Cathode Materials For Lithium-ion Batteries Research Articles

Constructing Targeted Strong Nb4d-O2p-Li2s Configurations to Obtain Excellent Energy Density and Long Life for Li-rich Cathodes.

The Li-rich Mn-based cathode materials (LMRs) deliver excellent energy density and exhibit low cost, which are considered as the most promising cathode materials for the next generation lithium-ion batteries. However, the irreversible redox reaction of the oxygen atoms directly leads to release oxygen and intensifies phase transformation. Besides, the local stress and strain will be generated due to the unit-cell volume difference between R-3m and C2/m phases, which continuously aggravates the collapse of secondary particles. Herein, the strong Nb4d-O2p-Li2s configurations at the Li1 sites of the TM-layer in the C2/m phase and secondary particles with the radial arrangement of refined primary particles are designed to inhibit oxygen release and relieve lattice stress by Nb2O5 treatment. Meanwhile, the preferential growth of the active {010} planes is presented to obtain an excellent transmission rate of Li+. As a result, the designed LMR delivers remarkable electrochemical properties with high discharge capacity and initial coulomb efficiency of 276 mA h g-1 and 85% at 0.1 C, outstanding cycling retention rate of 81% after 300 cycles. This novel crystal structure combining oxygen coordination regulation and micro-nano scale design provides inspiration for the design of high-performance LMRs.

Improving Lithium-Ion Battery Performance: Nano Al2O3 Coatings on High-Mass Loading LiFePO4 Cathodes via Atomic Layer Deposition

Lithium iron phosphate (LiFePO4 or LFP) is a promising cathode material for lithium-ion batteries (LIBs), but side reactions between the electrolyte and the LFP electrode can degrade battery performance. This study introduces an innovative coating strategy, using atomic layer deposition (ALD) to apply a thin (5 nm and 10 nm) Al2O3 layer onto high-mass loading LFP electrodes. Galvanostatic charge–discharge cycling and electrochemical impedance spectroscopy (EIS) were used to assess the electrochemical performance of coated and uncoated LFP electrodes. The results show that Al2O3 coatings enhance the cycling performance at room temperature (RT) and 40 °C by suppressing side reactions and stabilizing the cathode–electrolyte interface (CEI). The coated LFP retained 67% of its capacity after 100 cycles at 1C and RT, compared to 57% for the uncoated sample. Post-mortem analyses, including scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS), were conducted to investigate the mechanisms behind the improved performance. These analyses reveal that Al2O3 coatings are highly effective in reducing LFP electrode degradation during cycling, demonstrating the potential of ALD Al2O3 coatings to enhance the durability and performance of LFP electrodes in LIBs.

Enhanced interfacial and cycle stability of 4.6 V LiCoO2 cathode achieved by surface modification of KAlF4

Lithium cobalt oxide is one of the most popular cathode materials for lithium-ion batteries. Due to its relatively low capacity, increasing the output voltage is often necessary to release more capacity. However, subjecting cathode materials to high charging potentials inevitably induces surface-side reactions, compromising the integrity of the crystal structure and accelerating capacity degradation. Therefore, the stability of cathode materials at high voltage becomes crucial for lithium-ion batteries. In this study, we employed the ternary compound KAlF4 (KAF) as a surface modification coating for LiCoO2 (LCO). With the optimized ratio (1 wt%) of KAF, coated LCO cathodes exhibited enhanced capacity retention, excellent cycling, and rate stability. In the high voltage range of 3.0–4.6 V, the specific capacity of the initial discharge at a rate of 0.5 C reached 198.30 mA h g−1. Remarkably, the coated LCO retained 91.56 % of its initial capacity after 200 cycles at 0.5 C. Even at a high rate of 5 C, the coated sample retained a discharge capacity of 120.87 mA h g−1, significantly higher than that of bare LCO (80.24 mA h g−1). After a thorough investigation into the structure changes before and after cycling, we elucidated the mechanism of KAF coating in improving the stability of high-voltage LCO cathodes. The results indicated that KAF forms a stable passivation layer on the surface of LCO, which suppresses cracking and corrosion during charging and discharging, eventually stabilizes the crystal structure, and enhances the cycling stability of LCO.

Enhanced high-rate and long-cycle performance of Mg2+-Al3+ co-doped spinel LiMn2O4 cathode materials for Li-ion batteries

Spinel LiMn2O4 has the potential to be used as a cathode material in lithium-ion batteries because of its affordability, low toxicity, and excellent charge/discharge capability. However, severe capacity attenuation results from the degradation of its long-cycle and high-rate performance caused by the Jahn-Teller distortion and Mn dissolution. Herein, a simple solid-state combustion process is used to successfully prepare the Mg2+-Al3+ co-doped LiMn2O4 with truncated octahedral morphology. The Jahn-Teller distortion is inhibited by the stable Mn-O framework and the decreased lattice constant, which in turn lowers the dissolution of Mn. Moreover, Mg2+-Al3+ co-doped LiMn2O4 have lower activation energy and greater Li+ diffusion coefficient. As a result, the optimized LiMg0.03Al0.10Mn1.87O4 delivers satisfied initial capacity of 102.1 mAh‧g−1 with a capacity retention of 76.2 % after 1000 cycles at 10 C. Even at the ultra-high rate of 15 C and 20 C, Mg2+-Al3+ co-doped sample also remain desired structure stability and cycling performance, which remains 73.8 % of its original capacity after 1000 cycles at 20 C. This work provides a reference for developing high-performance and stability cathode materials for lithium-ion battery.

