bluuebunny/crossref_metadata_2025 huggingface dataset:
Life Cost Assessment of Using Binders of Sulfide-Based All Solid-State Lithium Batteries for Lithium-Ion Batteries
Authors: Montes Susan , Beutl Alexander , Jahn Marcus , Tron Artur
Published: February 2024

PVDF is commonly a binder used for cathode materials in generation 3 Li ion batteries due to the good binding ability to active material and the current collector with reasonable electrochemical stability and maintaining facile lithium transport. However, organic solvent N-methyl pyrrolidone (NMP) is required for the preparation of slurry in order to dissolve PVDF [1]. These drawbacks of high cost and environmental issues are worsened by the fact that PVDF can easily react with components of liquid electrolytes with possible formation of LiF leading to the unstable performance [2]. Furthermore, fluorinated polymers are considered an environmental risk and are a major concern for recycling efforts [3]. Therefore, reducing the use of polyvinylidene difluoride binder in combination with toxic and expensive N-methyl pyrrolidone (NMP) organic solvent, resulting in safe use and utilization during the battery manufacturing process, is the aim of this work. Here, the sulfide solid state binders are attractive candidates for the anode and cathode composites from the point of view of environmentally friendly use of materials, low cost, and easy electrode processing with subsequent disposal. This study reports the performance of the cathode and anode materials applied to these types of binders and reference binders of polyvinylidene difluoride (PVDF) for these as-obtained samples for lithium-ion batteries. The obtained cathode and anode materials are analyzed by XRD and SEM methods. The electrochemical performance of the obtained electrodes is tested by galvanostatic cycling, cyclic voltammetry, and electrochemical impedance spectroscopy. The obtained electrodes exhibit stable electrochemical performance due to the better uniform distribution of electrode particles with strong adhesion to the current collector for long cycle life and stable formed SEI layer compared to the PVDF-based sample. In addition, these samples maintain stable cycle life after various rate capabilities due to the facilitated lithium-ion diffusion and electronic conductivity.

Acknowledgments

This work was supported by the financial support of the Austrian Federal Ministry for Climate Action, Environment, Energy, Mobility, Innovation and Technology.

References

[1] G.B. Xia, L. Cao, G.L. Bi, A review on battery thermal management in electric vehicle application, J. Power Sources 367 (2017) 90–105.

[2] D. Bresser, D. Buchholz, A. Moretti, A. Varzi, S. Passerini, Alternative binders for sustainable electrochemical energy storage – the transition to aqueous electrode processing and bio-derived polymers, Energy Environ. Sci. 11 (2018) 30963127.

[3] R. Lohmann, I.T. Cousins, J.C. DeWitt, J. Glüge, G. Goldenman, D. Herzke, A. B. Lindstrom, M. F. Miller, C. A. Ng, S. Patton, M. Scheringer, X. Trier, Z. Wang, Are Fluoropolymers Really of Low Concern for Human and Environmental Health and Separate from Other PFAS? Environ. Sci. Technol. 54 (20) (2020) 12820–12828.
Battery Production Solvent Alternative to NMP - Jeffsol® MEOX
Authors: White Victoria , Zhou Hui , Zhang Ke , Gazda Jerzy , Lacey Steven David
Published: February 2024

Solvents are commonly used in in battery manufacturing to dissolve binders, aid in slurry dispersion, stability, and the coating process [1]. For the cathode, N-Methylpyrrolidone (NMP) is the commonly used solvent for working with PVDF binder. However, it has been classified as Reprotoxic, and labeled as a CMR substance. Due to the classification, there are existing strict emission regulations and increasing regulations on the handling and use of the solvent [1,2]. As a result of these regulations with NMP, there has been increased interest for replacements that can improve the safety without significantly affecting the existing processes. Huntsman has developed JEFFSOL® MEOX, a solvent which may be less hazardous to handle while having similar performance capability to NMP.

JEFFSOL® MEOX and NMP are both clear, colorless, and odorless aprotic solvents. They also share similar dipole moments and dispersion energy parameters. Therefore, JEFFSOL®MEOX may have an advantage in solubility performance in some applications when compared with other NMP alternatives (Table 1). Due to these comparable characteristics and the ease of handling, JEFFSOL® MEOX can be used in a wide variety of applications. In addition to use as a solvent for PVDF or PAN binders in batteries, JEFFSOL® MEOX can be applied in chemical reactions and polymerization applications [3]. Due to its usefulness in multiple markets, there are multiple grades of MEOX available, including E-Grade® MEOX which contains ultra-low metals and can be used in semiconductor production without contaminating the wafer.

As an example of the comparable solubility performance, Figure 1 shows results of NMP and JEFFSOL® MEOX with multiple PVDF samples that are commonly used in battery production, including mono- and co-polymers of low and high molecular weights. With both solvents, heat and agitation decreased the time needed to fully dissolve the PVDF.

In addition to MEOX, Huntsman offers other experimental solvents which could be used as NMP replacements as well. In addition to the range of solvents currently offered, Huntsman has the capability to synthesize new solvents based on user feedback. This Huntsman technology gives users greater flexibility and capabilities in selecting the ideal solvent for their unique processes while shifting away from NMP.

This presentation shows the latest results with JEFFSOL®MEOX benchmarked against industry standard NMP.

