High-energy Lithium-ion Batteries Research Articles

Defect Chemistry in High-Voltage Cathode Materials for Lithium-Ion Batteries.

High-voltage cathodes (HVCs) have emerged as a paramount role for the next-generation high-energy-density lithium-ion batteries (LIBs). However, the pursuit of HVCs comes with inherent challenges related to defective structures, which significantly impact the electrochemical performance of LIBs. The current obstacle lies in the lack of a comprehensive understanding of defects and their precise effects. This perspective aims to provide insights into defect chemistry for governing HVCs. The classifications, formation mechanisms, and evolution of defects are outlined to explore the intricate relationship between defects and electrochemical behavior. The pressing need for cutting-edge characterization techniques that comprehensively investigate defects across various temporal and spatial scales is emphasized. Building on these fundamental understandings, engineering strategies such as composition tailoring, morphology design, interface modification, and structural control to mitigate or utilize defects are thoroughly discussed for enhanced HVCs performance. These insights are expected to provide vital guidelines for developing high-performance HVCs for next-generation high-energy lithium-ion batteries.

Triple salts electrolyte for high cyclability and high capability in practical safe nickel-rich batteries

The pursuit of extended driving ranges of electric vehicles has spurred the use of nickel-rich layered cathodes, yet raised safety concerns. Existing ethylene carbonate-free electrolytes improve safety but compromise electrochemical performances due to the delicate balance between anode interphases. We introduce a novel electrolyte composed of propylene carbonate (PC) and triple lithium salts, which synergistically reinforces both cathode and anode interfaces. PC's low kinetic reactivity with LiNi0.8Mn0.1Co0.1O2 (NCM811) at the cathode minimizes heat generation and oxygen evolution. To stabilize the anode, bis(fluorosulfonyl)imide (FSI-) anions are integrated to construct an anion-driven interface, while difluoro(oxalato)borate (DFOB-) is added to lower PC's de-solvation energy and prevent co-intercalation. NCM811/Graphite pouch cells utilizing this electrolyte show enhanced safety, cyclability, and rate capability, surviving 60 min at 180℃ without incident. Post-mortem analysis reveals suppressed parasitic reactions and the formation of a robust solid electrolyte interphase (SEI). This research offers a critical framework for the design of electrolytes tailored for high-energy lithium-ion batteries.

Microsphere LiMn0.6Fe0.4PO4/C cathode with unique rod-like secondary architecture for high energy lithium ion batteries

LiMnxFe1-xPO4/C is considered a promising next-generation cathode material with significant commercial potential, inheriting the safety of LiFePO4 while offering higher energy densities. However, the extremely low conductivity and the Jahn-Teller effect induced by Mn3+ limit its practical capacity and rate performance. Effective modifications can be achieved through particle nanonization and uniform carbon coating. Here, we synthesized microspherical LiMn0.6Fe0.4PO4/C cathode materials using a hydrothermal method combined with spray drying carbon coating. The cathode material exhibits a microsphere structure composed of aggregated nanorods with a uniform 3 nm carbon coating, showing good dispersibility, small specific surface area and high tap density. In-situ diffraction analysis showed that expanding the single-phase solid solution region during (de)lithiation can reduce the energy barrier for electron transport, improve the kinetics of the (dis)charge process, and enhance both cycling and rate performance. The initial capacity at 0.1C can reach 155 mAh/g, and the capacity remains at 133.5 mAh/g with a retention rate of 97.1 % after 300 cycles. The synergistic effect of particle nanonization and uniform carbon coating endows the LiMnxFe1-xPO4/C material with excellent electrochemical performance.

