Graphite For Lithium-ion Batteries Research Articles

Electrolyte Design Enables Stable and Energy‐Dense Potassium‐Ion Batteries

AbstractFree from strategically important elements such as lithium, nickel, cobalt, and copper, potassium‐ion batteries (PIBs) are heralded as promising low‐cost and sustainable electrochemical energy storage systems that complement the existing lithium‐ion batteries (LIBs). However, the reported electrochemical performance of PIBs is still suboptimal, especially under practically relevant battery manufacturing conditions. The primary challenge stems from the lack of electrolytes capable of concurrently supporting both the low‐voltage anode and high‐voltage cathode with satisfactory Coulombic efficiency (CE) and cycling stability. Herein, we report a promising electrolyte that facilitates the commercially mature graphite anode (>3 mAh cm−2) to achieve an initial CE of 91.14 % (with an average cycling CE around 99.94 %), fast redox kinetics, and negligible capacity fading for hundreds of cycles. Meanwhile, the electrolyte also demonstrates good compatibility with the 4.4 V (vs. K+/K) high‐voltage K2Mn[Fe(CN)6] (KMF) cathode. Consequently, the KMF||graphite full‐cell without precycling treatment of both electrodes can provide an average discharge voltage of 3.61 V with a specific energy of 316.5 Wh kg−1−(KMF+graphite), comparable to the LiFePO4||graphite LIBs, and maintain 71.01 % capacity retention after 2000 cycles.

Electrolyte Design Enables Stable and Energy-Dense Potassium-Ion Batteries.

Free from strategically important elements such as lithium, nickel, cobalt, and copper, potassium-ion batteries (PIBs) are heralded as promising low-cost and sustainable electrochemical energy storage systems that complement the existing lithium-ion batteries (LIBs). However, the reported electrochemical performance of PIBs is still suboptimal, especially under practically relevant battery manufacturing conditions. The primary challenge stems from the lack of electrolytes capable of concurrently supporting both the low-voltage anode and high-voltage cathode with satisfactory Coulombic efficiency (CE) and cycling stability. Herein, we report a promising electrolyte that facilitates the commercially mature graphite anode (>3 mAh cm-2) to achieve an initial CE of 91.14 % (with an average cycling CE around 99.94 %), fast redox kinetics, and negligible capacity fading for hundreds of cycles. Meanwhile, the electrolyte also demonstrates good compatibility with the 4.4 V (vs. K+/K) high-voltage K2Mn[Fe(CN)6] (KMF) cathode. Consequently, the KMF||graphite full-cell without precycling treatment of both electrodes can provide an average discharge voltage of 3.61 V with a specific energy of 316.5 Wh kg-1-(KMF+graphite), comparable to the LiFePO4||graphite LIBs, and maintain 71.01 % capacity retention after 2000 cycles.

Environment Friendly Synthesis of Reduced Graphene Oxide from Spent Lithium-Ion Battery Graphite and Its Nanocomposite with MoO3 Nanorods for Photocatalytic Hydrogen Evolution

Environment Friendly Synthesis of Reduced Graphene Oxide from Spent Lithium-Ion Battery Graphite and Its Nanocomposite with MoO₃ Nanorods for Photocatalytic Hydrogen Evolution

Photodiode-based focus monitoring in ultrashort-pulsed laser structuring of graphite anodes for lithium-ion batteries

In recent years, there has been an increased demand for elaborate monitoring techniques in laser material processing. This has been driven by the need for fast and cost-efficient quality assurance processes. At the same time, ultrashort-pulsed (USP) laser radiation has emerged as a promising technology for creating intricate microstructures in lithium-ion battery graphite anodes due to its high precision and negligible thermal impact. However, the integration of process monitoring in USP laser applications for graphite anode structuring is still unexplored. There is a lack of clarity on suitable sensors, observable parameters, and extractable process-relevant insights. The presented study addressed this gap by demonstrating the capability of state-of-the-art photodiode-based monitoring systems in collecting process-relevant data and deriving valuable insights. A sensor equipped with three photodiodes was employed to address these challenges. Exploratory data analysis and machine learning methodologies were leveraged to develop a data pipeline for processing the acquired information. The data were used to train convolutional neural networks that could accurately predict the focal position. At the same time, the limitations of traditional regression approaches could be shown. The findings advanced the understanding of the possibilities of process monitoring in USP laser applications and emphasized the significance of data-driven approaches in optimizing manufacturing processes.

