An anode composition material and process for the preparation thereof

Abstract

The present invention relates to an electrode material. Specifically, the present invention relates to a MoO3-x-COF material. More specifically, the present invention relates to a MoO3-x -Tp Azo COF nanocomposite material for lithium-ion battery applications as an anode. Further, the present invention relates to a process for the preparation of MoO3-x-COF material. Also, the MoO3-x -COF material is synthesized by a mechanochemical process which is simple, cost- effective, energy-efficient, environmentally friendly, and scalable, making it suitable for large- scale production.

Description

[0001] PT / 2025 / 17226

[0002] AN ANODE COMPOSITION MATERIAL AND PROCESS FOR THE PREPARATION THEREOF

[0003] FIELD OF THE INVENTION

[0004] The present invention relates to an electrode material. Specifically, the present invention relates to anode composition material for lithium-ion battery applications. The anode composition comprising a nanocomposite material of molybdenum oxide and a covalent organic framework (COF). The invention also relates to the process for the preparation of anode composition material, which is simple, cost- effective, energy-efficient, environmentally friendly, and scalable, making it suitable for large-scale production.

[0005] BACKGROUND AND PRIOR ART OF THE INVENTION

[0006] The growing global demand for energy underscores the urgent need for advanced and reliable energy storage solutions. Energy sources can broadly be categorized into renewable and nonrenewable sources, with electricity emerging as a primary player in meeting household and industrial energy needs. Electricity generation encompasses a variety of methods, including solar panels, windmills, geothermal power plants, thermal power plants, hydroelectric power plants, and nuclear power plants. In the 21stcentury, technological advancements have led to the development of various electronic devices aimed at streamlining processes and reducing human effort. Central to these innovations are batteries, which power a wide array of electronic gadgets. Moreover, there is a growing global shift towards sustainable transportation, with electric vehicles (EVs) positioned as the future of the transport sector. However, the realization of this electric and technological revolution hinges on the availability of high-quality batteries capable of delivering high capacity, efficient charge-discharge cycles, and long-term durability. Lithium-ion batteries (Li-ion batteries) stand out as a key player in this scenario, with their cathode and anode materials playing crucial roles in the charge-discharge cycle. While cathode materials primarily consist of metal oxides such as LiM CU, V2O5, MoeSs, LiFePCU, and LiCoCh. The anode materials include graphene, graphitized carbon, and other metal oxides. Researchers have extensively investigated various metal oxide active materials for Li-ion batteries. However, challenges such as metal poisoning and limited recyclability have prompted exploration into alternative materials. The lithium-ion batteries (LIBs) stand out due to their high energy density, efficiency, and widespread use in various applications. However,PT / 2025 / 17226

[0007] conventional LIB materials, such as metal oxides, are plagued by challenges including metal poisoning, limited recyclability, and environmental concerns, which hinder their long-term sustainability. To address these issues, there is a significant shift towards the exploration of composite materials, especially those involving porous polymers and crystalline structures like Covalent Organic Frameworks (COFs). Porous polymers and crystalline structures like Covalent Organic Frameworks (COFs), Metal-Organic Materials (MOFs), and Porous Organic Polymers (POPs) have emerged as promising candidates. These metal oxide composite materials offer the potential to combine the unique qualities of each constituent material, with COFs exhibiting high surface areas, good crystallinity, and electron -rich species conducive to battery applications. Nevertheless, a significant challenge associated with COFs is their poor conductivity.

[0008] The Tp-Azo COF (Tp: 1,3,5 Triformyphologlucinol) follows the Schiff base reaction protocol where the aldehyde and amine react together and form an imine bond. In the synthesis of Tp-Azo COF, Tp (1,3,5-triformylphloroglucinol) and 4,4'-azodianiline react, forming a ketoenol intermediate with water as a byproduct. After heating, the product is obtained in the keto form. The keto form of Tp-Azo COF is stable, whereas enol form is unstable; rather it is not known or characterized due to instability.

[0009] Genfu Zhao et al., (2020) in ACS Energy Lett., 5, 1022-1031 reports Pure Tp-Azo COF and it is the stable Keto form used for battery application. It describes the use of Tp-Azo COF as an anode for lithium-ion battery applications and reports the material being synthesized through a solvothermal method (3 days). However, this method presents significant challenges in terms of scalability, making it less practical for large-scale production. Additionally, the reported lithium storage capacity for the Tp-Azo COF is limited to 306 mAh / g.

[0010] Mohammed, A. K. et al., (2023) in Set. Rep., 13 (1), 1-7 reports phase engineering played around Tp-Azo COF by inserting Cu metal, but it is stabilized in Keto form and Cu metal is weakly bound to the free lone pairs of Oxygen and Nitrogen. This material is not used for battery applications.

[0011] Wang, H. et al., (2022) “Nanostructured Molybdenum-Oxide Anodes for Lithium-Ion Batteries: An Outstanding Increase in Capacity” in Nanomaterials, 12 (1), 1-22 reports purePT / 2025 / 17226

[0012] MoOs material used for battery applications, where its average capacity is less than 400 mAh / g and the stability of the material is up to 700 cycles.

[0013] Lin, Y. M. et al., reports a-Fe2O3 Nanorods as Anode Material for Lithium Ion Batteries in J. Phys. Chem. Lett. 2011, 2 (22), 2885-2891 wherein pure Fe2C>3 material is used as anode for Li-ion battery application. Its average capacity is 837 mAh / g but it was not stable for more than 30 cycles.

[0014] Vikram Singh et.al., (2021) “Thiazole-Linked Covalent Organic Framework Promoting Fast Two-Electron Transfer for Lithium-Organic Batteries”; in Adv. Energy Mater., 11, 2003735, reports a material composition (Azo-1, Azo-2, Azo-3 @CNT) wherein the synthesis was carried out using a chemical synthesis method, which required an extended reaction time of 5 days. This long synthesis duration poses significant challenges for scalability, particularly due to the use of carcinogenic solvents like trifluoroacetic acid. Handling these solvents on a bulk scale is not only hazardous but also complicates large-scale production. Furthermore, ensuring uniformity and quality in the final product is difficult with this chemical method, as yield and material consistency become critical issues. Also, carbon nanotubes (CNTs) were incorporated to enhance the battery performance. From all of these results it is clear that anode materials need specific properties to stabilize the redox reaction during charging and discharging carbonbased materials for stable battery performance and individual metals cannot be stable for longer cycles.

