

PubMed

Li, Weijie; Chou, Shu-Lei; Wang, Jia-Zhao; Kim, Jung Ho; Liu, Hua-Kun; Dou, Shi-Xue

2014-06-25

Sn4+x P3 @ amorphous Sn-P composites are a promising cheap anode material for sodium-ion batteries with high capacity (502 mA h g(-1) at a current density of 100 mA g(-1)), long cycling stability (92.6% capacity retention up to 100 cycles), and high rate capability (165 mA h g(-1) at the 10C rate). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

A siloxane-incorporated copolymer as an in situ cross-linkable binder for high performance silicon anodes in Li-ion batteries

NASA Astrophysics Data System (ADS)

Jeena, M. T.; Bok, Taesoo; Kim, Si Hoon; Park, Sooham; Kim, Ju-Young; Park, Soojin; Ryu, Ja-Hyoung

2016-04-01

The electrochemical performance of Li-ion batteries (LIBs) can be highly tuned by various factors including the morphology of the anode material, the nature of the electrolyte, the binding material, and the percentage of conducting materials. Binding materials have been of particular interest to researchers over the decades as a means to further improve the cycle durability and columbic efficiency of LIBs. Such approaches include the introduction of different polymeric binders such as poly(acrylic acid) (PAA), carboxymethyl cellulose (CMC), and alginic acid (Alg) into the Si anode of LIBs. To achieve a better efficiency of LIBs, herein, we introduce a novel copolymer, poly(tert-butyl acrylate-co-triethoxyvinylsilane) (TBA-TEVS), as an efficient binder with stable cycle retention and excellent specific capacity. The binder forms a highly interconnected three-dimensional network upon thermal treatment as a result of de-protection of the tert-butyl group and the consequent inter-intra condensation reaction, which minimizes pulverization of the Si nanoparticles. Moreover, the siloxane group is expected to promote the formation of stable solid-electrolyte-interface (SEI) layers. A series of random copolymers were synthesized by varying the molar ratio of tert-butyl acrylate and triethoxyvinylsilane. Twenty-one percent of TEVS in the TBS-TEVS copolymer gave rise to a superior performance as a binder for Si anodes, where the anodes showed a stable specific capacity of 2551 mA h g-1 over hundreds of cycles and an initial columbic efficiency (ICE) of 81.8%.The electrochemical performance of Li-ion batteries (LIBs) can be highly tuned by various factors including the morphology of the anode material, the nature of the electrolyte, the binding material, and the percentage of conducting materials. Binding materials have been of particular interest to researchers over the decades as a means to further improve the cycle durability and columbic efficiency of LIBs. Such approaches include the introduction of different polymeric binders such as poly(acrylic acid) (PAA), carboxymethyl cellulose (CMC), and alginic acid (Alg) into the Si anode of LIBs. To achieve a better efficiency of LIBs, herein, we introduce a novel copolymer, poly(tert-butyl acrylate-co-triethoxyvinylsilane) (TBA-TEVS), as an efficient binder with stable cycle retention and excellent specific capacity. The binder forms a highly interconnected three-dimensional network upon thermal treatment as a result of de-protection of the tert-butyl group and the consequent inter-intra condensation reaction, which minimizes pulverization of the Si nanoparticles. Moreover, the siloxane group is expected to promote the formation of stable solid-electrolyte-interface (SEI) layers. A series of random copolymers were synthesized by varying the molar ratio of tert-butyl acrylate and triethoxyvinylsilane. Twenty-one percent of TEVS in the TBS-TEVS copolymer gave rise to a superior performance as a binder for Si anodes, where the anodes showed a stable specific capacity of 2551 mA h g-1 over hundreds of cycles and an initial columbic efficiency (ICE) of 81.8%. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr01559j

Particulate inverse opal carbon electrodes for lithium-ion batteries.

PubMed

Kang, Da-Young; Kim, Sang-Ok; Chae, Yu Jin; Lee, Joong Kee; Moon, Jun Hyuk

2013-01-29

Inverse opal carbon materials were used as anodes for lithium ion batteries. We applied particulate inverse opal structures and their dispersion in the formation of anode electrodes via solution casting. We prepared aminophenyl-grafted inverse opal carbons (a-IOC), inverse opal carbons with mesopores (mIOC), and bare inverse opal carbons (IOC) and investigated the electrochemical behavior of these samples as anode materials. Surface modification by aminophenyl groups was confirmed by XPS measurements. TEM images showed mesopores, and the specific area of mIOC was compared with that of IOC using BET analysis. A half-cell test was performed to compare a-IOC with IOC and mIOC with IOC. In the case of the a-IOC structure, the cell test revealed no improvement in the reversible specific capacity or the cycle performance. The mIOC cell showed a reversible specific capacity of 432 mAh/g, and the capacity was maintained at 88%-approximately 380 mAh/g-over 20 cycles.

Novel iron oxide nanotube arrays as high-performance anodes for lithium ion batteries

NASA Astrophysics Data System (ADS)

Zhong, Yuan; Fan, Huiqing; Chang, Ling; Shao, Haibo; Wang, Jianming; Zhang, Jianqing; Cao, Chu-nan

2015-11-01

Nanostructured iron oxides can be promising anode materials for lithium ion batteries (LIBs). However, improvement on the rate capability and/or electrochemical cycling stability of iron oxide anode materials remains a key challenge because of their poor electrical conductivities and large volume expansion during cycling. Herein, the vertically aligned arrays of one-dimensional (1D) iron oxide nanotubes with 5.8 wt% carbon have been fabricated by a novel surfactant-free self-corrosion process and subsequent thermal treatment. The as-fabricated nanotube array electrode delivers a reversible capacity of 932 mAh g-1 after 50 charge-discharge cycles at a current of 0.6 A g-1. The electrode still shows a reversible capacity of 610 mAh g-1 even at a very high rate (8.0 A g-1), demonstrating its prominent rate capability. Furthermore, the nanotube array electrode also exhibits the excellent electrochemical cycling stability with a reversible capacity of 880 mAh g-1 after 500 cycles at a current of 4 A g-1. The nanotube array electrode with superior lithium storage performance reveals the promising potential as a high-performance anode for LIBs.

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

Gu, Meng; He, Yang; Zheng, Jianming

Silicon (Si), associated with its natural abundance, low discharge voltage vs. Li/Li+, and extremely high theoretical discharge capacity (~ 4200 mAh g-1,), has been extensively explored as anode for lithium ion battery. One of the key challenges for using Si as anode is the large volume change upon lithiation and delithiation, which causes a fast capacity fading. Over the last few years, dramatic progress has been made for addressing this issue. In this paper, we summarize the progress towards tailoring of Si as anode for lithium ion battery. The paper is organized such that it covers the fundamentals, the promisemore » offered based on nanoscale designing, and the remaining challenges that need to be attacked to allow using of Si based materials as anode for battery.« less

Monodisperse Porous Silicon Spheres as Anode Materials for Lithium Ion Batteries

NASA Astrophysics Data System (ADS)

Wang, Wei; Favors, Zachary; Ionescu, Robert; Ye, Rachel; Bay, Hamed Hosseini; Ozkan, Mihrimah; Ozkan, Cengiz S.

2015-03-01

Highly monodisperse porous silicon nanospheres (MPSSs) are synthesized via a simple and scalable hydrolysis process with subsequent surface-protected magnesiothermic reduction. The spherical nature of the MPSSs allows for a homogenous stress-strain distribution within the structure during lithiation and delithiation, which dramatically improves the electrochemical stability. To fully extract the real performance of the MPSSs, carbon nanotubes (CNTs) were added to enhance the electronic conductivity within the composite electrode structure, which has been verified to be an effective way to improve the rate and cycling performance of anodes based on nano-Si. The Li-ion battery (LIB) anodes based on MPSSs demonstrate a high reversible capacity of 3105 mAh g-1. In particular, reversible Li storage capacities above 1500 mAh g-1 were maintained after 500 cycles at a high rate of C/2. We believe this innovative approach for synthesizing porous Si-based LIB anode materials by using surface-protected magnesiothermic reduction can be readily applied to other types of SiOx nano/microstructures.

Atom-Level Understanding of the Sodiation Process in Silicon Anode Material.

PubMed

Jung, Sung Chul; Jung, Dae Soo; Choi, Jang Wook; Han, Young-Kyu

2014-04-03

Despite the exceptionally large capacities in Li ion batteries, Si has been considered inappropriate for applications in Na ion batteries. We report an atomic-level study on the applicability of a Si anode in Na ion batteries using ab initio molecular dynamics simulations. While crystalline Si is not suitable for alloying with Na atoms, amorphous Si can accommodate 0.76 Na atoms per Si atom, corresponding to a specific capacity of 725 mA h g(-1). Bader charge analyses reveal that the sodiation of an amorphous Si electrode continues until before the local Na-rich clusters containing neutral Na atoms are formed. The amorphous Na0.76Si phase undergoes a volume expansion of 114% and shows a Na diffusivity of 7 × 10(-10) cm(2) s(-1) at room temperature. Overall, the amorphous Si phase turns out quite attractive in performance compared to other alloy-type anode materials. This work suggests that amorphous Si might be a competitive candidate for Na ion battery anodes.

Monodisperse porous silicon spheres as anode materials for lithium ion batteries.

PubMed

Wang, Wei; Favors, Zachary; Ionescu, Robert; Ye, Rachel; Bay, Hamed Hosseini; Ozkan, Mihrimah; Ozkan, Cengiz S

2015-03-05

Highly monodisperse porous silicon nanospheres (MPSSs) are synthesized via a simple and scalable hydrolysis process with subsequent surface-protected magnesiothermic reduction. The spherical nature of the MPSSs allows for a homogenous stress-strain distribution within the structure during lithiation and delithiation, which dramatically improves the electrochemical stability. To fully extract the real performance of the MPSSs, carbon nanotubes (CNTs) were added to enhance the electronic conductivity within the composite electrode structure, which has been verified to be an effective way to improve the rate and cycling performance of anodes based on nano-Si. The Li-ion battery (LIB) anodes based on MPSSs demonstrate a high reversible capacity of 3105 mAh g(-1). In particular, reversible Li storage capacities above 1500 mAh g(-1) were maintained after 500 cycles at a high rate of C/2. We believe this innovative approach for synthesizing porous Si-based LIB anode materials by using surface-protected magnesiothermic reduction can be readily applied to other types of SiOx nano/microstructures.

Potassium vanadate K0.23V2O5 as anode materials for lithium-ion and potassium-ion batteries

NASA Astrophysics Data System (ADS)

Liu, Cailing; Luo, Shaohua; Huang, Hongbo; Wang, Zhiyuan; Wang, Qing; Zhang, Yahui; Liu, Yanguo; Zhai, Yuchun; Wang, Zhaowen

2018-06-01

A layered potassium vanadate K0.23V2O5 has been successfully prepared by the hydrothermal method and evaluated as an anode material for lithium-ion and potassium-ion batteries. High structural stability is demonstrated by the ex situ X-ray diffraction (XRD) and ex situ scanning electron microscopy (SEM). When used as an anode material for lithium-ion batteries, the K0.23V2O5 exhibits a reversible capacity of 480.4 mAh g-1 at 20 mA g-1 after 100 cycles and 439.7 mAh g-1 at 200 mA g-1 after 300 cycles as well as good cycling stability. Even at a high current density of 800 mA g-1, a high reversible capacity of 202.5 mAh g-1 can be retained, indicating excellent rate performance. Whereas in potassium-ion batteries, it retains a capacity of 121.6 mAh g-1 after 150 cycles at 20 mA g-1 and 97.6 mAh g-1 at 100 mA g-1 after 100 cycles. Such superior electrochemical performance of K0.23V2O5 can be ascribed to the special flower-like morphology and structure. Overall, the results highlight the great potential of K0.23V2O5 as an anode material for both lithium-ion and potassium-ion batteries.

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

Chemical bonding between antimony and ionic liquid-derived nitrogen-doped carbon for sodium-ion battery anode

NASA Astrophysics Data System (ADS)

Xu, Xin; Si, Ling; Zhou, Xiaosi; Tu, Fengzhang; Zhu, Xiaoshu; Bao, Jianchun

2017-05-01

Antimony has received a great deal of attention as a promising anode material for sodium-ion batteries (SIBs) due to its high theoretical capacity of 660 mAh g-1. However, this application is significantly hampered by inherent large volume change and sluggish kinetics. To address these issues, an antimony-cyano-based ionic liquid-derived nitrogen-doped carbon (Sbsbnd CNC) hybrid is proposed and synthesized by ball-milling and subsequent pyrolysis treatment. As an anode material for SIBs, the as-synthesized Sbsbnd CNC hybrid delivers reversible capacities of 475 mAh g-1 at a current density of 100 mA g-1 and 203 mAh g-1 at 5000 mA g-1, and a 92.4% capacity retention based on the first-cycle capacity after 150 cycles at 100 mA g-1. Using ex situ X-ray photoelectron spectroscopy and elemental mapping techniques, we attribute the good structural integrity to the formation of Sbsbnd Nsbnd C bonds between Sb and the cyano-based ionic liquid-derived N-doped carbon matrix. Moreover, the presence of N-doped carbon network in the hybrid material serves as a robust protective cover and an electrical highway, buffering the substantial volume expansion of Sb nanoparticles and ensuring the fast electron transport for stable cycling operation.

Self-Supported CoP Nanorod Arrays Grafted on Stainless Steel as an Advanced Integrated Anode for Stable and Long-Life Lithium-Ion Batteries.

PubMed

Xu, Xijun; Liu, Jun; Hu, Renzong; Liu, Jiangwen; Ouyang, Liuzhang; Zhu, Min

2017-04-19

To alleviate the capacity degradation of anode materials for Li-ion batteries, caused by serious volume expansion and particle aggregation, intensive attention has been devoted to the rational design and fabrication of novel anode architectures. Herein, self-supported CoP nanorod arrays have been facilely synthesized using hydrothemally deposited Co(CO 3 ) 0.5 (OH)⋅0.11 H 2 O nanorod arrays as the precursor, through a gas-phase phosphidation method. As the anode for Li-ion batteries, such 3D interconnected CoP nanorod arrays show an initial discharge capacity of 1067 mAh g -1 and a high reversible charge capacity of 737 mAh g -1 at 0.4 Ag -1 . After 400 cycles, their specific capacity can reach 510 mAh g -1 ; even after 900 cycles, they can still deliver a specific capacity of 390 mAh g -1 . CoP//LiCoO 2 full-cells also exhibit a high reversible capacity of 400 mAh g -1 after 50 cycles. These unique 3D interconnected CoP nanorod arrays also show ultrastable cycling performance over 500 cycles when used as the anode in a Na-ion battery. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Magnesium Hydride Nanoparticles Self-Assembled on Graphene as Anode Material for High-Performance Lithium-Ion Batteries.

PubMed

Zhang, Baoping; Xia, Guanglin; Sun, Dalin; Fang, Fang; Yu, Xuebin

2018-04-24

MgH 2 nanoparticles (NPs) uniformly anchored on graphene (GR) are fabricated based on a bottom-up self-assembly strategy as anode materials for lithium-ion batteries (LIBs). Monodisperse MgH 2 NPs with an average particle size of ∼13.8 nm are self-assembled on the flexible GR, forming interleaved MgH 2 /GR (GMH) composite architectures. Such nanoarchitecture could effectively constrain the aggregation of active materials, buffer the strain of volume changes, and facilitate the electron/lithium ion transfer of the whole electrode, leading to a significant enhancement of the lithium storage capacity of the GMH composite. Furthermore, the performances of GMH composite as anode materials for LIBs are enabled largely through robust interfacial interactions with poly(methyl methacrylate) (PMMA) binder, which plays multifunctional roles in forming a favorable solid-electrolyte interphase (SEI) film, alleviating the volume expansion and detachment of active materials, and maintaining the structural integrity of the whole electrode. As a result, these synergistic effects endow the obtained GMH composite with a significantly enhanced reversible capacity and cyclability as well as a good rate capability. The GMH composite with 50 wt % MgH 2 delivers a high reversible capacity of 946 mA h g -1 at 100 mA g -1 after 100 cycles and a capacity of 395 mAh g -1 at a high current density of 2000 mA g -1 after 1000 cycles.

A confined "microreactor" synthesis strategy to three dimensional nitrogen-doped graphene for high-performance sodium ion battery anodes

NASA Astrophysics Data System (ADS)

Li, Jiajie; Zhang, Yumin; Gao, Tangling; Han, Jiecai; Wang, Xianjie; Hultman, Benjamin; Xu, Ping; Zhang, Zhihua; Wu, Gang; Song, Bo

2018-02-01

In virtue of abundant sodium resources, sodium ion batteries (SIBs) have been regarded as one of the most promising alternatives for large-scale energy storage applications. However, the absence of a suitable anode material makes it difficult to realize these applications. Here, we demonstrate an effective synthesis strategy of using a "microreactor" consisting of melamine fiber (inside) and graphene oxide (GO, outside) to fabricate three dimensional (3D) nitrogen doped (N-doped) graphene as high-performance anode materials for sodium ion batteries. Through a controlled pyrolysis, the inside melamine fiber and the outside GO layer has been converted into N-doped graphene and reduced graphene oxide (r-GO) respectively, and thus the "microreactor" is transformed into interconnected 3D N-doped graphene structures. Such highly desired 3D graphene structures show reversible sodium storage capacities up to ∼305 mA h g-1 after 500 cycles at a current density of 0.2 A g-1 and promising long cycling stability with a stable capacity of ∼198 mA h g-1 at 5 A g-1 after 5000 cycles. The high capacity and superior durability in combination with the facile synthesis procedure of the 3D graphene structure make it a promising anode material for SIBs and other energy storage applications.

Facile synthesis of Fe4N/Fe2O3/Fe/porous N-doped carbon nanosheet as high-performance anode for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Zhang, Dan; Li, Guangshe; Yu, Meijie; Fan, Jianming; Li, Baoyun; Li, Liping

2018-04-01

Iron nitrides are considered as highly promising anode materials for lithium-ion batteries because of their nontoxicity, high abundance, low cost, and higher electrical conductivity. Unfortunately, their limited synthesis routes are available and practical application is still hindered by their fast capacity decay. Herein, a facile and green route is developed to synthesize Fe4N/Fe2O3/Fe/porous N-doped carbon nanosheet composite. The size of Fe4N/Fe2O3/Fe particles is small (10-40 nm) and they are confined in porous N-doped carbon nanosheet. These features are conducive to accommodate volume change well, shorten the diffusion distance and further elevate electrical conductivity. When tested as anode material for lithium-ion batteries, a high discharge capacity of 554 mA h g-1 after 100 cycles at 100 mA g-1 and 389 mA h g-1 after 300 cycles at 1000 mA g-1 are retained. Even at 2000 mA g-1, a high capacity of 330 mA h g-1 can be achieved, demonstrating superior cycling stability and rate performance. New prospects will be brought by this work for the synthesis and the potential application of iron nitrides materials as an anode for LIBs.

Inward Lithium-Ion Breathing of Hierarchically Porous Silicon Anodes

DOE PAGES

Xiao, Qiangfeng; Gu, Meng; Yang, Hui; ...

2015-11-05

Silicon has been identified as one of the most promising candidates as anode for high performance lithium-ion batteries. The key challenge for Si anodes is the large volume change induced chemomechanical fracture and subsequent rapid capacity fading upon cyclic charge and discharge. Improving capacity retention thus critically relies on smart accommodation of the volume changes through nanoscale structural design. In this work, we report a novel fabrication method for hierarchically porous Si nanospheres (hp-SiNSs), which consist of a porous shell and a hollow core. Upon charge/discharge cycling, the hp-SiNSs accommodate the volume change through reversible inward expansion/contraction with negligible particle-levelmore » outward expansion. Our mechanics analysis revealed that such a unique volume-change accommodation mechanism is enabled by the much stiffer modulus of the lithiated layer than the unlithiated porous layer and the low flow stress of the porous structure. Such inward expansion shields the hp-SiNSs from fracture, opposite to the outward expansion in solid Si during lithiation. Lithium ion battery assembled with this new nanoporous material exhibits high capacity, high power, long cycle life and high coulombic efficiency, which is superior to the current commercial Si-based anode materials. We find the low cost synthesis approach reported here provides a new avenue for the rational design of hierarchically porous structures with unique materials properties.« less

Enabling High Energy Density Li-Ion Batteries through Li{sub 2}O Activation.

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

Abouimrane, Ali; Cui, Yanjie; Chen, Zonghai

2016-09-01

Lithium oxide (Li2O) is activated in the presence of a layered composite cathode material (HEM) significantly increasing the energy density of lithium-ion batteries. The degree of activation depends on the current rate, electrolyte salt, and anode type. In full-cell tests, the Li2O was used as a lithium source to counter the first-cycle irreversibility of high-capacity composite alloy anodes. When Li2O is mixed with HEM to serve as a cathode, the electrochemical performance was improved in a full cell having an SiO-SnCoC composite as an anode. The mechanism behind the Li2O activation could also explain the first charge plateau and themore » abnormal high capacity associated with these high energy cathode materials.« less

Sn-Based Nanocomposite for Li-Ion Battery Anode with High Energy Density, Rate Capability, and Reversibility.

PubMed

Park, Min-Gu; Lee, Dong-Hun; Jung, Heechul; Choi, Jeong-Hee; Park, Cheol-Min

2018-03-27

To design an easily manufactured, large energy density, highly reversible, and fast rate-capable Li-ion battery (LIB) anode, Co-Sn intermetallics (CoSn 2 , CoSn, and Co 3 Sn 2 ) were synthesized, and their potential as anode materials for LIBs was investigated. Based on their electrochemical performances, CoSn 2 was selected, and its C-modified nanocomposite (CoSn 2 /C) as well as Ti- and C-modified nanocomposite (CoSn 2 / a-TiC/C) was straightforwardly prepared. Interestingly, the CoSn 2 , CoSn 2 /C, and CoSn 2 / a-TiC/C showed conversion/nonrecombination, conversion/partial recombination, and conversion/full recombination during Li insertion/extraction, respectively, which were thoroughly investigated using ex situ X-ray diffraction and extended X-ray absorption fine structure analyses. As a result of the interesting conversion/full recombination mechanism, the easily manufactured CoSn 2 / a-TiC/C nanocomposite for the Sn-based Li-ion battery anode showed large energy density (first reversible capacity of 1399 mAh cm -3 ), high reversibility (first Coulombic efficiency of 83.2%), long cycling behavior (100% capacity retention after 180 cycles), and fast rate capability (appoximately 1110 mAh cm -3 at 3 C rate). In addition, degradation/enhancement mechanisms for high-capacity and high-performance Li-alloy-based anode materials for next-generation LIBs were also suggested.

Electrochemistry and safety of Li 4Ti 5O 12 and graphite anodes paired with LiMn 2O 4 for hybrid electric vehicle Li-ion battery applications

NASA Astrophysics Data System (ADS)

Belharouak, Ilias; Koenig, Gary M.; Amine, K.

A promising anode material for hybrid electric vehicles (HEVs) is Li 4Ti 5O 12 (LTO). LTO intercalates lithium at a voltage of ∼1.5 V relative to lithium metal, and thus this material has a lower energy compared to a graphite anode for a given cathode material. However, LTO has promising safety and cycle life characteristics relative to graphite anodes. Herein, we describe electrochemical and safety characterizations of LTO and graphite anodes paired with LiMn 2O 4 cathodes in pouch cells. The LTO anode outperformed graphite with regards to capacity retention on extended cycling, pulsing impedance, and calendar life and was found to be more stable to thermal abuse from analysis of gases generated at elevated temperatures and calorimetric data. The safety, calendar life, and pulsing performance of LTO make it an attractive alternative to graphite for high power automotive applications, in particular when paired with LiMn 2O 4 cathode materials.

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.

Nitrogen-doped carbon coated MnO nanopeapods as superior anode materials for lithium ion batteries

NASA Astrophysics Data System (ADS)

Ding, Yu; Chen, Lihui; Pan, Pei; Du, Jun; Fu, Zhengbing; Qin, Caiqin; Wang, Feng

2017-11-01

High performance nitrogen-doped carbon (NC) materials decorated with MnO hybrid (MnO@NC) composites with a nanopeapod appearance were synthesized by with a simple hydrothermal method and insuit-polymeric route. As an anode material for lithium ion batteries (LIBs), the nanopeapod structure of MnO@NC composites with internal void spaces exhibits good rate capability, high conductivity and excellent cycling stability. After 200 cycles, the nanopeapod composites yield a specific capacity of 775.4 mAh g-1 at 100 mA g-1 and a high-rate capacity of 559.7 mAh g-1 at 1000 mA g-1. The proposed synthesis of nanopeapod structure composites with an internal room is an efficient design with excellent electrode materials for rechargeable LIBs.

Engineering three-dimensionally electrodeposited Si-on-Ni inverse opal structure for high volumetric capacity Li-ion microbattery anode.

PubMed

Liu, Hao; Cho, Hyung-Man; Meng, Ying Shirley; Li, Quan

2014-06-25

Aiming at improving the volumetric capacity of nanostructured Li-ion battery anode, an electrodeposited Si-on-Ni inverse opal structure has been proposed in the present work. This type of electrode provides three-dimensional bi-continuous pathways for ion/electron transport and high surface area-to-volume ratios, and thus exhibits lower interfacial resistance, but higher effective Li ions diffusion coefficients, when compared to the Si-on-Ni nanocable array electrode of the same active material mass. As a result, improved volumetric capacities and rate capabilities have been demonstrated in the Si-on-Ni inverse opal anode. We also show that optimization of the volumetric capacities and the rate performance of the inverse opal electrode can be realized by manipulating the pore size of the Ni scaffold and the thickness of the Si deposit.

Tin phosphide-based anodes for sodium-ion batteries: synthesis via solvothermal transformation of Sn metal and phase-dependent Na storage performance

PubMed Central

Shin, Hyun-Seop; Jung, Kyu-Nam; Jo, Yong Nam; Park, Min-Sik; Kim, Hansung; Lee, Jong-Won

2016-01-01

There is a great deal of current interest in the development of rechargeable sodium (Na)-ion batteries (SIBs) for low-cost, large-scale stationary energy storage systems. For the commercial success of this technology, significant progress should be made in developing robust anode (negative electrode) materials with high capacity and long cycle life. Sn-P compounds are considered promising anode materials that have considerable potential to meet the required performance of SIBs, and they have been typically prepared by high-energy mechanical milling. Here, we report Sn-P-based anodes synthesised through solvothermal transformation of Sn metal and their electrochemical Na storage properties. The temperature and time period used for solvothermal treatment play a crucial role in determining the phase, microstructure, and composition of the Sn-P compound and thus its electrochemical performance. The Sn-P compound prepared under an optimised solvothermal condition shows excellent electrochemical performance as an SIB anode, as evidenced by a high reversible capacity of ~560 mAh g−1 at a current density of 100 mA g−1 and cycling stability for 100 cycles. The solvothermal route provides an effective approach to synthesising Sn-P anodes with controlled phases and compositions, thus tailoring their Na storage behaviour. PMID:27189834

Tailored Organic Electrode Material Compatible with Sulfide Electrolyte for Stable All-Solid-State Sodium Batteries.

PubMed

Chi, Xiaowei; Liang, Yanliang; Hao, Fang; Zhang, Ye; Whiteley, Justin; Dong, Hui; Hu, Pu; Lee, Sehee; Yao, Yan

2018-03-01

All-solid-state sodium batteries (ASSSBs) with nonflammable electrolytes and ubiquitous sodium resource are a promising solution to the safety and cost concerns for lithium-ion batteries. However, the intrinsic mismatch between low anodic decomposition potential of superionic sulfide electrolytes and high operating potentials of sodium-ion cathodes leads to a volatile cathode-electrolyte interface and undesirable cell performance. Here we report a high-capacity organic cathode, Na 4 C 6 O 6 , that is chemically and electrochemically compatible with sulfide electrolytes. A bulk-type ASSSB shows high specific capacity (184 mAh g -1 ) and one of the highest specific energies (395 Wh kg -1 ) among intercalation compound-based ASSSBs. The capacity retentions of 76 % after 100 cycles at 0.1 C and 70 % after 400 cycles at 0.2 C represent the record stability for ASSSBs. Additionally, Na 4 C 6 O 6 functions as a capable anode material, enabling a symmetric all-organic ASSSB with Na 4 C 6 O 6 as both cathode and anode materials. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Disordered 3 D Multi-layer Graphene Anode Material from CO2 for Sodium-Ion Batteries.

PubMed

Smith, Kassiopeia; Parrish, Riley; Wei, Wei; Liu, Yuzi; Li, Tao; Hu, Yun Hang; Xiong, Hui

2016-06-22

We report the application of disordered 3 D multi-layer graphene, synthesized directly from CO2 gas through a reaction with Li at 550 °C, as an anode for Na-ion batteries (SIBs) toward a sustainable and greener future. The material exhibited a reversible capacity of ∼190 mA h g(-1) with a Coulombic efficiency of 98.5 % at a current density of 15 mA g(-1) . The discharge capacity at higher potentials (>0.2 V vs. Na/Na(+) ) is ascribed to Na-ion adsorption at defect sites, whereas the capacity at low potentials (<0.2 V) is ascribed to intercalation between graphene sheets through electrochemical characterization, Raman spectroscopy, and small-angle X-ray scattering experiments. The disordered multi-layer graphene electrode demonstrated a great rate capability and cyclability. This novel approach to synthesize disordered 3 D multi-layer graphene from CO2 gas makes it attractive not only as an anode material for SIBs but also to mitigate CO2 emission. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Operando Synchrotron Measurement of Strain Evolution in Individual Alloying Anode Particles within Lithium Batteries

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

Cortes, Francisco Javier Quintero; Boebinger, Matthew G.; Xu, Michael

Alloying anode materials offer high capacity for next-generation batteries, but the performance of these materials often decays rapidly with cycling because of volume changes and associated mechanical degradation or fracture. The direct measurement of crystallographic strain evolution in individual particles has not been reported, however, and this level of insight is critical for designing mechanically resilient materials. Here, we use operando X-ray diffraction to investigate strain evolution in individual germanium microparticles during electrochemical reaction with lithium. The diffraction peak was observed to shift in position and diminish in intensity during reaction because of the disappearance of the crystalline Ge phase.more » The compressive strain along the [111] direction was found to increase monotonically to a value of -0.21%. This finding is in agreement with a mechanical model that considers expansion and plastic deformation during reaction. This new insight into the mechanics of large-volume-change transformations in alloying anodes is important for improving the durability of high-capacity batteries.« less

Biphase-Interface Enhanced Sodium Storage and Accelerated Charge Transfer: Flower-Like Anatase/Bronze TiO2/C as an Advanced Anode Material for Na-Ion Batteries.

PubMed

Chu, Chenxiao; Yang, Jing; Zhang, Qianqian; Wang, Nana; Niu, Feier; Xu, Xuena; Yang, Jian; Fan, Weiliu; Qian, Yitai

2017-12-20

Flower-like assembly of ultrathin nanosheets composed of anatase and bronze TiO 2 embedded in carbon is successfully synthesized by a simple solvothermal reaction, followed with a high-temperature annealing. As an anode material in sodium-ion batteries, this composite exhibits outstanding electrochemical performances. It delivers a reversible capacity of 120 mA h g -1 over 6000 cycles at 10 C. Even at 100 C, there is still a capacity of 104 mA h g -1 . Besides carbon matrix and hierarchical structure, abundant interfaces between anatase and bronze greatly enhance the performance by offering additional sites for reversible Na + storage and improving the charge-transfer kinetics. The interface enhancements are confirmed by discharge/charge profiles, rate performances, electrochemical impedance spectra, and first-principle calculations. These results offer a new pathway to upgrade the performances of anode materials in sodium-ion batteries.

Preparation of a porous Sn@C nanocomposite as a high-performance anode material for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Zhang, Yanjun; Jiang, Li; Wang, Chunru

2015-07-01

A porous Sn@C nanocomposite was prepared via a facile hydrothermal method combined with a simple post-calcination process, using stannous octoate as the Sn source and glucose as the C source. The as-prepared Sn@C nanocomposite exhibited excellent electrochemical behavior with a high reversible capacity, long cycle life and good rate capability when used as an anode material for lithium ion batteries.A porous Sn@C nanocomposite was prepared via a facile hydrothermal method combined with a simple post-calcination process, using stannous octoate as the Sn source and glucose as the C source. The as-prepared Sn@C nanocomposite exhibited excellent electrochemical behavior with a high reversible capacity, long cycle life and good rate capability when used as an anode material for lithium ion batteries. Electronic supplementary information (ESI) available: Detailed experimental procedure and additional characterization, including a Raman spectrum, TGA curve, N2 adsorption-desorption isotherm, TEM images and SEM images. See DOI: 10.1039/c5nr03093e

Graphene--nanotube--iron hierarchical nanostructure as lithium ion battery anode.

PubMed

Lee, Si-Hwa; Sridhar, Vadahanambi; Jung, Jung-Hwan; Karthikeyan, Kaliyappan; Lee, Yun-Sung; Mukherjee, Rahul; Koratkar, Nikhil; Oh, Il-Kwon

2013-05-28

In this study, we report a novel route via microwave irradiation to synthesize a bio-inspired hierarchical graphene--nanotube--iron three-dimensional nanostructure as an anode material in lithium-ion batteries. The nanostructure comprises vertically aligned carbon nanotubes grown directly on graphene sheets along with shorter branches of carbon nanotubes stemming out from both the graphene sheets and the vertically aligned carbon nanotubes. This bio-inspired hierarchical structure provides a three-dimensional conductive network for efficient charge-transfer and prevents the agglomeration and restacking of the graphene sheets enabling Li-ions to have greater access to the electrode material. In addition, functional iron-oxide nanoparticles decorated within the three-dimensional hierarchical structure provides outstanding lithium storage characteristics, resulting in very high specific capacities. The anode material delivers a reversible capacity of ~1024 mA · h · g(-1) even after prolonged cycling along with a Coulombic efficiency in excess of 99%, which reflects the ability of the hierarchical network to prevent agglomeration of the iron-oxide nanoparticles.

Silicon Framework Allotropes for Li-ion and Na-ion Batteries: New Insight for a Reversible Capacity.

NASA Astrophysics Data System (ADS)

Marzouk, Asma; Soto, Fernando; Burgos, Juan; Balbuena, Perla; El-Mellouhi, Fadwa

Silicon has the capacity to host a large amount of Li which makes it an attractive anode material despite suffering from swelling problem leading to irreversible capacity loss. The possibility of an easy extraction of Na atoms from Si24Na4 inspired us to adopt the Si24 as an anode material for Lithium-ion and sodium-ion Batteries. Using DFT, we evaluate the specific capacity and the intercalation potential of Si24 allotrope. Enhanced capacities are sought by designing a new silicon allotrope. We demonstrated that these Si24 allotropes show a negligible volume expansion and conserve their periodic structures after the maximum insertion/disinsertion of the ions which is crucial to prevent the capacity loss during cycling. DFT and ab-initio molecular dynamics (AIMD) studies give insights on the most probable surface adsorption and reaction sites, lithiation and sodiation, as well as initial stages of SEI formation and ionic diffusion. Qatar National Research Fund (QNRF) (NPRP 7-162-2-077).

A new binder-free and conductive-additive-free TiO2/WO3-W integrative anode material produced by laser ablation

NASA Astrophysics Data System (ADS)

Su, Yibo; Zhang, Hongjun; Liang, Peng; Liu, Kai; Cai, Mingyong; Huang, Zeya; Wang, Chang-An; Zhong, Minlin

2018-02-01

Although transition metal oxides anodes have attracted lots of attention, there are still many problems to be resolved. Complicated fabrication process, high cost and poor electrochemical performances are the most important ones, together hindering transition metal oxides anodes for practical use. Herein, we provide a new approach to fabricate a binder-free and conductive-additive-free TiO2/WO3-W integrative anode material through the nanosecond laser ablation and dip-coating technology, which simplifies the entire anode preparation process with no need for a conventional tape-casting procedure. Using this method, great time cost, machine cost and labor cost related to mixing and tape-casting process can be saved on the basis of good electrochemical performances. The prepared TiO2/WO3-W integrative anode realizes a first Coulombic efficiency of 75.6% and attains to a stable capacity within the first five cycles. It can still maintain a capacity of 600 mAh g-1 in the range of 0.01-3 V vs. Li+/Li at a current rate of 0.2 C after 500 cycles. This work offers a new way to achieve a fast fabrication of the integrative anode for lithium ion battery, which is universal for other transition metals (such as Fe, Cu, Ni, Co, Mo, W etc.).

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).

An all-organic rechargeable battery using bipolar polyparaphenylene as a redox-active cathode and anode.

PubMed

Zhu, L M; Lei, A W; Cao, Y L; Ai, X P; Yang, H X

2013-01-21

An all-organic rechargeable battery is realized by use of polyparaphenylene as both cathode- and anode-active material. This new battery can operate at a high voltage of 3.0 V with fairly high capacity, offering a renewable and cheaper alternative to conventional batteries.

Nanostructured Black Phosphorus/Ketjenblack-Multiwalled Carbon Nanotubes Composite as High Performance Anode Material for Sodium-Ion Batteries.

PubMed

Xu, Gui-Liang; Chen, Zonghai; Zhong, Gui-Ming; Liu, Yuzi; Yang, Yong; Ma, Tianyuan; Ren, Yang; Zuo, Xiaobing; Wu, Xue-Hang; Zhang, Xiaoyi; Amine, Khalil

2016-06-08

Sodium-ion batteries are promising alternatives to lithium-ion batteries for large-scale applications. However, the low capacity and poor rate capability of existing anodes for sodium-ion batteries are bottlenecks for future developments. Here, we report a high performance nanostructured anode material for sodium-ion batteries that is fabricated by high energy ball milling to form black phosphorus/Ketjenblack-multiwalled carbon nanotubes (BPC) composite. With this strategy, the BPC composite with a high phosphorus content (70 wt %) could deliver a very high initial Coulombic efficiency (>90%) and high specific capacity with excellent cyclability at high rate of charge/discharge (∼1700 mAh g(-1) after 100 cycles at 1.3 A g(-1) based on the mass of P). In situ electrochemical impedance spectroscopy, synchrotron high energy X-ray diffraction, ex situ small/wide-angle X-ray scattering, high resolution transmission electronic microscopy, and nuclear magnetic resonance were further used to unravel its superior sodium storage performance. The scientific findings gained in this work are expected to serve as a guide for future design on high performance anode material for sodium-ion batteries.

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.

Sandwich-like C@SnO2/Sn/void@C hollow spheres as improved anode materials for lithium ion batteries

NASA Astrophysics Data System (ADS)

Wang, Huijun; Jiang, Xinya; Chai, Yaqin; Yang, Xia; Yuan, Ruo

2018-03-01

As lithium ion batteries (LIBs) anode, SnO2 suffers fast capacity fading due to its large volume expansion during discharge/charge process. To overcome the problem, sandwich-like C@SnO2/Sn/void@C hollow spheres (referred as C@SnO2/Sn/void@C HSs) are prepared by in-situ polymerization and carbonization, using hollow SnO2 as self-template and dopamine as carbon source. The C@SnO2/Sn/void@C HSs possesses the merits of hollow and core/void/shell structure, so that they can accommodate the volume change under discharge/charge process, shorten the transmission distance of Li ions, own more contact area for the electrolyte. Thanks to these advantages, C@SnO2/Sn/void@C HSs display excellent electrochemical performance as anode materials for LIBs, which deliver a high capacity of 786.7 mAh g-1 at the current density of 0.5 A g-1 after 60 cycles. The simple synthesis method for C@SnO2/Sn/void@C HSs with special structure will provide a promising method for preparing other anode materials for LIBs.

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.

Metallic borophene polytypes as lightweight anode materials for non-lithium-ion batteries.

PubMed

Xiang, Pan; Chen, Xianfei; Zhang, Wentao; Li, Junfeng; Xiao, Beibei; Li, Longshan; Deng, Kuisen

2017-09-20

Applications of rechargeable non-lithium-ion batteries (Na + , K + , Ca 2+ , Mg 2+ , and Al 3+ NLIBs) are significantly hampered by the deficiency of suitable electrode materials. Searching for anode materials with desirable electrochemical performance is urgent for the large-scale energy storage demands of next generation renewable energy technologies. In this study, three types of recently synthesized borophenes are predicted to serve as high-performing anodes for NLIBs based on density functional theory. All the borophenes considered here are metallic with favorable in-plane stiffness. Dirac fermions were identified in two types of borophenes, guaranteeing their high electron mobility. Moreover, borophene configuration-dependent metal-ion migration, theoretical capacities, and open-circuit voltages were demonstrated with respect to the different adsorption behaviors and atom mass densities of anode materials. Our results provide insights into the configuration-dependent electrode performance of borophene and the corresponding metal-ion storage mechanism.

Bundled and densified carbon nanotubes (CNT) fabrics as flexible ultra-light weight Li-ion battery anode current collectors

NASA Astrophysics Data System (ADS)

Yehezkel, Shani; Auinat, Mahmud; Sezin, Nina; Starosvetsky, David; Ein-Eli, Yair

2016-04-01

Carbon nanotubes (CNT) fabrics were studied and evaluated as anode current collectors, replacing the traditional copper foil current collector in Li-ion batteries. Glavanostatic measurements reveal high values of irreversible capacities (as high as 28%), resulted mainly from the formation of the solid electrolyte interphase (SEI) layer at the CNT fabric surface. Various pre-treatments to the CNT fabric prior to active anode material loading have shown that the lowest irreversible capacity is achieved by immersing and washing the CNT fabric with iso-propanol (IPA), which dramatically modified the fabric surface. Additionally, the use of very thin CNT fabrics (5 μm) results in a substantial irreversible capacity minimization. A combination of IPA rinse action and utilization of the thinnest CNT fabric provides the lowest irreversible capacity of 13%. The paper describes innovative and rather simple techniques towards a complete implementation of CNT fabric as an anode current collector in Li-ion batteries, instead of the relatively heavy and expensive copper foil, enabling an improvement in the gravimetric and volumetric energy densities of such advanced batteries.

Rapid, in Situ Synthesis of High Capacity Battery Anodes through High Temperature Radiation-Based Thermal Shock.

PubMed

Chen, Yanan; Li, Yiju; Wang, Yanbin; Fu, Kun; Danner, Valencia A; Dai, Jiaqi; Lacey, Steven D; Yao, Yonggang; Hu, Liangbing

2016-09-14

High capacity battery electrodes require nanosized components to avoid pulverization associated with volume changes during the charge-discharge process. Additionally, these nanosized electrodes need an electronically conductive matrix to facilitate electron transport. Here, for the first time, we report a rapid thermal shock process using high-temperature radiative heating to fabricate a conductive reduced graphene oxide (RGO) composite with silicon nanoparticles. Silicon (Si) particles on the order of a few micrometers are initially embedded in the RGO host and in situ transformed into 10-15 nm nanoparticles in less than a minute through radiative heating. The as-prepared composites of ultrafine Si nanoparticles embedded in a RGO matrix show great performance as a Li-ion battery (LIB) anode. The in situ nanoparticle synthesis method can also be adopted for other high capacity battery anode materials including tin (Sn) and aluminum (Al). This method for synthesizing high capacity anodes in a RGO matrix can be envisioned for roll-to-roll nanomanufacturing due to the ease and scalability of this high-temperature radiative heating process.

Superior Sodium Storage in 3D Interconnected Nitrogen and Oxygen Dual-Doped Carbon Network.

PubMed

Wang, Min; Yang, Zhenzhong; Li, Weihan; Gu, Lin; Yu, Yan

2016-05-01

Carbonaceous materials have attracted immense interest as anode materials for Na-ion batteries (NIBs) because of their good chemical, thermal stabilities, as well as high Na-storage capacity. However, the carbonaceous materials as anodes for NIBs still suffer from the lower rate capability and poor cycle life. An N,O-dual doped carbon (denoted as NOC) network is designed and synthesized, which is greatly favorable for sodium storage. It exhibits high specific capacity and ultralong cycling stability, delivering a capacity of 545 mAh g(-1) at 100 mA g(-1) after 100 cycles and retaining a capacity of 240 mAh g(-1) at 2 A g(-1) after 2000 cycles. The NOC composite with 3D well-defined porosity and N,O-dual doped induces active sites, contributing to the enhanced sodium storage. In addition, the NOC is synthesized through a facile solution process, which can be easily extended to the preparation of many other N,O-dual doped carbonaceous materials for wide applications in catalysis, energy storage, and solar cells. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanoporous TiNb2O7/C Composite Microspheres with Three-Dimensional Conductive Network for Long-Cycle-Life and High-Rate-Capability Anode Materials for Lithium-Ion Batteries.

PubMed

Zhu, Guozhen; Li, Qing; Zhao, Yunhao; Che, Renchao

2017-11-29

On the basis of the advantages of ideal cycling stability, high discharge voltage (1.65 V), and excellent reversibility, more and more attention has been focused on TiNb 2 O 7 (marked as TNO) as an anode material candidate for lithium-ion batteries. However, the poor electronic conductivity and low ionic diffusion rate intrinsically restrict its practical use. Herein, we first synthesize the TNO/C composite microspheres with three-dimensionally (marked as 3D) electro-conductive carbon network and abundant nanoporous structure by a simple spray-drying method. The microspheres are constructed by irregularly primary cubic nanoparticle units with size of 100-200 nm. The nanopores throughout the microspheres range from 1 to 50 nm. As an anode material, the prepared TNO/C composite microspheres demonstrate a prominent charge/discharge capacity of 323.2/326 mA h g -1 after 300 cycles at 0.25 C (1 C = 388 mA g -1 ) and 259.9/262.5 mA h g -1 after 1000 long cycles at a high current density of 5 C, revealing the ideal reversible capacity and long cycling life. Meanwhile, the TNO/C composite microspheres present ideal rate performance, showing the discharge capacity of 120 mA h g -1 at 30 C after 10 cycles. The super electrochemical performance could be attributed to the 3D electro-conductive carbon network and nanoporous structure. The nanopores facilitate the permeation of electrolyte into the intercontacting regions of the anode materials. Carbon layers disperse uniformly throughout the 3D microspheres, effectively improving the electrical conductivity of the electrode. Hence, the prepared TNO/C composite microspheres have great potential to be used as an anode material for lithium-ion batteries.

Amorphous MoS 3 Infiltrated with Carbon Nanotubes as an Advanced Anode Material of Sodium-Ion Batteries with Large Gravimetric, Areal, and Volumetric Capacities

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

Ye, Hualin; Wang, Lu; Deng, Shuo

The search for earth-abundant and high-performance electrode materials for sodium-ion batteries represents an important challenge to current battery research. 2D transition metal dichalcogenides, particularly MoS2, have attracted increasing attention recently, but few of them so far have been able to meet expectations. In this study, it is demonstrated that another phase of molybdenum sulfide—amorphous chain-like MoS3—can be a better choice as the anode material of sodium-ion batteries. Highly compact MoS3 particles infiltrated with carbon nanotubes are prepared via the facile acid precipitation method in ethylene glycol. Compared to crystalline MoS2, the resultant amorphous MoS3 not only exhibits impressive gravimetric performance—featuringmore » excellent specific capacity (≈615 mA h g-1), rate capability (235 mA h g-1 at 20 A g-1), and cycling stability but also shows exceptional volumetric capacity of ≈1000 mA h cm-3 and an areal capacity of >6.0 mA h cm-2 at very high areal loadings of active materials (up to 12 mg cm-2). The experimental results are supported by density functional theory simulations showing that the 1D chains of MoS3 can facilitate the adsorption and diffusion of Na+ ions. At last, it is demonstrated that the MoS3 anode can be paired with an Na3V2(PO4)3 cathode to afford full cells with great capacity and cycling performance.« less

Hydrothermal synthesis and potential applicability of rhombohedral siderite as a high-capacity anode material for lithium ion batteries

NASA Astrophysics Data System (ADS)

Zhao, Shiqiang; Yu, Yue; Wei, Shanshan; Wang, Yuxi; Zhao, Chenhao; Liu, Rui; Shen, Qiang

2014-05-01

Natural siderite is a valuable iron mineral composed of ferrous carbonate (FeCO3), which is commonly found in hydrothermal veins and contains no sulfur or phosphorus. In this paper, micro-sized FeCO3 crystallites are synthesized via a facile hydrothermal route, and almost all of them possess a rhombohedral shape similar to that of natural products. When applied as an anode material for lithium ion batteries, the synthetic siderite can deliver an initial specific discharge capacity of ∼1587 mAh g-1 with a coulombic efficiency of 68% at 200 mA g-1, remaining a reversible value of 1018 mAh g-1 over 120 cycles. Even at a high current density of 1000 mA g-1, after 120 cycles the residual specific capacity (812 mAh g-1) is still higher than the theoretical capacity of FeCO3 (463 mAh g-1). Moreover, a novel reversible conversion mechanism accounts for the excellent electrochemical performances of rhombohedral FeCO3 to a great extent, implying the potential applicability of synthetic siderite as lithium ion battery anodes.

