bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Invited) Design of Specific Polymer Binders for Stabilization of Si Based Anode in Lib
Authors: Matsumi Noriyoshi 
Published: February 2024

In recent years, intense efforts have been focused on stabilization of silicon-based anode in Li ion secondary batteries due to their remarkably high theoretical capacity. At the same time, strategy has not yet been established on how to stabilize the silicon based anode sufficiently during long cycles so that it will be feasible for practical use.
In this talk, several different approaches on stabilization of silicon-based anode will be introduced both in terms of polymer binders design and active materials design.
Our group synthesized several self-healing polymer binder and polymer coating material which are efficient for the use in silicon-based anode. Poly(borosiloxane) (PBS)1 was prepared by dehydrocoupling polymerization between mesitylborane and diphenylsilanediol in the presence of transition metal catalyst. PBS was found to show self-healing property at 45oC when coated onto Si electrode. When PBS coated Si electrode was employed for anodic half cell (Si/EC:DEC (1/1=v/v)/Li), it showed much improved durability when compared with PVDF coated Si based cell or bare Si based cell. We also reported a design of BIAN (bis-imino-acenaphthene) based conjugated polymer (P-BIAN) /Poly(acrylic acid) (PAA) composite binder for Si based anode2,3. Due to combination of n-type imine-based conjugated polymer (H-bonding acceptor) and PAA (H-bonding donor), synergistic effect in stabilization of Si/C composite anode was observed due to both of desirable electronic structure of P-BIAN and H-bonding based self-healing properties. In this system, anodic half cell delivered specific discharging capacity of above 2000 mAhg-1 for 600 cycles. As alternative approaches, we are also working on preparation of specific Si based anodic active materials which showed extremely high durability. b-SiC/N-doped carbon4 was found to show excellent durability even in the presence of conventional binder materials due to restricted volumetric changes of b-SiC during lithiation/delithiation. We also report coating of mechanically highly robust silicon oxycarbide on micro silicon5, which was also found to be quite effective.
References
1) Patnaik, S. G.; Jayakumar, T. P.; Sawamura, Y. Matsumi, N. ACS Appl. Ener. Mater.
2021, 4, 2241.
2) Gupta, A.; Badam, R.; Matsumi, N. ACS Appl. Ener. Mater.
2022, 5, 7977.
3) Gupta, A.; Badam, R.; Nag, A.; Kaneko, T.; Matsumi, N. ACS Appl. Ener. Mater.
2021, 4, 2231
4) Nandan, R.; Takamori, N.; Higashimine, K.; Badam, R.; Matsumi, N. J. Mater. Chem. A.
2022, 10, 5230.
5) Nandan, R.; Takamori, N.; Higashimine, K.; Badam, R.; Matsumi, N. J. Mater. Chem. A.
2022, 10, 15960.
(Invited) Coordinatively Cross-Linked Binders for Silicon-Based Electrodes for Lithium Ion Batteries
Authors: Huet Lucas , Moreau Philippe , Devic Thomas , Dupre Nicolas , Roue Lionel , Lestriez Bernard 
Published: February 2024

We have proposed a simple and versatile preparation of Cu(II)- or Zn(II)-poly(carboxylates) reticulated binders by the addition of Cu(II) or Zn(II) precursors into a pre-optimized carboxymethyl cellulose / citric acid binder solution. These binders lead systematically to a significantly improved electrochemical performance when used for the formulation of silicon-based negative electrodes [1,2]. Mechanical characterizations reveal that the coordinated binders offer a better electrode coating cohesion and adhesion to the current collector, as well as higher hardness and elastic modulus, which are even preserved in presence of a carbonate solvent (i.e. in battery operation conditions). Ultimately, as shown from operando dilatometry experiments, the electrode expansion during lithiation is reduced, mitigating electrode mechanical failure [2]. In complement, we used scanning transmission electron microscopy coupled with energy dispersive X-ray spectroscopy to probe the nanoscale morphology of such electrodes. This technique reveals the homogeneous coordination of carboxylated binder with Zn cations and its layering on the silicon surface. The SEI formed after the first cycle is denser with Zn-coordinated binder and preferentially observed on binder-depleted zones [3]. In summary, the superiority of coordinated binders can be attributed to their capacity to better stabilize the electrode and the SEI layer due to improved mechanical properties. This resulted in a lower SEI impedance, a higher first cycle coulombic efficiency, and a 40% improvement of capacity retention after 60 cycles for highly loaded electrodes of over 6 mAh.cm-2. Noteworthy, this formulation principle allows for better reproducibility and manufacturing quality of the electrodes [4].
[1] D. Mazouzi, R. Grissa, M. Paris, Z. Karkar, L. Huet, D. Guyomard, L. Roué, T. Devic, B. Lestriez, Electrochimica Acta, 304 (2019) 495-504
[2] L. Huet, D. Mazouzi, P. Moreau, N. Dupré, M. Paris, S. Mittelette, D. Laurencin, T. Devic, L. Roué, B. Lestriez, ACS Applied Materials & Interfaces, 15 (2023) 15509-15524
[3] L. Huet, P. Moreau, N. Dupré, T. Devic, L. Roué, B. Lestriez, Small Methods, 2022, 2200827
[4] L. Huet, H. Houisse, N. Herkendaal, T. Devic, L. Roué, B. Lestriez, Energy Technology, 2023, 2201483

