bluuebunny/crossref_metadata_2025 huggingface dataset:
Investigation of Ultra-Low Temperature Li/CF
x
Batteries in the Liquefied Gas Electrolyte
Authors: Liu Alex Ruili , Yin Yijie , Holoubek John , Li Weikang , Meng Shirley
Published: September 2023

Lithium-fluorinated carbon (Li/CFx) is one of the most promising chemistries to serve as a reliable high-energy density primary energy storage system in applications where rechargeability is not required. Though Li/CFx demonstrates high energy density (>2100 Wh kg–1) under ambient conditions, achieving such a high energy density when exposed to subzero temperatures remains challenging, particularly under high current density.

Liquefied gas electrolytes (LGE) are regarded as one of the most promising electrolyte systems, offering excellent ionic conductivities at wide temperature ranges from -80 to + 60 oC due to low viscosity and low freezing point of gas molecules. Moreover, the LGE can significantly improve the capacity retention of Li-metal batteries operated at reduced temperatures.

Here, we report a liquefied gas electrolyte with an anion-pair solvation structure based on dimethyl ether with a low melting point (−141 oC) and low viscosity (0.12 mPa×S, 20 oC), leading to high ionic conductivity (> 3.5 mS cm–1) between −70 and 60 oC. Besides that, through systematic X-ray photoelectron spectroscopy (XPS) integrated with transmission electron microscopy (TEM) characterizations, we evaluate the CFx interphase from the low-temperature discharge process. We conclude that the fast transport and anion-pairing solvation structure of the electrolyte bring about reduced charge transfer resistance at low temperatures, which resulted in significantly enhanced performance of Li/CFx cells (1690 Wh kg–1, −60 oC;1172 Wh kg–1, −70 oC based on active materials). Utilizing 50 mg cm-2 loading CFx electrodes, the Li/CFx displayed 1530 Wh kg–1 at −60 oC. This work provides insights into the electrolyte design that may overcome the operational limits of batteries in extreme environments.
Mg(TFSI)2-Based Solid-State Eutectic Electrolyte Towards Safer Magnesium Batteries
Authors: Chen Feiyang , Xu Zheng-Long
Published: September 2023

Magnesium (Mg) batteries are regarded as safer alternatives for Li+-dominated batteries by virtue of the unique dendrite-free property of Mg element. However, traditional liquid electrolytes applied in Mg batteries are mainly based on chloride salts and highly flammable organic solvents, which might cause numerous safety issues such as fire, electrochemical corrosion, and leakage of hazardous chemicals. These kinds of electrolytes seriously violate the original purpose of developing Mg-based batteries. Therefore, exploring non-flammable chloride-free solid-state electrolytes is of significant importance for realizing safer Mg batteries. Here in this work, a novel non-flammable eutectic electrolyte based on chloride-free Mg(TFSI)2 salt is first proposed as a solid electrolyte for safer Mg metal batteries. Our recent results demonstrate that compared with traditional Mg(TFSI)2-based electrolytes which dissolve in flammable organic solvents such as EC, PC, and THF solvent, this Mg(TFSI)2-based eutectic solid electrolyte is non-flammable with robust mechanical structures. When applied in Mg//Mg symmetric batteries, this novel eutectic solid electrolyte could greatly suppress the overpotential phenomenon that occurs in traditional Mg-based electrolytes and achieves stable Mg plating/stripping reversibility with more than 150 h. Furthermore, the practical feasibility of this eutectic solid electrolyte is also demonstrated in Mg//V2O5 full cell, which shows competitive electrochemical performance. We believe that the research on such new electrolytes could provide a new strategy for developing safe and sustainable Mg-based batteries.
Horizontally Aligned Zn Crystals Deposition with 1T VSe2 Functional Layer for Dendrite-Free Zn Metal Anodes
Authors: LI Yuyin , Luo Zhengtang , Wong Hoilun , Wang Jun , Peng Weiliang , Shen Yidi , Xu Mengyang , An Qi , Kim Jang Kyo , Yuan Bin , Goddard William
Published: September 2023

To fulfill the high requirement for high-energy-density storage, Zn ions batteries (ZIBs) has been garnering great scientific attention and considered the promising candidate due to the moderate redox potential, high safety and reasonable cost. However, the problem of the inferior reversibility and limited-service period owing to the issues of side reactions and Zn dendrites hinder its application. In our study, the hexagonal 1T VSe2, owns metallic appearance, was used as the zincophilic film to replace the conventional metal and graphene-based matrix for hexagonal closest packed (HCP) typed Zn metal electrodeposition in ZIBs. Our experimental results discovers that 1T VSe2/Zn anode is beneficial to regulating Zn crystal morphology from randomly oriented to horizontally (002)-oriented plate-like. Combining with computational modelling, the early stage of Zn nucleation and morphological evolution is investigated from atomistic to meso scale. VSe2 substrate exhibits higher adsorption energy (-0.54 eV) with Zn, contrasting with graphene (-0.38 eV) and pure Zn (-0.48 eV) based on the density functional theory (DFT) calculations. And classical molecular dynamic (MD) simulations reveal the plate-like Zn electrodeposits undergo a reorientation transition with a higher fraction of the (002) facet due to the rapid adatom diffusion coefficient, which effectively prohibits the dendrite formation. The symmetric cell with modified electrodes shows an ultra-stable cyclic life with 50 mV overpotential up to 2500 cycles in the condition of 1 mA cm-2 and 1 mAh cm-2.
Fallen Leaves-Based Femtosecond-Laser-Induced-Graphene for High-Performance Flexible Micro-Supercapacitors
Authors: Lee Yeong A , Jang Kyuyeon , Dinh Le Truong-Son , Nam Han Ku , Yang Dongwook , Kim Byunggi , Yim Kanghoon , Kim Seung-Woo , Kim Young-Jin , Yoon Hana
Published: September 2023