An integrated simulation and experimental study of calendering process in water-based manufacturing of lithium-ion battery graphite electrode

Lithium-ion batteries produced from water-based manufacturing processes are favored for their environmental and economic advantages, while currently sacrificing some technical performance. This paper reports an integrated study on the calendering process of water-based manufacturing of lithium-ion battery graphite electrode, aiming to improve electrochemical performance of the manufactured lithium-ion batteries. The interactive mechanism between the calendering process and the porous microstructure of the produced graphite electrode was systematically investigated. It reveals that the graphite electrode with 40 % of porosity produced under 79,509 N/m calendering force achieves an optimal 333 mAh/g of specific capacity and 91.2 % of capacity retention after 100 cycles.

Evolution of aging mechanisms and performance degradation of lithium-ion battery from moderate to severe capacity loss scenarios

The aging mechanisms of Nickel-Manganese-Cobalt-Oxide (NMC)/Graphite lithium-ion batteries are divided into stages from the beginning-of-life (BOL) to the end-of-life (EOL) of the battery. The corresponding changes in the battery performance across these stages have been analyzed, and a digital twin model is established to quantify the primary parameters that influence these aging mechanisms. Post-mortem analysis is applied to validate the results. This paper compares the aging mechanisms from BOL to EOL using two charging protocols: a multi-step fast charge protocol and a common constant-current fast charge protocol that applies the average current of multi-step currents. Notably, a transition from a linear to a non-linear degradation trend in capacity fade is observed, beginning from a 10% capacity reduction to EOL. From BOL to 10% degradation, the resistance of solid electrolyte interphase (SEI) grows steadily. The graphite anode’s crack depth exhibits a significant increase, accompanied by an evident collapse of cathode materials in all the test cases following a 10% degradation until EOL. This phenomenon can be attributed to one primary reason—the expansion of the corresponding simulated resistance of charge transfer (Rct). Post-mortem analysis revealed the change in morphology, structure, and composition of various degradation conditions. This analysis proved that the primary driver of the linear aging stage is the SEI growth. Furthermore, it is evident that the transition to a non-linear aging degradation is dominated by electrode defects resulting from continuous mechanical stress during long-term aging.

Development of Coal-Derived Graphite for Lithium-Ion Batteries

Graphite is one of many critical minerals that are utilized in lithium-ion batteries. The requirements for domestic sourcing of critical minerals used in Li-ion batteries as outlined in the Inflation Reduction Act have generated interest in exploring alternative production methods and feedstocks for critical minerals. An alternative feedstock for the production of graphite that is being evaluated is coal. Coal is an excellent candidate as a feedstock due to its abundance in the United States and its chemical structure.In this poster, the characterization and electrochemical performance of multiple coal-derived graphites will be presented. A focus will be put on linking electrochemical performance to the microstructure of each material. Electrochemical performance data such as initial capacity loss, gravimetric capacity and columbic efficiency will be presented for both coin and pouch cells. The application of the Multi-Species, Multi-Reaction model on coal-derived graphite will also be presented.

Characterization and Analysis of Coal-Derived Graphite for Lithium-Ion Batteries

Graphite is a critical material used as the negative electrode in lithium-ion batteries. Both natural and synthetic graphites are utilized, with the latter obtained from a range of carbon raw materials. In this work, efforts to synthesize graphite from coal as a domestic feedstock for synthetic graphite are reported. The performance in lithium-ion coin cells of this coal derived graphite is compared to commercial battery-grade graphite. This includes characterization of the thermodynamics of the coal derived graphite using the multi-species, multi-reaction (MSMR) model, characterization of the entropy and enthalpy of the material, and estimation of the rate capability. This enables modeling of synthetic coal-derived graphites and virtual evaluation[1] of these materials towards electric vehicle and grid storage applications.