Figure 1
Next-Generation Battery Components Derived from Soft Dendritic Colloids
Authors: Petrecca Michael J. , Shenoy Akhil , Leatherman Jaden R. , Velev Orlin D. , Fedkiw Peter S. 
Published: February 2024

Growing demands for energy storage are causing rapid development of next-generation batteries. Researchers typically use commercially available Li-ion components and processing techniques to investigate new chemistries and cell architectures. Herein, we propose an emerging materials-development platform: shear- driven precipitation of polymeric materials to develop application-specific battery components. In this process, polymer particles with high aspect ratios, called soft dendritic colloids (SDCs), are formed via turbulent solvent-nonsolvent induced phase separation. Two specific component applications are presented.
The first application is nano-composite redox active polymer electrodes for Li-ion batteries. Redox polymer electrodes are currently limited by low intrinsic electronic conductivity. As a result, large amounts of conductive additives are added to the composite electrodes, lowering the gravimetric performance. The network forming capabilities of the SDC morphology provides intimate contact between active material and conductive material to enable free-standing electrodes that are produced via simple vacuum filtration. We present cyclic voltammetry and charge/discharge data using poly(2,2,6,6-tetramethyl-1-piperidinyloxy methacrylate) as the SDC material.
The second application is composite separator assemblies to mitigate lithium polysulfide shuttling in Li-S batteries. Polysulfide shuttling is considered a technological hurdle plaguing Li-S battery development. Separators can be functionalized to reduce polysulfide shuttling by incorporating additives onto or within the separator matrix, which either bind or repel the soluble species to prevent crossover to the anode. We demonstrate that SDC materials are a promising platform for fabricating nanocomposite separators using a variety of nanomaterials. The nano composite separators show increased thermal stability, cycling stability, and polysulfide rejection as compared to commercial materials.
(Best Presentation Award - 3rd Place) Evaluating the Safety Limits of Soft Shorting in Li-Ion Batteries
Authors: Schumacher Bret , Marbella Lauren , Steingart Daniel A. 
Published: February 2024

This study aims to redefine the safety limitations of lithium dendrite soft shorting in lithium-ion batteries using isothermal microcalorimetry and thermal reduction tests. Lithium dendrites are generally assumed to pose a safety risk by causing fatal short circuits, which can lead to thermal runaway and catastrophic battery failure. This assumption has led to massive amounts of time and capital on dendrite suppression and elimination research.
Thermal reduction tests on delithiated lithium cobalt oxide were conducted to determine the absolute temperature at which thermal runaway occurs in one of the most volatile conventional systems. Isothermal microcalorimetry was conducted on the same system to measure the heat generated by the soft short circuit. Our results showed that the absolute temperature generated by the lithium dendrite soft short circuit was significantly less than the onset of thermal runaway via a thermal reduction route. These findings challenge the general assumption that lithium dendrites will directly lead to thermal runaway events in lithium-ion batteries.
Our study suggests that while lithium dendritic shorting may pose a safety risk in lithium-ion batteries, it will not directly lead to a catastrophic thermal event. Further research is needed to explore the potential implications of deactivating the metallic lithium in the system via this soft shorting pathway.
(Invited) Estimating OCP-Temperature Dynamics for Determining Lithium-Ion Battery Entropy Coefficients
Authors: Widanalage Dhammika , Queisser Oliver , Paarmann Sabine , Wetzel Thomas 
Published: February 2024