The rapid growth of wearable and portable electronics has led to the development of microscale energy storage devices. Among these devices, microsupercapacitors (MSCs) have emerged as promising flexible energy storage devices owing to their high power density, fast charge/discharge rate, and long-term cycling stability [1-4]. Flexible MSCs were mainly made from non-biodegradable synthetic polymers, resulting a massive electronic waste. Moreover, complex manufacturing processes increase production costs.

To address these challenges, we present a novel approach to fabricate green and flexible MSCs using naturally fallen leaves as a carbon precursor [5]. Our method utilize ultrashort laser pulses to create highly conductive and intrinsically flexible microelectrodes without any additional materials. The laser-induced-graphene is formed on leaves in ambient air, resulting in hierarchically porous graphene with 3D mesoporous few-layer structures.

Our green flexible MSCs demonstrated excellent electrochemical performance and were confirmed to work as a power sources for various applications such as LEDs and thermometers. Furthermore, our approach offers a low-cost, renewable, and environmentally friendly alternative to traditional manufacturing processes. Overall, our green and flexible MSCs have significant potential for use in energy-storage devices for flexible/wearable electronics.

References

[1] M. F. El-Kady, R. B. Kaner, Nat. Commun. 4, 1475 (2013).

[2] S.-K. Hyeong, M. Park, S.-I. Kim, S. Park, K.-H. Choi, M. Im, N. Kim, T.-W. Kim, S. Lee, J.-W. Park, S. Bae, J.-H. Lee, S.-K. Lee, Adv. Mater. Technol. 7, 2101105 (2022)

[3] D. Pech, M. Brunet, H. Durou, P. Huang, V. Mochalin, Y. Gogotsi, P. -L. Taberna, P. Simon, at. Nanotech. 5, 651 (2010).

[4] Y. Lee, J. Lim, Y. Cho, H. Lee, S. Park, G.-W. Lee, C.-Y. Yoo, S. Park, V. Murukeshan, S. Kim, Y.-J. Kim, H. Yoon, Chem. Eng. J. 386, 123972 (2020)

[5] T. –S. Le, Y. Lee, H. Nam, K. Jang, D. Yang, B. Kim, K. Yim, S.-W. Kim, H. Yoon, Y.-J. Kim, Adv. Funct. Mater. 32, 2107768 (2022)
New Mechanism Insights on Ca-Ion Storage in Small Molecular Crystal
Authors: LI Renjie , Xu Zheng-Long
Published: September 2023

Rechargeable calcium-ion batteries have become intriguing alternatives for grid-scale energy storage devices. However, the strong electrostatic interaction caused by the intrinsic divalent nature of Ca2+ leads to sluggish ion diffusion kinetics, thus resulting in low capacity. Herein, a small molecular crystal organic material is employed as the electrode material for the aqueous calcium-ion batteries. This kind of organic material could not only bypass the sluggish ion diffusion through carbonyl enolization but also avoid electrode inevitable dissolution due to the intermolecular hydrogen bonding, and flexible structure. In addition, the robust crystal structure allows fast Ca-ion diffusion and storage. Electrochemical characterization including electrochemical quartz crystal microbalance combined with first-principles density calculations and in(ex)-situ spectroscopy methods reveals the whole Ca-ion storage mechanism at the atomistic and macroscopic levels. The reversible enolization redox process, diffusion path, and structure change of molecular crystals have been clearly clarified. Consequently, the materials yield a premier rate capability (70.2 mAh g−1 at 5 A g−1), and excellent cycling stability (retention of 80.3% over 1000 cycles at 2 A g−1). This study extends the boundary of molecular crystal systems for battery chemistry to construct high-performance multivalent ion batteries.
Rational Design of Graphene-Supported Single Atom Catalysts for High Performance Lithium-Oxygen Batteries
Authors: Wong Helen , Liu Tongchao , Tamtaji Mohsen , Hossain Md Delowar , Cai Yuting , Liu Zhenjing , Liu Hongwei , Goddard William , Luo Zhengtang
Published: September 2023

