Microwave-assisted solvothermal synthesis of LiVyM1-yOPO4 (M = Mn, Cr, Ti, Zr, Nb, Mo, W) cathode materials for lithium-ion batteries
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Disclosed are electrochemical devices, such as lithium battery electrodes, lithium ion conducting solid state electrolytes, and solid-state lithium metal batteries including these electrodes and solid state electrolytes. In one embodiment, a method for forming an electrochemical device is disclosed in which a precursor electrolyte is heated to remove at least a portion of a resistive surface region of the precursor electrolyte.
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A stable solid electrolyte interphase (SEI) layer is key to high performing lithium ion batteries for metrics such as calendar and cycle life. The SEI must be mechanically robust to withstand large volumetric changes in anode materials such as lithium and silicon, so understanding the mechanical properties and behavior of the SEI is essential for the rational design of artificial SEI and anode form factors. The mechanical properties and mechanical failure of the SEI are challenging to study, because the SEI is thin at only ~ 10 – 200 nm thick and is air sensitive. Furthermore, the SEI changes as a function of electrode material, electrolyte and additives, temperature, potential, and formation protocols. A variety of in situ and ex situ techniques have been used to study the mechanics of the SEI on a variety of lithium ion battery anode candidates; however, there hasn't been a succinct review of the findings thus far. Because of the difficultly of isolating the true SEI and its mechanical properties, there have been a limited number of studies that can fully de-convolute the SEI from the anode it forms on. A review of past research will be helpful for culminating current knowledge and helping to inspire new innovations to better quantify and understand the mechanical behavior of the SEI. This review will summarize the different experimental and theoretical techniques used to study the mechanics of SEI on common lithium ion battery anodes and their strengths and weaknesses.
The study of lithium-sulfur (Li-S) batteries has generated various rationally designed cathodes and modified separators. However, the shuttle of soluble lithium polysulfides (LiPSs) and the sluggish kinetics of transformation of LiPSs to Li2S2/Li2S still hinder the achievement of long-life cycling and high-rate of Li-S batteries. Even though several kinds of nanocatalysts have been studied, the catalytic effects for Li-S batteries are not ideal. Single atoms (SAs) with high surface free energy are found to serve as both anchoring and electrocatalytic centers for LiPSs. Furthermore, atomically dispersed metal catalyst on carbon provide conductive and flexible host for dielectric sulfur. Moreover, SAs as the uniform lithiophilic sites can reduce the nucleation overpotential and ensure uniformly plating of Li. In this review, the latest strategies for preparation of SAs supported on carbons are provided on the application of Li-S batteries, including cathode, modified separator and Li metal anode. In addition, it also discusses how SAs with high catalytic activity can help build better Li-S batteries and the design principles for SAs. Finally, the future directions of SAs in energy storage applications is proposed.
Li–O 2 batteries have recently emerged to meet nowadays elevated electric energy demands. Redox mediators (RMs) for solution-inducing decomposition of discharge products are one approach to increase energy efficiency and reduce high overpotentials in these batteries. However, multiple obstacles hinder their usage such as redox shuttling, capacity fading, electrolyte degradation, etc. Herein, we present a new chemistry based on a combination of LiNO 3 , TEGDME and an ionic liquid that enables LiI (1 M) to lower the charge potential (3.5V) with a long cycle life of 270 cycles. 0.1 M LiI increases the cyclability up to 500 with a slightly increased charge potential (~4V) for a fixed capacity of 1000 mAh/g. Up to 100 cycles, this battery system retained ~95% Li 2 O 2 capacity with a ~0.8 V charge-discharge polarization gap. The addition of LiNO 3 to the electrolyte provides a protective solid electrolyte interface (SEI) on anode that works in synergy with the LiI RM. Moreover, we found that this electrolyte blend results in domain formation of ionic and neutral species enhancing the discharge and charge processes. Finally, DFT calculations provide a better understanding of the role of the anode SEI layer and the Li 2 O 2 decomposition promoted by the LiI during charge on the cathode.