[1] Y. Liu, R. Zhang, J. Wang, Y. Wang: Current and future lithium-ion battery
manufacturing (iScience, Volume 24, Issue 4, 2021)

[2] REACH COMMISSION REGULATION (EU) 2018/588 (2018)

[3] V. White. H. Zhou, K. Zhang, J. Gazda: Advanced Battery Materials as reported at the International Battery Seminar (2023)

Figure 1
Enhancing Thermal Stability of Lithium-Ion Battery Separators with Sub-Micron Boehmite Coating
Authors: Jang Mi , Baek Jong-Oh , Chae Ji Su , Choi Junghyun , Park Chanwoong , Park Dae-bok , Kim Byung Hyun , Roh Kwang Chul
Published: February 2024

Recently, lithium-ion batteries have been increasingly used as energy sources for electric vehicles, and research has highlighted the need to improve the stability of these batteries. In this study, we propose a novel inorganic coating method that utilizes sub-micron boehmite particles as coating agents to enhance the thermal and mechanical stability of the battery separator. Sub-micron-sized boehmite was synthesized via hydrothermal synthesis, with the addition of a specific amount of finely pulverized crystalline boehmite as an additive. And then, porous polyolefin separator was made of 14 um thick fabric using a pilot film forming process. The coating slurry was made using an aqueous binder and was coated to a thickness of 4 um on one side of the separator. The direct effect of the boehmite coating layer on the improvement of thermal stability was evaluated by comparing the shrinkage behavior before and after the thermal stability test. Electrochemical characteristic analysis was performed using a pouch-type cell, with graphite as an anode and NCM as a cathode. After 100 cycles of charging and discharging at 1C, the capacity maintenance was about 98%, and the rate capability was 76% compared to 0.1C and 2C capability. In particular, the 0.1C capacity measured after 2 weeks in a 60°C oven showed excellent thermal stability with a retention rate of about 100%.
The Particle Size Distribution of Ni-Rich NMC Particles Determines Their Electrochemical Performance at Cylindrical Li-Ion Battery Cells
Authors: Anansuksawat Nichakarn , Sawangphruk Montree
Published: February 2024

Developing lithium-ion batteries with high stability and increased energy density is crucial. In this study, we examined two potential cathode materials, LiNi0.8Mn0.1Co0.1O2 (NMC80) and LiNi0.9Mn0.05Co0.05O2 (NMC90), for use in commercial lithium-ion batteries. We utilized the 18650-cylindrical cell configuration to investigate their performance. While higher Ni mole ratios typically result in high energy, they also lead to poor stability. Our findings revealed that the uniformity of NMC particles is more critical than the Ni content. As a result, NMC90 outperformed NMC80 in terms of energy density, stability, and rate capability. These results suggest that controlling the particle size of Ni-rich layered oxide material will be crucial for further developing high-performance Li-ion batteries.
On the Chemo-Mechanics of Advanced Electrode Materials Via Operando Acoustic Transmission
Authors: Sun Kerry , Thorsteinsson Gunnar , Zhao Dingyi , Steingart Daniel A.
Published: February 2024

Silicon anodes have emerged as a viable strategy for a negative material in solid-state batteries to balance their reactivity with high energy density. Compared to conventional graphite electrodes, silicon anodes have a large theoretical capacity of 3600 mAh/g compared to 372 mAh/g in graphite. This large capacity comes from the fact that lithiated silicon (Si4Li15) can accommodate 15 Li atoms per 4 Si atoms as opposed to LiC6. As a result, silicon anodes experience large volumetric expansions up to ~300% as Li ions alloy into the Si negative electrode. Acoustic transmission utilizes sound propagation to nondestructively probe electrode chemo-mechanics in operando.

c = √(E/ρ)

The speed of sound through a material is proportional to its Young’s modulus (E) and inversely proportional to density. Previous works have shown that acoustic transmission can detect gas formation and dewetting in commercial Li-ion cells and Li metal cells. There has also been a study showing acoustics can detect void formation during Li stripping in solid-state Li symmetric cells. To the best of our knowledge, there has not been an acoustic study of an all solid state Li full cell.

This work intends to show that acoustic transmission can monitor Si expansion and contraction as a function of waveform damping and the Young’s modulus of the Si electrode. This works gives insight into the mechanical considerations and possible loss of contact as Si lithiates and delithiates repeatedly. The reliance of Si anodes on stack pressure is not well understood and is further elucidated in this work. We hope to give a better understanding of the intersection between the electrochemical reactions at the Si electrode and the mechanical stresses induced on the cell.

Figure 1
(Invited) Chemomechanical Phenomena during Lithium Metal Plating
Authors: Sheldon Brian W. , Cho Jung Hwi , Xiao Xingcheng , Gao Huajian , Athanasiou Christos E. , Liu Xing , Fincher Cole D. , Carter W. Craig , Chiang Yet-Ming , Kim Kunjoong , Rupp Jennifer L.M. , Shi Changmin
Published: February 2024