Automotive assessment of carbon-silicon composite anodes and methods of fabrication

NASA Astrophysics Data System (ADS)

Karulkar, Mohan; Blaser, Rachel; Kudla, Bob

2015-01-01

To assess the potential of carbon silicon composite anodes for automotive applications, C-Si anodes were fabricated and certain improvements employed. The use of a PVDF buffer layer is demonstrated for the first time with a C-Si composite material. The buffer layer increases adhesion by 89%, and increases capacity by 50-80%. Also, a limited capacity range is employed to improve cycle life by up to 200%, and enable currents as high as 2 mA cm-1. The combined use of a buffer layer and limited capacity range has not been reported before. A model is also presented for comparing C-Si performance with real-world automotive targets from USABC, including energy density, power density, specific energy, and specific power. The analysis reveals a capacity penalty that arises from pairing C-Si with a traditional cathode (NCA), and which prevents the cell from meeting all targets. Scenarios are presented in which a higher-capacity cathode (250 mAh g-1) allows all targets to be hypothetically met.

Novel Co(OH)2 with cotton-like structure as anode material for alkaline secondary batteries

NASA Astrophysics Data System (ADS)

Zhao, W.; Liao, Y. L.; Qiu, S. J.; Chu, H. L.; Zou, Y. J.; Xiang, C. L.; Zhang, H. Z.; Xu, F.; Sun, L. X.

2018-01-01

The cotton-like Co(OH)2 (S-Co(OH)2) was successfully synthesized and its electrochemical performance was systematically investigated. S-Co(OH)2 was prepared through the “destruction” of the newly formed colloid Co(OH)2 by the reduction using sodium borohydride. The crystal structure and surface morphology were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectrometry (EDS). Used as an anode material for alkaline secondary batteries, S-Co(OH)2 sample exhibited better cycle stability, higher electrochemical capacity, and higher rate performance than those of conventional β-Co(OH)2. At a discharge current density of 100 mA/g, the initial discharge capacity of S-Co(OH)2 is 549.3 mAh/g and the discharge capacity is still sustained to be 329.2 mAh/g after 100 charge-discharge cycles with a capacity retention of 59.9%.

Graphene-Oxide-Assisted Synthesis of GaN Nanosheets as a New Anode Material for Lithium-Ion Battery.

PubMed

Sun, Changlong; Yang, Mingzhi; Wang, Tailin; Shao, Yongliang; Wu, Yongzhong; Hao, Xiaopeng

2017-08-16

As the most-studied III-nitride, theoretical researches have predicted the presence of gallium nitride (GaN) nanosheets (NSs). Herein, a facile synthesis approach is reported to prepare GaN NSs using graphene oxide (GO) as sacrificial template. As a new anode material of Li-ion battery (LIBs), GaN NSs anodes deliver the reversible discharge capacity above 600 mA h g -1 at 1.0 A g -1 after 1000 cycles, and excellent rate performance at current rates from 0.1 to 10 A g -1 . These results not only extend the family of 2D materials but also facilitate their use in energy storage and other applications.

Hybrid aerogel-derived Sn-Ni alloy immobilized within porous carbon/graphene dual matrices for high-performance lithium storage.

PubMed

Zhang, Hao; Zhang, Mengru; Zhang, Meiling; Zhang, Lin; Zhang, Anping; Zhou, Yiming; Wu, Ping; Tang, Yawen

2017-09-01

Nanoporous networks of tin-based alloys immobilized within carbon matrices possess unique structural and compositional superiorities toward lithium-storage, and are expected to manifest improved strain-accommodation and charge-transport capabilities and thus desirable anodic performance for advanced lithium-ion batteries (LIBs). Herein, a facile and scalable hybrid aerogel-derived thermal-autoreduction route has been developed for the construction of nanoporous network of SnNi alloy immobilized within carbon/graphene dual matrices (SnNi@C/G network). When applied as an anode material for LIBs, the SnNi@C/G network manifests desirable lithium-storage performances in terms of specific capacities, cycle life, and rate capability. The facile aerogel-derived route and desirable Li-storage performance of the SnNi@C/G network facilitate its practical application as a high-capacity, long-life, and high-rate anode material for advanced LIBs. Copyright © 2017 Elsevier Inc. All rights reserved.

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.

Synthesis and electrochemical performance of mesoporous SiO{sub 2}–carbon nanofibers composite as anode materials for lithium secondary batteries

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

Hyun, Yura; Choi, Jin-Yeong; Park, Heai-Ku

Highlights: • Mesoporous SiO{sub 2}–carbon nanofibers composite synthesized on Ni foam without any binder. • This composite was directly applied as anode material of Li secondary batteries. • Showed the highest initial (2420 mAh/g) and discharging (2092 mAh/g) capacity. • This material achieved a retention rate of 86.4% after 30 cycles. - Abstract: In this study, carbon nanofibers (CNFs) and mesoporous SiO{sub 2}–carbon nanofibers composite were synthesized and applied as the anode materials in lithium secondary batteries. CNFs and mesoporous SiO{sub 2}–CNFs composite were grown via chemical vapor deposition method with iron-copper catalysts. Mesoporous SiO{sub 2} materials were prepared bymore » sol–gel method using tetraethylorthosilicate as the silica source and cetyltrimethylammoniumchloride as the template. Ethylene was used as the carbon source and passes into a quartz reactor of a tube furnace heated to 600 °C, and the temperature was maintained at 600 °C for 10 min to synthesize CNFs and mesoporous SiO{sub 2}–CNFs composite. The electrochemical characteristics of the as-prepared CNFs and mesoporous SiO{sub 2}–CNFs composite as the anode of lithium secondary batteries were investigated using a three-electrode cell. In particular, the mesoporous SiO{sub 2}–CNFs composites synthesized without binder after depositing mesoporous SiO{sub 2} on Ni foam showed the highest charging and discharging capacity and retention rate. The initial capacity (2420 mAh/g) of mesoporous SiO{sub 2}–CNFs composites decreased to 2092 mAh/g after 30 cycles at a retention rate of 86.4%.« less

Facile fabrication of 3D porous MnO@GS/CNT architecture as advanced anode materials for high-performance lithium-ion battery.

PubMed

Wang, Junyong; Deng, Qinglin; Li, Mengjiao; Wu, Cong; Jiang, Kai; Hu, Zhigao; Chu, Junhao

2018-08-03

To overcome inferior rate capability and cycle stability of MnO-based anode materials for lithium-ion batteries (LIBs), we reported a novel 3D porous MnO@GS/CNT composite, consisting of MnO nanoparticles homogeneously distributed on the conductive interconnected framework based on 2D graphene sheets (GS) and 1D carbon nanotubes (CNTs). The distinctive architecture offers highly interpenetrated network along with efficient porous channels for fast electron transfer and ionic diffusion as well as abundant stress buffer space to accommodate the volume expansion of the MnO nanoparticles. The MnO@GS/CNT anode exhibits an ultrahigh capacity of 1115 mAh g -1 at 0.2 A g -1 after 150 cycles and outstanding rate capacity of 306 mAh g -1 at 10.0 A g -1 . Moreover, a stable capacity of 405 mAh g -1 after 3200 cycles can still be achieved, even at a large current density of 5.0 A g -1 . When coupled with LiMn 2 O 4 (LMO) cathode, the LMO [Formula: see text] MnO@GS/CNT full cell characterizes an excellent cycling stability and rate capability, indicating the promising application of MnO@GS/CNT anode in the next-generation LIBs.

Carbon Cryogel and Carbon Paper-Based Silicon Composite Anode Materials for Lithium-Ion Batteries

NASA Technical Reports Server (NTRS)

Woodworth, James; Baldwin, Richard; Bennett, William

2010-01-01

A variety of materials are under investigation for use as anode materials in lithium-ion batteries, of which, the most promising are those containing silicon. 6 One such material is a composite formed via the dispersion of silicon in a resorcinol-formaldehyde (RF) gel followed by pyrolysis. Two silicon-carbon composite materials, carbon microspheres and nanofoams produced from nano-phase silicon impregnated RF gel precursors have been synthesized and investigated. Carbon microspheres are produced by forming the silicon-containing RF gel into microspheres whereas carbon nano-foams are produced by impregnating carbon fiber paper with the silicon containing RF gel to create a free standing electrode. 1-5 Both materials have demonstrated their ability to function as anodes and utilize the silicon present in the material. Stable reversible capacities above 400 mAh/g for the bulk material and above 1000 mAh/g of Si have been observed.

Silicon Composite Anode Materials for Lithium Ion Batteries Based on Carbon Cryogels and Carbon Paper

NASA Technical Reports Server (NTRS)

Woodworth, James; Baldwin, Richard; Bennett, William

2010-01-01

A variety of materials are under investigation for use as anode materials in lithium-ion batteries, of which, the most promising are those containing silicon. One such material is a composite formed via the dispersion of silicon in a resorcinol-formaldehyde (RF) gel followed by pyrolysis. Two silicon-carbon composite materials, carbon microspheres and nanofoams produced from nano-phase silicon impregnated RF gel precursors have been synthesized and investigated. Carbon microspheres are produced by forming the silicon-containing RF gel into microspheres whereas carbon nanofoams are produced by impregnating carbon fiber paper with the silicon containing RF gel to create a free standing electrode. Both materials have demonstrated their ability to function as anodes and utilize the silicon present in the material. Stable reversible capacities above 400 mAh/g for the bulk material and above 1000 mAh/g of Si have been observed.

Carbon Cryogel Silicon Composite Anode Materials for Lithium Ion Batteries

NASA Technical Reports Server (NTRS)

Woodworth James; Baldwin, Richard; Bennett, William

2010-01-01

A variety of materials are under investigation for use as anode materials in lithium-ion batteries, of which, the most promising are those containing silicon. 10 One such material is a composite formed via the dispersion of silicon in a resorcinol-formaldehyde (RF) gel followed by pyrolysis. Two silicon-carbon composite materials, carbon microspheres and nanofoams produced from nano-phase silicon impregnated RF gel precursors have been synthesized and investigated. Carbon microspheres are produced by forming the silicon-containing RF gel into microspheres whereas carbon nano-foams are produced by impregnating carbon fiber paper with the silicon containing RF gel to create a free standing electrode. 1-4,9 Both materials have demonstrated their ability to function as anodes and utilize the silicon present in the material. Stable reversible capacities above 400 mAh/g for the bulk material and above 1000 mAh/g of Si have been observed.

High Efficiency Flexible Battery Based on Graphene-carbon Nanotube Hybrid Structure

DTIC Science & Technology

2015-02-26

Publications: 1. Multi Layered Si-CuO Quantum Dots Wrapped by Graphene for High-Performance Anode Material in Lithium - Ion Battery , B. Rangasamy, J. Hwang, W...at different C-rates. Task III. High capacity and excellent stability of lithium ion battery anode using interface- controlled binder-free MWCNT...Material in Lithium - Ion Battery Various approaches to improve the efficiency of Lithium ion batteries (LiB) by using Si have been suggested

Scalable synthesis of NiMoO4 microspheres with numerous empty nanovoids as an advanced anode material for Li-ion batteries

NASA Astrophysics Data System (ADS)

Park, Jin-Sung; Cho, Jung Sang; Kang, Yun Chan

2018-03-01

Closely in line with advances in next-generation energy storage materials, anode materials for lithium-ion batteries (LIBs) with high capacity and long cycle life have been widely explored. As part of the current effort, nickel molybdate (NiMoO4) microspheres with empty nanovoids are synthesized via spray drying process and subsequent one-step calcination in air. Dextrin in the atomized droplet is phase segregated during the spray drying process and calcined in air atmosphere, resulting in numerous empty nanovoids well-distributed within a microsphere. The empty nanovoids alleviate volume expansion during cycling, shorten lithium-ion diffusion length, and facilitate contact between electrode and electrolyte materials. Along with the high discharge capacity of NiMoO4 material, as high as 1240 mA h g-1 for the 2nd cycle at a high current density of 1 A g-1, uniquity of the structure enables longer cycle life and higher quality performances. The discharge capacity corresponding to the 500th cycle is 1020 mA h g-1 and the capacity retention calculated from the 2nd cycle is 82%. In addition, a discharge capacity of 413 mA g-1 is obtained at an extremely high current density of 10 A g-1.

TiO₂ Nanobelt@Co₉S₈ Composites as Promising Anode Materials for Lithium and Sodium Ion Batteries.

PubMed

Zhou, Yanli; Zhu, Qian; Tian, Jian; Jiang, Fuyi

2017-09-02

TiO₂ anodes have attracted great attention due to their good cycling stability for lithium ion batteries and sodium ion batteries (LIBs and SIBs). Unfortunately, the low specific capacity and poor conductivity limit their practical application. The mixed phase TiO₂ nanobelt (anatase and TiO₂-B) based Co₉S₈ composites have been synthesized via the solvothermal reaction and subsequent calcination. During the formation process of hierarchical composites, glucose between TiO₂ nanobelts and Co₉S₈ serves as a linker to increase the nucleation and growth of sulfides on the surface of TiO₂ nanobelts. As anode materials for LIBs and SIBs, the composites combine the advantages of TiO₂ nanobelts with those of Co₉S₈ nanomaterials. The reversible specific capacity of TiO₂ nanobelt@Co₉S₈ composites is up to 889 and 387 mAh·g -1 at 0.1 A·g -1 after 100 cycles, respectively. The cooperation of excellent cycling stability of TiO₂ nanobelts and high capacities of Co₉S₈ nanoparticles leads to the good electrochemical performances of TiO₂ nanobelt@Co₉S₈ composites.

Gold-coated silicon nanowire-graphene core-shell composite film as a polymer binder-free anode for rechargeable lithium-ion batteries

NASA Astrophysics Data System (ADS)

Kim, Han-Jung; Lee, Sang Eon; Lee, Jihye; Jung, Joo-Yun; Lee, Eung-Sug; Choi, Jun-Hyuk; Jung, Jun-Ho; Oh, Minsub; Hyun, Seungmin; Choi, Dae-Geun

2014-07-01

We designed and fabricated a gold (Au)-coated silicon nanowires/graphene (Au-SiNWs/G) hybrid composite as a polymer binder-free anode for rechargeable lithium-ion batteries (LIBs). A large amount of SiNWs for LIB anode materials can be prepared by metal-assisted chemical etching (MaCE) process. The Au-SiNWs/G composite film on current collector was obtained by vacuum filtration using an anodic aluminum oxide (AAO) membrane and hot pressing method. Our experimental results show that the Au-SiNWs/G composite has a stable reversible capacity of about 1520 mA h/g which was maintained for 20 cycles. The Au-SiNWs/G composite anode showed much better cycling performance than SiNWs/polyvinylidene fluoride (PVDF)/Super-P, SiNWs/G composite, and pure SiNWs anodes. The improved electrochemical properties of the Au-SiNWs/G composite anode material is mainly ascribed to the composite's porous network structure.

Biologically derived melanin electrodes in aqueous sodium-ion energy storage devices

PubMed Central

Kim, Young Jo; Wu, Wei; Chun, Sang-Eun; Whitacre, Jay F.; Bettinger, Christopher J.

2013-01-01

Biodegradable electronics represents an attractive and emerging paradigm in medical devices by harnessing simultaneous advantages afforded by electronically active systems and obviating issues with chronic implants. Integrating practical energy sources that are compatible with the envisioned operation of transient devices is an unmet challenge for biodegradable electronics. Although high-performance energy storage systems offer a feasible solution, toxic materials and electrolytes present regulatory hurdles for use in temporary medical devices. Aqueous sodium-ion charge storage devices combined with biocompatible electrodes are ideal components to power next-generation biodegradable electronics. Here, we report the use of biologically derived organic electrodes composed of melanin pigments for use in energy storage devices. Melanins of natural (derived from Sepia officinalis) and synthetic origin are evaluated as anode materials in aqueous sodium-ion storage devices. Na+-loaded melanin anodes exhibit specific capacities of 30.4 ± 1.6 mAhg−1. Full cells composed of natural melanin anodes and λ-MnO2 cathodes exhibit an initial potential of 1.03 ± 0.06 V with a maximum specific capacity of 16.1 ± 0.8 mAhg−1. Natural melanin anodes exhibit higher specific capacities compared with synthetic melanins due to a combination of beneficial chemical, electrical, and physical properties exhibited by the former. Taken together, these results suggest that melanin pigments may serve as a naturally occurring biologically derived charge storage material to power certain types of medical devices. PMID:24324163

Anode property of carbon coated LiFePO4 nanocrystals

NASA Astrophysics Data System (ADS)

Ni, Jiangfeng; Jiang, Jiaxing; Savilov, S. V.; Aldoshin, S. M.

2016-10-01

Nanostructured LiFePO4 is appealing cathode material for rechargeable lithium batteries. Herein, however, we report the intriguing anode properties of carbon coated LiFePO4 nanocrystals. In the potential range of 0-3.0 V, the LiFePO4 nanocrystal electrodes afford high reversible capacity of 373 mAhg-1 at a current rate of 0.05 Ag-1 and retains 239 mAhg-1 at a much higher rate of 1.25 Ag-1. In addition, it is capable of sustaining 1000 cycles at 1.25 Ag-1 without any capacity fading. Such superior properties indicate that nanostructured LiFePO4 could also be promising anode for rechargeable battery applications.

3D macroporous electrode and high-performance in lithium-ion batteries using SnO2 coated on Cu foam

PubMed Central

Um, Ji Hyun; Choi, Myounggeun; Park, Hyeji; Cho, Yong-Hun; Dunand, David C.; Choe, Heeman; Sung, Yung-Eun

2016-01-01

A three-dimensional porous architecture makes an attractive electrode structure, as it has an intrinsic structural integrity and an ability to buffer stress in lithium-ion batteries caused by the large volume changes in high-capacity anode materials during cycling. Here we report the first demonstration of a SnO2-coated macroporous Cu foam anode by employing a facile and scalable combination of directional freeze-casting and sol-gel coating processes. The three-dimensional interconnected anode is composed of aligned microscale channels separated by SnO2-coated Cu walls and much finer micrometer pores, adding to surface area and providing space for volume expansion of SnO2 coating layer. With this anode, we achieve a high reversible capacity of 750 mAh g−1 at current rate of 0.5 C after 50 cycles and an excellent rate capability of 590 mAh g−1 at 2 C, which is close to the best performance of Sn-based nanoscale material so far. PMID:26725652

Electrochemical properties of Sn/C nanoparticles fabricated by redox treatment and pulsed wire evaporation method

NASA Astrophysics Data System (ADS)

Song, Ju-Seok; Cho, Gyu-Bong; Ahn, Jou-Hyeon; Cho, Kwon-Koo

2017-09-01

Tin (Sn) based anode materials are the most promising anode materials for lithium-ion batteries due to their high theoretical capacity corresponding to the formation of Li4.4Sn composition (Li4.4Sn, 994 mAh/g). However, the applications of tin based anodes to lithium-ion battery system are generally limited by a large volume change (>260%) during lithiation and delithiation cycle, which causes pulverize and poor cycling stability. In order to overcome this shortcoming, we fabricate a Sn/C nanoparticle with a yolk-shell structure (Sn/void/C) by using pulsed wire evaporation process and oxidation/reduction heat treatment. Sn nanoparticles are encapsulated by a conductive carbon layer with structural buffer that leaves enough room for expansion and contraction during lithium insertion/desertion. We expect that the yolk-shell structure has the ability to accommodate the volume changes of tin and leading to an improved cycle performance. The Sn/Void/C anode with yolk-shell structure shows a high specific capacity of 760 mAh/g after 50 cycles.

An electrode comprising of graphene nanopowder inserted in an enclosed structure in anodic aluminium oxide coated with PANI by using low temperature hydrothermal process

NASA Astrophysics Data System (ADS)

Shivhare, Sugam; Vyas, Supriya; Bagal, Vivekanand S.; Sharma, Malvika; Gautam, Mangla Dave

2018-04-01

Elements like C and its allotropes (Graphene) Sn, Al, Ge, and their compounds are commonly used anodic materials in Li-ion secondary batteries. Out of them Graphene is a promising anodic material for Li-ion batteries as it having high theoretical capacity of 4100 mAh/g as it formed Li4.4C. However, the formation of Li4.4C induces a large volume expansion in the electrode and leads to a rapid drop in capacity. To overcome this problem many experiments and theoretical efforts have been focused on enhancing structural stability of Graphene in electrode. Several methods have been also reported for the fabrication of three-dimensional electrode arrays. In this study, we report an improvement of the cycling performance of graphene nanopowder-based electrode. Graphene nanopowder was inserted and confined on the anodic aluminum oxide coated with polyaniline (PANI) by using a new method. It is confirmed from this study that cycling behavior of the graphene powder electrode can be significantly improved by using the method proposed in this study.

Engineering empty space between Si nanoparticles for lithium-ion battery anodes.

PubMed

Wu, Hui; Zheng, Guangyuan; Liu, Nian; Carney, Thomas J; Yang, Yuan; Cui, Yi

2012-02-08

Silicon is a promising high-capacity anode material for lithium-ion batteries yet attaining long cycle life remains a significant challenge due to pulverization of the silicon and unstable solid-electrolyte interphase (SEI) formation during the electrochemical cycles. Despite significant advances in nanostructured Si electrodes, challenges including short cycle life and scalability hinder its widespread implementation. To address these challenges, we engineered an empty space between Si nanoparticles by encapsulating them in hollow carbon tubes. The synthesis process used low-cost Si nanoparticles and electrospinning methods, both of which can be easily scaled. The empty space around the Si nanoparticles allowed the electrode to successfully overcome these problems Our anode demonstrated a high gravimetric capacity (~1000 mAh/g based on the total mass) and long cycle life (200 cycles with 90% capacity retention). © 2012 American Chemical Society

Copper Silicate Hydrate Hollow Spheres Constructed by Nanotubes Encapsulated in Reduced Graphene Oxide as Long-Life Lithium-Ion Battery Anode.

PubMed

Wei, Xiujuan; Tang, Chunjuan; Wang, Xuanpeng; Zhou, Liang; Wei, Qiulong; Yan, Mengyu; Sheng, Jinzhi; Hu, Ping; Wang, Bolun; Mai, Liqiang

2015-12-09

Hierarchical copper silicate hydrate hollow spheres-reduced graphene oxide (RGO) composite is successfully fabricated by a facile hydrothermal method using silica as in situ sacrificing template. The electrochemical performance of the composite as lithium-ion battery anode was studied for the first time. Benefiting from the synergistic effect of the hierarchical hollow structure and conductive RGO matrix, the composite exhibits excellent long-life performance and rate capability. A capacity of 890 mAh/g is achieved after 200 cycles at 200 mA/g and a capacity of 429 mAh/g is retained after 800 cycles at 1000 mA/g. The results indicate that the strategy of combining hierarchical hollow structures with conductive RGO holds the potential in addressing the volume expansion issue of high capacity anode materials.

One-Step Fast-Synthesized Foamlike Amorphous Co(OH)2 Flexible Film on Ti Foil by Plasma-Assisted Electrolytic Deposition as a Binder-Free Anode of a High-Capacity Lithium-Ion Battery.

PubMed

Li, Tao; Nie, Xueyuan

2018-05-23

This research prepared an amorphous Co(OH) 2 flexible film on Ti foil using plasma-assisted electrolytic deposition within 3.5 min. Amorphous Co(OH) 2 structure was determined by X-ray diffraction and X-ray photoelectron spectroscopy. Its areal capacity testing as the binder and adhesive-free anode of a lithium-ion battery shows that the cycling capacity can reach 2000 μAh/cm 2 and remain at 930 μAh/cm 2 after 50 charge-discharge cycles, which benefits from the emerging Co(OH) 2 active material and amorphous foamlike structure. The research introduced a new method to synthesize amorphous Co(OH) 2 as the anode in a fast-manufactured low-cost lithium-ion battery.

Multiwalled carbon nanotube@a-C@Co9S8 nanocomposites: a high-capacity and long-life anode material for advanced lithium ion batteries

NASA Astrophysics Data System (ADS)

Zhou, Yanli; Yan, Dong; Xu, Huayun; Liu, Shuo; Yang, Jian; Qian, Yitai

2015-02-01

A one-dimensional MWCNT@a-C@Co9S8 nanocomposite has been prepared via a facile solvothermal reaction followed by a calcination process. The amorphous carbon layer between Co9S8 and MWCNT acts as a linker to increase the loading of sulfides on MWCNT. When evaluated as anode materials for lithium ion batteries, the MWCNT@a-C@Co9S8 nanocomposite shows the advantages of high capacity and long life, superior to Co9S8 nanoparticles and MWCNT@Co9S8 nanocomposites. The reversible capacity could be retained at 662 mA h g-1 after 120 cycles at 1 A g-1. The efficient synthesis and excellent performances of this nanocomposite offer numerous opportunities for other sulfides as a new anode for lithium ion batteries.A one-dimensional MWCNT@a-C@Co9S8 nanocomposite has been prepared via a facile solvothermal reaction followed by a calcination process. The amorphous carbon layer between Co9S8 and MWCNT acts as a linker to increase the loading of sulfides on MWCNT. When evaluated as anode materials for lithium ion batteries, the MWCNT@a-C@Co9S8 nanocomposite shows the advantages of high capacity and long life, superior to Co9S8 nanoparticles and MWCNT@Co9S8 nanocomposites. The reversible capacity could be retained at 662 mA h g-1 after 120 cycles at 1 A g-1. The efficient synthesis and excellent performances of this nanocomposite offer numerous opportunities for other sulfides as a new anode for lithium ion batteries. Electronic supplementary information (ESI) available: Infrared spectrogram (IR) of glucose treated MWCNT; TEM images of MWCNT@a-C treated by different concentrations of glucose; SEM and TEM images of the intermediate product obtained from the solvothermal reaction between thiourea and Co(Ac)2; EDS spectrum of MWCNT@a-C@Co9S8 composites; SEM and TEM images of MWCNT@Co9S8 nanocomposites obtained without the hydrothermal treatment by glucose; SEM and TEM images of Co9S8 nanoparticles; Galvanostatic discharge-charge profiles and cycling performance of MWCNT@a-C; TEM images of the anode material at different state of charge (SOC) and depth of discharge (DOD); the comparison of cycling performances of reported cobalt sulfide nanocomposites. See DOI: 10.1039/c4nr07143c

Next Generation Anodes for Lithium Ion Batteries: Thermodynamic Understanding and Abuse Performance.

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

Fenton, Kyle R.; Allcorn, Eric; Nagasubramanian, Ganesan

As we develop new materials to increase performance of lithium ion batteries for electric vehicles, the impact of potential safety and reliability issues become increasingly important. In addition to electrochemical performance increases (capacity, energy, cycle life, etc.), there are a variety of materials advancements that can be made to improve lithium-ion battery safety. Issues including energetic thermal runaway, electrolyte decomposition and flammability, anode SEI stability, and cell-level abuse tolerance behavior. Introduction of a next generation materials, such as silicon based anode, requires a full understanding of the abuse response and degradation mechanisms for these anodes. This work aims to understandmore » the breakdown of these materials during abuse conditions in order to develop an inherently safe power source for our next generation electric vehicles. The effect of materials level changes (electrolytes, additives, silicon particle size, silicon loading, etc.) to cell level abuse response and runaway reactions will be determined using several techniques. Experimentation will start with base material evaluations in coin cells and overall runaway energy will be evaluated using techniques such as differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and accelerating rate calorimetry (ARC). The goal is to understand the effect of materials parameters on the runaway reactions, which can then be correlated to the response seen on larger cells (18650). Experiments conducted showed that there was significant response from these electrodes. Efforts to minimize risk during testing were taken by development of a smaller capacity cylindrical design in order to quantify materials decision and how they manifest during abuse response.« less

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.

Preparation of a Si/SiO2 -Ordered-Mesoporous-Carbon Nanocomposite as an Anode for High-Performance Lithium-Ion and Sodium-Ion Batteries.

PubMed

Zeng, Lingxing; Liu, Renpin; Han, Lei; Luo, Fenqiang; Chen, Xi; Wang, Jianbiao; Qian, Qingrong; Chen, Qinghua; Wei, Mingdeng

2018-04-03

In this work, an Si/SiO 2 -ordered-mesoporous carbon (Si/SiO 2 -OMC) nanocomposite was initially fabricated through a magnesiothermic reduction strategy by using a two-dimensional bicontinuous mesochannel of SiO 2 -OMC as a precursor, combined with an NaOH etching process, in which crystal Si/amorphous SiO 2 nanoparticles were encapsulated into the OMC matrix. Not only can such unique porous crystal Si/amorphous SiO 2 nanoparticles uniformly dispersed in the OMC matrix mitigate the volume change of active materials during the cycling process, but they can also improve electrical conductivity of Si/SiO 2 and facilitate the Li + /Na + diffusion. When applied as an anode for lithium-ion batteries (LIBs), the Si/SiO 2 -OMC composite displayed superior reversible capacity (958 mA h g -1 at 0.2 A g -1 after 100 cycles) and good cycling life (retaining a capacity of 459 mA h g -1 at 2 A g -1 after 1000 cycles). For sodium-ion batteries (SIBs), the composite maintained a high capacity of 423 mA h g -1 after 100 cycles at 0.05 A g -1 and an extremely stable reversible capacity of 190 mA h g -1 was retained even after 500 cycles at 1 A g -1 . This performance is one of the best long-term cycling properties of Si-based SIB anode materials. The Si/SiO 2 -OMC composites exhibited great potential as an alternative material for both lithium- and sodium-ion battery anodes. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Semi-solid electrodes having high rate capability

DOEpatents

Chiang, Yet-Ming; Duduta, Mihai; Holman, Richard; Limthongkul, Pimpa; Tan, Taison

2016-07-05

Embodiments described herein relate generally to electrochemical cells having high rate capability, and more particularly to devices, systems and methods of producing high capacity and high rate capability batteries having relatively thick semi-solid electrodes. In some embodiments, an electrochemical cell includes an anode, a semi-solid cathode that includes a suspension of an active material and a conductive material in a liquid electrolyte, and an ion permeable membrane disposed between the anode and the cathode. The semi-solid cathode has a thickness in the range of about 250 .mu.m-2,500 .mu.m, and the electrochemical cell has an area specific capacity of at least 5 mAh/cm.sup.2 at a C-rate of C/2.

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

Chiang, Yet-Ming; Duduta, Mihai; Holman, Richard

Embodiments described herein relate generally to electrochemical cells having high rate capability, and more particularly to devices, systems and methods of producing high capacity and high rate capability batteries having relatively thick semi-solid electrodes. In some embodiments, an electrochemical cell includes an anode, a semi-solid cathode that includes a suspension of an active material and a conductive material in a liquid electrolyte, and an ion permeable membrane disposed between the anode and the cathode. The semi-solid cathode has a thickness in the range of about 250 .mu.m-2,500 .mu.m, and the electrochemical cell has an area specific capacity of at leastmore » 5 mAh/cm.sup.2 at a C-rate of C/2.« less

Semi-solid electrodes having high rate capability

DOEpatents

Chiang, Yet-Ming; Duduta, Mihai; Holman, Richard; Limthongkul, Pimpa; Tan, Taison

2015-11-10

Embodiments described herein relate generally to electrochemical cells having high rate capability, and more particularly to devices, systems and methods of producing high capacity and high rate capability batteries having relatively thick semi-solid electrodes. In some embodiments, an electrochemical cell includes an anode, a semi-solid cathode that includes a suspension of an active material and a conductive material in a liquid electrolyte, and an ion permeable membrane disposed between the anode and the cathode. The semi-solid cathode has a thickness in the range of about 250 .mu.m-2,500 .mu.m, and the electrochemical cell has an area specific capacity of at least 5 mAh/cm.sup.2 at a C-rate of C/2.

Fabrication and Performance of High Energy Li-Ion Battery Based on the Spherical Li[Li(0.2)Ni(0.16)Co(0.1)Mn(0.54)]O2 Cathode and Si Anode.

PubMed

Ye, Jing; Li, Yi-xuan; Zhang, Li; Zhang, Xue-ping; Han, Min; He, Ping; Zhou, Hao-shen

2016-01-13

The cathode materials of Li-ion batteries for electric vehicles require not only a large gravimetric capacity but also a high volumetric capacity. A new Li-rich layered oxide cathode with superior capacity, Li[Li0.20Ni0.16Co0.10Mn0.54]O2 (denoted as LNCM), is synthesized from precursor, a coprecipitated spherical metal hydroxide. The preparation technology of precursor such as stirring speed, concentration of metal solution, and reaction time are regulated elaborately. The final product LNCM shows a well-ordered, hexagonal-layer structure, as confirmed by Rietveld refinement of X-ray diffraction pattern. The particle size of the final product has an average diameter of about 10 μm, and the corresponding tap density is about 2.25 g cm(-3). Electrochemical measurements indicate that as-prepared LNCM has great initial columbic efficiency, reversible capacity, and cycling stability, with specific discharge capacities of 278 and 201 mAh g(-1) at 0.03 and 0.5 C rates, respectively. Cycling at 0.1 C, LNCM delivers a discharge capacity of 226 mAh g(-1) with 95% retention capacity after 50 cycles. Si/LNCM cell is fabricated using Si submicroparticle as anode against LNCM. The cell can exhibit a specific energy of 590 Wh kg(-1) based on the total weight of cathode and anode materials.

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.

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.

Nanostructured Si(₁-x)Gex for tunable thin film lithium-ion battery anodes.

PubMed

Abel, Paul R; Chockla, Aaron M; Lin, Yong-Mao; Holmberg, Vincent C; Harris, Justin T; Korgel, Brian A; Heller, Adam; Mullins, C Buddie

2013-03-26

Both silicon and germanium are leading candidates to replace the carbon anode of lithium ions batteries. Silicon is attractive because of its high lithium storage capacity while germanium, a superior electronic and ionic conductor, can support much higher charge/discharge rates. Here we investigate the electronic, electrochemical and optical properties of Si(1-x)Gex thin films with x = 0, 0.25, 0.5, 0.75, and 1. Glancing angle deposition provided amorphous films of reproducible nanostructure and porosity. The film's composition and physical properties were investigated by X-ray photoelectron spectroscopy, four-point probe conductivity, Raman, and UV-vis absorption spectroscopy. The films were assembled into coin cells to test their electrochemical properties as a lithium-ion battery anode material. The cells were cycled at various C-rates to determine the upper limits for high rate performance. Adjusting the composition in the Si(1-x)Gex system demonstrates a trade-off between rate capability and specific capacity. We show that high-capacity silicon anodes and high-rate germanium anodes are merely the two extremes; the composition of Si(1-x)Gex alloys provides a new parameter to use in electrode optimization.

Improving the sodium storage capacity of tunnel structured NaxFexTi2-xO4 (x = 1, 0.9 & 0.8) anode materials by tuning sodium deficiency

NASA Astrophysics Data System (ADS)

Bhange, Deu S.; Ali, Ghulam; Kim, Ji-Young; Chung, Kyung Yoon; Nam, Kyung-Wan

2017-10-01

Due to their abundance and environmentally benign nature, iron and titanium present as the most attractive potential elements for use in rechargeable sodium-ion batteries (SIBs). Accordingly, two structurally different Fe and Ti based compounds, stoichiometric NaFeTiO4 and sodium deficient NaxFexTi2-xO4 (where x = 0.9, and 0.8), are explored as anode materials for SIBs. Their structure and sodium storage capacity are systematically investigated by using combined structural and electrochemical analysis. Rietveld refinement analysis reveals that the sodium deficiency leads to the structural transformation from a single-tunnel structure (NaFeTiO4) to a zigzag-type double-tunnel structure (Na0.9Fe0.9Ti1.1O4 and Na0.8Fe0.8Ti1.2O4). The series of sodium deficient compounds bears systematic sodium ion vacancies in their structure up to 20%. Sodium deficiency in the NaxFexTi2-xO4 logically provides additional space for accommodating the excess sodium ions as such the NaxFexTi2-xO4 compounds with higher level of sodium deficiency show higher specific capacities than the stoichiometric NaFeTiO4. All the compounds exhibited very good electrochemical cycling stability, with minimal capacity loss during cycling. The present approach is a model example of improvement in the sodium storage capacity of the anode materials by tuning the chemical composition, and could facilitate the performance improvement of known or new electrode materials for SIBs.

Life cycle environmental impact of high-capacity lithium ion battery with silicon nanowires anode for electric vehicles.

PubMed

Li, Bingbing; Gao, Xianfeng; Li, Jianyang; Yuan, Chris

2014-01-01

Although silicon nanowires (SiNW) have been widely studied as an ideal material for developing high-capacity lithium ion batteries (LIBs) for electric vehicles (EVs), little is known about the environmental impacts of such a new EV battery pack during its whole life cycle. This paper reports a life cycle assessment (LCA) of a high-capacity LIB pack using SiNW prepared via metal-assisted chemical etching as anode material. The LCA study is conducted based on the average U.S. driving and electricity supply conditions. Nanowastes and nanoparticle emissions from the SiNW synthesis are also characterized and reported. The LCA results show that over 50% of most characterized impacts are generated from the battery operations, while the battery anode with SiNW material contributes to around 15% of global warming potential and 10% of human toxicity potential. Overall the life cycle impacts of this new battery pack are moderately higher than those of conventional LIBs but could be actually comparable when considering the uncertainties and scale-up potential of the technology. These results are encouraging because they not only provide a solid base for sustainable development of next generation LIBs but also confirm that appropriate nanomanufacturing technologies could be used in sustainable product development.

Highly Porous FeS/Carbon Fibers Derived from Fe-Carrageenan Biomass: High-capacity and Durable Anodes for Sodium-Ion Batteries.

PubMed

Li, Daohao; Sun, Yuanyuan; Chen, Shuai; Yao, Jiuyong; Zhang, Yuhui; Xia, Yanzhi; Yang, Dongjiang

2018-05-08

The nanostructured metal sulfides have been reported as promising anode materials for sodium-ion batteries (SIBs) due to their high theoretical capacities but have suffered from the unsatisfactory electronic conductivity and poor structural stability during a charge/discharge process, thus limiting their applications. Herein, the one-dimensional (1D) porous FeS/carbon fibers (FeS/CFs) micro/nanostructures are fabricated through facile pyrolysis of double-helix-structured Fe-carrageenan fibers. The FeS nanoparticles are in situ formed by interacting with sulfur-containing group of natural material ι-carrageenan and uniformly embedded in the unique 1D porous carbon fibrous matrix, significantly enhancing the sodium-ion storage performance. The obtained FeS/CFs with optimized sodium storage performance benefits from the appropriate carbon content (20.9 wt %). The composite exhibits high capacity and excellent cycling stability (283 mAh g -1 at current density of 1 A g -1 after 400 cycles) and rate performance (247 mAh g -1 at 5 A g -1 ). This work provides a simple strategy to construct 1D porous FeS/CFs micro/nanostructures as high-performance anode materials for SIBs via a unique sustainable and environmentally friendly way.

Hot-Chemistry Structural Phase Transformation in Single-Crystal Chalcogenides for Long-Life Lithium Ion Batteries.

PubMed

Hassan, Fathy M; Hu, Qianqian; Fu, Jing; Batmaz, Rasim; Li, Jingde; Yu, Aiping; Xiao, Xingcheng; Chen, Zhongwei

2017-06-21

Tuned chalcogenide single crystals rooted in sulfur-doped graphene were prepared by high-temperature solution chemistry. We present a facile route to synthesize a rod-on-sheet-like nanohybrid as an active anode material and demonstrate its superior performance in lithium ion batteries (LIBs). This nanohybrid contains a nanoassembly of one-dimensional (1D) single-crystalline, orthorhombic SnS onto two-dimensional (2D) sulfur-doped graphene. The 1D nanoscaled SnS with the rodlike single-crystalline structure possesses improved transport properties compared to its 2D hexagonal platelike SnS 2 . Furthermore, we blend this hybrid chalcogenide with biodegradable polymer composite using water as a solvent. Upon drying, the electrodes were subjected to heating in vacuum at 150 °C to induce polymer condensation via formation of carboxylate groups to produce a mechanically robust anode. The LIB using the as-developed anode material can deliver a high volumetric capacity of ∼2350 mA h cm -3 and exhibit superior cycle stability over 1500 cycles as well as a high capacity retention of 85% at a 1 C rate. The excellent battery performance combined with the simplistic, scalable, and green chemistry approach renders this anode material as a very promising candidate for LIB applications.

Mesoporous Germanium Anode Materials for Lithium-Ion Battery with Exceptional Cycling Stability in Wide Temperature Range.

PubMed

Choi, Sinho; Cho, Yoon-Gyo; Kim, Jieun; Choi, Nam-Soon; Song, Hyun-Kon; Wang, Guoxiu; Park, Soojin

2017-04-01

Porous structured materials have unique architectures and are promising for lithium-ion batteries to enhance performances. In particular, mesoporous materials have many advantages including a high surface area and large void spaces which can increase reactivity and accessibility of lithium ions. This study reports a synthesis of newly developed mesoporous germanium (Ge) particles prepared by a zincothermic reduction at a mild temperature for high performance lithium-ion batteries which can operate in a wide temperature range. The optimized Ge battery anodes with the mesoporous structure exhibit outstanding electrochemical properties in a wide temperature ranging from -20 to 60 °C. Ge anodes exhibit a stable cycling retention at various temperatures (capacity retention of 99% after 100 cycles at 25 °C, 84% after 300 cycles at 60 °C, and 50% after 50 cycles at -20 °C). Furthermore, full cells consisting of the mesoporous Ge anode and an LiFePO 4 cathode show an excellent cyclability at -20 and 25 °C. Mesoporous Ge materials synthesized by the zincothermic reduction can be potentially applied as high performance anode materials for practical lithium-ion batteries. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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.

High-performance Li-ion Sn anodes with enhanced electrochemical properties using highly conductive TiN nanotubes array as a 3D multifunctional support

NASA Astrophysics Data System (ADS)

Pu, Jun; Du, Hongxiu; Wang, Jian; Wu, Wenlu; Shen, Zihan; Liu, Jinyun; Zhang, Huigang

2017-08-01

High capacity electrodes are demanded to increase the energy and power density of lithium ion batteries. However, the cycling and rate properties are severely affected by the large volume changes caused by the lithium insertion and extraction. Structured electrodes with mechanically stable scaffolds are widely developed to mitigate the adverse effects of volume changes. Tin, as a promising anode material, receives great attentions because of its high theoretic capacity. There is a critical value of tin particle size above which tin anodes readily crack, leading to low cyclability. The electrode design using mechanical scaffolds must retain tin particles below the critical size and concurrently enable high volumetric capacity. It is a challenge to guarantee the critical size for high cyclability and space utilization for high volumetric capacity. This study provides a highly conductive TiN nanotubes array with submicron diameters, which enable thin tin coating without sacrificing the volumetric capacity. Such a structured electrode delivers a capacity of 795 mAh gSn-1 (Sn basis) and 1812 mAh cmel-3 (electrode basis). The long-term cycling shows only 0.04% capacity decay per cycle.

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

Towards deriving Ni-rich cathode and oxide-based anode materials from hydroxides by sharing a facile co-precipitation method.

PubMed

Qiu, Haifa; Du, Tengfei; Wu, Junfeng; Wang, Yonglong; Liu, Jian; Ye, Shihai; Liu, Sheng

2018-05-22

Although intensive studies have been conducted on layered transition metal oxide(TMO)-based cathode materials and metal oxide-based anode materials for Li-ion batteries, their precursors generally follow different or even complex synthesis routes. To share one route for preparing precursors of the cathode and anode materials, herein, we demonstrate a facile co-precipitation method to fabricate Ni-rich hydroxide precursors of Ni0.8Co0.1Mn0.1(OH)2. Ni-rich layered oxide of LiNi0.8Co0.1Mn0.1O2 is obtained by lithiation of the precursor in air. An NiO-based anode material is prepared by calcining the precursor or multi-walled carbon nanotubes (MWCNTs) incorporated precursors. The pre-addition of ammonia solution can simplify the co-precipitation procedures and the use of an air atmosphere can also make the heat treatment facile. LiNi0.8Co0.1Mn0.1O2 as the cathode material delivers a reversible capacity of 194 mA h g-1 at 40 mA g-1 and a notable cycling retention of 88.8% after 100 cycles at 200 mA g-1. This noticeable performance of the cathode arises from a decent particle morphology and high crystallinity of the layered oxides. As the anode material, the MWCNTs-incorporated oxides deliver a much higher reversible capacity of 811.1 mA h g-1 after 200 cycles compared to the pristine oxides without MWCNTs. The improvement on electrochemical performance can be attributed to synergistic effects from MWCNTs incorporation, including reinforced electronic conductivity, rich meso-pores and an alleviated volume effect. This facile and sharing method may offer an integrated and economical approach for commercial production of Ni-rich electrode materials for Li-ion batteries.

Amorphous Zn₂GeO₄ Nanoparticles as Anodes with High Reversible Capacity and Long Cycling Life for Li-ion Batteries

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

Yi, Ran; Feng, Jinkui; Lv, Dongping

2013-07-30

Amorphous and crystalline Zn₂GeO₄ nanoparticles were prepared and characterized as anode materials for Li-ion batteries. A higher reversible specific capacity of 1250 mAh/g after 500 cycles and excellent rate capability were obtained for amorphous Zn₂GeO₄ nanoparticles, compared to that of crystalline Zn₂GeO₄ nanoparticles. Small particle size, amorphous phase and incorporation of zinc and oxygen contribute synergetically to the improved performance by effectively mitigating the huge volume variations during lithiation and delithiation process.

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.

Conversion Reaction-Based Oxide Nanomaterials for Lithium Ion Battery Anodes.

PubMed

Yu, Seung-Ho; Lee, Soo Hong; Lee, Dong Jun; Sung, Yung-Eun; Hyeon, Taeghwan

2016-04-27

Developing high-energy-density electrodes for lithium ion batteries (LIBs) is of primary importance to meet the challenges in electronics and automobile industries in the near future. Conversion reaction-based transition metal oxides are attractive candidates for LIB anodes because of their high theoretical capacities. This review summarizes recent advances on the development of nanostructured transition metal oxides for use in lithium ion battery anodes based on conversion reactions. The oxide materials covered in this review include oxides of iron, manganese, cobalt, copper, nickel, molybdenum, zinc, ruthenium, chromium, and tungsten, and mixed metal oxides. Various kinds of nanostructured materials including nanowires, nanosheets, hollow structures, porous structures, and oxide/carbon nanocomposites are discussed in terms of their LIB anode applications. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Embroidered Copper Microwire Current Collector for Improved Cycling Performance of Silicon Anodes in Lithium-Ion Batteries.

PubMed

Breitung, Ben; Aguiló-Aguayo, Noemí; Bechtold, Thomas; Hahn, Horst; Janek, Jürgen; Brezesinski, Torsten

2017-10-12

Si holds great promise as an alloying anode material for Li-ion batteries with improved energy density because of its high theoretical specific capacity and favorable operation voltage range. However, the large volume expansion of Si during electrochemical reaction with Li and the associated adverse effects strongly limit its prospect for application. Here, we report on the use of three-dimensional instead of flat current collectors for high-capacity Si anodes in an attempt to mitigate the loss of electrical contact of active electrode regions as a result of structural disintegration with cycling. The current collectors were produced by technical embroidery and consist of interconnected Cu wires of diameter <150 µm. In comparison to Si/Li cells using a conventional Cu foil current collector, the embroidered microwire network-based cells show much enhanced capacity and reversibility due to a higher degree of tolerance to cycling.

Integration of high capacity materials into interdigitated mesostructured electrodes for high energy and high power density primary microbatteries

NASA Astrophysics Data System (ADS)

Pikul, James H.; Liu, Jinyun; Braun, Paul V.; King, William P.

2016-05-01

Microbatteries are increasingly important for powering electronic systems, however, the volumetric energy density of microbatteries lags behind that of conventional format batteries. This paper reports a primary microbattery with energy density 45.5 μWh cm-2 μm-1 and peak power 5300 μW cm-2 μm-1, enabled by the integration of large volume fractions of high capacity anode and cathode chemistry into porous micro-architectures. The interdigitated battery electrodes consist of a lithium metal anode and a mesoporous manganese oxide cathode. The key enabler of the high energy and power density is the integration of the high capacity manganese oxide conversion chemistry into a mesostructured high power interdigitated bicontinuous cathode architecture and an electrodeposited dense lithium metal anode. The resultant energy density is greater than previously reported three-dimensional microbatteries and is comparable to commercial conventional format lithium-based batteries.

