Energy Density Lithium-ion Batteries Research Articles

Smart-responsive sustained-release capsule design enables superior air storage stability and reinforced electrochemical performance of cobalt-free nickel-rich layered cathodes for lithium-ion batteries

Nickel-rich layered oxide stands as one of the most promising cathodes in demand for higher energy density of lithium-ion batteries (LIBs) in next generation. While increasing nickel content brings more capacity, it also makes this kind of cathode more vulnerable to the ambient, both the air outside the cell and the electrolyte inside, causing aggravated storage, structural and thermal instability. The cathode surface, as the first line of defense against the ambient attack, is the essential place to address these issues. Enlightened by the mechanism of “sustained-release capsule”, here we decorate the polydimethylsiloxane (PDMS), a skin with exceptional moisture-resistance and chemical stability, onto the surface of LiNi0.9Mn0.1O2. This PDMS skin demonstrated the smart response to the surrounding environment that the hydrophobic surface guarantees the ambient air storage stability by cutting off residual alkali accumulation and the protective role of coating could be relayed as another functional mechanism once entering the battery. The detrimental HF species generated from water-induced electrolyte decomposition are effectively captured and eliminated to defend cathode corrosion and enhance interfacial stability during long-term cycling. Attributed to the seamless protection from the outside to the inside of the battery, this well-capsuled Ni-rich cathode exhibits negligible capacity fading compared with fresh state even after long ambient exposure, and realizes superior cycling and thermal stability. This work demonstrates new guidelines to design smart-responsive coatings for cathode materials to reduce their susceptibility to the surrounding environment, towards improving both ambient storage stability and cycling stability.

PO43--doped layer @ spinel @ rGO sandwich-structured lithium-rich manganese-based cathode material with enhancing rate capability and cycle stability for Li-ion battery

The Li-rich Mn-based cathode (LRM) material faces challenges like low initial coulombic efficiency (ICE) and reduced capacity retention, which limit their commercial viability in high energy density lithium-ion batteries (LIBs). These challenges primarily arise from the irreversible migration of transition metal ions (TMn+) and the escape of lattice oxygen. Herein, this study proposes a novel approach to enhance Li-rich cathodes by implementing a PO43--doped layer @ spinel @ rGO sandwich structure, which effectively addresses the aforementioned challenges. Through the synergistic effects of PO43- doping and rGO surface modification, the modified samples demonstrate remarkable electrochemical properties. These include an impressive initial coulombic efficiency (ICE) of 87.54%, and a superior capacity of 187.12 mAhg−1 and 149.44 mAhg−1 at 25°C and 45°C, respectively, following 200 cycles at 1 C. Additionally, they exhibit an outstanding rate capability of 82.3 mAhg−1 at 10 C and a minimal voltage decrease of 0.504 V after 200 cycles. The synergetic strategy presented in this work serves as an inspiring source for the exploration of high energy density and long-cycle cathode materials.

Borate-Functionalized Disiloxane as Effective Electrolyte Additive for 4.5 V LiNi0.8Co0.1Mn0.1O2/Graphite Batteries.

Ni-rich LiNi0.8Co0.1Mn0.1O2 (NCM811) is considered the most prominent cathode material to establish a practical high energy density of lithium-ion batteries (LIBs) for future electric vehicles. The energy density of LIBs is greatly determined by the capacity of electrode materials and the operating voltage of the cells. To further improve the cycle lifespan of NCM811 batteries to meet the requirement of driving range for the electric vehicle market, it is vital to design a novel electrolyte additive that can enhance the stability of the cathode/electrolyte interface at a wide range of voltage. Herein, a novel borate functionalized disiloxane compound, 1,1,1,3,3-pentamethyl-3-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)propyl) disiloxane (PMBPDS), is synthesized as cathode electrolyte interphase (CEI) film-forming additive to improve the cycling performance of NCM811 batteries. Systematic studies reveal that PMBPDS can construct a stable CEI film on the NCM811 surface and efficiently scavenge hydrofluoric acid (HF). The PMBPDS-derived CEI prevents the dissolution of transmission metals in the NCM811 cathode and enhances the capacity retention of NCM811/graphite cells from 68.3 to 70.6% after 200 cycles at 1 C in the voltage window of 3-4.5 V. This work provides more understanding on designing the molecular structure of additive compounds for improving the electrochemical performance of LIBs.