The stresses that evolve during plating and stripping in lithium metal electrodes can have a significant impact on battery performance. We have used several different in situ techniques to investigate these stresses, during electrochemical cycling with both liquid and solid electrolytes. Finite element modelling (FEM) was also employed to interpret many of these measurements. With liquid electrolytes, the experiments show that stresses are generally limited by plasticity in the lithium metal, and the FEM shows that these are too low to destabilize the Li / SEI interface. However, the properties of the SEI (including internal residual stresses) can lead to interfacial wrinkling in ways that lead to mechanical failure of the SEI films. Research on Li plating with oxide and sulfide solid electrolytes that exhibit different mechanical properties will also be presented. Here, the experimental results and corresponding FEM indicate that chemomechanical phenomena have a critical impact on stress evolution in the metal electrode, and on dendritic lithium metal penetration through solid electrolytes. A key difference between the oxides (e.g., LLZO) and sulfides (e.g., LPS glass and argyrodite) is the role of viscoplasticity in the latter. Approaches for controlling lithium dendrites based on chemical and microstructural modifications that impact stresses in the solid electrolytes will also be presented.
The Effects of Small Amounts of Cobalt in LiNi1-XCoxO2 on Lithium Diffusion
Authors: Zsoldos Eniko , Cormier Marc M. E. , Ball Mitchell Afheldt , Rathore Divya , Dahn Jeff R.
Published: February 2024

Lithium-ion batteries with Co-free Ni-rich cathodes have attracted interest due to lower cost and supply chain issues compared to cobalt-containing cathodes1. However, cobalt is thought to provide some benefits in cycling stability and rate performance. In this work, cobalt substitution for nickel in the positive electrode material LiNi1-xCoxO2 at 0 ≤ x ≤ 0.10 is systematically investigated to determine the impact of Co and material synthesis conditions on Li diffusivity, measured using the Atlung Method for Intercalant Diffusion (AMID)2,3 in coin cells vs Li metal negative electrodes. Cobalt was found to have no impact on Li diffusivity in the intermediate voltage range (4.2 V to 3.7 V), while cation mixing (%Ni in Li layer) was found to have a strong correlation to slow Li diffusivity. At high voltage (4.3 V to 4.2 V), 0 to 10% cobalt incrementally suppresses the H2-H3 phase transition4,5 enabling significantly faster lithium diffusion. Cation mixing can be minimized through synthesis conditions, improving Li diffusivity for the low and intermediate voltage regions, without using Co. In summary, with optimal positive electrode material synthesis conditions and limiting cell upper cutoff voltage to 4.2 V, Co-free Ni-rich materials can be made with similar rate performance as 10% Cobalt-containing materials. Additionally, cobalt was found to have minimal impact on the following material properties: crystallinity of LiNi1-xCoxO2, surface impurities, particle size, and electronic conductivity. Cobalt substituted for nickel from 0% to 10% was found to decrease first cycle discharge capacity in the voltage range between 3.0 V and 4.3 V and improve capacity retention in coin cell cycling vs Li metal negative electrodes. The capacity retention improvement is most likely due to the suppression of the H2-H3 phase transition as Co is added5.

Figure 1. (a), (b) shows %Ni in Li layer vs Cobalt content, obtained from powder XRD Rietveld refinement from a series of LiNi1-xCoxO2 materials. (a), (b) were synthesized under two different O2 flow velocities, both at 700oC for 20 hours, with a Li:TM ratio of 1.02:1. (c), (d) Show the lithium chemical diffusion coefficient vs cell voltage for the materials from (a), (b), respectively, measured using the Atlung Method for Intercalant Diffusion (AMID), in coin cells at 30oC. The protocol consists of 2C to C/160-rate discharge steps per voltage interval (0.1V), with OCV relaxation in between discharge steps.

Figure 1
The in Operando/Situ Analytical Techniques Assisted Study of Pre-Lithiated MoOx @ TiO2 As the Anode Material of Lithium Ion Batteries
Authors: Chong Zhen , Huang Jow-Lay , Chang Chia-Chin , Shen Yu-Min
Published: February 2024

Nowadays, as more environmental-friendly and safe energy storage, Lithium-ion Batteries (LIBs) is being pursued, TiO2 is suggested as the anode material, having desirable performance in stability and cycle, but there is the main challenge of low specific capacity (330mAh/g theoretically). To overcome, modifying molybdenum (Mo) into TiO2 reduces the impedance and increases the Li ion diffusion rate. The MoOx@TiO2 is synthesized by the by reacting (NH4)2MoO4 and TiO2 (rutile and anatase phase mixed) followed by annealing at elevated temperature (700°C). From the TEM and XRD results, we had synthesized MoOx@TiO2 shell-core structure. With the modifying of Mo, the specific capacity had reached 1273mAh/g and 995mAh/g in the first cycle under 0.1C and 0.2C current respectively. The fading of the capacity in different current showed the similar tendency, having the irreversible capacity of 36% and 29% after the first cycle. The loss of capacity during cycling is inevitable, thus the electrochemical pre-lithiation method was used by applying various constant voltage for certain duration to force the forming of solid electrolyte interphase (SEI) layer and the diffusion of lithium ion into the electrode. Pre-lithiated MoOx@TiO2 has better Coulombic efficiency (CE) and reversible capacity. The complex mechanism of pre-lithiation is studied by the assistance of In Operando/Situ techniques (In Operando XRD and Raman). The In Operando experiments would be done on the single holed coin cell (CR2030). With the dealt challenge, MoOx@TiO2 would be the potential dominant material for the anode material of LIBs.