[0015] The drawbacks of conventional metal oxide and graphite anodes include limited specific capacity wherein graphite has a relatively low specific capacity (372 mAh / g), limiting energy storage and metal oxides offers higher capacity than graphite but suffer from poor cycling stability and degradation over time. Graphite has slow lithium-ion diffusion which limits its fast charge / discharge capabilities and metal oxides can offer improved charge capacity but often suffer from slow electron transport, reducing overall efficiency. Graphite cycle stability degrades over time due to side reactions with the electrolyte, losing capacity after many cycles and metal oxides suffer from significant volume expansion during cycling, leading to cracking, structural degradation, and capacity loss. Graphite is prone to dendrite formation during fast charging, increasing the risk of short circuits and battery failure and metal oxides may lead to unwanted side reactions, including metal poisoning, compromising the safety and longevity of the battery. The extraction and processing of graphite are resource-intensive, with significantPT / 2025 / 17226

[0016] environmental impacts and traditional synthesis methods involve harmful solvents and energy-intensive processes, leading to environmental concerns and challenges in recycling. Graphite shows minimal volume expansion but limited in energy density applications and metal oxides undergo significant volume expansion during cycling, leading to mechanical failure and loss of capacity. Graphite is susceptible to thermal degradation at high temperatures, posing a safety risk and metal oxides can contribute to thermal runaway, especially under high temperatures or overcharging conditions.

[0017] There is an unmet need in the art to provide an improved anode material that overcomes drawbacks of one or more prior arts.

[0018] OBJECTIVES OF THE INVENTION

[0019] The main objective of the present invention is to provide an anode composition material for lithium-ion battery applications as an anode.

[0020] Another objective of the present invention is to provide a process for the preparation of anode composition material.

[0021] Yet another objective of the present invention is to provide an anode composition material which is synthesized by a process that is simple, cost- effective, energy-efficient, environmentally friendly, and scalable, making it suitable for large-scale production.

[0022] SUMMARY OF THE INVENTION

[0023] In an aspect, the present invention provides an anode composition material for a lithium-ion battery comprising a nanocomposite material of molybdenum oxide and a covalent organic framework (MoOs-x-COF)

[0024] wherein:

[0025] - molybdenum oxide is non-stoichiometric;

[0026] - “x” is oxygen deficiency in the range of 0<x <1;

[0027] In an embodiment, the covalent organic framework is a Tp-Azo COF.PT / 2025 / 17226

[0028] The anode composition material employed in the lithium-ion battery comprises two-dimensional exfoliated Tp-Azo covalent organic framework sheets having a specific surface area of about 889 m2 / g and two-dimensional exfoliated MoCh-x-covalent organic framework sheets having a specific area of about 245 m2 / g.

[0029] The anode composition material shows capacity of 517 mAh / g, with capacity retention of 100% after 1100 cycles.

[0030] In another aspect, the present invention provides a process for the preparation of anode composition material comprising a nanocomposite material of molybdenum oxide and a covalent organic framework (MoCh-x -COF), wherein COF is Tp-Azo COF, comprising the steps of:

[0031] a) adding 4,4 ’-Azodianiline (Azo) to para-toluenesulfonic acid (PTS A);

[0032] b) grinding the contents of step (a) to obtain a homogeneous mixture;

[0033] c) incorporating 1,3,5-triformylphloroglucinol (Tp) to the mixture obtained in step (b) and the grinding was continued to obtain a uniform reaction mixture;

[0034] d) adding dropwise an aqueous solution of ammonium heptamolybdate tetrahydrate to the reaction mixture of step (c) to obtain a fine paste of MoOs-x -COF;

[0035] e) molding the resulting MoO3-x -COF paste into rods followed by heating to obtain a crystalline MoO3-x-COF; and

[0036] f) washing the crude product of step (e) to obtain pure anode composition material (MoO3- x-COF).

[0037] In an embodiment, the grinding steps (b) and (c) are each carried out for a duration in the range of about 5 to about 10 minutes. The step of molding MoO3-x-COF paste into rods in step (e) of the process is preferably carried out using plastic syringes, and the heating step (e) is performed at a temperature in the range of about 80 °C to about 100 °C for a time period in the range of about 12 to about 24 hours. The washing of the crude product in step (f) is preferably done byPT / 2025 / 17226

[0038] sonication. During the synthesis the reaction proceeds through a keto-enol tautomeric intermediate, with water as a byproduct.

[0039] In another embodiment, the anode composition material (MoCh-x-COF) is synthesized by a mechanochemical process which is simple, cost- effective, energy-efficient, environmentally friendly, and scalable, making it suitable for large-scale production.

[0040] In a further embodiment, the present invention provides a synthesis of MoO 3 -xnanodot loaded onto COF nanocomposite material for enhanced Li-ion battery performance and cyclic stability.

[0041] In a further aspect, the present invention provides a lithium-ion battery comprising:

[0042] Li Foil as cathode;

[0043] a membrane separator;

[0044] MoOs-x- Tp Azo covalent organic framework (COF) as anode; and

[0045] LiTFSI-DOL / DME as electrolyte.

[0046] In some embodiments, the separator employed in the lithium-ion battery is composed of a trilayer PP-PE-PP (Poly propylene-polyethylene-poly propylene) with a pore size of 0.03 pm - 0.1 pm.

[0047] The electrolyte employed in the lithium-ion battery is LiTFSI (6 M Lithium bis(trifluoromethanesulfonyl)imide in 1,3-dioxolane / dimethoxyethane (DOL / DME) in a ratio of 1 : 1 v / v, with 5.0 wt. % LiNOs.