Lithium ion transportation in lignin infused polyvinyl alcohol based eutectogel: A molecular dynamics framework

Eutectogels are an arising material in the field of energy storage applications like high-energy Lithium-Ion batteries (LIBs) due to their properties like higher ionic conductivity, environment friendly and enhanced safety. However, it is important to understand the working mechanism of eutectogels at an atomistic level with the help of Molecular Dynamics (MD) simulations, in order to enhance their performance as electrolytes for LIBs. Eutectogels are formed by integrating deep eutectic solvent (DES) involving Lithium Chloride (LiCl) and ethylene glycol (EG) in the molar ratio of 1:5 with the polymeric matrix of Polyvinyl alcohol (PVA) chains considered for this study. Thereafter, lignin molecules are induced in the eutectogel system to improve the characteristics of an eutectogel. The elaborate study of the effect of lignin on the lithium ions movement through the lignin-added-eutectogel is involved in this work. The increase in hydrogen bonds among PVA polymeric chains and lignin molecules show the strength enhancement. From the Radial Distribution Function results it is derived that the lithium ions are showing enhanced interactions with chlorine ions than any other component of the system. Mean Square Displacement gives an idea about diffusivity of lithium ions through the systems and it suggests that the Li+ ion diffusivity is improved after Lignin imposition. On the basis of findings from this work, the modified Lignin infused PVA based eutectogel can be the potential candidate for the battery and energy storage applications.

A Fast Self-Healing Binder for Highly Stable SiOx Anodes in Lithium-Ion Batteries.

Silicon oxide-based (SiOx-based) materials show great promise as anodes for high-energy lithium-ion batteries due to their high specific capacity. However, their practical application is hindered by the inevitable volumetric expansion during the lithiation/delithiation process. Constructing high-performance binders for SiOx-based anodes has been regarded as an efficient strategy to mitigate their volume expansion and preserve structural integrity. In this work, we propose a green water-solution PAA-LS binder composed of poly(acrylic acid) (PAA) and sodium lignosulfonate (LS) with fast self-healing properties. The designed binder can be restored due to the strong affinity between Fe3+-catechol coordination bonds, thereby effectively alleviating the volumetric strain of SiOx-based anodes. Notably, with an optimized LS content of 0.5%, the SiOx@PAA-LS electrode exhibits excellent performance, delivering a high capacity of 997.3 mAh g-1 after 450 cycles at 0.5 A g-1. Furthermore, the SiOx||NCM622 full cell also demonstrates superior cycling stability, maintaining a discharge capacity of 147.58 mAh g-1 after 100 cycles at 0.5 A g-1, with an impressive capacity retention rate of 82.72%.

Study on the Commercial Metalized Plastic Current Collector PET-Cu and PP-Cu Toward High-Energy Lithium-Ion Battery.

Commercial metalized plastic current collector (MPCC) is receiving widespread attention from the business and academic communities, due to its properties of excellent electrical conductivity and low mass density. However, the application of MPCC on the side of copper is rarely studied. Herein, sandwich-like polyethylene terephthalate-based (PET) and polypropylene-based (PP) copper (Cu) current collectors via magnetron sputtering and electroplating are fabricated. Most importantly, the electrical performance, mechanical safety quality, and revealed the corresponding failure mechanism for the MPCC cells are first systematically evaluated. First, during the 45°C electrical cycling tests, PET-Cu CC (82.67%) and PP-Cu CC (82.32%) cells both have comparable capacity retention with the traditional Cu CC (Tra-Cu CC) cell (84.55%) after 500 cycles. The slight reduction in the cycling performance is induced by the crack of the Cu layer around the embedded SiO2 particle for PET-Cu CC cell and the detachment of Cu layer for PP-Cu CC cell. Second, during the nail-penetration test, MPCC cells maintain no fire and explosion for more than 5min, since the heat-shrinkable function of polymeric film can interrupt the continuous Joule heat released by internal short-circuit. This work provides important guidance for the large-scale application of MPCC in the field of lithium-ion batteries.

Artificial Electron Channels Enable Contact Prelithiation of Li-Ion Battery Anodes with Ultrahigh Li-Source Utilization.

Contact prelithiation is widely used for compensating the initial capacity loss of lithium-ion batteries (LIBs). However, the low Li-source utilization suffering from the deteriorated contact interfaces results in cycling degeneration. Herein, Li-Ag alloy-based artificial electron channels (AECs) are established in Li source/graphite anode contact interfaces to promote Li-source conversion. Due to the shielding effect of the Li-Ag alloy (50 at. % Li) on Li-ion diffusion, the dry-state corrosion of contact interfaces is restricted. The unblocked electronic conduction across the AEC-involved interface not only facilitates the Li source conversion but also accelerates the prelithiation kinetics during the wet-state process, resulting in an ultrahigh Li-source utilization (90.7%). Thereby, implementing AEC-assisted prelithiation in a LiNi0.5Co0.2Mn0.3O2 pouch cell yields a 35.8% increase in energy density and stable cycling over 600 cycles. This finding affords significant insights into the construction of an efficient prelithiation technology toward the development of high-energy LIBs.