Operando Raman observation of lithium-ion battery graphite composite electrodes with various densities and thicknesses

Understanding the mechanisms of inhomogeneous charging and discharging reactions in an electrode is critical to improving the rate capability of lithium-ion batteries. Various methods have been developed to observe the distribution of electrode structure or lithium ions within an electrode; however, most of these methods require large-scale equipment or entail complex procedures. To simplify reaction distribution measurements within electrodes, this study developed specially designed cells and conducted operando observations of reaction distribution in graphite composite electrodes using Raman spectroscopy. Behaviors on both the electrolyte and current collector sides of the electrodes were compared, and electrodes of various densities and thicknesses were examined. For electrodes with low density, the changes in graphite structure were almost simultaneous on the electrolyte and current collector sides and were hardly dependent on the electrode thickness. In contrast, the changes in electrode structure with increased density were dependent on their thickness. This implies that the ion transportation length is responsible for the reaction distribution in the electrodes when ion channels connecting the current collector and electrolyte sides decrease owing to the increased electrode density. The simple method developed in this study is expected to further contribute to the understanding of the distribution of reactions within graphite composite electrodes.

The development of China’s monopoly over cobalt battery materials

While previous resource conflicts have often been linked to fuel minerals such as oil, future resource conflict may revolve around nonfuel minerals that enable strategic emerging technologies. During a 2010 diplomatic dispute, China reportedly blocked exports of rare earth elements to Japan, thereby leveraging China’s near-monopoly to threaten Japanese manufacturers of advanced technologies including batteries and permanent magnets. Although this caused significant concern for manufacturers outside China, China’s control over other critical minerals has yet to be studied comprehensively. Besides rare earth elements, perhaps no mineral has received more attention for its supply risks than cobalt. Here Chinese control is estimated for each cobalt material at each stage of the cobalt supply chain from 2000 through 2022. The results show that from mining, to refining, consumption, recycling, stocks, and trade, China dominates the cobalt materials that feed lithium-ion battery cathode production. Specifically, the results show that in 2022 Chinese firms had control over 62% of cobalt mine materials primarily used for cobalt chemical refining, 95% control of refined commercial-grade cobalt chemicals, 92% control of battery-grade tricobalt tetroxide, 85% control of battery-grade cobalt sulfate, and 91% control of nickel–cobalt-manganese cathode precursor materials. China’s monopoly over cobalt battery materials may imply a serious supply risk to non-Chinese battery producing and consuming industries—especially given rising geopolitical tensions and the reemergence of critical mineral export restrictions including gallium for semiconductors, germanium for solar panels, graphite for lithium-ion batteries, and (again) rare earth elements.

Catalytic decomposition of ethylene carbonate by pyrrolic-N to stabilize solid electrolyte interphase on graphite anode under extreme conditions

Despite the dominated anode materials of graphite for lithium-ion batteries (LIBs), the poor rate capability and inferior cyclability restain their applications under extreme conditions due to their deficient interfacial chemistry. Herein, an ultrathin but Li2CO3-rich solid electrolyte interphase (SEI) is manipulated by the decomposition of ethylene carbonate (EC) on graphite anode with nitrogenous amorphous carbon coating (denoted as GMIB-2P). Specifically, Li2CO3 can enable a decreased charge transfer resistance and faster Li+ diffusion capability. In addition, we demonstrate the catalytic effect of pyrrolic-N on graphite surface with prominent wettability induces the rapid decomposition of EC with low reaction energy barrier through density function theory (DFT) calculation. Consequently, GMIB-2P delivers an outstanding capacity retention ratio of 90.82% after 300 cycles at 1 C and an improved initial Coulombic efficiency (ICE, 90.77% vs. 85.35%). More importantly, GMIB-2P possesses durable-cycling capability even with lean electrolytes of 5 μL mg-1 and as well as 85.68% capacity retention for over 300 cycles at 60 ℃. Our work highlights the key role of EC in tailoring interfacial chemistry from structure regulations and provides new guidelines to design more reliable anodes for LIBs under extreme conditions.