Engineering a high-performance low-cobalt single crystalline Li1.2Ni0.167Co0.067Mn0.567O2 cathode material for lithium-ion battery

Li-rich manganese-based layered oxides (LRM) can be regarded as the next-generation cathode materials for high-energy-density Li-ion batteries. The single crystalline LRMs make it have the potential to further application due to the higher compaction density and the absence of intergranular cracks. However, it can't meet the requirements for high energy density cathode materials because of its poor discharge capacity and unsatisfactory stability. In this study, we demonstrate the F doped single-crystal LRM (F-LRM) with the size is >800 nm giving an initial discharge capacity of 309 mAh g−1 at current density of 0.1 C (25 mA g−1) and the capacity retention is reaching up to 97.4 % after 100 cycles. Additionally, its rate capability is up to 206 mAh g−1 under 250 mA g−1 with 90.6 % and 80.6 % retention after 300 and 500 cycles, respectively. X-ray Diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS) and Raman indicated that the F-doped LRM forms strong TM-F bonds and creates a suitable oxygen vacancies (OVs) concentration. Furthermore, operando Differential Electrochemical Mass Spectrometer (DEMS) and High-resolution Transmission Electron Microscopy (HRTEM) analysis revealed that O2 for F-LRM does not appear during the (de)lithiation with the layered structure maintained after cycling. The design of high-performance, low-cobalt single crystal materials offers a novel approach for the future development of lithium-rich cathodes.

Grain Analysis of NCM Cathode Materials by ASTAR Technique and Its Effect on Battery Performance

Lithium-ion batteries (LIBs) are one of the most promising energy storage systems for portable electronic devices, electric vehicles, and renewable energy systems. Among the various cathode materials for LIBs, nickel cobalt manganese (NCM) oxide has attracted considerable attention due to its high specific capacity, good cycling stability, and appropriate cost for commercialization. However, Ni-rich NCM (Ni >80%) showed poor cyclability and huge gas evolution because of surface instability.Single crystal NCM has been suggested as a solution to these issues due to its excellent properties. However, it is difficult to quantify the degree of single crystallinity because it is so far subjective. In this study, we employed ASTAR technique (transmission electron microscopy combined with electron backscatter diffraction) to investigate the microstructural features of NCM cathode materials. Our ASTAR analysis showed that NCM cathode materials consist of complex grain and grain boundary structures with varying orientations and sizes. By analyzing the grain size and its morphology, we were able to define the single crystallinity of NCM cathode materials, including the poly NCM and single crystal NCM particles.Furthermore, we found that the grain size and its distribution significantly affects the battery performance and lifespan of NCM cathode materials. Specifically, the poly NCM particles exhibited a larger grain boundary and surface area compared to the single crystal NCM particles. The poly NCM particles also showed a faster DC-IR increase and a shorter lifespan than the single crystal NCM particles, indicating that the grain size has a critical influence on the battery performance and lifespan of NCM cathode materials.Our results provide insights into the design and optimization of NCM cathode materials for next-generation LIBs. By controlling the grain size and its distribution of NCM cathode materials, it is possible to enhance the battery performance and lifespan. Therefore, our study highlights the importance of understanding the microstructural features of NCM cathode materials for developing high-performance and stable LIBs.

(General Student Poster Award Winner, 3rd Place) Lithium Niobate Coatings on Lithium Iron Phosphate Cathode Materials for Applications in Lithium-Ion Batteries