Figure 1
Surface Modification on TiNb2O7 Anode Via Atmospheric Pressure Plasma Jet for High-Rate Lithium-Ion Battery
Authors: Wu Che-Ya , Hsiao Shih-Nan , Kuo Rui-Tung , Lin Tzu-Ying , Hori Masaru , Duh Jenq-Gong
Published: February 2024

Lithium-ion battery is one of the most vital energy storage devices due to high energy density property. In anode, TiNb2O7 (TNO) demonstrates high capacity as compared to Li4Ti5O12 materials. It is attractive for its high safety because of adequate Fermi level, implying that the solid electrolyte interface would not form during the charging and discharging process. This work provides a promising method of modifying the electrode, which includes PVdF, conductive carbon, and TNO, using the technology of atmospheric pressure plasma jet (APPj) treatment. This method is potential to accomplish roll-to-roll modification in the industry without any complex synthesis processes. In addition, APPj method is a time-effective process to treat the electrode. It has found that the treatment via APPj enhances the electrochemical performance by N-doped decoration on conductive carbon, as well as defects manufacturing of the TNO anode materials, and electrolyte wettability improvement on binder. The surface free energy of the APP-20 sample increases, improving the wettability of the electrolyte and contributing to an enhanced electrochemical performance. The C-rate performance of APP-20 improves significantly at 10C as compared to the sample without treatment. Also, the cycle test of APP-10 provides high retention after 300 cycles at 1C. In summary, this work promotes a feasible and facile treatment for roll-to-roll processing, and the mechanism could be established. APPj In short, the modification technique of APPj is an affordable method to apply in the lithium-ion battery of the industry manufacturing.
Technoeconomic Assessment of Large-Scale Ethylene Production via the Electrochemical Reduction of CO2
Authors: Flake John , Bachar Cameron , Dalum Albert S , Huynh Bruce , Porta Hannah , Ramaraju Rahul , Sheets Ella , Yi Hingyu , Guillory Barry , Pendergast John , Jiao Feng
Published: February 2024

In the last five years, several works have shown that CO2 may be electrochemically reduced to C2 products such as ethylene at current densities over 1 A cm-2 and Faradaic efficiencies over 70%. For the first time, these current densities and Faradaic efficiencies are comparable with commercial electrolytic processes. For reference, over 100 million metric tons per year of chlorine per is manufactured via the Chlor-alkali process at current densities near 0..4 A cm-2 and Faradaic efficiencies to Cl2 over 80%. While the current densities and Faradaic efficiencies for CO2 reduction are compelling; other metrics such as energy efficiency, selectivity, carbon efficiency, electrolyzer scaling, electrolyzer costs and post-electrolysis separation are not yet at the levels needed for commercialization.

In this presentation, we consider the technoeconomics of ethylene production at large scales (25,000 to 150,000 metric tons per year). We investigate the impact of cell potential, Faradaic efficiencies, conversion level, process scaling and post-electrolysis separations on the cost of electrolytic ethylene production. Our results indicate that the “green” ethylene made using CO2 as a feedstock requires anywhere from approximately 1 to 10 times greater manufacturing costs than conventional cracking of ethane depending on factors such as electrical energy cost, electrolyzer costs and other parameters. In this case, we consider key technical and economic needs including: price premiums, tax incentives, CO2 emission taxes, and other factors that could enable electrolytic ethylene manufacturing at large scales within the next decade.
Durability of CO and CO2 Electrolyzers with Copper Electrocatalysts, Gas Diffusion Electrodes, and Anion Exchange Membranes
Authors: Flake John C. , Bello Mustapha , Dauda Monsuru Olatunji , Hendershot John C , Gonçlaves Ricardo , Jiao Feng , Yan Yushan , Yao Koffi
Published: February 2024

Recent works have shown that the electrochemical reduction of CO2 or CO to C2 products may be carried out at high rates and selectivities using electrolyzers with copper catalysts, gas diffusion electrodes (GDEs), and anion exchange membranes (AEMs). The current densities and Faradaic efficiencies reported for CO2 reduction are similar to those used in the commercial production of chlorine via the Chlor-alkali process; however, other performance metrics related to the energetic efficiency, carbon efficiency, single-pass conversion, crossover, and durability or operating lifetime are also important considerations.

Work in our labs indicates that operating lifetimes are typically related to flooding, precipitation, or catalyst deactivation. As shown in Figure 1a, flooding in CO2 electrolyzers is typically observed with a sharp increase in hydrogen production and increased cathode gas flows. Figure 1b shows evidence of carbonate precipitation including variations in cell potential and lower cathode flow.

In this talk, we consider the relationships between AEM properties (conductivity, water transport, counter ion transport), binder properties (viz. hydrophobicity), and catalysts on operating lifetimes of CO2 electrolyzers.

Figure 1
What Is Needed for Industrial Carbon-Dioxide Electroreduction: From Electrode Development to Process Optimization
Authors: Janaky Csaba
Published: February 2024

Electrochemical reduction of CO2 is a promising method for converting a greenhouse gas into value-added products, utilizing renewable energy. Novel catalysts, electrode assemblies, and cell configurations are all necessary to achieve economically appealing performance. In this talk, I am going to present a zero gap electrolyzer cell, which converts gas phase CO2 to products without the need for any liquid catholyte. This is the first report of a CO2 electrolyzer cell, where multiple cells are connected into a stack, thus scaling up the electrolysis process. I will show how proper cell components and operational conditions result in unprecedentedly high partial current densities in zero-gap cells. I will demonstrate the role of each component of the membrane electrode assembly, such as the catalysts, the porous transport layers, the membrane, and the ionomers.