Recycling lithium-ion battery graphite: Synthesis of adsorbent materials for highly efficient removal of dye and metal ions from wastewater

The fate of residual graphite derived from hydrometallurgical treatment of spent Lithium-ion batteries remains uncertain. This study dwells on the aim of identifying the potentialities of recycling residual graphite for wastewater treatment. Graphite was recovered hydrometallurgically, and new adsorption materials: graphite oxide (GO) and graphene oxide (GrO) were synthesized from the residual graphite using the chemical oxidization method. Synthesized materials showed higher interlayer spacings (GO = 0.81 nm, GrO = 0.78 nm) than the commercially available similar materials. Adsorption studies revealed higher adsorption capacities for both dye (>550 mg/g in all cases) and metal ions (highest ∼93 mg/g for Ni2+ and lowest ∼68 mg/g for Zn2+). GrO showed superior results than GO due to its high surface area and porosity despite GO having more functional groups. Moreover, produced materials showed about 97 % removal of dye and about 94 % removal of contaminated metals which are higher performance than existing commercial or similar materials. These findings highlight the promising recycling capabilities of waste graphite and suggest its potential as a substitute for natural graphite.

Is silicon worth it? Modelling degradation in composite silicon–graphite lithium-ion battery electrodes

The addition of silicon into graphite lithium-ion battery anodes has the potential to increase cell energy density. However, understanding the complex degradation behaviour in these composite systems remains a research challenge. Here, we developed a coupled electrochemical–mechanical model of a composite silicon/graphite electrode, including stress-driven crack formation and solid electrolyte interphase layer growth for each material, validated with experimental degradation data from an LG M50T cell. The model reveals self-limiting loss of silicon due to decreasing stress in the silicon as the silicon activity shifts to a lower state-of-charge. Higher C-rates can lead to lower degradation due to lower phase utilisation as voltage cut-offs are reached earlier. Increasing silicon content can reduce the stress in the silicon by distributing reaction current density over more material. Using this model, we explored whether the extra capacity from silicon is generally ‘worth’ the faster degradation compared to graphite-only electrodes. The model shows if you use the silicon, you lose it, as the higher initial capacity is rapidly lost with regular high depth-of-discharge events. However, silicon does have value if it enables full graphite utilisation without range anxiety; if high depth-of-discharge events are minimised then graphite’s superior longevity can be utilised while exploiting silicon’s high specific capacity. The model is integrated into PyBaMM (an open-source physics-based modelling platform); providing the research community and industry with the capability to reproduce our results and further explore the dynamic lifetime behaviour of composite electrodes.

Modulating the graphitic domains of hard carbons via tuning resin crosslinking degree to achieve high rate and stable sodium storage

Sodium-ion batteries (SIBs) are regarded as an outstanding alternative to lithium-ion batteries (LIBs) due to abundant sodium sources and their similar chemistry. As a most promising anode of SIBs, hard carbons (HCs) receive extensive attention because of their low potential and low cost, but their rational design for commercial SIBs is restricted by their variable and complicated microstructure, which is analogous to that of graphite in LIBs. Herein, a series of controllable HC materials derived from 3-aminophenol formaldehyde resin (AFR) were designed and fabricated. We discover that the optimized HC features expanded graphite regions, highly developed nanopores, and reduced defect content, contributing to the enhanced Na+ storage. This optimization is achieved by adjusting the resin crosslinking degree of the precursor. Specifically, a resin precursor with a higher crosslinking degree can produce HC with a larger interlayer distance, relatively higher crystallinity, and a lower specific surface area. Encouragingly, the as-optimized AFR-HC electrode manifests superior electrochemical performance in the aspect of high capacity (383 mAh·g-1 at 0.05 A·g-1), better rate capability (140 mAh·g-1 at 20 A·g-1), and high initial coulombic efficiency (82%) than other contrast samples. Moreover, the as-constructed full cell coupled with a Na3V2(PO4)3 cathode shows an energy density of 250 Wh·kg-1. Together with the simple synthesis, cost-efficiency of the precursors and superior electrochemical performance, AFR-HCs are promising for the commercial application.