Lithium-ion batteries have become a crucial tool in countering global fossil fuel reliance; when paired with electric motors, they provide an alternative to petroleum-based energy storage for internal combustion engines. Typical cathode materials used in lithium-ion batteries present a unique set of challenges. Some of the electrochemical materials that have a relatively high performance also have serious impacts on the environment and human health.1 Other materials that lack these specific drawbacks, such as lithium iron phosphate (LFP), face other issues. For example, LFP suffers from a relatively low electrical conductivity and a relatively slow lithium-ion diffusion, both of which affect the general electrochemical performance of this material. These weaknesses can be addressed using coatings applied to LFP nanoparticles. Carbon coatings have already been shown to improve the performance of LFP nanoparticles, but materials with higher ionic conductivities have remained relatively undeveloped.2 By synthesizing a composite coating of both carbon and lithium niobate, further improvements to LFP nanoparticles were sought to enable a wider range of applications for this cathode material.In this work, lithium niobate coatings on carbon coated LFP nanoparticles were synthesized using a low temperature solvothermal method. Lithium niobate coatings have been shown to improve the specific capacity, rate capability, and durability of other cathode materials for lithium-ion batteries.3 Half-cells were fabricated to examine the effect of adding a lithium niobate coating to the carbon coated LFP cathode materials. Electrochemical testing techniques such as galvanostatic cycling and cyclic voltammetry were used to compare the properties and performance of the composite coated LFP relative to the carbon coated LFP. The composite coatings were also characterized using transmission electron microscopy, energy dispersive spectroscopy, and X-ray photoelectron spectroscopy. This coating method has resulted in the successful synthesis of lithium niobate coatings on carbon coated LFP nanoparticles with an observed improvement in durability. Goodenough, J. B.; Kim, Y. Challenges for Rechargeable Li Batteries. Mater. 2010, 22 (3), 587–603.Wang, J.; Sun, X. Understanding and Recent Development of Carbon Coating on LiFePO4 Cathode Materials for Lithium-Ion Batteries. Energy Environ. Sci. 2012, 5 (1), 5163–5185.Kim, J. H.; Kim, H.; Choi, W.; Park, M.-S. Bifunctional Surface Coating of LiNbO3 on High-Ni Layered Cathode Materials for Lithium-Ion Batteries. ACS Appl. Mater. Interfaces 2020, 12 (31), 35098–35104.

Efficient Direct Recycling of Spent Cathode Materials in Lithium-Ion Batteries

The demand for lithium-ion batteries (LIBs) has surged in recent years, driven by the rapid growth of electric vehicles (EVs) and emerging energy storage technologies. Yet, this surge in demand has also resulted from a significant increase in the number of spent batteries. Given the potential for environment pollution wastage, it is absolutely crucial to prioritize the recovery and recycling of these used lithium-ion batteries.The common techniques employed in large-scale industrial settings for battery recycling are pyrometallurgy and hydrometallurgy. These are pivotal multi-step processes, particularly suitable for materials containing Cobalt (Co) and Nickel (Ni), such as NMC (LiNixMnyCozO2). Aside from NMC, there has been a surge in the adoption of LFP (LiFePO4) as a cathode material target for lithium-ion batteries in electric vehicles worldwide over the past few decades. However, these established industrial recycling methods are not applicable to LFP due to the comparatively lower value of iron. This necessitates the pursuit of direct recycling approaches.In order to accomplish this goal, direct recycling stands out as the most suitable technique for regenerating spent batteries1. Unlike processes involving solution-based or high-temperature steps that entail potentially wasteful steps, thisapproach aims to reduce energy consumption and costs, all while maintaining environmental integrity through a judicious utilization of resources, materials, and energy. Consequently, our attention is directed towards this specific LFP material, prompting us to detail a direct recycling procedure for spent LFP cathodes via a chemical lithiation process at room temperature in a solution containing lithium iodide (LiI) and various solvents2 (Fig. 1).

Bridging the Gap: Scaling up Processes for the Development of Li-Rich Mn-Rich Layered Oxides

As the global demand for more powerful and long-lasting energy storage solutions continues to grow, Li-rich Mn-rich layered oxides (LMR) emerges as a promising class of next-generation cathode materials for lithium-ion batteries. The LMR material stands out due to its impressive electrochemical specific capacity, surpassing 280 mAh g–1, along with a high discharge voltage exceeding 3.5 V. It also boasts a remarkable specific energy density close to 1000 Wh kg–1, all while maintaining a relatively lower cost.Current synthesis methods often rely on batch coprecipitation reactions followed by the calcination of precipitated Mn-rich precursors. However, the inherent challenges of batch reactions, particularly in terms of reproducibility and quality, prompt the exploration of more sophisticated approaches. Moreover, the transition from benchtop experiments to large-scale production introduces a distinct set of challenges. Parameters that work seamlessly on a smaller scale may not translate as effectively when producing the material at the kilogram scale. This scaling-up process involves navigating complexities such as chemical handling risks, and challenges related to reaction heat transfer and mixing efficiency. These factors collectively underscore the difficulties in achieving precise control over critical precursor characteristics, including primary and secondary particle size, morphology, tap density, and stoichiometry.In response to these challenges, this presentation will discuss an innovative approach. High-quality Li-rich Mn-rich materials are synthesized using continuous coprecipitation, facilitated by a pre-pilot scale Taylor Vortex Reactor (TVR) at the Materials Engineering Research Facility (MERF) in Argonne National Lab (ANL). This emerging synthesis technology offers a scalable solution for the production of high-quality cathode materials. This presentation will delve into the intricacies of the synthesis process, providing valuable insights into the relationship between the characteristics of the synthesized LMR precursors and their subsequent impact on cathode performance.