Aprotic lithium-oxygen batteries (LOBs) have been considered as one of the next-generation battery technologies, due to its ultrahigh theoretical energy density (~3600 Wh kg -1), 5-10 times higher than the state-of-the-art lithium-ion batteries (LIBs), supporting the development of electric vehicles (EVs). However, the battery system suffers from poor cyclability, low round-trip efficiency and inferior rate capability, mainly originated from the inertness of oxygen gas and the poor electrical conductivity of lithium peroxide (Li2O2), leading to the sluggish kinetics of oxygen reduction reaction (ORR)/ oxygen evolution reaction (OER). In response to the challenges, developing a highly efficient catalyst at the cathode is vital to boost the reaction rate and reduce the reaction overpotentials, eventually address the problem. Heterogeneous single-atom catalysts (SACs) on solid support are emerging as a new frontier in this research field. Here, we use the density of state (DFT) calculation to determine the catalytic activities of a wide range of transition metal single atoms distributing on the nitrogen doped graphene support and found that Zn-SAC exhibits the highest ORR/OER activities. We discovered that Zn-N4 moieties, functioning as catalytic centers, bind with LiO2 not very strongly, reduce the reaction overpotentials, facilitates the reaction rate and enhance the stability of the catalyst. The catalytic activity of SACs is highly correlated to the Gibbs free energy of the adsorbed LiO2. A descriptor, F of the catalysts determining the catalytic activity was developed from the metal properties of electronegativity (EN), enthalpy of vaporization (EV) and number of electrons in d orbital, by using supervised machine learning (ML) method, providing guidance for designing useful SACs in ORR/OER process. This work systematically provides guidance to design highly efficient SAC for LOBs and provides fundamental insights in choosing the proper metal for the ORR/ OER application.
Lithium Morphology Evolution through Crosslinked Poly(ethylene oxide) Solid Polymer Electrolyte
Authors: Owensby Kyra , Tsai Wan-Yu , Sahore Ritu , Chen Xi
Published: September 2023

Solid-state, lithium metal batteries are promising candidates for developing the safe, energy-dense devices needed to transition to an electrified economy. However, lithium is highly reactive, making it thermodynamically unstable when in contact with many electrolyte materials. Achieving uniform Li plating and stripping during cycling is the key for enabling high energy Li metal batteries. The lithium stripping and plating mechanism is complicated as it can be affected by the cathode, electrolyte and lithium anode, and the resulting solid electrolyte interphase (SEI). In particular, the mechanism is not well understood in solid polymer electrolytes.

In this work, we investigate lithium morphology evolution through a solid polymer electrolyte at different stages of battery cycling. Crosslinked poly(ethylene oxide) (xPEO) solid polymer electrolyte is used as a model electrolyte and full cells using single crystal LiNi0.6Mn0.2Co0.2O2 (NMC622) cathode, dry xPEO electrolyte and lithium from two commercial sources are assembled. Our results show that different lithium sources lead to different Coulombic efficiencies and capacity fade rate of the full cells assembled. The lithium morphology evolution at different stages of cycling is examined using scanning electron microscopy and the lithium plating/stripping mechanism are compared between these two commercial lithium anodes. Furthermore, the lithium morphology is compared to a gel polymer composite electrolyte with the same host polymer (xPEO). The dry solid polymer produces a smoother morphology than the gel polymer composite electrolyte without pit formation. A better understanding of the roles of each of these components (pristine Li surface chemistry, microstructure, dry vs gel polymer electrolyte) is essential to control for uniform lithium stripping and plating.
Fabrication of Internal Electric Field Sns/Sb2S3 with Engineered Porous Structure for Fast Kinetics Sodium Ion Storage
Authors: Mu Yuhe , He Wei , Sagar Lamsal Buddhi , Pokharel Jyotshna , Zhou Yue
Published: September 2023

Benefiting from the abundance and low cost of sodium, sodium-ion batteries show great potential as lithium-ion batteries in application of large-scale energy storage. However, anode material graphite with high theoretical capacity 372 mAh g-1, low charge-discharge plateau potential and good cyclability, widely applied in lithium-ion batteries, exhibited poor electrochemical performance. The larger radius of Na-ion compared to Li-ion hinders the mass and ion transfer during charge-discharge cycling. Thus, anode material with large abundance, stability and high conductivity is crucial for the development and further application of sodium-ion batteries.

Sodium-ion batteries have the potential to benefit greatly from metallic sulfide anodes, which offer high theoretical capacities. Unfortunately, the practical use of these anodes is limited by poor electrochemical performance, as sulfides tend to expand significantly in volume and Na+ ions exhibit sluggish kinetics during cycling. We have developed a facile and scalable approach to synthesizing a SnS/Sb2S3 heterostructure that is porous and bimetallic, with an additional sulfur and nitrogen co-doped carbon matrix encapsulation (SnS/Sb2S3@SNC). The PAN precursor is mixed homogeneously with SnSbx and S with a ball milling process. The sulfur evaporates from the mixture and reacts with the SnSbx alloy, leading to the formation of bimetallic sulfides SnS/Sb2S3. As a result, voids are generated, which in turn contributes to the development of a porous structure. At the same time, the PAN is carbonized, generating a S, N co-doped carbon matrix. SnS and Sb2S3 are two highly promising anode materials for sodium-ion batteries, with high theoretical specific capacity of 1022 mAh g-1 and 947 mAh g-1, respectively. Moreover, bimetallic sulfides possess different bandgap make them ideal components for generating a strong internal electric field on the hetero-interface, which allows to improve the charge carrier transport and interface reaction kinetics. The porous nature of the structure can contain the volume expansion of sulfides during cycling, thereby ensuring superior structural stability. The distinctive heterostructure, in combination with the S, N co-doped carbon matrix, enables fast-charge transport and accelerate Na-ion storage kinetics.

The SnS/Sb2S3@SNC anode demonstrates impressive electrochemical performance, with high capacities of 425 mAh g-1 at 200 mA g-1 after 100 cycles, and 302 mAh g-1 at 500 mA g-1 after 400 cycles. Additionally, the SnS/Sb2S3 @SNC anode exhibits remarkable rate capability, with a capacity of over 200 mAh g-1 at a high current density of 5000 mA g-1.