Facile synthesis and electrochemical performance of the nanoscaled FePy anode

NASA Astrophysics Data System (ADS)

Wang, Guixin; Zhang, Ruibo; Jiang, Tianchan; Chernova, Natasha A.; Dong, Zhixin; Whittingham, M. Stanley

2014-12-01

Fe-P alloys with high phosphorous content have been targeted as promising anode materials because of their high theoretical capacity. However, the synthesis and cycling performance remain great challenges. Hereby FePy (3 ≤ y ≤ 4) nanoparticles are facilely synthesized through a dry mechanochemical method by reacting iron and red phosphorus powders in an inert atmosphere. The morphology and crystal structure of this material are characterized by SEM and XRD, respectively, while the electrochemical performance is evaluated by a number of different techniques. The 1st and 2nd discharge capacity of FePy reaches 1984 mAh g-1 and 1486 mAh g-1, respectively, and after 10 cycles at 0.03 mA cm-2 (20 mA g-1, 0.03C), the capacity remains 1089 mAh g-1 with a coulombic efficiency of 97%, much higher than the reported results to date. The cyclability of this material becomes fairly better at a higher current density, but the specific capacity is lower compared to that of the smaller current density. By adding fluoroethylene carbonate (FEC) to the electrolyte, the cycling performance of this material was improved. The EIS analysis has also been performed in order to better understand the capacity fade mechanism of FePy.

High-capacity aqueous zinc batteries using sustainable quinone electrodes

PubMed Central

Zhao, Qing; Huang, Weiwei; Luo, Zhiqiang; Liu, Luojia; Lu, Yong; Li, Yixin; Li, Lin; Hu, Jinyan; Ma, Hua; Chen, Jun

2018-01-01

Quinones, which are ubiquitous in nature, can act as sustainable and green electrode materials but face dissolution in organic electrolytes, resulting in fast fading of capacity and short cycle life. We report that quinone electrodes, especially calix[4]quinone (C4Q) in rechargeable metal zinc batteries coupled with a cation-selective membrane using an aqueous electrolyte, exhibit a high capacity of 335 mA h g−1 with an energy efficiency of 93% at 20 mA g−1 and a long life of 1000 cycles with a capacity retention of 87% at 500 mA g−1. The pouch zinc batteries with a respective depth of discharge of 89% (C4Q) and 49% (zinc anode) can deliver an energy density of 220 Wh kg−1 by mass of both a C4Q cathode and a theoretical Zn anode. We also develop an electrostatic potential computing method to demonstrate that carbonyl groups are active centers of electrochemistry. Moreover, the structural evolution and dissolution behavior of active materials during discharge and charge processes are investigated by operando spectral techniques such as IR, Raman, and ultraviolet-visible spectroscopies. Our results show that batteries using quinone cathodes and metal anodes in aqueous electrolyte are reliable approaches for mass energy storage. PMID:29511734

High-capacity aqueous zinc batteries using sustainable quinone electrodes.

PubMed

Zhao, Qing; Huang, Weiwei; Luo, Zhiqiang; Liu, Luojia; Lu, Yong; Li, Yixin; Li, Lin; Hu, Jinyan; Ma, Hua; Chen, Jun

2018-03-01

Quinones, which are ubiquitous in nature, can act as sustainable and green electrode materials but face dissolution in organic electrolytes, resulting in fast fading of capacity and short cycle life. We report that quinone electrodes, especially calix[4]quinone (C4Q) in rechargeable metal zinc batteries coupled with a cation-selective membrane using an aqueous electrolyte, exhibit a high capacity of 335 mA h g -1 with an energy efficiency of 93% at 20 mA g -1 and a long life of 1000 cycles with a capacity retention of 87% at 500 mA g -1 . The pouch zinc batteries with a respective depth of discharge of 89% (C4Q) and 49% (zinc anode) can deliver an energy density of 220 Wh kg -1 by mass of both a C4Q cathode and a theoretical Zn anode. We also develop an electrostatic potential computing method to demonstrate that carbonyl groups are active centers of electrochemistry. Moreover, the structural evolution and dissolution behavior of active materials during discharge and charge processes are investigated by operando spectral techniques such as IR, Raman, and ultraviolet-visible spectroscopies. Our results show that batteries using quinone cathodes and metal anodes in aqueous electrolyte are reliable approaches for mass energy storage.

Synthesis and Electrochemical Properties of Amorphous Carbon Coated Sn Anode Material for Lithium Ion Batteries and Sodium Ion Batteries.

PubMed

Choi, Ji-Seub; Lee, Hoi-Jin; Ha, Jong-Keun; Cho, Kwon-Koo

2018-09-01

Sn is one of the promising anode material for lithium-ion and sodium-ion batteries because of Sn has many advantages such as a high theoretical capacity of 994 mAh/g, inexpensive, abundant and nontoxic. However, Sn-based anodes have a critical problem from pulverization of the particles due to large volume change (>300% in lithium-ion battery and 420% in the sodium-ion battery) during alloying/dealloying reaction. To overcome this problem, we fabricate Sn/C particle of core/shell structure. Sn powder was produced by pulsed wire explosion in liquid media, and amorphous carbon coating process was prepared by hydrothermal synthesis. The charge capacity of Sn electrode and amorphous carbon coated Sn electrode was 413 mAh/g and 452 mAh/g after 40 cycles in lithium half-cell test. The charge capacity of Sn electrode and amorphous carbon coated Sn electrode was 240 mAh/g and 487 mAh/g after 40 cycles in sodium half-cell test. Amorphous carbon coating contributed to the improvement of capacity in lithium and sodium battery systems. And the effect of amorphous carbon coating in sodium battery system was superior to that in lithium battery system.

Partially etched Ti3AlC2 as a promising high capacity Lithium-ion battery anode.

PubMed

Chen, Xifan; Zhu, Yuanzhi; Zhu, Xiaoquan; Peng, Wenchao; Li, Yang; Zhang, Guoliang; Zhang, Fengbao; Fan, Xiaobin

2018-06-25

MXenes, a family of two-dimensional transition-metal carbide and nitride materials, are supposed to be the promising materials in energy storage because of the high electronic conductivity, hydrophilic surfaces and low diffusion barriers. MXenes are generally prepared by removing the "A" elements (A = Al, Si, Sn, etc.) from their corresponding MAX phases by using hydrofluoric acid (HF) and the other etching agents, despite the fact that these "A" elements usually have great volumetric and gravimetric capacities. Herein, we studied the etching progress of Ti3AlC2 and evaluated their anode performance in Lithium-ion batteries. We found that a partially etched sample (0.5h-peTi3C2Tx) showed much higher capacity (160 mA h g-1, 331.6 mA h cm-3 at 1C) when compared with the fully etched Ti3C2Tx (110 mA h g-1, 190.3 mA h cm-3 at 1C). Besides, a 99% capacity retention was observed even after 1000 cycles in the 0.5h-peTi3C2Tx anode. This interesting result can be explained, at least in part, by the alloying of the residue Al element during lithiation. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Charge–discharge properties of tin dioxide for sodium-ion battery

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

Park, Jinsoo; Park, Jin-Woo; Han, Jeong-Hui

Highlights: • The electrochemical reaction of SnO2 as an anode for Na-ion batteries was studied. • The SnO2 electrode delivered the initial discharge capacity of 747 mAh/g. • Alarge irreversible capacity (597 mAh/g)was observedin the first cycle. • The in-plain crack in the electrode caused the incompletereduction of SnO{sub 2}. - Abstract: Tin dioxide was investigated as an anode material for sodium-ion batteries. The Na/SnO{sub 2} cell delivered a first discharge capacity of 747 mAh/g, but the first charge capacity was 150 mAh/g. The irreversible capacity in the first cycle was examined through characterization by X-ray diffraction and scanning electron microscopy.more » X-ray diffraction analysis revealed that the SnO{sub 2} active material was not reduced fully to metallic Sn. Furrows and wrinkles were formed on the electrode surface owing to the volumetric expansion upon first discharge, which led to a deterioration of the electrode structure and a loss of electrical contact between the active materials. The analysis is summarized in the schematic drawing.« less

High-rate capability of three-dimensionally ordered macroporous T-Nb2O5 through Li+ intercalation pseudocapacitance

NASA Astrophysics Data System (ADS)

Lou, Shuaifeng; Cheng, Xinqun; Wang, Long; Gao, Jinlong; Li, Qin; Ma, Yulin; Gao, Yunzhi; Zuo, Pengjian; Du, Chunyu; Yin, Geping

2017-09-01

Orthorhombic Niobium oxide (T-Nb2O5) has been regarded as a promising anode material for high-rate lithium ion batteries (LIBs) due to its potential to operate at high rates with improved safety and high theoretical capacity of 200 mA h g-1. Herein, three-dimensionally ordered macroporous (3DOM) T-Nb2O5, with mesoporous hierarchical structure, was firstly prepared by a simple approach employing self-assembly polystyrene (PS) microspheres as hard templates. The obtained T-Nb2O5 anode material presents obvious and highly-efficiency pseudocapacitive Li+ intercalation behaviour, which plays a dominant role in the kinetics of electrode process. As a result, rapid Li+ intercalation/de-intercalation are achieved, leading to excellent rate capability and long cycle life. The 3DOM T-Nb2O5 shows a remarkable high capacity of 106 and 77 mA h g-1 at the rate of 20C and 50C. The work presented herein holds great promise for future design of material structure, and demonstrates the great potential of T-Nb2O5 as a practical high-rate anode material for LIBs.

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.

Stannic oxide spherical nanoparticles: an anode material with long-term cyclability for Li-ion rechargeable batteries

NASA Astrophysics Data System (ADS)

Kalubarme, Ramchandra S.; Kale, Bharat B.; Gosavi, Suresh W.

2017-08-01

Transition metal oxides are widely used in energy storage applications. Stannic oxide nanostructures are prepared using a controlled, NaOH assisted, simple precipitation method. The morphology of the prepared material confirms the formation of fine nanoparticles having a rutile stannic oxide (SnO2) phase, with cassiterite structure, and size distribution ~20 nm. On testing, as an anode material for a Li-ion battery, stannic oxide delivers a reversible charge capacity of 957 mAh g-1 at an applied current rate of C/10. The stannic oxide shows excellent rate performance displaying capacity of 577 mAh g-1 at 10 C and capacity of 919 mAh g-1 retained after 200 cycles at an applied current rate of C/2. The super performance of stannic oxide fine particles stem from both the effective diffusion of Li-ions to reaction sites through porous channels and weaker stress/strain during Li insertion/desertion owing to its fine size.

Flexible phosphorus doped carbon nanosheets/nanofibers: Electrospun preparation and enhanced Li-storage properties as free-standing anodes for lithium ion batteries

NASA Astrophysics Data System (ADS)

Li, Desheng; Wang, Dongya; Rui, Kun; Ma, Zhongyuan; Xie, Ling; Liu, Jinhua; Zhang, Yu; Chen, Runfeng; Yan, Yan; Lin, Huijuan; Xie, Xiaoji; Zhu, Jixin; Huang, Wei

2018-04-01

The emerging wearable and foldable electronic devices drive the development of flexible lithium ion batteries (LIBs). Carbon materials are considered as one of the most promising electrode materials for LIBs due to their light weight, low cost and good structural stability against repeated deformations. However, the specific capacity, rate capability and long-term cycling performance still need to be improved for their applications in next-generation LIBs. Herein, we report a facile approach for immobilizing phosphorus into a large-area carbon nanosheets/nanofibers interwoven free-standing paper for LIBs. As an anode material for LIBs, it shows high reversible capacity of 1100 mAh g-1 at a current density of 200 mA g-1, excellent rate capabilities (e.g., 200 mAh g-1 at 20,000 mA g-1). Even at a high current density of 1000 mA g-1, it still maintains a superior specific capacity of 607 mAh g-1 without obvious decay.

Interconnected silicon hollow nanospheres for lithium-ion battery anodes with long cycle life.

PubMed

Yao, Yan; McDowell, Matthew T; Ryu, Ill; Wu, Hui; Liu, Nian; Hu, Liangbing; Nix, William D; Cui, Yi

2011-07-13

Silicon is a promising candidate for the anode material in lithium-ion batteries due to its high theoretical specific capacity. However, volume changes during cycling cause pulverization and capacity fade, and improving cycle life is a major research challenge. Here, we report a novel interconnected Si hollow nanosphere electrode that is capable of accommodating large volume changes without pulverization during cycling. We achieved the high initial discharge capacity of 2725 mAh g(-1) with less than 8% capacity degradation every hundred cycles for 700 total cycles. Si hollow sphere electrodes also show a Coulombic efficiency of 99.5% in later cycles. Superior rate capability is demonstrated and attributed to fast lithium diffusion in the interconnected Si hollow structure.

Enhancing cycling durability of Li-ion batteries with hierarchical structured silicon-graphene hybrid anodes.

PubMed

Loveridge, Melanie J; Lain, Michael J; Huang, Qianye; Wan, Chaoying; Roberts, Alexander J; Pappas, George S; Bhagat, Rohit

2016-11-09

Hybrid anode materials consisting of micro-sized silicon (Si) particles interconnected with few-layer graphene (FLG) nanoplatelets and sodium-neutralized poly(acrylic acid) as a binder were evaluated for Li-ion batteries. The hybrid film has demonstrated a reversible discharge capacity of ∼1800 mA h g -1 with a capacity retention of 97% after 200 cycles. The superior electrochemical properties of the hybrid anodes are attributed to a durable, hierarchical conductive network formed between Si particles and the multi-scale carbon additives, with enhanced cohesion by the functional polymer binder. Furthermore, improved solid electrolyte interphase (SEI) stability is achieved from the electrolyte additives, due to the formation of a kinetically stable film on the surface of the Si.

Expanding pore sizes of ZIF-8-derived nitrogen-doped microporous carbon via C60 embedding: toward improved anode performance for the lithium-ion battery.

PubMed

Guan, Jian; Zhong, Xiongwu; Chen, Xiang; Zhu, Xianjun; Li, Panlong; Wu, Jianhua; Lu, Yalin; Yu, Yan; Yang, Shangfeng

2018-02-01

Porous carbon and nanocarbons have been extensively applied as anode materials for high-energy density lithium-ion batteries (LIBs). However, as another representative nanocarbon, fullerenes, such as C 60 , have been scarcely utilized in LIBs because of their poor electrochemical reversibility. Herein, we designed a novel C 60 -embedded nitrogen-doped microporous carbon material (denoted as C 60 @N-MPC), which was derived from a zeolitic imidazolate framework-8 (ZIF-8) precursor, demonstrating its promising application as a superior anode material for LIB. We first embedded C 60 in situ into a ZIF-8 matrix via a facile solid-state mechanochemical route, which acted as a precursor and was transformed to C 60 @N-MPC after carbonization. The C 60 @N-MPC was applied as a novel anode for LIBs, showing an improved reversible specific capacity of ≈1351 mA h g -1 at 0.1 A g -1 and a better rate capacity (≈1077 mA h g -1 at 1 A g -1 after 400 cycles) relative to those based on the unmodified N-MPC anode. The role of C 60 in the superior lithium storage performance of C 60 @N-MPC was elucidated, revealing that C 60 functioned as a pore expander for N-MPC with 3-20 nm mesopores (versus sub-1 nm micropores for the unmodified N-MPC), which facilitated the rapid diffusion of the organic electrolyte.

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.

High performance carbon nanotube-Si core-shell wires with a rationally structured core for lithium ion battery anodes.

PubMed

Fan, Yu; Zhang, Qing; Lu, Congxiang; Xiao, Qizhen; Wang, Xinghui; Tay, Beng Kang

2013-02-21

Core-shell Si nanowires are very promising anode materials. Here, we synthesize vertically aligned carbon nanotubes (CNTs) with relatively large diameters and large inter-wire spacing as core wires and demonstrate a CNT-Si core-shell wire composite as a lithium ion battery (LIB) anode. Owing to the rationally engineered core structure, the composite shows good capacity retention and rate performance. The excellent performance is superior to most core-shell nanowires previously reported.

Red Phosphorus-Embedded Cross-Link-Structural Carbon Films as Flexible Anodes for Highly Reversible Li-Ion Storage

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

Ruan, Jiafeng; Yuan, Tao; Pang, Yuepeng

Red phosphorus (P) is considered to be one of the most attractive anodic materials for lithium-ion batteries (LIBs) due to its high theoretical capacity of 2596 mAh g–1. However, intrinsic characteristics such as the poor electronic conductivity and large volume expansion at lithiation impede the development of red P. Here, we design a new strategy to embed red P particles into a cross-link-structural carbon film (P–C film), in order to improve the electronic conductivity and accommodate the volume expansion. The red P/carbon film is synthesized via vapor phase polymerization (VPP) followed by the pyrolysis process, working as a flexible binder-freemore » anode for LIBs. High cycle stability and good rate capability are achieved by the P–C film anode. With 21% P content in the film, it displays a capacity of 903 mAh g–1 after 640 cycles at a current density of 100 mA g–1 and a capacity of 460 mAh g–1 after 1000 cycles at 2.0 A g–1. Additionally, the Coulombic efficiency reaches almost 100% for each cycle. The superior properties of the P–C films together with their facile fabrication make this material attractive for further flexible and high energy density LIB applications.« less

Facile Synthesis of ZnO Nanoparticles on Nitrogen-Doped Carbon Nanotubes as High-Performance Anode Material for Lithium-Ion Batteries

PubMed Central

Li, Haipeng; Liu, Zhengjun; Yang, Shuang; Zhao, Yan; Feng, Yuting; Zhang, Chengwei; Yin, Fuxing

2017-01-01

ZnO/nitrogen-doped carbon nanotube (ZnO/NCNT) composite, prepared though a simple one-step sol-gel synthetic technique, has been explored for the first time as an anode material. The as-prepared ZnO/NCNT nanocomposite preserves a good dispersity and homogeneity of the ZnO nanoparticles (~6 nm) which deposited on the surface of NCNT. Transmission electron microscopy (TEM) reveals the formation of ZnO nanoparticles with an average size of 6 nm homogeneously deposited on the surface of NCNT. ZnO/NCNT composite, when evaluated as an anode for lithium-ion batteries (LIBs), exhibits remarkably enhanced cycling ability and rate capability compared with the ZnO/CNT counterpart. A relatively large reversible capacity of 1013 mAh·g−1 is manifested at the second cycle and a capacity of 664 mAh·g−1 is retained after 100 cycles. Furthermore, the ZnO/NCNT system displays a reversible capacity of 308 mAh·g−1 even at a high current density of 1600 mA·g−1. These electrochemical performance enhancements are ascribed to the reinforced accumulative effects of the well-dispersed ZnO nanoparticles and doping nitrogen atoms, which can not only suppress the volumetric expansion of ZnO nanoparticles during the cycling performance but also provide a highly conductive NCNT network for ZnO anode. PMID:28934141

Facile Synthesis of ZnO Nanoparticles on Nitrogen-Doped Carbon Nanotubes as High-Performance Anode Material for Lithium-Ion Batteries.

PubMed

Li, Haipeng; Liu, Zhengjun; Yang, Shuang; Zhao, Yan; Feng, Yuting; Bakenov, Zhumabay; Zhang, Chengwei; Yin, Fuxing

2017-09-21

ZnO/nitrogen-doped carbon nanotube (ZnO/NCNT) composite, prepared though a simple one-step sol-gel synthetic technique, has been explored for the first time as an anode material. The as-prepared ZnO/NCNT nanocomposite preserves a good dispersity and homogeneity of the ZnO nanoparticles (~6 nm) which deposited on the surface of NCNT. Transmission electron microscopy (TEM) reveals the formation of ZnO nanoparticles with an average size of 6 nm homogeneously deposited on the surface of NCNT. ZnO/NCNT composite, when evaluated as an anode for lithium-ion batteries (LIBs), exhibits remarkably enhanced cycling ability and rate capability compared with the ZnO/CNT counterpart. A relatively large reversible capacity of 1013 mAh·g -1 is manifested at the second cycle and a capacity of 664 mAh·g -1 is retained after 100 cycles. Furthermore, the ZnO/NCNT system displays a reversible capacity of 308 mAh·g -1 even at a high current density of 1600 mA·g -1 . These electrochemical performance enhancements are ascribed to the reinforced accumulative effects of the well-dispersed ZnO nanoparticles and doping nitrogen atoms, which can not only suppress the volumetric expansion of ZnO nanoparticles during the cycling performance but also provide a highly conductive NCNT network for ZnO 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 properties of tin oxide anodes for sodium-ion batteries

NASA Astrophysics Data System (ADS)

Lu, Ying Ching; Ma, Chuze; Alvarado, Judith; Kidera, Takafumi; Dimov, Nikolay; Meng, Ying Shirley; Okada, Shigeto

2015-06-01

Few tin (Sn)-oxide based anode materials have been found to have large reversible capacity for both sodium (Na)-ion and lithium (Li)-ion batteries. Herein, we report the synthesis and electrochemical properties of Sn oxide-based anodes for sodium-ion batteries: SnO, SnO2, and SnO2/C. Among them, SnO is the most suitable anode for Na-ion batteries with less first cycle irreversibility, better cycle life, and lower charge transfer resistance. The energy storage mechanism of the above-mentioned Sn oxides was studied, which suggested that the conversion reaction of the Sn oxide anodes is reversible in Na-ion batteries. The better anode performance of SnO is attributed by the better conductivity.

Reconstruction of Mini-Hollow Polyhedron Mn2O3 Derived from MOFs as a High-Performance Lithium Anode Material.

PubMed

Cao, Kangzhe; Jiao, Lifang; Xu, Hang; Liu, Huiqiao; Kang, Hongyan; Zhao, Yan; Liu, Yongchang; Wang, Yijing; Yuan, Huatang

2016-03-01

A mini-hollow polyhedron Mn 2 O 3 is used as the anode material for lithium-ion batteries. Benefiting from the small interior cavity and intrinsic nanosize effect, a stable reconstructed hierarchical nanostructure is formed. It has excellent energy storage properties, exhibiting a capacity of 760 mAh g -1 at 2 A g -1 after 1000 cycles. This finding offers a new perspective for the design of electrodes with large energy storage.

Preparation of PPy-Coated MnO2 Hybrid Micromaterials and Their Improved Cyclic Performance as Anode for Lithium-Ion Batteries

NASA Astrophysics Data System (ADS)

Feng, Lili; Zhang, Yinyin; Wang, Rui; Zhang, Yanli; Bai, Wei; Ji, Siping; Xuan, Zhewen; Yang, Jianhua; Zheng, Ziguang; Guan, Hongjin

2017-09-01

MnO2@PPy core-shell micromaterials are prepared by chemical polymerization of pyrrole on the MnO2 surface. The polypyrrole (PPy) is formed as a homogeneous organic shell on the MnO2 surface. The thickness of PPy shell can be adjusted by the usage of pyrrole. The analysis of SEM, FT-IR, X-ray photoelectron spectroscopy (XPS), thermo-gravimetric analysis (TGA), and XRD are used to confirm the formation of PPy shell. Galvanostatic cell cycling and electrochemical impedance spectroscopy (EIS) are used to evaluate the electrochemical performance as anode for lithium-ion batteries. The results show that after formation of MnO2@PPy core-shell micromaterials, the cyclic performance as anode for lithium-ion batteries is improved. Fifty microliters of PPy-coated caddice-clew-like MnO2 has the best cyclic performances as has 620 mAh g-1 discharge specific capacities after 300 cycles. As a comparison, the discharge specific capacity of bare MnO2 materials falls to below 200 mAh g-1 after 10 cycles. The improved lithium-storage cyclic stability of the MnO2@PPy samples attributes to the core-shell hybrid structure which can buffer the structural expansion and contraction of MnO2 caused by the repeated embedding and disengagement of Li ions and can prevent the pulverization of MnO2. This experiment provides an effective way to mitigate the problem of capacity fading of the transition metal oxide materials as anode materials for (lithium-ion batteries) LIBs.

Preparation of PPy-Coated MnO2 Hybrid Micromaterials and Their Improved Cyclic Performance as Anode for Lithium-Ion Batteries.

PubMed

Feng, Lili; Zhang, Yinyin; Wang, Rui; Zhang, Yanli; Bai, Wei; Ji, Siping; Xuan, Zhewen; Yang, Jianhua; Zheng, Ziguang; Guan, Hongjin

2017-09-02

MnO 2 @PPy core-shell micromaterials are prepared by chemical polymerization of pyrrole on the MnO 2 surface. The polypyrrole (PPy) is formed as a homogeneous organic shell on the MnO 2 surface. The thickness of PPy shell can be adjusted by the usage of pyrrole. The analysis of SEM, FT-IR, X-ray photoelectron spectroscopy (XPS), thermo-gravimetric analysis (TGA), and XRD are used to confirm the formation of PPy shell. Galvanostatic cell cycling and electrochemical impedance spectroscopy (EIS) are used to evaluate the electrochemical performance as anode for lithium-ion batteries. The results show that after formation of MnO 2 @PPy core-shell micromaterials, the cyclic performance as anode for lithium-ion batteries is improved. Fifty microliters of PPy-coated caddice-clew-like MnO 2 has the best cyclic performances as has 620 mAh g -1 discharge specific capacities after 300 cycles. As a comparison, the discharge specific capacity of bare MnO 2 materials falls to below 200 mAh g -1 after 10 cycles. The improved lithium-storage cyclic stability of the MnO 2 @PPy samples attributes to the core-shell hybrid structure which can buffer the structural expansion and contraction of MnO 2 caused by the repeated embedding and disengagement of Li ions and can prevent the pulverization of MnO 2 . This experiment provides an effective way to mitigate the problem of capacity fading of the transition metal oxide materials as anode materials for (lithium-ion batteries) LIBs.

Formation of Hierarchical Cu-Doped CoSe2 Microboxes via Sequential Ion Exchange for High-Performance Sodium-Ion Batteries.

PubMed

Fang, Yongjin; Yu, Xin-Yao; Lou, Xiong Wen David

2018-04-06

Electrode materials based on electrochemical conversion reactions have received considerable interest for high capacity anodes of sodium-ion batteries. However, their practical application is greatly hindered by the poor rate capability and rapid capacity fading. Tuning the structure at nanoscale and increasing the conductivity of these anode materials are two effective strategies to address these issues. Herein, a two-step ion-exchange method is developed to synthesize hierarchical Cu-doped CoSe 2 microboxes assembled by ultrathin nanosheets using Co-Co Prussian blue analogue microcubes as the starting material. Benefitting from the structural and compositional advantages, these Cu-doped CoSe 2 microboxes with improved conductivity exhibit enhanced sodium storage properties in terms of good rate capability and excellent cycling performance. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

In situ formed Si nanoparticle network with micron-sized Si particles for lithium-ion battery anodes.

PubMed

Wu, Mingyan; Sabisch, Julian E C; Song, Xiangyun; Minor, Andrew M; Battaglia, Vincent S; Liu, Gao

2013-01-01

To address the significant challenges associated with large volume change of micrometer-sized Si particles as high-capacity anode materials for lithium-ion batteries, we demonstrated a simple but effective strategy: using Si nanoparticles as a structural and conductive additive, with micrometer-sized Si as the main lithium-ion storage material. The Si nanoparticles connected into the network structure in situ during the charge process, to provide electronic connectivity and structure stability for the electrode. The resulting electrode showed a high specific capacity of 2500 mAh/g after 30 cycles with high initial Coulombic efficiency (73%) and good rate performance during electrochemical lithiation and delithiation: between 0.01 and 1 V vs Li/Li(+).

Chemical dealloying synthesis of porous silicon anchored by in situ generated graphene sheets as anode material for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Feng, Jinkui; Zhang, Zhen; Ci, Lijie; Zhai, Wei; Ai, Qing; Xiong, Shenglin

2015-08-01

A novel one-pot chemical dealloying method has been developed to prepare nanocomposite of reduced graphene oxide (RGO) and silicon dendrite from cheap commercial Al-Si eutectic precursor. The RGO anchoring could act as both conductive agent and buffer layer for Si volume change in the application of lithium ion batteries (LIBs). The Si/RGO composites show an initial reversible capacity of 2280 mAh g-1, excellent capacity retention of 1942 mAh g-1 even after 100 cycles, and a high capacity of 1521 mAh g-1 even at the rate of 4000 mA g-1. Electrochemical impedance spectroscopy (EIS) measurement proved that Si/RGO composite has the lower charge transfer resistance. This work proposes an economic and facile method to prepare silicon based anode material for next generation LIBs with high energy density.

Molecular Spring Enabled High-Performance Anode for Lithium Ion Batteries

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

Zheng, Tianyue; Jia, Zhe; Lin, Na

Flexible butyl interconnection segments are synthetically incorporated into an electronically conductive poly(pyrene methacrylate) homopolymer and its copolymer. The insertion of butyl segment makes the pyrene polymer more flexible, and can better accommodate deformation. This new class of flexible and conductive polymers can be used as a polymer binder and adhesive to facilitate the electrochemical performance of a silicon/graphene composite anode material for lithium ion battery application. They act like a “spring” to maintain the electrode mechanical and electrical integrity. High mass loading and high areal capacity, which are critical design requirements of high energy batteries, have been achieved in themore » electrodes composed of the novel binders and silicon/graphene composite material. A remarkable area capacity of over 5 mAh/cm 2 and volumetric capacity of over 1700 Ah/L have been reached at a high current rate of 333 mA/g.« less

Molecular Spring Enabled High-Performance Anode for Lithium Ion Batteries

DOE PAGES

Zheng, Tianyue; Jia, Zhe; Lin, Na; ...

2017-11-29

Flexible butyl interconnection segments are synthetically incorporated into an electronically conductive poly(pyrene methacrylate) homopolymer and its copolymer. The insertion of butyl segment makes the pyrene polymer more flexible, and can better accommodate deformation. This new class of flexible and conductive polymers can be used as a polymer binder and adhesive to facilitate the electrochemical performance of a silicon/graphene composite anode material for lithium ion battery application. They act like a “spring” to maintain the electrode mechanical and electrical integrity. High mass loading and high areal capacity, which are critical design requirements of high energy batteries, have been achieved in themore » electrodes composed of the novel binders and silicon/graphene composite material. A remarkable area capacity of over 5 mAh/cm 2 and volumetric capacity of over 1700 Ah/L have been reached at a high current rate of 333 mA/g.« less

Constructing inorganic/polymer microsphere composite as lithium ion battery anode material

NASA Astrophysics Data System (ADS)

Zhou, Nan; Dong, Hui; Xu, Yunlong; Luo, Lei; Zhao, Chongjun; Wang, Di; Li, Haoran; Liu, Dong

2018-03-01

Spinel Li4Ti5O12 (LTO) holds great potential used as lithium ion battery(LIB) anode material for various hybrid, plug-in, and pure electrical vehicle applications. However, the low intrinsic conductivity and much underused capacity pose serious obstacles in practice for its wider and deeper utilization. Here we demonstrate a facile approach by which an LTO/Si/cyclized-polyacrylonitrile (PAN) inorganic/polymer composite is designed and implemented in attempt to tackle both challenges. Our results show that an optimal Si amount is needed in the composite so as to fully promote underused LTO capacity in a stable state while cyclized PAN not only improves conductivity, reaction kinetics and charge transfer resistance of the electrode through its turbostratic transition, but to much extent acts as a resilient binder to offset volumetric expansion caused by Si. The optimized composite exhibits admirable capacity and cycling performance during long-term operation.

Template-Free Synthesis of Hollow-Structured Co 3 O 4 Nanoparticles as High-Performance Anodes for Lithium-Ion Batteries

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

Wang, Deli; Yu, Yingchao; He, Huan

2015-02-24

We have developed a template-free procedure to synthesize Co3O4 hollow-structured nanoparticles on a Vulcan XC-72 carbon support. The material was synthesized via an impregnation–reduction method followed by air oxidation. In contrast to spherical particles, the hollow-structured Co3O4 nanoparticles exhibited excellent lithium storage capacity, rate capability, and cycling stability when used as the anode material in lithium-ion batteries. Electrochemical testing showed that the hollow-structured Co3O4 particles delivered a stable reversible capacity of about 880 mAh/g (near the theoretical capacity of 890 mAh/g) at a current density of 50 mA/g after 50 cycles. The superior electrochemical performance is attributed to its uniquemore » hollow structure, which combines nano- and microscale properties that facilitate electron transfer and enhance structural robustness.« less

Rational Design of Si@SiO2/C Composites Using Sustainable Cellulose as a Carbon Resource for Anodes in Lithium-Ion Batteries.

PubMed

Shen, Dazhi; Huang, Chaofan; Gan, Lihui; Liu, Jian; Gong, Zhengliang; Long, Minnan

2018-03-07

In this work, we propose a novel and facile route for the rational design of Si@SiO 2 /C anode materials by using sustainable and environment-friendly cellulose as a carbon resource. To simultaneously obtain a SiO 2 layer and a carbon scaffold, a specially designed homogeneous cellulose solution and commercial Si nanopowder are used as the starting materials, and the cellulose/Si composite is directly assembled by an in situ regenerating method. Subsequently, Si@SiO 2 /C composite is obtained after carbonization. As expected, Si@SiO 2 is homogeneously encapsulated in the cellulose-derived carbon network. The obtained Si@SiO 2 /C composite shows a high reversible capacity of 1071 mA h g -1 at a current density of 420 mA g -1 and 70% capacity retention after 200 cycles. This novel, sustainable, and effective design is a promising approach to obtain high-performance and cost-effective composite anodes for practical applications.

Engineering Hollow Carbon Architecture for High-Performance K-Ion Battery Anode.

PubMed

Bin, De-Shan; Lin, Xi-Jie; Sun, Yong-Gang; Xu, Yan-Song; Zhang, Ke; Cao, An-Min; Wan, Li-Jun

2018-05-31

K-ion batteries (KIBs) are now drawing increasing research interest as an inexpensive alternative to Li-ion batteries (LIBs). However, due to the large size of K + , stable electrode materials capable of sustaining the repeated K + intercalation/deintercalation cycles are extremely deficient especially if a satisfactory reversible capacity is expected. Herein, we demonstrated that the structural engineering of carbon into a hollow interconnected architecture, a shape similar to the neuron-cell network, promised high conceptual and technological potential for a high-performance KIB anode. Using melamine-formaldehyde resin as the starting material, we identify an interesting glass blowing effect of this polymeric precursor during its carbonization, which features a skeleton-softening process followed by its spontaneous hollowing. When used as a KIB anode, the carbon scaffold with interconnected hollow channels can ensure a resilient structure for a stable potassiation/depotassiation process and deliver an extraordinary capacity (340 mAh g -1 at 0.1 C) together with a superior cycling stability (no obvious fading over 150 cycles at 0.5 C).

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

Facile synthesis of Sb2S3/MoS2 heterostructure as anode material for sodium-ion batteries.

PubMed

Zhang, Zhendong; Zhao, Jiachang; Xu, Meilan; Wang, Hongxia; Gong, Yanmei; Xu, Jingli

2018-05-18

A novel Sb2S3/MoS2 heterostructure in which Sb2S3 nanorods are coated with MoS2 nanosheets to form core-shell structure has been fabricated via a facile two-step hydrothermal process. The Sb2S3/MoS2 heterostructure utilized as anode of sodium-ion batteries (SIBs) shows higher capacity, superior rate capability and better cycling performance compared with individual Sb2S3 nanorods and MoS2 nanosheets. Specifically, the Sb2S3/MoS2 electrode shows an initial reversible capacity of 701 mAh g-1 at the current density of 100 mA g-1, which is remained 80.1% of the initial perforance after 100 cycles at the same current density. This outstanding electrochemical performance indicates Sb2S3/MoS2 heterostructure is a very promising anode material for high-performance SIBs. © 2018 IOP Publishing Ltd.

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 ).

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

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.

Enhancement of the electrochemical performance of hydrothermally prepared anatase nanoparticles for optimal use as high capacity anode materials in lithium ion batteries (LIBs)

NASA Astrophysics Data System (ADS)

Sanad, M. M. S.; Rashad, M. M.; Powers, K.

2015-02-01

Mesoporous TiO2 nanoparticles have been synthesized via facile hydrolytic hydrothermal technique without incorporation any template. The precious metallic nanoparticles; Ag, Pt and Pd have been embedded between the anatase particles using in situ reduction step. The structural properties of the as-synthesized samples were investigated by X-ray diffraction, transmission electron microscopic and N2 adsorption-desorption isotherm ( S BET). The electrochemical studies for the as-prepared anode materials including, cyclic voltammetry and electrochemical impedance spectroscopy indicated a significant improvement in the electronic conductivity of the lithium-TiO2 cells. Therefore, the charge-discharge rates were noticeably promoted as a result of the enhancement of Li-ion diffusion and charge transfer. The cycling results of Pd-TiO2 revealed a marvelous improvement in both charge and discharge capacities by 89.4 and 88 % after 10 cycles at C/5 rate. Generally, all the as-prepared TiO2 nanocomposites showed enhanced specific capacity, cycling stability and rate capability compared to the pure TiO2, providing a promising behavior for use as anodes in lithium ion batteries (LIBs).

Microwave-Assisted Preparation and Characterization of a Polyoxometalate-Based Inorganic 2D Framework Anode for Enhancing Lithium-Ion Battery Performance.

PubMed

Nie, Yan-Mei; Liang, Shuang; Yu, Wei-Dong; Yuan, Hao; Yan, Jun

2018-05-04

A pure inorganic 2D network molybdophosphate, [Mn 3 Mo 12 O 24 (OH) 6 (HPO 3 ) 8 (H 2 O) 6 ] 4- (1 a), synthesized through microwave irradiation with the existence of Mn 2+ and organic cations and isolated as [(CH 3 ) 2 NH 2 ] 3 Na[Mn 3 Mo 12 O 24 (OH) 6 (HPO 3 ) 8 (H 2 O) 6 ]⋅12 H 2 O (1), is found to possess highly enhanced performance in lithium-ion batteries' anode materials. The molecule shows multielectron redox properties suitable for producing anode materials with a specific capacity of 602 mA h g -1 at 100 mA g -1 after 50 cycles in lithium-ion batteries, although its specific capacity is the highest among all the reported pure inorganic 2D polyoxometalates to date, the cyclic stability is not that satisfactory. A hybrid nanocomposite of this 2D network and polypyrrole cations effectively reduces the capacity fading in initial cycles, and increases the stability and improves the electrochemical performance of lithium-ion batteries as well. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Database Approach for Predicting and Monitoring Baked Anode Properties

NASA Astrophysics Data System (ADS)

Lauzon-Gauthier, Julien; Duchesne, Carl; Tessier, Jayson

2012-11-01

The baked anode quality control strategy currently used by most carbon plants based on testing anode core samples in the laboratory is inadequate for facing increased raw material variability. The low core sampling rate limited by lab capacity and the common practice of reporting averaged properties based on some anode population mask a significant amount of individual anode variability. In addition, lab results are typically available a few weeks after production and the anodes are often already set in the reduction cells preventing early remedial actions when necessary. A database approach is proposed in this work to develop a soft-sensor for predicting individual baked anode properties at the end of baking cycle. A large historical database including raw material properties, process operating parameters and anode core data was collected from a modern Alcoa plant. A multivariate latent variable PLS regression method was used for analyzing the large database and building the soft-sensor model. It is shown that the general low frequency trends in most anode physical and mechanical properties driven by raw material changes are very well captured by the model. Improvements in the data infrastructure (instrumentation, sampling frequency and location) will be necessary for predicting higher frequency variations in individual baked anode properties. This paper also demonstrates how multivariate latent variable models can be interpreted against process knowledge and used for real-time process monitoring of carbon plants, and detection of faults and abnormal operation.

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.

Sustainable Potassium-Ion Battery Anodes Derived from Waste-Tire Rubber

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

Li, Yunchao; Adams, Ryan A.; Arora, Anjela

The recycling of waste-tire rubber is of critical importance since the discarded tires pose serious environmental and health hazards to our society. Here, we report a new application for hard-carbon materials derived from waste-tires as anodes in potassium-ion batteries. The sustainable tire-derived carbons show good reversible potassium insertion at relatively high rates. Long-term stability tests exhibit capacities of 155 and 141 mAh g –1 for carbon pyrolyzed at 1100°C and 1600°C, respectively, after 200 cycles at current rate of C/2. As a result, this study provides an alternative solution for inexpensive and environmental benign potassium-ion battery anode materials.

Sustainable Potassium-Ion Battery Anodes Derived from Waste-Tire Rubber

DOE PAGES

Li, Yunchao; Adams, Ryan A.; Arora, Anjela; ...

2017-04-13

The recycling of waste-tire rubber is of critical importance since the discarded tires pose serious environmental and health hazards to our society. Here, we report a new application for hard-carbon materials derived from waste-tires as anodes in potassium-ion batteries. The sustainable tire-derived carbons show good reversible potassium insertion at relatively high rates. Long-term stability tests exhibit capacities of 155 and 141 mAh g –1 for carbon pyrolyzed at 1100°C and 1600°C, respectively, after 200 cycles at current rate of C/2. As a result, this study provides an alternative solution for inexpensive and environmental benign potassium-ion battery anode materials.

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.

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.

NaAlTi 3O 8, A Novel Anode Material for Sodium Ion Battery

DOE PAGES

Ma, Xuetian; An, Ke; Bai, Jianmin; ...

2017-03-13

Sodium ion batteries are being considered as an alternative to lithium ion batteries in large-scale energy storage applications owing to the low cost. In this paper, a novel titanate compound, NaAlTi 3O 8, was successfully synthesized and tested as a promising anode material for sodium ion batteries. Powder X-ray Diffraction (XRD) and refinement were used to analyze the crystal structure. Electrochemical cycling tests under a C/10 rate between 0.01 - 2.5 V showed that ~83 mAh/g capacity could be achieved in the second cycle, with ~75% of which retained after 100 cycles, which corresponds to 0.75 Na + insertion andmore » extraction. The influence of synthesis conditions on electrochemical performances was investigated and discussed. Finally, NaAlTi 3O 8 not only presents a new anode material with low average voltage of ~0.5 V, but also provides a new type of intercalation anode with a crystal structure that differentiates from the anodes that have been reported.« less

Theoretical prediction of honeycomb carbon as Li-ion batteries anode material

NASA Astrophysics Data System (ADS)

Hu, Junping; Zhang, Xiaohang

2018-05-01

First principles calculations are performed to study the electronic properties and Li storage capability of honeycomb carbon. We find its right model consistent with the experimental result, the honeycomb carbon and its Li-intercalated configurations are all metallic which is beneficial to the electrode materials for lithium-ion batteries. The model 1 configuration shows fast Li diffusion and theoretical Li storage capacity of 319 mAh/g. Moreover, the average intercalation potentials for honeycomb carbon material is calculated to be low relatively. Our results suggest that the honeycomb carbon would be a new promising pure carbon anode material for Li-ion batteries.

Ultra-low cost and highly stable hydrated FePO4 anodes for aqueous sodium-ion battery

NASA Astrophysics Data System (ADS)

Wang, Yuesheng; Feng, Zimin; Laul, Dharminder; Zhu, Wen; Provencher, Manon; Trudeau, Michel L.; Guerfi, Abdelbast; Zaghib, Karim

2018-01-01

The growing demands for large-scale energy storage devices have put a spotlight on aqueous sodium-ion batteries, which possess a number of highly desirable features, such as sodium abundance, low cost and safety over organic electrolytes. While lots of cathode materials were reported, only few candidate materials like active carbon and NaTi2(PO4)3 were proposed as anodes. It is a long-standing common knowledge that the low cost, non-toxicity, and highly reversible FePO4·2H2O is known as an attractive cathode material for non-aqueous lithium- and sodium-ion batteries, but we demonstrate for the first time that nano-size non-carbon coated amorphous FePO4·2H2O can be used as the anode for an aqueous sodium-ion battery. Its optimum operating voltage (∼2.75 V vs. Na+/Na) avoids hydrogen evolution. The capacity is as high as 80 mAh/g at a rate of 0.5 C in a three-electrode system. The full cell, using the Na0.44MnO2 as cathode, maintained 90% of the capacity at 300 cycles at a rate of 3 C. The calculations also show that its volume change during the intercalation of Na ions is below 2%. Its low cost, high safety, along with its outstanding electrochemical performance makes amorphous FePO4·2H2O a promising anode material for aqueous sodium-ion batteries.

Fe3O4/C composite with hollow spheres in porous 3D-nanostructure as anode material for the lithium-ion batteries

NASA Astrophysics Data System (ADS)

Yang, Zhao; Su, Danyang; Yang, Jinping; Wang, Jing

2017-09-01

3d transition-metal oxides, especially Fe3O4, as anode materials for the lithium-ion batteries have been attracting intensive attentions in recent years due to their high energy capacity and low toxicity. A new Fe3O4/C composite with hollow spheres in porous three-dimensional (3D) nanostructure, which was synthesized by a facile solvothermal method using FeCl3·6H2O and porous spongy carbon as raw materials. The specific surface area and microstructures of composite were characterized by nitrogen adsorption-desorption isotherm method, FE-SEM and HR-TEM. A homogeneous distribution of hollow Fe3O4 spheres (diameter ranges from 120 nm to 150 nm) in the spongy carbon (pore size > 200 nm) conductive 3D-network significantly reduced the lithium-ion diffusion length and increased the electrochemical reaction area, and further more enhanced the lithium ion battery performance, such as discharge capacity and cycle life. As an anode material for the lithium-ion battery, the title composite exhibit excellent electrochemical properties. The Fe3O4/C composite electrode achieved a relatively high reversible specific capacity of 1450.1 mA h g-1 in the first cycle at 100 mA g-1, and excellent rate capability (69% retention at 1000 mA g-1) with good cycle stability (only 10% loss after 100 cycles).

Selenium and selenium-sulfur cathode materials for high-energy rechargeable magnesium batteries

NASA Astrophysics Data System (ADS)

Zhao-Karger, Zhirong; Lin, Xiu-Mei; Bonatto Minella, Christian; Wang, Di; Diemant, Thomas; Behm, R. Jürgen; Fichtner, Maximilian

2016-08-01

Magnesium (Mg) is an attractive metallic anode material for next-generation batteries owing to its inherent dendrite-free electrodeposition, high capacity and low cost. Here we report a new class of Mg batteries based on both elemental selenium (Se) and selenium-sulfur solid solution (SeS2) cathode materials. Elemental Se confined into a mesoporous carbon was used as a cathode material. Coupling the Se cathode with a metallic Mg anode in a non-nucleophilic electrolyte, the Se cathode delivered a high initial volumetric discharge capacity of 1689 mA h cm-3 and a reversible capacity of 480 mA h cm-3 was retained after 50 cycles at a high current density of 2 C. The mechanistic insights into the electrochemical conversion in Mg-Se batteries were investigated by microscopic and spectroscopic methods. The structural transformation of cyclic Se8 into chainlike Sen upon battery cycling was revealed by ex-situ Raman spectroscopy. In addition, the promising battery performance with a SeS2 cathode envisages the perspective of a series of SeSn cathode materials combining the benefits of both selenium and sulfur for high energy Mg batteries.

Rational Design of 1-D Co3O4 Nanofibers@Low content Graphene Composite Anode for High Performance Li-Ion Batteries

PubMed Central

Cho, Su-Ho; Jung, Ji-Won; Kim, Chanhoon; Kim, Il-Doo

2017-01-01

Cobalt oxide that has high energy density, is the next-generation candidate as the anode material for LIBs. However, the practical use of Co3O4 as anode material has been hindered by limitations, especially, low electrical conductivity and pulverization from large volume change upon cycling. These features lead to hindrance to its electrochemical properties for lithium-ion batteries. To improve electrochemical properties, we synthesized one-dimensional (1-D) Co3O4 nanofibers (NFs) overed with reduced graphene oxide (rGO) sheets by electrostatic self-assembly (Co3O4 NFs@rGO). The flexible graphene oxide sheets not only prevent volume changes of active materials upon cycling as a clamping layer but also provide efficient electrical pathways by three-dimensional (3-D) network architecture. When applied as an anode for LIBs, the Co3O4 NFs@rGO exhibits superior electrochemical performance: (i) high reversible capacity (615 mAh g−1 and 92% capacity retention after 400 cycles at 4.0 A g−1) and (ii) excellent rate capability. Herein, we highlighted that the enhanced conversion reaction of the Co3O4 NFs@rGO is attributed to effective combination of 1-D nanostructure and low content of rGO (~3.5 wt%) in hybrid composite. PMID:28345589

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

Amorphous silicon-carbon nanospheres synthesized by chemical vapor deposition using cheap methyltrichlorosilane as improved anode materials for Li-ion batteries.