[0048] BRIEF DESCRIPTION OF THE DRAWINGS

[0049] Figure 1: shows a) Powder X-ray Diffractogram (PXRD), b) UV-Vis Spectroscopy analysis, c) FTIR spectroscopy analysis, and d) EPR Spectrum of MoOs-x-COF.

[0050] Figure 2: shows the13C Solid-state NMR of Tp azo and13C NMR of MoOs-x-Tp-Azo COF.

[0051] Figure 3: shows the XPS Spectra of MoOs-x-COF with a) Cis, b) Ols, c) Nls and d) Mo3d.PT / 2025 / 17226

[0052] Figure 4: shows (a) FESEM, (b) HRTEM, (c) EDS, (d) HAADF-STEM image, (e)-(g) elemental mapping of the Tp-Azo COF

[0053] Figure 5: shows (a) FESEM image, (b) HRTEM image; inset shows fringes of MoCh-xNPs, (c) EDS, (d) HAADF-STEM image, (e)-(h) elemental mapping, and (i) line mapping of the MoCh-x-Tp-Azo COF NCs.

[0054] Figure 6: shows the BET sorption analysis isotherm a) Tp-Azo COF c) MoO3-x-COF and Pore size distribution b) Tp-Azo COF d) MoO3-x-COF e) Thermogravimetric Analysis (TGA) of Tp-Azo and MoO3-x-COF.

[0055] Figure 7: shows the (a-c) Plots of Tp-Azo COF (a) Cyclic voltammetry, (b) Galvanostatic charge-discharge curve, (c) Cycling stability and Coulombic Efficiency, (d-f) Plots of MoO3-x-Tp-Azo COF NCs (d) Cyclic voltammetry, (e) Galvanostatic charge-discharge curve, (f) Cycling stability and Coulombic Efficiency plot.

[0056] Figure 8: shows Electrochemical Impedance spectroscopy (EIS) of MoO3-x-Tp-Azo COF NCs.

[0057] Figure 9: shows the half-cell lithium-ion battery set up.

[0058] DETAILED DESCRIPTION OF THE INVENTION

[0059] The invention will now be described in detail in connection with certain preferred and optional embodiments, so that various aspects thereof may be more fully understood and appreciated. In an aspect, the present invention provides an anode composition material for a lithium-ion battery comprising a nanocomposite material of molybdenum oxide and a covalent organic framework (MoO3-x-COF)

[0060] wherein:

[0061] - molybdenum oxide is non-stoichiometric;

[0062] - “x” is oxygen deficiency in the range of 0<x <1.

[0063] In an embodiment of the present invention, the COF is Tp Azo COF.PT / 2025 / 17226

[0064] The anode composition material employed in the lithium-ion battery comprises two-dimensional exfoliated Tp-Azo covalent organic framework sheets having a specific surface area of about 889 m2 / g and two-dimensional exfoliated MoOs-x-covalent organic framework sheets having a specific area of about 245 m2 / g.

[0065] In another embodiment of the present invention, the MoCh-x-Tp Azo COF anode shows capacity of 517 mAh / g, with capacity retention of 100% after 1100 cycles.

[0066] In an embodiment, the new anode composition material of MoCh-x loaded Tp Azo COF nanocomposite is porous and crystalline in nature. The porous nature of the Tp-Azo COF provides a large surface area and accessible channels, which facilitate the diffusion of lithium ions. The in situ loading of MoO3-x further improve these pathways for enhanced ionic conductivity.

[0067] In another embodiment of the present invention, the incorporation of MoO3-x introduces conductive pathways within the Tp-Azo COF structure, improving the overall electrical conductivity. This enhances electron transport, leading to faster charge / discharge rates in Li-ion batteries. Further, the hybrid MoO3-x-COF structure can store a higher number of lithium ions due to the active sites provided by both the COF and MoO3-x. This results in enhanced lithium storage capacity and increased energy density, making the material suitable for high-capacity Li-ion batteries.

[0068] In another embodiment of the present invention, the MoO3-x helps reinforce the structural integrity of the COF during battery cycling. This prevents degradation, maintaining the structural stability and capacity retention of the electrode material over prolonged charge / discharge cycles. Further, the MoO3-x contributes to multiple redox reactions that can enhance the overall electrochemical performance of the Li-ion battery. This leads to improved reversible capacity, which is crucial for maintaining energy efficiency over time.

[0069] In another embodiment of the present invention, the MoO3-x loaded COF nanocomposite employed in the lithium-ion battery gives a stable framework for electron balancing, and MoO3 gives more active site for lithium / de-lithiation. The flexible COF framework accommodates volume changes during lithiation / de-lithiation, improving cycling stability and reducing degradation. This ensures better long-term performance and longer cycle life than both graphitePT / 2025 / 17226

[0070] and metal oxides. Further, MoCh-x-loaded Tp-Azo COF nanocomposite exhibits enhanced thermal stability due to the hybrid nature of the material, reducing the risk of overheating and improving battery safety under extreme conditions.

[0071] In another embodiment of the present invention, the MoCh-x-loaded Tp-Azo COF nanocomposite significantly improves lithium-ion storage capacity due to the multiple redox reactions provided by MoO3-x and the high surface area of the COF, offering higher energy density while maintaining stability. The porous COF structure allows for rapid ion diffusion and improved electron transport, enhancing charge / discharge rates compared to both graphite and metal oxides. Further, the MoOs-x-loaded Tp-Azo COF nanocomposite provides improved safety by reducing the likelihood of dendrite formation and preventing metal poisoning through the protective COF matrix, thus enhancing battery durability and safety. The MoOs-x-loaded Tp-Azo COF nanocomposite accommodates volume changes within its porous framework, maintaining structural integrity and enabling higher energy density applications without degradation.