Ultra-high rate performance of single-crystalline NMC cathodes enabled by a TEP-based electrolyte

Harnessing the full potential of Ni-rich single-crystal cathodes (LiNixMnyCo1-x-yO2, NMC) for next-generation high-energy lithium batteries is hindered by their slow reaction kinetics and susceptibility to interfacial decay. Our research introduces a novel strategy utilizing triethyl phosphate (TEP) and fluoroethylene carbonate (FEC) to optimize the Li+ solvation environment, lowering the coordination number and diminishing the energy threshold for Li+ transport. Mechanistic studies indicate that this intervention not only accelerates the Li+ transfer at the electrode/electrolyte interface but also catalyzes the development of a robust LiF-rich CEI layer. As a result, the single-crystal NMC83 cathode exhibits remarkable high-rate discharge capacities of approximately 209 mAh g−1 at 0.1 C and 192 mAh g−1 at 0.5 C. The robust CEI layer also mitigates parasitic reactions, substantially improving the cycle life, with capacity retention increasing from 46.1 % to 88.2 % after 300 cycles at 1 C. This work underscores the transformative impact of solvation sheath engineering on the interfacial dynamics of single-crystal cathodes, paving the way for more durable and efficient energy storage solutions.

Optimizing high-energy lithium-ion batteries: a review of single crystalline and polycrystalline nickel-rich layered cathode materials: performance, synthesis and modification

Layered Ni-rich Li [NixCoyMnz]O2 (NMC) and Li [NixCoyAlz]O2 (NCA) cathode materials have been used in the realm of extended-range electric vehicles, primarily because of their superior energy density, cost-effectiveness, and commendable rate capability. However, they face challenges such as structural instability, cation mixing, and surface degradation, which limit their practical application. This review comprehensively discusses the synthesis, modification, and performance optimization of nickel-rich cathodes, with a focus on single-crystal (SC) NMC cathodes. The unique properties and challenges of single-crystal nickel-rich cathodes are explored in comparison to polycrystalline (PC) cathodes, with a focus on performance-enhancing strategies such as doping and surface modification.

In situ multilevel covalent crosslinking binder with high ionic conductivity for high-performance Si anodes

Silicon (Si) anode has emerged as a promising material for high-energy-density lithium-ion batteries (LIBs), thanks to its high theoretical capacity. However, the commercial application of Si anodes is hindered by inadequate cycling performance and poor interfacial stability, stemming from unfavorable stress conditions. In this study, a multiple crosslinking binder with high ionic conductivity is proposed combining high mechanical strength and high adhesion to current collector and active Si particles by coupling poly(acrylic acid), polyvinyl alcohol, and polyethylene glycol. The designed polymer binder not only efficiently dissipates the inner stress with its multiple crosslinked networks, but also establishes a fast lithium-ion conduction pathway to facilitate the electrode reaction kinetic. The resultant Si anode using the designed binder exhibits significantly improved cycling stability and superior rate performance. This work presents a straightforward yet highly effective method to alleviate the detrimental stress incurred by high-capacity anodes in high-energy LIBs.

Comparative Investigation of Water-Based CMC and LA133 Binders for CuO Anodes in High-Performance Lithium-Ion Batteries.

