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1. (Digital Presentation) Ultrathin Stabilized Zn Metal Anode for Highly Reversible Aqueous Zn-Ion Batteries

   https://doi.org/10.1149/MA2022-024439mtgabs  

   Zhang, Yuxuan ; Song, Han Wook ; Lee, Sunghwan ( October 2022 , ECS Meeting Abstracts)

   Ever-increasing demands for energy, particularly being environmentally friendly have promoted the transition from fossil fuels to renewable energy.¹Lithium-ion batteries (LIBs), arguably the most well-studied energy storage system, have dominated the energy market since their advent in the 1990s.²However, challenging issues regarding safety, supply of lithium, and high price of lithium resources limit the further advancement of LIBs for large-scale energy storage applications.³Therefore, attention is being concentrated on an alternative electrochemical energy storage device that features high safety, low cost, and long cycle life. Rechargeable aqueous zinc-ion batteries (ZIBs) is considered one of the most promising alternative energy storage systems due to the high theoretical energy and power densities where the multiple electrons (Zn²⁺) . In addition, aqueous ZIBs are safer due to non-flammable electrolyte (e.g., typically aqueous solution) and can be manufactured since they can be assembled in ambient air conditions.⁴As an essential component in aqueous Zn-based batteries, the Zn metal anode generally suffers from the growth of dendrites, which would affect battery performance in several ways. Second, the led by the loose structure of Zn dendrite may reduce the coulombic efficiency and shorten the battery lifespan.⁵

   Several approaches were suggested to improve the electrochemical stability of ZIBs, such as implementing an interfacial buffer layer that separates the active Zn from the bulk electrolyte.⁶However, the and thick thickness of the conventional Zn metal foils remain a critical challenge in this field, which may diminish the energy density of the battery drastically. According to a theretical calculation, the thickness of a Zn metal anode with an areal capacity of 1 mAh cm^-2is about 1.7 μm. However, existing extrusion-based fabrication technologies are not capable of downscaling the thickness Zn metal foils below 20 μm.

   Herein, we demonstrate a thickness controllable coating approach to fabricate an ultrathin Zn metal anode as well as a thin dielectric oxide separator. First, a 1.7 μm Zn layer was uniformly thermally evaporated onto a Cu foil. Then, Al₂O₃, the separator was deposited through sputtering on the Zn layer to a thickness of 10 nm. The inert and high hardness Al₂O₃layer is expected to lower the polarization and restrain the growth of Zn dendrites. Atomic force microscopy was employed to evaluate the roughness of the surface of the deposited Zn and Al₂O₃/Zn anode structures. Long-term cycling stability was gauged under the symmetrical cells at 0.5 mA cm^-2for 1 mAh cm^-2. Then the fabricated Zn anode was paired with MnO₂as a full cell for further electrochemical performance testing. To investigate the evolution of the interface between the Zn anode and the electrolyte, a home-developed in-situ optical observation battery cage was employed to record and compare the process of Zn deposition on the anodes of the Al₂O₃/Zn (demonstrated in this study) and the procured thick Zn anode. The surface morphology of the two Zn anodes after circulation was characterized and compared through scanning electron microscopy. The tunable ultrathin Zn metal anode with enhanced anode stability provides a pathway for future high-energy-density Zn-ion batteries.

   Obama, B., The irreversible momentum of clean energy.Science2017,355(6321), 126-129.

   Goodenough, J. B.; Park, K. S., The Li-ion rechargeable battery: a perspective.J Am Chem Soc2013,135(4), 1167-76.

   Li, C.; Xie, X.; Liang, S.; Zhou, J., Issues and Future Perspective on Zinc Metal Anode for Rechargeable Aqueous Zinc‐ion Batteries.Energy & Environmental Materials2020,3(2), 146-159.

   Jia, H.; Wang, Z.; Tawiah, B.; Wang, Y.; Chan, C.-Y.; Fei, B.; Pan, F., Recent advances in zinc anodes for high-performance aqueous Zn-ion batteries.Nano Energy2020,70.

   Yang, J.; Yin, B.; Sun, Y.; Pan, H.; Sun, W.; Jia, B.; Zhang, S.; Ma, T., Zinc Anode for Mild Aqueous Zinc-Ion Batteries: Challenges, Strategies, and Perspectives.Nanomicro Lett2022,14(1), 42.

   Yang, Q.; Li, Q.; Liu, Z.; Wang, D.; Guo, Y.; Li, X.; Tang, Y.; Li, H.; Dong, B.; Zhi, C., Dendrites in Zn-Based Batteries.Adv Mater2020,32(48), e2001854.

   Acknowledgment

   This work was partially supported by the U.S. National Science Foundation (NSF) Award No. ECCS-1931088. S.L. and H.W.S. acknowledge the support from the Improvement of Measurement Standards and Technology for Mechanical Metrology (Grant No. 22011044) by KRISS.

