Graphite Anode Research Articles

A non-destructive heating method for lithium-ion batteries at low temperatures

Low temperatures seriously affect the performance of lithium-ion batteries. This study proposes a non-destructive low-temperature bidirectional pulse current (BPC) heating method. Different from existing heating approaches, this method not only optimizes heating frequency and amplitude but also considers the optimization of the charge/discharge pulse duration ratio. To optimize the BPC heating strategy, a precise electro-thermal coupled model is established, and a neural network is employed to delineate the relationship among model parameters, temperature, and state of charge (SOC). Additionally, the interplay between the impedance of the graphite anode and that of the full cell is analyzed by constructing a three-electrode battery. Then, a novel full-cell-oriented lithium plating criterion is introduced. Finally, based on the constructed electro-thermal coupled model, lithium plating criterion, and terminal voltage constraint, a novel non-destructive BPC heating method is proposed. The results show a significant improvement in heating efficiency compared to conventional BPC heating. Especially for high SOCs, the heating power is increased at least 8 times. When the battery SOC is below 40 %, the average heating rate from −10 °C to 10 °C is 11.28 °C/min. Even at 90 % SOC, the heating rate remains at 2.88 °C/min. Furthermore, the capacity and impedance of a battery at 50 % SOC exhibit no significant changes after 60 heating cycles using the optimal BPC heating strategy at 100 Hz. These findings show that the optimized method proposed in this study has high heating efficiency and no damage to the battery.

Rapid Regeneration of Graphite Anodes via Self‐Induced Microwave Plasma

Rapid Regeneration of Graphite Anodes via Self‐Induced Microwave Plasma

Mildly expanded graphite with exceptional performance from waste lithium ion batteries by space-confined intercalation of deep eutectic solvent

Reclaiming the spent graphite (SG) in the anodes of end-of-life lithium-ion batteries (LIBs) is of tremendous significance for addressing resource shortage and eco-friendliness. The impurities embedded into the graphite interlayer after multiple charge–discharge cycles hinder the free migration of lithium ions, resulting in inferior lithium storage capacity. Herein, a space-confined intercalation of deep eutectic solvent (DES) strategy is proposed, to dissolve the impurities by utilizing its great ability to form hydrogen bonds (O–H…Cl-, O–H…O and O–H…F) with PVDF binder, SEI film and the residual electrolytes within the SG, simultaneously enlarging the interlayer distance to upgrade the anode graphite. After the further pyrolysis, the as-obtained mildly expanded graphite (MEG-800) exhibited well-defined graphite microcrystalline layer structure and high graphitization degree. The moderately enlarged graphite layers provided more space for the insertion and extraction of lithium ions, endowing MEG-800 with exceptional performance in LIBs, such as extremely high charge capacity of 477.4 mAh/g at a current density of 0.1 A/g and superior reversibility and desirable cycle stability. After 100 cycles at 0.1 A/g, its capacity still retained 470.9 mAh/g with a Coulombic efficiency as high as 99.76 %. The structure-dependent lithium-ion diffusion features of MEG-800 were also examined by electrochemical kinetics analysis. This study opened up a prospective avenue for the green and efficient recycling of spent anode graphite in retired LIBs, offering a solution to the problem of shortage of battery materials and promoting sustainable development.

Relationship between Silicon Percentage in Graphite Anode to Achieve High-Energy-Density Lithium-Ion Batteries.

High-weight-percentage silicon (Si) in graphite (Gr) anodes face commercialization hurdles due to fundamental and interrelated challenges. Nevertheless, using the existing manufacturing line, the optimized Si/Gr ratio is the most efficient and valuable way to fabricate high-energy-density lithium-ion batteries (LIBs). Still, literature has not thoroughly examined the Si/Gr ratio. This study addresses this critical gap by systematically evaluating Si content (5-20 wt %) in commercial graphite. The goal is to optimize the Si/Gr ratio for exceptional specific capacity while mitigating inherent Si limitations like cyclic stability and first-cycle irreversible capacity loss. This work employs a multidirectional approach, including in situ electrochemical impedance spectroscopy for interface analysis, rate capability assessment (up to 3 C-rate), Li diffusion coefficient measurement, and thorough cyclic stability evaluation. Increasing the silicon (Si) weight percent from 10% to 15% in the Si15Gr75 composite anode resulted in significant improvements in the first lithiation and delithiation capacities by approximately 16.8% and 16.0%, respectively. The Si15Gr75 cell delivered a high initial Coulombic efficiency of roughly 82.9%, nearly equivalent to a pure graphite anode. Furthermore, the Si15Gr75 Li cell exhibited excellent cyclic stability at a current rate of 0.5 C, retaining about 60% of its capacity after 215 cycles. Additionally, full-cell testing against a commercial NMC622 cathode showcases excellent performance across various current rates (0.1-0.5 C). This study paves the way for the development of high-energy-density LIBs by providing valuable insights into the optimization of Si/Gr composite anodes for commercial viability.

