Understanding conversion mechanism of NiO anodic materials for Li-ion battery using in situ X-ray absorption near edge structure spectroscopy

Jang, Jue‐Hyuk; Chae, Byung-Mok; Oh, Hyun-Jung; Lee, Yong‐Kul

doi:10.1016/j.jpowsour.2015.11.009

Cited by 12 publications

(6 citation statements)

References 32 publications

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“…• C are in close agreement with previous reports on various NiO nanostructures, 52,53 indicating that there is a significant amount of NiO present on the surface of the foam after heating. This is also in close agreement with the XRD results shown in Figure 1.…”

Section: Resultssupporting

confidence: 92%

Assessing Charge Contribution from Thermally Treated Ni Foam as Current Collectors for Li-Ion Batteries

Geaney

McNulty

O’Connell

et al. 2016

J. Electrochem. Soc.

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In this report we have investigated the use of Ni foam substrates as anode current collectors for Li-ion batteries. As the majority of reports in the literature focus on hydrothermal formation of materials on Ni foam followed by a high temperature anneal/oxidation step, we probed the fundamental electrochemical responses of as received Ni foam substrates and those subjected to heating at 100 • C, 300 • C and 450 • C. Through cyclic voltammetry and galvanostatic testing, it is shown that the as received and 100 • C annealed Ni foam show negligible electrochemical activity. However, Ni foams heated to higher temperature showed substantial electrochemical contributions which may lead to inflated capacities and incorrect interpretations of CV responses for samples subjected to high temperature anneals. XRD, XPS and SEM analyses clearly illustrate that the formation of electrochemically active NiO nanoparticles on the surface of the foam is responsible for this behavior. To further investigate the contribution of the oxidized Ni foam to the overall electrochemical response, we formed Co 3 O 4 nanoflowers directly on Ni foam at 450 • C and showed that the resulting electrochemical response was dominated by NiO after the first 10 charge/discharge cycles. This report highlights the importance of assessing current collector activity for active materials grown on transition metal foam current collectors for Li-ion applications. Lithium-ion batteries have found widespread use in portable electronic devices due to their improved performance in comparison with other battery chemistries (e.g. lead-acid, NiMH etc.).1-4 Stimulated by the need for improved batteries for more demanding applications, the field has seen a wave of interest in the development of novel materials for every component of the battery (anode, cathode, current collectors and electrolytes).5-10 Practically all literature studies focused on the development of materials for Li-ion batteries report specific capacities primarily in terms of mAhg −1 . 11-13 While the use of common specific capacity units allows different material systems to be compared quickly, it often means that important considerations for real-world applications are ignored. For example, materials with low tap densities or a high degree of porosity can lead to electrodes which exhibit fantastic capacities in terms of mAhg −1 but poor mass loadings and thus areal/volumetric capacities which are unsuited to real-world devices. This is particularly true for nanoscale materials which often lead to sub-mg level electrode mass loadings. In fact, it is well established that materials tend to perform better when using low mass loadings, 14-17 making the concept of using low mass loadings particularly attractive in terms of maximizing the calculated capacity in terms of mAhg −1 . Given that the merits of materials are often assessed solely on the specific capacity (in terms of mAhg −1 ), it is crucial that the specific capacity values calculated for a system is a genuine representation of the material...

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Section: Resultssupporting

confidence: 92%

Assessing Charge Contribution from Thermally Treated Ni Foam as Current Collectors for Li-Ion Batteries

Geaney

McNulty

O’Connell

et al. 2016

J. Electrochem. Soc.

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“…iii) Conversion (Redox) reaction: lithium ions can participate in the conversion reaction with the M x O y process directly and generate metal M and Li 2 O, which will participate in reaction in the subsequent cycles together with small volume change. The typical representative oxides are NiO, Co 3 O 4 , Fe 3 O 4, and MnO 2 , etc . iv) Both alloying/dealloying and conversion reaction: that is, lithium ions participate the electrochemical reactions through the two mechanisms at the same time, such as ZnM 2 O 4 (M = Co and Fe), CdFe 2 O 4 , M 2 SnO 4 (M = Co, Mn, Mg, and Zn) and metal carbonates, etc .…”

Section: Introductionmentioning

confidence: 99%

Ti‐Based Oxide Anode Materials for Advanced Electrochemical Energy Storage: Lithium/Sodium Ion Batteries and Hybrid Pseudocapacitors