Re-Functionalization of Aged Lithium Iron Phosphate Cathode Materials

As lithium-ion batteries continue to be implemented in everyday technologies, it is imperative to repurpose these battery materials upon their degradation. Carbon-coated lithium iron phosphate (LFP/C) is considered one of the most stable cathode materials for application in lithium-ion batteries. Due to this stability, LFP/C possesses a remarkably long cycle life of greater than 3000 cycles.1 Extended cycling of these cathode materials may result in multiple modes of degradation, including degradation of the carbon coating, and loss of contact between the cathode and the current collector.2,3 In this work, a suitable process and reagents have been selected to isolate and purify the LFP/C from the cathodes of cycled batteries. Isolating and purifying aged LFP/C materials enables the diagnosis of the mode(s) of degradation of these materials and their coatings using a variety of techniques including X-ray diffraction, scanning electron microscopy, and transmission electron microscopy methods.Furthermore, additional work was pursued to give new life to these isolated, spent cathode materials. The addition of a coating with a relatively high lithium conductivity to the aged LFP/C particles was sought to provide a second life to these electrochemically aged materials. Half-cells were fabricated using the coated, aged LFP/C cathode materials to compare their performance to both pristine LFP/C nanoparticles and aged LFP/C nanoparticles without the addition of this custom coating. Electrochemical testing techniques such as galvanostatic cycling, cyclic voltammetry, and electrochemical impendence spectroscopy were used to probe the performance of each type of LFP/C nanoparticle as cathode materials in lithium-ion batteries. The coated, aged LFP/C particles were also characterized using transmission electron microscopy, energy dispersive spectroscopy, and X-ray photoelectron spectroscopy techniques. The techniques developed herein can be used to isolate, purify, and re-functionalize other cathode materials from lithium-ion batteries. Lewerenz, M.; Munnix, J.; Schmalstieg, J.; Kabitz, S.; Knips, M.; Sauer, D. U. Systematic aging of commercial LiFePO4|Graphite cylindrical cells including a theory explaining rise of capacity during aging. Power Sources. 2017, 345, 254-263.Wang, L.; Qiu, J.; Wang, X.; Chen, L.; Cao, G.; Wang, J.; Zhang, H.; He, X. Insights for understanding multiscale degradation of LiFePO4 cathodes. eScience 2022, 2(2), 125-137.

Glassy Oxides as Positive Electrode Materials for Sustainable and High Energy Density Li-Ion and Na-Ion Batteries: First Attempts to Establish Relationships between Glass Compositions, Physicochemical Characterizations and Electrochemical Properties with Machine Learning and Design of Experiments Approaches

Today, rechargeable lithium-ion batteries (LIBs) represent one of the best alternatives to reduce our dependency on fossil fuels. LIBs are using cathode materials based on polycrystalline oxides or polyanionic compounds [1]. However, their performances can be limited by their crystalline structure when other compounds suffer from metallic dissolution and irreversible phase changes during cycling [2]. To overcome these key shortcomings, implementing glasses or glass-ceramics as cathode materials is an interesting approach [3]. Glasses have a structure composed of more free volume, and, in the literature that is mainly concerning glasses containing Vanadium transition metal, the glasses can so accept a large amount of lithium [4] and easily accommodate structural changes upon lithium ions extraction/insertion [5]. Furthermore, glass production is a scalable process and can be commercially easier to implement than most of synthesis processes of conventional cathode materials.The main objective targeted is to develop high capacity positive electrodes (up to 300mAh/g) for Li-ion batteries based on glassy oxides without critical transition metals such as Cobalt and Vanadium. The ambitious target is to exceed 1000Wh/kg at the active material level and so enable energy densities of 300-350 Wh/kg at the Li-Ion cell level. Additionally, the electrochemical behavior of some alkali-free glass compositions will be evaluated in sodium-ion configuration. The major scientific objective is to correlate the most relevant physicochemical properties of glass with the corresponding electrochemical performances using machine learning approaches or design of experiment methodology. For a better understanding of involved processes, three oxides glass families are studied as promising cathode materials for sustainable and high energy density lithium batteries. These oxides are composed of: i) a glass network-forming element (Si, B, P) leading to the 3 different families, ii) a transition metal (Mn, Fe, ...) and optionally iii) an alkali (Li, Na).The influence of the nature of the transition metal and the polyanionic group corresponding to the network-forming element (PO4, BO3, SiO4) on the electrical properties of the as-prepared glasses measured at different temperatures will be presented mainly for the lithiated compounds. For microstructural characterization, several techniques were coupled such as X-Ray Diffraction (XRD), SEM-EDX, DTA/TGA, Raman, IR and UV-Vis spectroscopies, Electrochemical Impedance Spectroscopy (EIS) and chronoamperometry.Finally, the electrochemical properties in terms of specific capacity, redox potentials, first cycle capacity loss, coulombic and energetic efficiencies of these materials were investigated in coin-cells vs lithium (or sodium) metal electrode. To understand the electrochemical processes involved in these materials at room temperature, SEM-EDX, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Mossbauër Spectroscopy for iron based compounds were coupled and performed on the as-prepared glasses and on ex-situ (after cycling) materials at different electrochemical states of charge.All the generated data and measurements were analyzed by machine learning approach and tools and in some cases compared with a more classical Design of Experiments (DOE) approach. For instance, figure 1 illustrates the contour diagram of first discharge capacities in the mixture diagram of phosphate glasses based on 3 different transition metal oxides. The final goal is to establish more precisely the relationships between the different glassy oxides structures and their electrochemical performances. First results of this important work of elaboration, characterization and data analysis will be presented here. This new study will bring significant elements to optimize both the glass composition and its elaboration conditions to obtain high performance cathode materials without critical materials.[1] Nitta, N. et al., Li-ion battery materials: present and future. Materials Today 18, 252–264 (2015).[2] Tesfamhret, Y. et al., On the Manganese Dissolution Process from LiMn2O4 Cathode Materials. ChemElectroChem 8, 1516–1523 (2021).[3] K. Kercher et al., « Mixed polyanion glass cathodes: Glass-state conversion reactions », J. Electrochem. Soc., vol. 163, no 2, p. A131-A137, 2016, doi: 10.1149/2.0381602jes [4] Afyon, S. et al., New High Capacity Cathode Materials for Rechargeable Li-ion Batteries. Scientific Reports 4, 7113 (2015).[5] Kindle, M. et al., Alternatives to Cobalt. ACS Sustainable Chemistry Engineering 9, 629–638 (2021). Figure 1