Figure 1
Design and Synthesis of a Highly Soluble Catholyte Moiety for Stable Aqueous Organic Redox Flow Batteries
Authors: Kim Kyungmi , Seo Noh Uk , Yang Jung Hoon , Chae Junghyun
Published: September 2023

Aqueous Organic Redox Flow Batteries (AORFB) are promising grid-scale energy storage because of their nonflammable stability, low cost, and diverse structural availability of redox active organic compounds. As an organic catholyte, 4-hydroxy-(2,2,6,6-Tetramethylpiperidin-1-yl)oxyl (4-OH TEMPO), is well-known for its air stability and water-solubility (ca. 2.1 M) and has a high redox potential (>0.6 V vs Ag/AgCl). However, 4-OH TEMPO is reported chemically unstable in aqueous systems. To address these disadvantages of 4-OH TEMPO, we designed the MIMAcO-TEMPO, which features an ester group as an electron-withdrawing group that provides a slightly higher redox potential (>0.64 V vs Ag/AgCl) and an ionic liquid as a soluble moiety that enhances solubility (approximately 3.3 M). Our experiments showed that MIMAcO-TEMPO is chemically and electrochemically more stable in AORFB systems than 4-OH TEMPO and we successfully performed AORFB with 2.5 M MIMAcO-TEMPO combined with bis-(trimethylammonio) propyl viologen (BTMAP-Vi), achieving a discharge capacity of 57.1 Ah/L.
Investigation of Reduced Graphene Oxide Modified Zinc Anodes Using Various Electrochemical Techniques
Authors: Sellathurai Andrew J , Barz Dominik P.J. , Zhang Bo Xiao
Published: September 2023

Zinc ion batteries are promising battery energy storage systems due to their high capacity, abundancy and low cost, but are held back by competing reactions, passivation, and dendrite formation which all greatly reduce performance. We modify zinc anode by introducing a self-reducing graphene oxide coating. This protects against dendrite formation and reduces side reactions, increasing the performance of the cell. Half-cell experiments are performed to determine whether sodium sulphate, sodium acetate, or a combination of the provides any advantage over the other, as well as to determine the effect the pattern of the reduced graphene oxide coating on performance. Additionally, symmetric zinc coin cells are assembled, and studied by galvanostatic charge/discharge cycles, and chronopotentiometry. The effect of the reduced graphene oxide coating, electrolyte composition, choice of separator (paper/glass) on the cycling stability and over potential of zinc deposition is studied. The partially covered (island) zinc anode greatly reduces the nucleation overpotential to 8.75 mV when assembled in a symmetric coin cell. Excellent cycling stability is observed at a current density of 5 mA cm-2 charged to 5 mAh cm-2 when using a combination background electrolyte of sodium sulphate and sodium acetate using a glass fibre separator.
Improving the Ionic Conductivity and Electrochemical Performance of NASICON Based Ca2+ Doped NZSP Solid-State Electrolyte for Solid State Sodium Batteries
Authors: Patel Khushi , Banik Trapa , Bhattacharya Indranil
Published: September 2023

Major efforts have been made in the search of high-energy and power density batteries to keep up with the demands of the rapidly growing portable electronics market and EV industry. Though lithium-ion batteries have dominated this field, sodium ion batteries are increasing in popularity due it’s wide availability and low cost. Conventional Sodium ion batteries with liquid electrolyte usually have several problems, including limited electrochemical window, flammability, and leakages which are a potential safety hazard. One of the most promising approaches to improve the safety of a battery is to replace the liquid ion conducting electrolyte to a solid ion conducting electrolyte. Even so, how to develop such a high-performance solid-state electrolyte (SSE) that is compatible with both the anode and cathode interface is still challenging. Furthermore, low ionic conductivity electrolytes, dendrite formation and poor cycling capabilities are adding on to the challenges. As one means to tackle these challenges and improve the electrochemical performances of the battery, cation substitution can be considered. Here, NASICON (Sodium Super Ionic Conductor) based Na1+xZr2SixP3-xO12 (NZSP) solid state electrolyte, its phase behavior and its performances in solid state batteries are introduced. Current trends & perspectives on interface engineering and cation substitution of the NZSP electrolyte is also discussed. Although NASICON material lacks mechanical flexibility, it has high ionic conductivity. Substitutions with La3+ and Sc3+ have shown to improve the ionic conductivity of the battery but have also proven to be expensive. In order to make it more feasible, cations such as Ca2+ should be considered. Pure phase NZSP materials with Ca2+ substitution for Zr4+ will be synthesized using solid-state sintering. Along with the Ca-ion substitution, addition of excess sodium into the Ca-ion substituted NZSP system will be performed and a comparative analysis will be conducted. Here, we will analyze the electrochemical performance through XRD Analysis, SEM Analysis, Impedance Spectroscopy and Galvanostatic Charge/Discharge testing. The development of solid-state sodium electrolytes lead to a brighter future where all solid state sodium batteries could be used to power electric vehicles, electronic devices and contribute towards large scale storage and grid applications.
Pyrochlore Electrocatalyst for Cathodes in Potassium-Oxygen Batteries
Authors: Ashoka Sahadevan Suchithra , Saha Sulay , Sankarasubramanian Shrihari , Ramani Vijay K
Published: September 2023