PubMed

Zhang, Zailei; Zhang, Meiju; Wang, Yanhong; Tan, Qiangqiang; Lv, Xiao; Zhong, Ziyi; Li, Hong; Su, Fabing

2013-06-21

We report the preparation and characterization of amorphous silicon-carbon (Si-C) nanospheres as anode materials in Li-ion batteries. These nanospheres were synthesized by a chemical vapor deposition at 900 °C using methyltrichlorosilane (CH3SiCl3) as both the Si and C precursor, which is a cheap byproduct in the organosilane industry. The samples were characterized by X-ray diffraction, transmission electron microscopy, scanning electron microscopy, nitrogen adsorption, thermal gravimetric analysis, Raman spectroscopy, and X-ray photoelectron spectroscopy. It was found that the synthesized Si-C nanospheres composed of amorphous C (about 60 wt%) and Si (about 40 wt%) had a diameter of 400-600 nm and a surface area of 43.8 m(2) g(-1). Their charge capacities were 483.6, 331.7, 298.6, 180.6, and 344.2 mA h g(-1) at 50, 200, 500, 1000, and 50 mA g(-1) after 50 cycles, higher than that of the commercial graphite anode. The Si-C amorphous structure could absorb a large volume change of Si during Li insertion and extraction reactions and hinder the cracking or crumbling of the electrode, thus resulting in the improved reversible capacity and cycling stability. The work opens a new way to fabricate low cost Si-C anode materials for Li-ion batteries.

Evaluation of Carbon Anodes for Rechargeable Lithium Cells

NASA Technical Reports Server (NTRS)

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

1993-01-01

Both liquid phase intercalation technique and electrochemical intercalation technique were examined for the Li-carbon material preparation. The electrochemical techniques include a intermittent discharge method and a two step method. These two electrochemical techniques can ensure to achieve the maximum reversible Li capacity for common commercially available carbon materials. The carbon materials evaluated by the intercalacation method includes: pitch coke, petroleum cole, PAN fiber and graphite materials. Their reversible Li capacity were determined and compared. In this paper, we also demonstrate the importance of EPDM binder composition in the carbon electrode. Our results indicated that it can impact the Li intercalation and de-intercalation capacity in carbon materials. Finally, two possibilities that may help explain the capacity degradation during practical cell cycling were proposed.

Template-free fabrication of graphene-wrapped mesoporous ZnMn2O4 nanorings as anode materials for lithium-ion batteries.

PubMed

Zhou, Weiwei; Wang, Dong; Zhao, Limin; Ding, Chunyan; Jia, Xingtao; Du, Yu; Wen, Guangwu; Wang, Huatao

2017-06-16

We rationally designed a facile two-step approach to synthesize ZnMn 2 O 4 @G composite anode material for lithium-ion batteries (LIBs), involving a template-free fabrication of ZnMn 2 O 4 nanorings and subsequent coating of graphene sheets. Notably, it is the first time that ring-like ZnMn 2 O 4 nanostructure is reported. Moreover, our system has been demonstrated to be quite powerful in producing ZnMn 2 O 4 nanorings regardless of the types of Zn and Mn-containing metal salts reactants. The well-known inside-out Ostwald ripening process is tentatively proposed to clarify the formation mechanism of the hollow nanorings. When evaluated as anode material for LIBs, the resulting ZnMn 2 O 4 @G hybrid displays significantly improved lithium-storage performance with high specific capacity, good rate capability, and excellent cyclability. After 500 cycles, the ZnMn 2 O 4 @G hybrid can still deliver a reversible capacity of 958 mAh g -1 at a current density of 200 mA g -1 , much higher than the theoretical capacity of 784 mAh g -1 for pure ZnMn 2 O 4 . The outstanding electrochemical performance should be reasonably ascribed to the synergistic interaction between hollow and porous ZnMn 2 O 4 nanorings and the three-dimensional interconnected graphene sheets.

Hierarchical Carbon with High Nitrogen Doping Level: A Versatile Anode and Cathode Host Material for Long-Life Lithium-Ion and Lithium-Sulfur Batteries.

PubMed

Reitz, Christian; Breitung, Ben; Schneider, Artur; Wang, Di; von der Lehr, Martin; Leichtweiss, Thomas; Janek, Jürgen; Hahn, Horst; Brezesinski, Torsten

2016-04-27

Nitrogen-rich carbon with both a turbostratic microstructure and meso/macroporosity was prepared by hard templating through pyrolysis of a tricyanomethanide-based ionic liquid in the voids of a silica monolith template. This multifunctional carbon not only is a promising anode candidate for long-life lithium-ion batteries but also shows favorable properties as anode and cathode host material owing to a high nitrogen content (>8% after carbonization at 900 °C). To demonstrate the latter, the hierarchical carbon was melt-infiltrated with sulfur as well as coated by atomic layer deposition (ALD) of anatase TiO2, both of which led to high-quality nanocomposites. TiO2 ALD increased the specific capacity of the carbon while maintaining high Coulombic efficiency and cycle life: the composite exhibited stable performance in lithium half-cells, with excellent recovery of low rate capacities after thousands of cycles at 5C. Lithium-sulfur batteries using the sulfur/carbon composite also showed good cyclability, with reversible capacities of ∼700 mA·h·g(-1) at C/5 and without obvious decay over several hundred cycles. The present results demonstrate that nitrogen-rich carbon with an interconnected multimodal pore structure is very versatile and can be used as both active and inactive electrode material in high-performance lithium-based batteries.

Facile synthesis and lithium storage properties of a porous NiSi2/Si/carbon composite anode material for lithium-ion batteries.

PubMed

Jia, Haiping; Stock, Christoph; Kloepsch, Richard; He, Xin; Badillo, Juan Pablo; Fromm, Olga; Vortmann, Britta; Winter, Martin; Placke, Tobias

2015-01-28

In this work, a novel, porous structured NiSi2/Si composite material with a core-shell morphology was successfully prepared using a facile ball-milling method. Furthermore, the chemical vapor deposition (CVD) method is deployed to coat the NiSi2/Si phase with a thin carbon layer to further enhance the surface electronic conductivity and to mechanically stabilize the whole composite structure. The morphology and porosity of the composite material was evaluated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and nitrogen adsorption measurements (BJH analysis). The as-prepared composite material consists of NiSi2, silicon, and carbon phases, in which the NiSi2 phase is embedded in a silicon matrix having homogeneously distributed pores, while the surface of this composite is coated with a carbon layer. The electrochemical characterization shows that the porous and core-shell structure of the composite anode material can effectively absorb and buffer the immense volume changes of silicon during the lithiation/delithiation process. The obtained NiSi2/Si/carbon composite anode material displays an outstanding electrochemical performance, which gives a stable capacity of 1272 mAh g(-1) for 200 cycles at a charge/discharge rate of 1C and a good rate capability with a reversible capacity of 740 mAh g(-1) at a rate of 5C.

Structure and Performance of Epoxy Resin Cladded Graphite Used as Anode

NASA Astrophysics Data System (ADS)

Zhou, Zhentao; Li, Haijun

This paper is concerning to prepare modified natural graphite which is low-cost and advanced materials used as lithium ion battery anode using the way of cladding natural graphite with epoxy resin. The results shows that the specific capacity and circular performance of the modified natural graphite, which is prepared in the range of 600°C and 1000°C, have been apparently improved compare with the not-modified natural graphite. The first reversible capacity of the modified natural graphite is 338mAh/g and maintain more than 330mAh/g after 20 charge/discharge circles.

Co9 S8 /Co as a High-Performance Anode for Sodium-Ion Batteries with an Ether-Based Electrolyte.

PubMed

Zhao, Yingying; Pang, Qiang; Wei, Yingjin; Wei, Luyao; Ju, Yanming; Zou, Bo; Gao, Yu; Chen, Gang

2017-12-08

Co 9 S 8 has been regarded as a desirable anode material for sodium-ion batteries because of its high theoretical capacity. In this study, a Co 9 S 8 anode material containing 5.5 wt % Co (Co 9 S 8 /Co) was prepared by a solid-state reaction. The electrochemical properties of the material were studied in carbonate and ether-based electrolytes (EBE). The results showed that the material had a longer cycle life and better rate capability in EBE. This excellent electrochemical performance was attributed to a low apparent activation energy and a low overpotential for Na deposition in EBE, which improved the electrode kinetic properties. Furthermore, EBE suppressed side reactions of the electrode and electrolyte, which avoided the formation of a solid electrolyte interphase film. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preparation of Advanced CuO Nanowires/Functionalized Graphene Composite Anode Material for Lithium Ion Batteries.

PubMed

Zhang, Jin; Wang, Beibei; Zhou, Jiachen; Xia, Ruoyu; Chu, Yingli; Huang, Jia

2017-01-17

The copper oxide (CuO) nanowires/functionalized graphene (f-graphene) composite material was successfully composed by a one-pot synthesis method. The f-graphene synthesized through the Birch reduction chemistry method was modified with functional group "-(CH₂)₅COOH", and the CuO nanowires (NWs) were well dispersed in the f-graphene sheets. When used as anode materials in lithium-ion batteries, the composite exhibited good cyclic stability and decent specific capacity of 677 mA·h·g -1 after 50 cycles. CuO NWs can enhance the lithium-ion storage of the composites while the f-graphene effectively resists the volume expansion of the CuO NWs during the galvanostatic charge/discharge cyclic process, and provide a conductive paths for charge transportation. The good electrochemical performance of the synthesized CuO/f-graphene composite suggests great potential of the composite materials for lithium-ion batteries anodes.

Tin Oxynitride Anodes by Atomic Layer Deposition for Solid-State Batteries

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

Stewart, David M.; Pearse, Alexander J.; Kim, Nam S.

Major advances in thin-film solid-state batteries (TFSSBs) may capitalize on 3D structuring using high-aspect-ratio substrates such as nanoscale pits, pores, trenches, flexible polymers, and textiles. This will require conformal processes such as atomic layer deposition (ALD) for every active functional component of the battery. In this paper, we explore the deposition and electrochemical properties of SnO 2, SnN y, and SnO xN y thin films as TFSSB anode materials, grown by ALD using tetrakisdimethylamido(tin), H 2O, and N 2 plasma as precursors. By controlling the dose ratio between H 2O and N 2, the N–O fraction can be tuned betweenmore » 0% N and 95% N. The electrochemical properties of these materials were tested across a composition range varying from pure SnO 2, to SnON intermediates, and pure SnNy. In TFSSBs, the SnNy anodes are found to be more stable during cycling than the SnO 2 or SnO xN y films, with an initial reversible capacity beyond that of Li–Sn alloying, retaining 75% of their capacity over 200 cycles compared to only 50% for SnO 2. Lastly, the performance of the SnO xN y anodes indicates that SnN y anodes should not be negatively impacted by small levels of O contamination.« less

Tin Oxynitride Anodes by Atomic Layer Deposition for Solid-State Batteries

DOE PAGES

Stewart, David M.; Pearse, Alexander J.; Kim, Nam S.; ...

2018-03-30

Major advances in thin-film solid-state batteries (TFSSBs) may capitalize on 3D structuring using high-aspect-ratio substrates such as nanoscale pits, pores, trenches, flexible polymers, and textiles. This will require conformal processes such as atomic layer deposition (ALD) for every active functional component of the battery. In this paper, we explore the deposition and electrochemical properties of SnO 2, SnN y, and SnO xN y thin films as TFSSB anode materials, grown by ALD using tetrakisdimethylamido(tin), H 2O, and N 2 plasma as precursors. By controlling the dose ratio between H 2O and N 2, the N–O fraction can be tuned betweenmore » 0% N and 95% N. The electrochemical properties of these materials were tested across a composition range varying from pure SnO 2, to SnON intermediates, and pure SnNy. In TFSSBs, the SnNy anodes are found to be more stable during cycling than the SnO 2 or SnO xN y films, with an initial reversible capacity beyond that of Li–Sn alloying, retaining 75% of their capacity over 200 cycles compared to only 50% for SnO 2. Lastly, the performance of the SnO xN y anodes indicates that SnN y anodes should not be negatively impacted by small levels of O contamination.« less

A Scalable Strategy To Develop Advanced Anode for Sodium-Ion Batteries: Commercial Fe3O4-Derived Fe3O4@FeS with Superior Full-Cell Performance.

PubMed

Hou, Bao-Hua; Wang, Ying-Ying; Guo, Jin-Zhi; Zhang, Yu; Ning, Qiu-Li; Yang, Yang; Li, Wen-Hao; Zhang, Jing-Ping; Wang, Xin-Long; Wu, Xing-Long

2018-01-31

A novel core-shell Fe 3 O 4 @FeS composed of Fe 3 O 4 core and FeS shell with the morphology of regular octahedra has been prepared via a facile and scalable strategy via employing commercial Fe 3 O 4 as the precursor. When used as anode material for sodium-ion batteries (SIBs), the prepared Fe 3 O 4 @FeS combines the merits of FeS and Fe 3 O 4 with high Na-storage capacity and superior cycling stability, respectively. The optimized Fe 3 O 4 @FeS electrode shows ultralong cycle life and outstanding rate capability. For instance, it remains a capacity retention of 90.8% with a reversible capacity of 169 mAh g -1 after 750 cycles at 0.2 A g -1 and 151 mAh g -1 at a high current density of 2 A g -1 , which is about 7.5 times in comparison to the Na-storage capacity of commercial Fe 3 O 4 . More importantly, the prepared Fe 3 O 4 @FeS also exhibits excellent full-cell performance. The assembled Fe 3 O 4 @FeS//Na 3 V 2 (PO 4 ) 2 O 2 F sodium-ion full battery gives a reversible capacity of 157 mAh g -1 after 50 cycles at 0.5 A g -1 with a capacity retention of 92.3% and the Coulombic efficiency of around 100%, demonstrating its applicability for sodium-ion full batteries as a promising anode. Furthermore, it is also disclosed that such superior electrochemical properties can be attributed to the pseudocapacitive behavior of FeS shell as demonstrated by the kinetics studies as well as the core-shell structure. In view of the large-scale availability of commercial precursor and ease of preparation, this study provide a scalable strategy to develop advanced anode materials for SIBs.

Hierarchical porous nitrogen-rich carbon nanospheres with high and durable capabilities for lithium and sodium storage.

PubMed

Ma, Lianbo; Chen, Renpeng; Hu, Yi; Zhu, Guoyin; Chen, Tao; Lu, Hongling; Liang, Jia; Tie, Zuoxiu; Jin, Zhong; Liu, Jie

2016-10-20

To improve the energy storage performance of carbon-based materials, considerable attention has been paid to the design and fabrication of novel carbon architectures with structural and chemical modifications. Herein, we report that hierarchical porous nitrogen-rich carbon (HPNC) nanospheres originating from acidic etching of metal carbide/carbon hybrid nanoarchitectures can be employed as high-performance anode materials for both lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs). The structural advantages of HPNC nanospheres are that the exceptionally-high content of nitrogen (17.4 wt%) can provide abundant electroactive sites and enlarge the interlayer distance (∼3.5 Å) to improve the capacity, and the large amount of micropores and mesopores can serve as reservoirs for storing lithium/sodium ions. In LIBs, HPNC based anodes deliver a high reversible capacity of 1187 mA h g -1 after 100 cycles at 100 mA g -1 , a great rate performance of 470 mA h g -1 at 5000 mA g -1 , and outstanding cycling stabilities with a capacity of 788 mA h g -1 after 500 cycles at 1000 mA g -1 . In SIBs, HPNC based anodes exhibit a remarkable reversible capacity of 357 mA h g -1 at 100 mA g -1 and high long-term stability with a capacity of 136 mA h g -1 after 500 cycles at 1000 mA g -1 .

Inexpensive method for producing macroporous silicon particulates (MPSPs) with pyrolyzed polyacrylonitrile for lithium ion batteries

PubMed Central

Thakur, Madhuri; Sinsabaugh, Steven L.; Isaacson, Mark J.; Wong, Michael S.; Biswal, Sibani Lisa

2012-01-01

One of the most exciting areas in lithium ion batteries is engineering structured silicon anodes. These new materials promise to lead the next generation of batteries with significantly higher reversible charge capacity than current technologies. One drawback of these materials is that their production involves costly processing steps, limiting their application in commercial lithium ion batteries. In this report we present an inexpensive method for synthesizing macroporous silicon particulates (MPSPs). After being mixed with polyacrylonitrile (PAN) and pyrolyzed, MPSPs can alloy with lithium, resulting in capacities of 1000 mAhg−1 for over 600+ cycles. These sponge-like MPSPs with pyrolyzed PAN (PPAN) can accommodate the large volume expansion associated with silicon lithiation. This performance combined with low cost processing yields a competitive anode material that will have an immediate and direct application in lithium ion batteries. PMID:23139860

Synthesis of homogeneous CaMoO4 microspheres with nanopits for high-capacity anode material in Li-ion battery

NASA Astrophysics Data System (ADS)

You, Jiangfeng; Xin, Ling; Yu, Xiao; Zhou, Xiang; Liu, Yong

2018-03-01

Homogeneous CaMoO4 microspheres with interesting nanopit morphology were prepared by a simple one-step hydrothermal method. These microspheres had a very promising alternative structure for application in Li-ion batteries (LIBs), because they combined the advantages of both the primary nanosized and secondary microsized structures. The nanopits distributed on CaMoO4 material can accommodate volume change, increase their contacting surface and wetting property with electrolyte, and improve wetting contact between CaMoO4 material and electrolyte, leading to enhanced cycling stability and electrochemical performance. Meanwhile, the robust microsphere structure can both prevent aggregation and provide high tap density. When used as an anode in LIBs, the electrodes delivered a high discharge capacity of 434 mAh/g after 50 charge-discharge cycles at a current density of 200 mA/g, showing good cycling performance.

Ultrasmall Fe2GeO4 nanodots anchored on interconnected carbon nanosheets as high-performance anode materials for lithium and sodium ion batteries

NASA Astrophysics Data System (ADS)

Han, Jinzhi; Qin, Jian; Guo, Lichao; Qin, Kaiqiang; Zhao, Naiqin; Shi, Chunsheng; Liu, Enzuo; He, Fang; Ma, Liying; He, Chunnian

2018-01-01

Poor intrinsic conductivity and huge volume expansion during charge/discharge process greatly limit the development of Ge-based ternary oxide as anode material for both lithium-ion batteries and sodium-ion batteries. To alleviate these issues, an ideal strategy is developed to achieve active particle nanocrystallization and composite with conductive carbon materials, simultaneously. Therefore, ultrasmall Fe2GeO4 nanodots (∼4.6 nm) uniformly and tightly anchored on 3D interconnected N-doped ultrathin carbon nanosheets (3D Fe2GeO4/N-CNSs) were constructed via one-step high temperature calcination process. This unique hybrid nanostructure can not only effectively enhance electron conductivity but also restrict the aggregation and volume fluctuation of Fe2GeO4 during the charge/discharge process. As a result, the 3D Fe2GeO4/N-CNSs electrode exhibited excellent electrochemical performances for both lithium-ion and sodium-ion battery anodes. When utilized for lithium-ion battery anode, the electrode delivered a highly reversible specific capacity (1280 mA h g-1 at 0.4 A g-1 after 180 cycles). It is the first time that Fe2GeO4 was applied for sodium-ion battery anode, which showed a remarkable rate capability (350 mA h g-1 at 0.1 A g-1 and 180 mA h g-1 at 22.8 A g-1), and ultralong cycling stability (∼86% reversible capacity retention after 6000 cycles).

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).

Reduced Graphene Oxide-Wrapped FeS2 Composite as Anode for High-Performance Sodium-Ion Batteries

NASA Astrophysics Data System (ADS)

Wang, Qinghong; Guo, Can; Zhu, Yuxuan; He, Jiapeng; Wang, Hongqiang

2018-06-01

Iron disulfide is considered to be a potential anode material for sodium-ion batteries due to its high theoretical capacity. However, its applications are seriously limited by the weak conductivity and large volume change, which results in low reversible capacity and poor cycling stability. Herein, reduced graphene oxide-wrapped FeS2 (FeS2/rGO) composite was fabricated to achieve excellent electrochemical performance via a facile two-step method. The introduction of rGO effectively improved the conductivity, BET surface area, and structural stability of the FeS2 active material, thus endowing it with high specific capacity, good rate capability, as well as excellent cycling stability. Electrochemical measurements show that the FeS2/rGO composite had a high initial discharge capacity of 1263.2 mAh g-1 at 100 mA g-1 and a high discharge capacity of 344 mAh g-1 at 10 A g-1, demonstrating superior rate performance. After 100 cycles at 100 mA g-1, the discharge capacity remained at 609.5 mAh g-1, indicating the excellent cycling stability of the FeS2/rGO electrode.

Micro-Intertexture Carbon-Free Iron Sulfides as Advanced High Tap Density Anodes for Rechargeable Batteries.

PubMed

Xiao, Ying; Hwang, Jang-Yeon; Sun, Yang-Kook

2017-11-15

Numerous materials have been considered as promising electrode materials for rechargeable batteries; however, developing efficient materials to achieving good cycling performance and high volumetric energy capacity simultaneously remains a great challenge. Considering the appealing properties of iron sulfides, which include low cost, high theoretical capacity, and favorable electrochemical conversion mechanism, in this work, we demonstrate the feasibility of carbon-free microscale Fe 1-x S as high-efficiency anode materials for rechargeable batteries by designing hierarchical intertexture architecture. The as-prepared intertexture Fe 1-x S microspheres constructed from nanoscale units take advantage of both the long cycle life of nanoscale units and the high tap density (1.13 g cm -3 ) of the micro-intertexture Fe 1-x S. As a result, high capacities of 1089.2 mA h g -1 (1230.8 mA h cm -3 ) and 624.7 mA h g -1 (705.9 mA h cm -3 ) were obtained after 100 cycles at 1 A g -1 in Li-ion and Na-ion batteries, respectively, demonstrating one of the best performances for iron sulfide-based electrodes. Even after deep cycling at 20 A g -1 , satisfactory capacities could be retained. Related results promote the practical application of metal sulfides as high-capacity electrodes with high rate capability for next-generation rechargeable batteries.

Mesoporous Hollow Ge Microspheres Prepared via Molten-Salt Metallothermic Reaction for High-Performance Li-Storage Anode.

PubMed

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

2018-03-14

Generally, Ge-based anodes are prepared by metallothermic reduction of GeO 2 with Mg at 650 °C. Herein, a molten-salt system is developed a low-temperature metallothermic reduction of GeO 2 to prepare nanostructured Ge based anode materials. Typically, mesoporous hollow Ge microspheres are prepared by reduction of GeO 2 with metallic Mg in molten ZnCl 2 (mp 292) at 350 °C. Monodispersed Ge particles are synthesized through reduction of GeO 2 with Mg in molten AlCl 3 (mp 192 °C) at 250 °C. The meso-porous Ge anode delivers the reversible capacity of 1291 mA h g -1 at 0.2 C after 150 cycles with a retention of 97.3%, 1217 mA h g -1 at 0.8 C after 400 cycles with a retention of 91.9%, and superior rate capability with a capacity of 673 mA h g -1 even at 10 C. Then, the reaction mechanism and full-cell performance of as-prepared Ge anodes are studied systemically.

Micro-sized organometallic compound of ferrocene as high-performance anode material for advanced lithium-ion batteries

NASA Astrophysics Data System (ADS)

Liu, Zhen; Feng, Li; Su, Xiaoru; Qin, Chenyang; Zhao, Kun; Hu, Fang; Zhou, Mingjiong; Xia, Yongyao

2018-01-01

An organometallic compound of ferrocene is first investigated as a promising anode for lithium-ion batteries. The electrochemical properties of ferrocene are conducted by galvanostatic charge and discharge. The ferrocene anode exhibits a high reversible capacity and great cycling stability, as well as superior rate capability. The electrochemical reaction of ferrocene is semi-reversible and some metallic Fe remains in the electrode even after delithiation. The metallic Fe formed in electrode and the stable solid electrolyte interphase should be responsible for its excellent electrochemical performance.

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.

Minimizing Polysulfide Shuttle Effect in Lithium-Ion Sulfur Batteries by Anode Surface Passivation.

PubMed

Liu, Jian; Lu, Dongping; Zheng, Jianming; Yan, Pengfei; Wang, Biqiong; Sun, Xueliang; Shao, Yuyan; Wang, Chongmin; Xiao, Jie; Zhang, Ji-Guang; Liu, Jun

2018-06-25

Lithium-ion sulfur batteries use nonlithium materials as the anode for extended cycle life. However, polysulfide shuttle reactions still occur on the nonmetal anodes (such as graphite and Si), and result in undesirable low Coulombic efficiency. In this work, we used Al 2 O 3 layers coated by atomic layer deposition (ALD) technique to suppress the shuttle reactions. With the optimal thickness of 2 nm Al 2 O 3 coated on graphite anode, the Coulombic efficiency of the sulfur cathode was improved from 84% to 96% in the first cycle, and from 94% to 97% in the subsequent cycles. As a result, the discharge capacity of the sulfur cathode was increased to 550 mAh g -1 in the 100th cycle, as compared with 440 mAh g -1 when the pristine graphite anode was used. The Al 2 O 3 passivation layer minimizes the formation of insoluble sulfide (Li 2 S 2 , Li 2 S) on the surface of graphite anode and improves the efficiency and capacity retention of the graphite-sulfur batteries. The surface passivation strategy could also be used in other sulfur based battery systems (with Li, Si, and Sn anodes), to minimize side reactions and enable high-performance sulfur batteries.

Interface chemistry engineering for stable cycling of reduced GO/SnO2 nanocomposites for lithium ion battery.

PubMed

Wang, Lei; Wang, Dong; Dong, Zhihui; Zhang, Fengxing; Jin, Jian

2013-04-10

From the whole anode electrode of view, we report in this work a system-level strategy of fabrication of reduced graphene oxide (RGO)/SnO2 composite-based anode for lithium ion battery (LIB) to enhance the capacity and cyclic performance of SnO2-based electrode materials. RGO/SnO2 composite was first coated by a nanothick polydopamine (PD) layer and the PD-coated RGO/SnO2 composite was then cross-linked with poly(acrylic acid) (PAA) that was used as a binder to accomplish a whole anode electrode. The cross-link reaction between PAA and PD produced a robust network in the anode system to stabilize the whole anode during cycling. As a result, the designed anode exhibits an outstanding energy capacity up to 718 mAh/g at current density of 100 mA/g after 200 cycles and a good rate performance of 811, 700, 641, and 512 mAh/g at current density of 100, 250, 500, and 1000 mA/g, respectively. Fourier transform IR spectra confirm the formation of cross-link reaction and the stability of the robust network after long-term cycling. Our results indicate the importance of designing interfaces in anode system on achieving improved performance of electrode of LIBs.

Mechanochemically Reduced SiO2 by Ti Incorporation as Lithium Storage Materials.

PubMed

Kim, Kyungbae; Moon, Janghyuk; Lee, Jaewoo; Yu, Ji-Sang; Cho, Maenghyo; Cho, Kyeongjae; Park, Min-Sik; Kim, Jae-Hun; Kim, Young-Jun

2015-09-21

This study presents a simple and effective method of reducing amorphous silica (a-SiO2 ) with Ti metal through high-energy mechanical milling for improving its reactivity when used as an anode material in lithium-ion batteries. Through thermodynamic calculations, it is determined that Ti metal can easily take oxygen atoms from a-SiO2 by forming a thermodynamically stable SiO2-x /TiOx composite, meaning that electrochemically inactive a-SiO2 is partially reduced by the addition of Ti metal powder during milling. This mechanically reduced SiO2-x /TiOx composite anode exhibits a greatly improved electrochemical reactivity, with a reversible capacity of more than 700 mAh g(-1) and excellent cycle performance over 100 cycles. Furthermore, an enhancement in the mechanical and thermal stability of the composite during cycling can be mainly attributed to the in situ formation of the SiO2-x /TiOx phase. These findings provide new insight into the rational design of robust, high-capacity, Si-based anode materials, as well as their reaction mechanism. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Integrating 3D Flower-Like Hierarchical Cu2NiSnS4 with Reduced Graphene Oxide as Advanced Anode Materials for Na-Ion Batteries.

PubMed

Yuan, Shuang; Wang, Sai; Li, Lin; Zhu, Yun-hai; Zhang, Xin-bo; Yan, Jun-min

2016-04-13

Development of an anode material with high performance and low cost is crucial for implementation of next-generation Na-ion batteries (NIBs) electrode, which is proposed to meet the challenges of large scale renewable energy storage. Metal chalcogenides are considered as promising anode materials for NIBs due to their high theoretical capacity, low cost, and abundant sources. Unfortunately, their practical application in NIBs is still hindered because of low conductivity and morphological collapse caused by their volume expansion and shrinkage during Na(+) intercalation/deintercalation. To solve the daunting challenges, herein, we fabricated novel three-dimensional (3D) Cu2NiSnS4 nanoflowers (CNTSNs) as a proof-of-concept experiment using a facile and low-cost method. Furthermore, homogeneous integration with reduced graphene oxide nanosheets (RGNs) endows intrinsically insulated CNTSNs with superior electrochemical performances, including high specific capacity (up to 837 mAh g(-1)), good rate capability, and long cycling stability, which could be attributed to the unique 3D hierarchical structure providing fast ion diffusion pathway and high contact area at the electrode/electrolyte interface.

Centrifugal Spinning: An Alternative for Large Scale Production of Silicon-Carbon Composite Nanofibers for Lithium Ion Battery Anodes.

PubMed

Nava, Rocío; Cremar, Lee; Agubra, Victor; Sánchez, Jennifer; Alcoutlabi, Mataz; Lozano, Karen

2016-11-02

Composites made of silicon nanostructures in carbon matrixes are promising materials for anodes in Li ion batteries given the synergistic storage capacity of silicon combined with the chemical stability and electrical conductivity of carbonaceous materials. This work presents the development of Si/C composite fine fiber mats produced by carbonization of poly(vinyl alcohol) (PVA)/Si composites. PVA has a high carbon content (ca. 54.5%) and, being water-soluble, it promotes the development of environmentally friendly materials. Si nanoparticles were dispersed in PVA solutions and transformed into fine fibers using a centrifugal spinning technique given its potential for large scale production. The Si/PVA fibers mats were then subjected to dehydration by exposing them to sulfuric acid vapor. The dehydration improved the thermal and chemical stability of the PVA matrix, allowing further carbonization at 800 °C. The resulting Si/C composite fibers produced binder-free anodes for lithium ion batteries that delivered specific discharge and charge capacities of 952 mA h g -1 and 862 mA g -1 , respectively, with a Columbic efficiency of 99% after 50 cycles.

Ultrasmall Fe2O3 nanoparticles/MoS2 nanosheets composite as high-performance anode material for lithium ion batteries.

PubMed

Qu, Bin; Sun, Yue; Liu, Lianlian; Li, Chunyan; Yu, Changjian; Zhang, Xitian; Chen, Yujin

2017-02-20

Coupling ultrasmall Fe 2 O 3 particles (~4.0 nm) with the MoS 2 nanosheets is achieved by a facile method for high-performance anode material for Li-ion battery. MoS 2 nanosheets in the composite can serve as scaffolds, efficiently buffering the large volume change of Fe 2 O 3 during charge/discharge process, whereas the ultrasmall Fe 2 O 3 nanoparticles mainly provide the specific capacity. Due to bigger surface area and larger pore volume as well as strong coupling between Fe 2 O 3 particles and MoS 2 nanosheets, the composite exhibits superior electrochemical properties to MoS 2 , Fe 2 O 3 and the physical mixture Fe 2 O 3 +MoS 2 . Typically, after 140 cycles the reversible capacity of the composite does not decay, but increases from 829 mA h g -1 to 864 mA h g -1 at a high current density of 2 A g -1 . Thus, the present facile strategy could open a way for development of cost-efficient anode material with high-performance for large-scale energy conversion and storage systems.

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.

Carbon-Coated, Diatomite-Derived Nanosilicon as a High Rate Capable Li-ion Battery Anode

PubMed Central

Campbell, Brennan; Ionescu, Robert; Tolchin, Maxwell; Ahmed, Kazi; Favors, Zachary; Bozhilov, Krassimir N.; Ozkan, Cengiz S.; Ozkan, Mihrimah

2016-01-01

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 cm2 g−1, compared to a value of 7.3 cm2 g−1 for the original DE. DE contains SiO2 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 gSi−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 gSi−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). PMID:27713474

Carbon-Coated, Diatomite-Derived Nanosilicon as a High Rate Capable Li-ion Battery Anode

NASA Astrophysics Data System (ADS)

Campbell, Brennan; Ionescu, Robert; Tolchin, Maxwell; Ahmed, Kazi; Favors, Zachary; Bozhilov, Krassimir N.; Ozkan, Cengiz S.; Ozkan, Mihrimah

2016-10-01

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 cm2 g-1, compared to a value of 7.3 cm2 g-1 for the original DE. DE contains SiO2 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 gSi-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 gSi-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).

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.

Low-surface-area hard carbon anode for Na-ion batteries via graphene oxide as a dehydration agent

DOE PAGES

Luo, Wei; Bommier, Clement; Jian, Zelang; ...

2015-02-04

Na-ion batteries are emerging as one of the most promising energy storage technologies, particularly for grid-level applications. Among anode candidate materials, hard carbon is very attractive due to its high capacity and low cost. However, hard carbon anodes often suffer a low first-cycle Coulombic efficiency and fast capacity fading. In this study, we discover that doping graphene oxide into sucrose, the precursor for hard carbon, can effectively reduce the specific surface area of hard carbon to as low as 5.4 m²/g. We further reveal that such doping can effectively prevent foaming during caramelization of sucrose and extend the pyrolysis burn-offmore » of sucrose caramel over a wider temperature range. Thus, the obtained low-surface-area hard carbon greatly improves the first-cycle Coulombic efficiency from 74% to 83% and delivers a very stable cyclic life with 95% of capacity retention after 200 cycles.« less

Three-dimensional graphene foam supported Fe₃O₄ lithium battery anodes with long cycle life and high rate capability.

PubMed

Luo, Jingshan; Liu, Jilei; Zeng, Zhiyuan; Ng, Chi Fan; Ma, Lingjie; Zhang, Hua; Lin, Jianyi; Shen, Zexiang; Fan, Hong Jin

2013-01-01

Fe3O4 has long been regarded as a promising anode material for lithium ion battery due to its high theoretical capacity, earth abundance, low cost, and nontoxic properties. However, up to now no effective and scalable method has been realized to overcome the bottleneck of poor cyclability and low rate capability. In this article, we report a bottom-up strategy assisted by atomic layer deposition to graft bicontinuous mesoporous nanostructure Fe3O4 onto three-dimensional graphene foams and directly use the composite as the lithium ion battery anode. This electrode exhibits high reversible capacity and fast charging and discharging capability. A high capacity of 785 mAh/g is achieved at 1C rate and is maintained without decay up to 500 cycles. Moreover, the rate of up to 60C is also demonstrated, rendering a fast discharge potential. To our knowledge, this is the best reported rate performance for Fe3O4 in lithium ion battery to date.

Low-Surface-Area Hard Carbon Anode for Na-Ion Batteries via Graphene Oxide as a Dehydration Agent

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

Luo, W; Bommier, C; Jian, ZL

2015-02-04

Na-ion batteries are emerging as one of the most promising energy storage technologies, particularly for grid-level applications. Among anode candidate materials, hard carbon is very attractive due to its high capacity and low cost. However, hard carbon anodes often suffer a low first-cycle Coulombic efficiency and fast capacity fading. In this study, we discover that doping graphene oxide into sucrose, the precursor for hard carbon, can effectively reduce the specific surface area of hard carbon to as low as 5.4 m(2)/g. We further reveal that such doping can effectively prevent foaming during caramelization of sucrose and extend the pyrolysis burnoffmore » of sucrose caramel over a wider temperature range. The obtained low-surface-area hard carbon greatly improves the first-cycle Coulombic efficiency from 74% to 83% and delivers a very stable cyclic life with 95% of capacity retention after 200 cycles.« less

Graphene-bonded and -encapsulated si nanoparticles for lithium ion battery anodes.

PubMed

Wen, Yang; Zhu, Yujie; Langrock, Alex; Manivannan, Ayyakkannu; Ehrman, Sheryl H; Wang, Chunsheng

2013-08-26

Silicon (Si) has been considered a very promising anode material for lithium ion batteries due to its high theoretical capacity. However, high-capacity Si nanoparticles usually suffer from low electronic conductivity, large volume change, and severe aggregation problems during lithiation and delithiation. In this paper, a unique nanostructured anode with Si nanoparticles bonded and wrapped by graphene is synthesized by a one-step aerosol spraying of surface-modified Si nanoparticles and graphene oxide suspension. The functional groups on the surface of Si nanoparticles (50-100 nm) not only react with graphene oxide and bind Si nanoparticles to the graphene oxide shell, but also prevent Si nanoparticles from aggregation, thus contributing to a uniform Si suspension. A homogeneous graphene-encapsulated Si nanoparticle morphology forms during the aerosol spraying process. The open-ended graphene shell with defects allows fast electrochemical lithiation/delithiation, and the void space inside the graphene shell accompanied by its strong mechanical strength can effectively accommodate the volume expansion of Si upon lithiation. The graphene shell provides good electronic conductivity for Si nanoparticles and prevents them from aggregating during charge/discharge cycles. The functionalized Si encapsulated by graphene sample exhibits a capacity of 2250 mAh g⁻¹ (based on the total mass of graphene and Si) at 0.1C and 1000 mAh g⁻¹ at 10C, and retains 85% of its initial capacity even after 120 charge/discharge cycles. The exceptional performance of graphene-encapsulated Si anodes combined with the scalable and one-step aerosol synthesis technique makes this material very promising for lithium ion batteries. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hierarchical columnar silicon anode structures for high energy density lithium sulfur batteries

NASA Astrophysics Data System (ADS)

Piwko, Markus; Kuntze, Thomas; Winkler, Sebastian; Straach, Steffen; Härtel, Paul; Althues, Holger; Kaskel, Stefan

2017-05-01

Silicon is a promising anode material for next generation lithium secondary batteries. To significantly increase the energy density of state of the art batteries with silicon, new concepts have to be developed and electrode structuring will become a key technology. Structuring is essential to reduce the macroscopic and microscopic electrode deformation, caused by the volume change during cycling. We report pulsed laser structuring for the generation of hierarchical columnar silicon films with outstanding high areal capacities up to 7.5 mAh cm-2 and good capacity retention. Unstructured columnar electrodes form a micron-sized block structure during the first cycle to compensate the volume expansion leading to macroscopic electrode deformation. At increased silicon loading, without additional structuring, pronounced distortion and the formation of cracks through the current collector causes cell failure. Pulsed laser ablation instead is demonstrated to avoid macroscopic electrode deformation by initial formation of the block structure. A full cell with lithiated silicon versus a carbon-sulfur cathode is assembled with only 15% overbalanced anode and low electrolyte amount (8 μl mgsulfur-1). While the capacity retention over 50 cycles is identical to a cell with high excess lithium anode, the volumetric energy density could be increased by 30%.

Influence of the ZnO nanoarchitecture on the electrochemical performances of binder-free anodes for Li storage

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

Dall'Asta, V.; Tealdi, C.; Resmini, A.

Zinc oxide nanoarchitectures may be employed as binder-free, high specific capacity anodes for lithium batteries. By means of simple and low-impact wet chemistry approaches, we synthesized 1D (nanorods), 2D (single- and multi-layered nanosheets), and 3D (nanobrushes) ZnO arrays. These nanoarchitectures were compared as far as concerns their electrochemical properties and the structural modifications upon lithiation/delithiation. The best results were offered by 2D nanosheets, which showed reversible capacity of the order of 400 mAhg{sup −1} after 100 cycles at 1 Ag{sup −1}. This was due to: i) small nanoparticles, with average diameter of about 10 nm, which maximize the array specificmore » surface area and favor the formation of the LiZn alloy; ii) the presence of a mesoporous texture, which allows larger space for accommodating the volume changes upon lithiation/delithiation. However, also these 2D structures showed large irreversible capacity losses. Our work highlights the need for more efficient buffering solutions in ZnO binder-free nanostructured anodes. - Graphical abstract: ZnO nanosheets as anode materials for lithium batteries.« less

Molecular dynamics simulations of the first charge of a Li-ion—Si-anode nanobattery

DOE PAGES

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

2017-03-16

Rechargeable lithium-ion batteries are the most popular devices for energy storage but still a lot of research needs to be done to improve their cycling and storage capacity. Silicon has been proposed as an anode material because of its large theoretical capacity of ~3600 mAh/g. Therefore, focus is needed on the lithiation process of silicon anodes where it is known that the anode increases its volume more than 300%, producing cracking and other damages. In this study, we performed molecular dynamics atomistic simulations to study the swelling, alloying, and amorphization of a silicon nanocrystal anode in a full nanobattery modelmore » during the first charging cycle. A dissolved salt of lithium hexafluorophosphate in ethylene carbonate was chosen as the electrolyte solution and lithium cobalt oxide as cathode. External electric fields are applied to emulate the charging, causing the migration of the Li-ions from the cathode to the anode, by drifting through the electrolyte solution, thus converting pristine Si gradually into Li 14Si 5 when fully lithiated. When the electric field is applied to the nanobattery, the temperature never exceeds 360 K due to a temperature control imposed resembling a cooling mechanism. The volume of the anode increases with the amorphization of the silicon as the external field is applied by creating a layer of LiSi alloy between the electrolyte and the silicon nanocrystal and then, at the arrival of more Li-ions changing to an alloy, where the drift velocity of Li-ions is greater than the velocity in the initial nanocrystal structure. Charge neutrality is maintained by concerted complementary reduction-oxidation reactions at the anode and cathode, respectively. Also, the nanobattery model developed here can be used to study charge mobility, current density, conductance and resistivity, among several other properties of several candidate materials for rechargeable batteries and constitutes the initial point for further studies on the formation of the solid electrolyte interphase in the anode.« less

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.

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

2D Electrides as Promising Anode Materials for Na-Ion Batteries from First-Principles Study.

PubMed

Hu, Junping; Xu, Bo; Yang, Shengyuan A; Guan, Shan; Ouyang, Chuying; Yao, Yugui

2015-11-04

Searching for suitable anodes with good performance is a key challenge for rechargeable Na-ion batteries (NIBs). Using the first-principles method, we predict that 2D nitrogen electride materials can be served as anode materials for NIBs. Particularly, we show that Ca2N meets almost all the requirements of a good NIB anode. Each formula unit of a monolayer Ca2N sheet can absorb up to four Na atoms, corresponding to a theoretical specific capacity of 1138 mAh·g(-1). The metallic character for both pristine Ca2N and its Na intercalated state NaxCa2N ensures good electronic conduction. Na diffusion along the 2D monolayer plane can be very fast even at room temperature, with a Na migration energy barrier as small as 0.084 eV. These properties are key to the excellent rate performance of an anode material. The average open-circuit voltage is calculated to be 0.18 V vs Na/Na(+) for the chemical stoichiometry of Na2Ca2N and 0.09 V for Na4Ca2N. The relatively low average open-circuit voltage is beneficial to the overall voltage of the cell. In addition, the 2D monolayers have very small lattice change upon Na intercalation, which ensures a good cycling stability. All these results demonstrate that the Ca2N monolayer could be an excellent anode material for NIBs.

2D Frameworks of C2 N and C3 N as New Anode Materials for Lithium-Ion Batteries.

PubMed

Xu, Jiantie; Mahmood, Javeed; Dou, Yuhai; Dou, Shixue; Li, Feng; Dai, Liming; Baek, Jong-Beom

2017-09-01

Novel layered 2D frameworks (C 3 N and C 2 N-450) with well-defined crystal structures are explored for use as anode materials in lithium-ion batteries (LIBs) for the first time. As anode materials for LIBs, C 3 N and C 2 N-450 exhibit unusual electrochemical characteristics. For example, C 2 N-450 (and C 3 N) display high reversible capacities of 933.2 (383.3) and 40.1 (179.5) mAh g -1 at 0.1 and 10 C, respectively. Furthermore, C 3 N shows a low hypothetical voltage (≈0.15 V), efficient operating voltage window with ≈85% of full discharge capacity secured at >0.45 V, and excellent cycling stability for more than 500 cycles. The excellent electrochemical performance (especially of C 3 N) can be attributed to their inherent 2D polyaniline frameworks, which provide large net positive charge densities, excellent structural stability, and enhanced electronic/ionic conductivity. Stable solid state interface films also form on the surfaces of the 2D materials during the charge/discharge process. These 2D materials with promising electrochemical performance should provide insights to guide the design and development of their analogues for future energy applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An ultrastable anode for long-life room-temperature sodium-ion batteries.

PubMed

Yu, Haijun; Ren, Yang; Xiao, Dongdong; Guo, Shaohua; Zhu, Yanbei; Qian, Yumin; Gu, Lin; Zhou, Haoshen

2014-08-18

Sodium-ion batteries are important alternative energy storage devices that have recently come again into focus for the development of large-scale energy storage devices because sodium is an abundant and low-cost material. However, the development of electrode materials with long-term stability has remained a great challenge. A novel negative-electrode material, a P2-type layered oxide with the chemical composition Na(2/3)Co(1/3)Ti(2/3)O2, exhibits outstanding cycle stability (ca. 84.84 % capacity retention for 3000 cycles, very small decrease in the volume (0.046 %) after 500 cycles), good rate capability (ca. 41 % capacity retention at a discharge/charge rate of 10 C), and a usable reversible capacity of about 90 mAh g(-1) with a safe average storage voltage of approximately 0.7 V in the sodium half-cell. This P2-type layered oxide is a promising anode material for sodium-ion batteries with a long cycle life and should greatly promote the development of room-temperature sodium-ion batteries. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Application of silicon zig-zag wall arrays for anodes of Li-ion batteries

NASA Astrophysics Data System (ADS)

Li, G. V.; Rumyantsev, A. M.; Levitskii, V. S.; Beregulin, E. V.; Zhdanov, V. V.; Terukov, E. I.; Astrova, E. V.

2016-01-01

Cyclic tests of anodes based on zigzag wall arrays fabricated by the electrochemical etching and post-anodization treatment of silicon have been performed. Compared with anodes based on nanowires and planar thin films, these structures have several advantages. An ex situ analysis of the morphology and structural transformations in a material subjected to cyclic lithiation was conducted by electron microscopy and micro-Raman spectroscopy. The effect of geometrical parameters and a cycling mode on the degradation rate was studied. It is shown that a significant rise in the cycle life of the anode can be obtained by the restriction of the inserted amount of lithium. The anode, subjected to galvanostatic cycling at a rate C/2.8 at a limited charge capacity of 1000 mA · h g-1, demonstrates no degradation after 1200 cycles.

Metallurgically lithiated SiOx anode with high capacity and ambient air compatibility

PubMed Central

Zhao, Jie; Lee, Hyun-Wook; Sun, Jie; Yan, Kai; Liu, Yayuan; Liu, Wei; Lu, Zhenda; Lin, Dingchang; Zhou, Guangmin; Cui, Yi

2016-01-01

A common issue plaguing battery anodes is the large consumption of lithium in the initial cycle as a result of the formation of a solid electrolyte interphase followed by gradual loss in subsequent cycles. It presents a need for prelithiation to compensate for the loss. However, anode prelithiation faces the challenge of high chemical reactivity because of the low anode potential. Previous efforts have produced prelithiated Si nanoparticles with dry air stability, which cannot be stabilized under ambient air. Here, we developed a one-pot metallurgical process to synthesize LixSi/Li2O composites by using low-cost SiO or SiO2 as the starting material. The resulting composites consist of homogeneously dispersed LixSi nanodomains embedded in a highly crystalline Li2O matrix, providing the composite excellent stability even in ambient air with 40% relative humidity. The composites are readily mixed with various anode materials to achieve high first cycle Coulombic efficiency (CE) of >100% or serve as an excellent anode material by itself with stable cyclability and consistently high CEs (99.81% at the seventh cycle and ∼99.87% for subsequent cycles). Therefore, LixSi/Li2O composites achieved balanced reactivity and stability, promising a significant boost to lithium ion batteries. PMID:27313206

A Facile Electrophoretic Deposition Route to the Fe3O4/CNTs/rGO Composite Electrode as a Binder-Free Anode for Lithium Ion Battery.