Direct and rapid thermal shock for recycling spent graphite in lithium-ion batteries

Due to the rapid increase in the number of spent lithium-ion batteries, there has been a growing interest in the recovery of degraded graphite. In this work, a rapid thermal shock (RTS) strategy is proposed to regenerate spent graphite for use in lithium-ion batteries. The results of structural and morphological characterization demonstrate that the graphite is well regenerated by the RTS process. Additionally, an amorphous carbon layer forms and coats onto the surface of the graphite, contributing to excellent rate performance. The regenerated graphite (RG-1000) displays excellent rate performance, with capacities of 413 mAh g−1 at 50 mA g−1 and 102.1 mAh g−1 at 1000 mA g−1, respectively. Furthermore, it demonstrates long-term cycle stability, maintaining a capacity of 80 mAh g−1 at 1000 mA g−1 with a capacity retention of 78.4 % after 600 cycles. This RTS method enables rapid and efficient regeneration of spent graphite anodes for lithium-ion batteries, providing a facile and environmentally friendly strategy for their direct regeneration.

Study on the effect of low-temperature cycling on the thermal and gas production behaviors of Ni0.8Co0.1Al0.1/graphite lithium-ion batteries

With their high energy density and long cycle life, lithium-ion batteries (LIBs) are currently the most promising electrochemical energy storage system for electric vehicles. However, their safety and cycling performance can be significantly compromised in low-temperature environments due to lithium plating and other factors. Therefore, it is essential to study the safety of aging batteries. In this study, we focused on a commercially available high-specific-energy Ni0.8Co0.1Al0.1 cathode system battery and simulated the aging of the battery by long-term cycling at 0 ℃. This study compares and analyzes the samples on the basis of the previous ones in terms of heat production power, thermal runaway (TR) characteristics and gas production characteristics. It reveals the influence of low-temperature aging on the comprehensive performance of lithium batteries in a more comprehensive way. The results show that the charging pattern of all three characteristics is related to the aging degree of the battery. In terms of the thermal characteristics, the relative change in specific heat capacity of the aged battery is only between 0.32 % and 1.08 % compared to that of a fresh battery, so the effect of ageing on the specific heat capacity of the battery is negligible. The average heat generation power of batteries with different state of health (SOH) is not monotonically increasing with the decrease of SOH, the threshold of dramatic increase is SOH = 80 %. In terms of TR characteristics, the onset temperature of exothermic reactions (TOER) of aged batteries is significantly lower than that of fresh batteries. With the decrease of SOH, TOER also decreases gradually. Compared with batteries with different SOHs, the more seriously aged the battery safety valve opens earlier, and the TR occurs earlier. In terms of the TR gas production characteristics, the more severely aged the battery, the earlier the safety valve opens compared to a fresh battery. The most gas is produced when SOH = 70 %, which increases the risk of catastrophic damage.

Unravelling the Mechanism of Pulse Current Charging for Enhancing the Stability of Commercial LiNi0.5Mn0.3Co0.2O2/Graphite Lithium‐Ion Batteries

AbstractThe key to advancing lithium‐ion battery (LIB) technology, particularly with respect to the optimization of cycling protocols, is to obtain comprehensive and in‐depth understanding of the dynamic electrochemical processes during battery operation. This work shows that pulse current (PC) charging substantially enhances the cycle stability of commercial LiNi0.5Mn0.3Co0.2O2 (NMC532)/graphite LIBs. Electrochemical diagnosis unveils that pulsed current effectively mitigates the rise of battery impedance and minimizes the loss of electrode materials. Operando and ex situ Raman and X‐ray absorption spectroscopy reveal the chemical and structural changes of the negative and positive electrode materials during PC and constant current (CC) charging. Specifically, Li‐ions are more uniformly intercalated into graphite and the Ni element of NMC532 achieves a higher energy state with less Ni─O bond length variation under PC charging. Besides, PC charging suppresses the electrolyte decomposition and continuous thickening of the solid‐electrolyte‐interphase (SEI) layer on graphite anode. These findings offer mechanistic insights into Li‐ion storage in graphite and NMC532 and, more importantly, the role of PC charging in enhancing the battery cycling stability, which will be beneficial for advancing the cycling protocols for future LIBs and beyond.

