More Like this

1. (Digital Presentation) Accelerating the Conversion Process of Polysulfides in High Mass Loading Sulfur Cathode for the Longevity Li-S Battery

   https://doi.org/10.1149/MA2022-012383mtgabs  

   Zhang, Yuxuan ; Kivevele, Thomas ; Song, Han Wook ; Lee, Sunghwan ( July 2022 , ECS Meeting Abstracts)

   Conventional lithium-ion batteries are unable to meet the increasing demands for high-energy storage systems, because of their limited theoretical capacity. 1 In recent years, intensive attention has been paid to enhancing battery energy storage capability to satisfy the increasing energy demand in modern society and reduce the average energy capacity cost. Among the candidates for next generation high energy storage systems, the lithium sulfur battery is especially attractive because of its high theoretical specific energy (around 2600 W h kg-1) and potential cost reduction. In addition, sulfur is a cost effective and environmentally friendly material due to its abundance and low-toxicity. 2 Despite all of these advantages, the practical application of lithium sulfur batteries to date has been hindered by a series of obstacles, including low active material loading, poor cycle life, and sluggish sulfur conversion kinetics. 3 Achieving high mass loading cathode in the traditional 2D planar thick electrode has been challenged. The high distorsion of the traditional planar thick electrodes for ion/electron transfer leads to the limited utilization of active materials and high resistance, which eventually results in restricted energy density and accelerated electrode failure. 4 Furthermore, of the electrolyte to pores in the cathode and utilization ratio of active materials. Catalysts such as MnO 2 and Co dopants were employed to accelerate the sulfur conversion reaction during the charge and discharge process. 5 However, catalysts based on transition metals suffer from poor electronic conductivity. Other catalysts such as transition metal dopants are also limited due to the increased process complexities. . In addition, the severe shuttle effects in Li-S batteries may lead to fast failures of the battery. Constructing a protection layer on the separator for limiting the transmission of soluble polysulfides is considered an effective way to eliminate the shuttle phenomenon. However, the soluble sulfides still can largely dissolve around the cathode side causing the sluggish reaction condition for sulfur conversion. 5 To mitigate the issues above, herein we demonstrate a novel sulfur electrode design strategy enabled by additive manufacturing and oxidative vapor deposition (oCVD). Specifically, the electrode is strategically designed into a hierarchal hollow structure via stereolithography technique to increase sulfur usage. The active material concentration loaded to the battery cathode is controlled precisely during 3D printing by adjusting the number of printed layers. Owing to its freedom in geometry and structure, the suggested design is expected to improve the Li ions and electron transport rate considerably, and hence, the battery power density. The printed cathode is sintered at 700 °C at N 2 atmosphere to achieve carbonization of the cathode during which intrinsic carbon defects (e.g., pentagon carbon) as catalytic defect sites are in-situ generated on the cathode. The intrinsic carbon defects equipped with adequate electronic conductivity. The sintered 3D cathode is then transferred to the oCVD chamber for depositing a thin PEDOT layer as a protection layer to restrict dissolutions of sulfur compounds in the cathode. Density functional theory calculation reveals the electronic state variance between the structures with and without defects, the structure with defects demonstrates the higher kinetic condition for sulfur conversion. To further identify the favorable reaction dynamic process, the in-situ XRD is used to characterize the transformation between soluble and insoluble polysulfides, which is the main barrier in the charge and discharge process of Li-S batteries. The results show the oCVD coated 3D printed sulfur cathode exhibits a much higher kinetic process for sulfur conversion, which benefits from the highly tailored hierarchal hollow structure and the defects engineering on the cathode. Further, the oCVD coated 3D printed sulfur cathode also demonstrates higher stability during long cycling enabled by the oCVD PEDOT protection layer, which is verified by an absorption energy calculation of polysulfides at PEDOT. Such modeling and analysis help to elucidate the fundamental mechanisms that govern cathode performance and degradation in Li-S batteries. The current study also provides design strategies for the sulfur cathode as well as selection approaches to novel battery systems. References: Bhargav, A., (2020). Lithium-Sulfur Batteries: Attaining the Critical Metrics. Joule 4 , 285-291. Chung, S.-H., (2018). Progress on the Critical Parameters for Lithium–Sulfur Batteries to be Practically Viable. Advanced Functional Materials 28 , 1801188. Peng, H.-J.,(2017). Review on High-Loading and High-Energy Lithium–Sulfur Batteries. Advanced Energy Materials 7 , 1700260. Chu, T., (2021). 3D printing‐enabled advanced electrode architecture design. Carbon Energy 3 , 424-439. Shi, Z., (2021). Defect Engineering for Expediting Li–S Chemistry: Strategies, Mechanisms, and Perspectives. Advanced Energy Materials 11 . Figure 1 

   more » « less
2. Comparison of Lithium Diffusion Coefficient Measurements in Tellurium Electrodes via Different Electrochemical Techniques

   https://doi.org/10.1149/1945-7111/acd43e  

   Wang, Jing ; Koenig, Jr, Gary M. ( May 2023 , Journal of The Electrochemical Society)