Transition metal oxides are considered to be highly promising anode materials for high-energy lithium-ion batteries. While carbon matrices have demonstrated effectiveness in enhancing the electrical conductivity and accommodating the volume expansion of transition metal oxide-based anode materials in lithium-ion batteries (LIBs), achieving an optimized utilization ratio remains a challenging obstacle. In this investigation, we have devised a straightforward synthesis approach to fabricate CuO nano powder integrated with carbon matrix. We found that with the use of a sodium carboxymethyl cellulose (CMC) based binder and fluoroethylene carbonate additives, this anode exhibits enhanced performance compared to acrylonitrile multi-copolymer binder (LA133) based electrodes. CuO@CMC electrodes reveal a notable capacity ~1100 mA h g-1 at 100 mA g-1 following 170 cycles, and exhibit prolonged cycling stability, with a capacity of 450 mA h g-1 at current density 300 mA g-1 over 500 cycles. Furthermore, they demonstrated outstanding rate performance and reduced charge transfer resistance. This study offers a viable approach for fabricating electrode materials for next-generation, high energy storage devices.

Si/Graphite@C Composite Fabricated by Electrostatic Self-Assembly and Following Thermal Treatment as an Anode Material for Lithium-Ion Battery.

Commercial graphite anode has advantages such as low potential platform, high electronic conductivity, and abundant reserves. However, its theoretical capacity is only 372 mA h g-1. High-energy lithium-ion batteries have been a research hotspot. The Si anode has an extremely high specific capacity, but its application is hindered by defects such as large volume changes, poor electronic conductivity, and a small lithium-ion diffusion coefficient. Here, the Si/thermally reduced graphite oxide@carbon (Si/RGtO@C) composite was fabricated by electrostatic self-assembly followed by thermal treatment. The RGtO synergistic carbon coating layer can effectively compensate for the low electronic conductivity and buffer the volume expansion effect of the Si nanoparticles during charge/discharge cycles. The Si/RGtO@C anode demonstrated a significantly increased capacity compared to the RGtO. After 300 cycles, Si/RGtO@C kept a discharged capacity of 367.6 mA h g-1 at a high current density of 1.0 A g-1. The Si/RGtO@C anode shows an application potential for commercial high-energy lithium-ion batteries.

Asymmetric electrolyte design for high-energy lithium-ion batteries with micro-sized alloying anodes

Asymmetric electrolyte design for high-energy lithium-ion batteries with micro-sized alloying anodes

In-situ Ti4+-doped modification of layer-structured Ni-rich LiNi0.83Co0.11Mn0.06O2 cathode materials for high-energy lithium-ion batteries

The further commercialization of layer-structured Ni-rich LiNi0.83Co0.11Mn0.06O2 (NCM83) cathode for high-energy lithium-ion batteries (LIBs) has been challenged by severe capacity decay and thermal instability owing to the microcracks and harmful phase transitions. Herein, Ti4+-doped NCM83 cathode materials are rationally designed via a simple and low-cost in-situ modification method to improve the crystal structure and electrode–electrolyte interface stability by inhibiting irreversible polarizations and harmful phase transitions of the NCM83 cathode materials due to Ti4+-doped forms stronger metal-O bonds and a stable bulk structural. In addition, the optimal doping amount of the composite cathode material is also determined through the results of physical characterization and electrochemical performance testing. The optimized Ti4+-doped NCM83 cathode material presents wider Li+ ions diffusion channels (c = 14.1687 Å), lower Li+/Ni2+ mixing degree (2.68 %), and compact bulk structure. The cell assembled with the optimized Ti4+-doped NCM83 cathode material exhibits remarkable capacity retention ratio of 95.4 % after 100cycles at 2.0C and room temperature, and outstanding reversible discharge specific capacity of 148.2 mAh g−1 at 5.0C. Even under elevated temperature of 60 °C, it delivers excellent capacity retention ratio of 92.2 % after 100cycles at 2.0C, which is significantly superior to the 47.9 % of the unmodified cathode material. Thus, the in-situ Ti4+-doped strategy presents superior advantages in enhancing the structural stability of Ni-rich cathode materials for LIBs.