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2. Facile Functionalization of Graphene to Tune Response of Printed Electrochemical Sensors to Neurotransmitters

   https://doi.org/10.1149/MA2023-01532651mtgabs  

   Kammarchedu, Vinay ; Butler, Derrick ; Khamsi, Pouya Soltan ; Ebrahimi, Aida ( August 2023 , ECS Meeting Abstracts)

   Neurotransmitters are small molecules involved in neuronal signaling and can also serve as stress biomarkers.¹Their abnormal levels have been also proposed to be indicative of several neurological diseases such as Alzheimer’s disease, Parkinson’s disease, Huntington disease, among others. Hence, measuring their levels is highly important for early diagnosis, therapy, and disease prognosis. In this work, we investigate facile functionalization methods to tune and enhance sensitivity of printed graphene sensors to neurotransmitters. Sensors based on direct laser scribing and screen-printed graphene ink are studied. These printing methods offer ease of prototyping and scalable fabrication at low cost.

   The effect of functionalization of laser induced graphene (LIG) by electrodeposition and solution-based deposition of TMDs (molybdenum disulfide²and tungsten disulfide) and metal nanoparticles is studied. For different processing methods, electrochemical characteristics (such as electrochemically active surface area: ECSA and heterogenous electron transfer rate: k⁰) are extracted and correlated to surface chemistry and defect density obtained respectively using X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. These functionalization methods are observed to directly impact the sensitivity and limit of detection (LOD) of the graphene sensors for the studied neurotransmitters. For example, as compared to bare LIG, it is observed that electrodeposition of MoS₂on LIG improves ECSA by 3 times and k⁰by 1.5 times.³Electrodeposition of MoS₂also significantly reduces LOD of serotonin and dopamine in saliva, enabling detection of their physiologically relevant concentrations (in pM-nM range). In addition, chemical treatment of LIG sensors is carried out in the form of acetic acid treatment. Acetic acid treatment has been shown previously to improve C-C bonds improving the conductivity of LIG sensors.⁴In our work, in particular, acetic acid treatment leads to larger improvement of LOD of norepinephrine compared to MoS₂electrodeposition.

   In addition, we investigate the effect of plasma treatment to tune the sensor response by modifying the defect density and chemistry. For example, we find that oxygen plasma treatment of screen-printed graphene ink greatly improves LOD of norepinephrine up to three orders of magnitude, which may be attributed to the increased defects and oxygen functional groups on the surface as evident by XPS measurements. Defects are known to play a key role in enhancing the sensitivity of 2D materials to surface interactions, and have been explored in tuning/enhancing the sensor sensitivity.⁵Building on our previous work,³we apply a custom machine learning-based data processing method to further improve that sensitivity and LOD, and also to automatically benchmark different molecule-material pairs.

   Future work includes expanding the plasma chemistry and conditions, studying the effect of precursor mixture in laser-induced solution-based functionalization, and understanding the interplay between molecule-material system. Work is also underway to improve the machine learning model by using nonlinear learning models such as neural networks to improve the sensor sensitivity, selectivity, and robustness.

   References

   A. J. Steckl, P. Ray, (2018), doi:10.1021/acssensors.8b00726.

   Y. Lei, D. Butler, M. C. Lucking, F. Zhang, T. Xia, K. Fujisawa, T. Granzier-Nakajima, R. Cruz-Silva, M. Endo, H. Terrones, M. Terrones, A. Ebrahimi,Sci. Adv.6, 4250–4257 (2020).

   V. Kammarchedu, D. Butler, A. Ebrahimi,Anal. Chim. Acta.1232, 340447 (2022).

   H. Yoon, J. Nah, H. Kim, S. Ko, M. Sharifuzzaman, S. C. Barman, X. Xuan, J. Kim, J. Y. Park,Sensors Actuators B Chem.311, 127866 (2020).

   T. Wu, A. Alharbi, R. Kiani, D. Shahrjerdi,Adv. Mater.31, 1–12 (2019).

    

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3. Discovery of a Damped Lyα Absorber Originating in a Spectacular Interacting Dwarf Galaxy Pair at z = 0.026

   https://doi.org/10.3847/2041-8213/ac5250  

   Boettcher, Erin ; Gupta, Neeraj ; Chen, Hsiao-Wen ; Chen, Mandy C. ; Józsa, Gyula I. G. ; Rudie, Gwen C. ; Cantalupo, Sebastiano ; Johnson, Sean D. ; Balashev, S. A. ; Combes, Françoise ; et al ( February 2022 , The Astrophysical Journal Letters)