PubMed

Yang, Yang; Li, Jiaqi; Chen, Dingqiong; Zhao, Jinbao

2016-10-12

Fe 3 O 4 is regarded as an attractive anode material for lithium ion batteries (LIBs) due to its high theoretical capacity, natural abundance, and low cost. However, the poor cyclic performance resulting from the low conductivity and huge volume change during cycling impedes its application. Here we have developed a facile electrophoretic deposition route to fabricate the Fe 3 O 4 /CNTs (carbon nanotubes)/rGO (reduced graphene oxide) composite electrode, simultaneously achieving material synthesis and electrode assembling. Even without binders, the adhesion and mechanical firmness of the electrode are strong enough to be used for LIB anode. In this specific structure, Fe 3 O 4 nanoparticles (NPs) interconnected by CNTs are sandwiched by rGO layers to form a robust network with good conductivity. The resulting Fe 3 O 4 /CNTs/rGO composite electrode exhibits much improved electrochemical performance (high reversible capacity of 540 mAh g -1 at a very high current density of 10 A g -1 , and a remarkable capacity of 1080 mAh g -1 can be maintained after 450 cycles at 1 A g -1 ) compared with that of commercial Fe 3 O 4 NPs electrode.

Review on recent progress of nanostructured anode materials for Li-ion batteries

NASA Astrophysics Data System (ADS)

Goriparti, Subrahmanyam; Miele, Ermanno; De Angelis, Francesco; Di Fabrizio, Enzo; Proietti Zaccaria, Remo; Capiglia, Claudio

2014-07-01

This review highlights the recent research advances in active nanostructured anode materials for the next generation of Li-ion batteries (LIBs). In fact, in order to address both energy and power demands of secondary LIBs for future energy storage applications, it is required the development of innovative kinds of electrodes. Nanostructured materials based on carbon, metal/semiconductor, metal oxides and metal phosphides/nitrides/sulfides show a variety of admirable properties for LIBs applications such as high surface area, low diffusion distance, high electrical and ionic conductivity. Therefore, nanosized active materials are extremely promising for bridging the gap towards the realization of the next generation of LIBs with high reversible capacities, increased power capability, long cycling stability and free from safety concerns. In this review, anode materials are classified, depending on their electrochemical reaction with lithium, into three groups: intercalation/de-intercalation, alloy/de-alloy and conversion materials. Furthermore, the effect of nanoscale size and morphology on the electrochemical performance is presented. Synthesis of the nanostructures, lithium battery performance and electrode reaction mechanisms are also discussed. To conclude, the main aim of this review is to provide an organic outline of the wide range of recent research progresses and perspectives on nanosized active anode materials for future LIBs.

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.

Si/C hybrid nanostructures for Li-ion anodes: An overview

NASA Astrophysics Data System (ADS)

Terranova, Maria Letizia; Orlanducci, Silvia; Tamburri, Emanuela; Guglielmotti, Valeria; Rossi, Marco

2014-01-01

This review article summarizes recent and increasing efforts in the development of novel Li ion cell anode nanomaterials based on the coupling of C with Si. The rationale behind such efforts is based on the fact that the Si-C coupling realizes a favourable combination of the two materials properties, such as the high lithiation capacity of Si and the mechanical and conductive properties of C, making Si/C hybrid nanomaterials the ideal candidates for innovative and improved Li-ion anodes. Together with an overview of the methodologies proposed in the last decade for material preparation, a discussion on relationship between organization at the nanoscale of the hybrid Si/C systems and battery performances is given. An emerging indication is that the enhancement of the batteries efficiency in terms of mass capacity, energy density and cycling stability, resides in the ability to arrange Si/C bi-component nanostructures in pre-defined architectures. Starting from the results obtained so far, this paper aims to indicate some emerging directions and to inspire promising routes to optimize fabrication of Si/C nanomaterials and engineering of Li-ion anodes structures. The use of Si/C hybrid nanostructures could represents a viable and effective solution to the foreseen limits of present lithium ion technology.

Spectral observations of hole injection with transition metal oxides for an efficient organic light-emitting diode

NASA Astrophysics Data System (ADS)

Chiu, Tien-Lung; Chuang, Ya-Ting

2015-02-01

Transition metal oxides, such as molybdenum trioxide (MoO3), tungsten trioxide (WO3) and vanadium pent-oxide (V2O5), are well-known hole injection materials used for organic electronic devices. These materials promote work functions of anodes, reduce energy barriers, and facilitate hole transport at the interface between the inorganic anode and organic hole-transporting layer (HTL). In this study, we characterized the transmittance spectra and work function of these materials. Furthermore, we employed a hole-injection layer (HIL) in a blue phosphorescent organic light-emitting diode (OLED) to evaluate their hole-injection capacity by detecting the variation in the emission spectra. Thus, we utilized an OLED structure that has fast electron transporting dynamics to establish the recombination zone located at emitting layer and a partial HTL close to the anode. We used these three transition metal oxides individually as HILs sandwiched between the ITO anode and HTL and concluded that the strength of emissive light from the HTL was determined by their hole-injection capacity, depending on work function. The small amount of HTL emission light of the V2O5 OLED was explained by the high work function of 5.8 eV for the V2O5 film. However, the V2O5 OLED demonstrated the least favorable optoelectrical performance because of its low transmittance and high resistance of the V2O5 film. Ultimately, the 5 nm-MoO3 OLED exhibited the highest device performance because of its high material conductivity and transparency in the visible band.

A silicon nanowire-reduced graphene oxide composite as a high-performance lithium ion battery anode material.

PubMed

Ren, Jian-Guo; Wang, Chundong; Wu, Qi-Hui; Liu, Xiang; Yang, Yang; He, Lifang; Zhang, Wenjun

2014-03-21

Toward the increasing demands of portable energy storage and electric vehicle applications, silicon has been emerging as a promising anode material for lithium-ion batteries (LIBs) owing to its high specific capacity. However, serious pulverization of bulk silicon during cycling limits its cycle life. Herein, we report a novel hierarchical Si nanowire (Si NW)-reduced graphene oxide (rGO) composite fabricated using a solvothermal method followed by a chemical vapor deposition process. In the composite, the uniform-sized [111]-oriented Si NWs are well dispersed on the rGO surface and in between rGO sheets. The flexible rGO enables us to maintain the structural integrity and to provide a continuous conductive network of the electrode, which results in over 100 cycles serving as an anode in half cells at a high lithium storage capacity of 2300 mA h g(-1). Due to its [111] growth direction and the large contact area with rGO, the Si NWs in the composite show substantially enhanced reaction kinetics compared with other Si NWs or Si particles.

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

Xu, Gui-Liang; Chen, Zonghai; Zhong, Gui-Ming

Sodium-ion batteries are promising alternatives to lithium-ion batteries for large-scale applications. However, the low capacity and poor rate capability of existing anodes for sodium-ion batteries are bottlenecks for future developments. Here, we report a high performance nanostructured anode material for sodium-ion batteries that is fabricated by high energy ball milling to form black phosphorus/Ketjenblack–multiwalled carbon nanotubes (BPC) composite. With this strategy, the BPC composite with a high phosphorus content (70 wt %) could deliver a very high initial Coulombic efficiency (>90%) and high specific capacity with excellent cyclability at high rate of charge/discharge (~1700 mAh g–1 after 100 cycles atmore » 1.3 A g–1 based on the mass of P). In situ electrochemical impedance spectroscopy, synchrotron high energy X-ray diffraction, ex situ small/wide-angle X-ray scattering, high resolution transmission electronic microscopy, and nuclear magnetic resonance were further used to unravel its superior sodium storage performance. The scientific findings gained in this work are expected to serve as a guide for future design on high performance anode material for sodium-ion batteries.« less

Lithium ion batteries based on nanoporous silicon

DOEpatents

Tolbert, Sarah H.; Nemanick, Eric J.; Kang, Chris Byung-Hwa

2015-09-22

A lithium ion battery that incorporates an anode formed from a Group IV semiconductor material such as porous silicon is disclosed. The battery includes a cathode, and an anode comprising porous silicon. In some embodiments, the anode is present in the form of a nanowire, a film, or a powder, the porous silicon having a pore diameters within the range between 2 nm and 100 nm and an average wall thickness of within the range between 1 nm and 100 nm. The lithium ion battery further includes, in some embodiments, a non-aqueous lithium containing electrolyte. Lithium ion batteries incorporating a porous silicon anode demonstrate have high, stable lithium alloying capacity over many cycles.

Unique Cobalt Sulfide/Reduced Graphene Oxide Composite as an Anode for Sodium-Ion Batteries with Superior Rate Capability and Long Cycling Stability.

PubMed

Peng, Shengjie; Han, Xiaopeng; Li, Linlin; Zhu, Zhiqiang; Cheng, Fangyi; Srinivansan, Madhavi; Adams, Stefan; Ramakrishna, Seeram

2016-03-09

Exploitation of high-performance anode materials is essential but challenging to the development of sodium-ion batteries (SIBs). Among all proposed anode materials for SIBs, sulfides have been proved promising candidates due to their unique chemical and physical properties. In this work, a facile solvothermal method to in situ decorate cobalt sulfide (CoS) nanoplates on reduced graphene oxide (rGO) to build CoS@rGO composite is described. When evaluated as anode for SIBs, an impressive high specific capacity (540 mAh g(-1) at 1 A g(-1) ), excellent rate capability (636 mAh g(-1) at 0.1 A g(-1) and 306 mAh g(-1) at 10 A g(-1)), and extraordinarily cycle stability (420 mAh g(-1) at 1 A g(-1) after 1000 cycles) have been demonstrated by CoS@rGO composite for sodium storage. The synergetic effect between the CoS nanoplates and rGO matrix contributes to the enhanced electrochemical performance of the hybrid composite. The results provide a facile approach to fabricate promising anode materials for high-performance SIBs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microwave-Assisted Synthesis of NiCo2O4 Double-Shelled Hollow Spheres for High-Performance Sodium Ion Batteries

NASA Astrophysics Data System (ADS)

Zhang, Xiong; Zhou, Yanping; Luo, Bin; Zhu, Huacheng; Chu, Wei; Huang, Kama

2018-03-01

The ternary transitional metal oxide NiCo2O4 is a promising anode material for sodium ion batteries due to its high theoretical capacity and superior electrical conductivity. However, its sodium storage capability is severely limited by the sluggish sodiation/desodiation reaction kinetics. Herein, NiCo2O4 double-shelled hollow spheres were synthesized via a microwave-assisted, fast solvothermal synthetic procedure in a mixture of isopropanol and glycerol, followed by annealing. Isopropanol played a vital role in the precipitation of nickel and cobalt, and the shrinkage of the glycerol quasi-emulsion under heat treatment was responsible for the formation of the double-shelled nanostructure. The as-synthesized product was tested as an anode material in a sodium ion battery, was found to exhibit a high reversible specific capacity of 511 mAh g-1 at 100 mA g-1, and deliver high capacity retention after 100 cycles. [Figure not available: see fulltext.

Bulk antimony sulfide with excellent cycle stability as next-generation anode for lithium-ion batteries

PubMed Central

Yu, Denis Y. W.; Hoster, Harry E.; Batabyal, Sudip K.

2014-01-01

Nanomaterials as anode for lithium-ion batteries (LIB) have gained widespread interest in the research community. However, scaling up and processibility are bottlenecks to further commercialization of these materials. Here, we report that bulk antimony sulfide with a size of 10–20 μm exhibits a high capacity and stable cycling of 800 mAh g−1. Mechanical and chemical stabilities of the electrodes are ensured by an optimal electrode-electrolyte system design, with a polyimide-based binder together with fluoroethylene carbonate in the electrolyte. The polyimide binder accommodates the volume expansion during alloying process and fluoroethylene carbonate suppresses the increase in charge transfer resistance of the electrodes. We observed that particle size is not a major factor affecting the charge-discharge capacities, rate capability and stability of the material. Despite the large particle size, bulk antimony sulfide shows excellent rate performance with a capacity of 580 mAh g−1 at a rate of 2000 mA g−1. PMID:24691396

Electrochemical performance of potassium-doped wüstite nanoparticles supported on graphene as an anode material for lithium ion batteries

NASA Astrophysics Data System (ADS)

Jung, Dong-Won; Jeong, Jae-Hoon; Han, Sang-Wook; Oh, Eun-Suok

2016-05-01

A graphene composite with potassium-doped FeO nanoparticles (K-FeO/graphene) is synthesized by the thermal diffusion of potassium into Fe2O3/graphene using polyol reduction. This is applied as anode material in lithium ion batteries in order to enhance the electrochemical performance of conventional iron oxides (hematite or magnetite). Rhombohedral Fe2O3 crystals are transformed into face-centered cubic FeO crystals, which show a broad d-spacing (5.2 Å) between their (111) crystal planes, by the calcination of potassium-added Fe2O3/graphene. Because of its structural characteristics, the K-FeO/graphene composite demonstrates an excellent discharge capacity of 1776 mA h g-1 at the 50th cycle at a current of 100 mA h g-1 with stable capacity retention. Even with the very high current density of 18.56 A g-1, its capacity remains at 851 mA h g-1 after 800 cycles.

A high performance lithium ion capacitor achieved by the integration of a Sn-C anode and a biomass-derived microporous activated carbon cathode

NASA Astrophysics Data System (ADS)

Sun, Fei; Gao, Jihui; Zhu, Yuwen; Pi, Xinxin; Wang, Lijie; Liu, Xin; Qin, Yukun

2017-02-01

Hybridizing battery and capacitor materials to construct lithium ion capacitors (LICs) has been regarded as a promising avenue to bridge the gap between high-energy lithium ion batteries and high-power supercapacitors. One of the key difficulties in developing advanced LICs is the imbalance in the power capability and charge storage capacity between anode and cathode. Herein, we design a new LIC system by integrating a rationally designed Sn-C anode with a biomass-derived activated carbon cathode. The Sn-C nanocomposite obtained by a facile confined growth strategy possesses multiple structural merits including well-confined Sn nanoparticles, homogeneous distribution and interconnected carbon framework with ultra-high N doping level, synergically enabling the fabricated anode with high Li storage capacity and excellent rate capability. A new type of biomass-derived activated carbon featuring both high surface area and high carbon purity is also prepared to achieve high capacity for cathode. The assembled LIC (Sn-C//PAC) device delivers high energy densities of 195.7 Wh kg-1 and 84.6 Wh kg-1 at power densities of 731.25 W kg-1 and 24375 W kg-1, respectively. This work offers a new strategy for designing high-performance hybrid system by tailoring the nanostructures of Li insertion anode and ion adsorption cathode.

A high performance lithium ion capacitor achieved by the integration of a Sn-C anode and a biomass-derived microporous activated carbon cathode.

PubMed

Sun, Fei; Gao, Jihui; Zhu, Yuwen; Pi, Xinxin; Wang, Lijie; Liu, Xin; Qin, Yukun

2017-02-03

Hybridizing battery and capacitor materials to construct lithium ion capacitors (LICs) has been regarded as a promising avenue to bridge the gap between high-energy lithium ion batteries and high-power supercapacitors. One of the key difficulties in developing advanced LICs is the imbalance in the power capability and charge storage capacity between anode and cathode. Herein, we design a new LIC system by integrating a rationally designed Sn-C anode with a biomass-derived activated carbon cathode. The Sn-C nanocomposite obtained by a facile confined growth strategy possesses multiple structural merits including well-confined Sn nanoparticles, homogeneous distribution and interconnected carbon framework with ultra-high N doping level, synergically enabling the fabricated anode with high Li storage capacity and excellent rate capability. A new type of biomass-derived activated carbon featuring both high surface area and high carbon purity is also prepared to achieve high capacity for cathode. The assembled LIC (Sn-C//PAC) device delivers high energy densities of 195.7 Wh kg -1 and 84.6 Wh kg -1 at power densities of 731.25 W kg -1 and 24375 W kg -1 , respectively. This work offers a new strategy for designing high-performance hybrid system by tailoring the nanostructures of Li insertion anode and ion adsorption cathode.

A high performance lithium ion capacitor achieved by the integration of a Sn-C anode and a biomass-derived microporous activated carbon cathode

PubMed Central

Sun, Fei; Gao, Jihui; Zhu, Yuwen; Pi, Xinxin; Wang, Lijie; Liu, Xin; Qin, Yukun

2017-01-01

Hybridizing battery and capacitor materials to construct lithium ion capacitors (LICs) has been regarded as a promising avenue to bridge the gap between high-energy lithium ion batteries and high-power supercapacitors. One of the key difficulties in developing advanced LICs is the imbalance in the power capability and charge storage capacity between anode and cathode. Herein, we design a new LIC system by integrating a rationally designed Sn-C anode with a biomass-derived activated carbon cathode. The Sn-C nanocomposite obtained by a facile confined growth strategy possesses multiple structural merits including well-confined Sn nanoparticles, homogeneous distribution and interconnected carbon framework with ultra-high N doping level, synergically enabling the fabricated anode with high Li storage capacity and excellent rate capability. A new type of biomass-derived activated carbon featuring both high surface area and high carbon purity is also prepared to achieve high capacity for cathode. The assembled LIC (Sn-C//PAC) device delivers high energy densities of 195.7 Wh kg−1 and 84.6 Wh kg−1 at power densities of 731.25 W kg−1 and 24375 W kg−1, respectively. This work offers a new strategy for designing high-performance hybrid system by tailoring the nanostructures of Li insertion anode and ion adsorption cathode. PMID:28155853

SnS2 /Sb2 S3 Heterostructures Anchored on Reduced Graphene Oxide Nanosheets with Superior Rate Capability for Sodium-Ion Batteries.

PubMed

Wang, Shijian; Liu, Shuaishuai; Li, Xuemei; Li, Cong; Zang, Rui; Man, Zengming; Wu, Yuhan; Li, Pengxin; Wang, Guoxiu

2018-03-12

Tin disulfide, as a promising high-capacity anode material for sodium-ion batteries, exhibits high theoretical capacity but poor practical electrochemical properties due to its low electrical conductivity. Constructing heterostructures has been considered to be an effective approach to enhance charge transfer and ion-diffusion kinetics. In this work, composites of SnS 2 /Sb 2 S 3 heterostructures with reduced graphene oxide nanosheets were synthesized by a facile one-pot hydrothermal method. When applied as anode material in sodium-ion batteries, the composite showed a high reversible capacity of 642 mA h g -1 at a current density of 0.2 A g -1 and good cyclic stability without capacity loss in 100 cycles. In particular, SnS 2 /Sb 2 S 3 heterostructures exhibited outstanding rate performance with capacities of 593 and 567 mA h g -1 at high current densities of 2 and 4 A g -1 , respectively, which could be ascribed to the dramatically improved Na + diffusion kinetics and electrical conductivity. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

NiCo2S4 nanotube arrays grown on flexible nitrogen-doped carbon foams as three-dimensional binder-free integrated anodes for high-performance lithium-ion batteries.

PubMed

Wu, Xiaoyu; Li, Songmei; Wang, Bo; Liu, Jianhua; Yu, Mei

2016-02-14

Binary metal sulfides, especially NiCo2S4, hold great promise as anode materials for high-performance lithium-ion batteries because of their excellent electronic conductivity and high capacity compared to mono-metal sulfides and oxides. Here, NiCo2S4 nanotube arrays are successfully grown on flexible nitrogen-doped carbon foam (NDCF) substrates with robust adhesion via a facile surfactant-assisted hydrothermal route and the subsequent sulfurization treatment. The obtained NiCo2S4/NDCF composites show unique three-dimensional architectures, in which NiCo2S4 nanotubes of ∼5 μm in length and 100 nm in width are uniformly grown on the NDCF skeletons to form arrays. When used directly as integrated anodes for lithium-ion batteries without any conductive additives and binders, the NiCo2S4/NDCF composites exhibit a high reversible capacity of 1721 mA h g(-1) at a high current density of 500 mA g(-1), enhanced cycling performance with the capacity maintained at 1182 mA h g(-1) after 100 cycles, and a remarkable rate capability. The excellent lithium storage performances of the composites could be attributed to the unique material composition, a rationally designed hollow nanostructure and an integrated smart architecture, which offer fast electron transport and ion diffusion, enhanced material/-electrolyte contact area and facile accommodation of strains during the lithium insertion and extraction process.

Nanoconfined phosphorus film coating on interconnected carbon nanotubes as ultrastable anodes for lithium ion batteries

NASA Astrophysics Data System (ADS)

Xu, Zhiwei; Zeng, Yan; Wang, Liyuan; Li, Nan; Chen, Cheng; Li, Cuiyu; Li, Jing; Lv, Hanming; Kuang, Liyun; Tian, Xu

2017-07-01

Elemental phosphorus (P) is extensively explored as promising anode candidates due to its abundance, low-cost and high theoretical specific capacity. However, it is of great challenge for P-based materials as practical high-energy-density and long-cycling anodes for its large volume expansion and low conductibility. Here, we significantly improve both cycling and rate performance of red P by cladding the nanoconfined P film on interconnected multi-walled carbon nanotube networks (P-MWCNTs composite) via facile wet ball-milling. The red P-MWCNTs anode presents a superior high reversible capacity of 1396.6 mAh g-1 on the basis of P-MWCNTs composite weight at 50 mA g-1 with capacity retention reaching at ∼90% over 50 cycles. Even at 1000 mA g-1, it still maintains remarkable specific reversible capacity of 934.0 mAh g-1. This markedly enhanced performance is ascribed to synergistic advantages of this unique structure: Intimate contacts between nanosized red P and entangled MWCNTs not only shorten the transmission routes of ions through MWCNTs toward red P, but also motivate the access with electrolyte to open structures of P film. Besides, the confined nanosized P film moderate volume expansions effectively and the entangled MWCNTs networks acted as conductive channels activate high ionic/electronic conductivity of the whole electrodes.

Performance Enhancement and Side Reactions in Rechargeable Nickel-Iron Batteries with Nanostructured Electrodes.

PubMed

Lei, Danni; Lee, Dong-Chan; Magasinski, Alexandre; Zhao, Enbo; Steingart, Daniel; Yushin, Gleb

2016-01-27

We report for the first time a solution-based synthesis of strongly coupled nanoFe/multiwalled carbon nanotube (MWCNT) and nanoNiO/MWCNT nanocomposite materials for use as anodes and cathodes in rechargeable alkaline Ni-Fe batteries. The produced aqueous batteries demonstrate very high discharge capacities (800 mAh gFe(-1) at 200 mA g(-1) current density), which exceed that of commercial Ni-Fe cells by nearly 1 order of magnitude at comparable current densities. These cells also showed the lack of any "activation", typical in commercial batteries, where low initial capacity slowly increases during the initial 20-50 cycles. The use of a highly conductive MWCNT network allows for high-capacity utilization because of rapid and efficient electron transport to active metal nanoparticles in oxidized [such as Fe(OH)2 or Fe3O4] states. The flexible nature of MWCNTs accommodates significant volume changes taking place during phase transformation accompanying reduction-oxidation reactions in metal electrodes. At the same time, we report and discuss that high surface areas of active nanoparticles lead to multiple side reactions. Dissolution of Fe anodes leads to reprecipitation of significantly larger anode particles. Dissolution of Ni cathodes leads to precipitation of Ni metal on the anode, thus blocking transport of OH(-) anions. The electrolyte molarity and composition have a significant impact on the capacity utilization and cycling stability.

Flexible Overoxidized Polypyrrole Films with Orderly Structure as High-Performance Anodes for Li- and Na-Ion Batteries.

PubMed

Yuan, Tao; Ruan, Jiafeng; Zhang, Weimin; Tan, Zhuopeng; Yang, Junhe; Ma, Zi-Feng; Zheng, Shiyou

2016-12-28

Flexible polypyrrole (PPy) films with highly ordered structures were fabricated by a novel vapor phase polymerization (VPP) process and used as the anode material in lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs). The PPy films demonstrate excellent rate performance and cycling stability. At a charge/discharge rate of 1 C, the reversible capacities of the PPy film anode reach 284.9 and 177.4 mAh g -1 in LIBs and SIBs, respectively. Even at a charge/discharge rate of 20 C, the reversible capacity of the PPy film anode retains 54.0% and 52.9% of the capacity of 1 C in LIBs and SIBs, respectively. After 1000 electrochemical cycles at a rate of 10 C, there is no obvious capacity fading. The molecular structure and electrochemical behaviors of Li- and Na-ion doping and dedoping in the PPy films are investigated by XPS and ex situ XRD. It is believed that the PPy film electrodes in the overoxidized state can be reversibly charged and discharged through the doping and dedoping of lithium or sodium ions. Because of the self-adaptation of the doped ions, the ordered pyrrolic chain structure can realize a fast charge/discharge process. This result may substantially contribute to the progress of research into flexible polymer electrodes in various types of batteries.

Li3PO4 Matrix Enables a Long Cycle Life and High Energy Efficiency Bismuth-Based Battery.

PubMed

Sun, Chuan-Fu; Hu, Junkai; Wang, Peng; Cheng, Xi-Yuan; Lee, Sang Bok; Wang, YuHuang

2016-09-14

Bismuth is a lithium-ion battery anode material that can operate at an equilibrium potential higher than graphite and provide a capacity twice as high as that of Li4Ti5O12, making it intrinsically free from lithium plating that may cause catastrophic battery failure. However, the potential of bismuth is hampered by its inferior cyclability (limited to tens of cycles). Here, we propose an "ion conductive solid-state matrix" approach to address this issue. By homogeneously confining bismuth nanoparticles in a solid-state γ-Li3PO4 matrix that is electrochemically formed in situ, the resulting composite anode exhibits a reversible capacity of 280 mA hours per gram (mA h/g) at a rate of 100 mA/g and a record cyclability among bismuth-based anodes up to 500 cycles with a capacity decay rate of merely 0.071% per cycle. We further show that full-cell batteries fabricated from this composite anode and commercial LiFePO4 cathode deliver a stable cell voltage of ∼2.5 V and remarkable energy efficiency up to 86.3%, on par with practical batteries (80-90%). This work paves a way for harnessing bismuth-based battery chemistry for the design of high capacity, safer lithium-ion batteries to meet demanding applications such as electric vehicles.

Free standing Cu2Te, new anode material for sodium-ion battery

NASA Astrophysics Data System (ADS)

Sarkar, Ananta; Mallick, Md. Mofasser; Panda, Manas Ranjan; Vitta, Satish; Mitra, Sagar

2018-05-01

Sodium-ion battery is the most popular alternative to lithium-ion energy storage system due to its low cost and huge abundant resources throughout the world. Although recent literature showed cathode materials for sodium ion battery performs almost equivalent to lithium-ion counterpart but the anode of this sodium-ion battery is in premature state. Here, we introduced free-standing copper telluride (Cu2Te), a new anode materials for sodium-ion battery. For making the electrode we did not use any conductive carbon or current collector which increase the volumetric density as well as reduce the cost of the cell. This metallic Cu2Te alloy exhibited a high reversible capacity of ˜275 mAh g-1 at 50 mA g-1 current density and ˜200 mAh g-1 at higher current density of 100 mA g-1, operating between 0.1 to 2.0 V.

Surfactant-Free Aqueous Synthesis of Pure Single-Crystalline SnSe Nanosheet Clusters as Anode for High Energy- and Power-Density Sodium-Ion Batteries.

PubMed

Yuan, Shuang; Zhu, Yun-Hai; Li, Wang; Wang, Sai; Xu, Dan; Li, Lin; Zhang, Yu; Zhang, Xin-Bo

2017-01-01

SnSe with 3D hierarchical nanostructure composed of interconnected single-crystal SnSe nanosheets is synthesized via a fast and effective strategy. Unexpectedly, when used as the anode material for Na-ion batteries (NIBs), the SnSe exhibits a high capacity (738 mA h g -1 ), superior rate capability (40 A g -1 ), and high energy density in a full cell. These results provide the possibility of SnSe use as NIBs anodes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesized Li4Ti5O12 from Technical Grade Raw Material by Excess LiOH.H2O as Anode Lithium Ion Battery

NASA Astrophysics Data System (ADS)

Priyono, S.; Primasari, R. D.; Saptari, S. A.; Prihandoko, B.

2017-07-01

Li4Ti5O12 powder as anode lithium ion battery was synthesized via solid state reaction with excess LiOH.H2O. Technical grades raw materials like LiOH.H2O and TiO2 were used as starting materials. LiOH.H2O excess was varied from 0; 2.5; 5 and 7.5% to get higher optimum phases and capacity of Li4Ti5O12. All raw materials were mixed stoichiometry then followed by calcination and sintering process to get final products. The obtained products were characterized by XRD, SEM, and PSA to get properties of active materials and the electrochemical properties were done by cyclic voltametry and charge-discharge test. The XRD test showed that 5% excess have highest Li4Ti5O12 phases. All samples have same in morphology, agglomerate and same in particle size distribution. Sample with 5% excess showed good reversible process and chargedischarge test showed that increasing Li4Ti5O12 phase can improve specific capacity.

Electrochemical investigation of MoTe2/rGO composite materials for sodium-ion battery application

NASA Astrophysics Data System (ADS)

Panda, Manas Ranjan; Anish Raj, K.; Sarkar, Ananta; Bao, Qiaoliang; Mitra, Sagar

2018-05-01

2D layered materials are found to be promising anode materials for renewable energy storage devices like sodium and Li-ion batteries and have become attractive options due to their high specific capacity, abundance and low cost. In this work, we synthesized 2D MoTe2 layers embedded in reduced graphene oxide (rGO) anode material for sodium-ion battery applications. 2D MoTe2 was prepared by a solid-state reaction in vacuum at a temperature of 800 °C. The prepared composite material MoTe2/rGO showed excellent electrochemical performance against the sodium metal. The discharge capacity of MoTe2/rGO was observed to be 280 mAh g-1 at a current rate of 1.0 A g-1 for 100 cycles. rGO plays an important role in embedding the MoTe2 structure, thus improving the electrical and mechanical properties, leading to a superior cycling stability and excellent electrochemical performances of MoTe2 for sodium-ion battery applications.

Incommensurate Graphene Foam as a High Capacity Lithium Intercalation Anode

PubMed Central

Paronyan, Tereza M.; Thapa, Arjun Kumar; Sherehiy, Andriy; Jasinski, Jacek B.; Jangam, John Samuel Dilip

2017-01-01

Graphite’s capacity of intercalating lithium in rechargeable batteries is limited (theoretically, 372 mAh g−1) due to low diffusion within commensurately-stacked graphene layers. Graphene foam with highly enriched incommensurately-stacked layers was grown and applied as an active electrode in rechargeable batteries. A 93% incommensurate graphene foam demonstrated a reversible specific capacity of 1,540 mAh g−1 with a 75% coulombic efficiency, and an 86% incommensurate sample achieves above 99% coulombic efficiency exhibiting 930 mAh g−1 specific capacity. The structural and binding analysis of graphene show that lithium atoms highly intercalate within weakly interacting incommensurately-stacked graphene network, followed by a further flexible rearrangement of layers for a long-term stable cycling. We consider lithium intercalation model for multilayer graphene where capacity varies with N number of layers resulting LiN+1C2N stoichiometry. The effective capacity of commonly used carbon-based rechargeable batteries can be significantly improved using incommensurate graphene as an anode material. PMID:28059110

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.

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

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

Rechargeable lithium-ion batteries are the most popular devices for energy storage but still a lot of research needs to be done to improve their cycling and storage capacity. Silicon has been proposed as an anode material because of its large theoretical capacity of ~3600 mAh/g. Therefore, focus is needed on the lithiation process of silicon anodes where it is known that the anode increases its volume more than 300%, producing cracking and other damages. In this study, we performed molecular dynamics atomistic simulations to study the swelling, alloying, and amorphization of a silicon nanocrystal anode in a full nanobattery modelmore » during the first charging cycle. A dissolved salt of lithium hexafluorophosphate in ethylene carbonate was chosen as the electrolyte solution and lithium cobalt oxide as cathode. External electric fields are applied to emulate the charging, causing the migration of the Li-ions from the cathode to the anode, by drifting through the electrolyte solution, thus converting pristine Si gradually into Li 14Si 5 when fully lithiated. When the electric field is applied to the nanobattery, the temperature never exceeds 360 K due to a temperature control imposed resembling a cooling mechanism. The volume of the anode increases with the amorphization of the silicon as the external field is applied by creating a layer of LiSi alloy between the electrolyte and the silicon nanocrystal and then, at the arrival of more Li-ions changing to an alloy, where the drift velocity of Li-ions is greater than the velocity in the initial nanocrystal structure. Charge neutrality is maintained by concerted complementary reduction-oxidation reactions at the anode and cathode, respectively. Also, the nanobattery model developed here can be used to study charge mobility, current density, conductance and resistivity, among several other properties of several candidate materials for rechargeable batteries and constitutes the initial point for further studies on the formation of the solid electrolyte interphase in the anode.« less

Electrodeposited three-dimensional Ni-Si nanocable arrays as high performance anodes for lithium ion batteries.

PubMed

Liu, Hao; Hu, Liangbin; Meng, Ying Shirley; Li, Quan

2013-11-07

A configuration of three-dimensional Ni-Si nanocable array anodes is proposed to overcome the severe volume change problem of Si during the charging-discharging process. In the fabrication process, a simple and low cost electrodeposition is employed to deposit Si instead of the common expansive vapor phase deposition methods. The optimum composite nanocable array electrode achieves a high specific capacity ~1900 mA h g(-1) at 0.05 C. After 100 cycles at 0.5 C, 88% of the initial capacity (~1300 mA h g(-1)) remains, suggesting its good capacity retention ability. The high performance of the composite nanocable electrode is attributed to its excellent adhesion of the active material on the three-dimensional current collector and short ionic/electronic transport pathways during cycling.

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

Facile preparation of a zinc-based alloy composite as a novel anode material for rechargeable lithium-ion batteries

NASA Astrophysics Data System (ADS)

Hung, Nguyen Thanh; Bae, Joonwon; Kim, Ji Hyeon; Son, Hyung Bin; Kim, Il Tae; Hur, Jaehyun

2018-01-01

We report a new Zn-based nanocomposite anode material (Zn-Ti-C) for lithium-ion batteries synthesized by thermal treatment and a high energy mechanical milling process. X-ray diffraction and high-resolution transmission electron microscopy revealed the formation of active Zn nanoparticles finely dispersed in the hybrid titanium carbide (TiC) and carbon matrix. Electrochemical analyses show that the formation of the TiC and carbon buffer matrix significantly contributed to the improved performance of the Zn-based electrode by mitigating the volume changes of the Zn nanoparticles during the charge/discharge processes. Furthermore, we optimized the stoichiometric ratio of Zn and Ti in terms of specific capacity, cycling performance, and rate capability in the presence of carbon. The material with a 2:1 atomic ratio (ZnTi(2:1)-C) exhibited the best cycle life, with a gravimetric capacity of 363.6 mAh g-1 and a volumetric capacity of 472.7 mAh cm-3 after 300 charge/discharge cycles (78.1% retention). At this ratio, Zn-Ti-C consistently showed the best rate capability measurements up to 3000 mA g-1 (85% of its capacity at 100 mA g-1). Therefore, our Zn-Ti-C composite is a promising alternative negative electrode material for lithium-ion batteries.

Molecular dynamics simulations of the first charge of a Li-ion-Si-anode nanobattery.

PubMed

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

2017-04-01

Rechargeable lithium-ion batteries are the most popular devices for energy storage but still a lot of research needs to be done to improve their cycling and storage capacity. Silicon has been proposed as an anode material because of its large theoretical capacity of ∼3600 mAh/g. Therefore, focus is needed on the lithiation process of silicon anodes where it is known that the anode increases its volume more than 300%, producing cracking and other damages. We performed molecular dynamics atomistic simulations to study the swelling, alloying, and amorphization of a silicon nanocrystal anode in a full nanobattery model during the first charging cycle. A dissolved salt of lithium hexafluorophosphate in ethylene carbonate was chosen as the electrolyte solution and lithium cobalt oxide as cathode. External electric fields are applied to emulate the charging, causing the migration of the Li-ions from the cathode to the anode, by drifting through the electrolyte solution, thus converting pristine Si gradually into Li 14 Si 5 when fully lithiated. When the electric field is applied to the nanobattery, the temperature never exceeds 360 K due to a temperature control imposed resembling a cooling mechanism. The volume of the anode increases with the amorphization of the silicon as the external field is applied by creating a layer of LiSi alloy between the electrolyte and the silicon nanocrystal and then, at the arrival of more Li-ions changing to an alloy, where the drift velocity of Li-ions is greater than the velocity in the initial nanocrystal structure. Charge neutrality is maintained by concerted complementary reduction-oxidation reactions at the anode and cathode, respectively. In addition, the nanobattery model developed here can be used to study charge mobility, current density, conductance and resistivity, among several other properties of several candidate materials for rechargeable batteries and constitutes the initial point for further studies on the formation of the solid electrolyte interphase in the anode. Graphical Abstract Nanobattery: LiCoO 2 cathode, electrolyte solution of 1M Li + PF 6 - in ethylene carbonate, and Si crystal anode, which changes its volume due to lithiation during the first charge.

Cryogenic plasma-processed silicon microspikes as a high-performance anode material for lithium ion-batteries

NASA Astrophysics Data System (ADS)

Sakai, Joe; Luais, Erwann; Wolfman, Jérôme; Tillocher, Thomas; Dussart, Rémi; Tran-Van, Francois; Ghamouss, Fouad

2017-10-01

Micro- or nano-structuring is essential in order to use Si as an anode material for lithium ion batteries. In the present study, we attempted to use Si wafers with a spiky microstructure (SMS), the so-called black-Si, prepared by a cryogenic reactive ion etching process with an SF6/O2 gas mixture, for Li half-cells. The SMS with various sizes of spikes from 2.0 μm (height) × 0.2 μm (width) to 21 μm × 1.0 μm was etched by varying the SF6/O2 gas flow ratio. An anode of SMS of 11 μm-height in average showed stable charge/discharge capacity and Coulombic efficiency higher than 99% for more than 300 cycles, causing no destruction to any part of the Si wafer. The spiky structure turned columnar after cycles, suggesting graded lithiation levels along the length. The present results suggest a strategy to utilize a wafer-based Si material for an anode of a lithium ion battery durable against repetitive lithiation/delithiation cycles.

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.

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.

Preparation of Advanced CuO Nanowires/Functionalized Graphene Composite Anode Material for Lithium Ion Batteries

PubMed Central

Zhang, Jin; Wang, Beibei; Zhou, Jiachen; Xia, Ruoyu; Chu, Yingli; Huang, Jia

2017-01-01

The copper oxide (CuO) nanowires/functionalized graphene (f-graphene) composite material was successfully composed by a one-pot synthesis method. The f-graphene synthesized through the Birch reduction chemistry method was modified with functional group “–(CH2)5COOH”, and the CuO nanowires (NWs) were well dispersed in the f-graphene sheets. When used as anode materials in lithium-ion batteries, the composite exhibited good cyclic stability and decent specific capacity of 677 mA·h·g−1 after 50 cycles. CuO NWs can enhance the lithium-ion storage of the composites while the f-graphene effectively resists the volume expansion of the CuO NWs during the galvanostatic charge/discharge cyclic process, and provide a conductive paths for charge transportation. The good electrochemical performance of the synthesized CuO/f-graphene composite suggests great potential of the composite materials for lithium-ion batteries anodes. PMID:28772432

Eutectic Nano-Droplet Template Injection into Bulk Silicon to Construct Porous Frameworks with Concomitant Conformal Coating as Anodes for Li-Ion Batteries

PubMed Central

Qu, Fei; Li, Chilin; Wang, Zumin; Wen, Yuren; Richter, Gunther; Strunk, Horst P.

2015-01-01

Building porosity in monolithic materials is highly desired to design 3D electrodes, however ex-situ introduction or in-situ generation of nano-scale sacrificial template is still a great challenge. Here Al-Si eutectic droplet templates are uniformly injected into bulk Si through Al-induced solid-solid convection to construct a highly porous Si framework. This process is concomitant with process-inherent conformal coating of ion-conductive oxide. Such an all-in-one method has generated a (continuously processed) high-capacity Si anode integrating longevity and stable electrolyte-anode diaphragm for Li-ion batteries (e.g. a reversible capacity as large as ~1800 mAh/g or ~350 μAh/cm2-μm with a CE of ~99% at 0.1 C after long-term 400 cycles). PMID:25988370

Lithium metal protection enabled by in-situ olefin polymerization for high-performance secondary lithium sulfur batteries

NASA Astrophysics Data System (ADS)

An, Yongling; Zhang, Zhen; Fei, Huifang; Xu, Xiaoyan; Xiong, Shenglin; Feng, Jinkui; Ci, Lijie

2017-09-01

Lithium metal is considered to be the optimal choice of next-generation anode materials due to its ultrahigh theoretical capacity and the lowest redox potential. However, the growth of dendritic and mossy lithium for rechargeable Li metal batteries lead to the possible short circuiting and subsequently serious safety issues during charge/discharge cycles. For the further practical applications of Li anode, here we report a facile method for fabricating robust interfacial layer via in-situ olefin polymerization. The resulting polymer layer effectively suppresses the formation of Li dendrites and enables the long-term operation of Li metal batteries. Using Li-S cells as a test system, we also demonstrate an improved capacity retention with the protection of tetramethylethylene-polymer. Our results indicate that this method could be a promising strategy to tackle the intrinsic problems of lithium metal anodes and promote the development of Li metal batteries.

Eutectic nano-droplet template injection into bulk silicon to construct porous frameworks with concomitant conformal coating as anodes for Li-ion batteries.

PubMed

Qu, Fei; Li, Chilin; Wang, Zumin; Wen, Yuren; Richter, Gunther; Strunk, Horst P

2015-05-19

Building porosity in monolithic materials is highly desired to design 3D electrodes, however ex-situ introduction or in-situ generation of nano-scale sacrificial template is still a great challenge. Here Al-Si eutectic droplet templates are uniformly injected into bulk Si through Al-induced solid-solid convection to construct a highly porous Si framework. This process is concomitant with process-inherent conformal coating of ion-conductive oxide. Such an all-in-one method has generated a (continuously processed) high-capacity Si anode integrating longevity and stable electrolyte-anode diaphragm for Li-ion batteries (e.g. a reversible capacity as large as ~1800 mAh/g or ~350 μAh/cm(2)-μm with a CE of ~99% at 0.1 C after long-term 400 cycles).

Conformal Fe3O4 sheath on aligned carbon nanotube scaffolds as high-performance anodes for lithium ion batteries.

PubMed

Wu, Yang; Wei, Yang; Wang, Jiaping; Jiang, Kaili; Fan, Shoushan

2013-02-13

A uniform Fe(3)O(4) sheath is magnetron sputtered onto aligned carbon nanotube (CNT) scaffolds that are directly drawn from CNT arrays. The Fe(3)O(4)-CNT composite electrode, with the size of Fe(3)O(4) confined to 5-7 nm, exhibits a high reversible capacity over 800 mAh g(-1) based on the total electrode mass, remarkable capacity retention, as well as high rate capability. The excellent performance is attributable to the superior electrical conductivity of CNTs, the uniform loading of Fe(3)O(4) sheath, and the structural retention of the composite anode on cycling. As Fe(3)O(4) is inexpensive and environmentally friendly, and the synthesis of Fe(3)O(4)-CNT is free of chemical wastes, this composite anode material holds considerable promise for high-performance lithium ion batteries.

Lithium ion batteries with titania/graphene anodes

DOEpatents

Liu, Jun; Choi, Daiwon; Yang, Zhenguo; Wang, Donghai; Graff, Gordon L; Nie, Zimin; Viswanathan, Vilayanur V; Zhang, Jason; Xu, Wu; Kim, Jin Yong

2013-05-28

Lithium ion batteries having an anode comprising at least one graphene layer in electrical communication with titania to form a nanocomposite material, a cathode comprising a lithium olivine structure, and an electrolyte. The graphene layer has a carbon to oxygen ratio of between 15 to 1 and 500 to 1 and a surface area of between 400 and 2630 m.sup.2/g. The nanocomposite material has a specific capacity at least twice that of a titania material without graphene material at a charge/discharge rate greater than about 10 C. The olivine structure of the cathode of the lithium ion battery of the present invention is LiMPO.sub.4 where M is selected from the group consisting of Fe, Mn, Co, Ni and combinations thereof.

Borophane as a Benchmate of Graphene: A Potential 2D Material for Anode of Li and Na-Ion Batteries.

PubMed

Jena, Naresh K; Araujo, Rafael B; Shukla, Vivekanand; Ahuja, Rajeev

2017-05-17

Borophene, single atomic-layer sheet of boron ( Science 2015 , 350 , 1513 ), is a rather new entrant into the burgeoning class of 2D materials. Borophene exhibits anisotropic metallic properties whereas its hydrogenated counterpart borophane is reported to be a gapless Dirac material lying on the same bench with the celebrated graphene. Interestingly, this transition of borophane also rendered stability to it considering the fact that borophene was synthesized under ultrahigh vacuum conditions on a metallic (Ag) substrate. On the basis of first-principles density functional theory computations, we have investigated the possibilities of borophane as a potential Li/Na-ion battery anode material. We obtained a binding energy of -2.58 (-1.08 eV) eV for Li (Na)-adatom on borophane and Bader charge analysis revealed that Li(Na) atom exists in Li + (Na + ) state. Further, on binding with Li/Na, borophane exhibited metallic properties as evidenced by the electronic band structure. We found that diffusion pathways for Li/Na on the borophane surface are anisotropic with x direction being the favorable one with a barrier of 0.27 and 0.09 eV, respectively. While assessing the Li-ion anode performance, we estimated that the maximum Li content is Li 0.445 B 2 H 2 , which gives rises to a material with a maximum theoretical specific capacity of 504 mAh/g together with an average voltage of 0.43 V versus Li/Li + . Likewise, for Na-ion the maximum theoretical capacity and average voltage were estimated to be 504 mAh/g and 0.03 V versus Na/Na + , respectively. These findings unambiguously suggest that borophane can be a potential addition to the map of Li and Na-ion anode materials and can rival some of the recently reported 2D materials including graphene.

A self-supported metal-organic framework derived Co3O4 film prepared by an in-situ electrochemically assistant process as Li ion battery anodes

NASA Astrophysics Data System (ADS)

Zhao, Guangyu; Sun, Xin; Zhang, Li; Chen, Xuan; Mao, Yachun; Sun, Kening

2018-06-01

Derivates of metal-organic frameworks are promising materials of self-supported Li ion battery anodes due to the good dispersion of active materials, conductive scaffold, and mass transport channels in them. However, the discontinuous growth and poor adherence of metal-organic framework films on substrates hamper their development in self-supported electrodes. In the present study, cobalt-based metal-organic frameworks are anchored on Ti nanowire arrays through an electrochemically assistant method, and then the metal-organic framework films are pyrolyzed to carbon-containing, porous, self-supported anodes of Li ion battery anodes. Scanning electron microscope images indicate that, a layer cobaltosic oxide polyhedrons inserted by the nanowires are obtained with the controllable in-situ synthesis. Thanks to the good dispersion and adherence of cobaltosic oxide polyhedrons on Ti substrates, the self-supported anodes exhibit remarkable rate capability and durability. They possess a capacity of 300 mAh g-1 at a rate current of 20 A g-1, and maintain 2000 charge/discharge cycles without obvious decay.

Preparation and electrochemical properties of core-shell carbon coated Mn-Sn complex metal oxide as anode materials for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Zhang, Ruixue; Fang, Guoqing; Liu, Weiwei; Xia, Bingbo; Sun, Hongdan; Zheng, Junwei; Li, Decheng

2014-02-01

In this study, we synthesized a carbon coated Mn-Sn metal oxide composite with core-shell structure (MTO@C) via a simple glucose hydrothermal reaction and subsequent carbonization approach. When the MTO@C composite was applied as an anode material for lithium-ion batteries, it maintained a reversible capacity of 409 mA h g-1 after 200 cycles at a current density of 100 mA g-1. The uniformed and continuous carbon layer formed on the MTO nanoparticles, effectively buffered the volumetric change of the active material and increased electronic conductivity, which thus prolonged the cycling performance of the MTO@C electrode.