Additive manufacturing has the potential to revolutionize the fabrication of lithium-ion batteries for a diversity of applications including in portable, biomedical, aerospace, and the transportation fields. Standard commercial batteries consist of stacked layers of various components (current collectors, cathode, anode, separator and electrolyte) in a two-dimensional manner. By leveraging the latest advances in additive manufacturing and computer-aided design, an improved geometric and electrochemical configuration of these batteries can maximize energy efficiency while allowing design optimization to reduce dead space for a given application. In this work, a composite UV photosensitive resin was prepared and used as feedstock in a vat photopolymerization system. The resin was loaded with LiCoO 2 acting as electrochemically active material for the cathode of a lithium-ion battery, and was further improved with the addition of conductivity-enhancing carbonaceous additives. Challenges to additive manufacturing arise from the opacity and high viscosity of the composite nature of these electrochemically-active resins, which cause light refraction during selective UV curing. Subsequently, items were printed and subjected to a thermal post-processing step to obtain an adequate compromise between electrochemical performance and mechanical integrity. Both sintered and green state 3D printed cathodes were assembled into half-cell lithium-ion batteries using lithium metal as a reference and counter electrode. Electrochemical cycling of these batteries yielded satisfactory results approaching commercial LiCoO 2 cathodes’ performance, with the potential advantages of additive manufacturing – high surface area anode–cathode configurations for power performance as well as shape conformability.
Despite the exceptionally high energy density of lithium metal anodes, the practical application of lithium-metal batteries (LMBs) is still impeded by the instability of the interphase between the lithium metal and the electrolyte. To formulate a functional electrolyte system that can stabilize the lithium-metal anode, the solvation behavior of the solvent molecules must be understood because the electrochemical properties of a solvent can be heavily influenced by its solvation status. Here, we unambiguously demonstrated the solvation rule for the solid-electrolyte interphase (SEI) enabler in an electrolyte system. In this study, fluoroethylene carbonate was used as the SEI enabler due to its ability to form a robust SEI on the lithium metal surface, allowing relatively stable LMB cycling. The results revealed that the solvation number of fluoroethylene carbonate must be ≥ 1 to ensure the formation of a stable SEI in which the sacrificial reduction of the SEI enabler subsequently leads to the stable cycling of LMBs.
Solid-state lithium metal batteries (SSLMBs) are promising next-generation high-energy rechargeable batteries. However, the practical energy densities of the reported SSLMBs have been significantly overstated due to the use of thick solid-state electrolytes, thick lithium (Li) anodes, and thin cathodes. Here, a high-performance NASICON-based SSLMB using a thin (60 µm) Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 (LAGP) electrolyte, ultrathin (36 µm) Li metal, and high-loading (8 mg cm -2 ) LiFePO 4 (LFP) cathode is reported. The thin and dense LAGP electrolyte prepared by hot-pressing exhibits a high Li ionic conductivity of 1 × 10 -3 S cm -1 at 80 °C. The assembled SSLMB can thus deliver an increased areal capacity of ≈1 mAh cm -2 at C/5 with a high capacity retention of ≈96% after 50 cycles under 80 °C. Furthermore, it is revealed by synchrotron X-ray absorption spectroscopy and in situ high-energy X-ray diffraction that the side reactions between LAGP electrolyte and LFP cathode are significantly suppressed, while rational surface protection is required for Ni-rich layered cathodes. This study provides valuable insights and guidelines for the development of high-energy SSLMBs towards practical conditions.