Exceptional fabrication of dead-weight-free silicon and graphitic heterostructures anodes for the next advancement of Li-ion batteries

Silicon (Si)-graphite and graphite (without Si) anodes for Li-ion batteries are developed at ambient conditions through the direct irradiation of CO2 laser, resulting in avoiding the use of binders, conductive carbon additives, and organic and water-based solvents. Furfuryl alcohol (FA) is mixed with Si-graphite and graphite, prepared viscous slurry through the heating, cast on the copper foil, and dried. Irradiation of CO2 laser at the electrode of Si-graphite-FA generates in-situ hetero-structures of Si particles, SiC/Si-SiC nanowires made of spontaneously carbon-coated/oxidized nano-layer (∼ 3nm), and graphitic carbon containing few layers of graphene. All the laser-fabricated electrode material is electrochemically active (∼ 0% dead weight) in the Si-graphite and graphite anodes since the FA converts to the graphitic carbon containing few layers of graphene; thus, the fabrication method could benefit the next industrial development. The discharge capacity of the Si-graphite electrode with total material loading is recorded at 502.2 mAh/g (∼ 1.9 mAh cm−2) and capacity retention of ∼ 80 % over the 50 cycles vs. Li/Li+. Also, it shows good discharge capacity when fabricated with NMC622 in full-cell format. Therefore, this performance is highly stable without any binder and conductive carbon, especially for Si-based battery, which fails rapidly due to substantial volume changes (∼ 300 %). Moreover, the performance is highly stable for graphite anode with a discharge capacity retention of 91 % over the 160 cycles as considered 100 % (∼ 345 mAh/g) after the formation cycle.

Long-Life Na3V2(PO4)3||Graphite Energy Storage Device Enabled via Regulating the Area Density of Anode

Abstract The regular graphite can only provide the negligible capacity for Na-ion intercalation, due to the narrow layer spacing and unstable thermodynamic factor. In this study, an energy storage device is created using the prelithiated graphite and Na3V2(PO4)3&NaClO4-based electrolyte, achieving an initial energy density of 317 W h kg−1 and a long lifespan of 1000 cycles with a 71.3% energy retention under the current rate of 1 C. Additionally, the prelithiated graphite anode could be recognized as an artificial Li metal with a strong skeleton, which reduces the volume changes and provides the growth substrate for Na-ion storage by the plating/stripping behavior. When the Li is depleted by participating in the reconstruction of SEI and the occurrence of complex side reactions, the battery system would die as a result. Therefore, the amounts of excess Li have a significant impact on the electrochemical performance of this device. That is to say that regulating the area density of anode enables a long-life Na3V2(PO4)3||graphite energy storage device.

An effective strategy for synthesizing high-performance photocatalyst by recycling the graphite target wastes

The tide of new energy vehicles and modern semiconductor devices releases a myriad of graphite anode and graphite target wastes. Recycling graphite wastes for catalysis preparation turns out to be a win-win and efficient way to deal with rampant environmental pollution. In this work, a graphite target waste was efficiently recycled into 2D few-layer graphite as the raw materials for the subsequent synthesis of nanoscale photocatalysts. The as-developed photocatalyst demonstrates a gain of 19 % in photocatalytic efficiency and superior photostability in sunlight-driven photodegradation of organic pollutants. Furthermore, the impact of temperature and pH value on the photocatalytic degradation efficiency was systematically investigated. The work affords an effective strategy for high-efficiency waste reclamation through full utilization of the graphite target wastes.

PVA generated carbon-coated natural graphite anode material for enhanced performances of lithium-ion batteries

PVA generated carbon-coated natural graphite anode material for enhanced performances of lithium-ion batteries

Design of Localized High Concentration Electrolytes for Fast-Charging Lithium-Ion Batteries.