The open-circuit potential (OCP) of a li-ion cell is a function of both state-of-charge and temperature. Characterising its dependence on temperature is important for thermal simulations as the derivative of the OCP with temperature acts as a reversible heat source term in the model. Known as the entropy coefficient, this derivative is a thermodynamic quantity that varies over the cell’s state-of-charge (SoC). The potentiometric approach [1] is widely used to characterise the entropy coefficient for a given SoC. This involves applying step changes in the temperature and allowing the cell OCP to reach (or approach) a steady-state value, which can take several hours (>8 hours), for a given SoC of interest.
Robust techniques are required that can significantly reduce the experimental time and quantify the entropy coefficient over the full SoC window, leading to higher fidelity battery thermal models. In this work, the dynamics between the OCP and cell temperature are exploited via system identification techniques to derive the entropy coefficient. This is achieved by estimating the underlying kernel function between the cell OCP and temperature dynamics. The kernel function is a non-parametric estimate of the dynamics from which the entropy coefficient can be determined.
In this work temperature signals are designed with multiple frequency components and applied to a cell via Peltier elements. The corresponding OCP response is then analysed, in the frequency domain, to estimate the kernel function. Unlike the potentiometric method, which drives the battery to steady-state and necessitates long experimental durations, the kernel function can be estimated under transients, facilitating faster characterisation. The figure demonstrates comparable results of the entropy coefficient, over the full SoC interval, when estimated via the kernel function and the potentiometric approach. The approach, compared to the potentiometric method, however, brings around a two to three times reduction in experimental time per SoC and gives insight into the OCP and temperature dynamics. The signal design, kernel estimation and entropy coefficient estimation procedures are detailed in this talk.

Schmidt, J. P., Weber, A., et al., Electrochimica Acta
2014, 137, 311-319. DOI 10.1016/j.electacta.2014.05.153

Figure 1
Cell to Pack Modelling of Li-Ion Batteries for Electric Vehicle Applications: Development and Potential Challenges
Authors: Rashid Muhammad , Zhu Tao , Atalay Selcuk , Saniee Nessa Fereshteh , Dinh Truong , McGordon Andrew 
Published: February 2024

Electric vehicles (EVs) and hybrid electric vehicles (HEVs) which are powered by Li-ion batteries (LIBs) have the potential to address the challenges of reducing the dependence on fossil fuels and environmental pollution caused by the transportation sector. However, for the reliable and safe operation of the EVs and HEVs, an accurate estimation of the state of charge (SOC) and state-of-health (SOH) of the battery pack is required. The battery capacity degrades with cycling and calendar ageing over time and usage of the vehicles, which reduces the power capability and driving range of the vehicle. An accurate prediction of the battery SOC and SOH can assist the vehicle user in planning to reach the next charging station or the destination with enough range left before the battery gets fully discharged, hence avoiding annoying circumstances.
Battery models have been widely employed in battery health and SOC prediction and can successfully predict the SOC and SOH of individual cells. However, the translation of these models from cell to pack levels adds several unknown critical factors which affect the model prediction capability significantly.
Our proposed ECM model is based on the electrical and thermal behavior of individual cells, and it accounts for critical factors such as cell-to-cell variations, temperature gradients, and aging effects. We also incorporate a series-parallel configuration to simulate the behavior of multiple cells at the module and pack levels. By upscaling the model in this way, we can accurately predict the SOC and SOH of the entire battery pack, and provide reliable estimates of the remaining driving range and charging requirements.
We anticipate that our proposed ECM model will significantly improve the accuracy of SOC and SOH predictions, which will enable EV/HEV users to better plan their trips, avoid unexpected battery failures, and improve the safety of EV/HEV batteries. Furthermore, our study has the potential to inform the design of future battery technologies and contribute to the transition toward sustainable transportation powered by clean energy sources.
(Invited) On the Role of Thermo-Electrochemical Coupling in Li-Ion Batteries
Authors: Kingston Todd A. , Pint Cary L. , Carter Rachel Elizabeth , Love Corey T. , Ishtiaque MD Mahdi UL , Harkaway Andrew , Ramamurthy Jayanth R. 
Published: February 2024