Lou

Zhao

Wang

et al. 2019

Small

149

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The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/smll.201904740.Titanium-based oxides including TiO 2 and M-Ti-O compounds (M = Li, Nb, Na, etc.) family, exhibit advantageous structural dynamics (2D ion diffusion path, open and stable structure for ion accommodations) for practical applications in energy storage systems, such as lithium-ion batteries, sodium-ion batteries, and hybrid pseudocapacitors. Further, Ti-based oxides show high operating voltage relative to the deposition of alkali metal, ensuring full safety by avoiding the formation of lithium and sodium dendrites. On the other hand, high working potential prevents the decomposition of electrolyte, delivering excellent rate capability through the unique pseudocapacitive kinetics. Nevertheless, the intrinsic poor electrical conductivity and reaction dynamics limit further applications in energy storage devices. Recently, various work and in-depth understanding on the morphologies control, surface engineering, bulk-phase doping of Ti-based oxides, have been promoted to overcome these issues. Inspired by that, in this review, the authors summarize the fundamental issues, challenges and advances of Ti-based oxides in the applications of advanced electrochemical energy storage. Particularly, the authors focus on the progresses on the working mechanism and device applications from lithium-ion batteries to sodium-ion batteries, and then the hybrid pseudocapacitors. In addition, future perspectives for fundamental research and practical applications are discussed. www.advancedsciencenews.com

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“…For example, X-ray absorption spectroscopy (XAS) has been successfully implemented to investigate the average redox mechanisms since XAS can demonstrate the physicochemical variations with an emphasis on the oxidation states and local bonding properties (bonding neighbors, bond length, coordination numbers, etc. ). − Also, conversion-induced phase transformations and morphological changes have been identified with both ex situ and in situ transmission electron microscopy (TEM). − While structural evolutions during conversion (Li accommodation) have been intensively investigated, ,− during reconversion (Li extraction), they have been barely explored. The fundamental understanding of reconversion is still lacking although both reactions are evenly important for overall battery operations.…”

Section: Introductionmentioning

confidence: 99%

Asymmetric Reaction Pathways of Conversion-Type Electrodes for Lithium-Ion Batteries

Shadike

Kwon

et al. 2021

Chem. Mater.

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Metal oxides have been actively explored as promising conversion-type electrode materials for lithium-ion batteries due to high deliverable capacity but are still notorious for poor cyclability, capacity fading, voltage hysteresis, and so forth. However, the fundamental reason for the undesirable properties of metal oxides behind the repetitive conversion process is still obscure. In this work, we take advantage of synchrotron X-ray techniques as well as transmission electron microscopy to monitor the structural changes during both conversion (lithiation) and reconversion (delithiation) reactions. The difference in diffusion rates of lithium and metal plays a decisive role in determining the reaction pathway. We find that lithium accommodation and extraction occur via different reaction routes: lithiation follows a kinetically driven way while delithiation adopts a route close to the thermodynamic ground state path. Thermodynamic structural evolution features the formation of an intermediate phase of Li−metal (M)−O, suggesting that lithium removal accompanies the Li/ M ionic exchange and rearrangement of the oxygen framework. The slow diffusion of metal ions and the high kinetic and energy barrier for dissociating the intermediate phase are mainly responsible for uncompleted reconversion reaction, evidenced by the remaining Li−M−O phase at the end of charge. Imperfect reconversion reaction eventually limits the utilization of lithium ions over the repeated cycling. This work sheds light on structural changes occurring at metal oxides during both conversion and reconversion processes, which is strongly linked with the performances of conversion-type materials in applications.

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Understanding conversion mechanism of NiO anodic materials for Li-ion battery using in situ X-ray absorption near edge structure spectroscopy

Cited by 12 publications

References 32 publications

Assessing Charge Contribution from Thermally Treated Ni Foam as Current Collectors for Li-Ion Batteries

Assessing Charge Contribution from Thermally Treated Ni Foam as Current Collectors for Li-Ion Batteries

Ti‐Based Oxide Anode Materials for Advanced Electrochemical Energy Storage: Lithium/Sodium Ion Batteries and Hybrid Pseudocapacitors

Asymmetric Reaction Pathways of Conversion-Type Electrodes for Lithium-Ion Batteries

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