Measurement of Li-Ion Self-Diffusion in Laser Structured Electrodes

It is generally stated that a limiting factor in fast charging and high-power discharging of lithium-ion batteries (LiB) stems from the diffusion kinetics of Li+ in the electrode pore network. Numerous approaches in enabling fast charging of LiBs include active material development, electrolytes with high ionic conductivity and the management of the charging and discharging temperature. Another promising method is laser micro structuring to modify the electrode architecture regarding an enhanced lithium-ion diffusion kinetics. An increased high-rate capability and boost in cell lifetime have been demonstrated with such 3D electrodes [1, 2] but the related mechanisms leading to a substantial impact to diffusion kinetics are still poorly understood. Furthermore, it is imperative to find an optimal ablation pattern with regard to the desired application scenario that minimizes active mass loss in order to create the economic basis for efficient upscaling of the process.Nuclear Magnetic Resonance (NMR) measurements of longitudinal (T1) and transverse relaxation times (T2), as well as the T2/T2 exchange, are routinely used for the identification of different molecular species. The exchange NMR experiment is a well-known technique for studying local environments of nuclei such as liquids in pores and approximating their shapes and sizes [3]. The evolution of the transverse relaxation rate (T2) of a probed nuclei allows to determine if the specie is confined (shorter T2) or in liquid bulk (longer T2). In this work, so-called Exchange Nuclear Magnetic Resonance (T2/T2 exchange or EXSY), is conceptualized to study the impact of laser generated 3D patterns in pore self-diffusion of electrolyte species.Exchange NMR and T1 and T2 measurements were realized at various soaking times and electrolyte amounts for the following electrolyte species: Li+, PF6 -, ethyl carbonate (EC), and ethyl methyl carbonate (EMC), using laser structured, graphite-based electrodes casted on non-metallic substrates (to reduce RF interference). 2D exchange maps show the presence of confined species as well as the approximation of the diffusion properties. Using isotope exchange experiments with 6Li enriched electrolyte, concentration maps revealed the rate of 6LiPF6 intrusion into 7LiPF6 rich pre-soaked electrodes. The impact of laser generated 3D patterns in pore diffusion will be discussed in detail.[1]. Zheng, Y. et al. 3D silicon/graphite composite electrodes for high-energy lithium-ion batteries. Electrochim. Acta 317, 502–508 (2019).[2]. Smyrek, P., Pröll, J., Rakebrandt, J.-H., Seifert, H. J. & Pfleging, W. Manufacturing of advanced Li(NiMnCo)O2 electrodes for lithium-ion batteries . Laser-based Micro- Nanoprocessing IX 9351, 93511D (2015).[3]. Mitchell, J. et al. Validation of NMR relaxation exchange time measurements in porous media. J. Chem. Phys. 127, (2007).

Study on the interface of high specific energy High stability

High nickel terterial oxide, with high specific capacity and low cost advantages, is the preferred positive electrode for high specific energy lithium-ion power batteries at present. However, the high nickel ternary cathode material is easy to have side reactions with the electrolyte in the high delithium state, which can not only lead to the dissolution of transition metal ions and the formation of the surface salt phase, but also cause the lattice oxygen loss and surface interface side reactions, resulting in rapid attenuation of electrode capacity. In this paper, the development history and structural characteristics of high nickel ternary cathode materials are introduced, and the surface interface problems leading to capacity attenuation and structural degradation are comprehensively analyzed. From this perspective, three effective strategies for improving electrochemical performance of high nickel ternary cathode materials are summarized. Finally, by describing the advantages and disadvantages of these layered cathode materials, the challenges faced by these layered cathode materials are discussed, and it is pointed out that in the future, composite modification strategies should be adopted to optimize their structures and improve their properties.

Unraveling the delithiation mechanism of air-stabilized fluorinated lithium iron oxide pre-lithiation material

Integrating pre-lithiation materials into the cathode to compensate for the irreversible loss of active lithium ions due to the anodes is one of the essential technologies for achieving high-energy lithium-ion batteries. Li5FeO4 (LFO) has emerged as an appealing candidate for its high initial charge specific capacity, cost-effective, and suitability for the solvents/binders. Unfortunately, suffering from notorious degradation while in storage hinders its large-scale application. Furthermore, the delithiation mechanism and the impacts of oxygen species during charging remain elusive. Herein, a fluorinated LFO, featuring the F-doped carbon layer on the surface and gradient fluorination in the bulk, is synthesized to overcome the above obstacles. Surface modification enhances the air stability in storage and prevents oxygen species from attacking the electrolyte upon charging. The introduction of fluorine is proposed to lower the migration barrier of Fe from the tetrahedral interstitial site to the octahedral one and narrow the band gap, thus maintaining a stable phase transition at high charge density. As a result, the fluorinated LFO possesses excellent air stability (541.9 mAh g−1 after humid air exposure of 24H) and exhibits attractive initial charge specific capacity (703.4/580.5 mAh g−1 at 0.05/1.0C rate) as well as slight electrolyte decomposition during the charging process. This work opens up an alternative avenue to developing industry-applicable pre-lithiation materials for high-energy batteries.