High voltage electrolytes for lithium-ion batteries with micro-sized silicon anodes

Micro-sized silicon anodes can significantly increase the energy density of lithium-ion batteries with low cost. However, the large silicon volume changes during cycling cause cracks for both organic-inorganic interphases and silicon particles. The liquid electrolytes further penetrate the cracked silicon particles and reform the interphases, resulting in huge electrode swelling and quick capacity decay. Here we resolve these challenges by designing a high-voltage electrolyte that forms silicon-phobic interphases with weak bonding to lithium-silicon alloys. The designed electrolyte enables micro-sized silicon anodes (5 µm, 4.1 mAh cm−2) to achieve a Coulombic efficiency of 99.8% and capacity of 2175 mAh g−1 for >250 cycles and enable 100 mAh LiNi0.8Co0.15Al0.05O2 pouch full cells to deliver a high capacity of 172 mAh g−1 for 120 cycles with Coulombic efficiency of >99.9%. The high-voltage electrolytes that are capable of forming silicon-phobic interphases pave new ways for the commercialization of lithium-ion batteries using micro-sized silicon anodes.

Delineating the Effects of Transition-Metal-Ion Dissolution on Silicon Anodes in Lithium-Ion Batteries.

Silicon anode is an appealing alternative to enhance the energy density of lithium-ion batteries due to its high capacity, but it suffers from severe capacity fade caused by its fast degradation. The crossover of dissolved transition-metal (TM) ions from the cathode to the anode is known to catalyze the decomposition of electrolyte on the graphite anode surface, but the relative impact of dissolved Mn2+ versus Ni2+ versus Co2+ on silicon anode remains to be delineated. Since all three TM ions can dissolve from LiNi1-x-yMnxCoyO2 (NMC) cathodes and migrate to the anode, here a LiFePO4 cathode is paired with SiOx anode and assess the impact by introducing a specific amount of Mn2+ or Ni2+ or Co2+ ions into the electrolyte. It is found that Mn2+ ions cause a much larger increase in SiOx electrode thickness during cycling due to increased electrolyte decomposition and solid-electrolyte interphase (SEI) formation compared to Ni2+ and Co2+ ions, similar to previous findings with graphite anode. However, with a lower impedance, the SEI formed with Mn2+ protects the Si anode from excessive degradation compared to that with Co2+ or Ni2+ ions. Thus, Mn2+ ions have a less detrimental effect on Si anodes than Co2+ or Ni2+ ions, which is the opposite of that seen with graphite anodes.

Selenium treatment towards enhanced cyclic stability for single-crystal Ni-rich cathode at ultra-high voltage of 4.7 V

Developing high-voltage (≥4.3 V vs Li/Li+) single-crystal Ni-rich LiNixCoyMn1-x-yO2 offers an enticing strategy to achieve high energy density for lithium-ion batteries. However, at high-voltage operation, the cathode will be vulnerable to induce the intrinsic Oα- (α < 2) migration, triggering the serious structural degradation, notorious parasitic reaction and oxygen loss, which may ultimately result in the battery performance attenuation. Herein, an outside-in oriented nanostructure is well designed and constructed on the single-crystal LiNi0.6Co0.1Mn0.3O2 (SC-NCM) cathode materials, exhibiting an “anti-aging” effect of inhibiting the escape of oxygen from SC-NCM particles during the ultra-high voltage (4.7 V) cycling. Both theoretical calculation and experimental results confirm that the outside-in nanostructure would stabilize the oxygen lattice and suppress O2 release during long-term cycling. Meanwhile, the surface modification of thin Se layer will alleviate the parasitic reactions and improve the electronic conductivity. Under the synergistic strategy of surface modification and interface doping, the obtained SC-NCM exhibits boosted cyclic stability in coin half-cell and pouch full-cell simultaneously. Therefore, the reversible capacity of LiNi0.6Co0.1Mn0.3O2 at high voltage is competitive with comercial LiNixCoyMn1-x-yO2 (x ≥ 0.8), demonstrating more superior safety ability and cyclic property. It provides an effective approach for improving the long-term performance of Ni-rich cathode materials for practical application under ultra-high working voltage.