   Both thin (55μm) composite and thick (350μm) all active material battery porous electrodes were prepared for estimating the diffusion coefficient of Li⁺($D_{{\mathit{Li}}^{+}})$in tellurium (Te) during electrochemical lithiation. Galvanostatic intermittent titration technique (GITT), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS) were applied to quantify the chemical lithium solid-state diffusion coefficient within the Te active material in the electrodes. Multiple methods of GITT and EIS were assessed. For the composite Te electrodes, the$D_{{\mathit{Li}}^{+}}$was on the order of 10⁻¹¹cm²s⁻¹from both CV and GITT methods, but 10⁻⁹cm²s⁻¹from EIS. For the thick tellurium electrodes, both GITT and EIS resulted in lithium diffusion coefficient estimates in the range of 10⁻¹¹–10⁻¹²cm²s⁻¹. The general trend across all methods that quantified the diffusion coefficient as a function of lithiation of tellurium was that the$D_{{\mathit{Li}}^{+}}$decreased rapidly when the Te material was initially lithiated. The$D_{{\mathit{Li}}^{+}}$at the phase transition voltage plateau (∼1.7 V, vs Li/Li⁺, where both Te and Li₂Te were expected) had the lowest$D_{{\mathit{Li}}^{+}},$while the$D_{{\mathit{Li}}^{+}}$both before and after the plateau was generally higher. Among all the electrochemical measurements of$D_{{\mathit{Li}}^{+}},$the modified GITT method with modelling the relaxation region resulted in relatively low scatter in the data, provided values as a function of lithiation, and was well suited to thick electrodes with a flat discharge plateau as was the case herein.

    

   more » « less
3. Electrochemical Fluoridation of Manganese Oxide by Perfluorinated‐Gas Conversion for Lithium‐Ion Cathodes

   https://doi.org/10.1002/batt.202100139  

   Gao, Haining ; He, Mingfu ; Guo, Rui ; Gallant, Betar M. ( September 2021 , Batteries & Supercaps)

   Fluoridation of Lithium‐ion (Li‐ion) cathodes is of growing interest for high‐capacity Li⁺storage materials, but well‐controlled fluoridation processes are elusive. We investigated an electrochemical methodology to grow lithium fluoride (LiF) by reduction of perfluorinated gas onto metal oxides (MO), which then forms M−O−F by splitting of LiF upon charge, using MnO as an example target phase. Unlike current methods where particle size <10 nm is necessary for high MnO utilization (subsequent discharge/lithiation capacity), owing to the nano‐crystallinity and intimate contact of electrochemically‐grown LiF, high MnO utilization (∼0.9 e⁻/MnO, 340 mAh g_MnO⁻¹) is achieved with large MnO particle size (∼400 nm), exceeding comparable MnO/LiF systems reported to date. Additionally, incorporation of perfluorinated‐gas additive benefits cycling, with capacity of ∼270 mAh g_MnO⁻¹retained after 20 cycles. This work demonstrates the opportunity for electrochemically driven fluoridation to achieve high capacities with larger particle sizes needed to bring oxyfluorides closer to practical reality.

    

   more » « less
4. (Digital Presentation) Activating the Ion Transmission at the Cathode-Electrolyte Interface in All-Solid-State Batteries

   https://doi.org/10.1149/MA2022-012384mtgabs  

   Zhang, Yuxuan ; Kivevele, Thomas ; Song, Han Wook ; Lee, Sunghwan ( July 2022 , ECS Meeting Abstracts)