In the second part of my talk, I will show that while precipitate formation in the cathode gas diffusion electrode is detrimental for the long-term stability, the presence of alkali metal cations at the cathode improves performance. To overcome this contradiction, I will present different approaches which help to extend the lifetime of the electrolyzer cell. As an outlook, I will present a complex machine learning based approach, through which we aim to find the optimal operating conditions of such CO2 electrolyzer cells.

References:

Janáky et. al.: Multilayer Electrolyzer Stack Converts Carbon Dioxide to Gas Products at High Pressure with High Efficiency, ACS Energy Letters 4 (2019) 1770-1777

Janáky et. al.:High carbonate ion conductance of PiperION membrane allows industrial current density and conversion in zero-gap carbon dioxide electrolyzer cell Energy & Environ. Science, 13 (2020) 4098-4105

Janáky et. al. : Operando cathode activation with alkali metal cations allows high current density operation of water-fed zero-gap carbon dioxide electrolyzers, Nature Energy, 6, (2021) 439–448

Janáky et. al.: Coupling electrochemical CO2 conversion with value-added anode processes: an emerging paradigm, Current Opinion in Electrochemistry, 25 (2021) 100621

Janáky et. al.:Local Chemical Environment Governs Anode Processes in CO2 Electrolyzers ACS Energy Letters, 6 (2021) 3801-3808

Janáky et. al.:Systematic screening of gas diffusion layers for high performance CO2 electrolysis, Communications Chemistry, 6 (2023) 41

Janáky et. al.:Membrane Electrode Assembly for Electrocatalytic CO2 Reduction: Principle and Application, Angewandte Chemistry International Edition, in press, DOI: 10.1002/ange.202302789
Low-Cost and Scalable Electrodes for Anodic Production of Hydrogen Peroxide Via 2e- Water Oxidation
Authors: Pangotra Dhananjai , Vieira Luciana , Roth Arne
Published: February 2024

Hydrogen peroxide (H2O2) is a crucial chemical that is widely utilized in various industrial processes. The conventional anthraquinone process for H2O2 production has limitations in terms of energy consumption, high costs, and waste generation [1]. An alternative, greener and more sustainable approach is the electrochemical production of H2O2 from oxygen and water using renewable energy. Our research group has been extensively investigating the two electron (2e-) water oxidation reaction (WOR) for production of H2O2 using various electrode materials, including metal oxides, commercial carbon materials, and boron-doped diamond (BDD) [2, 3]. We also investigated the role of carbonate ions (HCO3
- and CO3
2-) in the process of water oxidation to H2O2. The enhancing effect e of CO3
2- ions on anodic H2O2 production was studied in a continuous flow reactor, where the optimal flow rate, process configuration and cell design, and chemical stabilizer were determined. Among other parameters, chemical composition and pH regime of the electrolyte were found to be crucial.

Recently, we explored the use of graphite bipolar plates (BPP) as a low-cost alternative to BDD electrodes for anodic H2O2 generation [4]. Three different commercial BPPs with varying fluoropolymer content were examined, and a correlation was found between fluoropolymer content and H2O2 generation. In that study we found that a BPP sample with high fluoropolymer content resulted in a stable H2O2 production for up to 100 hours at a current density of 200 mA cm–2, with a constant faradaic efficiency of 40%. The results demonstrate that low-cost commercial carbon electrode materials can selectively oxidize water to H2O2, enabling economically viable technical applications of anodic H2O2 production.

References

[1] S.C. Perry, D. Pangotra, L. Vieira, L.-I. Csepei, V. Sieber, L. Wang, C. Ponce de León, F.C. Walsh, Electrochemical synthesis of hydrogen peroxide from water and oxygen, Nature Reviews Chemistry, 3 (2019) 442-458.

[2] D. Pangotra, L.-I. Csepei, A. Roth, C. Ponce de León, V. Sieber, L. Vieira, Anodic production of hydrogen peroxide using commercial carbon materials, Applied Catalysis B: Environmental, 303 (2022) 120848.

[3] D. Pangotra, L.-I. Csepei, A. Roth, V. Sieber, L. Vieira, Anodic generation of hydrogen peroxide in continuous flow, Green Chemistry, 24 (2022) 7931-7940.

[4] D. Pangotra, A. Roth, V. Sieber, L. Vieira, Electrochemical Water Oxidation to Hydrogen Peroxide on Bipolar Plates, ACS Sustainable Chemistry & Engineering, 11 (2023) 2680-2685.
Zincate Replacement, an Economical a Sustainable Alternative for the Metal-Coating of Aluminum
Authors: Walter Anke , Tomin Bogdan , Kohlmann Lars , Krause Carsten , Brunner Heiko
Published: February 2024

Aluminum parts are of great value for many industries as they are cost-effective, very lightweight combined with a good mechanical strength. However, when parts are exposed to corrosive and abrasive conditions it is preferred to protect them with anodizing, powder coating, or for technical critical applications with nickel-phosphorus (NiP) coatings. Most preferred for functional parts such as scroll compressors, connectors,... is electroless NiP (EN) as it is has a low thickness variation in the final deposit and does not need the application of current like galvanic NiP coatings.

