The importance of “going nano” for high power battery materials

Bresser, Dominic; Paillard, Elie; Copley, Mark; Bishop, P J; Winter, Martin; Passerini, Stefano

doi:10.1016/j.jpowsour.2012.07.035

Cited by 74 publications

(74 citation statements)

References 36 publications

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“…43 Following our previous investigation, 21 the electrode slurries were cast on copper foil. In fact, this combination (LTO-CMC-Cu) is expected to enable the optimum electrochemical performance of nanoparticulate The results, obtained by galvanostatic cycling of such electrodes, are presented in Figure 6.…”

Section: Resultsmentioning

confidence: 99%

“…9,13,[18][19][20][21] Indeed, downsizing the particle size to the nanometer-scale resulted in excellent power performance, 21-25 allowing (dis-)charging LTObased electrodes in as little as a few seconds. However, one of the major challenges toward the commercialization of nano-sized LTO is the development of easily scalable synthesis methods, providing large batches of active material at competitive prices.…”

mentioning

confidence: 99%

“…2 While the enhanced safety and advanced long-term cycling stability, resulting from the relatively higher lithium (de-)insertion potential and the negligible volume variation upon (de-)lithiation, [14][15][16][17] respectively, are, to a great extent intrinsic to LTO, the high power performance, i.e., the rate capability, of the material is highly dependent on the utilized synthesis method and the resulting particle size and morphology. 9,13,[18][19][20][21] Indeed, downsizing the particle size to the nanometer-scale resulted in excellent power performance, [21][22][23][24][25] allowing (dis-)charging LTObased electrodes in as little as a few seconds. However, one of the major challenges toward the commercialization of nano-sized LTO is the development of easily scalable synthesis methods, providing large batches of active material at competitive prices.…”

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confidence: 99%

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Scaling up “Nano” Li₄Ti₅O₁₂for High-Power Lithium-Ion Anodes Using Large Scale Flame Spray Pyrolysis

Birrozzi

Copley

Zamory

et al. 2015

J. Electrochem. Soc.

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Herein, we present the upscaled synthesis of nanoparticulate Li 4 Ti 5 O 12 (LTO) by means of flame spray pyrolysis (FSP), yielding high phase purity and appropriate morphology for application as high-power lithium-ion anode material. Electrodes based on this optimized LTO nanopowder, carboxymethyl cellulose (CMC) as binder, and copper as current collector revealed excellent rate performance, providing specific capacities of 133, 131, 129, 127, 124, and 115 mAh g −1 when applying C rates of 1C, 2C, 5C, 10C, 20C, and 50C, respectively. Targeting the commercial application of thus synthesized nanoparticles, we optimized also the electrode composition, comparing three different binding agents (CMC, PVdF, and poly(acrylic acid), PAA) and substituting the copper current collector by aluminum. The results of this comparative analysis show, that the combination of nanoparticulate LTO, CMC, and an aluminum current collector appears most suitable toward the realization of environmentally friendly and cost-efficient lithium-ion anodes, presenting very stable cycling performance for more than 1000 cycles at 10C without substantial capacity decay. While lithium-ion batteries are already the energy storage device of choice for portable electronic devices, they are recently gaining importance for large-scale applications like (hybrid) electric vehicles and stationary energy storage.1-5 However, beside advances regarding the energy density, such applications still require an improved safety, long-term cycling stability, as well as enhanced power densities with respect to state-of-the-art lithium-ion cells, commonly employing graphite as anode material.1-5 Spinel-structured Li 4 Ti 5 O 12 (LTO), reported for the first time by Colbow et al. in 1989, 6 is presently considered as one of the most promising alternative anode materials for realizing safer, long-lasting, high power lithium-ion batteries 7-13 and is, for such reasons, already utilized in commercial cells.2 While the enhanced safety and advanced long-term cycling stability, resulting from the relatively higher lithium (de-)insertion potential and the negligible volume variation upon (de-)lithiation, 14-17 respectively, are, to a great extent intrinsic to LTO, the high power performance, i.e., the rate capability, of the material is highly dependent on the utilized synthesis method and the resulting particle size and morphology. 9,13,[18][19][20][21] Indeed, downsizing the particle size to the nanometer-scale resulted in excellent power performance, 21-25 allowing (dis-)charging LTObased electrodes in as little as a few seconds. However, one of the major challenges toward the commercialization of nano-sized LTO is the development of easily scalable synthesis methods, providing large batches of active material at competitive prices.13 A highly attractive method for the large-scale preparation of metal oxide nanoparticles appears to be flame spray pyrolysis (FSP). 26,27 We have recently reported the electrochemical characterization of the first generation of FSP-synthesi...