Corrigendum: Application of the Multi-Species, Multi-Reaction Model to Coal-Derived Graphite for Lithium-Ion Batteries [ J. Electrochem. Soc., 171, 023501 (2024)

Abstract Acknowledgements: This was supported by the U.S. Department of Energy under Award Number DE-FE0032144, "Utilization of Carbon Supply Chain Wastes and Byproducts to Manufacture Graphite for Energy Storage Applications."

Fabrication of Li4Ti5O12 (LTO) as Anode Material for Li-Ion Batteries.

The most popular anode material in commercial Li-ion batteries is still graphite. However, its low intercalation potential is close to that of lithium, which results in the dendritic growth of lithium at its surface, and the formation of a passivation film that limits the rate capability and may result in safety hazards. High-performance anodes are thus needed. In this context, lithium titanite oxide (LTO) has attracted attention as this anode material has important advantages. Due to its higher lithium intercalation potential (1.55 V vs. Li+/Li), the dendritic deposition of lithium is avoided, and the safety is increased. In addition, LTO is a zero-strain material, as the volume change upon lithiation-delithiation is negligible, which increases the cycle life of the battery. Finally, the diffusion coefficient of Li+ in LTO (2 × 10-8 cm2 s-1) is larger than in graphite, which, added to the fact that the dendritic effect is avoided, increases importantly the rate capability. The LTO anode has two drawbacks. The energy density of the cells equipped with LTO anode is lower compared with the same cells with graphite anode, because the capacity of LTO is limited to 175 mAh g-1, and because of the higher redox potential. The main drawback, however, is the low electrical conductivity (10-13 S cm-1) and ionic conductivity (10-13-10-9 cm2 s-1). Different strategies have been used to address this drawback: nano-structuration of LTO to reduce the path of Li+ ions and electrons inside LTO, ion doping, and incorporation of conductive nanomaterials. The synthesis of LTO with the appropriate structure and the optimized doping and the synthesis of composites incorporating conductive materials is thus the key to achieving high-rate capability. That is why a variety of synthesis recipes have been published on the LTO-based anodes. The progress in the synthesis of LTO-based anodes in recent years is such that LTO is now considered a substitute for graphite in lithium-ion batteries for many applications, including electric cars and energy storage to solve intermittence problems of wind mills and photovoltaic plants. In this review, we examine the different techniques performed to fabricate LTO nanostructures. Details of the synthesis recipes and their relation to electrochemical performance are reported, allowing the extraction of the most powerful synthesis processes in relation to the recent experimental results.

Superior initial Coulombic efficiency and areal capacity of hard carbon anode enabled by graphite-assisted carbonization for sodium-ion battery

Hard carbons are perceived as promising anode materials in sodium-ion batteries, while their practical implementation is largely impeded by the insufficient initial Coulombic efficiency (ICE). Hard carbons with self-supporting architecture are intriguing to enhance ICE owing to the omission of binder and conductive agent; whereas elaborate architecture and microstructure design are still required to further raise the ICE to the level of commercial graphite in lithium-ion batteries, especially under high areal capacity. Herein, we propose a graphite-assisted pressurization strategy during carbonization to achieve remarkable ICE and high areal capacity in resulting self-supporting cellulose tissue derived hard carbon anode. The intimate contact of graphite plate enables suitable local ordering of pseudo-graphitic nanodomains with low intrinsic defects, responsible for enhanced ICE. While the pressure-reinforced dense yet self-interwoven fibrous networks render high areal capacity. Consequently, the as-prepared self-supporting hard carbon anode displays remarkable ICE to 95% and areal capacity of 2.4 mAh cm−2, far exceeding the reported value of less than 0.8 mAh cm−2. Meanwhile, the rate and durability are not scarified under such superior ICE due to the well-manipulated pseudo-graphitic nanodomains and porous fibrous networks. The practicality is further demonstrated in coin-type and pouch-type full cells delivering high capacity and long-term stability. Our finding offers an impetus for the development of high ICE and areal capacity for sodium-ion battery anode.