Li-ion batteries have revolutionized a wide range of industries, from consumer electronics to vehicles. Their relatively high power and energy density and exceptional Coulombic efficiency are particularly advantageous for portable applications. Significant efforts have gone into studying the impact of thermal conditions on the electrochemical characteristics of Li-ion batteries because, in part, of the wide range of temperatures these devices are operated in. Recently, we have shown that thermo-electrochemical coupling in Li-ion batteries is of critical importance. In this talk, we will highlight some of our recent work that measures the local thermal conditions within the cell using embedded instrumentation and illustrates how significant thermal variations within the cell, specifically thermal gradients, are on electrochemical behavior. Moreover, we will discuss our efforts to pinpoint the underlying mechanisms that give rise to these effects.
Acknowledgments:
The authors thank Dr. Michele Anderson (Office of Naval Research, grant N00014-22-1-2411) for financial support of this work.
(Battery Division Early Career Award Sponsored by Neware Technology Limited) Towards Scalable and Sustainable Battery Recycling for Circular Energy Storage
Authors: Chen Zheng 
Published: February 2024

The development of electric vehicles (EVs) and grid storage heavily relies on lithium-ion batteries (LIBs) that exhibit significantly improved performance, low cost, a reduced carbon footprint, and an abundance of resources. However, the growing consumption of LIBs has led to concerns regarding resource scarcity and price hikes for lithium and critical transition metals (such as Co and Ni) that are essential for LIB production. Currently, the recycling industry utilizes pyrometallurgical and hydrometallurgical processes to treat spent batteries. Although these methods are scalable, there is a pressing need for enhanced overall energy efficiency, reduced processing costs, and minimized environmental impact.
Next-generation technologies, such as direct recycling, hold promise as a more cost-effective and energy-efficient alternative. However, the scalability of these approaches must be proven at an industrial scale. This presentation aims to delve into the state-of-the-art LIB battery recycling by comparing various technologies. In particular, we will extensively discuss the technical aspects of direct recycling, focusing on different LIB materials. Furthermore, we will address the key challenges and provide insights for the future development of LIB recycling.
Development of High Electrochemical Performance-Reliability TiO2 Nanoparticle-Mulberry Paper Based Supercapacitor
Authors: Lee Seonghun , Yoon Hyungsub , Yun Tae Gwang 
Published: February 2024

The paper-based energy storage systems with lightweight, thin and large scalability have been attracted much attention in the field of next generation research. Along with the advantages of these papers, they have excellent flexibility and wettability, so they have high power density even under mechanical bending and twisting deformation, making them suitable for wearable devices. However, conventional paper has limited electrochemical stability due to its low chemical resistance and decomposition in organic or acidic electrolytes.
Mulberry paper can be an outstanding alternative for overcoming the limitations of conventional paper-based energy storage systems. Mulberry fibers form a stronger mechanical network and are longer than conventional paper fibers, so they have excellent chemical strength. Therefore, in this study, a supercapacitor with high electrochemical performance and reliability was produced based on mulberry paper.
As high electrochemical performance active materials, TiO2 nanoparticle and graphene oxide nanocomposites were used. A TiO2 nanoparticle was coated on a mulberry paper substate, graphene oxide was coated, and heat treatment was performed at 700℃ under nitrogen atmosphere for 3 hours. Mulberry paper was carbonized to increase areal energy density. It was strongly fixed by the reduced graphene oxide to maintain the flexibility of carbonized mulberry paper and prevent the delamination of the TiO2 nanotube without protection layer.
Therefore, it is suitable for wearable energy storage systems because it can maintain excellent charge-discharge cycle reliability and flexibility carbonized mulberry paper by improving areal energy density from carbonized mulberry paper and metal oxides and preventing the delamination of the metal oxide.
NMC811 Electrodes with High Mass Loadings Enabled By Non-Solvent Induced Phase Inversion
Authors: Weijers Mark , Karanth Pranav , Ombrini Pierfrancesco , Ripepi Davide , Ooms Frans , Mulder Fokko M. 
Published: February 2024