[0072] In another aspect, the present invention provides a process for the preparation of anode composition material comprising a nanocomposite material of molybdenum oxide and a covalent organic framework (MoO3-x -COF), wherein COF is Tp-Azo COF, comprising the steps of:

[0073] a) adding 4,4 ’-Azodianiline (Azo) to para-toluenesulfonic acid (PTS A);

[0074] b) grinding the contents of step (a) to obtain a homogeneous mixture;

[0075] c) incorporating 1,3,5-triformylphloroglucinol (Tp) to the mixture obtained in step (b) and the grinding was continued to obtain a uniform reaction mixture;

[0076] d) adding dropwise an aqueous solution of ammonium heptamolybdate tetrahydrate to the reaction mixture of step (c) to obtain a fine paste of MoOs-x -COF;

[0077] e) molding the resulting MoO3-x -COF paste into rods followed by heating to obtain a crystalline MoO3-x-COF; andPT / 2025 / 17226

[0078] f) washing the crude product of step (e) to obtain pure anode composition material (MoO3- x-COF).

[0079] Tp (1,3,5-triformylphloroglucinol) and 4,4'-Azodianiline are used as the organic precursors with p-toluene sulphonic acid (PTSA) as catalyst for synthesis the Tp-Azo COF. MoO3-x is prepared separately and introduced as a precursor for in situ loading during the COF synthesis. In step (a) of the process, the organic precursors (4,4'-Azodianiline, PTSA and Tp) are mixed in a mortar Pestle with the MoO3-x precursor. The grinding process mechanically activates the reactants by subjecting them to high-energy collisions, promoting chemical bond formation (Schiff base reaction) without the need for solvents. The mechanical energy facilitates the formation of imine bonds between the aldehyde and amine groups, driving the formation of the Tp-Azo COF. In an embodiment, the grinding steps (b) and (c) are each carried out for a duration in the range of about 5 to about 10 minutes. During the grinding process, MoO3-x is uniformly dispersed within the COF matrix. The mechanical forces help integrate MoO3-x into the COF’s porous structure. This step is critical as it allows the metal oxide to be arranged in a controlled manner within the COF, ensuring even distribution and stabilizing the enol form of the COF. Further grinding and mild heating can drive the conversion toward the desired stable form of the material, typically the keto form, unless stabilized in the enol form by MoO3-x.

[0080] The step of molding MoO3-x-COF paste into rods in step (e) of the process is preferably carried out using plastic syringes, and the heating step (e) is performed at a temperature in the range of about 80 °C to about 100 °C for a time period in the range of about 12 to about 24 hours.

[0081] The washing of the crude product in step (f) is preferably done by sonication. The paratoluenesulfonic acid (PTSA) in step (a) of the process is a catalyst which slows down the reaction. The 4,4’ -Azodianiline (Azo) and 1,3,5-triformylphloroglucinol (Tp) are main COF linkers which builds the framework. Also, ammonium heptamolybdate tetrahydrate (AHM) is MoO3 source for the synthesis.

[0082] In another embodiment of the present invention, during the synthesis the reaction proceeds through a keto-enol tautomeric intermediate, with water as a byproduct. The present invention shows that when Tp Azo COF forms composition with non-stoichiometric Mo oxide, wherein the new composition of MoO3-x loaded Tp Azo COF nanocomposite material is stable even in enol form. The in-situ synthesis of MoO3-x loaded Tp-Azo COF nanocomposite, the metalPT / 2025 / 17226

[0083] oxide arranged in a proper way that stabilized material enol form and MoO3 also formed a bond and gave stable plasmonic structure.

[0084] In another embodiment of the present invention, the anode composition material (MoO3-x-COF) is synthesized by a mechanochemical process which is simple, cost- effective, energyefficient, environmentally friendly, and scalable, making it suitable for large-scale production. The mechanochemical synthesis process relies on mechanical forces rather than high temperatures or solvents, significantly reducing energy consumption. It avoids the use of harmful solvents, making the process greener. Mechanochemical synthesis can easily be scaled up, offering the potential for mass production without complex reactors or large amounts of reagents. Further, reduced need for solvents, shorter reaction times, and lower energy inputs make the process economically advantageous. Mechanochemistry often results in high product yield with fewer byproducts.

[0085] In another embodiment of the present invention, the MoCh-x-loaded Tp-Azo COF nanocomposite synthesized via an environmentally friendly mechanochemical process avoids the use of solvents, reduces energy consumption, and offers better recyclability due to its stable and robust structure, addressing the environmental drawbacks of both graphite and metal oxides.

[0086] In another embodiment, the present invention provides a synthesis of MoO 3 -x nanodot loaded onto COF nanocomposite material for enhanced Li-ion battery performance and cyclic stability.

[0087] In a further aspect, the present invention provides a half-cell lithium-ion battery set up shown in Figure 9 comprising:

[0088] Li Foil as cathode (2);

[0089] a membrane separator (3);

[0090] MoO3-x- Tp Azo covalent organic framework (COF) as anode (4); and

[0091] LiTFSI-DOL / DME as electrolyte.

[0092] Further, the setup comprises a positive metal case (1), a metal spacer (5), a metal spring (6) and a negative metal case (7).PT / 2025 / 17226

[0093] In some embodiments, the separator employed in lithium-ion battery set up is composed of trilayer PP-PE-PP (poly propylene-polyethylene-poly propylene) with pore size of 0.03 pm - 0.1 pm.

[0094] The electrolyte employed in lithium-ion battery set up is LiTFSI (6 M Lithium bis(trifluoromethanesulfonyl)imide in 1,3-dioxolane / dimethoxyethane (DOL / DME) in a ratio of 1 : 1 v / v, with 5.0 wt. % LiNCE.

[0095] In another embodiment, the present invention enhances lithium-ion battery (LIB) performance by addressing the limitations of traditional battery materials by focusing on innovative composite materials, particularly Covalent Organic Frameworks (COFs). While conventional LIB materials such as metal oxides are associated with issues like metal poisoning, recyclability concerns, and limited environmental sustainability, the present invention integrates advanced composite structures to overcome these challenges. The present invention contributes to the field through the development of a MoO3-x loaded Tp Azo COF nanocomposite material, synthesized using a mechanochemical approach. This method not only distinguishes itself by being energy-efficient and environmentally friendly, but it also offers scalability a critical advantage over traditional synthesis methods that are often complex, costly, and less adaptable for mass production.