Localized high-concentration electrolytes (LHCEs) have emerged as a promising class of electrolytes to improve the cycle life and energy density of lithium-ion batteries (LIBs). While their application in batteries with lithium-metal anodes is extensively investigated, their behavior in systems with graphite anodes has received less research attention. Herein, the behaviors of four electrolytes in Graphite | LiNiO2 cells are compared. By systematically varying the electrolyte compositions, the impacts of the solvation structure, solvent composition, and salt composition of LHCEs are identified on the rate capability, stability, and propensity for lithium plating in LIB full-cells. It is found that while the solvation structure and solvent composition each play an important role in determining rate capability, the substitution of LiPF6 salt with LiFSI maximizes the rate capability and suppresses irreversible lithium plating. It is now demonstrated via constant-potential cycling, that an appropriately formulated LHCE can, therefore, maintain high reversible capacity and safety under arbitrarily fast charging conditions.

Nondisassembly Repair of Degraded LiFePO4 Cells via Lithium Restoration from the Solid Electrolyte Interphase.

The disposal of degraded batteries will be a severe challenge with the expanding market demand for lithium iron phosphate (LiFePO4 or LFP) batteries. However, due to a lack of economic and technical viability, conventional metal extraction and material regeneration are hindered from practical application. Herein, we propose a nondisassembly repair strategy for degraded cells through a lithium restoration method based on deep discharge, which can elevate the anodic potential to result in the selective oxidative decomposition and thinning of the solid electrolyte interphase (SEI) on the graphite anode. The decomposed SEI acts as a lithium source to compensate for the Li loss and eliminate Li-Fe antisite defects for degraded LFP. Through this design, the repaired pouch cells show improved kinetic characteristics, significant capacity restoration, and an extended lifespan. This proposed repair scheme relying on SEI rejuvenation is of great significance for extending the service life and promoting the secondary use of degraded cells.

Enhancing the Mn Redox Kinetics of LiMn0.5Fe0.5PO4 Cathodes Through a Synergistic Co-Doping with Niobium and Magnesium for Lithium-Ion Batteries.

The concerns on the cost of lithium-ion batteries have created enormous interest on LiFePO4 (LFP) and LiMn1-xFexPO4 (LMFP) cathodes However, the inclusion of Mn into the olivine structure causes a non-uniform atomic distribution of Fe and Mn, resulting in a lowering of reversible capacity and hindering their practical application. Herein, a co-doping of LMFP with Nb and Mg is presented through a co-precipitation reaction, followed by a spray-drying process and calcination. It is found that LiNbO3 formed with the aliovalent Nb doping resides mainly on the surface, while the isovalent Mg2+ doping occurs into the bulk of the particle. Full cells assembled with the co-doped LMFP cathode and graphite anode demonstrate superior cycling stability and specific capacity, while maintaining good tap density, compared to the undoped or mono-doped (only with Nb or Mg). The co-doped sample exhibits a capacity retention of 99% over 300 cycles at a C/2 rate. The superior performance stems from the enhanced ionic/electronic transport facilitated by Nb coating and the enhanced Mn2+/3+ redox kinetics resulting from bulk Mg doping. Altogether, this work reveals the importance of the synergistic effect of different dopants in enhancing the capacity and cycle stability of LMFP.

Introducing surface adsorption lithium storage mechanism to enhance safety of graphite

The thermal stability of lithiated graphite plays an important role in the thermal safety of lithium-ion batteries (LIBs). However, a safer graphite anode usually leads to a lower energy density. This article starts from multiple hazardous factors of lithiated graphite when thermal runaway occurs, considering the impact of defects on the electrochemical performance and thermal safety of graphite electrodes. In this study, turbostratic graphite was prepared as the anode for LIBs. The stacking of graphite was altered to form narrow pores and spherical aggregates, and introducing defects. By varying the ball-milling time, the structural changes of different ball-milled graphites were analyzed. The impact mechanism of defect structure on electrode electrochemical performance and safety performance was investigated. The results show that the spherical structure and large specific surface area are beneficial to increase the active sites and delay the self-heating of the battery. The formation of defects and pores increases the adsorption sites, which makes the surface adsorption of Li+ dominant and improves the ion diffusion. In addition, the dominance of surface adsorption and desorption effectively suppresses the problem of graphite flake peeling and intensified thermal runaway caused by graphite phase transition and lithium evolution heat release at high temperature. The thermal safety test was carried out by accelerated calorimeter (ARC), and its thermodynamics and reaction kinetics were quantitatively analyzed. It was proved that the introduction of surface adsorption lithium storage method successfully delayed the thermal runaway of the battery, realizing the balance between high electrochemical performance and high safety.