   All-solid-state batteries (ASSBs) have garnered increasing attention due to the enhanced safety, featuring nonflammable solid electrolytes as well as the potential to achieve high energy density. 1 The advancement of the ASSBs is expected to provide, arguably, the most straightforward path towards practical, high-energy, and rechargeable batteries based on metallic anodes. 1 However, the sluggish ion transmission at the cathode-electrolyte (solid/solid) interface would result in the high resistant at the contact and limit the practical implementation of these all solid-state materials in real world batteries. 2 Several methods were suggested to enhance the kinetic condition of the ion migration between the cathode and the solid electrolyte (SE). 3 A composite strategy that mixes active materials and SEs for the cathode is a general way to decrease the ion transmission barrier at the cathode-electrolyte interface. 3 The active material concentration in the cathode is reduced as much as the SE portion increases by which the energy density of the ASSB is restricted. In addition, the mixing approach generally accompanies lattice mismatches between the cathode active materials and the SE, thus providing only limited improvements, which is imputed by random contacts between the cathode active materials and the SE during the mixing process. Implementing high-pressure for the electrode and electrolyte of ASSB in the assembling process has been verified is a but effective way to boost the ion transmission ability between the cathode active materials and the SE by decreasing the grain boundary impedance. Whereas the short-circuit of the battery would be induced by the mechanical deformation of the electrolyte under high pressure. 4 Herein, we demonstrate a novel way to address the ion transmission problem at the cathode-electrolyte interface in ASSBs. Starting from the cathode configuration, the finite element method (FEM) was employed to evaluate the current concentration and the distribution of the space charge layer at the cathode-electrolyte interface. Hierarchical three-dimensional (HTD) structures are found to have a higher Li + transfer number (t Li+ ), fewer free anions, and the weaker space-charge layer at the cathode-electrolyte interface in the resulting FEM simulation. To take advantage of the HTD structure, stereolithography is adopted as a manufacturing technique and single-crystalline Ni-rich (SCN) materials are selected as the active materials. Next, the manufactured HTD cathode is sintered at 600 °C in an N 2 atmosphere for the carbonization of the resin, which induces sufficient electronic conductivity for the cathode. Then, the gel-like Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 (LATP) precursor is synthesized and filled into the voids of the HTD structure cathode sufficiently. And the filled HTD structure cathodes are sintered at 900 °C to achieve the crystallization of the LATP gel. Scanning transmission electron microscopy (STEM) is used to unveil the morphology of the cathode-electrolyte interface between the sintered HTD cathode and the in-situ generated electrolyte (LATP). A transient phase has been found generated at the interface and matched with both lattices of the SCN and the SE, accelerating the transmission of the Li-ions, which is further verified by density functional theory calculations. In addition, Electron Energy Loss Spectroscopy demonstrates the preserved interface between HTD cathode and SEs. Atomic force microscopy is employed to measure the potential image of the cross-sectional interface by the peak force tapping mode. The average potential of modified samples is lower than the sample that mix SCN and SEs simply in the 2D planar structure, which confirms a weakened space charge layer by the enhanced contact capability as well as the ion transmission ability. To see if the demonstrated method is universally applicable, LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811) is selected as the cathode active material and manufactured in the same way as the SCN. The HTD cathode based on NCM811 exhibits higher electrochemical performance compared with the reference sample based on the 2D planar mixing-type cathode. We believe such a demonstrated universal strategy provides a new guideline to engineer the cathode/electrolyte interface by revolutionizing electrode structures that can be applicable to all-solid-state batteries. Figure 1. Schematic of comparing of traditional 2D planar cathode and HTD cathode in ASSB Tikekar, M. D. , et al. , Nature Energy (2016) 1 (9), 16114 Banerjee, A. , et al. , Chem Rev (2020) 120 (14), 6878 Chen, R. , et al. , Chem Rev (2020) 120 (14), 6820 Cheng, X. , et al. , Advanced Energy Materials (2018) 8 (7) Figure 1 

   more » « less
5. Phase transformation and electrochemical charge storage properties of vanadium oxide/carbon composite electrodes synthesized via integration with dopamine

   https://doi.org/10.1111/jace.18502  

   Andris, Ryan ; Averianov, Timofey ; Pomerantseva, Ekaterina ( April 2022 , Journal of the American Ceramic Society)

   Chemically preintercalated dopamine (DOPA) molecules were used as both reducing agent and carbon precursor to prepare δ-V2O5∙nH2O/C, H2V3O8/C, VO2(B)/C and V2O3/C nanocomposites via hydrothermal treatment or hydrothermal treatment followed by annealing under Ar flow. We found that the phase composition and morphology of the produced composites are influenced by the DOPA:V2O5 ratio used to synthesize (DOPA)xV2O5 precursors through DOPA diffusion into the interlayer region of δ-V2O5∙nH2O framework. The increase of DOPA concentration in the reaction mixture led to more pronounced reduction of vanadium and a higher fraction of carbon in the composites’ structure, as evidenced by XPS and Raman spectroscopy measurements. The electrochemical charge storage properties of the synthesized nanocomposites were evaluated in Li-ion cells with non-aqueous electrolyte. δ-V2O5∙nH2O/C, H2V3O8/C, VO2(B)/C, and V2O3/C electrodes delivered high initial capacities of 214, 252, 279, and 637 mAh·g–1, respectively. The insights provided by this investigation open up the possibility of creating new nanocomposite oxide/carbon electrodes for a variety of applications such as energy storage, sensing and electrochromic devices. 

   more » « less