Unsuspected Organometallic Fibers Used As Potential Separators for Supercapacitors Device

Since the last decade, the interest of organic frameworks for electrochemical application the been more studied.1 In general, very few works have been found in the literature. We can mainly mention the use of these derivatives in the presence of inorganic materials both to form solid electrolytes or to protect electrodes. For example, 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (H4DOTA) has been used to functionalize PVA to coat the surface of the negative electrode in order to suppress its degradation.2 This resulted in the improvement of the electrochemical properties of the LMNO/graphite cell. Recently, Kim et al. reported the addition of 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane to a carbonate-based electrolyte intended to stabilize the Li metal-electrolyte interface by improving the solid electrolyte interphase.3 More recently, Liu et al. reported a novel carbonyl network polymer NP4 used as a cathode material for organic lithium batteries.4 Very few examples of fully organic frameworks used as separators have been reported.Therefore, our investigation to develop new supramolecular metal-based objects via a self-assembly process of molecular bricks will be presented. The work on cyclen derivatives allows to obtain metal complexes very stable able to pack in a well oriented dimension. Cyclen derivatives, in the presence of metal salts such as copper or zinc chlorides and polar solvents such as aliphatic alcohols, have a strong affinity for metals and spontaneously assemble in some conditions.5 In terms of applications, these self-assembled "organometallic" fibers represent an original and relatively easy to access substrate for fabricating 1D organic objects. Moreover, taking advantage of the properties and potentialities of these materials, we format an adequate shape to handle it as a potential separator for application in Energy Storage Systems (ESS).After a presentation of their synthesis and their formatting as potential separators for supercapacitors, preliminary electrochemical studies will be discussed. 1. J. Mater.Chem. A 2016, 4, 16812; ACS Energy let., 2022, 7, 885.2. ACS Appl. Energy Mater., 2021, 4, 128.3. ACS Appl. Matter. Interface, 2022, 14, 35645.4. J. Electoanalytical. Chem. 2023, 117251.5. Chem. Commun. 2010, 46, 1464. Figure 1

Optimizing O3-Type Fe-Mn-Based Cathodes for Na-Ion Batteries: Unveiling the Synergistic Impact of Chemical Co-Substitution