Higher energy density Li-ion batteries that can enable longer driving ranges are currently subject to intensive research interest. Increasing the thickness of electrodes and reducing the proportion of inactive components per cell is one way to achieve this. In thick electrodes, a higher electronic and ionic overpotential and mechanical failure (cracking, delamination etc.) induced by binder migration during the drying process leads to sluggish (dis)charge performance or even cell failure respectively. Here we report non-solvent induced phase inversion as a scalable, effective method to arrive at thick NMC811 electrodes.
By tuning the non-solvent properties and other processing conditions to be compatible with Ni-rich electrodes, it was possible to obtain NMC811 electrodes with mass loadings up to 11 mAh/cm2 (single sided) which outperform their conventional processed counterparts in Li/NMC half cells. This improvement could be attributed to the altered carbon-binder structure, which improves the pore connectivity and lowers the electrode tortuosity factor. The rapid solvent removal also reduces the long-range binder migration during drying. With imaging and porosimetry techniques we show the structural change which leads to the observed improved electrochemical performance. The method also shows good compatibility with double sided slot-die electrode coating procedure, making this a technique with potentially high industrial feasibility towards making thicker NMC811 and other electrodes.
Highly Conformal Solid Electrolyte for Li-Ion Batteries By Atomic Layer Deposition
Authors: Madadi Milad , Heikkinen Mari , Philip Anish , Karppinen Maarit 
Published: February 2024

Lithium phosphorus oxynitride (LiP
x
O
y
N
z
, commonly known as LiPON) is a state-of-the-art solid electrolyte material with suitably low resistivity and high ionic conductivity for all-solid-state thin-film microbatteries [1,2]. Thin and pinhole-free layers of LiPON can be fabricated using atomic layer deposition (ALD) [3]. Uniquely among thin-film fabrication methods, ALD is a technique that works for coating even challenging 3D interfaces [4,5]. In this work, LiPON ALD processes were optimized for two different lithium precursors at reasonable temperatures (~300 °C) and precursor pulse/purge lengths (< 5 s), and LiPON films were deposited onto PillarHall® lateral high-aspect-ratio (LHAR) test structures to investigate the conformality of the material. Comparative testing was performed between the two lithium precursors.
The results indicated that more conformal LiPON films can be deposited using the appropriate precursors – in this case, lithium tert-butoxide (LiO
t
Bu) yielded greater penetration depths than lithium hexamethyldisilazide (Li-HMDS). The improved conformality observed when using LiO
t
Bu indicates that this precursor is a better choice for LiPON coatings on high-aspect-ratio structures. The ALD technique allowed for the deposition of highly conformal LiPON films, ~50–115 µm deep into 100–500 nm gaps. This opens possibilities for the use of LiPON as a solid electrolyte in batteries with high-surface-area electrodes. High surface areas are important not only for unlocking higher power densities (faster charging and discharging) in batteries, but also for enabling the use of thin-film technology in fabricating microbatteries with meaningful energy storage capacities.
References
[1] LaCoste, J. D.; Zakutayev, A.; Fei, L. A Review on Lithium Phosphorus Oxynitride. J. Phys. Chem. C
2021, 125, 3651–3667.
[2] Oudenhoven, J. F. M.; Baggetto, L.; Notten, P. H. L. All-Solid-State Lithium-Ion Microbatteries: A Review of Various Three-Dimensional Concepts. Adv. Energy Mater.
2011, 1, 10–33. https://doi.org/10.1002/aenm.201000002.
[3] Nisula, M.; Shindo, Y.; Koga, H.; Karppinen, M. Atomic Layer Deposition of Lithium Phosphorus Oxynitride. Chem. Mater.
2015, 27, 6987–6993.
[4] Oudenhoven, J. F. M.; Baggetto, L.; Notten, P. H. L. All-Solid-State Lithium-Ion Microbatteries: A Review of Various Three-Dimensional Concepts. Adv. Energy Mater.
2011, 1, 10–33.
[5] Xia, Q.; Zan, F.; Zhang, Q.; Liu, W.; Li, Q.; He, Y.; Hua, J.; Liu, J.; Xu, J.; Wang, J.; Wu, C.; Xia, H. All-Solid-State Thin Film Lithium/Lithium-Ion Microbatteries for Powering the Internet of Things. Adv. Mater.
2023, 35, 1–48.

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