   We present the discovery of neutral gas detected in both damped Lyαabsorption (DLA) and Hi21 cm emission outside of the stellar body of a galaxy, the first such detection in the literature. A joint analysis between the Cosmic Ultraviolet Baryon Survey and the MeerKAT Absorption Line Survey reveals an Hibridge connecting two interacting dwarf galaxies (log (M_star/M_⊙) = 8.5 ± 0.2) that host az= 0.026 DLA with log[N(Hi)/cm⁻²] = 20.60 ± 0.05 toward the QSO J2339−5523 (z_QSO= 1.35). At impact parameters ofd= 6 and 33 kpc, the dwarf galaxies have no companions more luminous than ≈0.05L_*within at least Δv= ±300 km s⁻¹andd≈ 350 kpc. The Hi21 cm emission is spatially coincident with the DLA at the 2σ–3σlevel per spectral channel over several adjacent beams. However, Hi21 cm absorption is not detected against the radio-bright QSO; if the background UV and radio sources are spatially aligned, the gas is either warm or clumpy (with a spin temperature to covering factor ratioT_s/f_c> 1880 K). Observations with VLT-MUSE demonstrate that theα-element abundance of the ionized interstellar medium (ISM) is consistent with the DLA (≈10% solar), suggesting that the neutral gas envelope is perturbed ISM gas. This study showcases the impact of dwarf–dwarf interactions on the physical and chemical state of neutral gas outside of star-forming regions. In the SKA era, joint UV and Hi21 cm analyses will be critical for connecting the cosmic neutral gas content to galaxy environments.

    

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4. A Stable, Low Permeable TEMPO Catholyte for Aqueous Total Organic Redox Flow Batteries

   https://doi.org/10.1002/aenm.202102577  

   Hu, Bo ; Hu, Maowei ; Luo, Jian ; Liu, T. Leo ( December 2021 , Advanced Energy Materials)

   Aqueous organic redox flow batteries (AORFBs) are highly attractive for large‐scale energy storage because of their nonflammability, low cost, and sustainability. (2,2,6,6‐Tetramethylpiperidin‐1‐yl)oxyl (TEMPO) derivatives, a class of redox active molecules bearing air‐stable free nitroxyl radicals and high redox potential (>0.8 V vs NHE), has been identified as promising catholytes for AORFBs. However, reported TEMPO based molecules are either permeable through ion exchange membranes or not chemically stable enough for long‐term energy storage. Herein, a new TEMPO derivative functionalized with a dual‐ammonium dicationic group,N¹, N¹, N¹, N³, N³, 2, 2, 6, 6‐nonamethyl‐N³‐(piperidinyloxy)propane‐1,3‐bis(ammonium) dichloride (N₂‐TEMPO) as a stable, low permeable catholyte for AORFBs is reported. Ultraviolet–visible (UV–vis) and proton nuclear magnetic resonance (¹H‐NMR) spectroscopic studies reveal its exceptional stability and ultra‐low permeability (1.49 × 10⁻¹² cm² s⁻¹). Coupled with 1,1′‐bis[3‐(trimethylammonio)propyl]‐4,4′‐bipyridinium tetrachloride ((NPr)₂V) as an anolyte, a 1.35 VN₂‐TEMPO/(NPr)₂V AORFB with 0.5 melectrolytes (9.05 Wh L⁻¹) delivers a high power density of 114 mW cm⁻²and 100% capacity retention for 400 cycles at 60 mA cm⁻². At 1.0 melectrolyte concentrations, theN₂‐TEMPO/(NPr)₂V AORFB achieves an energy density of 18.1 Wh L⁻¹and capacity retention of 90% for 400 cycles at 60 mA cm⁻².

    

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5. A Nonheme Mononuclear {FeNO} 7 Complex that Produces N 2 O in the Absence of an Exogenous Reductant

   https://doi.org/10.1002/ange.202109062  

   Dey, Aniruddha ; Gordon, Jesse B. ; Albert, Therese ; Sabuncu, Sinan ; Siegler, Maxime A. ; MacMillan, Samantha N. ; Lancaster, Kyle M. ; Moënne‐Loccoz, Pierre ; Goldberg, David P. ( August 2021 , Angewandte Chemie)

   A new nonheme iron(II) complex, Fe^II(Me₃TACN)((OSi^Ph2)₂O) (1), is reported. Reaction of1with NO_(g)gives a stable mononitrosyl complex Fe(NO)(Me₃TACN)((OSi^Ph2)₂O) (2), which was characterized by Mössbauer (δ=0.52 mm s⁻¹, |ΔE_Q|=0.80 mm s⁻¹), EPR (S=3/2), resonance Raman (RR) and Fe K‐edge X‐ray absorption spectroscopies. The data show that2is an {FeNO}⁷complex with anS=3/2 spin ground state. The RR spectrum (λ_exc=458 nm) of2combined with isotopic labeling (¹⁵N,¹⁸O) reveals ν(N‐O)=1680 cm⁻¹, which is highly activated, and is a nearly identical match to that seen for the reactive mononitrosyl intermediate in the nonheme iron enzyme FDPnor (ν(NO)=1681 cm⁻¹). Complex2reacts rapidly with H₂O in THF to produce the N‐N coupled product N₂O, providing the first example of a mononuclear nonheme iron complex that is capable of converting NO to N₂O in the absence of an exogenous reductant.

    

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