Layered transition metal oxide-Na x MO2 (M = transition metal) is the most widely explored class of cathode materials in lithium and sodium-ion batteries (LIBs and SIBs).1 The replacement of expensive Co and Ni with cheaper elements like Fe and Mn is appealing, which can reduce the overall cost of the battery. Despite the higher operating voltage of Fe3+/Fe4+ and the large specific capacity of Mn3+/Mn4+, issues like irreversible Fe-migration and J. T. distortion of Mn3+/Mn4+ are yet to be overcome.2,3 To improve the electrochemical performances of layered oxide cathodes, various cationic substitutions (e.g., Li+, Cu2+, Mg2+, Zn2+, and Ti4+) are partially substituted in the place of M.4–6 Along this line, in search of better Fe/Mn-based cathodes, we selected an O3-type Na[Fe0.50Mn0.50]O2 (NFMO) material and co-substituted Li+ and Cu2+ in the transition metal layer to create a composition of Na[LixCuyFe0.50-x-yMn0.50]O2 (NCLFMO) and compared their electrochemical performances.. Both materials crystallize in a rhombohedral structure and Rietveld refinement and TEM analyses suggest an enhanced O-Na-O spacing after substitution. The NFMO and NCLFMO cathodes display a capacity of 135 and 121 mAh g-1 in the potential window of 4.0–2.0 V at 0.1 C rate, with an average voltage (Vavg) of 2.63 V and 3.31 V respectively, which leads to an increased energy density of 400 Wh kg-1 for NCLFMO.7 Following substitution, the capacity contributions of Mn and Fe become 20.2% and 79.8%, respectively, instead of 49.8% and 50.2% in NFMO. Clearly, it indicates a pronounced Fe4+/Fe3+ redox activity with a suppressed J. T. distortion for Mn4+/Mn3+ redox. Chemical co-substitution significantly improves capacity retention, with NCLFMO retaining 98% of its initial discharge capacity after 500 cycles, compared to 52% for NFMO. Better rate capability, faster diffusion coefficient of Na+ ions from GITT, and reduced cell resistance from impedance spectroscopy support the enhanced performances of NCLFMO. In-situ XRD measurement reveals a reversible O3-P3-O’3-P3-O3 phase transition and ex-situ x-ray absorption spectroscopy analysis confirms a prominent Fe4+/Fe3+ redox with a suppressed Mn4+/Mn3+ redox during charge-discharge cycling. More significantly, NCLFMO remains air-stable, retaining its structure and electrochemical properties after exposure to air for 30 days. Finally, a full cell with precycled HC is constructed, delivering a capacity of 105 mAh g-1 with a Vavg of 3.15 V in the potential window of 4.0-1.5 V at a 0.1 C rate. In conclusion, the (Li + Cu)-co-substitution strategy improves the overall performance of the Fe-Mn-based layered oxide cathode, paving the way for developing better cathodes for commercialized SIBs. References J. Y. Hwang, S. T. Myung, and Y. K. Sun, Chem. Soc. Rev., 46, 3529–3614 (2017).S. Komaba, N. Yabuuchi, T. Nakayama, A. Ogata, T. Ishikawa and I. Nakai, Inorg. Chem., 51, 6211–6220 (2012).B. Mortemard De Boisse, J. H. Cheng, D. Carlier, M. Guignard, C. J. Pan, S. Bordère, D. Filimonov, C. Drathen, E. Suard, B. J. Hwang, A. Wattiaux and C. Delmas, J. Mater. Chem. A, 3, 10976–10989 (2015).L. Yang, X. Li, J. Liu, S. Xiong, X. Ma, P. Liu, J. Bai, W. Xu, Y. Tang, Y. Y. Hu, M. Liu and H. Chen, J. Am. Chem. Soc., 141, 6680–6689 (2019).G. Singh, N. Tapia-Ruiz, J. M. Lopez Del Amo, U. Maitra, J. W. Somerville, A. R. Armstrong, J. Martinez De Ilarduya, T. Rojo and P. G. Bruce, Chem. Mater., 28, 5087–5094 (2016).L. Wang, Y. G. Sun, L. L. Hu, J. Y. Piao, J. Guo, A. Manthiram, J. Ma and A. M. Cao J. Mater. Chem. A, 5, 8752–8761 (2017).A. Ghosh, R. Hegde, K. Kumar and P. Senguttuvan, J. Am. Chem. Soc., submitted(2023).

Modeling and Experimental Validation on a Bipolar Membrane Electrodialysis Stack for Lithium Sulfate Separation

Recycling lithium-ion battery materials is a crucial step to achieving a circular economy. Among a few methods for recycling spent battery materials, a novel hydrometallurgical recycling process with leaching by acids and precipitation by bases was proposed [1]. Lithium sulfate (Li2SO4) leachate solution is generated at the end of the closed-loop recycling process. Such Li2SO4 solution can be separated by electrodialysis (ED) to form H2SO4 and LiOH solutions, which are reused for leaching and precipitation of the recycling process. The present study attempts to model this ED process and validate the model with experimental data.An ED stack based on bipolar membranes (EDBM); see Fig. 1a, was built with repetitive unit cells, each consisting of a bipolar membrane, anion exchange membrane (AEM), and cation exchange membrane (CEM). Li2SO4 enters the dilute channel and splits into SO4 2- and Li+, which travel through the AEM and CEM, respectively. Water electrolysis occurs within the bipolar membrane to produce H+ and OH-, which react with SO4 2- and Li+ to form H2SO4 and LiOH, respectively; see Fig. 1b. A two-dimensional (2D) multiphysics model is developed to elucidate the coupled transport processes within the unit cell. Conservation equations for mass, momentum, and species are solved. The transport of ions is described by the Nernst-Planck equation. Electroneutrality equations are satisfied in these membranes and channels. Electro-osmotic water transport across the membranes is considered.The effective cross-sectional area of the stack was 121.8 cm2 (70mm×174mm). The flow channel between consecutive membranes was 0.8 mm, with a mesh inserted to facilitate mixing. Experiments were carried out with the EDBM stack over different conditions such as current density, number of cell pairs, and flow rates. All experiments were operated at constant current mode [2]. The feed, acid, and base solutions were recirculated through their tanks at initial concentrations of 1.1, 0.1, and 0.1 mol/L. The ion concentrations of the solutions were measured periodically with inductively coupled plasma (ICP) mass spectrometry. The weight and the pH value of the solution tanks were also recorded.The concentration of H2SO4 is found to increase with time linearly, whereas that of LiOH levels off due to a significant electro-osmosis that drags water through the CEM into the concentrate channel. This drag reduces the performance of EDBM due to the dilution of water into the concentrate compartment. However, electro-osmotic water transport also leads to a velocity increase in the concentrate channel, which is consistent with the simulation results in our previous ED model [3]. It is found that the voltage loss across the bipolar membrane ca. 1V accounts for a significant part of the unit cell of about 1.27V.The migration of ions in electrodialysis mainly relies on diffusion and electric drive. The streamlines and the concentration distribution of Li+ under different voltages indicate that increasing voltage accelerates ion migration, see Fig. 1(c). Furthermore, the effect of the potential and concentration variations on EDBM performance is also investigated. The effects of applied current density and inlet velocity are studied on species concentrations and fluxes. Increasing the stack current density accelerates the separation process, see Fig. 1(d). It is found that increasing the solution flow rate can increase LiOH solution concentration, ion recovery rate, and current efficiency. However, the impact of the flow rate is low.This work demonstrates that EDBM can be a simple and energy-saving alternative to the current chemical precipitation method to produce LiOH from Li2SO4. The present study provides new insights into optimal operation and design for Li2SO4 EDBM. The findings are helpful in determining how the stack can be scaled up for practical application.[1] A review of recycling spent lithium-ion battery cathode materials using hydrometallurgical treatments, JCY Jung, PC Sui, J Zhang, J. Energy Storage 35, 102217, 2021.[2] Electrodialysis of a Lithium Sulphate Solution: An Experimental Investigation. B Kang, D Kang, JCY Jung, A Asadi, PC Sui, J. Electrochem. Soc. 169 (6), 063515, 2022.[3] A Comprehensive Computational Fluid Dynamics Modeling of Lithium Sulphate Electrodialysis, A Asadi, HB Harandi, JCY Jung, PC Sui, J. Electrochem. Soc. 170(9), 093502, 2023. Figure 1