Metal−oxygen (M−O2) batteries promise some of the highest theoretical energy densities amongst battery systems (Li-O2 ~3458 Wh/kg, Na-O2 ~1605 Wh/kg, K-O2~935 Wh/kg). Despite the high energy density, Li-O2 batteries suffer critical challenges such as high overpotential, limited cycle life and low practical capacities.1 In this context, K−O2 batteries received greater attention as it exhibits the lowest charge/discharge overpotentials (50 mV), high stability and reversibility of the superoxide product (KO2) formed via a single electron transfer reaction. This is in contrast to the higher charge overpotentials (1000 mV/200 mV) and peroxides products formed in Li–O2/Na–O2 batteries.2 The choice of DMSO as an electrolyte for K-O2 batteries, due to its high donor number and KO2 production was previously studied in our group.3,4 In this work, 1M potassium triflate in DMSO is used as electrolyte and different platinum and pyrochlore-based electrocatalyst (Pb2Ru2O7-x) are studied to enhance oxygen reduction reaction (ORR) activity. The charge-discharge polarization was further studied using a symmetric cell with carbon felt and Pb2Ru2O7−x coated carbon felt using DMSO-based K+ electrolytes. The cathode electrodes are characterized using Raman and SEM-EDX.

Chem Rev.
2020, 120, 6626–6683; 2. J. Phys. Chem. Lett. 2020, 11, 7849–7856; 3. J. Phys. Chem. C
2018, 122, 19319–19327; PNAS. 2019, 116, 14899-14904

Figure 1
Defect and Structural Evolution during the Synthesis/Charging of Layered Li(Ni,Co,Mn)O2 Oxides
Authors: Fung Kuan-Zong , Tsai Shu-Yi , Yang Jen-Hao , Chen Yu-Hsuan , Fung Kenneth
Published: September 2023

With the increasing awareness of environmental protection, the installation of renewable energy including solar cells and wind mills has become the priority in government development policy. Due to the intermittent nature of renewable energy, a good energy storage system such as Li ion batteries is needed. The cost of cathode materials may take as much as 50% based on the breakdown of the whole battery. Recently, the single-crystal process of layered oxides received great attention due to its better electrochemical performance. For NMC layered oxides, multiple-step co-precipitation process is commonly used. In additions, “single-crystal” process typically requires more heat energy at higher temperatures. Therefore, the main objective of this study is to develop a cost-effective process for the synthesis of single-crystal Ni-rich layered oxides electrode. For instance, the synthesis of layered oxides may adopt the simple solid state reaction routes. The heating procedures may be optimized through the understanding of calcination and grain-growth processes. Ni-rich layered oxides, namely NCA and NMC 811 are selected and prepared. The crystal structure and microstructure of cathodes were examined using XRD and SEM. The electrochemical properties are monitored using CV, EIS and charge/discharge tests.
In-Operando Isothermal Microcalorimetry to Accelerate Screening of New Battery Chemistries
Authors: May Jeremy , Lau Hang Kuen
Published: September 2023

Screening new cell chemistries using traditional electrochemical methods is a time prohibitive process that significantly slows the pace of research. These methods involve cycling the cell until signs of degradation or sufficient capacity fade are evident, and typically take months to complete. In-operando isothermal microcalorimetry is an established but underutilized technique for measuring the activity of parasitic, or non-reversible reactions during charge cycling [1,2,3,4]. A parasitic reaction is a blanket term for any side reactions that occur within a battery, including solvent breakdown, lithium plating, self-discharge reactions, and growth or decomposition of the solid electrolyte interphase. Battery formulations with high parasitic heat are strongly correlated with early cell failure. Compared to electrochemical cycling, the average parasitic heat over the full voltage range can be determined in a time frame as low as 2 weeks, allowing researchers to realize a time savings up to 75%. Additional time savings are also possible if only a narrow voltage range is of interest.

In this study, we present results that demonstrate the measurement of the parasitic heat of a commercial 18650 lithium-ion battery using the TA Instruments Battery Cycler Microcalorimeter Solution. This method involves slow galvanostatic cycling at isothermal conditions with a simultaneous measurement of heat flow, voltage, and applied current. The parasitic heat is isolated from the total heat flow using the Integration-Subtraction method, with calculations performed automatically by the software [1]. The coulombic efficiency is also measured per cycle, showing an inverse relationship to the parasitic power. As a screening tool, this data could be used to select battery formulations most likely to meet performance goals in long-term cycling experiments, rather than wasting valuable time and lab space on a trial-and-error approach. The results highlight how in-operando isothermal microcalorimetry is a powerful screening tool for investigating the efficiency of new cell chemistries and electrolyte formulations in a fraction of the time compared to traditional methods.

[1] L.J. Krause, L.D. Jensen, V.L. Chevrier. Measurement of Li-Ion Battery Electrolyte Stability by Electrochemical Calorimetry. J. Electrochem. Soc. 2017, 164 (4), A889-A896.

[2] L.J. Krause, L.D. Jensen, J.R. Dahn. Measurement of Parasitic Reactions in Li Ion Cells by Electrochemical Calorimetry. J. Electrochem. Soc. 2012, 159 (7), A937-A943.

[3] J.C. Burns, Adil Kassam, N.N. Sinha, L.E. Downie, Lucie Solnickova, B.M. Way, J.R. Dahn. Predicting and Extending the Lifetime of Li-Ion Batteries. J. Electrochem. Soc.
2013, 160, A1451.