Depositing an adherent layer of electroless NiP onto aluminum needs an alloy-specific pre-treatment. The largest challenge in pre-treatment lies in the very fast formation of Al2O3 oxide under neutral pH conditions of 4 - 9. For decades a very effective way to inhibit the re-oxidation of aluminum is the use of alkaline zinc as interim coatings that dissolve in the electroless NiP electrolyte before NiP deposition starts. Commercial solutions are optimized to produce an as thin and homogenous as possible zinc deposit to minimize the drag-in of zinc into the NiP electrolyte. At levels of 80 - 200 mg/l zinc starts to lower the adhesion and plating rate of deposited EN coatings. As results the nickel process needs to be discarded before nickel deposition capacity of electrolyte is fully reached (~ 40 g/l plated Ni). The impact of Zn contamination is most critical as lower the thickness of the EN layer is. At very thin thicknesses below 4 µm the increase of zinc is very large, and electrolytes need to be discarded at 6-12 g/l plated nickel creating higher chemical waste, maintenance effort, and cost. Due to technical changes in many applications, different and more parts will be composed of aluminum. In contrast to established applications NiP that exhibit EN layers > 5 µm new applications arise with the upcoming EV and Battery market that request thinner NiP layers. The most extreme case is reel-to-reel plating of thin (< 50 µm) foils with NiP deposits below 4 µm.

In the present work, the application of a new chemical concept of aluminum pre-treatment for low-thickness EN coatings will be presented that reduces the number of needed process steps compared to double zincate by at least 2 steps (excl. rinses) without the need for special equipment such as pulse plating and others. Differences in the initiation of electroless NiP deposition and the correlated adhesion will be evaluated. As a model case, the application of thin NiP layers (< 4 µm) on pure Aluminum foils will be shown and discussed.

Figure 1
Improving the Electrochemical Performance of Sio Anode Material by Dual-Doping with Lithium and Titanium
Authors: Kim Seungeun , Jeong Won Joon , Chung Dong Jae , Youn Donghan , Kim Nam Gyu , Kim Junho , Ko Da Young , Kim Hansu
Published: February 2024

Silicon monoxide (SiO) has been considered as a potential candidate of high capacity anode material for lithium-ion batteries; however, its low initial Coulombic efficiency (ICE) is a critical problem to overcome. Although a solid-state prelithiation method for SiO using LiH was reported to enhance ICE up to 90.5 %, there are still cycle performance issues that need to be resolved before commercial application. In this presentation, we propose SiO anode material dual-doped with lithium and titanium using metal hydrides to enhance both ICE and cycle performance. This Li-Ti dual-doped SiO material shows improved cycle performance than prelithiated SiO with LiH for up to 500 cycles without sacrificing ICE, because the TiSi2 mechanical buffer phases formed by the reaction with TiH2 accommodate the volume expansion during cycling. Li-Ti dual-doped SiO material also exhibits improved thermal stability at elevated temperatures and rate capability compared to prelithiated SiO with LiH. More detailed material and electrochemical properties of Li-Ti dual-doped SiO will be discussed further in the presentation.
A Scalable Furnace Technique to Grow Silicon Nanoparticles for High-Performance Li-Ion Battery Anodes
Authors: Patil Rohan , Phadatare Manisha , Örtegren Jonas , Hummelgård Magnus , Blomquist Nicklas , Olin Håkan , Limaye Santosh , Bäckström Joakim , Zanghellini Ezio , Brandell Daniel , Hernández Guiomar
Published: February 2024

Lithium-ion battery (LIB) technology is one of the key technologies to lower the emission from fossil fuel while maintaining stable supply of energy to the society. One way to increase the capacity of LIBs is to add silicon to the graphite anode, since silicon can store much more lithium ions than graphite. Silicon does however expand and contract during lithiation and delithiation, leading to cracks which deteriorates the performance of the LIB anode. Mechanical cracking can be avoided by using sufficiently small silicon nanoparticles. Several high-performance schemes utilizing silicon nano materials such as nanoparticles, nanotubes, nanorods etc. have been demonstrated but industrial-scale implementation of these solutions still poses a challenge. The Siemens process is one of the most commonly used methods to create silicon nanoparticles and uses chemical vapor deposition (CVD) processes involving silane or silane derivatives as precursors. Due to the flammable and toxic nature of silane, the CVD process requires special handling care and expensive instrumentation. In this work, a novel scalable furnace technique to create silicon nanoparticles attached to graphene flakes LIB anode applications is presented. With this technique, we can avoid the silane precursor. In addition, the instrumentation requirements of the furnace technique are quite simple and inexpensive and the technology is compatible with already established industrial-scale electrode manufacturing techniques.

In the work presented here we demonstrate how silicon nanoparticles are grown from micro sized silicon powder onto graphene flakes using simple thermal treatment. Thermal gravitometry, mass spectrometry and differential scanning calorimetry was used to show how silicon powder and a binder can be converted to silicon nanoparticles by simple pyrolysis. The silicon nanoparticles are grown on top of graphene flakes to create a LIB anode. The anode, when tested in a half cell assembly shows a capacity that is considerably higher than standard graphene/graphite electrodes.
Understanding the Self-Discharge Redox Shuttle Mechanism of Dimethyl Terephthalate in Lithium-Ion Batteries
Authors: Bötticher Tom , Adamson Anu , Buchele Sebastian , Alter Ethan D. , Metzger Michael
Published: February 2024