Achieving stable interfacial chemistry in lithium–sulfur batteries under practical conditions remains a key barrier to commercialization. Here, we demonstrate that interfacial dynamics can be effectively regulated by coupling solvation-power control with intrinsic heterogeneity of sulfur redox chemistry through the introduction of a weakly solvating fluorinated cosolvent, LIB 1200ET (1200ET). Compared with conventional fluorinated ethers, 1200ET efficiently shifts Li + solvation environment toward a more non-coordinated configuration at low volume fractions, enabling substantial solvation modulation without significantly impairing sulfur redox kinetics. This solvation transition weakens Li + –solvent interactions while strengthening Li + –anion and Li + –lithium polysulfide (LPS) coordination, suppressing LPS solubility and promoting reconstruction of solid–electrolyte interphase (SEI). Regulated LPS chemistry, together with 1200ET, leads to formation of a S 4+ -rich, LiF-reinforced SEI with enhanced ionic conductivity and mechanical robustness. Spatially resolved sulfur K-edge X-ray absorption spectroscopy on pouch cells reveals pronounced current-density-dependent chemical heterogeneity, distinguishing kinetically dominated and solvation-controlled regions. Under practical conditions (3.7 mg cm −2 sulfur loading, E/S = 6 µL mg −1 ), a single-layer pouch cell delivers 527 mAh g −1 over 200 cycles at C/3, while an Ah-level multilayer pouch cell achieves an energy density of 358 Wh kg −1 . These results establish non-coordinating cosolvent-driven solvation engineering as a scalable strategy for practical Li–S batteries.
The growth of lithium (Li) dendrites and the accumulation of dead Li (i.e., Li metal regions which are electronically disconnected from the current collector) significantly undermine the safety and performance of Li metal batteries. This study employs kilogram-scale atomic layer deposition technology to construct zinc oxide with a preferential (002) crystal orientation, which homogeneously forms on commercial carbon nanotube papers. Our approach emphasizes the importance of achieving a moderate Li adsorption energy and low Li migration energy barriers to suppress Li dendrite growth. In this work, we introduce the concept of "catalytic" effect for dead Li reconversion, as validated through time-of-flight secondary ion mass spectrometry, leading to a Li plating/stripping efficiency of 99.89%. The Ah-level Li metal pouch cells with high-nickel positive electrodes achieve a specific energy of 380 Wh kg -1 (based on the mass of the whole pouch cell) and demonstrate stable cycling under demanding conditions. Analysis of the cycled pouch cells confirms the structural integrity and provides insights into the mechanism of the dead Li "catalytic" conversion.
Abstract End of life (EoL) lithium‐ion batteries (LIBs) are piling up at an intimidating rate, which is alarming for environmental health. With further expected rapid growth of LIB use, the magnitude of spent battery accumulation is also expected to grow. LiNi x Co y Mn z O 2 (NCM) cathode materials are a dominant chemistry in high energy LIBs, and make up a huge portion of this waste accumulation. Direct recycling is one of the most promising ways to turn this waste to wealth, but has been limited to lab‐scale, due to lack of robustness, namely the tedious pretreatment required that involves toxic organic solvents. Herein, a process that integrates the pretreatment and relithiation of the cathode black mass is demonstrated. Cathode material from EoL electric vehicle (EV) batteries is treated in a 100 g per batch operation and the regenerated cathode active material demonstrates 100% electrochemical performance recovery, with 91% yield rate, and shows promise for further scale up. This process has the advantages of integration, scalability, and universality, which clears the barricade for direct recycling to move from lab to industry scale with considerable profitability.
A lithium‐ion battery's maximum charge rate and energy density are intrinsically limited by the ion diffusion rate in the electrolyte. Most research focuses on materials science solutions to this problem, with gradual improvement over the years. A mechanical solution is proposed to integrate an MHz‐order frequency surface acoustic wave (SAW) device into an existing 1.8 Ah multilayered Li‐ion pouch cell to enhance the ion diffusion rate and the overall battery performance. Both the charging rate and cycling lifetime are improved from SAW. At a 6C (10 min) charge and C/3 discharge rate, typical of electric vehicle applications, integrating SAW into the Li‐ion cell doubles the energy density and maintains at least 72% of the battery's initial capacity after 2000 cycles. Moreover, using SAW quantifiably reduces battery degradation in these conditions as determined by optical imaging, scanning electron microscopy, X‐ray diffraction, and neutron diffraction. The use of SAW appears to offer a method to avoid undesirable Li metal plating on the graphite anode during charging, and leads to a much longer battery lifetime and good charge capacity, all despite rapid charging.
