Carbon Coated ZnFe<sub>2</sub>O<sub>4</sub> Nanoparticles for Advanced Lithium‐Ion Anodes

Bresser, Dominic; Paillard, Elie; Kloepsch, Richard; Krueger, Steffen; Fiedler, Martin; Schmitz, René; Baither, D.; Winter, Martin; Passerini, Stefano

doi:10.1002/aenm.201200735

Cited by 324 publications

(327 citation statements)

References 79 publications

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“…As discussed previously, an additional reaction was proposed accounting for the extra specific capacity increase caused by the LiZn alloy formation. 10 It should be noted here that the distinction of the alloying reaction was made during the first lithiation step that made up a fully amorphous phase consisting of highly dispersed LiZn and Fe 0 in an amorphous Li 2 O matrix. After the subsequent delithiation sweep, the formation of ZnO and Fe 2 O 3 appears likely (see Figure 2), but a mixture of ZnO, Fe 2 O 3 , and Zn x Fe 2+x O 4 (x ≤ 1) is also conceivable, although the definite structural composition in the charged (delithiated) state is not yet fully understood.…”

Section: ■ Discussionmentioning

confidence: 99%

“…Additionally, the carbon coating is observed to enhance the electrode kinetics by ensuring electron supply to the nanoparticles. 10 This good rate performance suggests us that ion diffusion cannot be regarded as a limiting process of the electrode kinetic response and that ZnFe 2 O 4 −C based anodes are proper candidates to explore the kinetics of the lithiation mechanisms avoiding diffusion hindrance.…”

Section: ■ Introductionmentioning

confidence: 99%

“…At rates as high as 1 A g −1 only about 10% of the low-rate specific capacity is lost, and the rate advantage is preserved when compared to nanoparticulate LTO. 3,10 Carbon coating improves significantly not only the high rate capability of the resulting electrodes but also the cycling stability as well as the capacity retention after the applied C rate test. Comparing the discharge voltage profiles for carbon-coated ZnFe 2 O 4 −C and uncoated ZnFe 2 O 4 , an important reduction of the initial voltage drop is observed at elevated C rates for the former material.…”

Section: ■ Introductionmentioning

confidence: 99%

“…10 This is achieved by carbon coating ZnFe 2 O 4 nanoparticles, resulting in an amorphous carbon shell covering them. This procedure assures specific capacities of ca.…”

Section: ■ Introductionmentioning

confidence: 99%

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Probing Lithiation Kinetics of Carbon-Coated ZnFe₂O₄ Nanoparticle Battery Anodes

et al. 2014

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The investigation of the lithiation−delithiation kinetics of anodes comprising carbon-coated ZnFe 2 O 4 nanoparticles is reported in here. The study confirmed that, as occurring with other conversion electrodes, lithiation of ZnFe 2 O 4 nanoparticles is a multistep process involving the presence of intermediate Li−Zn−Fe−O phases as precursors for the formation of amorphous Li 2 O. A detailed knowledge on the reaction kinetics of the involved electrochemical mechanisms has been achieved by using impedance spectroscopy. It has been observed that lithiation reactions introduce a long delay that limits the electrode charging, not related to diffusion mechanisms. The sloping curve following the conversion plateau of the galvanostatic discharge is connected to a retardation effect in the reaction kinetics. This limitation is seen as an additional resistive process originated by the specific lithiation microscopic features. It is concluded that capacitance spectra allow distinguishing two separate processes: formation of kinetically favored intermediate Li−Zn−Fe−O phases and subsequent reaction to produce highly dispersed LiZn and Fe 0 in an amorphous Li 2 O matrix. A detailed electrical model is provided accounting for the overall electrode lithiation process. ■ INTRODUCTIONLi-ion batteries have become core devices for the consumer electronics industry. Materials for commercial battery electrodes are mostly chosen from a set of intercalation compounds that reversibly accommodate lithium ions in host sites in the lattice without severely distorting the structure. In most transition metal compounds such as LiCoO 2 , LiNi 1−y−z Mn y Co z O 2 , LiFePO 4 , and Li 4 Ti 5 O 12, redox activity is restricted to a few exchanged electrons. Therefore, intercalation materials exhibit intrinsic limitations that make them unviable when high capacity requirements have to be fulfilled as in the case of large scale or automotive applications.1−3 During the past decades a new family of electrode materials operating under the so-called conversion reaction has been intensely studied.4 For these compounds lithiation occurs through the reaction that involves a complete metal reduction as M a X b + (bn)Li ↔ aM + bLi n X, where M = transition metal, X = anion (O, S, N, P, and F), and n = anion formal oxidation state. Conversion reaction is able to accommodate larger amount of Li atoms into the lithium binary compound Li n X, which explains specific capacities exceeding 1000 mAh g −1 as reported for many compounds. Interestingly, conversion materials usually show good reversibility because of the formation of a nanostructured matrix that comprises metallic nanoparticles surrounded by amorphous Li n X phases. Intimate phase contact facilitates reactivity as evidenced by the observation of remaining metallic nanoparticles after extended oxidation/ reduction cycling. 4 Despite their potentialities, conversion compounds present a series of performance limitations that hinders their straightforward application in commercial devices. There...