Synthesis and characterization of hierarchically porous carbon anodes from furfural biorefinery residues for sustainable lithium-ion batteries

This study aims to valorize abundant lignocellulosic residues from furfural biorefineries into hierarchically porous carbon anodes for sustainable lithium-ion batteries (LIBs). Simultaneously, it addresses the growing demand for high-performance anode materials by leveraging renewable waste feedstocks. Sugarcane bagasse waste residues obtained after furfural extraction were used as the precursor. The furfural-derived bagasse residue (FDBR) underwent pyrolysis at 700 °C to produce a carbon-rich char, which was further activated using KOH and steam at 900 °C for 15–60 minutes to enhance porosity development. Comprehensive physicochemical characterizations, including proximate analysis, N2 adsorption-desorption, SEM-EDX, FTIR, and TGA/DTG, and Raman spectroscopy were performed to evaluate the properties of the synthesized activated carbons. The results demonstrated the successful generation of high surface area (405.8 m2/g) activated carbons with a hierarchical pore structure comprising micropores and mesopores. SEM and EDX analyses revealed a uniform, porous morphology enriched with 10.41 % at oxygen-containing functional groups. FTIR spectra confirmed the presence of hydroxyls, carbonyls, and carboxylic acid groups, beneficial for pseudocapacitive charge storage. The Raman analysis revealed a highly disordered and amorphous carbon structure with a significant concentration of defects, as evidenced by a high-intensity ratio (ID/IG ≈ 1.2–1.4) of the disordered carbon band to the graphitic band. The activated carbons exhibited a high initial discharge capacity of 1055 mAh/g in lithium half-cells, significantly exceeding the theoretical limit of commercial graphite anodes (372 mAh/g). This superior capacity was attributed to the high surface area, hierarchical porosity, and pseudocapacitive contributions from the oxygen functionalities. However, rapid capacity fading from 1055 to ∼250 mAh/g was observed over 100 cycles at a C/2 rate. The capacity retention stabilized at ∼88 % after 47 cycles, indicating irreversible capacity losses. These limitations were ascribed to the disordered amorphous structure, instability of the solid-electrolyte interphase, lithium trapping by oxygen groups, and structural changes during cycling. Optimizing activation conditions, incorporating conductive additives/coatings, exploring alternative binders, and surface functionalization are proposed to improve long-term cycling stability. Overall, this study demonstrates the feasibility of upcycling furfural biorefinery waste into sustainable LIB anodes while highlighting challenges and potential solutions for enhancing their electrochemical performance.

Alleviated volume changes of germanium anode via facile chemical confinement strategy

Germanium (Ge) anode shows great promise in overcoming unsatisfied capacity and dendrite formation concerns facing conventional graphite anodes in next generation lithium ion batteries. However, volume changes during repeated alloying and de-alloying cycles seriously impair structural stability and cycle lifespan. In this work, a facile chemical confinement strategy has been firstly proposed to alleviate volume changes of Ge anode. Benefited from strong binding interaction between Ge and ZnS, discrete Ge nanoparticle can be successfully encapsulated within thin protective ZnS shell and N-doped carbon layer (Ge-ZnS@N-C) after two-step carbonization and sulfurization of polydopamine-coating Zn2GeO4 nanorod precursors. In contrast, bulk Ge aggregates and hollow N-doped carbon nanotubes can be formed without chemical confinement of ZnS. The as-prepared Ge-ZnS@N-C sample displays multifold structural merits, including nanosized Ge particles with highly electrochemical activity, sufficient pores and functional groups that facilitate ion diffusion. Besides, protective ZnS shell and N-doped carbon layer can suppress volume changes of Ge nanoparticles and guarantee high electrode reversibility, demonstrated by a series of in-situ and ex-situ experiments. The as-synthesized Ge-ZnS@N-C anodes exhibit stable long-cycle performance (1389.7 mAh/g after 450 cycles at a current density of 0.5 A/g) and excellent rate performance (548.5 and 397.8 mAh/g at 5.0 and 8.0 A/g, respectively).