Thermal Runaway (TR) in lithium-ion batteries (LIB) is a critical technological and social concern. Whilst such events are rare, TR is characterized by uncontrollable heating leading to catastrophic failures. To deepen the understanding of the failure process and subsequently develop more accurate TR prediction models and as a result safer battery systems, we present in this work high-speed X-ray tomography for in-depth investigations of the copper current collector melting and agglomeration during TR. The melting process presents valuable real-time internal information about heat evolution during TR, previously challenging to access but crucially important for validating TR models. In this work, controlled failure studies combined with high-speed X-ray tomography were performed on two different commercial LIB models, subjecting them to both external heating and nail penetration to induce TR. Through real-time observation via high-speed tomography, followed by segmentation, rendering, and analysis, the formation of copper agglomerates was qualitatively and quantitatively characterized and visualized for the first time. Agglomerates tended to form either from the battery's outermost layers or centrally, depending on the method of TR initiation, and gives an indirect insight into the internal temperature evolution and distribution. Moreover, an initial comparative analysis between the battery models also revealed differences in agglomerate size, which has been linked to the thicker copper current collectors of one of the cell models. We further discuss the impact of larger copper agglomerates on heat distribution and safety. This study not only sheds light on the intricate dynamics of TR in LIBs but also underscores the pivotal role of 'gold-standard' imaging techniques in advancing battery safety, crucial for the robust modeling of TR and the future design of electric vehicle safety systems.
Artificial SEI layers passing lithium ions but blocking water molecules for long-lasting aqueous lithium-ion batteries.
The large scale recycling of lithium ion batteries (LIBs) is essential to satisfy global demands for the raw materials required to implement this technology as part of a clean energy strategy. However, despite what is rapidly becoming a critical need, an efficient and sustainable recycling process for LIBs has yet to be developed. Biological reactions occur with great selectivity under mild conditions, offering new avenues for the implementation of more environmentally sustainable processes. Here, we demonstrate a sequential process employing two bacterial species to recover Mn, Co and Ni, from vehicular LIBs through the biosynthesis of metallic nanoparticles, whilst Li remains within the leachate. Moreover the feasibility of Mn recovery from polymetallic solutions was demonstrated at semi-pilot scale in a 30 L bioreactor. Additionally, to provide insight into the biological process occurring, we investigated selectivity between Co and Ni using proteomics to identify the biological response and confirm the potential of a bio-based method to separate these two essential metals. Our approach determines the principles and first steps of a practical bio-separation and recovery system, underlining the relevance of harnessing biological specificity for recycling and up-cycling critical materials.
The overwhelming demand for lithium-ion batteries necessitates a sustainable and environment-friendly production of graphite anode materials. Catalytic graphitization of pyrolysis oil is promising for mass-scale production of biographite.
The increasing demand for lithium-ion batteries (LIBs) underscores the need for cost-effective alternative anode materials to ensure efficient Li-ion storage, given their pivotal role in various industries. This research focuses on the facile synthesis of nickel zinc ferrite (NZFO: Ni 0.65 Zn 0.35 Fe 2 O 4 ) and conducts comprehensive electrochemical analyses to evaluate its potential as a high-capacity alternative anode material for LIBs. The NZFO-CMR [sodium carboxymethyl cellulose (2%) and styrene-butadiene rubber (1%)] exhibited an initial delithiated capacity of ∼1232 mA h g −1 and maintained a stable capacity of around 358 mA h g −1 , along with an average Coulombic efficiency of 99.6% over 200 cycles. Cyclic voltammetry analysis revealed that Li-ion insertion was predominantly governed by ion diffusion, and the consistent correlation observed in electrochemical impedance spectroscopy spectra indicated stable electrochemical behavior throughout cycling. The facile synthesis approach and reasonable electrochemical performance of NZFO suggest its potential as an alternative anode material for advancing LIB's technology.