[0096] In another embodiment of the present invention, the anode material is synthesized by mechanochemical method (1 day) and can be scalable as per requirement. Additionally, the MoCL-x-loaded Tp-Azo COF nanocomposite achieves a much higher lithium storage capacity of up to 517 mAh / g. This substantial enhancement is due to the incorporation of MoO3-x within the COF structure. The addition of MoO3-x introduces extra sites for lithium-ion intercalation, which not only increases the capacity but also stabilizes the overall structure. This results in a more robust, durable battery with enhanced cycling performance.

[0097] In another embodiment of the present invention, the MoO3-x-loaded Tp-Azo COF nanocomposite is synthesized using a scalable and eco-friendly mechanochemical method, avoiding the complexities and hazards associated with trifluoroacetic acid. Second, the incorporation of MoO3-x directly within the COF structure offers additional lithiation sites, improving lithium storage capacity and battery performance without the need for externalPT / 2025 / 17226

[0098] additives like CNTs. This results in a more efficient, stable, and easily scalable material for lithium-ion battery applications.

[0099] In another embodiment, the present invention provides an innovative material composition by loading MoOs-x into Tp Azo COFs, to create a nanocomposite material that synergizes the high surface area, tunable porosity, and structural flexibility of COFs with the electrochemical activity of metal oxides. This combination enhances ion transport and improves the overall performance of LIBs.

[0100] In another embodiment, the present invention provides a mechanochemical synthesis method which is sustainable, cost-effective, significantly reduces the energy consumption and environmental impact compared to conventional chemical synthesis methods. Also, the mechanochemical synthesis technique is inherently scalable. This allows for large-scale production without compromising material quality, making it highly suitable for real-world applications. Thus, the said MoCL-xloaded Tp Azo COF nanocomposite material is synthesized by mechanochemical method wherein said method not only distinguishes itself by being energy-efficient and environmentally friendly, but it also offers scalability a critical advantage over traditional synthesis methods that are often complex, costly, and less adaptable for mass production.

[0101] In another embodiment, the present invention provides a MoCL-x loaded Tp Azo COF nanocomposite material that demonstrates improved electrochemical properties, including higher capacity retention, better cycle stability, and increased charge / discharge rates. This directly addresses the key performance limitations of traditional LIB materials.

[0102] In another embodiment, the present invention provides a composite material that offers enhanced recyclability compared to conventional metal oxides, aligning with the growing demand for sustainable energy solutions. The reduced reliance on toxic metals further minimizes environmental impact.

[0103] In another embodiment of the present invention, the escalating global demand for energy underscores the critical need for reliable energy storage solutions. The present invention explores the pivotal role of batteries, particularly lithium-ion batteries, in meeting this demand. The challenges associated with traditional lithium-ion battery materials are highlighted, suchPT / 2025 / 17226

[0104] as metal oxides, including metal poisoning and recyclability issues. To overcome these challenges, the present invention focusses on composite materials, specifically porous polymers and crystalline structures like Covalent Organic Frameworks (COFs). While COFs offer desirable properties for battery applications, such as high surface areas and good crystallinity, their poor conductivity poses a significant obstacle. A material was developed where non-stoichiometric MoO3-x loaded COF gives a significant increase in battery capacity density. MoO3-x-COF nanocomposite material has an excellent capacity of 517.8 mAh / g at a current of 0.3 A. g'1and cyclic stability of 1100 cycles, and the material delivers 100 % retention after 1100 cycles. The present invention focusses on leveraging non-stoichiometric metal oxides to enhance the conductivity of COFs, thereby improving battery performance and reliability.

[0105] In another embodiment of the present invention, the MoO3-x loaded Tp Azo COF nanocomposite demonstrates promising potential in enhancing battery performance, improving stability, and offering better recyclability compared to traditional materials. This advancement not only addresses the current limitations of lithium-ion batteries but also contributes to the broader goal of developing sustainable and efficient energy storage technologies to meet future energy demands. Also, the Tp-Azo COF provides a lightweight and flexible framework that, combined with MoO3-x, can be utilized in the development of next-generation flexible Li-ion batteries, ideal for portable and wearable electronics.

[0106] EXAMPLES

[0107] Examples are set forth below and are illustrative of varying reactants and reaction conditions that can be utilized in practicing the disclosure. The following examples are given to describe further the details of the instant invention.

[0108] Materials: All chemicals are taken analytical grade without any further purification. 1,3,5-triformyl phloroglucinol (Tp) and 4,4 ’-azodianiline (Azo) AR grade were purchased from Hygeia laboratories, Pune, p-toluenesulphonic acid monohydrate (PTSA) (>98.0 %) was purchased from Tokyo Chemical Industry, India. Ammonium heptamolybdate tetrahydrate (AHM) AR / ACS 99.3% purchased from Loba Chemie. Mili-Q water, N, N-DimethylFormamide (DMF) extra pure 99% (SRL Chemicals Pvt. Ltd.) was used for washing, and Isopropyl alcohol extra pure 99.0 % (Finar Chemicals Ltd.) was used for the drying.PT / 2025 / 17226

[0109] EXAMPLE 1: PROCESS OF SYNTHESIZING ANODE COMPOSITION MATERIAL

[0110] The mechanochemical method was adapted utilizing a mortar and pestle. Initially, 4 g (23.22 mmol) of para-toluenesulfonic acid (PTSA) was placed in the mortar. Subsequently, 0.768 g (3.61 mmol) of 4,4’-Azodianiline (Azo) was added. The mixture was ground for 5 minutes to achieve a homogeneous blend. Next, 0.512 g (2.43 mmol) of 1,3,5-triformylphloroglucinol (Tp) was incorporated and the grinding continued for an additional 5-10 minutes until a uniform product was obtained. Water was then introduced dropwise to the reaction mixture to form a fine paste. The resulting mixture was molded into rods using plastic syringes and heated at 90°C for 24 hours. For the synthesis of the MoCh-x-COF nanocomposite, the protocol was modified to facilitate the incorporation of molybdenum oxide into the imine-based COF. A 0.08 mmol / mL aqueous solution of ammonium heptamolybdate tetrahydrate was prepared and added dropwise in place of pure water. This adjustment optimized the synthesis, yielding a crystalline product with improved characteristics. Crude product washing was carried out by sonication method.