(Invited) Design Criteria of Ether Electrolytes and Stable Interphase Toward Reversible Intercalation Chemistry of Graphite Anode in Li-Ion Batteries

To date, it is extensively believed that ether electrolytes are incompatible with graphite anode in Li-ion batteries due to detrimental solvent co-intercalation and exfoliation. Here, we provide design criteria of ether electrolytes for reversible graphite anode without the high salt concentration. In short, for ether electrolytes, the reductive stability of anions (or their solvated complex) and the solid-electrolyte interphase (SEI) govern the reversibility of graphite anode. Exfoliation and co-intercalation are not the root cause of as-documented cell failures using graphite anodes. While reductive-instable lithium bis(fluorosulfonyl)imide (LiFSI) is the optimal salt paired with DOL, reductive-stable LiBF4 finds applications with DME. Individual 1,3-dioxolane (DOL) and 1,2-dimethoxyethane (DME) based electrolytes can enable ~99.9% Coulombic efficiency with excellent capacity retention and fast-charge capability using natural graphite. In DOL electrolytes, weakened Li-solvent interaction and preferential reduction of FSI anion coordinated with Li-ion contribute to homogeneous SEI enriched with inorganic species, for example, LiF. Therefore, electrolyte reduction and Li-DOL co-intercalation are inhibited. In DME electrolytes, we show that LiBF4 has limited reduction, majorly on the edge site. We discover that a self-terminating, heterogeneous interphase based on grainy LiF proves to be desirable for operating Li-solvent co-intercalation. Taking advantage of the anisotropic characteristics of natural graphite, we conducted a holistic investigation into the nature, function, and formation of the heterogeneous SEI. In these studies, we clarify a long-lasting confusing issue in LIBs community-that is, the compatibility between ether electrolytes and graphite anode. Our findings not only shed light on the enigmatic interphase formed by ether electrolytes but also offer critical insights into future electrolyte design for graphite anodes operated under extreme conditions.

Why Charge Rate Capability Tests Fail to Characterize Structured Electrodes in Lithium-Ion Batteries and How to Modify Them