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Section: ■ Discussionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

“…10 This is achieved by carbon coating ZnFe 2 O 4 nanoparticles, resulting in an amorphous carbon shell covering them. This procedure assures specific capacities of ca.…”

Section: ■ Introductionmentioning

confidence: 99%

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Probing Lithiation Kinetics of Carbon-Coated ZnFe₂O₄ Nanoparticle Battery Anodes

et al. 2014

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“…42,62,63 For the electrode preparation, 0.01 g of CMC was dissolved in 0.8 mL of deionized H 2 O. Subsequently, 0.07 g of TiO 2 (B) and 0.02 g of conductive carbon were added.…”

Section: Methodsmentioning

confidence: 99%

Nanocrystalline TiO₂(B) as Anode Material for Sodium-Ion Batteries

Wu¹,

Bresser²,

Buchholz³

et al. 2014

J. Electrochem. Soc.

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111

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High surface area, nanostructured, and phase-pure TiO 2 (B) noodles-like secondary particles were successfully synthesized by a facile one-pot synthesis, based on the hydrolysis of TiCl 3 using a mixture of ethylene glycol and water at moderate temperature. The primary nanoparticles have a uniform size and are about 15 nm in diameter as determined by TEM analysis and exhibit an increased exposure of the (010) facet as indicated by XRD analysis. Unlike the electrochemical reaction with lithium, the application as sodiumion electrode material reveals substantial differences, including the initial amorphization of the TiO 2 (B) particles, accompanied by a partial irreversibility of the sodium storage, presumably related to sodium trapping inside the active material particles and the absence of a stable solid electrolyte interphase, as indicated by galvanostatic cycling and electrochemical impedance spectroscopy, respectively. Besides, TiO 2 (B)-based electrodes show a stabilized reversible capacity of about 100 mAh g −1 and a very good C rate capability. While sodium-ion batteries were initially considered only as lowcost alternative for lithium-ion batteries with a particular focus on their application as stationary energy storage devices, 1-3 recent developments indicated that such devices might provide even similar energy densities in case suitable cathode and anode active materials are combined. [4][5][6] However, particularly regarding the anode side, the identification of long-term stable, environmentally friendly, and abundant active materials, providing high specific capacities and operating at a reasonably low potential, is still considered to be one of the major challenges for this technology. 4,6,7 47 Among these, the best results in terms of specific capacity, long-term cycling stability, and high rate capability were certainly reported for anatase TiO 2 . [40][41][42][43] However, the reversible sodium storage mechanism is obviously different from the classic (de-)insertion mechanism known for lithium, [48][49][50][51][52][53] as an initial reduction of TiO 2 to metallic titanium and an amorphous sodium titanate occurs. 42 TiO 2 (B) is a very well performing anode material for lithium-ion applications, 54-60 but so far -to the best of our knowledge -only one study reported its application as sodium-ion active material. The electrochemical performance, which might be best described by a rather rapid initial capacity fading and a low reversible capacity of about 50 mAh g −1 , is certainly not that promising, 47 although this might be also related to the cut-off potentials of 3.0 and 0.8 V vs. Na/Na + . Besides, the authors observed a rather huge expansion of the (001) 3+ and Ti 4+ at the nanotubes surface, while the general morphology of the tubes remained after sodiation. Consequently, a solid solution mechanism for the reversible sodium ion (de-)insertion comparable to the lithium ion storage mechanism was proposed.Herein, however, we show that TiO 2 (B) -similarly to anatase TiO 2 -presents a rath...

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Anticipated Progress in the Near‐ to Mid‐Term Future of LIBs

Myung

Kim

Sun

2020

Encyclopedia of Electrochemistry

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Since its commercialization in 1991, lithium‐ion batteries have been continuously studied to develop its energy density, power capability, and long‐term cycling characteristics. Unlike the earlier lithium‐ion battery based on the intercalation reaction such as LiCoO 2 cathode and graphite anode, various materials and reaction mechanisms have been investigated with the development of the technology. Also, in accordance with the improvement of the overall properties, lithium‐ion batteries are also being applied as energy storage systems (ESSs) for renewable energy facilities as well as power systems for electric vehicles (EVs). Moreover, in order to reduce the risk of explosion and to improve the stability of the battery, the electrolytes and separators in lithium‐ion batteries have been widely studied. This article highlights the current trend of the developments on the representative components in lithium‐ion battery.

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Carbon Coated ZnFe₂O₄ Nanoparticles for Advanced Lithium‐Ion Anodes

Cited by 324 publications

References 79 publications

Probing Lithiation Kinetics of Carbon-Coated ZnFe₂O₄ Nanoparticle Battery Anodes

Probing Lithiation Kinetics of Carbon-Coated ZnFe₂O₄ Nanoparticle Battery Anodes

Nanocrystalline TiO₂(B) as Anode Material for Sodium-Ion Batteries

Anticipated Progress in the Near‐ to Mid‐Term Future of LIBs

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Carbon Coated ZnFe2O4 Nanoparticles for Advanced Lithium‐Ion Anodes

Cited by 324 publications

References 79 publications

Probing Lithiation Kinetics of Carbon-Coated ZnFe2O4 Nanoparticle Battery Anodes

Probing Lithiation Kinetics of Carbon-Coated ZnFe2O4 Nanoparticle Battery Anodes

Nanocrystalline TiO2(B) as Anode Material for Sodium-Ion Batteries

Anticipated Progress in the Near‐ to Mid‐Term Future of LIBs

Contact Info

Product

Resources

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Carbon Coated ZnFe₂O₄ Nanoparticles for Advanced Lithium‐Ion Anodes

Probing Lithiation Kinetics of Carbon-Coated ZnFe₂O₄ Nanoparticle Battery Anodes

Probing Lithiation Kinetics of Carbon-Coated ZnFe₂O₄ Nanoparticle Battery Anodes

Nanocrystalline TiO₂(B) as Anode Material for Sodium-Ion Batteries