[4] E. R. Logan, A. J. Louli, Matthew Genovese, Simon Trussler,and J. R. Dahn. Investigating Parasitic Reactions in Anode-Free Li Metal Cells with Isothermal Microcalorimetry. J. Electrochem. Soc.
2021, 168, 060527.
Hybridization of Carbon Nanotube Tissue, MnO2 Catalyst and CFx as an Advanced Air Cathode in Metal–Air Batteries
Authors: Levy Natasha Ronith , Ein-Eli Yair
Published: September 2023

We first present the utilization of hybrid carbon nano-tube (CNT) – manganese dioxide (MnO2) tissues as air electrodes in nonaqueous aluminum- and lithium-based battery systems. The CNT tissues are impregnated with α-manganese dioxide nanoparticles via a straightforward binder-free ultrasonic treatment, thereby enabling an improved oxygen reduction reaction (ORR) catalytic activity. Half-cell potentiodynamic measurements along with full-cell discharge evaluations of Li- and Al-based battery systems are reported. Higher discharge potentials and capacities were obtained from generic and advanced hybrid CNT–MnO2 air cathodes. The discharge products obtained on the air cathode surface were studied using high-resolution scanning electron microscopy. Their chemical compositions were evaluated using elemental mapping energy-dispersive X-ray spectroscopy. The stability of the α-MnO2 catalyst was studied using X-ray photoelectron spectroscopy and electron paramagnetic resonance spectroscopy, thereby indicating the ongoing formation of an outer MnF2 shell layer, which affected the α-MnO2 functionality, as an efficient ORR catalyst. We conclude this part of the talk by showing that the function of the metal–air battery is enabled by using porous carbon nanotube (CNT)-based tissue substrates loaded with MnO2 catalyst.

In contrast, fluorinated graphite (CFx) coating on the CNT substrate provides an additional discharge process, enhancing discharge capacity. Two CFx loadings are investigated, and their performances are compared with that of a pristine CNT tissue. Electrochemical evaluations, including half- and full-cell measurements, are performed to examine the effect of the coating layer thickness on the ability of the cell to function at high discharge rates.
(Invited) Highly Transparent and Mechanically Robust Energy-Harvestable Piezocomposite with Embedded One-Dimensional P(VDF-TrFE) Nanofibers and Single-Walled Carbon Nanotubes
Authors: Jeon Il , Kauppinen Esko
Published: September 2023

Here, highly transparent, flexible, and ultrathin piezocomposite, in which electrospun poly(vinylidene fluoride-co-trifluoroethylene) [P(VDF-TrFE)] nanofibers (NFs) and aerosol-synthesized single-walled carbon nanotubes (SWCNTs) are embedded in elastomer matrix, is fabricated. The P(VDF-TrFE) NF mat is exploited as a piezoelectric layer of the piezocomposite while the SWCNT film is applied as a transparent conductive electrode (TCE) thereof. The use of these one-dimensional (1D) nanomaterials allows the piezocomposite not only to have a high transparency along with low diffusivity, but also to exhibit enhanced mechanical properties. In addition, the coupling effect of piezo- and flexoelectricity exhibited from the electrospun NFs and the acid-doping effect conducted on the SWCNTs facilitate a significant improvement in kinetic energy-harvesting performance, leading to a maximum output voltage of 26.8 V. Moreover, electrospinning and aerosol chemical vapor deposition (CVD) methods employed here are facile, scalable, and cost-effective, thus are expected to accelerate the development of industrially feasible next-generation wearable electronics.
A More Controllable Laser Reduction of Graphene Oxide Membrane for Electrode Applications
Authors: Stehle Yijing Yin , Kilby Luke , Bashant Caleb , Vlassiouk Ivan , Rowley Aiden , Zhou Qin
Published: September 2023

Reduced graphene oxide (rGO) has attracted significant attention as an active electrode material for sensors and flexible energy devices due to its high electric conductivity and large surface area. rGO is usually obtained from graphene oxide(GO) through a thermal, chemical, photochemical, and electrochemical reduction process. Compared to the other reduction strategy, laser reduction is a single-step, precise, low cost, and chemical-free processing that can be directly applied on the GO membrane at room temperature in an ambient condition.The laser irradiation parameter, such as laser source, power, speed, and frequency, plays an important role in reduction optimization. In general, the quality of the rGO is not as high as that of pristine graphene because of incomplete reduction, and oxygenated defects involved in the reduction process.The not fully removed oxygenated function group not only influence the sensitivity and selectivity of the electrode, but also influences response time and recovery time during sensing and the electrochemical window of the supercapacitor made with those rGO electrode.