Fast charging is one of the most essential criteria for the user acceptance of battery electric vehicles. Especially for high-loaded electrodes used in automotive applications, the rate capability is limited due to the transport limitations of lithium ions in the pores.1 Electrode structuring is a powerful tool to overcome those limitations by creating additional directed diffusion channels for lithium ions.2 Despite the frequently described reduction of the transport limitation of lithium-ion batteries,3 there are hardly any charge rate capability tests in the literature that demonstrate the improvement through structuring. Instead, most studies present discharge rate capability tests showing the desired performance increase due to structuring.4-8 This study will explain why charge rate capability tests fail to characterize electrodes in the transport-limiting C-rate range. For this purpose, graphite anodes underwent “structure calendering”, where electrodes are simultaneously mechanically structured and calendered using an embossing roller. Thus, identical electrode properties, except for the lower tortuosity, can be achieved compared to the non-structured graphite anodes that were only calendered. Despite their different tortuosities, we will show that structured and non-structured graphite anodes exhibit minimal capacity differences in the charge rate capability test. This is attributed to lithium plating, which shifts the anode potential to similar values, regardless of the transport properties of the investigated electrode. We will modify the test to characterize the charge rate capability of electrodes in the transport-limiting regime where lithium plating occurs. For this purpose, in the charge rate capability test, the current is superimposed with a sinusoidal signal and the voltage response is measured. This allows the continuous estimation of the cell impedance during charging. Previous studies have shown that this method allows to track the onset of the lithium plating reaction.9-10 Applying the modified charge rate capability test will demonstrate that this detrimental side reaction occurs significantly later in structured electrodes. Günter, F. J., & Wassiliadis, N. (2022). State of the Art of Lithium-Ion Pouch Cells in Automotive Applications: Cell Teardown and Characterization. Journal of The Electrochemical Society, 169(3), 030515. https://doi.org/10.1149/1945-7111/ac4e11Pfleging, W. (2017). A review of laser electrode processing for development and manufacturing of lithium-ion batteries. Nanophotonics, 7(3), 549–573. https://doi.org/10.1515/nanoph-2017-0044Mai, W., Usseglio-Viretta, F. L. E., Colclasure, A. M., & Smith, K. (2020). Enabling fast charging of lithium-ion batteries through secondary-/dual- pore network: Part II - numerical model. Electrochimica Acta, 341, 136013. https://doi.org/10.1016/j.electacta.2020.136013Keilhofer, J., Schaffranka, L., Wuttke, A., Günter, F., Hille, L., Dorau, F., & Daub, R. (2023). Mechanical Structuring of Lithium‐Ion Battery Electrodes Using an Embossing Roller. Energy Technology. https://doi.org/10.1002/ente.202200869Dubey, R., Zwahlen, M. D., Shynkarenko, Y., Yakunin, S., Fuerst, A., Kovalenko, M. V., & Kravchyk, K. V. (2021). Laser Patterning of High-Mass-Loading Graphite Anodes for High-Performance Li-Ion Batteries. Batteries and Supercaps, 4(3), 464–468. https://doi.org/10.1002/batt.202000253Habedank, J. B., Kriegler, J., & Zaeh, M. F. (2019). Enhanced Fast Charging and Reduced Lithium-Plating by Laser-Structured Anodes for Lithium-Ion Batteries. Journal of The Electrochemical Society, 166(16), A3940–A3949. https://doi.org/10.1149/2.1241915jesHabedank, J. B., Kraft, L., Rheinfeld, A., Krezdorn, C., Jossen, A., & Zaeh, M. F. (2018). Increasing the Discharge Rate Capability of Lithium-Ion Cells with Laser-Structured Graphite Anodes: Modeling and Simulation. Journal of The Electrochemical Society, 165(7), A1563–A1573. https://doi.org/10.1149/2.1181807jesHille, L., Xu, L., Keilhofer, J., Stock, S., Kriegler, J., & Zaeh, M. F. (2021). Laser structuring of graphite anodes and NMC cathodes – Proportionate influence on electrode characteristics and cell performance. Electrochimica Acta, 392, 139002. https://doi.org/10.1016/j.electacta.2021.139002Koseoglou, M., Tsioumas, E., Ferentinou, D., Jabbour, N., Papagiannis, D., & Mademlis, C. (2021). Lithium plating detection using dynamic electrochemical impedance spectroscopy in lithium-ion batteries. Journal of Power Sources, 512(September), 230508. https://doi.org/10.1016/j.jpowsour.2021.230508Straßer, A., Adam, A., & Li, J. (2023). In operando detection of Lithium plating via electrochemical impedance spectroscopy for automotive batteries. Journal of Power Sources, 580(July), 233366. https://doi.org/10.1016/j.jpowsour.2023.233366

Impact of Fast-Charging Rates on Electrode Degradation in NMC/Gr Pouch Cells

With the rapid expansion of the electric vehicles market, fast charging lithium-ion batteries has become increasingly imperative and inevitable. However, as fast-charging technologies entering electric vehicle market, persistent challenges related to safety issue and cell degradation, such as lithium dendrite growth, thermal runaway etc. necessitate meticulous consideration. In this study, we investigated fast-charging rate effects on electrode degradation in 1.6 Ah pouch cells using LiNi0.5Mn 0.3Co 0.2O2 cathode and graphite anode provided by Nanoramic Laboratories. Our investigation involves a comparative analysis of the aging behavior of NMC/Gr cells subjected to various charging rates — 0.5C, 2C, 4C, and 6C. Notably, we observed that pouch cells charged at rates of 0.5C and 2C could persist 80% capacity retention over 1000 cycles while cells using 4C and 6C can survive no more than 400 cycles with 80% retention. Through a series of post-mortem characterizations, including electrochemical impedance spectroscopy (EIS), Raman, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) with energy dispersive X-ray spectroscopy (EDS), we scrutinized the harvested NMC and graphite electrodes. As expected, more dendrite formation was observed on graphite anodes with 4C and 6C fast charging rates. The deterioration of cell performance primarily resulted from the degradation of the graphite anode. This degradation could be attributed to distinct dendrite morphologies at the graphite anode under varying charging rates (see Fig. 1). In addition to dendrite formation on graphite electrodes, we observed more severe pulverization of NMC secondary particles under higher charging rates despite their lower cycle numbers. This investigation provides a comprehensive understanding of how NMC and graphite degrade under different charging rates, offering valuable insights into the practical impacts of charging rates on cell lifespan and highlighting potential challenges that need to be addressed.AcknowledgementThis material is based upon work supported by the U. S. Department of Energy’s Office of Energy Efficiency and Renewable Energy (EERE) under the Advanced Manufacturing Office, award number DE-EE0009111. Argonne National Laboratory is operated for DOE Office of Science by UChicago Argonne, LLC under contract number DE-AC02-06CH11357 Figure 1