An ultrathin LiF film coated on NCM electrode surface via magnetron sputtering for optimized structure stability and cycling performance

Nickel-riched layered oxide cathode is one of the most promising cathode materials for high energy density lithium-ion batteries, but the capacity decay and poor cycling stability due to the occurrence of side reactions at the electrode-electrolyte interface are huge obstacles preventing its performance. Surface coating is an effective method to solve this problem. In this paper, nanoscale LiF films were deposited on the surface of Ni0.83Co0.11Mn0.06O2 (NCM811) by magnetron sputtering, which effectively improved the electrochemical performance of NCM811 in half-cells. Scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) showed that LiF was uniformly deposited onto the electrode surface and was not embedded in the cathode particles. After 100 cycles at 0.5C, the discharge specific capacity of the coated modified NCM was 181.82 mAh/g with a retention rate of 93.95%, which was much higher than that of the original NCM811 at 160.84 mAh/g with a capacity retention rate of 83.11%, while the capacity remained basically unchanged. In addition, the modified rate capability was also significantly improved, with the discharge specific capacity of the modified sample at 5C being 167.26 mAh/g, which was 12.45% higher than that of the uncoated sample at 148.73 mAh/g. The deposited LiF film can protect the electrode interface, inhibit the decomposition of electrolyte and thus protect the positive electrode, and stabilize the structure of the particles.

A strong nucleophilic fluorination agent to achieve highly stable in-situ 3D cross-linked gel polymer electrolyte for lithium-ion batteries

The Gel Polymer Electrolyte (GPE) is recognized as a promising alternative to conventional electrolytes, aiming to enhance the longevity and energy density of lithium-ion batteries (LIBs). However, several challenges persist, particularly concerning the conductivity and voltage window of GPE in battery systems. In this study, we introduce an in-situ 3D crosslinked GPE, using polymethyl methacrylate (PMMA) as the monomer and polyethylene glycol dimethacrylate (PEGDMA) as the crosslinking agent, to ensure structural stability and optimized ion conductivity. We also incorporate a potent nucleophilic fluorination agent, Tetrabutylammonium fluoride (TBAF), to augment the compatibility and oxidation resistance of the formulated FGPPE. The recurring (–CH2CH2O-) units of PEGDMA, coupled with in-situ lithium fluoride (LiF) and C-F groups introduced by TBAF, endow the FGPPE with a remarkable ionic conductivity of 7.8 mS cm−1 and a distinctly electrochemical stability of 4.65 V. Notably, the Li metal anode, featuring an F-rich solid-state interface (SEI), demonstrates uniform Li+ deposition, sustaining a cycling life of 1000 h and maintaining a commendable average coulomb efficiency of 98.5 % over 300 cycles. Additionally, the NCM811/SiC pouch cell integrated with FGPPE showcases superior cycling stability, retaining 99.4 % of its capacity after 600 cycles at an elevated voltage of 4.45 V. Such advancements in gel polymer electrolyte design can significantly expedite the commercial deployment of gel polymer Li-ion batteries.

A Critical Analysis of Chemical and Electrochemical Oxidation Mechanisms in Li-Ion Batteries.

Electrolyte decomposition limits the lifetime of commercial lithium-ion batteries (LIBs) and slows the adoption of next-generation energy storage technologies. A fundamental understanding of electrolyte degradation is critical to rationally design stable and energy-dense LIBs. To date, most explanations for electrolyte decomposition at LIB positive electrodes have relied on ethylene carbonate (EC) being chemically oxidized by evolved singlet oxygen (1O2) or electrochemically oxidized. In this work, we apply density functional theory to assess the feasibility of these mechanisms. We find that electrochemical oxidation is unfavorable at any potential reached during normal LIB operation, and we predict that previously reported reactions between the EC and 1O2 are kinetically limited at room temperature. Our calculations suggest an alternative mechanism in which EC reacts with superoxide (O2-) and/or peroxide (O22-) anions. This work provides a new perspective on LIB electrolyte decomposition and motivates further studies to understand the reactivity at positive electrodes.

Rich-Carbonyl Carbon Catalysis Facilitating the Li2CO3 Decomposition for Cathode Lithium Compensation Agent.