[0111] EXAMPLE 2: CHARACTERIZATION OF THE M0O3-X-COF ANODE COMPOSITION MATERIAL

[0112] The Tp-Azo COF demonstrates excellent crystallinity, which is also evident in the composite material, as confirmed by small-angle powder X-ray diffraction (XRD). The Tp-Azo COF exhibits characteristic diffraction peaks at the (100), (110), and (001) planes, with 29 values of 3.2°, 8.1°, and 27.2°, respectively. The MoO3-x-COF nanocomposite material, which contains nanolevel loading of MoO3-x, does not display separate peaks in the powder XRD (PXRD) pattern, as shown in Figure la.

[0113] To verify the non- stoichiometry of MoO3-x, UV-Vis spectroscopy was employed in Figure lb.

[0114] Both Tp-Azo and MoO3-x-COF exhibit an absorption peak at 379 nm, attributed to azo bond (N=N). Notably, Tp-Azo shows no absorption in the visible region, whereas MoO3-x-COF displays a distinct absorption peak at 571 nm, characteristic of MoCh-x.The FT-IR spectra further confirm the structural bonding within the framework. The Tp-Azo COF displays stretching vibrations of O-H, C=C, C-N, and =C-H at 3600, 1540, 1440, 1226, and 1143 cm respectively. In contrast, the MoO3-x-COF composite shows vibrations corresponding to O-H,PT / 2025 / 17226

[0115] C=C, C-N, =C-H, and M=O at 3450, 1620, 1573, 1460, 910, and 840 cm1, respectively as shown in Figure 1c.

[0116] Electron Paramagnetic Resonance (EPR) spectroscopy was employed to further substantiate the non-stoichiometry of MoCh-x, revealing distinct splitting at a 3400 G magnetic field, with a calculated g-value of 2.04 (Figure Id). Solid-state NMR spectroscopy was employed to elucidate the organic framework of Tp-Azo COF and MoCh-x-Tp-Azo COF as shown in Figure 2. The °C CP MAS spectra exhibit chemical shifts around 107.3, 120.6, 131.9, 139.8, 148.9, 164.7 and 184.3 ppm, indicative of distinct carbon environments within the framework. The both COF have shown C=O peak around 184.3 ppm and 107.3, 120.6, 131.9, 139.8, 148.9 ppm peak is for aromatic carbon environment. The MoOs-x-Tp-Azo COF shown unique peak from Tp-Azo COF around 164.5 ppm which is for Metal Oxide effect to carbamate structure which confirms the COF is in Keto-Enol tautomerism and most stabilizing form is Enol. Further characterization of MoO3-x-COF via X-ray Photoelectron Spectroscopy (XPS) confirms its non-stoichiometric composition. The XPS data, adjusted for charge, converges at 284.8 eV. Deconvolution of the Cis spectra Figure 3a reveals discernible peaks corresponding to C=C, C-N, C=O, and 7t-7t* at 284.04, 285.34, 287.34, and 290.44 eV, respectively. Similarly, in the Figure 3b Ols spectra, peaks representing C=O, C-O, chemisorbed H2O, and 7t-7t* are identified at 530.34, 531.54, 532.84, and 535.64 eV, respectively. The Nls spectra exhibit peaks denoting N-H, N=N, and chemisorbed N=O at 399.12, 401.72, and 404.62 eV in Figure 3c. To validate the non-stoichiometric composition of MoO3-x, deconvolution of the Mo3d spectra highlights the coexistence of Mo5+and Mo6+species. The 3ds / 26+and 3ds / 25+peaks manifest at 232.34 and 231.94 eV, while the 3d3 / 26+and 3d3 / 2 5+peaks emerge at 235.44 and 234.04 eV, respectively. Notably, the peak observed at 237.94 eV for Mo 3d3 / 26+suggests surface oxidation of the material attributable to atmospheric O2 mentioned in Figure 3d.

[0117] The morphological evaluation of Tp COF and MoO3-x-Tp COF NCs was conducted using FESEM and HRTEM analyses. The FESEM images showed that the synthesized Tp COF exhibited an aggregated lamellar morphology (Figure 4a). The MoO3-x-Tp COF NCs maintained this same morphology after the incorporation of the MoO3-x moiety into the COF framework (Figure 5a). The HRTEM images of Tp COF displayed lamellar sheet structures (Figure 4b). In contrast, the HRTEM image of the MoO3-x-Tp COF NCs clearly revealed encapsulated MoO3-x nanoparticles (NPs), which measured approximately 2-5 nm in size, as shown in Figure 5b. The d-spacing value for the MoO3 NPs was observed to be 0.17 nm. ThisPT / 2025 / 17226

[0118] indicates that the MoCh-x nanoparticles are homogeneously integrated within the COF framework at the nanoscale, ensuring consistent and stable loading. This integration preserves the intrinsic crystallinity of the COF, maintaining both its structural integrity and uniform functionalization. The EDS elemental analysis (Figure 5c and inset table), high-angle annular electron microscopy (HAADF-STEM) image (Figure 5d), elemental mapping (Figures 5e-h), and line mapping profile (Figure 5i) of the MoO3-X-Tp COF NCs confirmed the presence of Mo, C, N, and O, which supports the encapsulation and uniform distribution of MoO3-x within the Tp COF NCs. In comparison, the EDS analysis and elemental mapping of Tp COF confirmed only the presence of C, N, and O (Figure 4c and inset table, Figures 4d-g). The results indicate the successful integration of MoOi-xNPs within the COF framework, achieving a uniform nanoscale dispersion. This incorporation preserves the structural integrity of the COF while facilitating the effective integration of active sites, for enhanced performance in cutting- edge applications.