The capacity fading mechanism and improvement of cycling stability in MoS2-based anode materials for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Shu, Haibo; Li, Feng; Hu, Chenli; Liang, Pei; Cao, Dan; Chen, Xiaoshuang

2016-01-01

Two-dimensional (2D) layered MoS2 nanosheets possess great potential as anode materials for lithium ion batteries (LIBs), but they still suffer from poor cycling performance. Improving the cycling stability of electrode materials depends on a deep understanding of their dynamic structural evolution and reaction kinetics in the lithiation process. Herein, thermodynamic phase diagrams and the lithiation dynamics of MoS2-based nanostructures with the intercalation of lithium ions are studied by using first-principles calculations and ab initio molecular dynamics simulations. Our results demonstrate that the continuous intercalation of Li ions induces structural destruction of 2H phase MoS2 nanosheets in the discharge process that follows a layer-by-layer dissociation mechanism. Meanwhile, the intercalation of Li ions leads to a structural transition of MoS2 nanosheets from the 2H to the 1T phase due to the ultralow transition barriers (~0.1 eV). We find that the phase transition can slow down the dissociation of MoS2 nanosheets during lithiation. The result can be applied to explain extensive experimental observation of the fast capacity fading of MoS2-based anode materials between the first and the subsequent discharges. To suppress the dissociation of MoS2 nanosheets in the lithiation process, we propose a strategy by constructing a sandwich-like graphene/MoS2/graphene structure that indicates high chemical stability, superior conductivity, and high Li-ion mobility in the charge/discharge process, implying the possibility to induce an improvement in the anode cycling performance. This work opens a new route to rational design layered transition-metal disulfide (TMD) anode materials for LIBs with superior cycling stability and electrochemical performance.Two-dimensional (2D) layered MoS2 nanosheets possess great potential as anode materials for lithium ion batteries (LIBs), but they still suffer from poor cycling performance. Improving the cycling stability of electrode materials depends on a deep understanding of their dynamic structural evolution and reaction kinetics in the lithiation process. Herein, thermodynamic phase diagrams and the lithiation dynamics of MoS2-based nanostructures with the intercalation of lithium ions are studied by using first-principles calculations and ab initio molecular dynamics simulations. Our results demonstrate that the continuous intercalation of Li ions induces structural destruction of 2H phase MoS2 nanosheets in the discharge process that follows a layer-by-layer dissociation mechanism. Meanwhile, the intercalation of Li ions leads to a structural transition of MoS2 nanosheets from the 2H to the 1T phase due to the ultralow transition barriers (~0.1 eV). We find that the phase transition can slow down the dissociation of MoS2 nanosheets during lithiation. The result can be applied to explain extensive experimental observation of the fast capacity fading of MoS2-based anode materials between the first and the subsequent discharges. To suppress the dissociation of MoS2 nanosheets in the lithiation process, we propose a strategy by constructing a sandwich-like graphene/MoS2/graphene structure that indicates high chemical stability, superior conductivity, and high Li-ion mobility in the charge/discharge process, implying the possibility to induce an improvement in the anode cycling performance. This work opens a new route to rational design layered transition-metal disulfide (TMD) anode materials for LIBs with superior cycling stability and electrochemical performance. Electronic supplementary information (ESI) available: Models and energetics of Li adsorption/intercalation onto MoS2 sheets, details of the phase diagram calculations, schematic illustration for the structural evolution of lithiated MoS2 nanosheets, AIMD trajectories for lithiated silicene/MoS2/silicene composites, and movies for recording the AIMD simulation results. See DOI: 10.1039/c5nr07909h

Novel secondary assembled micro/nano porous spheres ZnCo2O4 with superior electrochemical performances as lithium ion anode material.

PubMed

Liu, Haowen; Hu, Qihong

2018-08-10

In this work, novel secondary assembled micro/nano porous spheres ZnCo 2 O 4 were firstly prepared by combining the hydrothermal method with post-synthesis calcinations. The structure and morphology of the obtained powder were characterized by x-ray powder diffraction and field emission-scanning electron microscopy. As the anode material of lithium-ion half-cells, the as-prepared ZnCo 2 O 4 delivered a very high capacity, extra cycling stability and excellent rate capability. A discharge capacity of 950 mAh g -1 with up to 99.7% retention corresponding to the second cycle at 0.1 C was achieved after 90 cycles, which was an improved cyclability over previous reports. The higher current charge-discharge and electrochemical impedance spectroscopy data indicate that the material's integrity was maintained. Therefore constructing the secondary assembled 3D micro/nano structure is an effective strategy to obtain the superior electrochemical performances.

Semi-solid electrodes having high rate capability

DOEpatents

Chiang, Yet-Ming; Duduta, Mihai; Holman, Richard; Limthongkul, Pimpa; Tan, Taison

2016-06-07

Embodiments described herein relate generally to electrochemical cells having high rate capability, and more particularly to devices, systems and methods of producing high capacity and high rate capability batteries having relatively thick semi-solid electrodes. In some embodiments, an electrochemical cell includes an anode and a semi-solid cathode. The semi-solid cathode includes a suspension of an active material of about 35% to about 75% by volume of an active material and about 0.5% to about 8% by volume of a conductive material in a non-aqueous liquid electrolyte. An ion-permeable membrane is disposed between the anode and the semi-solid cathode. The semi-solid cathode has a thickness of about 250 .mu.m to about 2,000 .mu.m, and the electrochemical cell has an area specific capacity of at least about 7 mAh/cm.sup.2 at a C-rate of C/4. In some embodiments, the semi-solid cathode slurry has a mixing index of at least about 0.9.

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

Chiang, Yet-Ming; Duduta, Mihai; Holman, Richard

Embodiments described herein relate generally to electrochemical cells having high rate capability, and more particularly to devices, systems and methods of producing high capacity and high rate capability batteries having relatively thick semi-solid electrodes. In some embodiments, an electrochemical cell includes an anode and a semi-solid cathode. The semi-solid cathode includes a suspension of an active material of about 35% to about 75% by volume of an active material and about 0.5% to about 8% by volume of a conductive material in a non-aqueous liquid electrolyte. An ion-permeable membrane is disposed between the anode and the semi-solid cathode. The semi-solidmore » cathode has a thickness of about 250 .mu.m to about 2,000 .mu.m, and the electrochemical cell has an area specific capacity of at least about 7 mAh/cm.sup.2 at a C-rate of C/4. In some embodiments, the semi-solid cathode slurry has a mixing index of at least about 0.9.« less

MoO2-ordered mesoporous carbon hybrids as anode materials with highly improved rate capability and reversible capacity for lithium-ion battery.

PubMed

Chen, Ailian; Li, Caixia; Tang, Rui; Yin, Longwei; Qi, Yongxin

2013-08-28

A novel hybrid of MoO2-ordered mesoporous carbon (MoO2-OMC) was prepared through a two-step solvothermal chemical reaction route. The electrochemical performances of the mesoporous MoO2-OMC hybrids were examined using galvanostatical charge-discharge, cyclic voltammetry, and electrochemical impedance spectroscopy (EIS) techniques. The MoO2-OMC hybrid exhibits significantly improved electrochemical performance of high reversible capacity, high-rate capability, and excellent cycling performance as an anode electrode material for Li ion batteries. It is revealed that the MoO2-OMC hybrid could deliver the first discharge capacity of 1641.8 mA h g(-1) with an initial Coulombic efficiency of 63.6%, and a reversible capacity as high as 1049.1 mA h g(-1) even after 50 cycles at a current density of 100 mA g(-1), much higher than the theoretical capacity of MoO2 (838 mA h g(-1)) and OMC materials. The MoO2-OMC hybrid demonstrates an excellent high rate capability with capacity of ∼600 mA h g(-1) even at a charge current density of 1600 mA g(-1) after 50 cycles, which is approximately 11.1 times higher than that of the OMC (54 mA h g(-1)) materials. The improved rate capability and reversible capacity of the MoO2-OMC hybrid are attributed to a synergistic reaction between the MoO2 nanoparticles and mesoporous OMC matrices. It is noted that the electrochemical performance of the MoO2-OMC hybrid is evidently much better than the previous MoO2-based hybrids.

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

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

Synthesis of nano-sized silicon from natural halloysite clay and its high performance as anode for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Zhou, Xiangyang; Wu, Lili; Yang, Juan; Tang, Jingjing; Xi, Lihua; Wang, Biao

2016-08-01

Recently, nanostructured Si has been intensively studied as a promising anode candidate for lithium ion batteries due to its ultrahigh capacity. However, the downsizing of Si to nanoscale dimension is often impeded by complicated and expensive methods. In this work, natural halloysite clay was utilized for the production of Si nanoparticles through selective acid etching and modified magnesiothermic reduction processes. The physical and chemical changes of these samples during the various processes have been analyzed. The as-prepared Hsbnd Si from halloysite clay is composed of many interconnected Si nanoparticles with an average diameter of 20-50 nm. Owing to the small size and porous nature, the Hsbnd Si nanoparticles exhibit a satisfactory performance as an anode for lithium ion batteries. Without further modification, a stable capacity over 2200 mAh g-1 at a rate of 0.2 C after 100 cycles and a reversible capacity above 800 mAh g-1 at a rate of 1 C after 1000 cycles can be obtained. As a result, this synthetic route is cost-effective and can be scaled up for mass production of Si nanoparticles, which may facilitate valuable utilization of halloysite clay and further commercial application of Si-based anode materials.

Melt-Spun Fe-Sb Intermetallic Alloy Anode for Performance Enhanced Sodium-Ion Batteries.

PubMed

Edison, Eldho; Sreejith, Sivaramapanicker; Madhavi, Srinivasan

2017-11-15

Owing to the high theoretical sodiation capacities, intermetallic alloy anodes have attracted considerable interest as electrodes for next-generation sodium-ion batteries (SIBs). Here, we demonstrate the fabrication of intermetallic Fe-Sb alloy anode for SIBs via a high-throughput and industrially viable melt-spinning process. The earth-abundant and low-cost Fe-Sb-based alloy anode exhibits excellent cycling stability with nearly 466 mAh g -1 sodiation capacity at a specific current of 50 mA g -1 with 95% capacity retention after 80 cycles. Moreover, the alloy anode displayed outstanding rate performance with ∼300 mAh g -1 sodiation capacity at 1 A g -1 . The crystalline features of the melt-spun fibers aid in the exceptional electrochemical performance of the alloy anode. Further, the feasibility of the alloy anode for real-life applications was demonstrated in a sodium-ion full-cell configuration which could deliver a sodiation capacity of over 300 mAh g -1 (based on anode) at 50 mA g -1 with more than 99% Coulombic efficiency. The results further exhort the prospects of melt-spun alloy anodes to realize fully functional sodium-ion batteries.

Surface Fluorination of Reactive Battery Anode Materials for Enhanced Stability

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

Zhao, Jie; Liao, Lei; Shi, Feifei

Significant increases in the energy density of batteries must be achieved by exploring new materials and cell configurations. Lithium metal and lithiated silicon are two promising high-capacity anode materials. Unfortunately, both of these anodes require a reliable passivating layer to survive the serious environmental corrosion during handling and cycling. Here we developed a surface fluorination process to form a homogeneous and dense LiF coating on reactive anode materials, with in situ generated fluorine gas, by using a fluoropolymer, CYTOP, as the precursor. The process is effectively a “reaction in the beaker”, avoiding direct handling of highly toxic fluorine gas. Formore » lithium metal, this LiF coating serves as a chemically stable and mechanically strong interphase, which minimizes the corrosion reaction with carbonate electrolytes and suppresses dendrite formation, enabling dendrite-free and stable cycling over 300 cycles with current densities up to 5 mA/cm 2. Lithiated silicon can serve as either a pre-lithiation additive for existing lithium-ion batteries or a replacement for lithium metal in Li–O 2 and Li–S batteries. However, lithiated silicon reacts vigorously with the standard slurry solvent N-methyl-2-pyrrolidinone (NMP), indicating it is not compatible with the real battery fabrication process. With the protection of crystalline and dense LiF coating, Li xSi can be processed in anhydrous NMP with a high capacity of 2504 mAh/g. With low solubility of LiF in water, this protection layer also allows Li xSi to be stable in humid air (~40% relative humidity). Furthermore, this facile surface fluorination process brings huge benefit to both the existing lithium-ion batteries and next-generation lithium metal batteries.« less

Surface Fluorination of Reactive Battery Anode Materials for Enhanced Stability

DOE PAGES

Zhao, Jie; Liao, Lei; Shi, Feifei; ...

2017-07-26

Significant increases in the energy density of batteries must be achieved by exploring new materials and cell configurations. Lithium metal and lithiated silicon are two promising high-capacity anode materials. Unfortunately, both of these anodes require a reliable passivating layer to survive the serious environmental corrosion during handling and cycling. Here we developed a surface fluorination process to form a homogeneous and dense LiF coating on reactive anode materials, with in situ generated fluorine gas, by using a fluoropolymer, CYTOP, as the precursor. The process is effectively a “reaction in the beaker”, avoiding direct handling of highly toxic fluorine gas. Formore » lithium metal, this LiF coating serves as a chemically stable and mechanically strong interphase, which minimizes the corrosion reaction with carbonate electrolytes and suppresses dendrite formation, enabling dendrite-free and stable cycling over 300 cycles with current densities up to 5 mA/cm 2. Lithiated silicon can serve as either a pre-lithiation additive for existing lithium-ion batteries or a replacement for lithium metal in Li–O 2 and Li–S batteries. However, lithiated silicon reacts vigorously with the standard slurry solvent N-methyl-2-pyrrolidinone (NMP), indicating it is not compatible with the real battery fabrication process. With the protection of crystalline and dense LiF coating, Li xSi can be processed in anhydrous NMP with a high capacity of 2504 mAh/g. With low solubility of LiF in water, this protection layer also allows Li xSi to be stable in humid air (~40% relative humidity). Furthermore, this facile surface fluorination process brings huge benefit to both the existing lithium-ion batteries and next-generation lithium metal batteries.« less

N/S Co-doped Carbon Derived From Cotton as High Performance Anode Materials for Lithium Ion Batteries.

PubMed

Xiong, Jiawen; Pan, Qichang; Zheng, Fenghua; Xiong, Xunhui; Yang, Chenghao; Hu, Dongli; Huang, Chunlai

2018-01-01

Highly porous carbon with large surface areas is prepared using cotton as carbon sources which derived from discard cotton balls. Subsequently, the sulfur-nitrogen co-doped carbon was obtained by heat treatment the carbon in presence of thiourea and evaluated as Lithium-ion batteries anode. Benefiting from the S, N co-doping, the obtained S, N co-doped carbon exhibits excellent electrochemical performance. As a result, the as-prepared S, N co-doped carbon can deliver a high reversible capacity of 1,101.1 mA h g -1 after 150 cycles at 0.2 A g -1 , and a high capacity of 531.2 mA h g -1 can be observed even after 5,000 cycles at 10.0 A g -1 . Moreover, excellently rate capability also can be observed, a high capacity of 689 mA h g -1 can be obtained at 5.0 A g -1 . This superior lithium storage performance of S, N co-doped carbon make it as a promising low-cost and sustainable anode for high performance lithium ion batteries.

N/S co-doped carbon derived from Cotton as high performance anode materials for lithium ion batteries

NASA Astrophysics Data System (ADS)

Xiong, Jiawen; Pan, Qichang; Zheng, Fenghua; Xiong, Xunhui; Yang, Chenghao; Hu, Dongli; Huang, Chunlai

2018-04-01

Highly porous carbon with large surface areas is prepared using cotton as carbon sources which derived from discard cotton balls. Subsequently, the sulfur-nitrogen co-doped carbon was obtained by heat treatment the carbon in presence of thiourea and evaluated as Lithium-ion batteries anode. Benefiting from the S, N co-doping, the obtained S, N co-doped carbon exhibits excellent electrochemical performance. As a result, the as-prepared S, N co-doped carbon can deliver a high reversible capacity of 1101.1 mA h g-1 after 150 cycles at 0.2 A g-1, and a high capacity of 531.2 mA h g-1 can be observed even after 5000 cycles at 10.0 A g-1. Moreover, excellently rate capability also can be observed, a high capacity of 689 mA h g-1 can be obtained at 5.0 A g-1. This superior lithium storage performance of S, N co-doped carbon make it as a promising low-cost and sustainable anode for high performance lithium ion batteries.

N/S Co-doped Carbon Derived From Cotton as High Performance Anode Materials for Lithium Ion Batteries

PubMed Central

Xiong, Jiawen; Pan, Qichang; Zheng, Fenghua; Xiong, Xunhui; Yang, Chenghao; Hu, Dongli; Huang, Chunlai

2018-01-01

Highly porous carbon with large surface areas is prepared using cotton as carbon sources which derived from discard cotton balls. Subsequently, the sulfur-nitrogen co-doped carbon was obtained by heat treatment the carbon in presence of thiourea and evaluated as Lithium-ion batteries anode. Benefiting from the S, N co-doping, the obtained S, N co-doped carbon exhibits excellent electrochemical performance. As a result, the as-prepared S, N co-doped carbon can deliver a high reversible capacity of 1,101.1 mA h g−1 after 150 cycles at 0.2 A g−1, and a high capacity of 531.2 mA h g−1 can be observed even after 5,000 cycles at 10.0 A g−1. Moreover, excellently rate capability also can be observed, a high capacity of 689 mA h g−1 can be obtained at 5.0 A g−1. This superior lithium storage performance of S, N co-doped carbon make it as a promising low-cost and sustainable anode for high performance lithium ion batteries. PMID:29755966

Synthesis of Ultrathin Si Nanosheets from Natural Clays for Lithium-Ion Battery Anodes.

PubMed

Ryu, Jaegeon; Hong, Dongki; Choi, Sinho; Park, Soojin

2016-02-23

Two-dimensional Si nanosheets have been studied as a promising candidate for lithium-ion battery anode materials. However, Si nanosheets reported so far showed poor cycling performances and required further improvements. In this work, we utilize inexpensive natural clays for preparing high quality Si nanosheets via a one-step simultaneous molten salt-induced exfoliation and chemical reduction process. This approach produces high purity mesoporous Si nanosheets in high yield. As a control experiment, two-step process (pre-exfoliated silicate sheets and subsequent chemical reduction) cannot sustain their original two-dimensional structure. In contrast, one-step method results in a production of 5 nm-thick highly porous Si nanosheets. Carbon-coated Si nanosheet anodes exhibit a high reversible capacity of 865 mAh g(-1) at 1.0 A g(-1) with an outstanding capacity retention of 92.3% after 500 cycles. It also delivers high rate capability, corresponding to a capacity of 60% at 20 A g(-1) compared to that of 2.0 A g(-1). Furthermore, the Si nanosheet electrodes show volume expansion of only 42% after 200 cycles.

Preventing the dissolution of lithium polysulfides in lithium-sulfur cells by using Nafion-coated cathodes.

PubMed

Oh, Soo Jung; Lee, Jun Kyu; Yoon, Woo Young

2014-09-01

The principal drawback of lithium-sulfur batteries is the dissolution of long-chain lithium polysulfides into the electrolyte, which limits cycling performance. To overcome this problem, we focused on the development of a novel cathode as well as anode material and designed Nafion-coated NiCrAl/S as a cathode and lithium powder as an anode. Nafion-coated NiCrAl/S cathode was synthesized using a two-step dip-coating technique. The lithium-powder anode was used instead of a lithium-foil anode to prohibit dendrite growth and to improve on the electrochemical behaviors. The cells showed an initial discharge capacity of about 900 mA g(-1) and a final discharge capacity of 772 mA g(-1) after 100 cycles at 0.1 C-rate. Scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) demonstrate that using the Nafion-coated NiCrAl/S cathode can suppress the dissolution of long-chain lithium polysulfides. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Zr doping effect with low-cost solid-state reaction method to synthesize submicron Li4Ti5O12 anode material

NASA Astrophysics Data System (ADS)

Seo, Inseok; Lee, Cheul-Ro; Kim, Jae-Kwang

2017-09-01

To improve the electrochemical properties, fine Zr-doping Li4Ti5O12 anode materials for rechargeable lithium batteries with a uniform particle size distribution were synthesized by a modified solid-state reaction using fine Li2CO3 and TiO2 (anatase) powders as precursors with a Li:Ti molar ratio of 4:5. The use of fine Li2CO3 and TiO2 (anatase) powders as precursors prevented the formation of ZrO2 at 0.1 mol Zr-doping. XRD analysis revealed that the substitution of Zr for Ti leads to the increase of lattice parameters, allowing improved Li diffusion. The discharge capacity retention increased slightly with Zr-doping and the 0.1 mol Zr-doped Li4Ti5O12 electrode achieved 99% retention of discharge capacity.

One-Pot Synthesis of Co-Based Coordination Polymer Nanowire for Li-Ion Batteries with Great Capacity and Stable Cycling Stability

NASA Astrophysics Data System (ADS)

Wang, Peng; Lou, Xiaobing; Li, Chao; Hu, Xiaoshi; Yang, Qi; Hu, Bingwen

2018-06-01

Nanowire coordination polymer cobalt-terephthalonitrile (Co-BDCN) was successfully synthesized using a simple solvothermal method and applied as anode material for lithium-ion batteries (LIBs). A reversible capacity of 1132 mAh g-1 was retained after 100 cycles at a rate of 100 mA g-1, which should be one of the best LIBs performances among metal organic frameworks and coordination polymers-based anode materials at such a rate. On the basis of the comprehensive structural and morphology characterizations including fourier transform infrared spectroscopy, 1H NMR, 13C NMR, and scanning electron microscopy, we demonstrated that the great electrochemical performance of the as-synthesized Co-BDCN coordination polymer can be attributed to the synergistic effect of metal centers and organic ligands, as well as the stability of the nanowire morphology during cycling.[Figure not available: see fulltext.

Epoxidized Natural Rubber/Chitosan Network Binder for Silicon Anode in Lithium-Ion Battery.

PubMed

Lee, Sang Ha; Lee, Jeong Hun; Nam, Dong Ho; Cho, Misuk; Kim, Jaehoon; Chanthad, Chalathorn; Lee, Youngkwan

2018-05-16

Polymeric binder is extremely important for Si-based anode in lithium-ion batteries due to large volume variation during charging/discharging process. Here, natural rubber-incorporated chitosan networks were designed as a binder material to obtain both adhesion and elasticity. Chitosan could strongly anchor Si particles through hydrogen bonding, while the natural rubber could stretch reversibly during the volume variation of Si particles, resulting in high cyclic performance. The prepared electrode exhibited the specific capacities of 1350 mAh/g after 1600 cycles at the current density of 8 A/g and 2310 mAh/g after 500 cycles at the current density of 1 A/g. Furthermore, the cycle test with limiting lithiation capacity was conducted to study the optimal binder properties at varying degree of the volume expansion of silicon, and it was found that the elastic property of binder material was strongly required when the large volume expansion of Si occurred.

Soft template strategy to synthesize iron oxide-titania yolk-shell nanoparticles as high-performance anode materials for lithium-ion battery applications.

PubMed

Lim, Joohyun; Um, Ji Hyun; Ahn, Jihoon; Yu, Seung-Ho; Sung, Yung-Eun; Lee, Jin-Kyu

2015-05-18

Yolk-shell-structured nanoparticles with iron oxide core, void, and a titania shell configuration are prepared by a simple soft template method and used as the anode material for lithium ion batteries. The iron oxide-titania yolk-shell nanoparticles (IO@void@TNPs) exhibit a higher and more stable capacity than simply mixed nanoparticles of iron oxide and hollow titania because of the unique structure obtained by the perfect separation between iron oxide nanoparticles, in combination with the adequate internal void space provided by stable titania shells. Moreover, the structural effect of IO@void@TNPs clearly demonstrates that the capacity retention value after 50 cycles is approximately 4 times that for IONPs under harsh operating conditions, that is, when the temperature is increased to 80 °C. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Spontaneous hybrids of graphene and carbon nanotube arrays at the liquid-gas interface for Li-ion battery anodes.

PubMed

Kim, Hyeri; Kim, Jongsoon; Jeong, Hee-Sung; Kim, Hyungsub; Lee, Hoyeon; Ha, Jae-Min; Choi, Sung-Min; Kim, Tae-Ho; Nah, Yoon-Chae; Shin, Tae Joo; Bang, Joona; Satija, Sushil K; Koo, Jaseung

2018-05-17

We demonstrate that hybrid structures of graphene and single-walled carbon nanotubes (SWNTs) are precisely controlled at the liquid-gas interface. The functionalized SWNT Langmuir monolayers anchor single-layer graphene nanosheets (GNSs) suspended in water via Coulomb interaction at the interface. This GNS/SWNT hybrid multilayer electrode can be a promising anode material for Li-ion batteries, offering high specific capacity, outstanding power capability, and excellent cyclability.

Bio-derived hierarchically macro-meso-micro porous carbon anode for lithium/sodium ion batteries

NASA Astrophysics Data System (ADS)

Elizabeth, Indu; Singh, Bhanu Pratap; Trikha, Sunil; Gopukumar, Sukumaran

2016-10-01

Nitrogen doped hierarchically porous carbon derived from prawn shells have been efficiently synthesized through a simple, economically viable and environmentally benign approach. The prawn shell derived carbon (PSC) has high inherent nitrogen content (5.3%) and possesses a unique porous structure with the co-existence of macro, meso and micropores which can afford facile storage and transport channels for both Li and Na ions. PSC is well characterized using X-ray diffraction (XRD), Field Emission Scanning Electron Microscopy (FE-SEM), Transmission electron Microscopy (TEM), High resolution TEM (HR-TEM) and X-ray photoelectron spectroscopy (XPS). Electron Paramagnetic Resonance (EPR) and Solid state-Nuclear Magnetic Resonance (NMR) studies have been conducted on pristine PSC and Li/Na interacted PSC. PSC as anode for Lithium ion batteries (LIBs) delivers superior electrochemical reversible specific capacity (740 mAh g-1 at 0.1 Ag-1 current density for 150 cycles) and high rate capability. When used as anode material for Sodium ion batteries (SIBs), PSC exhibits excellent reversible specific capacity of 325 mAh g-1 at 0.1 Ag-1 for 200 cycles and rate capability of 107 mAh g-1 at 2 Ag-1. Furthermore, this study demonstrates the employment of natural waste material as a potential anode for both LIB and SIB, which will definitively make a strike in the energy storage field.

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.

A densely packed Sb2O3 nanosheet-graphene aerogel toward advanced sodium-ion batteries.

PubMed

Zhou, Jing; Yan, Bingyi; Yang, Jie; Yang, Yun; Zhou, Wei; Lan, Hao; Wang, Hua; Guo, Lin

2018-05-17

As a promising anodic material for rechargeable batteries, Sb2O3 has drawn increasing attention due to its high theoretical capacity and abundant natural deposits. However, poor cyclability and rate performance of Sb2O3 derived from a large volume change during insertion/desertion reactions as well as a sluggish kinetic process restrict its practical application. Herein, we report a facile amorphous-to-crystalline strategy to synthesize a densely packed Sb2O3 nanosheet-graphene aerogel as a novel anode for sodium ion batteries (SIBs). This Sb2O3/graphene composite displays a reversible capacity as high as 657.9 mA h g-1 even after 100 cycles at 0.1 A g-1, along with an excellent rate capacity of 356.8 mA h g-1 at 5.0 A g-1. The superior electrochemical performance is attributed to the synergistic effects of densely packed Sb2O3 nanosheets and graphene aerogel, which serves as both a robust support and stable buffer layer to maintain the structural stability of the nanocomposite, and enhances the electrode kinetics of electrolyte diffusion and electron transfer simultaneously. Hence, this densely-packed two-dimensional Sb2O3 nanosheet-graphene aerogel can be a promising anode material for rechargeable SIBs due to its facile synthesis process and outstanding electrochemical performance.

Scalable synthesis of interconnected porous silicon/carbon composites by the Rochow reaction as high-performance anodes of lithium ion batteries.

PubMed

Zhang, Zailei; Wang, Yanhong; Ren, Wenfeng; Tan, Qiangqiang; Chen, Yunfa; Li, Hong; Zhong, Ziyi; Su, Fabing

2014-05-12

Despite the promising application of porous Si-based anodes in future Li ion batteries, the large-scale synthesis of these materials is still a great challenge. A scalable synthesis of porous Si materials is presented by the Rochow reaction, which is commonly used to produce organosilane monomers for synthesizing organosilane products in chemical industry. Commercial Si microparticles reacted with gas CH3 Cl over various Cu-based catalyst particles to substantially create macropores within the unreacted Si accompanying with carbon deposition to generate porous Si/C composites. Taking advantage of the interconnected porous structure and conductive carbon-coated layer after simple post treatment, these composites as anodes exhibit high reversible capacity and long cycle life. It is expected that by integrating the organosilane synthesis process and controlling reaction conditions, the manufacture of porous Si-based anodes on an industrial scale is highly possible. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Ma, Xuetian; An, Ke; Bai, Jianmin

Sodium ion batteries are being considered as an alternative to lithium ion batteries in large-scale energy storage applications owing to the low cost. In this paper, a novel titanate compound, NaAlTi 3O 8, was successfully synthesized and tested as a promising anode material for sodium ion batteries. Powder X-ray Diffraction (XRD) and refinement were used to analyze the crystal structure. Electrochemical cycling tests under a C/10 rate between 0.01 - 2.5 V showed that ~83 mAh/g capacity could be achieved in the second cycle, with ~75% of which retained after 100 cycles, which corresponds to 0.75 Na + insertion andmore » extraction. The influence of synthesis conditions on electrochemical performances was investigated and discussed. Finally, NaAlTi 3O 8 not only presents a new anode material with low average voltage of ~0.5 V, but also provides a new type of intercalation anode with a crystal structure that differentiates from the anodes that have been reported.« less

Tunnel-structured K xTiO 2 nanorods by in situ carbothermal reduction as a long cycle and high rate anode for sodium-ion batteries

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

Zhang, Qing; Wei, Yaqing; Yang, Haotian

Here, the low electronic conductivity and the sluggish sodium-ion diffusion in the compact crystal structure of Ti-based anodes seriously restrict their development in sodium-ion batteries. In this study, a new hollandite K xTiO 2 with large (2 × 2) tunnels is synthesized by a facile carbothermal reduction method, and its sodium storage performance is investigated. X-ray diffraction (XRD) and transmission electron microscopy (TEM) analyses illustrate the formation mechanism of the hollandite K xTiO 2 upon the carbothermal reduction process. Compared to the traditional layered or small (1 × 1) tunnel-type Ti-based materials, the hollandite K xTiO 2 with large (2more » × 2) tunnels may accommodate more sodium ions and facilitate the Na + diffusion in the structure; thus, it is expected to get a large capacity and realize high rate capability. The synthesized K xTiO 2 with large (2 × 2) tunnels shows a stable reversible capacity of 131 mAh g –1 (nearly 3 times of (1 × 1) tunnel-structured Na 2Ti 6O 13) and superior cycling stability with no obvious capacity decay even after 1000 cycles, which is significantly better than the traditional layered Na 2Ti 3O 7 (only 40% of capacity retention in 20 cycles). Moreover, the carbothermal process can naturally introduce oxygen vacancy and low-valent titanium as well as the surface carbon coating layer to the structure, which would greatly enhance the electronic conductivity of K xTiO 2 and thus endow this material high rate capability. With a good rate capability and long cyclability, this hollandite K xTiO 2 can serve as a new promising anode material for room-temperature long-life sodium-ion batteries for large-scale energy storage systems, and the carbothermal reduction method is believed to be an effective and facile way to develop novel Ti-based anodes with simultaneous carbon coating and Ti(III) self-doping.« less

Tunnel-structured K xTiO 2 nanorods by in situ carbothermal reduction as a long cycle and high rate anode for sodium-ion batteries

DOE PAGES

Zhang, Qing; Wei, Yaqing; Yang, Haotian; ...

2017-02-03

Here, the low electronic conductivity and the sluggish sodium-ion diffusion in the compact crystal structure of Ti-based anodes seriously restrict their development in sodium-ion batteries. In this study, a new hollandite K xTiO 2 with large (2 × 2) tunnels is synthesized by a facile carbothermal reduction method, and its sodium storage performance is investigated. X-ray diffraction (XRD) and transmission electron microscopy (TEM) analyses illustrate the formation mechanism of the hollandite K xTiO 2 upon the carbothermal reduction process. Compared to the traditional layered or small (1 × 1) tunnel-type Ti-based materials, the hollandite K xTiO 2 with large (2more » × 2) tunnels may accommodate more sodium ions and facilitate the Na + diffusion in the structure; thus, it is expected to get a large capacity and realize high rate capability. The synthesized K xTiO 2 with large (2 × 2) tunnels shows a stable reversible capacity of 131 mAh g –1 (nearly 3 times of (1 × 1) tunnel-structured Na 2Ti 6O 13) and superior cycling stability with no obvious capacity decay even after 1000 cycles, which is significantly better than the traditional layered Na 2Ti 3O 7 (only 40% of capacity retention in 20 cycles). Moreover, the carbothermal process can naturally introduce oxygen vacancy and low-valent titanium as well as the surface carbon coating layer to the structure, which would greatly enhance the electronic conductivity of K xTiO 2 and thus endow this material high rate capability. With a good rate capability and long cyclability, this hollandite K xTiO 2 can serve as a new promising anode material for room-temperature long-life sodium-ion batteries for large-scale energy storage systems, and the carbothermal reduction method is believed to be an effective and facile way to develop novel Ti-based anodes with simultaneous carbon coating and Ti(III) self-doping.« less

Tunnel-Structured KxTiO2 Nanorods by in Situ Carbothermal Reduction as a Long Cycle and High Rate Anode for Sodium-Ion Batteries.

PubMed

Zhang, Qing; Wei, Yaqing; Yang, Haotian; Su, Dong; Ma, Ying; Li, Huiqiao; Zhai, Tianyou

2017-03-01

The low electronic conductivity and the sluggish sodium-ion diffusion in the compact crystal structure of Ti-based anodes seriously restrict their development in sodium-ion batteries. In this study, a new hollandite K x TiO 2 with large (2 × 2) tunnels is synthesized by a facile carbothermal reduction method, and its sodium storage performance is investigated. X-ray diffraction (XRD) and transmission electron microscopy (TEM) analyses illustrate the formation mechanism of the hollandite K x TiO 2 upon the carbothermal reduction process. Compared to the traditional layered or small (1 × 1) tunnel-type Ti-based materials, the hollandite K x TiO 2 with large (2 × 2) tunnels may accommodate more sodium ions and facilitate the Na + diffusion in the structure; thus, it is expected to get a large capacity and realize high rate capability. The synthesized K x TiO 2 with large (2 × 2) tunnels shows a stable reversible capacity of 131 mAh g -1 (nearly 3 times of (1 × 1) tunnel-structured Na 2 Ti 6 O 13 ) and superior cycling stability with no obvious capacity decay even after 1000 cycles, which is significantly better than the traditional layered Na 2 Ti 3 O 7 (only 40% of capacity retention in 20 cycles). Moreover, the carbothermal process can naturally introduce oxygen vacancy and low-valent titanium as well as the surface carbon coating layer to the structure, which would greatly enhance the electronic conductivity of K x TiO 2 and thus endow this material high rate capability. With a good rate capability and long cyclability, this hollandite K x TiO 2 can serve as a new promising anode material for room-temperature long-life sodium-ion batteries for large-scale energy storage systems, and the carbothermal reduction method is believed to be an effective and facile way to develop novel Ti-based anodes with simultaneous carbon coating and Ti(III) self-doping.

MoO2-ordered mesoporous carbon nanocomposite as an anode material for lithium-ion batteries.

PubMed

Zeng, Lingxing; Zheng, Cheng; Deng, Cuilin; Ding, Xiaokun; Wei, Mingdeng

2013-03-01

In the present work, the nanocomposite of MoO2-ordered mesoporous carbon (MoO2-OMC) was synthesized for the first time using a carbon thermal reduction route and the mesoporous carbon as the nanoreactor. The synthesized nanocomposite was characterized by X-ray diffraction (XRD), thermogravimetric analysis (TGA), N2 adsorption-desorption, scanning electron microscopy (SEM), and transmission electron microscopy (TEM) measurements. Furthermore, this nanocomposite was used as an anode material for Li-ion intercalation and exhibited large reversible capacity, high rate performance, and good cycling stability. For instance, a high reversible capacity of 689 mAh g(-1) can remain after 50 cycles at a current density of 50 mA g(-1). It is worth mentioning that the MoO2-OMC nanocomposite electrode can attain a high reversible capacity of 401 mAh g(-1) at a current density as high as 2 A g(-1). These results might be due to the intrinsic characteristics of nanocomposite, which offered a better accommodation of the strain and volume changes and a shorter path for Li-ion and electron transport, leading to the improved capacity and enhanced rate capability.

Towards High Capacity Li-ion Batteries Based on Silicon-Graphene Composite Anodes and Sub-micron V-doped LiFePO4 Cathodes

NASA Astrophysics Data System (ADS)

Loveridge, M. J.; Lain, M. J.; Johnson, I. D.; Roberts, A.; Beattie, S. D.; Dashwood, R.; Darr, J. A.; Bhagat, R.

2016-11-01

Lithium iron phosphate, LiFePO4 (LFP) has demonstrated promising performance as a cathode material in lithium ion batteries (LIBs), by overcoming the rate performance issues from limited electronic conductivity. Nano-sized vanadium-doped LFP (V-LFP) was synthesized using a continuous hydrothermal process using supercritical water as a reagent. The atomic % of dopant determined the particle shape. 5 at. % gave mixed plate and rod-like morphology, showing optimal electrochemical performance and good rate properties vs. Li. Specific capacities of >160 mAh g-1 were achieved. In order to increase the capacity of a full cell, V-LFP was cycled against an inexpensive micron-sized metallurgical grade Si-containing anode. This electrode was capable of reversible capacities of approximately 2000 mAh g-1 for over 150 cycles vs. Li, with improved performance resulting from the incorporation of few layer graphene (FLG) to enhance conductivity, tensile behaviour and thus, the composite stability. The cathode material synthesis and electrode formulation are scalable, inexpensive and are suitable for the fabrication of larger format cells suited to grid and transport applications.

Towards High Capacity Li-ion Batteries Based on Silicon-Graphene Composite Anodes and Sub-micron V-doped LiFePO4 Cathodes

PubMed Central

Loveridge, M. J.; Lain, M. J.; Johnson, I. D.; Roberts, A.; Beattie, S. D.; Dashwood, R.; Darr, J. A.; Bhagat, R.

2016-01-01

Lithium iron phosphate, LiFePO4 (LFP) has demonstrated promising performance as a cathode material in lithium ion batteries (LIBs), by overcoming the rate performance issues from limited electronic conductivity. Nano-sized vanadium-doped LFP (V-LFP) was synthesized using a continuous hydrothermal process using supercritical water as a reagent. The atomic % of dopant determined the particle shape. 5 at. % gave mixed plate and rod-like morphology, showing optimal electrochemical performance and good rate properties vs. Li. Specific capacities of >160 mAh g−1 were achieved. In order to increase the capacity of a full cell, V-LFP was cycled against an inexpensive micron-sized metallurgical grade Si-containing anode. This electrode was capable of reversible capacities of approximately 2000 mAh g−1 for over 150 cycles vs. Li, with improved performance resulting from the incorporation of few layer graphene (FLG) to enhance conductivity, tensile behaviour and thus, the composite stability. The cathode material synthesis and electrode formulation are scalable, inexpensive and are suitable for the fabrication of larger format cells suited to grid and transport applications. PMID:27898104

Towards High Capacity Li-ion Batteries Based on Silicon-Graphene Composite Anodes and Sub-micron V-doped LiFePO4 Cathodes.

PubMed

Loveridge, M J; Lain, M J; Johnson, I D; Roberts, A; Beattie, S D; Dashwood, R; Darr, J A; Bhagat, R

2016-11-29

Lithium iron phosphate, LiFePO 4 (LFP) has demonstrated promising performance as a cathode material in lithium ion batteries (LIBs), by overcoming the rate performance issues from limited electronic conductivity. Nano-sized vanadium-doped LFP (V-LFP) was synthesized using a continuous hydrothermal process using supercritical water as a reagent. The atomic % of dopant determined the particle shape. 5 at. % gave mixed plate and rod-like morphology, showing optimal electrochemical performance and good rate properties vs. Li. Specific capacities of >160 mAh g -1 were achieved. In order to increase the capacity of a full cell, V-LFP was cycled against an inexpensive micron-sized metallurgical grade Si-containing anode. This electrode was capable of reversible capacities of approximately 2000 mAh g -1 for over 1 50 cycles vs. Li, with improved performance resulting from the incorporation of few layer graphene (FLG) to enhance conductivity, tensile behaviour and thus, the composite stability. The cathode material synthesis and electrode formulation are scalable, inexpensive and are suitable for the fabrication of larger format cells suited to grid and transport applications.

Fluorine-doped SnO2 nanoparticles anchored on reduced graphene oxide as a high-performance lithium ion battery anode

NASA Astrophysics Data System (ADS)

Cui, Dongming; Zheng, Zhong; Peng, Xue; Li, Teng; Sun, Tingting; Yuan, Liangjie

2017-09-01

The composite of fluorine-doped SnO2 anchored on reduced graphene oxide (F-SnO2/rGO) has been synthesized through a hydrothermal method. F-SnO2 particles with average size of 8 nm were uniformly anchored on the surfaces of rGO sheets and the resulting composite had a high loading of F-SnO2 (ca. 90%). Benefiting from the remarkably improved electrical conductivity and Li-ion diffusion in the electrode by F doping and rGO incorporation, the composite material exhibited high reversible capacity, excellent long-term cycling stability and superior rate capability. The electrode delivered a large reversible capacity of 1037 mAh g-1 after 150 cycles at 100 mA g-1 and high rate capacities of 860 and 770 mAh g-1 at 1 and 2 A g-1, respectively. Moreover, the electrode could maintain a high reversible capacities of 733 mAh g-1 even after 250 cycles at 500 mA g-1. The outstanding electrochemical performance of the as-synthesized composite make it a promising anode material for high-energy lithium ion batteries.

Ti n O2n-1-Coated Li4Ti5O12 Composite Anode Material for Lithium-Ion Batteries

NASA Astrophysics Data System (ADS)

Zhang, Xiaoyan; Xu, Wen; Liu, Wanying; Li, Xing; Zhong, Xiaoxi; Lin, Yuanhua

2018-01-01

In an effort to enhance the rate capability of Li4Ti5O12, the Ti n O2n-1-coated Li4Ti5O12 (Li4Ti5O12-Ti n O2n-1, 3 < n < 10) composite has been synthesized through a sol-gel process followed by heat treatment in H2 atmosphere. Compared with pure Li4Ti5O12, Li4Ti5O12-Ti n O2n-1 composite shows higher specific capacity, better rate capability and cycle stability. The initial discharge capacity of the Li4Ti5O12-Ti n O2n-1 composite electrode is 171.2 mAh g-1 at 0.2°C, and 103.8 mAh g-1 at 20°C. Moreover, the discharge capacity remains 79.5 mAh g-1 after 100 cycles at 20°C with a capacity loss of 23.4%. The improved rate capacity and cycling stability clarify the positive effects of Ti n O2n-1 coating layer in Li4Ti5O12-Ti n O2n-1 composite as an anode material for lithium ion batteries.

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.

Tailored synthesis of monodispersed nano/submicron porous silicon oxycarbide (SiOC) spheres with improved Li-storage performance as an anode material for Li-ion batteries

NASA Astrophysics Data System (ADS)

Shi, Huimin; Yuan, Anbao; Xu, Jiaqiang

2017-10-01

A spherical silicon oxycarbide (SiOC) material (monodispersed nano/submicron porous SiOC spheres) is successfully synthesized via a specially designed synthetic strategy involving pyrolysis of phenyltriethoxysilane derived pre-ceramic polymer spheres at 900 °C. In order to prevent sintering of the pre-ceramic polymer spheres upon heating, a given amount of hollow porous SiO2 nanobelts which are separately prepared from tetraethyl orthosilicate with CuO nanobelts as templates are introduced into the pre-ceramic polymer spheres before pyrolysis. This material is investigated as an anode for lithium-ion batteries in comparison with the large-size bulk SiOC material synthesized under the similar conditions but without hollow SiO2 nanobelts. The maximum reversible specific capacity of ca. 900 mAh g-1 is delivered at the current density of 100 mA g-1 and ca. 98% of the initial capacity is remained after 100 cycles at 100 mA g-1 for the SiOC spheres material, which are much superior to the bulk SiOC material. The improved lithium storage performance in terms of specific capacity and cyclability is attributed to its particular morphology of monodisperse nano/submicron porous spheres as well as its modified composition and microstructure. This SiOC material has higher Li-storage activity and better stability against volume expansion during repeated lithiation and delithiation cycling.

Uniform Li deposition regulated via three-dimensional polyvinyl alcohol nanofiber networks for effective Li metal anodes.

PubMed

Wang, Gang; Xiong, Xunhui; Lin, Zhihua; Zheng, Jie; Fenghua, Zheng; Li, Youpeng; Liu, Yanzhen; Yang, Chenghao; Tang, Yiwei; Liu, Meilin

2018-05-31

Lithium metal anodes are considered to be the most promising anode material for next-generation advanced energy storage devices due to their high reversible capacity and extremely low anode potential. Nevertheless, the formation of dendritic Li, induced by the repeated breaking and repairing of solid electrolyte interphase layers, always causes poor cycling performance and low coulombic efficiency, as well as serious safety problems, which have hindered the practical application of Li anodes for a long time. Herein, we design an electrode by covering a polyvinyl alcohol layer with a three-dimensional nanofiber network structure through an electrospinning technique. The polar functional groups on the surface of the polymer nanofibers can restrict the deposition of Li along the fibers and regulate the deposition of Li uniformly in the voids between the nanofibers. Owing to the structural features of the polymer, the modified Li|Cu electrode displays excellent cycle stability, with a high coulombic efficiency of 98.6% after 200 cycles at a current density of 1 mA cm-2 under a deposition capacity of 1 mA h cm-2, whilst the symmetric cell using the polymer modified Li anode shows stable cycling with a low hysteresis voltage of ∼80 mV over 600 h at a current density of 5 mA cm-2.

Preparation of yolk-shell MoS2 nanospheres covered with carbon shell for excellent lithium-ion battery anodes

NASA Astrophysics Data System (ADS)

Guo, Bangjun; Feng, Yu; Chen, Xiaofan; Li, Bo; Yu, Ke

2018-03-01

Molybdenum disulfide is regarded as one of the most promising electrode materials for high performance lithium-ion batteries. Designing firm basal structure is a key point to fully utilize the high capacity of layered MoS2 nanomaterials. Here, yolk-shell structured MoS2 nanospheres is firstly designed and fabricated to meet this needs. This unique yolk-shell nanospheres are transformed from solid nanospheres by a simply weak alkaline etching method. Then, the yolk-shell MoS2/C is synthesized by a facile process to protect the outside MoS2 shell and promote the conductivity. Taking advantages of high capacity and well-defined cavity space, allowing the core MoS2 to expand freely without breaking the outer shells, yolk-shell MoS2/C nanospheres delivers long cycle life (94% of capacity retained after 200 cycles) and high rate behaviour (830 mA h g-1 at 5 A g-1). This design of yolk-shell structure may set up a new strategy for preparing next generation anode materials for LIBs.

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

Fluidized bed reaction towards crystalline embedded amorphous Si anode with much enhanced cycling stability.

PubMed

Zhou, Yu; Guo, Huajun; Yan, Guochun; Wang, Zhixing; Li, Xinhai; Yang, Zhewei; Zheng, Anxiong; Wang, Jiexi

2018-04-10

A facile and large-scale fluidized bed reaction route was introduced for the first time to prepare crystalline embedded amorphous silicon nanoparticles with an average size of 50 nm as anode materials for lithium-ion batteries. By increasing the operating potential to control the electrochemically active degree, the resulting sample showed excellent cycle stability with a high capacity retention of 94.7% after 200 cycles at 1 A g-1 in the voltage range of 0.12-2.00 V.

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

Understanding Conversion-Type Electrodes for Lithium Rechargeable Batteries.