The active lithium loss of lithium-ion batteries can be well addressed by adding a cathode lithium compensation agent. Due to the poor conductivity and electrochemical activity, lithium carbonate (Li2CO3) is not considered as a candidate. Herein, an effective cathode lithium compensation agent, the recrystallized Li2CO3 combined with large specific surface area disordered porous carbon (R-LCO@SPC) is prepared. The screened SPC makes it easier for nano-sized Li2CO3 to adsorb and decompose on carbon substrate, meantime, exposing plenty of catalytic active sites of C═O, which can significantly improve the electrochemical activity and conductivity of Li2CO3, thus greatly reducing the decomposition potential of Li2CO3 (4.0V) and releasing high irreversible capacity (580mAhg-1) compared to the unmodified Li2CO3 (nearly no capacity above 4.6V). Meantime, the Li2CO3 can disappear completely without any by-product after the initial cycle accompanied by partially dissolved in electrolyte, optimizing the composition of SEI. The resultant lithium compensation agent applied to LMFP//graphite full cell exhibits a 19.1% increase in energy density, enhancing the rate and cycling performance, demonstrating great practical applications potential in high energy density lithium-ion batteries.

Progress in the application of silicon-based anode nanotechnology in lithium batteries

With the development of technology, graphite materials in traditional lithium batteries can no longer meet people’s needs due to their relatively low specific capacity, limited charging and discharging rates, and poor safety. Silicon has a very high theoretical specific capacity, far exceeding traditional graphite negative electrode materials, making silicon nanoparticles an ideal choice for improving the energy density of lithium-ion batteries. In this paper, we first introduce the silicon nanoparticle anode and its preparation methods: mechanical ball milling, and thermal cracking, and introduce the application of binders in it. Secondly, the silicon nanowire anode and the chemical deposition method for its preparation are introduced, and the high-performance silicon nanowire lithium battery of Amprius is introduced. Thirdly, the preparation of silicon thin film anode and two types of composite film was introduced. Finally, the three types of silicon nano anodes are summarized and prospected. This paper has reference significance for the future research of silicon-based lithium-ion batteries.

Electrophoretic assisted fabrication of additive-free WS2 nanosheet anodes for high energy density lithium-ion batteries.

2D WS2 nanosheets (NSs) are gaining popularity in the domain of Li-ion batteries (LIBs) due to their unique structures, which can enable reversible insertion and extraction of alkali metal ions. While synthesis methods have mostly relied on the exfoliation of bulk materials or direct growth on substrates, here we report an alternative approach involving colloidal hot-injection synthesis of 2D WS2 in 2H and 1T' crystal phases followed by their electrophoretic deposition (EPD) on the current collector. The produced 2D WS2 NSs' films do not require any additional additives during deposition, which boosts the energy density of the additive-free LIBs produced. The 1T' and 2H NSs exhibit long-term stable cyclic performance at C/5 for 600 cycles. At a high cycling rate (1C), the 2H NSs outperform the 1T' NSs, delivering a 1st cycle reversible capacity of 513 mA h g-1 with capacity retention of 73% after 100 cycles (compared to 205 mA h g-1, and 84 mA h g-1 respectively for NS-1T'). Post-cycling investigation confirms that there is no leaching or cracking of the active material on the surface of anodes after 100 cycles at C/5, which enables mechanical stability, and impressive battery performance of the WS2 NS electrodes.

Carbon-coated Ni0.5Mg0.5Fe1.7Mn0.3O4 nanoparticles as a novel anode material for high energy density lithium-ion batteries.