Designing Novel Solvents for High Voltage Li-Ion Batteries

The pursuit of higher energy density in lithium-ion batteries has led to the development of new cathode materials that can operate at elevated voltages and provide increased specific capacities. [1-2] One such class of materials is the nickel-rich layered oxide cathodes known as LiNixMnyCozO2 (NMC). These cathodes offer high specific capacities and demonstrate electrochemical stability at high cutoff voltages, making them promising candidates for advanced lithium-ion batteries. [3-4] However, NMC cathodes face a significant challenge in the form of capacity fading during cycling. This issue primarily arises from the voltage instability of the conventional carbonate-based electrolytes used in lithium-ion batteries, which are typically designed for the 4-V lithium-ion chemistry. [5-6] As a result, researchers and scientists have directed extensive efforts toward developing new and improved electrolyte systems that can withstand the high voltage requirements of NMC cathodes and other high-energy applications. [7-8]Designing and synthesizing new molecules for use as electrolyte solvents in lithium-ion batteries is indeed a complex and challenging task. Researchers often focus on optimizing one specific property, which can lead to the development of molecules that excel in that aspect while potentially overlooking other crucial features that are necessary for stable battery cycling. For example, the development of α-fluorinated sulfones as electrolyte solvents was driven by their exceptional anodic stability. [9] This stability is achieved by introducing strong electron-withdrawing trifluoromethyl groups directly attached to the sulfonyl group. However, while this electron-withdrawing effect enhances anodic stability, it can also significantly increase the reduction potential of α-fluorinated sulfones. This heightened reduction potential renders them unstable when used with graphite anodes, highlighting the delicate balance required in designing electrolyte solvents that perform well across various aspects of battery operation.In this presentation, we embraced the concept of a "golden middle way" when designing and synthesizing new electrolyte solvents. The recently developed β-fluorinated sulfone, TFPMS, doesn't claim to be the best in any single property, but it strikes a balance across various key characteristics. This equilibrium has proven to be highly effective in ensuring the long-term stability of high-voltage graphite||NMC622 full cells. Positioned at the β site of the sulfone molecule, the strong electron-withdrawing trifluoromethyl group renders β-fluorinated sulfone sufficiently stable against the high-voltage NMC622 cathode, even if it possesses a slightly lower oxidation potential compared to its α-fluorinated counterparts. Furthermore, its reduction potential is lower than that of α-fluorinated sulfone, making it considerably more stable when paired with the graphite anode. While it may not possess the same high lithium solvating power as the typical sulfone (EMS), the lithium solvating capacity of β-fluorinated sulfone falls somewhere in between, mitigating transition metal dissolution and deposition in the graphite||NMC622 full cell that utilizes a β-fluorinated sulfone-based electrolyte. As a result, the full cell equipped with TFPMS-based electrolyte demonstrates superior cycling performance, with a significantly higher average capacity than cells using regular sulfone or α-fluorinated sulfone-based electrolytes. In summary, our approach exemplifies the successful application of the "golden middle way" in designing and synthesizing new electrolyte solvents.Reference: Santhanam, R.; Rambabu, B., Power Sources 2010, 195, 5442.Lin, F.; Markus, I. M.; Nordlund, D.; Weng, T.-C.; Asta, M. D.; Xin, H. L.; Doeff, M. M., Commun. 2014, 5, 3529.Li, W.; Song, B.; Manthiram, A., Chemical Society Reviews 2017, 46 (10), 3006.Xu, J.; Lin, F.; Doeff, M. M.; Tong, W., Journal of Materials Chemistry A 2017, 5 (3), 874.Xia, J.; Petibon, R.; Xiong, D.; Ma, L.; Dahn, J., Journal of Power Sources 2016, 328, 124.Chen, S.; Wen, K.; Fan, J.; Bando, Y.; Golberg, D., Journal of Materials Chemistry A 2018, 6 (25), 11631.Zheng, J.; Lochala, J. A.; Kwok, A.; Deng, Z. D.; Xiao, J., Advanced Science 2017, 4 (8), 1700032.Yamada, Y.; Wang, J.; Ko, S.; Watanabe, E.; Yamada, A., Nature Energy 2019, 4 (4), 269.Su, C.-C.; He, M.; Redfern, P. C.; Curtiss, L. A.; Shkrob, I. A.; Zhang, Z., Environ. Sci. 2017, 10 (4), 900.