PubMed

Yu, Seung-Ho; Feng, Xinran; Zhang, Na; Seok, Jeesoo; Abruña, Héctor D

2018-02-20

The need/desire to lower the consumption of fossil fuels and its environmental consequences has reached unprecedented levels in recent years. A global effort has been undertaken to develop advanced renewable energy generation and especially energy storage technologies, as they would enable a dramatic increase in the effective and efficient use of renewable (and often intermittent) energy sources. The development of electrical energy storage (EES) technologies with high energy and power densities, long life, low cost, and safe use represents a challenge from both the fundamental science and technological application points of view. While the advent and broad deployment of lithium-ion batteries (LIBs) has dramatically changed the EES landscape, their performance metrics need to be greatly enhanced to keep pace with the ever-increasing demands imposed by modern consumer electronics and especially the emerging automotive markets. Current battery technologies are mostly based on the use of a transition metal oxide cathode (e.g., LiCoO 2 , LiFePO 4 , or LiNiMnCoO 2 ) and a graphite anode, both of which depend on intercalation/insertion of lithium ions for operation. While the cathode material currently limits the battery capacity and overall energy density, there is a great deal of interest in the development of high-capacity cathode materials as well as anode materials. Conversion reaction materials have been identified/proposed as potentially high-energy-density alternatives to intercalation-based materials. However, conversion reaction materials react during lithiation to form entirely new products, often with dramatically changed structure and chemistry, by reaction mechanisms that are still not completely understood. This makes it difficult to clearly distinguish the limitations imposed by the mechanism and practical losses from initial particle morphology, synthetic approaches, and electrode preparations. Transition metal compounds such as transition metal oxides, sulfides, fluorides, phosphides, and nitrides can undergo conversion reactions yielding materials with high theoretical capacity (generally from 500 to 1500 mA h g -1 ). In particular, a number of transition metal oxides and sulfides have shown excellent electrochemical properties as high-capacity anode materials. In addition, some transition metal fluorides have shown great potential as cathode materials for Li rechargeable batteries. In this Account we present mechanistic studies, with emphasis on the use of operando methods, of selected examples of conversion-type materials as both potentially high-energy-density anodes and cathodes in EES applications. We also include examples of the conceptually similar conversion-type reactions involving chalcogens and halogens, with emphasis on the Li-S system. In this case we focus on the problems arising from the low electrical conductivities of elemental sulfur and Li 2 S and the "redox shuttle" phenomena of polysulfides. In addition to mechanistic insights from the use of operando methods, we also cover several key strategies in electrode materials design such as controlling the size, morphology, composition, and architecture.

In situ consolidation of offshore petroleum well structural casings by electrokinetic methods

NASA Astrophysics Data System (ADS)

Wrixon, Robert Christopher

Offshore drilling operations encounter cement wash-out problems while setting the initial structural casing (0--200 ft depth) due to the soft, unconsolidated nature of the sea-bed. Structural casings set by alternative methods have failed in up to 50% of cases due to insufficient frictional bearing capacity. This dissertation presents a method of increasing the bearing capacity of a jet-drilled or slick-drilled casing in-situ by applying a potential difference such that the casing is anodic compared to a remote cathode. It has been shown experimentally that clayey formations will swell and stick to a simulated anodic casing by the combined electrokinetic processes of electroosmosis and electrophoresis. Any cavities around the "casing" are eliminated and the formation is flush against the metal surface, increasing bearing capacity. The formation around the "casing" dries out due to electroosmotic migration of water away from the anode, increasing the shear strength of the surrounding soil. Corrosion products at the anode can further increase the soil shear strength by a process known as electrochemical hardening. This investigation has shown that the bearing capacity of anodic casings can potentially be increased by a factor of up to 1,000% in soft clays and silty clays. The existence of an optimal level of electrokinetic consolidation, beyond which the soil shear strength begins to degrade, has been demonstrated. The difficulties of applying electrokinetic methods to saline soil environments have been addressed and the process has been shown to be successful, as long as the requisite electric field strength is maintained. The efficiency of the electrokinetic consolidation technique has been shown to be affected by the soil water content, soil mineralogy, power supplied, time of treatment and the choice of anode material. Experiments in marine sediment show that increases in bearing capacities of about 300% can be achieved at optimal treatment conditions. With likely current and power restrictions, increases of 50% to 100% are realistic. This level of increase still makes offshore electrokinetic casing consolidation a viable process, given that it is attainable quickly and at a modest power requirement and given the enormous cost of a structural casing collapse.

Remediation of phosphate-contaminated water by electrocoagulation with aluminium, aluminium alloy and mild steel anodes.

PubMed

Vasudevan, Subramanyan; Lakshmi, Jothinathan; Jayaraj, Jeganathan; Sozhan, Ganapathy

2009-05-30

The present study provides an electrocoagulation process for the remediation of phosphate-contaminated water using aluminium, aluminium alloy and mild steel as the anodes and stainless steel as the cathode. The various parameters like effect of anode materials, effect of pH, concentration of phosphate, current density, temperature and co-existing ions, and so forth, and the adsorption capacity was evaluated using both Freundlich and Langmuir isotherm models. The adsorption of phosphate preferably fitting the Langmuir adsorption isotherm suggests monolayer coverage of adsorbed molecules. The results showed that the maximum removal efficiency of 99% was achieved with aluminium alloy anode at a current density of 0.2 A dm(-2), at a pH of 7.0. The adsorption process follows second-order kinetics.

Glassy Metal Alloy Nanofiber Anodes Employing Graphene Wrapping Layer: Toward Ultralong-Cycle-Life Lithium-Ion Batteries.

PubMed

Jung, Ji-Won; Ryu, Won-Hee; Shin, Jungwoo; Park, Kyusung; Kim, Il-Doo

2015-07-28

Amorphous silicon (a-Si) has been intensively explored as one of the most attractive candidates for high-capacity and long-cycle-life anode in Li-ion batteries (LIBs) primarily because of its reduced volume expansion characteristic (∼280%) compared to crystalline Si anodes (∼400%) after full Li(+) insertion. Here, we report one-dimensional (1-D) electrospun Si-based metallic glass alloy nanofibers (NFs) with an optimized composition of Si60Sn12Ce18Fe5Al3Ti2. On the basis of careful compositional tailoring of Si alloy NFs, we found that Ce plays the most important role as a glass former in the formation of the metallic glass alloy. Moreover, Si-based metallic glass alloy NFs were wrapped by reduced graphene oxide sheets (specifically Si60Sn12Ce18Fe5Al3Ti2 NFs@rGO), which can prevent the direct exposure of a-Si alloy NFs to the liquid electrolyte and stabilize the solid-electrolyte interphase (SEI) layers on the surfaces of rGO sheets while facilitating electron transport. The metallic glass nanofibers exhibited superior electrochemical cell performance as an anode: (i) Si60Sn12Ce18Fe5Al3Ti2 NFs show a high specific capacity of 1017 mAh g(-1) up to 400 cycles at 0.05C with negligible capacity loss as well as superior cycling performance (nearly 99.9% capacity retention even after 2000 cycles at 0.5C); (ii) Si60Sn12Ce18Fe5Al3Ti2 NFs@rGO reveals outstanding rate behavior (569.77 mAh g(-1) after 2000 cycles at 0.5C and a reversible capacity of around 370 mAh g(-1) at 4C). We demonstrate the potential suitability of multicomponent a-Si alloy NFs as a long-cycling anode material.

In situ Scanning Electron Microscopy of Silicon Anode Reactions in Lithium-Ion Batteries during Charge/Discharge Processes

PubMed Central

Chen, Chih-Yao; Sano, Teruki; Tsuda, Tetsuya; Ui, Koichi; Oshima, Yoshifumi; Yamagata, Masaki; Ishikawa, Masashi; Haruta, Masakazu; Doi, Takayuki; Inaba, Minoru; Kuwabata, Susumu

2016-01-01

A comprehensive understanding of the charge/discharge behaviour of high-capacity anode active materials, e.g., Si and Li, is essential for the design and development of next-generation high-performance Li-based batteries. Here, we demonstrate the in situ scanning electron microscopy (in situ SEM) of Si anodes in a configuration analogous to actual lithium-ion batteries (LIBs) with an ionic liquid (IL) that is expected to be a functional LIB electrolyte in the future. We discovered that variations in the morphology of Si active materials during charge/discharge processes is strongly dependent on their size and shape. Even the diffusion of atomic Li into Si materials can be visualized using a back-scattering electron imaging technique. The electrode reactions were successfully recorded as video clips. This in situ SEM technique can simultaneously provide useful data on, for example, morphological variations and elemental distributions, as well as electrochemical data. PMID:27782200

3D Interconnected and Multiwalled Carbon@MoS2 @Carbon Hollow Nanocables as Outstanding Anodes for Na-Ion Batteries.

PubMed

Wang, Yan; Qu, Qunting; Li, Guangchao; Gao, Tian; Qian, Feng; Shao, Jie; Liu, Weijie; Shi, Qiang; Zheng, Honghe

2016-11-01

Currently, the specific capacity and cycling performance of various MoS 2 /carbon-based anode materials for Na-ion storage are far from satisfactory due to the insufficient structural stability of the electrode, incomplete protection of MoS 2 by carbon, difficult access of electrolyte to the electrode interior, as well as inactivity of the adopted carbon matrix. To address these issues, this work presents the rational design and synthesis of 3D interconnected and hollow nanocables composed of multiwalled carbon@MoS 2 @carbon. In this architecture, (i) the 3D nanoweb-like structure brings about excellent mechanical property of the electrode, (ii) the ultrathin MoS 2 nanosheets are sandwiched between and doubly protected by two layers of porous carbon, (iii) the hollow structure of the primary nanofibers facilitates the access of electrolyte to the electrode interior, (iv) the porous and nitrogen-doping properties of the two carbon materials lead to synergistic Na-storage of carbon and MoS 2 . As a result, this hybrid material as the anode material of Na-ion battery exhibits fast charge-transfer reaction, high utilization efficiency, and ultrastability. Outstanding reversible capacity (1045 mAh g -1 ), excellent rate behavior (817 mAh g -1 at 7000 mA g -1 ), and good cycling performance (747 mAh g -1 after 200 cycles at 700 mA g -1 ) are obtained. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ca-doped LTO using waste eggshells as Ca source to improve the discharge capacity of anode material for lithium-ion battery

NASA Astrophysics Data System (ADS)

Setiawan, D.; Subhan, A.; Saptari, S. A.

2017-07-01

The necessity of high charge-discharge capacity lithium-ion battery becomes very urgent due to its applications demand. Several researches have been done to meet the demand including Ca doping on Li4Ti5O12 for anode material of lithium-ion batteries. Ca-doped Li4Ti5O12 (LTO) in the form of Li4-xCaxTi5O12 (x = 0, 0.05, 0.075, and 0.1) have been synthesized using simple solid state reaction. The materials preparation involved waste eggshells in the form of CaCO3 as Ca source. The structure and capacity of as-prepared samples were characterized using X-Ray Diffractometer and Cyclic Voltametry. X-Ray Diffractometer characterization revealed that all amount of dopant had entered the lattice structure of LTO successfully. The crystalline sizes were obtained by using Scherrer equation. No significant differences are detected in lattice parameters (˜8.35 Å) and crystalline sizes (˜27 nm) between all samples. Cyclic Voltametry characterization shows that Li4-xCaxTi5O12 (x = 0.05) has highest charge-discharge capacity of 177.14 mAh/g and 181.92 mAh/g, respectively. Redox-potentials of samples show no significant differences with the average of 1.589 V.

Bouquet-Like Mn2SnO4 Nanocomposite Engineered with Graphene Sheets as an Advanced Lithium-Ion Battery Anode.

PubMed

Rehman, Wasif Ur; Xu, Youlong; Sun, Xiaofei; Ullah, Inam; Zhang, Yuan; Li, Long

2018-05-30

Volume expansion is a major challenge associated with tin oxide (SnO x ), which causes poor cyclability in lithium-ion battery anode. Bare tin dioxide (SnO 2 ), tin dioxide with graphene sheets (SnO 2 @GS), and bouquet-like nanocomposite structure (Mn 2 SnO 4 @GS) are prepared via hydrothermal method followed by annealing. The obtained composite material presents a bouquet structure containing manganese and tin oxide nanoparticle network with graphene sheets. Benefiting from this porous nanostructure, in which graphene sheets provide high electronic pathways to enhance the electronic conductivity, uniformly distributed particles offer accelerated kinetic reaction with lithium ion and reduced volume deviation in the tin dioxide (SnO 2 ) particle during charge-discharge testing. As a consequence, ternary composite Mn 2 SnO 4 @GS showed a high rate performance and outstanding cyclability of anode material for lithium-ion batteries. The electrode achieved a specific capacity of about 1070 mA h g -1 at a current density of 400 mA g -1 after 200 cycles; meanwhile, the electrode still delivered a specific capacity of about 455 mA h g -1 at a high current density of 2500 mA g -1 . Ternary Mn 2 SnO 4 @GS material could facilitate fabrication of unique structure and conductive network as advanced lithium-ion battery.

Alumina-coated and manganese monoxide embedded 3D carbon derived from avocado as high-performance anode for lithium-ion batteries

NASA Astrophysics Data System (ADS)

rehman, Wasif ur; Xu, Youlong; Du, Xianfeng; Sun, Xiaofei; Ullah, Inam; Zhang, Yuan; Jin, Yanling; Zhang, Baofeng; Li, Xifei

2018-07-01

Derived from avocado fruit, a three dimension (3D) carbon is prepared via a hydrothermal/pyrolysis process followed by embedding with MnO nanoparticles by a wet chemical method and coating with Al2O3 through an atomic layer deposition technique. The obtained material presents a hierarchical structure that MnO nanocrystals wrapped in 3D carbon and then encapsulated in a uniform Al2O3 layer with a thickness of about 5 nm. Benefiting from this hierarchical structure in which 3D carbon offers numerous electronic pathways to enhance the conductivity and Al2O3 nanolayer provide a shelter to keep away from dissolution of Mn4+ and volume changes during charge/discharge process. This material (marked as C/MnO@Al2O3) has exhibited high rate performance and excellent cyclability as an anode for lithium ion batteries. A high specific capacity of about 600 mA h g-1 is achieved at a current density of 1000 mA g-1 and the electrode can still deliver a high specific capacity of about 1165 mA h g-1 at 150 mA g-1 after 100 cycles. These results facilitate a green and high potential of anode materials towards promising devices for advance performance of lithium-ion batteries.

Porous carbon nanotubes decorated with nanosized cobalt ferrite as anode materials for high-performance lithium-ion batteries

NASA Astrophysics Data System (ADS)

Wang, Lingyan; Zhuo, Linhai; Cheng, Haiyang; Zhang, Chao; Zhao, Fengyu

2015-06-01

Generally, the fast ion/electron transport and structural stability dominate the superiority in lithium-storage applications. In this work, porous carbon nanotubes decorated with nanosized CoFe2O4 particles (p-CNTs@CFO) have been rationally designed and synthesized by the assistance of supercritical carbon dioxide (scCO2). When tested as anode materials for lithium-ion batteries, the p-CNTs@CFO composite exhibits outstanding electrochemical behavior with high lithium-storage capacity (1077 mAh g-1 after 100 cycles) and rate capability (694 mAh g-1 at 3 A g-1). These outstanding electrochemical performances are attributed to the synergistic effect of porous p-CNTs and nanosized CFO. Compared to pristine CNTs, the p-CNTs with substantial pores in the tubes possess largely increased specific surface area and rich oxygen-containing functional groups. The porous structure can not only accommodate the volume change during lithiation/delithiation processes, but also provide bicontinuous electron/ion pathways and large electrode/electrolyte interface, which facilitate the ion diffusion kinetics, improving the rate performance. Moreover, the CFO particles are bonded strongly to the p-CNTs through metal-oxygen bridges, which facilitate the electron fast capture from p-CNTs to CFO, and thus resulting in a high reversible capacity and excellent rate performance. Overall, the porous p-CNTs provide an efficient way for ion diffusion and continuous electron transport as anode materials.

Graphene nanocomposites for electrochemical cell electrodes

DOEpatents

Zhamu, Aruna; Jang, Bor Z.; Shi, Jinjun

2015-11-19

A composite composition for electrochemical cell electrode applications, the composition comprising multiple solid particles, wherein (a) a solid particle is composed of graphene platelets dispersed in or bonded by a first matrix or binder material, wherein the graphene platelets are not obtained from graphitization of the first binder or matrix material; (b) the graphene platelets have a length or width in the range of 10 nm to 10 .mu.m; (c) the multiple solid particles are bonded by a second binder material; and (d) the first or second binder material is selected from a polymer, polymeric carbon, amorphous carbon, metal, glass, ceramic, oxide, organic material, or a combination thereof. For a lithium ion battery anode application, the first binder or matrix material is preferably amorphous carbon or polymeric carbon. Such a composite composition provides a high anode capacity and good cycling response. For a supercapacitor electrode application, the solid particles preferably have meso-scale pores therein to accommodate electrolyte.

Electrospinning preparation of oxygen-deficient nano TiO2-x/carbon fibre membrane as a self-standing high performance anode for Li-ion batteries

PubMed Central

Li, Jing-quan; Han, Chong; Yao, Shan-shan; Zhang, Ji; Zhai, Hong-ai; Chen, Li-li; Shen, Xiang-qian; Xiao, Ke-song

2017-01-01

Improving the specific capacity and electronic conductivity of TiO2 can boost its practical application as a promising anode material for lithium ion batteries. In this work, a three-dimensional networking oxygen-deficient nano TiO2-x/carbon fibre membrane was achieved by combining the electrospinning process with a hot-press sintering method and directly used as a self-standing anode. With the synergistic effects of three-dimensional conductive networks, surface oxygen deficiency, high specific surface area and high porosity, binder-free and self-standing structure, etc., the nano TiO2-x/carbon fibre membrane electrode displays a high electrochemical reaction kinetics and a high specific capacity. The reversible capacity could be jointly generated from porous carbon, full-lithiation of TiO2 and interfacial lithium storage. At a current density of 100 mA g−1, the reversible discharge capacity can reach 464 mA h g−1. Even at 500 mA g−1, the discharge capacity still remains at 312 mA h g−1. Compared with pure carbon fibre and TiO2 powder, the TiO2-x/C fibre membrane electrode also exhibits an excellent cycle performance with a discharge capacity of 209 mA h g−1 after 700 cycles at the current density of 300 mA g−1, and the coulombic efficiency always remains at approximately 100%. PMID:28791160

Electrospinning preparation of oxygen-deficient nano TiO2-x/carbon fibre membrane as a self-standing high performance anode for Li-ion batteries

NASA Astrophysics Data System (ADS)

Jing, Mao-xiang; Li, Jing-quan; Han, Chong; Yao, Shan-shan; Zhang, Ji; Zhai, Hong-ai; Chen, Li-li; Shen, Xiang-qian; Xiao, Ke-song

2017-07-01

Improving the specific capacity and electronic conductivity of TiO2 can boost its practical application as a promising anode material for lithium ion batteries. In this work, a three-dimensional networking oxygen-deficient nano TiO2-x/carbon fibre membrane was achieved by combining the electrospinning process with a hot-press sintering method and directly used as a self-standing anode. With the synergistic effects of three-dimensional conductive networks, surface oxygen deficiency, high specific surface area and high porosity, binder-free and self-standing structure, etc., the nano TiO2-x/carbon fibre membrane electrode displays a high electrochemical reaction kinetics and a high specific capacity. The reversible capacity could be jointly generated from porous carbon, full-lithiation of TiO2 and interfacial lithium storage. At a current density of 100 mA g-1, the reversible discharge capacity can reach 464 mA h g-1. Even at 500 mA g-1, the discharge capacity still remains at 312 mA h g-1. Compared with pure carbon fibre and TiO2 powder, the TiO2-x/C fibre membrane electrode also exhibits an excellent cycle performance with a discharge capacity of 209 mA h g-1 after 700 cycles at the current density of 300 mA g-1, and the coulombic efficiency always remains at approximately 100%.

Few-layer MoS2-anchored graphene aerogel paper for free-standing electrode materials.

PubMed

Lee, Wee Siang Vincent; Peng, Erwin; Loh, Tamie Ai Jia; Huang, Xiaolei; Xue, Jun Min

2016-04-21

To reduce the reliance on polymeric binders, conductive additives, and metallic current collectors during the electrode preparation process, as well as to assess the true performance of lithium ion battery (LIB) anodes, a free-standing electrode has to be meticulously designed. Graphene aerogel is a popular scaffolding material that has been widely used with embedded nanoparticles for application in LIB anodes. However, the current graphene aerogel/nanoparticle composite systems still involve decomposition into powder and the addition of additives during electrode preparation because of the thick aerogel structure. To further enhance the capacity of the system, MoS2 was anchored onto a graphene aerogel paper and the composite was used directly as an LIB anode. The resultant additive-free MoS2/graphene aerogel paper composite exhibited long cyclic performance with 101.1% retention after 700 cycles, which demonstrates the importance of free-standing electrodes in enhancing cyclic stability.

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.

High Voltage Magnesium-ion Battery Enabled by Nanocluster Mg3Bi2 Alloy Anode in Noncorrosive Electrolyte.

PubMed

Tan, Yi-Hong; Yao, Wei-Tang; Zhang, Tianwen; Ma, Tao; Lu, Lei-Lei; Zhou, Fei; Yao, Hong-Bin; Yu, Shu-Hong

2018-05-03

Currently, developing high voltage (beyond 2 V) rechargeable Mg-ion batteries still remains a great challenge owing to the limit of corrosive electrolyte and low compatibility of anode material. Here we report a facile one step solid state alloying route to synthesize nanoclustered Mg 3 Bi 2 alloy as a high-performance anode to build up a 2 V Mg-ion battery using noncorrosive electrolyte. The fabricated nanoclustered Mg 3 Bi 2 anode delivers a high reversible specific capacity (360 mAh g -1 ) with excellent stability (90.7% capacity retention over 200 cycles) and high Coulombic efficiency (average 98%) at 0.1 A g -1 . The good performance is attributed to the stable nanostructures, which effectively accommodate the reversible Mg 2+ ion insertion/deinsertion without losing electric contact among clusters. Significantly, the nanoclustered Mg 3 Bi 2 anode can be coupled with high voltage cathode Prussian Blue to assemble a full cell using noncorrosive electrolyte, showing a stable cycling (88% capacity retention over 200 cycles at 0.2 A g -1 ) and good rate capability (103 mAh g -1 at 0.1 A g -1 and 58 mAh g -1 at 2 A g -1 ). The energy and power density of the as-fabricated full cell can reach up to 81 Wh kg -1 and 2850 W kg -1 , respectively, which are both the highest values among the reported Mg-ion batteries using noncorrosive electrolytes. This study demonstrates a cost-effective route to fabricate stable and high voltage rechargeable Mg-ion battery potentially for grid-scale energy storage.

Carbon-silicon core-shell nanowires as high capacity electrode for lithium ion batteries.

PubMed

Cui, Li-Feng; Yang, Yuan; Hsu, Ching-Mei; Cui, Yi

2009-09-01

We introduce a novel design of carbon-silicon core-shell nanowires for high power and long life lithium battery electrodes. Amorphous silicon was coated onto carbon nanofibers to form a core-shell structure and the resulted core-shell nanowires showed great performance as anode material. Since carbon has a much smaller capacity compared to silicon, the carbon core experiences less structural stress or damage during lithium cycling and can function as a mechanical support and an efficient electron conducting pathway. These nanowires have a high charge storage capacity of approximately 2000 mAh/g and good cycling life. They also have a high Coulmbic efficiency of 90% for the first cycle and 98-99.6% for the following cycles. A full cell composed of LiCoO(2) cathode and carbon-silicon core-shell nanowire anode is also demonstrated. Significantly, using these core-shell nanowires we have obtained high mass loading and an area capacity of approximately 4 mAh/cm(2), which is comparable to commercial battery values.

Enhanced capacity of chemically bonded phosphorus/carbon composite as an anode material for potassium-ion batteries

NASA Astrophysics Data System (ADS)

Wu, Xuan; Zhao, Wei; Wang, Hong; Qi, Xiujun; Xing, Zheng; Zhuang, Quanchao; Ju, Zhicheng

2018-02-01

Potassium-ion batteries are attracting great attention as a promising alternative to lithium-ion batteries due to the abundance and low price of potassium. Herein, the phosphorus/carbon composite, obtained by a simple ball-milling of 20 wt% commercial red phosphorus and 80 wt% graphite, is studied as a novel anode for potassium-ion batteries. Considering the high theoretical specific capacity of phosphorus and formation of stable phosphorus-carbon bond, which can alleviate the volume expansion efficiently, the phosphorus/carbon composite exhibits a high charge capacity of 323.5 mA h g-1 after 50 cycles at a current density of 50 mA g-1 with moderate rate capability and cycling stability. By the X-ray diffraction analysis, the alloying-dealloying mechanism of phosphorus is proposed to form a KP phase. Meanwhile, prepotassiation treatment is conducted to improve the low initial coulomb efficiency.

Mesoporous Ge/GeO2/Carbon Lithium-Ion Battery Anodes with High Capacity and High Reversibility.

PubMed

Hwang, Jongkook; Jo, Changshin; Kim, Min Gyu; Chun, Jinyoung; Lim, Eunho; Kim, Seongseop; Jeong, Sanha; Kim, Youngsik; Lee, Jinwoo

2015-05-26

We report mesoporous composite materials (m-GeO2, m-GeO2/C, and m-Ge-GeO2/C) with large pore size which are synthesized by a simple block copolymer directed self-assembly. m-Ge/GeO2/C shows greatly enhanced Coulombic efficiency, high reversible capacity (1631 mA h g(-1)), and stable cycle life compared with the other mesoporous and bulk GeO2 electrodes. m-Ge/GeO2/C exhibits one of the highest areal capacities (1.65 mA h cm(-2)) among previously reported Ge- and GeO2-based anodes. The superior electrochemical performance in m-Ge/GeO2/C arises from the highly improved kinetics of conversion reaction due to the synergistic effects of the mesoporous structures and the conductive carbon and metallic Ge.

ZnSe Microsphere/Multiwalled Carbon Nanotube Composites as High-Rate and Long-Life Anodes for Sodium-Ion Batteries.

PubMed

Tang, Chunjuan; Wei, Xiujuan; Cai, Xinyin; An, Qinyou; Hu, Ping; Sheng, Jinzhi; Zhu, Jiexin; Chou, Shulei; Wu, Liming; Mai, Liqiang

2018-06-13

Sodium-ion batteries (SIBs) are considered as one of the most favorable alternative devices for sustainable development of modern society. However, it is still a big challenge to search for proper anode materials which have excellent cycling and rate performance. Here, zinc selenide microsphere and multiwalled carbon nanotube (ZnSe/MWCNT) composites are prepared via hydrothermal reaction and following grinding process. The performance of ZnSe/MWCNT composites as a SIB anode is studied for the first time. As a result, ZnSe/MWCNTs exhibit excellent rate capacity and superior cycling life. The capacity retains as high as 382 mA h g -1 after 180 cycles even at a current density of 0.5 A g -1 . The initial Coulombic efficiency of ZnSe/MWCNTs can reach 88% and nearby 100% in the following cycles. The superior electrochemical properties are attributed to continuous electron transport pathway, improved electrical conductivity, and excellent stress relaxation.

Tire-derived carbon composite anodes for sodium-ion batteries

DOE PAGES

Li, Yunchao; Paranthaman, M. Parans; Akato, Kokouvi; ...

2016-04-04

We report that hard-carbon materials are considered as one of the most promising anodes for the emerging sodium-ion batteries. Here, we report a low-cost, scalable waste tire-derived carbon as an anode for sodium-ion batteries (SIBs). The tire-derived carbons obtained by pyrolyzing the acid-treated tire at 1100 °C, 1400 °C and 1600 °C show capacities of 179, 185 and 203 mAh g -1, respectively, after 100 cycles at a current density of 20 mA g -1 in sodium-ion batteries with good electrochemical stability. The portion of the low-voltage plateau region in the charge-discharge curves increases as the heat-treatment temperature increases. Themore » low-voltage plateau is beneficial to enhance the energy density of the full cell. However, this plateau suffers rapid capacity fade at higher current densities. This study provides a new pathway for inexpensive, environmentally benign and value-added waste tire-derived products towards large-scale energy storage applications.« less

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.

Cu-SnO2 nanostructures obtained via galvanic replacement control as high performance anodes for lithium-ion storage

NASA Astrophysics Data System (ADS)

Nguyen, Tuan Loi; Park, Duckshin; Hur, Jaehyun; Son, Hyung Bin; Park, Min Sang; Lee, Seung Geol; Kim, Ji Hyeon; Kim, Il Tae

2018-01-01

SnO2 has been considered as a promising anode material for lithium ion batteries (LIBs) because of its high theoretical capacity (782 mAh g-1). However, the reaction between lithium ions and Sn causes a large volume change, resulting in the pulverization of the anode, a loss of contact with the current collector, and a deterioration in electrochemical performance. Several strategies have been proposed to mitigate the drastic volume changes to extend the cyclic life of SnO2 materials. Herein, novel composites consisting of Cu and SnO2 were developed via the galvanic replacement reaction. The reaction was carried out at 180 °C for different durations and triethylene glycol was used as the medium solvent. The structure, morphology, and composition of the composites were analyzed by X-ray diffraction, transmission electron microscopy, and energy dispersive X-ray spectroscopy. The reaction time affected the particle size, which in turn affected the reaction kinetics. Furthermore, the novel nanostructures contained an inactive metal phase (Cu), which acted both as the buffer space against the volume change of Sn during the alloying reaction and as the electron conductor, resulting in a lower impedance of the composites. When evaluated as potential anodes for LIBs, the composite electrodes displayed extraordinary electrochemical performance with a high capacity and Coulombic efficiency, an excellent cycling stability, and a superior rate capability compared to a Sn electrode.

Efficient conversion of sand to nano-silicon and its energetic Si-C composite anode design for high volumetric capacity lithium-ion battery

NASA Astrophysics Data System (ADS)

Furquan, Mohammad; Raj Khatribail, Anish; Vijayalakshmi, Savithri; Mitra, Sagar

2018-04-01

Silicon is an attractive anode material for Li-ion cells, which can provide energy density 30% higher than any of the today's commercial Li-ion cells. In the current study, environmentally benign, high abundant, and low cost sand (SiO2) source has been used to prepare nano-silicon via scalable metallothermic reduction method using micro wave heating. In this research, we have developed and optimized a method to synthesis high purity nano silicon powder that takes only 5 min microwave heating of sand and magnesium mixture at 800 °C. Carbon coated nano-silicon electrode material is prepared by a unique method of coating, polymerization and finally in-situ carbonization of furfuryl alcohol on to the high purity nano-silicon. The electrochemical performance of a half cell using the carbon coated high purity Si is showed a stable capacity of 1500 mAh g-1 at 6 A g-1 for over 200 cycles. A full cell is fabricated using lithium cobalt oxide having thickness ≈56 μm as cathode and carbon coated silicon thin anode of thickness ≈9 μm. The fabricated full cell of compact size exhibits excellent volumetric capacity retention of 1649 mAh cm-3 at 0.5 C rate (C = 4200 mAh g-1) and extended cycle life (600 cycles). The full cell is demonstrated on an LED lantern and LED display board.

Size dependent polaronic conduction in hematite

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

Sharma, Monika; Banday, Azeem; Murugavel, Sevi

2016-05-23

Lithium Ion Batteries have been attracted as the major renewable energy source for all portable electronic devices because of its advantages like superior energy density, high theoretical capacity, high specific energy, stable cycling and less memory effects. Recently, α-Fe{sub 2}O{sub 3} has been considered as a potential anode material due to high specific capacity, low cost, high abundance and environmental benignity. We have synthesized α-Fe{sub 2}O{sub 3} with various sizes by using the ball milling and sol-gel procedure. Here, we report the dc conductivity measurement for the crystallite size ranging from 15 nm to 50 nm. It has been observedmore » that the enhancement in the polaronic conductivity nearly two orders in magnitude while reducing the crystallite size from bulk into nano scale level. The enhancement in the conductivity is due to the augmented to compressive strain developed in the material which leads to pronounced decrease in the hopping length of polarons. Thus, nanocrystaline α-Fe{sub 2}O{sub 3} may be a better alternative anode material for lithium ion batteries than earlier reported systems.« less

Potential Alternatives for Advanced Energy Material Processing in High Performance Li-ion Batteries (LIBs) via Atmospheric Pressure Plasma Treatment

NASA Astrophysics Data System (ADS)

Duh, Jenq-Gong; Chuang, Shang-I.; Lan, Chun-Kai; Yang, Hao; Chen, Hsien-Wei

2015-09-01

A new processing technique by atmospheric pressure plasma (APP) jet treatment of LIBs was introduced. Ar/N2 plasma enhanced the high-rate anode performance of Li4Ti5O12. Oxygen vacancies were discovered and nitrogen doping were achieved by the surface reaction between pristine Li4Ti5O12 and plasma reactive species (N* and N2+). Electrochemical impedance spectra confirm that plasma modification increases Li ions diffusivity and reduces internal charge-transfer resistance, leading to a superior capacity (132 mAh/g) and excellent stability with negligible capacity decay over 100 cycles under 10C rate. Besides 2D material surface treatment, a specially designed APP generator that are feasible to modify 3D TiO2 powders is proposed. The rate capacity of 20 min plasma treated TiO2 exhibited 20% increment. Plasma diagnosis revealed that excited Ar and N2 was contributed to TiO2 surface reduction as companied by formation of oxygen vacancy. A higher amount of oxygen vacancy increased the chance for excited nitrogen doped onto surface of TiO2 particle. These findings promote the understanding of APP on processing anode materials in high performance LIBs.

Synthesis of Mesoporous Co2+-Doped TiO2 Nanodisks Derived from Metal Organic Frameworks with Improved Sodium Storage Performance.

PubMed

Hong, Zhensheng; Kang, Meiling; Chen, Xiaohui; Zhou, Kaiqiang; Huang, Zhigao; Wei, Mingdeng

2017-09-20

TiO 2 is a most promising anode candidate for rechargeable Na-ion batteries (NIBs) because of its appropriate working voltage, low cost, and superior structural stability during chage/discharge process. Nevertheless, it suffers from intrinsically low electrical conductivity. Herein, we report an in situ synthesis of Co 2+ -doped TiO 2 through the thermal treatment of metal organic frameworks precursors of MIL-125(Ti)-Co as a superior anode material for NIBs. The Co 2+ -doped TiO 2 possesses uniform nanodisk morphology, a large surface area and mesoporous structure with narrow pore distribution. The reversible capacity, Coulombic efficiency (CE) and rate capability can be improved by Co 2+ doping in mesoporous TiO 2 anode. Co 2+ -doped mesoporous TiO 2 nanodisks exhibited a high reversible capacity of 232 mAhg -1 at 0.1 Ag 1- , good rate capability and cycling stability with a stable capacity of about 140 mAhg -1 at 0.5 Ag 1- after 500 cycles. The enhanced Na-ion storage performance could be due to the increased electrical conductivity revealed by Kelvin probe force microscopy measurements.

Binder-free 2D titanium carbide (MXene)/carbon nanotube composites for high-performance lithium-ion capacitors.

PubMed

Yu, Peng; Cao, Gejin; Yi, Sha; Zhang, Xiong; Li, Chen; Sun, Xianzhong; Wang, Kai; Ma, Yanwei

2018-03-29

Two-dimensional (2D) MXenes have a very good application prospect in the field of electrochemical energy storage due to their metallic conductivity, high volumetric capacity, mechanical and thermal stability. Herein, we report the preparation of titanium carbide (Ti3C2Tx)/carbon nanotube (CNT) flexible self-supporting composite films by vacuum filtration. The CNTs can effectively prevent Ti3C2Tx from stacking and improve the electrochemical performance. The as-fabricated Ti3C2Tx/CNT film shows a high reversible capacity of 489 mA h g-1 at a current density of 50 mA g-1 together with good cycling performance. The full-cell lithium-ion capacitor (LIC) is assembled using the Ti3C2Tx/CNT film as the anode and activated carbon as the cathode. The LIC exhibits a high energy density of 67 Wh kg-1 (based on the total weight of the anode and the cathode), and a good capacity retention of 81.3% after 5000 cycles. These results suggest that Ti3C2Tx-CNT films are promising as anode materials for lithium ion capacitors.

Nontraditional, Safe, High Voltage Rechargeable Cells of Long Cycle Life.

PubMed

Braga, Maria Helena; M Subramaniyam, Chandrasekar; Murchison, Andrew J; Goodenough, John B

2018-05-23

A room-temperature all-solid-state rechargeable battery cell containing a tandem electrolyte consisting of a Li + -glass electrolyte in contact with a lithium anode and a plasticizer in contact with a conventional, low cost oxide host cathode was charged to 5 V versus lithium with a charge/discharge cycle life of over 23,000 cycles at a rate of 153 mA·g -1 of active material. A larger positive electrode cell with 329 cycles had a capacity of 585 mAh·g -1 at a cutoff of 2.5 V and a current of 23 mA·g -1 of the active material; the capacity rose with cycle number over the 329 cycles tested during 13 consecutive months. Another cell had a discharge voltage from 4.5 to 3.7 V over 316 cycles at a rate of 46 mA·g -1 of active material. Both the Li + -glass electrolyte and the plasticizer contain electric dipoles that respond to the internal electric fields generated during charge by a redistribution of mobile cations in the glass and by extraction of Li + from the active cathode host particles. The electric dipoles remain oriented during discharge to retain an internal electric field after a discharge. The plasticizer accommodates to the volume changes in the active cathode particles during charge/discharge cycling and retains during charge the Li + extracted from the cathode particles at the plasticizer/cathode-particle interface; return of these Li + to the active cathode particles during discharge only involves a displacement back across the plasticizer/cathode interface and transport within the cathode particle. A slow motion at room temperature of the electric dipoles in the Li + -glass electrolyte increases with time the electric field across the EDLC of the anode/Li + -glass interface to where Li + from the glass electrolyte is plated on the anode without being replenished from the cathode, which charges the Li + -glass electrolyte negative and consequently the glass side of the Li + -glass/plasticizer EDLC. Stripping back the Li + to the Li + -glass during discharge is enhanced by the negative charge in the Li + -glass. Since the Li + -glass is not reduced on contact with metallic lithium, no passivating interface layer contributes to a capacity fade; instead, the discharge capacity increases with cycle number as a result of dipole polarization in the Li + -glass electrolyte leading to a capacity increase of the Li + -glass/plasticizer EDLC. The storage of electric power by both faradaic electrochemical extraction/insertion of Li + in the cathode and electrostatic stored energy in the EDLCs provides a safe and fast charge and discharge with a long cycle life and a greater capacity than can be provided by the cathode host extraction/insertion reaction. The cell can be charged to a high voltage versus a lithium anode because of the added charge of the EDLCs.

Core-Shell Coating Silicon Anode Interfaces with Coordination Complex for Stable Lithium-Ion Batteries.

PubMed

Zhou, Jinqiu; Qian, Tao; Wang, Mengfan; Xu, Na; Zhang, Qi; Li, Qun; Yan, Chenglin

2016-03-02

In situ core-shell coating was used to improve the electrochemical performance of Si-based anodes with polypyrrole-Fe coordination complex. The vast functional groups in the organometallic coordination complex easily formed hydrogen bonds when in situ modifying commercial Si nanoparticles. The incorporation of polypyrrole-Fe resulted in the conformal conductive coating surrounding each Si nanoparticle, not only providing good electrical connection to the particles but also promoting the formation of a stable solid-electrolyte-interface layer on the Si electrode surface, enhancing the cycling properties. As an anode material for Li-ion batteries, modified silicon powders exhibited high reversible capacity (3567 mAh/g at 0.3 A/g), good rate property (549.12 mAh/g at 12 A/g), and excellent cycling performance (reversible capacity of 1500 mAh/g after 800 cycles at 1.2 A/g). The constructed novel concept of core-shell coating Si particles presented a promising route for facile and large-scale production of Si-based anodes for extremely durable Li-ion batteries, which provided a wide range of applications in the field of energy storage of the renewable energy derived from the solar energy, hydropower, tidal energy, and geothermal heat.

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.

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.

Designed hybrid nanostructure with catalytic effect: beyond the theoretical capacity of SnO2 anode material for lithium ion batteries

PubMed Central

Wang, Ye; Huang, Zhi Xiang; Shi, Yumeng; Wong, Jen It; Ding, Meng; Yang, Hui Ying

2015-01-01

Transition metal cobalt (Co) nanoparticle was designed as catalyst to promote the conversion reaction of Sn to SnO2 during the delithiation process which is deemed as an irreversible reaction. The designed nanocomposite, named as SnO2/Co3O4/reduced-graphene-oxide (rGO), was synthesized by a simple two-step method composed of hydrothermal (1st step) and solvothermal (2nd step) synthesis processes. Compared to the pristine SnO2/rGO and SnO2/Co3O4 electrodes, SnO2/Co3O4/rGO nanocomposites exhibit significantly enhanced electrochemical performance as the anode material of lithium-ion batteries (LIBs). The SnO2/Co3O4/rGO nanocomposites can deliver high specific capacities of 1038 and 712 mAh g−1 at the current densities of 100 and 1000 mA g−1, respectively. In addition, the SnO2/Co3O4/rGO nanocomposites also exhibit 641 mAh g−1 at a high current density of 1000 mA g−1 after 900 cycles, indicating an ultra-long cycling stability under high current density. Through ex-situ TEM analysis, the excellent electrochemical performance was attributed to the catalytic effect of Co nanoparticles to promote the conversion of Sn to SnO2 and the decomposition of Li2O during the delithiation process. Based on the results, herein we propose a new method in employing the catalyst to increase the capacity of alloying-dealloying type anode material to beyond its theoretical value and enhance the electrochemical performance. PMID:25776280

Nb{sub 2}O{sub 5} hollow nanospheres as anode material for enhanced performance in lithium ion batteries

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

Sasidharan, Manickam; Gunawardhana, Nanda; Yoshio, Masaki, E-mail: yoshio@cc.saga-u.ac.jp

2012-09-15

Graphical abstract: Nb{sub 2}O{sub 5} hollow nanosphere constructed electrode delivers high capacity of 172 mAh g{sup −1} after 250 cycles and maintains structural integrity and excellent cycling stability. Highlights: ► Nb{sub 2}O{sub 5} hollow nanospheres synthesis was synthesized by soft-template. ► Nb{sub 2}O{sub 5} hollow nanospheres were investigated as anode material in Li-ion battery. ► Nanostructured electrode delivers high capacity of 172 mAh g{sup −1} after 250 cycles. ► The electrode maintains the structural integrity and excellent cycling stability. ► Nanosized shell domain facilitates fast lithium intercalation/deintercalation. -- Abstract: Nb{sub 2}O{sub 5} hollow nanospheres of average diameter ca. ∼29 nmmore » and hollow cavity size ca. 17 nm were synthesized using polymeric micelles with core–shell–corona architecture under mild conditions. The hollow particles were thoroughly characterized by transmission electron microscope (TEM), X-ray diffraction (XRD), infrared spectroscopy (FTIR), thermal (TG/DTA) and nitrogen adsorption analyses. Thus obtained Nb{sub 2}O{sub 5} hollow nanospheres were investigated as anode materials for lithium ion rechargeable batteries for the first time. The nanostructured electrode delivers high capacity of 172 mAh g{sup −1} after 250 cycles of charge/discharge at a rate of 0.5 C. More importantly, the hollow particles based electrodes maintains the structural integrity and excellent cycling stability even after exposing to high current density 6.25 A g{sup −1}. The enhanced electrochemical behavior is ascribed to hollow cavity coupled with nanosized Nb{sub 2}O{sub 5} shell domain that facilitates fast lithium intercalation/deintercalation kinetics.« less

A Novel Graphene-Polysulfide Anode Material for High-Performance Lithium-Ion Batteries

PubMed Central

Ai, Wei; Xie, Linghai; Du, Zhuzhu; Zeng, Zhiyuan; Liu, Juqing; Zhang, Hua; Huang, Yunhui; Huang, Wei; Yu, Ting

2013-01-01

We report a simple and efficient approach for fabrication of novel graphene-polysulfide (GPS) anode materials, which consists of conducting graphene network and homogeneously distributed polysulfide in between and chemically bonded with graphene sheets. Such unique architecture not only possesses fast electron transport channels, shortens the Li-ion diffusion length but also provides very efficient Li-ion reservoirs. As a consequence, the GPS materials exhibit an ultrahigh reversible capacity, excellent rate capability and superior long-term cycling performance in terms of 1600, 550, 380 mAh g−1 after 500, 1300, 1900 cycles with a rate of 1, 5 and 10 A g−1 respectively. This novel and simple strategy is believed to work broadly for other carbon-based materials. Additionally, the competitive cost and low environment impact may promise such materials and technique a promising future for the development of high-performance energy storage devices for diverse applications. PMID:23903017

Effect of Carbon Coating on Li4TiO12 of Anode Material for Hybrid Capacitor.

PubMed

Lee, Jong-Kyu; Lee, Byung-Gwan; Yoon, Jung-Rag

2015-11-01

The carbon-coated Li4Ti5O12 of anode material for hybrid capacitor was prepared by controlling carbonization time at 700 degrees C in nitrogen. With increasing of carbonization time, the discharge capacity and capacitance were decreased, while the equivalent series resistance was not changed remarkably. The rate capability and cycle performance of carbon-coated Li4Ti5O12 were larger than that of Li4Ti5O12. Carbon coating improved conductivity as well as Li-ion diffusion, and thus also resulted in good rate capabilities and cycle stability. The effects of carbon coating on the gas generation of hybrid capacitor were also discussed.

High Energy Density Li-ion Cells for EV’s Based on Novel, High Voltage Cathode Material Systems

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

Kepler, Keith D.; Slater, Michael

This Li-ion cell technology development project had three objectives: to develop advanced electrode materials and cell components to enable stable high-voltage operation; to design and demonstrate a Li-ion cell using these materials that meets the PHEV40 performance targets; and to design and demonstrate a Li-ion cell using these materials that meets the EV performance targets. The major challenge to creating stable high energy cells with long cycle life is system integration. Although materials that can give high energy cells are known, stabilizing them towards long-term cycling in the presence of other novel cell components is a major challenge. The majormore » technical barriers addressed by this work include low cathode specific energy, poor electrolyte stability during high voltage operation, and insufficient capacity retention during deep discharge for Si-containing anodes. Through the course of this project, Farasis was able to improve capacity retention of NCM materials for 4.4+ V operation, through both surface treatment and bulk-doping approaches. Other material advances include increased rate capability and of HE-NCM materials through novel synthesis approach, doubling the relative capacity at 1C over materials synthesized using standard methods. Silicon active materials proved challenging throughout the project and ultimately were the limiting factor in the energy density vs. cycle life trade off. By avoiding silicon anodes for the lower energy PHEV design, we manufactured cells with intermediate energy density and long cycle life under high voltage operation for PHEV applications. Cells with high energy density for EV applications were manufactured targeting a 300 Wh/kg design and were able to achieve > 200 cycles.« less

Universal quinone electrodes for long cycle life aqueous rechargeable batteries

NASA Astrophysics Data System (ADS)

Liang, Yanliang; Jing, Yan; Gheytani, Saman; Lee, Kuan-Yi; Liu, Ping; Facchetti, Antonio; Yao, Yan

2017-08-01

Aqueous rechargeable batteries provide the safety, robustness, affordability, and environmental friendliness necessary for grid storage and electric vehicle operations, but their adoption is plagued by poor cycle life due to the structural and chemical instability of the anode materials. Here we report quinones as stable anode materials by exploiting their structurally stable ion-coordination charge storage mechanism and chemical inertness towards aqueous electrolytes. Upon rational selection/design of quinone structures, we demonstrate three systems that coupled with industrially established cathodes and electrolytes exhibit long cycle life (up to 3,000 cycles/3,500 h), fast kinetics (>=20C), high anode specific capacity (up to 200-395 mAh g-1), and several examples of state-of-the-art specific energy/energy density (up to 76-92 Wh kg-1/ 161-208 Wh l-1) for several operational pH values (-1 to 15), charge carrier species (H+, Li+, Na+, K+, Mg2+), temperature (-35 to 25 °C), and atmosphere (with/without O2), making them a universal anode approach for any aqueous battery technology.

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.