Water Effect on the Electronic Properties and Lithium-Ion Conduction in a Defect-Engineered LiFePO4 Electrode

Defect-engineering accelerates the conduction of lithium ions in the cathode materials of lithium-ion batteries. However, the effects of defect-engineering on ion conduction and its mechanisms in humid environments remain unclear in the academic discourse. Here, we report on the effect of vacancy defects on the electronic properties of and Li-ion diffusion in a LiFePO4 material in humid environments. The research findings indicate that vacancy defects reduce the lattice constant and unit cell volume of LiFePO4. Additionally, the water molecules occupy the Li-ion vacancies, leading to an increase in the lattice constant of LiFePO4. The computational results of the electronic properties show that the introduction of water molecules induces a transition in LiFePO4 from a semiconductor to a metallic behavior, with a transfer of 0.38 e of charge from the water molecules to LiFePO4. Additionally, the migration barrier for Li ions in the H2O + LiFePO4 system is found to be 0.50 eV, representing an 11.1% increase compared to the pristine LiFePO4 migration barrier. Our findings suggest that water molecules impede the migration of Li ions and provide important insights into the effect of defect-engineering on electronic properties and ion conduction under humid conditions.

Computational and Machine Learning‐Assisted Discovery and Experimental Validation of Conjugated Sulfonamide Cathodes for Lithium‐Ion Batteries

AbstractConjugated sulfonamides (CSAs) stand out for their propitious electroactivity and notable stability in ambient conditions, making them suitable candidates for high‐potential cathode materials in lithium‐ion batteries (LIBs). This study employs a combination of machine learning, semi‐empirical quantum mechanics, and density functional theory methods to evaluate a large library of 11 432 CSA molecules, focusing on material properties crucial for application in batteries, such as synthetic complexity, redox potential, gravimetric charge capacity, and energy density. After applying the thresholds for the synthetic complexity score at 2.62 and the redox potential at 3.25 V versus Li/Li+, we identify 50 CSA molecules that are easy to synthesize and suitable for the positive electrode in LIBs. By ranking on the basis of redox potential, 13 CSA molecules having potentials greater than 3.50 V versus Li/Li+ are identified. Through further investigations using molecular dynamics simulations on these reactant molecules and their lithiated products, a molecule is singled out for synthesis and electrochemical evaluation. This molecule, lithium (2,5‐dicyano‐1,4‐phenylene)bis((methylsulfonyl)amide)(Li2‐DCN‐PDSA), demonstrates a redox potential surpassing those previously reported within the class of CSA molecules. Moreover, the study explores the quantitative structure‐property relations of CSAs, yielding insights for the development of CSA‐based LIB cathode materials, informed by the comprehensive data assembled.