Recent studies showed that LFP/graphite cells without additives show higher reversible self-discharge after 500 h of open-circuit voltage (OCV) storage at 40 or 60°C than NMC811/graphite cells.1 Furthermore, cells with lithium hexafluorophosphate (LiPF6), the most commonly used conducting salt in lithium-ion batteries, show higher self-discharge than cells with lithium bis(fluorosulfonyl)imide (LiFSI), an alternative salt with higher temperature stability.2 Recently, dimethyl terephthalate (DMT) was identified as the redox shuttle molecule responsible for the unwanted self-discharge of these lithium-ion batteries.3 In a lithium-ion cell, a reversible shuttle can gain an electron at the negative electrode by reduction, diffuse to the positive electrode, lose the electron by oxidation, and then repeat the process many times (see Figure 1). Adamson et al.4 proved that DMT is created in-situ as a breakdown product of polyethylene terephthalate (PET), which is a surprisingly common polymer for the adhesive tapes found in commercial batteries. The exact redox potential and electrochemical stability of DMT, as well as its shuttling mechanism across electrodes passivated with a solid-electrolyte interphase (SEI) however were not understood.

Based on an optimized coin cell cyclic voltammetry setup, ultra high precision coulometry measurements, OCV storage, and GC-MS experiments, we present new insights on the self-discharge redox shuttle mechanism of DMT in LFP/graphite pouch cells, investigate if this redox shuttle can account for the self-discharge differences in LiPF6 and LiFSI cells, and explore the stability of DMT in pouch cells.

References:

E. R. Logan, A. Eldesoky, E. Eastwood, H. Hebecker, C. P. Aiken, M. Metzger and J. R. Dahn, J Electrochem Soc, 2022, 169, 040560.

E. R. Logan, A. Eldesoky, E. Eastwood, H. Hebecker, C. P. Aiken, M. Metzger and J. R. Dahn, J Electrochem Soc, 2022, 169, 040560.

S. Buechele, A. Adamson, A. Eldesoky, T. Boetticher, L. Hartmann, T. Boulanger, S. Azam, M. B. Johnson, T. Taskovic, E. Logan and M. Metzger, J Electrochem Soc, 2023, 170, 010511.

A. Adamson, T. Bötticher, K. Tuul, M. Garayt, S. Azam and M. Metzger, Manuscript in Preparation, 2023.

Figure 1
Characterisation of Smoke Particles from Lithium-Ion Battery Fire: Morphology, Size and Composition
Authors: Adanouj Ibtissam , Napolitano Emilio , Sommariva Marco , Enzo Stefano , Lebedeva Natalia
Published: February 2024

The electrification of the transport sector is a necessary step to reduce the concentration of greenhouse gas emissions (GHGs) in the atmosphere in order to mitigate climate change. Li-ion batteries (LIBs) are considered a key enabling technology and are crucially important for the green energy transition. However, LIBs may pose safety concerns, as demonstrated by the recurrent fire accidents involving electric vehicles, according to news reports from recent years. Several studies concentrated mainly on the identification, composition and flammability of vented gases during LIBs thermal runaway and fires. Scarce work about the particle emissions during a LIB fire can be found in the literature. To fill up this research gap, in this study, we characterised smoke particles from Li-ion battery fire using Scanning Electron Microscopy/Energy Dispersive X-ray spectroscopy (SEM/EDX) and X-ray Diffraction (XRD) to evaluate their size, morphology, crystallographic and chemical composition. Our results show that battery fire smoke particles contain chemical components and crystallographic phases that are toxic for health and environment. Moreover, we confirm the presence of (ultra) fine particles, reported previously, which due to their small size are inhalable and can therefore pose a serious risk to human health. Recommendations for further experimental studies are outlined to establish e.g. a correlation between smoke particles emissions and battery SOC, chemistry, abuse scenario, etc.
(Invited) Recent Progress in Redox Flow Deionization
Authors: Kim Choonsoo , Kim Seonghwan
Published: February 2024

Recently, redox flow deionization (RFD) has gained great interest in water desalination as a promising electrochemical ion separation process. The RFD system advances the redox flow battery by adapting intervening channels for the water stream. As a unique cell feature, the system is comprised of multi-channels allowing the independent control of the flow streams (e.g., water stream and redox flows). This leads to several advantages compared to the conventional electrochemical ion separation processes such as capacitive deionization and electrodialysis: (1) sustainable redox reaction enables low operational cell voltage and high diversity in the employment of electrode materials, (2) the mild reaction environments allow less byproduct production and less variation in pH as this system facilitating downstream processes, and (3) the stored energy at redox couples provides energy recovery process with a simultaneous ion separation leading to high energy efficiency in water desalination.

In line with the development of RFD, this presentation aims to introduce the basic principle of the RFD system and recent progress, including cell architecture, electrodes, operations, and scale-up strategy. In addition, various applications are addressed such as resource recovery and pollutant control. Finally, we briefly propose the practical challenges and opportunities for future research direction.
3D Silver Sponge Electrodes for High-Rate Faradaic Deionization of High-Salinity Waters
Authors: Neale Zachary Garbe , DeBlock Ryan H. , Rolison Debra R. , Ford Hunter O. , Long Jeffrey W.
Published: February 2024