Solid state cathode materials for secondary magnesium-ion batteries that are compatible with magnesium metal anodes in water-free electrolyte

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

Crowe, Adam J.; Bartlett, Bart M., E-mail: bartmb@umich.edu

2016-10-15

With high elemental abundance, large volumetric capacity, and dendrite-free metal deposition, magnesium metal anodes offer promise in beyond-lithium-ion batteries. However, the increased charge density associated with the divalent magnesium-ion (Mg{sup 2+}), relative to lithium-ion (Li{sup +}) hinders the ion-insertion and extraction processes within many materials and structures known for lithium-ion cathodes. As a result, many recent investigations incorporate known amounts of water within the electrolyte to provide temporary solvation of the Mg{sup 2+}, improving diffusion kinetics. Unfortunately with the addition of water, compatibility with magnesium metal anodes disappears due to forming an ion-insulating passivating layer. In this short review, recentmore » advances in solid state cathode materials for rechargeable magnesium-ion batteries are highlighted, with a focus on cathode materials that do not require water contaminated electrolyte solutions for ion insertion and extraction processes. - Graphical abstract: In this short review, we present candidate materials for reversible Mg-battery cathodes that are compatible with magnesium metal in water-free electrolytes. The data suggest that soft, polarizable anions are required for reversible cycling.« less

Cobalt-based metal organic framework with superior lithium anodic performance

NASA Astrophysics Data System (ADS)

Hu, Xiaoshi; Hu, Huiping; Li, Chao; Li, Tian; Lou, Xiaobing; Chen, Qun; Hu, Bingwen

2016-10-01

The reversible charging of a Co-1,4-benzenedicarboxylate MOF (Co-BDC MOF) prepared via an one-pot solvothermal method was studied for use as the anode in a Li-ion cell. It was found that this MOF anode provides high reversible capacities (1090 and 611 mA h g-1 at current densities of 0.2 and 1 A g-1, respectively), and an impressive rate performance. Such an outstanding Li-ion storage property has not been reported previously for the LIB anodes within the MOFs category. Ex-situ X-ray photoelectron spectroscopy (XPS) and infrared spectroscopy (IR) studies of this material at different state of charge suggest that cobalt stays at Co2+ state during discharge/charge process, so that in this case Li+ may be inserted into the organic moiety without the direct participation of cobalt ions.

Template-Free Synthesis of Sb2S3 Hollow Microspheres as Anode Materials for Lithium-Ion and Sodium-Ion Batteries

NASA Astrophysics Data System (ADS)

Xie, Jianjun; Liu, Li; Xia, Jing; Zhang, Yue; Li, Min; Ouyang, Yan; Nie, Su; Wang, Xianyou

2018-03-01

Hierarchical Sb2S3 hollow microspheres assembled by nanowires have been successfully synthesized by a simple and practical hydrothermal reaction. The possible formation process of this architecture was investigated by X-ray diffraction, focused-ion beam-scanning electron microscopy dual-beam system, and transmission electron microscopy. When used as the anode material for lithium-ion batteries, Sb2S3 hollow microspheres manifest excellent rate property and enhanced lithium-storage capability and can deliver a discharge capacity of 674 mAh g-1 at a current density of 200 mA g-1 after 50 cycles. Even at a high current density of 5000 mA g-1, a discharge capacity of 541 mAh g-1 is achieved. Sb2S3 hollow microspheres also display a prominent sodium-storage capacity and maintain a reversible discharge capacity of 384 mAh g-1 at a current density of 200 mA g-1 after 50 cycles. The remarkable lithium/sodium-storage property may be attributed to the synergetic effect of its nanometer size and three-dimensional hierarchical architecture, and the outstanding stability property is attributed to the sufficient interior void space, which can buffer the volume expansion. [Figure not available: see fulltext.

Scallop-Inspired Shell Engineering of Microparticles for Stable and High Volumetric Capacity Battery Anodes.

PubMed

Zhang, Xinghao; Guo, Ruiying; Li, Xianglong; Zhi, Linjie

2018-06-01

Building stable and efficient electron and ion transport pathways are critically important for energy storage electrode materials and systems. Herein, a scallop-inspired shell engineering strategy is proposed and demonstrated to confine high volume change silicon microparticles toward the construction of stable and high volumetric capacity binder-free lithium battery anodes. As for each silicon microparticle, the methodology involves an inner sealed but adaptable overlapped graphene shell, and an outer open hollow shell consisting of interconnected reduced graphene oxide, mimicking the scallop structure. The inner closed shell enables simultaneous stabilization of the interfaces of silicon with both carbon and electrolyte, substantially facilitates efficient and rapid transport of both electrons and lithium ions from/to silicon, the outer open hollow shell creates stable and robust transport paths of both electrons and lithium ions throughout the electrode without any sophisticated additives. The resultant self-supported electrode has achieved stable cycling with rapidly increased coulombic efficiency in the early stage, superior rate capability, and remarkably high volumetric capacity upon a facile pressing process. The rational design and engineering of graphene shells of the silicon microparticles developed can provide guidance for the development of a wide range of other high capacity but large volume change electrochemically active materials. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Graphene oxide hydrogel as a restricted-area nanoreactor for synthesis of 3D graphene-supported ultrafine TiO2 nanorod nanocomposites for high-rate lithium-ion battery anodes

NASA Astrophysics Data System (ADS)

Cheng, Jianli; Gu, Guifang; Ni, Wei; Guan, Qun; Li, Yinchuan; Wang, Bin

2017-07-01

Three-dimensional graphene-supported TiO2 nanorod nanocomposites (3D GS-TNR) are prepared using graphene oxide hydrogel as a restricted-area nanoreactor in the hydrothermal process, in which well-distributed TiO2 nanorods with a width of approximately 5 nm and length of 30 nm are conformally embedded in the 3D interconnected graphene network. The 3D graphene oxide not only works as a restricted-area nanoreactor to constrain the size, distribution and morphology of the TiO2; it also work as a highly interconnected conducting network to facilitate electrochemical reactions and maintain good structural integration when the nanocomposites are used as anode materials in lithium-ion batteries. Benefiting from the nanostructure, the 3D GS-TNR nanocomposites show high capacity and excellent long-term cycling capability at high current rates. The 3D GS-TNR composites deliver a high initial charge capacity of 280 mAh g-1 at 0.2 C and maintain a reversible capacity of 115 mAh g-1, with a capacity retention of 83% at 20 C after 1000 cycles. Meanwhile, compared with that of previously reported TiO2-based materials, the 3D GS-TNR nanocomposites show much better performance, including higher capacity, better rate capability and long-term cycling stability.

Chemically Etched Silicon Nanowires as Anodes for Lithium-Ion Batteries

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

West, Hannah Elise

2015-08-01

This study focused on silicon as a high capacity replacement anode for Lithium-ion batteries. The challenge of silicon is that it expands ~270% upon lithium insertion which causes particles of silicon to fracture, causing the capacity to fade rapidly. To account for this expansion chemically etched silicon nanowires from the University of Maine were studied as anodes. They were built into electrochemical half-cells and cycled continuously to measure the capacity and capacity fade.

Surface Modification of Silicon Nanoparticles by an "Ink" Layer for Advanced Lithium Ion Batteries.

PubMed

Wu, Fang; Wang, Hao; Shi, Jiayuan; Yan, Zongkai; Song, Shipai; Peng, Bangheng; Zhang, Xiaokun; Xiang, Yong

2018-06-13

Owing to its high specific capacity, silicon is considered as a promising anode material for lithium ion batteries (LIBs). However, the synthesis strategies for previous silicon-based anode materials with a delicate hierarchical structure are complicated or hazardous. Here, Prussian blue analogues (PBAs), widely used in ink, are deposited on the silicon nanoparticle surface (PBAs@Si-450) to modify silicon nanoparticles with transition metal atoms and a N-doped carbon layer. A facile and green synthesis procedure of PBAs@Si-450 nanocomposites was carried out in a coprecipitation process, combined with a thermal treatment process at 450 °C. As-prepared PBAs@Si-450 delivers a reversible charge capacity of 725.02 mAh g -1 at 0.42 A g -1 after 200 cycles. Moreover, this PBAs@Si-450 composite exhibits an exceptional rate performance of ∼1203 and 263 mAh g -1 at current densities of 0.42 and 14 A g -1 , respectively, and fully recovered to 1136 mAh g -1 with the current density returning to 0.42 A g -1 . Such a novel architecture of PBAs@Si-450 via a facile fabrication process represents a promising candidate with a high-performance silicon-based anode for LIBs.

Electrochemical Investigation of Natural Ore Molybdenite (MoS2) as a First-Hand Anode for Lithium Storages.

PubMed

Li, Sijie; Tang, Honghu; Ge, Peng; Jiang, Feng; Zhou, Jiahui; Zhang, Chenyang; Hou, Hongshuai; Sun, Wei; Ji, Xiaobo

2018-02-21

Considering serious pollution from the traditional chemical synthesis process, the resource-rich, clean, and first-hand electrode materials are greatly desired. Natural ore molybdenite (MoS 2 ), as the low-cost, high-yield, and environmental-friendly natural source, is investigated as a first-hand anode material for lithium-ion batteries (LIBs). Compared with chemosynthetic pure MoS 2 , natural molybdenite provides an ordered ion diffusion channel more effectively owing to its excellent characteristics, containing well-crystalline, large lattice distance, and trance dopants. Even at a large current density of 2.0 A g -1 , a natural molybdenite electrode employing a carboxymethyl cellulose binder displays an initial charge capacity of 1199 mA h g -1 with a capacity retention of 72% after 1000 cycles, much higher than those of the electrodes utilizing a poly(vinylidene fluoride) binder. These types of binders play a crucial role in stabilizing a microstructure demonstrated by ex situ scanning electron microscopy and in affecting pseudocapacitive contributions quantitatively determined by a series of kinetic exploration. Briefly, this work might open up a new avenue toward the use of natural molybdenite as a first-hand LIB anode in scalable applications and deepen our understanding on the fundamental effect of binders in the metal-sulfide.

Investigation on porous MnO microsphere anode for lithium ion batteries

NASA Astrophysics Data System (ADS)

Zhong, Kaifu; Zhang, Bin; Luo, Shihai; Wen, Wen; Li, Hong; Huang, Xuejie; Chen, Liquan

MnO microspheres with and without carbon coating are prepared as anode materials for lithium ion batteries. The MnO microsphere material shows a reversible capacity of 800 mAh g -1 and an initial efficiency of 71%. It can deliver 600 mAh g -1 at a rate of 400 mA g -1. Results of Mn K-edge X-ray absorption near-edge structure (XANES) spectra and extended X-ray absorption fine structure (EXAFS) confirm further the conversion reaction mechanism, indicate that pristine MnO is reduced to Mn 0 after discharging to 0 V and part of reduced Mn 0 is not oxidized to Mn 2+ after charging to 3 V. This explains the origin of the initial irreversible capacity loss partially. The quasi open circuit voltage and the relationship between the current density and the overpotential are investigated. Both indicate that there is a significant voltage difference between the charging and discharging profiles even when the current density decreases to zero.

Silicon oxycarbide glass-graphene composite paper electrode for long-cycle lithium-ion batteries.

PubMed

David, Lamuel; Bhandavat, Romil; Barrera, Uriel; Singh, Gurpreet

2016-03-30

Silicon and graphene are promising anode materials for lithium-ion batteries because of their high theoretical capacity; however, low volumetric energy density, poor efficiency and instability in high loading electrodes limit their practical application. Here we report a large area (approximately 15 cm × 2.5 cm) self-standing anode material consisting of molecular precursor-derived silicon oxycarbide glass particles embedded in a chemically-modified reduced graphene oxide matrix. The porous reduced graphene oxide matrix serves as an effective electron conductor and current collector with a stable mechanical structure, and the amorphous silicon oxycarbide particles cycle lithium-ions with high Coulombic efficiency. The paper electrode (mass loading of 2 mg cm(-2)) delivers a charge capacity of ∼588 mAh g(-1)electrode (∼393 mAh cm(-3)electrode) at 1,020th cycle and shows no evidence of mechanical failure. Elimination of inactive ingredients such as metal current collector and polymeric binder reduces the total electrode weight and may provide the means to produce efficient lightweight batteries.

Reversible Redox Chemistry of Azo Compounds for Sodium-Ion Batteries

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

Luo, Chao; Xu, Gui-Liang; Ji, Xiao

Sustainable sodium-ion batteries (SSIBs) using renewable organic electrodes are promising alternatives to lithium-ion batteries for the large-scale renewable energy storage. However, the lack of high-performance anode material impedes the development of SSIBs. Herein, we report a new type of organic anode material based on azo group for SSIBs. Azobenzene-4,4'-dicarboxylic acid sodium salt is used as a model to investigate the electrochemical behaviors and reaction mechanism of azo compound. It exhibits a reversible capacity of 170 mAhg -1 at 0.2C. When current density is increased to 20C, the reversible capacities of 98 mAhg -1 can be retained for 2000 cycles, demonstratingmore » excellent cycling stability and high rate capability. The detailed characterizations reveal that azo group acts as an electrochemical active site to reversibly bond with Na +. The reversible redox chemistry between azo compound and Na ions offer opportunities for developing longcycle-life and high-rate SSIBs.« less

Reversible Redox Chemistry of Azo Compounds for Sodium-Ion Batteries

DOE PAGES

Luo, Chao; Xu, Gui-Liang; Ji, Xiao; ...

2018-01-29

Sustainable sodium-ion batteries (SSIBs) using renewable organic electrodes are promising alternatives to lithium-ion batteries for the large-scale renewable energy storage. However, the lack of high-performance anode material impedes the development of SSIBs. Herein, we report a new type of organic anode material based on azo group for SSIBs. Azobenzene-4,4'-dicarboxylic acid sodium salt is used as a model to investigate the electrochemical behaviors and reaction mechanism of azo compound. It exhibits a reversible capacity of 170 mAhg -1 at 0.2C. When current density is increased to 20C, the reversible capacities of 98 mAhg -1 can be retained for 2000 cycles, demonstratingmore » excellent cycling stability and high rate capability. The detailed characterizations reveal that azo group acts as an electrochemical active site to reversibly bond with Na +. The reversible redox chemistry between azo compound and Na ions offer opportunities for developing longcycle-life and high-rate SSIBs.« less

Solution-grown silicon nanowires for lithium-ion battery anodes.

PubMed

Chan, Candace K; Patel, Reken N; O'Connell, Michael J; Korgel, Brian A; Cui, Yi

2010-03-23

Composite electrodes composed of silicon nanowires synthesized using the supercritical fluid-liquid-solid (SFLS) method mixed with amorphous carbon or carbon nanotubes were evaluated as Li-ion battery anodes. Carbon coating of the silicon nanowires using the pyrolysis of sugar was found to be crucial for making good electronic contact to the material. Using multiwalled carbon nanotubes as the conducting additive was found to be more effective for obtaining good cycling behavior than using amorphous carbon. Reversible capacities of 1500 mAh/g were observed for 30 cycles.

Nitrogen-Doped Holey Graphene as an Anode for Lithium-Ion Batteries with High Volumetric Energy Density and Long Cycle Life.

PubMed

Xu, Jiantie; Lin, Yi; Connell, John W; Dai, Liming

2015-12-01

Nitrogen-doped holey graphene (N-hG) as an anode material for lithium-ion batteries has delivered a maximum volumetric capacity of 384 mAh cm(-3) with an excellent long-term cycling life up to 6000 cycles, and as an electrochemical capacitor has delivered a maximum volumetric energy density of 171.2 Wh L(-1) and a volumetric capacitance of 201.6 F cm(-3) . © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nb-doped rutile TiO₂: a potential anode material for Na-ion battery.

PubMed

Usui, Hiroyuki; Yoshioka, Sho; Wasada, Kuniaki; Shimizu, Masahiro; Sakaguchi, Hiroki

2015-04-01

The electrochemical properties of the rutile-type TiO2 and Nb-doped TiO2 were investigated for the first time as Na-ion battery anodes. Ti(1-x)Nb(x)O2 thick-film electrodes without a binder and a conductive additive were prepared using a sol-gel method followed by a gas-deposition method. The TiO2 electrode showed reversible reactions of Na insertion/extraction accompanied by expansion/contraction of the TiO2 lattice. Among the Ti(1-x)Nb(x)O2 electrodes with x = 0-0.18, the Ti(0.94)Nb(0.06)O2 electrode exhibited the best cycling performance, with a reversible capacity of 160 mA h g(-1) at the 50th cycle. As the Li-ion battery anode, this electrode also attained an excellent rate capability, with a capacity of 120 mA h g(-1) even at the high current density of 16.75 A g(-1) (50C). The improvements in the performances are attributed to a 3 orders of magnitude higher electronic conductivity of Ti(0.94)Nb(0.06)O2 compared to that of TiO2. This offers the possibility of Nb-doped rutile TiO2 as a Na-ion battery anode as well as a Li-ion battery anode.

Controllable Electrochemical Synthesis of Copper Sulfides as Sodium-Ion Battery Anodes with Superior Rate Capability and Ultralong Cycle Life.

PubMed

Li, Haomiao; Wang, Kangli; Cheng, Shijie; Jiang, Kai

2018-03-07

Sodium-ion batteries (SIBs) are prospective alternative to lithium-ion batteries for large-scale energy-storage applications, owing to the abundant resources of sodium. Metal sulfides are deemed to be promising anode materials for SIBs due to their low-cost and eco-friendliness. Herein, for the first time, series of copper sulfides (Cu 2 S, Cu 7 S 4 , and Cu 7 KS 4 ) are controllably synthesized via a facile electrochemical route in KCl-NaCl-Na 2 S molten salts. The as-prepared Cu 2 S with micron-sized flakes structure is first investigated as anode of SIBs, which delivers a capacity of 430 mAh g -1 with a high initial Coulombic efficiency of 84.9% at a current density of 100 mA g -1 . Moreover, the Cu 2 S anode demonstrates superior capability (337 mAh g -1 at 20 A g -1 , corresponding to 50 C) and ultralong cycle performance (88.2% of capacity retention after 5000 cycles at 5 A g -1 , corresponding to 0.0024% of fade rate per cycle). Meanwhile, the pseudocapacitance contribution and robust porous structure in situ formed during cycling endow the Cu 2 S anodes with outstanding rate capability and enhanced cyclic performance, which are revealed by kinetics analysis and ex situ characterization.

Silicon based nano-architectures for high power lithium-ion battery anodes

NASA Astrophysics Data System (ADS)

Krishnan, Rahul

Lithium-ion batteries have now become an inseparable part of modern day society as the power source for several portable electronics like cell phones, digital cameras and laptops. Their high energy density compared with other electrochemical battery systems has been their most attractive feature. This has lead to a great interest in developing lithium-ion batteries for hybrid and all-electric vehicles. Eventually such vehicles will help drastically reduce the carbon footprint making the environment cleaner and healthier. In spite of their high energy density, Li-ion batteries are known to have poor power densities. This forms a major limitation in their deployment as a power source on vehicles. Electric vehicles need power sources that can provide both high energy and power densities. This requires the development of anode, cathode and electrolyte materials that would transform the capabilities of existing Li-ion batteries. Among anode materials silicon has received great attention because of its very large theoretical capacity of ˜4200 mAh/g based on the alloy Li22Si5. It should be noted that storage of charge in the anode occurs through the alloying of Li with the host anode material. However, the large specific capacity of silicon also results in a ˜400% volume expansion which could lead to pulverization and delamination reducing the cycle life of the electrode. These failure processes are exacerbated at high rates making it extremely difficult to use silicon for high-power Li-ion battery anodes. The major research thrust supporting this Ph.D. thesis involved exploring silicon based nano-architectures that would provide high energy and power densities over a long cycle life. The key technique used to design different nano-architectures was DC Magnetron sputtering with oblique angle deposition. The main development of this research was a functionally strain graded Carbon-Aluminum-Silicon nanoscoop architecture for high-power Li-ion battery anodes. This consisted of Carbon nanorods with an intermediate Aluminum layer finally capped by a nanoscoop of Silicon. The strain gradation arises from the fact that each of these materials has differential volumetric expansions due to different extents of Li uptake. Such a strain gradation from Carbon towards Silicon would provide for a less abrupt transition across the material interfaces thereby reducing interfacial mismatch and improving the tolerance to delamination at very high rates. This nano-architecture provided average capacities of ˜412 mAh/g with a power output of ˜100 kW/kg electrode continuously over 100 cycles. Even when the power output was as high as ˜250 kW/kgelectrode, the average capacity over 100 cycles is still ˜90 mAh/g. Furthermore, scanning electron microscopy and X-ray photoelectron spectroscopy investigations revealed that the functionally strain graded nanostructures were being partially lithiated in the bulk even at high rates. The fact that charge storage was not merely a surface phenomenon supported the high energy densities obtained at high charge/discharge rates. In an attempt to improve the mass loading density of Silicon based nano-architectures, a nano-compliant layer (NCL) supported thin film architecture was also explored. This consisted of an array of oblique nanorods (the nano-compliant layer) sandwiched between the substrate and the thin film. The NCL layer was used to improve the stress tolerance of the thin film thereby allowing the use of bulk thin films as opposed to nanostructures. This would directly improve the mass loading density. Silicon films with Carbon NCLs and Carbon films with Silicon NCLs were both deposited and tested. It was found that Li+ diffusivity is higher in carbon than in silicon by at least two orders of magnitude. This was calculated from cyclic voltammetry tests using the Randles-Sevcik equation. This difference in Li+ diffusivity within the two materials was found to be the C-rate limiting factor for a given nano-architecture design.

Synthesis and Performance of Tungsten Disulfide/Carbon (WS2/C) Composite as Anode Material

NASA Astrophysics Data System (ADS)

Yuan, Zhengyong; Jiang, Qiang; Feng, Chuanqi; Chen, Xiao; Guo, Zaiping

2018-01-01

The precursors of an amorphous WS2/C composite were synthesized by a simple hydrothermal method using Na2WO4·2H2O and CH3CSNH2 as raw materials, polyethylene glycol as dispersant, and glucose as the carbon source. The as-synthesized precursors were further annealed at a low temperature in flowing argon to obtain the final materials (WS2/C composite). The structure and morphology of the WS2/C composite were characterized by x-ray diffraction, x-ray photoelectron spectroscopy, and scanning electron microscopy. The electrochemical properties were tested by galvanostatic charge/discharge testing and alternating current (AC) impedance measurements. The results show that the as-prepared amorphous WS2/C composite features both high specific capacity and good cycling performance at room temperature within the potential window from 3.0 V to 0.01 V (versus Li+/Li) at current density of 100 mAg-1. The achieved initial discharge capacity was 1080 mAhg-1, and 786 mAhg-1 was retained after 170 cycles. Furthermore, the amorphous WS2/C composite exhibited a lower charge/discharge plateau than bare WS2, which is more beneficial for use as an anode. The cyclic voltammetry and AC impedance testing further confirmed the change in the plateau and the decrease in the charge transfer resistance in the WS2/C composite. The chemical formation process and the electrochemical mechanism of the WS2/C composite are also presented. The amorphous WS2/C composite can be used as a new anode material for future applications.

Mesoporous activated carbon from corn stalk core for lithium ion batteries

NASA Astrophysics Data System (ADS)

Li, Yi; Li, Chun; Qi, Hui; Yu, Kaifeng; Liang, Ce

2018-04-01

A novel mesoporous activated carbon (AC) derived from corn stalk core is prepared via a facile and effective method which including the decomposition and carbonization of corn stalk core under an inert gas atmosphere and further activation process with KOH solution. The mesoporous activated carbon (AC) is characterized by X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Brunauer-Emmett-Teller (BET) measurements. These biomass waste derived from activated carbon is proved to be promising anode materials for high specific capacity lithium ion batteries. The activated carbon anode possesses excellent reversible capacity of 504 mAh g-1 after 100 cycles at 0.2C. Compared with the unactivated carbon (UAC), the electrochemical performance of activated carbon is significantly improved due to its mesoporous structure.

First principles calculations of stability and lithium intercalation potentials of ZnCo2O4

NASA Astrophysics Data System (ADS)

Yu, L. C.; Wu, J.; Liu, H.; Zhang, Y. N.

2015-03-01

Among the metal oxides, which are the most widely investigated alternative anodes for use in lithium ion batteries (LIBs), binary and ternary tin oxides have received special attention due to their high capacity values. ZnCo2O4 is a promising candidate as the anode material for LIB, and one can expect a total capacity corresponding to 7.0 - 8.33 mol of recyclable Li per mole of ZnCo2O4. Here we studied the structural stability, electronic properties, diffusion barrier and lithium intercalation potentials of ZnCo2O4 through density functional calculations. The calculated structural and energetic parameters are comparable with experiments. Our DFT studies provide insights in understanding the mechanism of lithium ion displacement reactions in this ternary metal oxide.

High capacity Li-ion battery anodes: Impact of crystallite size, surface chemistry and PEG-coating

DOE PAGES

Minnici, Krysten; Kwon, Yo Han; Huie, Matthew M.; ...

2017-12-06

Battery electrodes are complex mesoscale systems comprised of an active material, conductive agent, current collector, and polymeric binder. Previous work showed that introduction of poly [3-(potassium-4-butanoate) thiophene] (PPBT) as a binder component coupled with a polyethylene glycol (PEG) surface coating on magnetite (Fe 3O 4) nanoparticles enhanced electron and ion transport in the high capacity anode system. Here, the impact of Fe 3O 4 crystallite size (10 nm vs. 20 nm) and surface chemistry were explored to evaluate their effects on interfacial interactions within the composite PEG/PPBT based electrodes and resultant battery performance. The Fe 3O 4 synthesis methods inevitablymore » lead to differences in surface chemistry. For instance, the Fe 3O 4 particles synthesized using ammonium hydroxide appeared more dispersed, and afforded improved rate capability performance. Notably, chemical interactions between the active nanoparticles and PPBT binder were only seen with particles synthesized using triethylamine. Capacity retention and cycling performance were unaffected. Thus, this study provides fundamental insights into the significant impact of active material synthesis on the design and fabrication of composite battery electrodes.« less

Role of precursor chemistry in the direct fluorination to form titanium based conversion anodes for lithium ion batteries

DOE PAGES

Adcock, Jamie; Dai, Sheng; Veith, Gabriel M.; ...

2015-10-13

In this study, a new synthetic route for the formation of titanium oxydifluoride (TiOF 2) through the process of direct fluorination via a fluidized bed reactor system and the associated electrochemical properties of the powders formed from this approach are reported. The flexibility of this synthetic route was demonstrated using precursor powders of titanium dioxide (TiO 2) nanoparticles, as well as a reduced TiO xN y. An advantage of this synthetic method is the ability to directly control the extent of fluorination as a function of reaction temperature and time. The reversible capacity of TiOF 2 anodes was found tomore » depend greatly upon the precursor employed. The TiOF 2 synthesized from TiO 2 and TiO xN y showed reversible capacities of 300 mAh g -1 and 440 mAh g -1, respectively, over 100 cycles. The higher reversible capacity of the TiOF 2 powders derived from TiO xN y likely relate to the partial reduction of the Ti in the fluorinated electrode material, highlighting a route to optimize the properties of conversion electrode materials.« less

High capacity Li-ion battery anodes: Impact of crystallite size, surface chemistry and PEG-coating

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

Minnici, Krysten; Kwon, Yo Han; Huie, Matthew M.

Battery electrodes are complex mesoscale systems comprised of an active material, conductive agent, current collector, and polymeric binder. Previous work showed that introduction of poly [3-(potassium-4-butanoate) thiophene] (PPBT) as a binder component coupled with a polyethylene glycol (PEG) surface coating on magnetite (Fe 3O 4) nanoparticles enhanced electron and ion transport in the high capacity anode system. Here, the impact of Fe 3O 4 crystallite size (10 nm vs. 20 nm) and surface chemistry were explored to evaluate their effects on interfacial interactions within the composite PEG/PPBT based electrodes and resultant battery performance. The Fe 3O 4 synthesis methods inevitablymore » lead to differences in surface chemistry. For instance, the Fe 3O 4 particles synthesized using ammonium hydroxide appeared more dispersed, and afforded improved rate capability performance. Notably, chemical interactions between the active nanoparticles and PPBT binder were only seen with particles synthesized using triethylamine. Capacity retention and cycling performance were unaffected. Thus, this study provides fundamental insights into the significant impact of active material synthesis on the design and fabrication of composite battery electrodes.« less

One-pot solvothermal synthesis of graphene wrapped rice-like ferrous carbonate nanoparticles as anode materials for high energy lithium-ion batteries

NASA Astrophysics Data System (ADS)

Zhang, Fan; Zhang, Ruihan; Feng, Jinkui; Ci, Lijie; Xiong, Shenglin; Yang, Jian; Qian, Yitai; Li, Lifei

2014-11-01

Well dispersed rice-like FeCO3 nanoparticles were produced and combined with reduced graphene oxide (RGO) via a one-pot solvothermal route. SEM characterization shows that rice-like FeCO3 nanoparticles are homogeneously anchored on the surface of the graphene nanosheets; the addition of RGO is helpful to form a uniform morphology and reduce the particle size of FeCO3 to nano-grade. As anode materials for lithium-ion batteries, the FeCO3/RGO nanocomposites exhibit significantly improved lithium storage properties with a large reversible capacity of 1345 mA h g-1 for the first cycle and a capacity retention of 1224 mA h g-1 after 50 cycles with a good rate capability compared with pure FeCO3 particles. The superior electrochemical performance of the FeCO3/RGO nanocomposite electrode compared to the pure FeCO3 electrode can be attributed to the well dispersed RGO which enhances the electronic conductivity and accommodates the volume change during the conversion reactions. Our study shows that the FeCO3/RGO nanocomposite could be a suitable candidate for high capacity lithium-ion batteries.

Hybrid phosphorene/graphene nanocomposite as an anode material for Na-ion batteries: a first-principles study

NASA Astrophysics Data System (ADS)

Wang, Linxia; Jiang, Zhiqiang; Li, Wei; Gu, Xiao; Huang, Li

2017-04-01

The potential application of the hybrid phosphorene/graphene (P/G) composites as an anode material in Na-ion batteries (NIBs) has been explored based on first-principles calculations. The calculated elastic constants reveal that the P/G has an ultrahigh stiffness, which can effectively suppress the undesirable structural deformation during the sodiation and desodiation cycles. Na atoms can strongly bind with the phosphorene single-layer (SP), double-layer (DP), and their composites with graphene (SP/G, DP/G, G/DP/G), and can even cause a sliding between the layers when the DP/G accommodate more Na atoms. The migration of Na in P/G is anisotropic with the minimum energy path along the zigzag channel. The low diffusion barriers of only about several tens of meV ensure the high mobility of Na within the layers, and thus lead to rapid charge/discharge capacity of P/G. The electronic structures show that the hybrid P/G becomes metallic with the Na incorporation, which contributes to the good electric conductivity in P/G. We further demonstrate that the average open circuit voltage (OCV) of DP/G is 0.53 V, which is comparable to other anode materials. These results suggest that P/G composites hold great potential to be a good anode material in NIBs.

Robust Expandable Carbon Nanotube Scaffold for Ultrahigh-Capacity Lithium-Metal Anodes.

PubMed

Sun, Zhaowei; Jin, Song; Jin, Hongchang; Du, Zhenzhen; Zhu, Yanwu; Cao, Anyuan; Ji, Hengxing; Wan, Li-Jun

2018-06-19

There has been a renewed interest in using lithium (Li) metal as an anode material for rechargeable batteries owing to its high theoretical capacity of 3860 mA h g -1 . Despite extensive research, modifications to effectively inhibit Li dendrite growth still result in decreased Li loading and Li utilization. As a result, real capacities are often lower than values expected, if the total mass of the electrode is taken into consideration. Herein, a lightweight yet mechanically robust carbon nanotube (CNT) paper is demonstrated as a freestanding framework to accommodate Li metal with a Li mass fraction of 80.7 wt%. The highly conductive network made of sp2-hybridized carbon effectively inhibits formation of Li dendrites and affords a favorable coulombic efficiency of >97.5%. Moreover, the Li/CNT electrode retains practical areal and gravimetric capacities of 10 mA h cm -2 and 2830 mA h g -1 (vs the mass of electrode), respectively, with 90.9% Li utilization for 1000 cycles at a current density of 10 mA cm -2 . It is demonstrated that the robust and expandable nature is a distinguishing feature of the CNT paper as compared to other 3D scaffolds, and is a key factor that leads to the improved electrochemical performance of the Li/CNT anodes. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Synthesis and characterisation of Co-Co(OH)2 composite anode material on Cu current collector for energy storage devices

NASA Astrophysics Data System (ADS)

Yavuz, Abdulcabbar; Yakup Hacıibrahimoğlu, M.; Bedir, Metin

2017-04-01

A Co-Co(OH)2 modified electrode on inexpensive Cu substrate was synthesized at room temperature and demonstrated to be a promising anode material for energy storage devices. A modified Co film was obtained potentiostatically and was then potentiodynamically treated with KOH solution to form Co(OH)2. Co-Co(OH)2 coatings were obtained and were dominated by Co(OH)2 at the oxidized side, whereas Co dominant Co-Co(OH)2 occurred at the reduced side (-1.1 V). As OH- ions were able to diffuse into (out of) the film during oxidation (reduction) and did not react with the Cu current collector, the Co-Co(OH)2 electrode can be used as an anode material in energy storage devices. Although the specific capacitance of the electrodes varied depending on thickness, the redox reaction between the modified electrode and KOH electrolyte remained the same consisting of a surface-controlled and diffusion-controlled mechanism which had a desirable fast charge and discharge property. Capacity values remained constant after 250 cycles as the film evolved. Overall capacity retention was 84% for the film after 450 scans. A specific capacitance of 549 F g-1 was obtained for the Co-Co(OH)2 composite electrode in 6 M KOH at a scan rate of 5 mV s-1 and 73% of capacitance was retained when the scan rate was increased to 100 mV s-1.

Amorphous ZnO Quantum Dot/Mesoporous Carbon Bubble Composites for a High-Performance Lithium-Ion Battery Anode.

PubMed

Tu, Zhiming; Yang, Gongzheng; Song, Huawei; Wang, Chengxin

2017-01-11

Due to its high theoretical capacity (978 mA h g -1 ), natural abundance, environmental friendliness, and low cost, zinc oxide is regarded as one of the most promising anode materials for lithium-ion batteries (LIBs). A lot of research has been done in the past few years on this topic. However, hardly any research on amorphous ZnO for LIB anodes has been reported despite the fact that the amorphous type could have superior electrochemical performance due to its isotropic nature, abundant active sites, better buffer effect, and different electrochemical reaction details. In this work, we develop a simple route to prepare an amorphous ZnO quantum dot (QDs)/mesoporous carbon bubble composite. The composite consists of two parts: mesoporous carbon bubbles as a flexible skeleton and monodisperse amorphous zinc oxide QDs (smaller than 3 nm) encapsulated in an amorphous carbon matrix as a continuous coating tightly anchored on the surface of mesoporous carbon bubbles. With the benefits of abundant active sites, amorphous nature, high specific surface area, buffer effect, hierarchical pores, stable interconnected conductive network, and multidimensional electron transport pathways, the amorphous ZnO QD/mesoporous carbon bubble composite delivers a high reversible capacity of nearly 930 mA h g -1 (at current density of 100 mA g -1 ) with almost 90% retention for 85 cycles and possesses a good rate performance. This work opens the possibility to fabricate high-performance electrode materials for LIBs, especially for amorphous metal oxide-based materials.

A POM–organic framework anode for Li-ion battery

DOE PAGES

Yue, Yanfeng; Li, Yunchao; Bi, Zhonghe; ...

2015-10-12

Rechargeable Li-ion batteries (LIBs) are currently the dominant power source for portable electronic devices and electric vehicles, and for small-scale stationary energy storage. However, one bottleneck of the anode materials for LIBs is the poor cycling performance caused by the fact that the anodes cannot maintain their integrity over several charge–discharge cycles. In this work, we demonstrate an approach to improving the cycling performance of lithium-ion battery anodes by constructing an extended 3D network of flexible redox active polyoxometalate (POM) clusters with redox active organic linkers, herein described as POMOF. In addition, this architecture enables the accommodation of large volumemore » changes during cycling at relatively high current rates. For example, the POMOF anode exhibits a high reversible capacity of 540 mA h g –1 after 360 cycles at a current rate of 0.25C and a long cycle life at a current rate of 1.25C (>500 cycles).« less

Rational design of anode materials based on Group IVA elements (Si, Ge, and Sn) for lithium-ion batteries.

PubMed

Wu, Xing-Long; Guo, Yu-Guo; Wan, Li-Jun

2013-09-01

Lithium-ion batteries (LIBs) represent the state-of-the-art technology in rechargeable energy-storage devices and they currently occupy the prime position in the marketplace for powering an increasingly diverse range of applications. However, the fast development of these applications has led to increasing demands being placed on advanced LIBs in terms of higher energy/power densities and longer life cycles. For LIBs to meet these requirements, researchers have focused on active electrode materials, owing to their crucial roles in the electrochemical performance of batteries. For anode materials, compounds based on Group IVA (Si, Ge, and Sn) elements represent one of the directions in the development of high-capacity anodes. Although these compounds have many significant advantages when used as anode materials for LIBs, there are still some critical problems to be solved before they can meet the high requirements for practical applications. In this Focus Review, we summarize a series of rational designs for Group IVA-based anode materials, in terms of their chemical compositions and structures, that could address these problems, that is, huge volume variations during cycling, unstable surfaces/interfaces, and invalidation of transport pathways for electrons upon cycling. These designs should at least include one of the following structural benefits: 1) Contain a sufficient number of voids to accommodate the volume variations during cycling; 2) adopt a "plum-pudding"-like structure to limit the volume variations during cycling; 3) facilitate an efficient and permanent transport pathway for electrons and lithium ions; or 4) show stable surfaces/interfaces to stabilize the in situ formed SEI layers. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cobalt-based metal organic framework with superior lithium anodic performance

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

Hu, Xiaoshi; Hu, Huiping; Li, Chao

The reversible charging of a Co-1,4-benzenedicarboxylate MOF (Co-BDC MOF) prepared via an one-pot solvothermal method was studied for use as the anode in a Li-ion cell. It was found that this MOF anode provides high reversible capacities (1090 and 611 mA h g{sup −1} at current densities of 0.2 and 1 A g{sup −1}, respectively), and an impressive rate performance. Such an outstanding Li-ion storage property has not been reported previously for the LIB anodes within the MOFs category. Ex-situ X-ray photoelectron spectroscopy (XPS) and infrared spectroscopy (IR) studies of this material at different state of charge suggest that cobaltmore » stays at Co{sup 2+} state during discharge/charge process, so that in this case Li{sup +} may be inserted into the organic moiety without the direct participation of cobalt ions. - Graphical abstract: Co-1,4-benzenedicarboxylate MOF, synthesized through a straightforward solvothermal method, shows outstanding lithium storage performance. - Highlights: • Co-1,4-benzenedicarboxylate MOF is synthesized by a one-pot solvothermal method. • Reversible capacity of 1090 mA h g{sup −1} is achieved at a current density of 200 mA g{sup −1}. • Reversible capacity of 611 mA h g{sup −1} is achieved at a current density of 1 A g{sup −1}. • Li-ions may be inserted into the organic moieties.« less

Free-standing anode of N-doped carbon nanofibers containing SnO{sub x} for high-performance lithium batteries

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

Zou, Mingzhong; Li, Jiaxin, E-mail: ljx3012982@yahoo.com; Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002

2014-12-15

Highlights: • Self-standing SnO{sub x} N-CNF electrodes were synthesized by electrospinning. • The SnO{sub x} N-CNFs anode exhibits high capacity, good cyclic stability, and excellent rate performance for lithium ion batteries. • The enhanced performance is ascribed to the synergetic effects between N-CNFs and SnO{sub x} nanoparticles. - Abstract: Free-standing paper of N-doped carbon nanofibers (NCNFs) containing SnO{sub x} was prepared by electrospinning. The structure and morphology of the sample were analyzed by XRD, XPS, SEM, and TEM. The results show that nitrogen atoms were successfully doped into CNFs. The SnO{sub x} were homogenously embedded in the N-doped CNFs viamore » annealing treatment. Subsequently, the SnO{sub x} NCNF paper was cut into disks and used as anodes for lithium ion batteries (LIBs). The anodes of SnO{sub x} NCNFs exhibit excellent cycling stability and show high capacity of 520 mA h g{sup −1} tested at a 200 mA g{sup −1} after 100 cycles. More importantly, at a high current density of 500 mA g{sup −1}, a large reversible capacity of 430 mA h g{sup −1} after 100 cycles can still be obtained. The good electrochemical performance should be attributed to the good electronic conductivity from the NCNFs and the synergistic effects from NCNFs and SnO{sub x} materials.« less

Scalable Synthesis of Defect Abundant Si Nanorods for High-Performance Li-Ion Battery Anodes.

PubMed

Wang, Jing; Meng, Xiangcai; Fan, Xiulin; Zhang, Wenbo; Zhang, Hongyong; Wang, Chunsheng

2015-06-23

Microsized nanostructured silicon-carbon composite is a promising anode material for high energy Li-ion batteries. However, large-scale synthesis of high-performance nano-Si materials at a low cost still remains a significant challenge. We report a scalable low cost method to synthesize Al/Na-doped and defect-abundant Si nanorods that have excellent electrochemical performance with high first-cycle Coulombic efficiency (90%). The unique Si nanorods are synthesized by acid etching the refined and rapidly solidified eutectic Al-Si ingot. To maintain the high electronic conductivity, a thin layer of carbon is then coated on the Si nanorods by carbonization of self-polymerized polydopamine (PDA) at 800 °C. The carbon coated Si nanorods (Si@C) electrode at 0.9 mg cm(-2) loading (corresponding to area-specific-capacity of ∼2.0 mAh cm(-2)) exhibits a reversible capacity of ∼2200 mAh g(-1) at 100 mA g(-1) current, and maintains ∼700 mAh g(-1) over 1000 cycles at 1000 mA g(-1) with a capacity decay rate of 0.02% per cycle. High Coulombic efficiencies of 87% in the first cycle and ∼99.7% after 5 cycles are achieved due to the formation of an artificial Al2O3 solid electrolyte interphase (SEI) on the Si surface, and the low surface area (31 m(2) g(-1)), which has never been reported before for nano-Si anodes. The excellent electrochemical performance results from the massive defects (twins, stacking faults, dislocations) and Al/Na doping in Si nanorods induced by rapid solidification and Na salt modifications; this greatly enhances the robustness of Si from the volume changes and alleviates the mechanical stress/strain of the Si nanorods during the lithium insertion/extraction process. Introducing massive defects and Al/Na doping in eutectic Si nanorods for Li-ion battery anodes is unexplored territory. We venture this uncharted territory to commercialize this nanostructured Si anode for the next generation of Li-ion batteries.

Highly Reversible Zinc-ion Intercalation with Chevrel Phase Mo6S8 Nanocubes and Applications for Advanced Zinc-ion Batteries

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

Cheng, Yingwen; Luo, Langli; Zhong, Li

We demonstrate the application of the Chevrel phase Mo6S8 nanocubes as the anode material for rechargeable Zn-ion batteries. Mo6S8 can host Zn2+ ions reversibility both in aqueous and nonaqueous electrolytes with specific capacities around 90 mAh/g and exhibited remarkable intercalation kinetics as well as stability. Furthermore, we assembled full cells by integrating Mo6S8 anode with zinc-polyiodide (I-/I3-) based catholytes, and demonstrated that such fuel cells was also able to deliver outstanding rate performance and cyclic stability. This first demonstration of zinc intercalating anode could inspire the design of advanced Zn ion batteries.

S/N dual-doped carbon nanosheets decorated with Co x O y nanoparticles as high-performance anodes for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Wang, XiaoFei; Zhu, Yong; Zhu, Sheng; Fan, JinChen; Xu, QunJie; Min, YuLin

2018-03-01

In this work, we have successfully synthesized the S/N dual-doped carbon nanosheets which are strongly coupled with Co x O y nanoparticles (SNCC) by calcinating cobalt/dithizone complex precursor following KOH activation. The SNCC as anode shows the wonderful charge capacity of 1200 mAh g-1 after 400th cycles at 1000 mA g-1 for Li-ion storage. The superior electrochemical properties illustrate that the SNCC can be a candidate for high-performance anode material of lithium-ion batteries (LIBs) because of the facile preparation method and excellent performance. Significantly, we also discuss the mechanism for the SNCC from the strong synergistic effect perspective.

Synthesis and electrochemical characterization of Silicon clathrates as anode materials for Lithium ion batteries

NASA Astrophysics Data System (ADS)

Raghavan, Rahul

Novel materials for Li-ion batteries is one of the principle thrust areas for current research in energy storage, more so than most, considering its widespread use in portable electronic gadgets and plug-in electric and hybrid cars. One of the major limiting factors in a Li-ion battery's energy density is the low specific capacities of the active materials in the electrodes. In the search for high-performance anode materials for Li-ion batteries, many alternatives to carbonaceous materials have been studied. Both cubic and amorphous silicon can reversibly alloy with lithium and have a theoretical capacity of 3500 mAh/g, making silicon a potential high density anode material. However, a large volume expansion of 300% occurs due to changes in the structure during lithium insertion, often leading to pulverization of the silicon. To this end, a class of silicon based cage compounds called clathrates are studied for electrochemical reactivity with lithium. Silicon-clathrates consist of silicon covalently bonded in cage structures comprised of face sharing Si20, Si24 and/or Si28 clusters with guest ions occupying the interstitial positions in the polyhedra. Prior to this, silicon clathrates have been studied primarily for their superconducting and thermoelectric properties. In this work, the synthesis and electrochemical characterization of two categories of silicon clathrates - Type-I silicon clathrate with aluminum framework substitution and barium guest ions (Ba8AlxSi46-x) and Type-II silicon clathrate with sodium guest ions (Nax Si136), are explored. The Type-I clathrate, Ba8AlxSi46-x consists of an open framework of aluminium and silicon, with barium (guest) atoms occupying the interstitial positions. X-ray diffraction studies have shown that a crystalline phase of clathrate is obtained from synthesis, which is powdered to a fine particle size to be used as the anode material in a Li-ion battery. Electrochemical measurements of these type of clathrates have shown that capacities comparable to graphite can be obtained for up to 10 cycles and lower capacities can be obtained for up to 20 cycles. Unlike bulk silicon, the clathrate structure does not undergo excessive volume change upon lithium intercalation, and therefore, the crystal structure is morphologically stable over many cycles. X-ray diffraction of the clathrate after cycling showed that crystallinity is intact, indicating that the clathrate does not collapse during reversible intercalation with lithium ions. Electrochemical potential spectroscopy obtained from the cycling data showed that there is an absence of formation of lithium-silicide, which is the product of lithium alloying with diamond cubic silicon. Type II silicon clathrate, NaxSi136, consists of silicon making up the framework structure and sodium (guest) atoms occupying the interstitial spaces. These clathrates showed very high capacities during their first intercalation cycle, in the range of 3,500 mAh/g, but then deteriorated during subsequent cycles. X-ray diffraction after one cycle showed the absence of clathrate phase and the presence of lithium-silicide, indicating the disintegration of clathrate structure. This could explain the silicon-like cycling behavior of Type II clathrates.

Synthesis of Fe3O4 cluster microspheres/graphene aerogels composite as anode for high-performance lithium ion battery

NASA Astrophysics Data System (ADS)

Zhou, Shuai; Zhou, Yu; Jiang, Wei; Guo, Huajun; Wang, Zhixing; Li, Xinhai

2018-05-01

Iron oxides are considered as attractive electrode materials because of their capability of lithium storage, but their poor conductivity and large volume expansion lead to unsatisfactory cycling stability. We designed and synthesized a novel Fe3O4 cluster microspheres/Graphene aerogels composite (Fe3O4/GAs), where Fe3O4 nanoparticles were assembled into cluster microspheres and then embedded in 3D graphene aerogels framework. In the spheres, the sufficient free space between Fe3O4 nanoparticles could accommodate the volume change during cycling process. Graphene aerogel works as flexible and conductive matrix, which can not only significantly increase the mechanical stress, but also further improve the storage properties. The Fe3O4/GAs composite as an anode material exhibits high reversible capability and excellent cyclic capacity for lithium ion batteries (LIBs). A reversible capability of 650 mAh g-1 after 500 cycles at a current density of 1 A g-1 can be maintained. The superior storage capabilities of the composites make them potential anode materials for LIBs.

Investigation of electronic band structure and charge transfer mechanism of oxidized three-dimensional graphene as metal-free anodes material for dye sensitized solar cell application

NASA Astrophysics Data System (ADS)

Loeblein, Manuela; Bruno, Annalisa; Loh, G. C.; Bolker, Asaf; Saguy, Cecile; Antila, Liisa; Tsang, Siu Hon; Teo, Edwin Hang Tong

2017-10-01

Dye-sensitized solar cells (DSSCs) offer an optimal trade-off between conversion-efficiency and low-cost fabrication. However, since all its electrodes need to fulfill stringent work-function requirements, its materials have remained unchanged since DSSC's first report early-90s. Here we describe a new material, oxidized-three-dimensional-graphene (o-3D-C), with a band gap of 0.2 eV and suitable electronic band-structure as alternative metal-free material for DSSCs-anodes. o-3D-C/dye-complex has a strong chemical bonding via carboxylic-group chemisorption with full saturation after 12 sec at capacity of ∼450 mg/g (600x faster and 7x higher than optimized metal surfaces). Furthermore, fluorescence quenching of life-time by 28-35% was measured demonstrating charge-transfer from dye to o-3D-C.