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Section: Resultsmentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

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Scaling up “Nano” Li₄Ti₅O₁₂for High-Power Lithium-Ion Anodes Using Large Scale Flame Spray Pyrolysis

Birrozzi

Copley

Zamory

et al. 2015

J. Electrochem. Soc.

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“…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%

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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“…There are mainly three types of anode materials for LIBs according to the different lithiation storage mechanisms: (I) intercalation materials such as graphite 6 and insertion materials such as Li 4 Ti 5 O 12 spinel oxides or TiO 2 anatase, [7][8][9] (II) the so called "lithium alloying" materials, such as Si, Sn and Ge forming intermetallic phases with Li, [10][11][12][13] which depending on the used metals have various operating discharge potentials, with Si showing the lowest potential 11 and (III) conversion materials, such as transition metal oxides, -sufides or -nitrides, which store charge via a conversion reaction. The conversion reaction can be generalized by the equation: M a X b + (b · n) Li + + (b · n) e -a M + b Li n X, where M is the transition metal, X is the anion (most commonly oxygen in the case of anode materials) and n is the formal oxidation state of X.…”

Section: Introductionmentioning

confidence: 99%

Nanostructured ZnFe2O4 as Anode Material for Lithium-Ion Batteries: Ionic Liquid-Assisted Synthesis and Performance Evaluation with Special Emphasis on Comparative Metal Dissolution

Jia

Kloepsch

et al. 2016

ACSi

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In memoriam of Janez (Janko) Jamnik, a brilliant scientist with an exceptional combination of great leadership capabilities and a friendly and kind personality AbstractIn this work, a ZnFe 2 O 4 anode material was successfully synthesized by a novel ionic liquid-assisted synthesis method followed by a carbon coating procedure. The as-prepared ZnFe 2 O 4 particles demonstrate a relatively homogeneous particle size distribution with particle diameters ranging from 40 to 80 nm. This material, which is well known to offer an interesting combination of an alloying and conversion mechanism, is capable of accommodating nine equivalents of lithium per unit formula, resulting in a high specific capacity (≥ 1,000 mAh g -1 ). The resulting composite anode material displayed a stable capacity of ca. 1,091 mAh g -1 for 190 cycles at a medium de-lithiation potential of 1.7 V and at a charge/discharge rate of 1C. Furthermore, the material displays an excellent high rate capability up to 20C, displaying a reversible capacity of still 216 mAh g -1 . Studies on Fe and Zn losses of the ZnFe 2 O 4 active material by dissolution in the electrolyte were performed and compared to those of silicon-, germanium-and tin-based high-capacity anode materials. In conclusion, ion dissolution from metal containing anode materials should not be underestimated in view of its impact on the overall cell performance and cycling stability.

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The importance of “going nano” for high power battery materials

Cited by 74 publications

References 36 publications

Scaling up “Nano” Li₄Ti₅O₁₂for High-Power Lithium-Ion Anodes Using Large Scale Flame Spray Pyrolysis

Scaling up “Nano” Li₄Ti₅O₁₂for High-Power Lithium-Ion Anodes Using Large Scale Flame Spray Pyrolysis

Probing Lithiation Kinetics of Carbon-Coated ZnFe₂O₄ Nanoparticle Battery Anodes

Nanostructured ZnFe2O4 as Anode Material for Lithium-Ion Batteries: Ionic Liquid-Assisted Synthesis and Performance Evaluation with Special Emphasis on Comparative Metal Dissolution

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The importance of “going nano” for high power battery materials

Cited by 74 publications

References 36 publications

Scaling up “Nano” Li4Ti5O12for High-Power Lithium-Ion Anodes Using Large Scale Flame Spray Pyrolysis

Scaling up “Nano” Li4Ti5O12for High-Power Lithium-Ion Anodes Using Large Scale Flame Spray Pyrolysis

Probing Lithiation Kinetics of Carbon-Coated ZnFe2O4 Nanoparticle Battery Anodes

Nanostructured ZnFe2O4 as Anode Material for Lithium-Ion Batteries: Ionic Liquid-Assisted Synthesis and Performance Evaluation with Special Emphasis on Comparative Metal Dissolution

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Scaling up “Nano” Li₄Ti₅O₁₂for High-Power Lithium-Ion Anodes Using Large Scale Flame Spray Pyrolysis

Scaling up “Nano” Li₄Ti₅O₁₂for High-Power Lithium-Ion Anodes Using Large Scale Flame Spray Pyrolysis

Probing Lithiation Kinetics of Carbon-Coated ZnFe₂O₄ Nanoparticle Battery Anodes