[0119] The BET surface area analysis affirms the Type-IV isotherm characteristic for both Tp-Azo and MoO3-x-COF COFs, underscoring their microporous nature, as evidenced by the H4 type hysteresis. Notably, the specific surface areas for Tp-Azo COF and MoO3-x-COF measure 889.0 m2 / g and 245.28 m2 / g, respectively, determined via Density Functional Theory (DFT) utilizing N2 adsorption at 77 K on carbon, employing the slit pore model and NLDFT equilibrium model, as illustrated in the accompanying Figure 6 a-d.

[0120] Thermogravimetric analysis (TGA) reveals that Tp-Azo COF has excellent thermal stability. It loses crystalline water at 150°C and remains stable up to 375°C with only a 17% weight loss. A significant weight loss of 30% occurs at 514°C, and by 900°C, the material retains 50% of its initial weight. The thermal stability of MoO3-x-COF is slightly reduced due to the incorporation of MoO3-x, which introduces free electrons that facilitate structural degradation at lower temperatures. MoO3-x-COF shows a 24% weight loss at 374°C and an 80% weight loss after 500°C as shown in Figure 6e.

[0121] EXAMPLE 3: COMPARATIVE ELECTROCHEMICAL PERFORMANCE OF ANODE MATERIALSPT / 2025 / 17226

[0122] The table (Table -1) below summarizes the electrochemical performance of the anode material of the present invention in comparison with reported covalent organic framework (COF)-based and metal oxide-based anode materials disclosed in the art.

[0123] TABLE-1: COMPARATIVE ELECTROCHEMICAL PERFORMANCE OF ANODE MATERIALS

[0124]

[0125] PT / 2025 / 17226

[0126]

[0127] The MoCh x / Tp-Azo covalent organic framework anode of the present invention demonstrates a superior combination of high specific capacity, excellent cycling stability, and rapid mechanochemical synthesis. Achieving approximately 517 mAh / g with 100% capacity retention over more than 1100 cycles, the anode composition of the present invention matches the performance of existing COF-based and metal oxide anodes while requiring significantly reduced synthesis time.

[0128] EXAMPLE 4: BATTERY APPLICATION

[0129] The MoOs-x-COF material, characterized by its covalent organic framework (COF) with nanodots of non-stoichiometric molybdenum oxide (MoCh-x), exhibits a high concentration of free electrons suitable for redox reactions. In lithium-ion batteries, where lithiation and delithiation are spontaneous processes, the large surface area and abundant charge carriers of this material significantly enhanced battery performance. The electrochemical Li-ion battery measurements were conducted by fabricating CR 2032-type coin cells (Half cells). In this study, Tp COF and MoOs-x-Tp COF NCs are utilized as the anode material, while Li-foil is employed as both the counter and reference electrode. The electrochemical behavior was assessed by cyclic voltammetry (CV), conducted at a scan rate of 0.05 mV s-1within a potential window of 0.01 to 3.0 V, employing a Biologic (BT lab) potentiostat instrument.

[0130] Figure 7a shows CV graphs of pristine COF which revealed three cathodic peaks at 1.63, 0.81, and 0.01 V (vs. Li+ / Li) during the first cycle, corresponding to multistep lithium intercalation, electrochemical reduction, and solid electrolyte interphase (SEI) formation. The peak at 1.63

[0131] V was attributed to surface-active material reduction, while the diminishing 0.81 V peak indicated lithium occupation at C=O and N=N sites, forming strong ionic bonds. A peak at 0.01

[0132] V corresponded to lithium loading within the COF cavities. Figure 7b illustrates the galvanostatic discharge-charge profiles for the 1st, 2nd, 50th, and 100thcycles. The first dischargePT / 2025 / 17226

[0133] exhibits a wide and stable plateau starting at 1.8 V with a high capacity of 1371.6 mAh g’1. In the second cycle, a reversible capacity of 223.5 mAh g'1is achieved, with a discharge plateau at -0.02 V, consistent with the CV curves. The significant capacity loss of -1148 mAh g'1from the first to the second cycle is attributed to SEI formation. The discrepancy between theoretical and experimental capacities arises from inaccessible reactive sites of N=N and C=O units on the host framework, further reduced by electrostatic repulsion between azo bond nitrogen atoms and C=O oxygen atoms. Additionally, as a two-dimensional material, Tp COF forms a stacking structure between adjacent layers, concealing reactive sites. The capacity density of Tp COF declines sharply over 100 cycles, dropping to 64 mAh g'1due to pore inaccessibility for redox reactions and structural instability caused by oligomer formation and framework collapse. Despite this, the Tp COF demonstrates 100% coulombic efficiency and cyclic stability up to 100 cycles (Figure 7c).

[0134] To overcome the capacity fading issue with the pristine COF, we have incorporates oxygendeficient MoOs-x NPs into the Tp COF matrix. This modified COF i.e. MoOs-x-Tp COF NCs shows 3 peaks in CV curves s depicted in Figure 7d, the first cycle’s CV curve reveals three distinct cathodic peaks at 1.66, 0.50, and 0.01 V (vs Li+ / Li), indicative of a multistep lithium intercalation process followed by the electrochemical reduction of MoOs-x-Tp COF NCs. The peak at 1.66 V corresponds to the reduction of surface -active sites, leading to SEI formation, while the peak at 0.50 V diminishes progressively, signifying lithium ion occupation at the C=O and N=N functional groups, thereby forming strong ionic bonds such as Li-O- and Li-N- 29,48,49 Tecatholic pea|<a0.02 V is attributed to lithium loading within the porous structure of MoCE-x-Tp COF NCs. Subsequent cycles exhibit overlapping CV curves, indicating excellent reversibility and cycling stability of the MoOs-x-Tp COF NCs based anode. To evaluate the electrode’s efficiency in reversible lithium storage, galvanostatic dischargecharge tests were performed at a current density of 100 mA g'1within a voltage window of 0.01-3.0 V (vs Li+ / Li), further confirming the material's potential for high efficiency in lithium-ion intercalation and deintercalation processes.