Lithium-ion batteries (LIBs) have gained considerable attention from the scientific community due to their outstanding properties, such as high energy density, low self-discharge, and environmental sustainability. Among the prominent candidates for anode materials in next-generation LIBs are the spinel ferrites, represented by the MFe2O4 series, which offer exceptional theoretical capacities, excellent reversibility, cost-effectiveness, and eco-friendliness. In the scope of this study, Ni0.5Mg0.5Fe1.7Mn0.3O4 nanoparticles were synthesized using a sol-gel synthesis method and subsequently coated with a carbon layer to further enhance their electrochemical performance. TEM images confirmed the presence of the carbon coating layer on the Ni0.5Mg0.5Fe1.7Mn0.3O4/C composite. The analysis of the measured X-ray diffraction (XRD) and Raman spectroscopy results confirmed the formation of nanocrystalline Ni0.5Mg0.5Fe1.7Mn0.3O4 before coating and amorphous carbon in the Ni0.5Mg0.5Fe1.7Mn0.3O4/C after the coating. The Ni0.5Mg0.5Fe1.7Mn0.3O4 anode material exhibited a much higher specific capacity than the traditional graphite material, with initial discharge/charge capacities of 1275 and 874 mA h g-1, respectively, at a 100 mA g-1 current density and a first coulombic efficiency of 68.54%. The long-term cycling test showed a slight capacity fading, retaining approximately 85% of its initial capacity after 75 cycles. Notably, the carbon-coating layer greatly enhanced the stability and slightly increased the capacity of the as-prepared Ni0.5Mg0.5Fe1.7Mn0.3O4. The first discharge/charge capacities of Ni0.5Mg0.5Fe1.7Mn0.3O4/C at 100 mA g-1 current density reached 1032 and 723 mA h g-1, respectively, and a first coulombic efficiency of 70.06%, with an increase of discharge/charge capacities to 826.6 and 806.2 mA h g-1, respectively, after 75 cycles (with a capacity retention of 89.7%), and a high-rate capability of 372 mA h g-1 at 2C. Additionally, a full cell was designed using a Ni0.5Mg0.5Fe1.7Mn0.3O4/C anode and an NMC811 cathode. The output voltage was about 2.8 V, with a high initial specific capacity of 755 mA h g-1 at 0.125C, a high rate-capability of 448 mA h g-1 at 2C, and a high-capacity retention of 91% after 30 cycles at 2C. The carbon coating layer on Ni0.5Mg0.5Fe1.7Mn0.3O4 nanoparticles played a crucial role in the excellent electrochemical performance, providing conducting, buffering, and protective effects.

Unveiling olivine cathodes for high energy-density lithium-ion batteries: a comprehensive review from the atomic level to the electrode scale

We propose unifying strategies for the development of high-energy, low-cost, long-lasting olivine cathodes through atomic to electrode level engineering, focusing on: (1) high energy densities, (2) kinetics, and (3) structural stabilities.

An Innovative Power Management Strategy for Hybrid Battery–Supercapacitor Systems in Electric Vehicle

Currently, batteries and supercapacitors play a vital role as energy storage systems in industrial applications, particularly in electric vehicles. Electric vehicles benefit from the high energy density of lithium batteries as well as the high power density of supercapacitors. Hence, a robust and efficient energy management system is required to coordinate energy flows between these two storage systems, ensuring road safety. In this study, we develop a novel rule-based strategy called “Continuous Regulation with Dynamic Battery Power Limiting” to establish robust control between the lithium-ion battery and the supercapacitor. A comparative analysis is conducted to evaluate the performance of this proposed approach in comparison to conventional methods. The results show that this approach significantly enhances driving comfort and prevents depletion of the main energy source, resulting in a gain of nearly 30% compared to a lithium-ion battery electric vehicle. Additionally, this new rules-based strategy ensures that the supercapacitor is charged at the end of each drive cycle.

Extreme Fast Charging of High Energy Density Lithium Ion Battery

The demand for high-energy-density batteries using Ni-rich cathodes is increasing due to the continuous expansion of the electric vehicle (EV) market. U.S. Department of Energy has stated the need for extreme-fast-charging (XFC) batteries that achieve an 80% state of charge (SOC) in less than 15 min. However, Ni-rich cathodes tend to lose capacity quickly under XFC conditions, which compromises their structural integrity. In addition, XFC conditions rapidly generate significant heat due to the high current applied to the cell, leading to the degradation of cell components. It is challenging to create Ni-rich cathodes that can withstand XFC conditions while still maintaining maximum energy density and long-term cycling performance. In this study, a cathode called Li[Ni0.92Co0.06Al0.01Nb0.01]O2 (Nb-NCA93) is introduced, which has a high energy density of 869 Wh kg-1. The presence of Nb in the cathode induces grain refinement in its secondary particles, reducing internal stress and preventing heterogeneity of Li concentration during cycling. When used in a full-cell, the Nb-NCA93 cathode reaches full charge within 12 minutes and retains 85.3% of its initial capacity after 1000 cycles, cycled at full depth of discharge. Furthermore, the refined microstructure of the Nb-NCA93 cathode limits heat generation under XFC conditions. References H.-H. Ryu, K.-J. Park, C. S. Yoon, Y.-K. Sun, Chem. Mater. 2018, 30, 1155 C. S. Yoon, H.-H. Ryu, G.-T. Park, J.-H Kim, K.-H. Kim, Y.-K Sun, J. Mater. Chem. A 2018, 6, 4126 U.-H. Kim, H.-H. Ryu, J.-H. Kim, R. Mücke, P. Kaghazchi, C. S. Yoon, Y.-K. Sun, Adv. Energy Mater. 2019, 9, 1803902

