Mesoscopic magnetic iron oxide spheres for high performance Li-ion battery anode: a new pulsed laser induced reactive micro-bubble synthesis process

Biswal, Mandakini; Suryawanshi, Anil; Thakare, Vishal; Jouen, Samuel; Hannoyer, B.; Aravindan, Vanchiappan; Srinivasan, Madhavi; Ogale, Satishchandra

doi:10.1039/c3ta12790g

Cited by 18 publications

(18 citation statements)

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“…[ 352 ] Ji et al [ 353 ] fi rst demonstrated the performance of the Fe 3 O 4 -graphene composite as a conversion anode with layered type LiNi 1/3 Mn 1/3 Co 1/3 O 2 as the cathode. The magnetite phase is a perfect example of the inverse spinel structure with cubic close packed array of ions, where half of the octahedral sites are fi lled by all the Fe 2+ ions and Fe 3+ ions occupy the remaining octahedral and tetrahedral sites.…”

Section: Fe 3 Omentioning

confidence: 99%

Research Progress on Negative Electrodes for Practical Li‐Ion Batteries: Beyond Carbonaceous Anodes

Aravindan

Lee

Srinivasan

2015

Advanced Energy Materials

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433

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3 of 43) 1402225 wileyonlinelibrary.comhost matrix is observed and this process is called "topotactic reaction", which is either chemically or thermally reversible; a perfect example is Li-intercalation into a graphite matrix. Such intercalation chemistry has been successfully used in Li-ion batteries for both anode and cathode materials and has also been commercialized (i.e., LiCoO 2 /Li x C 6 and LiFePO 4 /Li x C 6 ). [ 4,5 ] The insertion type materials, i.e., metal oxides have several advantages over graphitic anodes when used in practical cells; these include a negligible amount of ICL, no Li-platting issues, no solvent co-intercalation, no electrolyte decomposition, no SEI required for the safe operation of the cell, it is capable of delivering high power density, and has an easy synthesis protocol. On the other hand, less reversible capacity and higher intercalation potential are the notable setbacks compared to graphite. Although numerous Li-intercalating materials are proposed as possible anodes for LIB applications, few of them have only been tested or commercialized in the "rocking-chair" confi guration, for instance Li 4 Ti 5 O 5 anode. Apart from the mentioned anode, few other insertion type materials have been also evaluated in the rocking-chair confi guration for LIBs. Accordingly, the next section describes the structural and electrochemical performance of various intercalation anodes evaluated in the rocking-chair confi guration. TiO 2The existence of several polymorphs is reported for the case of TiO 2 , but anatase, rutile, brookite, and bronze phases have only been reported for Li-storage. [ 26 ] Reversible insertion of one mole of Li is theoretically possible, independent of the polymorph, with a capacity of ≈335 mAh g −1 . However, variation in the Liinsertion potential and reaction mechanism has been observed for such polymorphs. Easy synthesis protocols, scalability, inexpensiveness, ease of tailoring the desired morphology, and eco-friendliness are other key features for utilizing TiO 2 polymorphs for the construction of Li-ion power packs. [27][28][29] AnataseThe anatase phase is one of the widely investigated polymorphs of TiO 2 for Li-storage. [ 27 ] Theoretically, one mole of Li is possible, but practically only ≈0.5 mole Li is reversible upon cycling. Several research attempts have been carried out to improve the reversible capacity, including utilizing high energy (0 0 1) facets because of their dominant higher surface energy (0.90 J m −2 ) compared to (1 0 0) facets (0.44 J m −2 ) and using thermodynamically more stable (1 0 1) facets (0.53 J m −2 ). [ 30,31 ] Although high Li-reversibility could be achieved for such (0 0 1) facets, capacity fading remains an issue upon cycling. [ 32 ] Li-diffusion co-effi cient ( D Li ) values for anatase phase are in the range of 1 × 10 −17 to 4 × 10 −17 cm 2 s −1 for Li-insertion and extraction processes, respectively. [ 27 ] In the crystal chemistry of the anatase phase, TiO 6 octahedra sharetwo adjacent edges with two other octahedral so that...

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Section: Fe 3 Omentioning

confidence: 99%

Research Progress on Negative Electrodes for Practical Li‐Ion Batteries: Beyond Carbonaceous Anodes

Aravindan

Lee

Srinivasan

2015

Advanced Energy Materials

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433

319

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“…The observed Raman results are consistent with the HR‐TEM and XRD studies, indicating the formation of inverse spinel magnetite particulates over rGO nanosheets. Furthermore, the A 1g vibration mode of the Fe 3 O 4 peak appeared at 668 cm −1 , which agrees well with the literature value for the formation of Fe 3 O 4 in the composite . To estimate the rGO content of the Fe 3 O 4 ‐rGO material, quantitative thermogravimetric analyses were performed by heating the samples at a rate of 10 °C min −1 in air (Figure d).…”

Section: Resultsmentioning

confidence: 99%

“…These electrodes are anticipated to improve the energy density and certainly boost the high power density as well. Among these metal oxides, magnetite (Fe 3 O 4 ) has been gained great attention as conversion type anode because of the advantages like high theoretical capacity (924 mAh g −1 ), low cost, eco‐friendly and naturally abundant ,, . Nevertheless, to the best of our knowledge, the magnetite phase has not been paired with Fe‐based cathode (i. e. LiFePO 4 ) for the fabrication of high energy LIB ,.…”