This study aims to develop reduced graphene oxide (rGO) through laser irradiation for application in supercapacitors and electrochemical sensors as electrodes. GO membranes were fabricated with a layer-by-layer assembly process first then further reduced through conventional CO2 laser reduction. The laser irradiation parameters including intensity, frequency, and scan speed will be optimized to achieve the reduction up to maximi, C/O ratio. The effects of the reduction will be characterized and evaluated using scanning electron microscope (SEM), Fourier Transform Infrared (FTIR) spectroscopy, Raman spectroscopy, X-ray diffraction (XRD)spectroscopy, and four-point probe station. The influence of the humidity on the impedance of the rGO electrode and the capacitance of the planar supercapacitor made with rGO electrode will also be analyzed for potential application of as-prepared rGO electrodes in supercapacitors and humidity sensors.
Porosity Engineering of Si Nanoparticle-Based Electrodes by Carbon Nanostructures
Authors: Kim Jae Ho , Pach Gregory F. , Carroll Gerard (MIke) Michael , Neale Nathan R.
Published: September 2023

Silicon (Si) has been considered as a next-generation anode material due to natural abundance, low operating potential (<0.5 V vs. Li/Li+), and high theoretical specific capacity of 4200 mAh g-1.1 However, the electrochemical alloying reaction of Si involves large volume changes of 400% during lithiation and delithiation, causing cracking and pulverization of Si.1 In addition, solid electrolyte interface (SEI) of Si anode experiences constant changes due to unstable SEI reactivity.2 Considerable efforts have been made to design nanostructured Si materials to address the issues because nanostructuring can relieve the mechanical strain.3 However, when compared to micrometer-sized active materials having sufficient electrolyte pathway through interparticle space, the nanoparticle (NP)-based electrodes tend to be densely packed. As mass loading is higher and electrode is thicker, ion transport issue can become more severe in the densely packed electrodes.4

In this work, we will present studies on engineered porosity impacts performance in Si NP electrodes by altering porosity with carbon nanostructures. We explore the extreme limit of effectively non-porous electrodes using quasi-spherical, 6 nm diameter Si NPs produced via plasma-enhanced chemical vapor deposition (PECVD), which result in densely packed electrodes when slurry is prepared with conventional carbon black. We engineer porosity using carbon nanostructures including single-walled carbon nanotubes and carbon nanorods in place of conventional carbon black to create pore structure in Si NP-based electrodes. These experiments provide a correlation between mass loading, porosity and silicon utilization in Si NP-based electrodes.

References

[1] C. K. Chan, H. Peng, G. Liu, K. Mcllwrath, X. F. Zhang, R. A. Huggins, Y. Cui, “High-performance lithium battery anodes using silicon nanowires”, Nat. Nanotechnol., 2008, 3, 31

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A Theory of Mechanical Stress-Induced H2O2 Signaling Waveforms in Planta
Authors: Porter Thomas K. , Heinz Michael N. , Lundberg Daniel James , Brooks Allan M. , Lew Tedrick Thomas Salim , Silmore Kevin S. , Koman Volodymyr B. , Ang Mervin Chun-Yi , Khong Duc Thinh , Singh Gajendra Pratap , Swan James W. , Sarojam Rajani , Chua Nam-Hai , Strano Michael S.
Published: September 2023

Recent progress in nanotechnology-enabled sensors that can be placed inside of living plants has shown that it is possible to relay and record real-time chemical signaling stimulated by various abiotic and biotic stresses. The mathematical form of the resulting local reactive oxygen species (ROS) wave released upon mechanical perturbation of plant leaves appears to be conserved across a large number of species, and produces a distinct waveform from other stresses including light, heat and pathogen-associated molecular pattern (PAMP)-induced stresses. Herein, we develop a quantitative theory of the local ROS signaling waveform resulting from mechanical stress in planta. We show that nonlinear, autocatalytic production and Fickian diffusion of H2O2 followed by first order decay well describes the spatial and temporal properties of the waveform. The reaction-diffusion system is analyzed in terms of a new approximate solution that we introduce for such problems based on a single term logistic function ansatz. The theory is able to describe experimental ROS waveforms and degradation dynamics such that species-dependent dimensionless wave velocities are revealed, corresponding to subtle changes in higher moments of the waveform through an apparently conserved signaling mechanism overall. This theory has utility in potentially decoding other stress signaling waveforms for light, heat and PAMP-induced stresses that are similarly under investigation. The approximate solution may also find use in applied agricultural sensing, facilitating the connection between measured waveform and plant physiology.
(Invited) Melanin-Inspired Functionalization of Single-Walled Carbon Nanotubes for Optical Detection of Metals
Authors: Bisker Gili
Published: September 2023

The accumulation of metal ions in organisms and the presence of heavy metals in water cause adverse effects on ecosystems and result in numerous human health issues such as cancer and neurogenerative diseases. Therefore, the development of novel platforms for metal-scavenging and rapid metal detection for in situ applications are of high importance. Here, this challenge is tackled by taking advantage of the metal chelation ability of a melanin-inspired material in combination with the near-infrared (NIR) fluorescence response of single-walled carbon nanotubes (SWCNTs) to surface binding. SWCNTs are functionalized by a melanin-like substance, obtained by enzymatic oxidative polymerization of a fluorenylmethyloxycarbonyl-tyrosine (FmocY) precursor. The resulting multicomponent system (SWCNT-FmocYOx) serves as a metal-ion scavenging platform that concurrently reports on metal binding with optical signal transduction. Upon binding of a library of mostly divalent transition metal-ions, the fluorescence emission of the functionalized SWCNTs is modulated, showing a concentration-dependent response with a limit of detection in the nanomolar range. Metal-binding and removal from water of up to 98% are further shown via inductively coupled plasma mass spectrometry. The SWCNT-FmocYOx hybrid system presents a novel platform with NIR optical signal for real-time feedback on metal-ion scavenging.
What DNA Sequence Strongly Binds to Carbon Nanotube? High-Throughput Study
Authors: Jeong Sanghwa , Lee Dakyeon
Published: September 2023