A Scalable Approach to Synthesize Cobalt-Free LNMO Cathode Materials for High Energy Density Lithium Ion Batteries

The rapid growing demand for electric vehicles (EVs) has highlighted the need for high-energy-density batteries. The cathode material plays a vital role in achieving this goal[1]. As the limitations of cathode capacity improvement are approached, the pursuit for high-voltage materials becomes a viable option[2]. Lithium nickel manganese oxide LNMO (LiNi0.5Mn1.5O4) stands out due to its remarkable attributes including a substantial reversible capacity, excellent thermal stability, cost-effectiveness, environmental friendliness, and a high energy density[3]. Moreover, its cobalt-free composition aligns with sustainability objectives. Despite extensive research, the large-scale production and deployment of LNMO remain formidable challenges.In this study an industrially applicable co-precipitation method-based scalable synthesis strategy is introduced. The LNMO spheres with controlled various sizes and morphologies were successfully fabricated by adjusting the pH environment during synthesis carefully (Fig. 1A). Scanning electron microscopy (SEM) revealed the presence of uniformly spherical particles with dimensions of appr. 6, 9, and 14 µm and unique morphological characteristics (Fig. 1Ad-f). Synchrotron X-ray diffraction (SXRD) of LNMO samples revealed a deviation from the optimal Ni-to-Mn ratio of 1:3 (Fig. 1B)[4,5]. This variation results from the pH-dependent metal ion precipitation dynamics during synthesis, introducing a fascinating dimension to LNMO material fabrication. As potential cathode materials for lithium-ion batteries, these samples underwent a thorough electrochemical evaluation as part of our research. Among the synthesized LNMO samples, LNMO-9 demonstrated the most promising specific capacity, surpassing approximately 138 mAh/g and working under high voltage of 4.75 V (Fig. 1C). Furthermore, the characterizations of the materials were also thoroughly investigated by a variety of advanced characterization techniques, including Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM).This research reveals a strategy for synthesizing LNMO materials with certain regulated features and presents a successful strategy for industrial manufacturing as well. Particularly in the context of the EV industry, this research acquires critical significance in answering the growing demand for high-performance, sustainable energy storage systems. Fig. 1 (A) Illustration of the synthesis process of LNMO-x samples with SEM images of (a‒c) NiMn-x precursors and (d‒f) LNMO-x products. (B) SXRD patterns with Rietveld refinements and (C) charge/discharge profile of LNMO-x samples. Reference [1] H.-H. Ryu, G.-C. Kang, R. Ismoyojati, G.-T. Park, F. Maglia, Y.-K. Sun, Intrinsic weaknesses of Co-free Ni–Mn layered cathodes for electric vehicles, Materials Today. (2022) S1369702122000645. https://doi.org/10.1016/j.mattod.2022.03.005.[2] T. Liu, A. Dai, J. Lu, Y. Yuan, Y. Xiao, L. Yu, M. Li, J. Gim, L. Ma, J. Liu, C. Zhan, L. Li, J. Zheng, Y. Ren, T. Wu, R. Shahbazian-Yassar, J. Wen, F. Pan, K. Amine, Correlation between manganese dissolution and dynamic phase stability in spinel-based lithium-ion battery, Nat Commun. 10 (2019) 4721. https://doi.org/10.1038/s41467-019-12626-3.[3] Y. Xue, L.-L. Zheng, J. Wang, J.-G. Zhou, F.-D. Yu, G.-J. Zhou, Z.-B. Wang, Improving Electrochemical Performance of High-Voltage Spinel LiNi 0.5 Mn 1.5 O 4 Cathode by Cobalt Surface Modification, ACS Appl. Energy Mater. 2 (2019) 2982–2989. https://doi.org/10.1021/acsaem.9b00564.[4] A. Gomez, G. Dina, S. Kycia, The high-energy x-ray diffraction and scattering beamline at the Canadian Light Source, Review of Scientific Instruments. 89 (2018) 063301. https://doi.org/10.1063/1.5017613.[5] H.M. Rietveld, A profile refinement method for nuclear and magnetic structures, J Appl Crystallogr. 2 (1969) 65–71. https://doi.org/10.1107/S0021889869006558. Figure 1