(Invited) Fluorinated Linear Carbonate Electrolyte for Lithium-Ion Batteries with Fast-Charging, High Voltage, and Wide Operating Temperatures

Lithium-ion batteries (LIBs) are key solutions to clean energy. Their high energy densities have led to the dominance of LIBs in mobile devices and electric vehicles. However, traditional electrolyte limits their operation at high voltage and extreme environmental temperatures. Here, we designed a new multifunctional electrolyte, in which lithium bis(fluorosulfonyl)imide (LiFSI) is used as salt and fluorinated diethyl carbonate (DFDEC) is used as the major solvent. With this optimized electrolyte, the graphite||LiNi0.8Mn0.1Co0.1O2 (NMC811) full cells are capable of fast-charging and can deliver long-term cycling with a cutoff voltage as high as 4.5V. Specifically, the battery shows the capacity retention of 84.3% after 500 cycles with an average coulombic efficiency (CE) as high as 99.93%. Synchrotron-based characterization suggests the formation of anion derived, LiF-rich interphases on the surfaces of both graphite anode and NMC811 cathode. Thanks to the fast ion transport and stable interphase, the cell in the optimized electrolyte demonstrates stable cycling behavior within a wide operating temperature. At high temperature (60 ºC), the full cell delivers 88.8% of its initial capacity after 130 cycles at a high current density of 1C. At low temperature (-20 ºC), the optimized electrolyte enables a capacity retention of 90.9% after 100 cycles when charging and discharging at 0.2C.Acknowledgment: The work done at Brookhaven National Laboratory was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technology Office of the U.S. DOE through Applied Battery Research for Transportation (ABRT) program under contract no. DE-SC0012704. The electrodes used in this study were produced at the U.S. Department of Energy’s (DOE) CAMP (Cell Analysis, Modeling and Prototyping) Facility, Argonne National Laboratory. The CAMP Facility is fully supported by the DOE Vehicle Technologies Office (VTO). This research used beamline 7-ID-2 (SST-2) of the National Synchrotron Light Source II, U.S. DOE Office of Science User Facilities, operated for the DOE Office of Science by Brookhaven National Laboratory under contract number DE-SC0012704. SEM measurements for this manuscript were performed at Center for Functional Nanomaterials, a U.S. DOE office of Science User Facility, at Brookhaven National Laboratory under the contract number DE-SC0012704.

The Influence of Calendering Process on the Graphite Anode

Calendering, or pressing, is the final property-defining process for battery electrode manufacturing to maximize the volumetric capacity of the cell through the compaction of an electrode between two large calender rollers12. On one hand, it can reduce the porosity of battery materials thus increase the conductivity of the materials. On the other hand, it can control the thickness of the electrodes, making sure it is uniform and proper thickness to guarantee the minimal variation in the cell thickness, reaching even stack pressure for module assembly and impacting the thermal management [3]. The calendering process significantly influence the performance of lithium-ion battery (LIB).Graphite anode coating on Cu foil was chosen as our baseline coating for this calendering process investigation. The slurry was mixed in a planetary and dispersive mixer and then coated using reverse comma coating method by a scale-up coater with drying zones of 70 °C. Then the coating was calendered by a calendering machine at various conditions.Calendering, though seemingly a simply process, is influenced by several different parameters significantly. In this study, we systematically investigated the calendering process by carrying-out a Design-of-experiment (DOE). The following calendering parameters were investigated: the parameters of calendering machine gap size, calendering pressure, and the speed of the coating web. The calendered graphite coating was then measured for the morphology by scanning electron microscopy (SEM), the pore size change by BET surface area measurement, and Direct current internal resistance (DCIR) by building half cells and cycling and Electrochemical Impedance Spectroscopy (EIS) at 50% State-of-Charge (SOC).The result showed that pressure is the most critical parameter for calendering and the internal resistance and ionic conductivity changes in response to the calendering parameters. The half-cell with calendering at the pressure of 37 MPa, gap size targeted for 30% porosity, the BET surface area around 0.75 m2/g showed highest cell capacity and lowest internal resistance.