The availability of potable water is a growing global challenge that requires implementing water-purification technologies across a range of production scales from municipal systems to personal, distributed use. Reverse osmosis effectively desalinates high-salinity waters (e.g., undiluted seawater) at large scale, yet may be less suited to small-scale use due to the high-pressure pumps and regular maintenance required for operation. Capacitive deionization (CDI) utilizes high-surface-area carbon electrodes that can offer a more down-scalable desalination approach, but the relatively low capacity of double-layer storage mechanisms limits their use to low-salinity input (brackish water). Alternatively, faradaic deionization (FDI) materials that exhibit redox mechanisms for ion storage present an opportunity to displace reverse-osmosis systems in small-scale desalination systems. As one example, the redox reaction, Ag(s) + Cl–(aq) ↔ AgCl(s) + e–, can be exploited for Cl– capture in desalination cells that pair Ag/AgCl electrodes separated by a cation exchange membrane.1,2 We use macroporous silver “sponges” developed at the U.S. Naval Research Laboratory as millimeters-thick flow-through electrodes that show practical salt absorption capacities >100 mg/g while maintaining high salt removal rate courtesy of this kinetically facile conversion reaction. We investigate different silver sponge architectures and their effect on desalination throughput (L/m2/h) and energy consumption (Wh/L) for inputs up to seawater-level salinity using a custom computer-controlled batch-testing system. These readily fabricated, scalable Ag sponges serve as an attractive archetype electrode for high-performance faradaic desalination.

1 P. Srimuk, S. Husmann, and V. Presser, RSC Adv., 2019, 9, 14849–14858.

2 J. Ahn, J. Lee, S. Kim, C. Kim, J. Lee, P.M. Biesheuvel, and J. Yoon, Desalination, 2020, 476, 114216.
Solid-State Electrolyte for Lithium Extraction from Salt Lake Brines
Authors: Lei Chong , Wu Hui
Published: February 2024

Lithium sources are of great significance for developing the next generation of lithium ion batteries. Most of the world’s lithium sources are found in salt lake brines. The main challenge of lithium extraction from salt lake brine is the separation of lithium ions from other coexisting ions, especially the separation of Li+ and Mg2+. However, the traditional precipitation method for salt lake lithium extraction is cumbersome. In this project, a new electrolytic device with a solid-state electrolyte was developed for high-efficient lithium extraction from salt lake brines. Li1+xAlxTi2−x(PO4)3 (LATP) is a promising NASICON-type solid-state electrolyte, which exhibits high ionic conductivity ( >10-4 S/cm) at room temperature. LATP can be used as a lithium ion conductor, that is only lithium ions can transfer through it, which is ideal for separating lithium ions from other ions in salt lake brines. In this project, high-quality LATP was fabricated at a low cost. An electrolytic device was developed for lithium extraction, in which LATP was used together with a sacrificial anode, molten salts, and an inert cathode. Salt lake brines need to be concentrated by solar and/or wind evaporation before lithium extraction. The electrolytic device was operated above the melting point of the concentrated brine water, at which LATP exhibits a higher ionic conductivity for fast lithium ion transfer. A tiny voltage was applied across the two electrodes to drive the electrochemical reaction. The composition of lithium sources before and after extraction was investigated by inductively coupled plasma-optical emission spectroscopy (ICP-OES). Results show that lithium sources with a higher purity level were successfully extracted with high efficiency. Impurity ions were almost completely blocked by LATP.
Activated Carbon Electrodes Obtained from Crude Glycerol for Capacitive Deionization Desalination
Authors: Ruotolo Luis Augusto Martins , Barcelos Kamilla Malverde , Oliveira Kaíque S. G. C. , Juchen Patricia Trevisani
Published: February 2024

The freshwater demand increases over the years to attend agriculture, industry, and human consumption demand. Water desalination by capacitive deionization (CDI) would be an interesting strategy to provide freshwater for populations suffering of water scarcity in arid and semi-arid regions in which brackish groundwater is available. CDI is an electrochemical technique based on the removal of ions using carbon electrodes. Besides low-cost, activated carbons (AC) produced from renewable sources are also desired due to sustainability demands. In parallel, appropriate routes for disposal or reuse of crude glycerol from biodiesel plants are also a major current concern (10 kg of biodiesel generates ~1.0 kg of glycerol). So, considering the water-waste nexus concept, in this work we proposed the use of crude glycerol as precursor to obtain a new sustainable activated carbon (PGAC), which was employed as an electrode for CDI desalination of brackish water. The crude glycerol is firstly converted to polyglycerol, which is carbonized and then chemically activated. The best desalination performance using the PGAC electrodes was achieved using membrane CDI configuration, applying 1.6 V, providing a stable salt adsorption capacity (SAC) of 27.1 mg of NaCl removed per g of PGAC over 50 desalination cycles. At this condition, co-ion repulsion is minimized and the charging efficiency (QE
) remained close to 100%. The high values of SAC and QE
, along with the low cost of PGAC electrode, led to a very low specific energy consumption (2.6 J per mg of NaCl removed), compared to other values reported in literature, making it a potential candidate for use in CDI desalination. In order to further improve the desalination performance, a new cell architecture was proposed, named percolation flow cell (PFC). The PFC cell combines the fast mass transfer rates of the flow-through cell (FTC) configuration and longer residence time of flow-by cells (FBC), in which the flow velocity and electric current fields are perpendicular. Taking advantage of the beneficial aspects of the FBC and FTC designs, the desalination carried out using the PFC was enhanced by 170 %, providing a remarkable water desalination rate of 1661 mg g-1 day-1 at 1.0 mA cm-2 and single pass operation (7.0 mL min-1). Despite these advantages, the high pressure drop (0.12 bar cm-1) imposes a challenging issue for the effective application of PFE cells.