Approach for Mitigating Interfacial Degradation in Silicon-Based Electrodes to Enhance Cycling Stability of Lithium-Ion Batteries and Capacitors

The growing demand for high energy density in lithium-ion batteries has led to extensive investigations on silicon negative electrodes. In this study, we propose a novel approach to address the interfacial degradation of electrodes caused by volume expansion during lithium insertion/extraction. The approach involves a sandwich structure consisting of a carbon nanofiber (CNF) undercoating electrode and a CNF-coated separator. The CNF is treated with acid to form carboxyl and hydroxyl groups on its surface, which improves the dispersion of the coating slurry and enhances adhesion to the electrode. Through electrochemical testing, the improved silicon electrode shows a high retention rate of 82% compared to the initial capacity after 100 cycles, and high electrochemical performance when applied to both lithium-ion batteries and lithium-ion capacitors. These results are attributed to the improved adhesion between the electrode and current collector, as well as the formation of a stable solid electrolyte interphase layer on the electrode surface. These findings suggest that the conductive coating process, applied to the separator and current collector, effectively mitigates interfacial issues that are associated with silicon-based electrodes. This approach has the potential to overcome the degradation characteristics of silicon electrodes and significantly contribute to improving the cycling stability of lithium-ion batteries and capacitors.

Simulation of Lithium-Sulfur Batteries and Optimization of Cathode Structure

Recently, the spread of the mobile devices and clean energy, the demand for high-power and high-capacity secondary batteries has been growing. However, the energy density of lithium-ion batteries (LiB) that is widely used nowadays is reaching its design limit. Instead of LiB, lithium-sulfur batteries (LiSB) are expected as one of the next-generation secondary batteries. Compared to LiB, LiSB has the advantages of higher energy density, lower cost, and easier weight saving. In LiB, the driving force is the insertion and desorption reaction of lithium ions between the cathode and anode, while in LiSB, is the complex sulfur dissolution and precipitation reaction. In LiSB, the electrolyte determines the dissolution and precipitation of sulfur, which is thought to have a significant impact on battery characteristics. Therefore, new electrolyte systems are being developed daily and techniques to elucidate the reaction mechanisms are needed. Furthermore, the effect of carbon black, a conductive material, on battery characteristics has also been considered. In this study, we investigated the optimal initial lithium ion concentration and calculation focused on the precipitation form of each carbon species for the design of optimal electrode structures.Kumaresan's one-dimensional model [1] based on porous electrode theory was used. Sulfur was used as the cathode active material and lithium metal as the anode active material. Electron and ionic potentials were calculated from the electro-neutrality condition, concentration distribution in the electrolyte was calculated from the non-stationary mass balance equation, and electrochemical reactions at the interface between active material and electrolyte were calculated using the Butler-Volmer equation. Furthermore, stepwise reactions were considered by incorporating the electrochemical reaction of sulfur and the dissolution and precipitation reactions into the concentration distribution and the interfacial reactions. The temperature in the electrode layer was assumed to be constant, and no heat loss or side reactions due to overvoltage were assumed to occur. In LiSB, sulfur dissolved in the electrolyte on the cathode surface is sequentially reduced as polysulfide ions as the discharge progresses. It then combines with lithium ions transferred from the anode and expands to about 1.8 times. Therefore, based on our previous research [2], the effect of the expansion and contraction of the electrode particles was reflected by dynamic changes in the structural properties of the electrode layer.Ionic conductivity and transport number are important parameters that affect the properties of the electrolyte. The higher the lithium ion concentration, the higher the transport number, but the lower the ionic conductivity [3]. In this study, we focused on sulfolane-based electrolyte and investigated the effect of initial lithium ion concentration on discharge capacity by incorporating the relationship between ionic conductivity and transport number into a model. As a result, the discharge capacity reached its maximum when the initial lithium ion concentration was 3.0 M. In the static state, the ionic conductivity was highest around 1.6 M, but considering the operating conditions during discharge, the concentration distribution became be more remarkable due to the low transport number, which may have resulted in excessive Li2S precipitation near the separator. As an extension to the microstructure of the electrode layer, we focused on carbon black (CB). Two types of CB (KB, MCND) were targeted. When MCND and KB were used as CB under the same conditions in the experiment, it was confirmed that the discharge characteristics of MCND were significantly better than those of KB. In LiSB, Li2S precipitation has a significant effect on discharge characteristics. Therefore, we focused on the pores of both CBs. We reconstructed the binarized structure from X-ray CT images of both CBs, hypothetically precipitated Li2S in the pores, and calculated the relative conductivity. The relative conductivity represents the transport property and is highly dependent on the structure of the electrode layer. As a calculation result, the relative conductivity of KB became significantly smaller as the porosity decreased. From the above, the transport properties in both CBs were confirmed by calculation.As described above, it was suggested that an optimum lithium ion concentration exists, and the effect of different CB structures on transport properties was qualitatively evaluated. In the future, it is necessary to confirm the validity of the optimal concentration through experiments and to quantitatively evaluate the effect of different CB.AcknowledgmentThis study was supported by JST ALCA-SPRING Grant JPMJAL1301, Japan.