Electrochemical properties of tungsten doped LiNi0.9Co0.1O2 lithium-ion battery cathode materials

High-nickel layered cathode materials for lithium-ion batteries have received widespread attention in new energy vehicles for their excellent specific energy and cost advantages, and are considered to be the most promising cathode materials for high-energy density lithium-ion batteries. Despite its many advantages, poor thermal stability and rapid capacity degradation have greatly limited its large-scale application. Ion doping is considered to be an effective way to improve its drawbacks, and in this paper, a series of W-doped LiNi0.9Co0.1O2 cathode materials were prepared using WO3 as a tungsten source. Among them, 1 mol% W doping was the most effective, and its reversible capacity of 204.44 mA g −1 still had 93.25 % capacity retention after 100 this cycles at 1C. Combined with DFT calculations, it is found that the introduction of W does not change the original layered structure and the material transitions from semi-metallic to metallic at lower doping concentrations, resulting in more electrons occupying the Fermi energy levels to enhance its electrical conductivity and leading to an elevated spin state and a lower oxidation state of Ni.

WO3 coating improves the cyclic stability of LiNi0.9Co0.05Mn0.05 as cathode materials for lithium-ion batteries

In this paper, WO3 uniformly coated LiNi0.9Co0.05Mn0.05O2 cathode materials are prepared by wet coating method using ammonium metatungstate as tungsten source. The XRD, SEM, and XPS tests show that the cladding process introduced W ions into the NCM lattice, increasing the layer spacing and improving the lithium diffusion rate. The charge/discharge test results indicate that a moderate amount of WO3 coating can enhance the rate-discharge performance and increase the long cycle life. After 100 cycles at 1C (180 mAh g−1), the reversible capacity of the material containing 0.5wt% WO3 coating is 157.9 mAh g−1, while that of the original material is only 130.9 mAh g−1, which indicates that the WO3 coating protects the cathode material from HF corrosion, thus improving the stability of the structure. DFT calculations show that the dangling bonds of O on the NCM surface are highly susceptible to binding with W, which reduces the possibility of WO3 coating exfoliation.WO3 and NCM are p-type semiconductors and semi-metallic materials, respectively, which form ohmic contacts at heterogeneous interfaces thereby increasing the electronic conductivity of the materials, and due to the synergistic effect, the diffusion barrier of Li near the heterogeneous interfaces is lower than that of the pristine materials.

LiFe0.3Mn0.7PO4-on-MXene heterostructures as highly reversible cathode materials for Lithium-ion batteries

Two-dimensional (2D) heterostructure materials, incorporating the collective strengths and synergetic properties of individual building blocks, have attracted great interest as a novel paradigm in electrode materials science. The family of 2D transition metal carbides and nitrides (e.g., MXenes) has become an appealing platform for fabricating functional materials with strong application performance. Herein, a 2D LiFe0.3Mn0.7PO4 (LFMP)–on-MXene heterostructure composite is prepared through an electrostatic self-assembly procedure. The functional groups on the surface of MXenes possess highly electronegative properties that facilitate the incorporation of LFMPs into MXenes to construct heterostructure composites. The special heterostructure of nanosized-LiFe0.3Mn0.7PO4 and MXene provides rapid Li+ and electron transport in the cathodes. This LiFe0.3Mn0.7PO4-3.0 wt% MXene composite can exhibit an excellent rate capability of 98.3 mAh g−1 at 50C and a very stable cycling performance with a capacity retention of 94.3 % at 5C after 1000 cycles. Furthermore, NaFe0.3Mn0.7PO4-3.0 wt% MXene with stable cyclability can be obtained by an electrochemical conversion method with LiFe0.3Mn0.7PO4-3.0 wt% MXene. Ex-situ XRD suggests that LiFe0.3Mn0.7PO4-on-MXene achieves a highly reversible structural evolution with a solid solution phase transformation (LFMP→LixFe0.3Mn0.7PO4 (LxFMP), LxFMP→LFMP) and a two-phase reaction (LxFMP←→Fe0.3Mn0.7PO4 (FMP)). This work provides a new direction for the use of MXenes to fabricate 2D heterostructures for lithium-ion batteries.

Impact of Cobalt Addition on Single-Crystal Li1+x(Ni0.6Mn0.4)1−xO2 Cathode Material Performance

Nickel and manganese-based layered oxides with a nickel content ranging from 50% to 80% are promising cathode materials for high-energy density lithium-ion batteries. However, these materials face challenges such as poor rate capability and limited cycling stability. The addition of excess lithium can mitigate these issues to some extent. This study examines the impact of incorporating small amounts of cobalt (5% or 10%) into these materials through an “all-dry” synthesis approach in stoichiometric and excess lithium-containing compositions. Results indicate that adding even these small amounts of cobalt decreases the cation mixing, improves crystallinity, reduces electronic resistance, and influences the morphology depending on whether nickel or manganese is replaced. The materials can accommodate up to 15% excess lithium without significant surface impurities. The addition of cobalt further enhances the rate capability of the material in excess lithium materials, but increasing cobalt content tends to compromise cycling stability when the materials are cycled up to 4.4 V. Materials in which 5% cobalt replaces nickel still exhibit superior rate capability and cycling performance compared to materials without cobalt. Therefore, incorporating small amounts of cobalt can positively impact the performance of Li1+x(Ni0.6Mn0.4)1−xO2 materials, offering a balance between improved rate capability and cycling stability.