Noncovalent functionalization of single-walled carbon nanotubes (SWCNT) with amphiphilic polymers has significantly advanced the colloidal SWCNT efficacy for biomedical optical sensors. Single-strand DNA (ssDNA), as an amphiphilic biocompatible polymer, has been employed to fabricate ssDNA-wrapped SWCNT complexes, however the correlation between DNA sequence and wrapping affinity is not fully studied. In this research, we evolved and screened high-affinity ssDNA sequences from ~1015 ssDNA (random 30-mer), and analyzed the influence of DNA sequence on the wrapping affinity. Wrapping affinity of specific ssDNA sequence was quantitatively measured by the rate constant when ssDNA at the surface was exchanged to sodium cholate. The wrapping affinity relies on the base composition and k-mer motif. Also, we build a machine learning model to identify the high affinity DNA sequence with >85% accuracy. These results indicate the presence of “sequence motif(s)” to control the wrapping affinity and chemical conformation of ssDNA molecule on the SWCNT surface, which can be useful for developing DNA-assisted carbon nanosensors.
(Invited) Near Infrared Fluorescence Lifetime Imaging of Biomolecules with Carbon Nanotubes
Authors: Kruss Sebastian
Published: September 2023

Single wall carbon nanotubes (SWCNTs) are versatile building blocks for biosensors. Their near infrared (NIR) fluorescence enables detection of biomolecules in the optical tissue transparency window. Their surface chemistry can be tailored to selectively interact with analytes, which typically changes the fluorescence intensity. However, such signals are affected by external factors such as sample movement or fluctuations in excitation light. Here, we demonstrate fluorescence lifetime imaging microscopy (FLIM) of SWCNT-based sensors in the NIR as absolute and calibration-free method.

For this purpose, we use a tailored laser scanning confocal microscope (LSCM) optimized for NIR signals (>800 nm) and time correlated single photon counting (TCSPC). (GT)10-DNA modified SWCNTs serve as sensor of the important neurotransmitter dopamine. The detected fluorescence signal > 900 nm increases in lifetime up to 25 %. These lifetime sensors are used as paint to cover cells and report extracellular dopamine in 3D. We therefore show the potential of using fluorescence lifetime in combination with confocal microscopy as readout for SWCNT-based sensors.
Protein Engineering to Modulate Carbon Nanotube Photoluminescence Response
Authors: Randall Ewelina , Kim Mijin , McCaan Jim , Koder Ronald , Heller Daniel A.
Published: September 2023

Semiconducting single-walled carbon nanotubes (SWCNTs) have been investigated as a promising nano-biosensor. Chemical functionalization of SWCNTs sensitizes their near-infrared fluorescence to various analytes with environmental responsivity as high as single-molecule levels. Covalent quantum defects on SWCNTs enable a newly developing category of SWCNT-based biosensors with their unique sensitivities and increased quantum yield. In this work, we present the development of a strategy to sensitize and enhance functionality of SWCNT-based biosensors for bioanalytes via protein engineering. We assess the time-resolved protein binding events on the nanotube surface in molecular level. The approach resulted in improved sensor sensitivity and longer shelf life, maintaining high specificity to their targets. The approach to construct robust and sensitive nanosensors could be readily adapted to the detection of many other disease biomarkers and use in technologies such as point-of-care and wearable/implantable devices.
(Invited) Commercializing Single Walled Carbon Nanotube-Based Sensors - Enzyme Activity and Beyond
Authors: Reuel Nigel , Kallmyer Nathaniel
Published: September 2023

The ECS carbon nanostructures community is well informed on the potential of single walled carbon nanotube (SWCNT)-based sensors and likewise the challenges associated with realizing practical applications outside of an academic laboratory. This talk will discuss our latest efforts in facile separation and sensor preparation methods. It will discuss potential use cases in improving high throughput screening of custom enzymes, with a current focus on recalcitrant substrates such as conventional polymers. This talk will also focus on latest efforts of reducing to practice optical fluorimeters (single, multi-channel, spatial, and temperature controlled) for field use applications. Finally, this talk will detail the on-going adventure of commercialization at Zymosense Inc. which we hope will serve as a practical guide to other groups considering transferring their technology from the lab.
Design and Analysis of Rapid Production Single Wall Carbon Nanotube Sensor Platforms
Authors: Acosta Ramirez Ivon , Sohail Wali , Sadak Omer , Iverson Nicole M
Published: September 2023

Single-wall carbon nanotubes (SWNT) have a strong and stable near-infrared (nIR) signal and can interact with target analytes selectively, even at the single molecule level, to alter fluorescence intensity and/or emission peak wavelength. SWNT have been employed as nIR optical sensors for detecting a variety of analytes. However, high cost, long fabrication time, and poor fluorescence yield limit the current methods for immobilizing SWNT sensors on solid substrates. Recently, our group reported a protocol for SWNT immobilization resulting in high fluorescence yield, signal longevity, fluorescence distribution, and quick sensing response time. However, it takes 5 days to fabricate these sensor arrays. We have improved our previously reported protocol to immobilize SWNT sensors with a method that takes only 2 days, results in a platform with similar surface morphology, and has a higher fluorescence intensity than the previous platforms without sacrificing the sensing capabilities.