Doped Micron Silicon and Mxene Based Composite Anodes for High-Performance Li-Ion Batteries

With the world's energy needs constantly increasing, renewable energy sources must be technologically advanced and integrated with energy storage devices to ensure their uninterrupted operation. In recent decades, researchers have devoted substantial efforts to improve the energy density of lithium-ion batteries (LIBs) [1]. While graphite remains the commercial anode in LIBs, it’s very low theoretical capacity (372 mAh g-1) restricts its use in high-energy applications. Silicon (Si), owing to its high theoretical capacity of 4200 mAh g-1, natural abundance, and appropriate Li uptake potential (0.4 V vs Li/Li+), is a promising anode material [2]. However, its massive volume expansion restricts its practical use.In this study, micron-sized Si particles are combined with graphite. Micron Si is less expensive, and the synthesis process is simpler. The well-ground mixture (Si-G) is mixed with a polymer solution to generate pyrolytic carbon (upon carbonising). This aids in the buffering of mechanical stresses caused by Si volume expansion. Furthermore, direct exposure of Si to the electrolyte is avoided, stabilising the solid electrolyte interphase (SEI). The addition of a dopant improves the intrinsic conductivity of the material, resulting in increased capacity by providing electron and Li-ion transport channels. To further enhance the composite's performance, synthesized Mxene is added to promote the charge transport between micron Si. Using various techniques such as SEM-EDAX, XRD, Raman, and XPS spectroscopy, the composite's morphology and structure is studied which reveals uniformly distributed Si, C, and Mxene sheets that retain the sheet architecture.As an anode, the composite exhibits outstanding electrochemical performance which was evident by its impressive lithium storage specific capacity of 2003 mAh g-1 (based on weight of Si) even after long term cycling (at 1C rate). Additionally, the composite demonstrates superior rate performance with a specific capacity of 2439 mAh g-1 at 10 C rate, highlighting its potential for high-power applications. Moreover, the electrode displayed a low charge transfer impedance and fast electron transport, which improved the electrochemical performance. The reason for this improved performance is the unique structure consisting of Mxene and doping, which significantly increased the Li ion diffusion and the active sites. Also, low-cost micron Si is used which has a high tap density. Thus, this work provides an approach to develop high-capacity LIBs based on silicon. Keywords: Lithium-ion battery, micron silicon anode, Mxene, doping. References Liu, L. Kang, J. Hu, E. Jung, J. Zhang, S.C. Jun, Y. Yamauchi, Unlocking the Potential of Oxygen-Deficient Copper-Doped Co 3 O 4 Nanocrystals Confined in Carbon as an Advanced Electrode for Flexible Solid-State Supercapacitors, ACS Energy Lett. 6 (2021) 3011–3019. https://doi.org/10.1021/acsenergylett.1c01373.Zhou, Y. Liu, C. Du, Y. Ren, T. Mu, P. Zuo, G. Yin, Y. Ma, X. Cheng, Y. Gao, Polyaniline-encapsulated silicon on three-dimensional carbon nanotubes foam with enhanced electrochemical performance for lithium-ion batteries, Journal of Power Sources. 381 (2018) 156–163. https://doi.org/10.1016/j.jpowsour.2018.02.009.