[0135] The galvanostatic discharge-charge profiles of MoOs-x-Tp COF NCs for 1st, 2nd, 50th, 100th, 500th, 1000th, and 1100thcycles are shown in Figure 7e. The first discharge profile reveals a wide and stable plateau starting from 1.8 V, exhibiting a high initial capacity of 1640.65 mAh g’1. In the second cycle, a reversible capacity of 378.38 mAh g'1is achieved, with a discharge capacity plateau at -0.02 V, consistent with the cyclic voltammetry (CV) data. The substantialPT / 2025 / 17226

[0136] capacity loss of approximately 1262 mAh g'1from the first to second cycle is attributed to the formation of the SEI. The discrepancy between theoretical and experimental capacities is likely due to the inaccessible reactive sites (N=N and C=O units) within the framework, hindered by electrostatic repulsion between the nitrogen atoms of azo bonds and the oxygen atoms of C=O. Furthermore, like Tp COF, MoCh-x-Tp COF NCs is a two-dimensional material with a stacking structure between adjacent layers, which conceals certain reactive sites. The capacity of MoO3-x-Tp COF NCs drops sharply up to 100 cycles, decreasing to 110 mAh g'1due to the nonopening of its pores for redox reactions. However, after 200 cycles, the capacity increases significantly, reaching 517 mAh g'1and it becomes remaining stable for over 1100 cycles. This performance can be attributed due to the activation of the non-stoichiometric MoO3-x nanoparticle, which generate free electrons and initiate redox reactions once the pores of the material open. Even after 1000 cycles, a high specific capacity of -517 mAh g'1is maintained at a current density of 100 mA g’1, showcasing excellent cycling stability upto 1100 cycles, the material demonstrates nearly 100% capacity retention with a coulombic efficiency around 100% (Figure 7f), shows the ultra-stability and efficient utilization of reactive sites in MoO3-x-Tp COF NCs.

[0137] Electrochemical Impedance Spectroscopy (EIS) before and after cell testing, which initially showing a large resistance generated due to a non-stabilized electric circuit gerts tremendously after 1100 cycles which shows the balancing of redox reaction during charge-discharge cycles shown in Figure 8.

[0138] The successful development of a novel COF nanocomposite material with controlled non-stoichiometric MoO3-x loading demonstrates significant promise for Li-ion battery applications. By optimizing MoO3-x loading within the COF framework, this nanocomposite material achieves an impressive specific discharge capacity of 517 mAh / g and robust cyclic stability, retaining performance up to 1100 cycles. These results highlight the potential of this COF -MoO3-x nanocomposite to enhance energy density and longevity in next-generation Li-ion batteries. This innovation underscores the scalability and adaptability of COF-based composites in energy storage applications, offering a pathway toward higher-performing, sustainable battery technologies.

[0139] ADVANTAGES OF THE INVENTIONPT / 2025 / 17226

[0140] • Innovative Material Composition

[0141] • Mechanochemical Synthesis

[0142] • Scalability and Practicality

[0143] • Enhanced Battery Performance

[0144] • Recyclability and Environmental Benefits

Claims

1. PT / 2025 / 17226We Claim:

1. An anode composition material for a lithium-ion battery comprising a nanocomposite material of molybdenum oxide and a covalent organic framework (COF),wherein:molybdenum oxide is non-stoichiometric; and“x” is oxygen deficiency in the range of 0<x <1.

2. The anode composition material as claimed in claim 1, wherein the covalent organic framework is a Tp-Azo COF.

3. The anode composition material as claimed in claim 1, wherein the anode composition comprises two-dimensional exfoliated Tp-Azo covalent organic framework sheets having a specific surface area of about 889 m2 / g and two-dimensional exfoliated MoOsx- covalent organic framework sheets having a specific surface area of about 245 m2 / g.

4. The anode composition material as claimed in claim 1, wherein the anode composition shows a capacity of 517 mAh / g, with capacity retention of 100% after 1100 cycles.

5. A process for the preparation of anode composition material comprising a nanocomposite material of molybdenum oxide and a covalent organic framework (MoCh-x -COF), wherein COF is Tp-Azo COF, comprising the steps of:a) adding 4,4 ’-Azodianiline (Azo) to para-toluenesulfonic acid (PTS A);b) grinding the contents of step (a) to obtain a homogeneous mixture;c) incorporating 1,3,5-triformylphloroglucinol (Tp) to the mixture obtained in step (b) and the grinding was continued to obtain a uniform reaction mixture;d) adding dropwise an aqueous solution of ammonium heptamolybdate tetrahydrate to the reaction mixture of step (c) to obtain a fine paste of MoCh-x-COF;e) molding the resulting MoCh-x -COF paste into rods followed by heating to obtain a crystalline MoOs-x-COF; andPT / 2025 / 17226f) washing the crude product of step (e) to obtain pure anode composition material (MoOs- x-COF).

6. The process as claimed in claim 5, wherein the grinding in step (b) and (c) is carried out for 5- 10 minutes.

7. The process as claimed in claim 5, wherein the heating in step (e) is carried out at a temperature in the range of 80°C to 100°C for a time period in the range of 12 to 24 hours.

8. A lithium-ion battery comprising:Li Foil as cathode;a membrane as separator;MoCh-x-Tp Azo covalent organic framework (COF) as anode; andLiTFSI-DOL / DME as electrolyte.

9. The claim as claimed in claim 8, wherein the separator is composed of trilayer PP-PE-PP (Poly propylene-polyethylene-poly propylene) with pore size of 0.03 pm - 0.1 pm.

10. The claim as claimed in claim 8, wherein the electrolyte is LiTFSI (6 M Lithium bis(trifluoromethanesulfonyl)imide in 1,3-dioxolane / dimethoxyethane (DOL / DME) in a ratio of 1 : 1 v / v, with 5.0 wt. % LiNCL.

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