Section: Introductionmentioning

confidence: 99%

Exploring High‐Energy Li‐I(r)on Batteries and Capacitors with Conversion‐Type Fe₃O₄‐rGO as the Negative Electrode

et al. 2017

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We report a microwave‐assisted solvothermal process for the preparation of magnetite (Fe3O4, ca. 5 nm)‐anchored reduced graphene oxide (rGO). It has been examined as a prospective conversion‐type negative electrode for multiple energy storage applications, such as Li‐ion batteries (LIBs) and Li‐ion capacitors (LICs). A LiFePO4/Fe3O4‐rGO cell is constructed and capable of delivering an energy density of approximately 139 Wh kg−1 with a notable cyclability (ca. 76 %) after 500 cycles. Prior to the fabrication of a LIB, the Fe3O4‐rGO is electrochemically pretreated to eliminate the irreversible capacity loss. In addition to the LIB, a high‐energy LIC is also fabricated by using the pre‐lithiated Fe3O4‐rGO composite as the anode and commercial activated carbon as the cathode. This LIC registered a maximum energy density of approximately 114 Wh kg−1 with good cyclability. For both the LIB and LIC, the mass loading between the electrodes was adjusted based on the performance with metallic Li. The improved electrochemical performance of Fe3O4‐rGO over existing materials is a promising development in the quest for novel, fast, low cost, and efficient energy storage systems without compromising the eco‐friendliness

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“…The theoretical reversible capacity is high (928 mAh g À1 ), it is abundant as it occurs in nature as the mineral magnetite, it is nontoxic; its low cost and high corrosion resistance are other characteristics. The limits come, as usual with all the anode elements based on conversion reactions, the degradation of the battery coming from the large change of volume (200 % [593]. An intermediate situation is provided by recent experiments on clusters of mesoporous 11-12 nm sized nanoparticles, with carbon-coating through bottom-up self assembly approach [594].…”

Section: Fe 3 Omentioning

confidence: 98%

Anodes for Li-Ion Batteries

et al. 2016

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Lithium-ion batteries (LiBs) have made considerable progress since the first commercial one by Sony in 1991, which had LiCoO 2 and graphite as active elements of the positive and negative electrodes, respectively. The LiBs are now the primary energy storage devices in the transportation and communications, from portable use in computers, up to electric and hybrid vehicles. More recently, they have also been used as back-up supply units, frequency regulators (load leveling) to integrate on smart grids the electricity produced by windmills and photovoltaic plants (for a recent review, see [1]). These applications require high energy densities, high power, and safety among others. Considerable efforts have been made to propose other electrodes to fulfill these requirements. We have recently reviewed the works and progress concerning the materials for the positive electrode [2][3][4][5][6]. The present work is devoted to the materials for the negative electrode counterpart. It is common to use the terminology anode and cathode for the negative and positive electrodes, respectively, although the electrodes play alternatively the role of anode and cathode during the charge and discharge process. We shall use this terminology in the following for conciseness purposes only.An ideal active anode element should fulfill the following requirements as follows: (1) It must be light and accommodate as much Li as possible to optimize the gravimetric capacity. (2) Its redox potential with respect to Li 0 /Li + must be as small as possible at any Li-concentration. The reason is that this potential is subtracted to the redox potential of the cathode material to give the overall voltage of the cell, and smaller voltage means smaller energy density. (3) It must possess good electronic and ionic conductivities since faster motion of the lithium ions and the electrons also mean higher power density of the cell. (4) It must not be soluble in the solvents of the electrolyte and not react with the lithium salt. (5) It must be safe, i.e. avoid any thermal runaway of the battery, a criterion that is not independent of the previous one, but deserves special attention, especially for use in transportation such as electric vehicles and planes. (6) It must be cheap and environmentally friendly. The different materials proposed as anode elements for Li-ion batteries must be discussed with respect to these different criteria.The graphite is still the most used anode material and is still the reference. The first works giving evidence of the insertion of lithium in graphite date from 1955 [7], confirmed by the synthesis of LiC 6 in 1965 [8]. The synthesis of LiC 6 , however, was not obtained by electrochemical process at that time. Another decade was spent before Besenhard and Eichinger discovered the reversible intercalation of lithium in graphite, proposing this material as an anode in 1976 [9,10]. Increasing the Li content in LiC 6 is possible [8], but no reversible cycling beyond LiC 6 could ever be obtained. The graphite anode can thus be cyc...

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Mesoscopic magnetic iron oxide spheres for high performance Li-ion battery anode: a new pulsed laser induced reactive micro-bubble synthesis process

Cited by 18 publications

References 66 publications

Research Progress on Negative Electrodes for Practical Li‐Ion Batteries: Beyond Carbonaceous Anodes

Research Progress on Negative Electrodes for Practical Li‐Ion Batteries: Beyond Carbonaceous Anodes

Exploring High‐Energy Li‐I(r)on Batteries and Capacitors with Conversion‐Type Fe₃O₄‐rGO as the Negative Electrode

Anodes for Li-Ion Batteries

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Mesoscopic magnetic iron oxide spheres for high performance Li-ion battery anode: a new pulsed laser induced reactive micro-bubble synthesis process

Cited by 18 publications

References 66 publications

Research Progress on Negative Electrodes for Practical Li‐Ion Batteries: Beyond Carbonaceous Anodes

Research Progress on Negative Electrodes for Practical Li‐Ion Batteries: Beyond Carbonaceous Anodes

Exploring High‐Energy Li‐I(r)on Batteries and Capacitors with Conversion‐Type Fe3O4‐rGO as the Negative Electrode

Anodes for Li-Ion Batteries

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Exploring High‐Energy Li‐I(r)on Batteries and Capacitors with Conversion‐Type Fe₃O₄‐rGO as the Negative Electrode