The Facile and Controllable Synthesis of Ultrafine Sn Nanocrystals Loaded on Carbon Black for High-Performance Lithium Storage.

Sn and C nanocomposites are ideal anode materials for high-energy and high-power density lithium ion batteries. However, their facile and controllable synthesis for practical applications is still a critical challenge. In this work, a facile one-step method is developed to controllably synthesize ultrafine Sn nanocrystals (< 5 nm) loaded on carbon black (Sn@C) through Na reducing SnCl4 by mechanical milling. Different from traditional up-down mechanical milling method, this method utilizes mechanical milling to trigger bottom-up reduction reaction of SnCl4. The in-situ formed Sn nanocrystals directly grow on carbon black, which results in the homogeneous composite and the size control of Sn nanocrystals. The obtained Sn@C electrode is revealed to possesses large lithium diffusion coefficient, low lithiation energy barrier and stable electrochemical property during cycle, thus showing excellent lithium storage performance with a high reversible capacity (942 mAh g-1 at a current density of 100 mA g-1), distinguished rate ability (480 mAh g-1 at 8000 mA g-1) and superb cycling performance (730 mAh g-1 at 1000 mA g-1 even after 1000 cycles).

Solvent-free in-situ polymerized plastic crystal electrolytes for long-cycling lithium metal batteries

Solid polymer electrolytes (SPEs) are regarded as the pivotal materials for next-generation battery technology on account of their improved safety and potentially enabling higher energy density chemistry compared to conventional liquid electrolytes. However, the practical application of SPEs still hindered by the limited room temperature ionic conductivity, insufficient physical contact and unstable solid electrolyte interface (SEI) with electrodes. Here we report a class of in-situ polymerized plastic crystal electrolytes (PPCEs) which break the trade-offs between degree of polymerization and ionic conductivity of in-situ polymerized SPEs. The complete polymerized electrolytes combined both the advantages of in-situ polymer electrolytes and plastic crystal electrolytes, exhibiting thin thickness, good ionic conductivity, outstanding electrochemical stability and low interfacial impedance. As a result, symmetric Li cells with PPCE showed a superior long lifespan over 2500 h under 0.5 mA cm−2 and Li/PPCE/LiFePO4 (LiNi0.8Co0.1Mn0.1O2) cells displayed excellent long-cycling performance under 1.0 C at room temperature. The in-situ polymerized electrolyte system provides an effective strategy for developing safe and high-energy solid-state lithium batteries.

Mitigating thermal runaway propagation in high specific energy lithium-ion battery modules through nanofiber aerogel composite material

Thermal runaway and its propagation within lithium-ion battery systems pose significant challenges to widespread adoption in electric vehicles and energy storage systems. Deploying a thermal barrier between adjacent batteries is a common and effective strategy to prevent thermal propagation. This experimental study evaluates the inhibitory effect of nanofiber aerogel on thermal propagation within high-energy-density lithium-ion battery modules. The results indicate that increasing the thickness of nanofiber aerogel prolongs the average time interval between thermal runaway propagation events between adjacent batteries and increases their peak temperature difference, while the maximum surface temperature of each battery exhibits an overall downward trend.Specifically, compared to no nanofiber aerogel, a 0.5 mm nanofiber aerogel extends the average propagation time by 2 times, and a 1.0 mm nanofiber aerogel successfully prevents thermal propagation from the third to the fourth battery, with an average time extension of nearly 6 times. Furthermore, it is found that thermal runaway propagation can be effectively prevented when the aerogel thickness exceeds 2.0 mm. The microstructure of both fresh and damaged nanofiber aerogels was examined using Scanning Electron Microscopy to validate and analyze their robust durability. This study provides valuable insights for designing safer high-energy-density battery systems.