Compositions, Related Systems and Articles, and Methods of Making and Using the Same

Abstract

The present disclosure relates to various compositions, related systems and articles, and methods of manufacture and use. In certain aspects, the present disclosure relates to compositions comprising nanostructured organic compounds, compositions comprising an organic compound and a metal organic framework embedded within the organic compound, and compositions comprising at least partially crystalline organic compounds and crystalline metal oxides dispersed within the organic compounds, related methods of manufacture (e.g., methods of depolymerizing polymers), methods of use (e.g., energy storage, contaminant removal), articles (e.g., electrodes), and systems (e.g., energy storage systems, systems including such energy storage systems). In certain aspects, the present disclosure relates to compositions comprising a silicon-containing material and a polymer made from an imide monomer, and related systems and articles, and methods of manufacturing and using the same.

Description

Technical Field

[0001] Cross-reference to related applications This application claims the benefit of the following U.S. patent applications: USSN 63 / 344,349, filed May 20, 2022, entitled "Method for Manufacturing Nanostructured Materials"; USSN 63 / 398,459, filed Aug. 16, 2022, entitled "Composition Comprising an Organic Compound and a Crystalline Metal Oxide and Method for Producing the Same"; USSN 63 / 439,688, filed Jan. 18, 2023, entitled "Method for Converting Waste Plastics into Nanostructured Monomers and Related Compounds". The entire disclosure of these applications is incorporated herein by reference.

[0002] Field of the invention The present disclosure relates to various compositions, related systems and articles, and methods for their manufacture and use. The present disclosure relates to compounds comprising nanostructured organic compounds, compounds comprising organic compounds and organometallic structures embedded in the organic compounds, compositions comprising organic compounds containing some crystals and crystalline metal oxides dispersed in the organic compounds, and related manufacturing methods (e.g., depolymerization methods of polymers), use methods (e.g., energy storage, pollutant removal), articles (e.g., electrodes), and systems (e.g., energy storage systems, systems including these energy storage systems). In one aspect, the present disclosure relates to compositions comprising polymers composed of silicon-containing substances and imide monomers, and related systems and articles, and methods for their manufacture and use.

Background Art

[0003] Background art Every year, a large amount of plastic is produced and consumed worldwide. For example, it is reported that about 30 million tons of polyethylene terephthalate (hereinafter referred to as "PET") are consumed annually for the production of various products, such as the manufacture of about 400 billion beverage bottles. These products are often discarded after a single use because there is no relatively simple and effective recycling method, which leads to pollution of the land and water environment.

[0004] Existing methods for chemically decomposing waste PET into monomers usually use high-temperature and high-pressure vessels and concentrated acid or alkali solutions. In addition, the use of enzymes is included in PET recovery methods, but since the reaction rate of enzymes is slow, a long process may be required in some cases. In many cases, existing polymer recovery methods produce different monomer compositions, so additional processes for separation and purification are required.

Summary of the Invention

[0005] Summary of the disclosure The present disclosure provides methods, articles, and systems related to energy storage, while being applicable to reducing the amount of waste plastic materials.

[0006] The present disclosure relates to various compositions, related systems and articles, and methods for their manufacture and use. In one aspect, the present disclosure relates to compounds containing nanostructured organic compounds, compounds containing organic compounds and organometallic structures embedded in organic compounds, and compositions containing organic compounds containing some crystals and crystalline metal oxides dispersed in the organic compounds, as well as related manufacturing methods, use methods, articles (for example, electrodes), and systems (for example, energy storage systems, systems including these energy storage systems). In one aspect, the disclosed features include compositions containing polymers composed of silicon-containing substances and imide monomers, as well as related systems, articles, methods for their manufacture and use.

[0007] The compositions, articles, and / or systems encompassed by the present disclosure can exhibit one or more beneficial properties. For example, in certain embodiments, an electrode comprising a composition according to the present disclosure can have higher electrical conductivity, metal ion storage capacity, Coulombic efficiency, and / or metal ion diffusion rate compared to certain other energy storage materials, articles, and / or systems. Further, as another example, in certain embodiments, an electrode comprising a composition according to the present disclosure can have lower resistance at the interface between the electrode and the electrolyte and / or a lower Warburg coefficient compared to certain other energy storage materials, articles, and systems. As another example, in certain embodiments, these compositions can be relatively inexpensive and / or have a low environmental impact compared to certain other energy storage materials, articles, and / or systems. Further, in certain embodiments, the technology according to the present disclosure can avoid electrochemical performance problems (such as electrode pulverization due to large volume changes) associated with other types of battery anode materials, energy storage materials, articles, and / or systems. As another case, in certain embodiments, electrodes made from these compositions can maintain stable performance without degrading over hundreds of cycles (e.g., the maximum capacity does not substantially decay). As another example, in certain embodiments, electrodes and batteries comprising a composition according to the present disclosure are safe while having a relatively high energy density compared to certain other electrodes and batteries. In certain embodiments, when inserting or extracting metal ions (such as lithium ions, sodium ions, or potassium ions) into / from the negative electrode comprising these compositions, the voltage is less than 1V, and the voltage with respect to the metal / metal ion (e.g., Li + / Li, Na+ / Na, K + / K) is sufficiently high. The voltage characteristics prevent the deposition of metal on the negative electrode of the energy storage device, improve safety, and at the same time achieve a relatively high energy density compared to other energy storage devices.

[0008] In certain embodiments, the composition can be applied to wastewater treatment to reduce the concentration of organic contaminants in water through adsorption and / or photocatalytic decomposition.

[0009] In one embodiment, in the disclosed method, waste plastics (e.g., polyethylene terephthalate (PET) from plastic bottles) can be decomposed (e.g., depolymerized) into monomers (e.g., terephthalic acid). In certain embodiments, the depolymerization of waste plastics is carried out without handling dangerous chemicals (e.g., acidic or alkaline), high pressure, high temperature, and / or catalysts and / or reducing agents for a long time. On the other hand, in one embodiment, in the disclosed method, it enables the use of relatively mild reagents (e.g., SnCl2, ZnCl2, LiCl, and / or KCl), relatively low temperature, relatively low pressure (e.g., atmospheric pressure), relatively short processing time, and does not require the use of acids, bases, and / or enzymes. Therefore, in certain embodiments, this method depolymerizes waste plastics in a relatively safe, simple, inexpensive, and rapid manner, while simultaneously improving scalability, separating monomers and related compounds relatively easily, eliminating the need for additional separation and purification steps, and having a lower cost compared to other depolymerization methods. In certain embodiments, in the disclosed method, the product can be produced and purified more easily (e.g., without a purification step). For example, in certain embodiments, in the disclosed method, a second organic compound that can be separated relatively easily from the first organic compound, composition (e.g., by evaporation) can be produced. Therefore, in one embodiment, in the disclosed method, PET can be decomposed into nanostructured terephthalic acid (TPA) at standard atmospheric pressure even in the absence of other monomers such as ethylene glycol.

[0010] In one embodiment, in this method, it is possible to depolymerize plastics into nanostructured and / or nanocrystalline monomers and related compounds. These monomers and compounds are morphologically and / or structurally different from some other materials (e.g., commercially available terephthalic acid without nanostructures and / or nanocrystals).

[0011] In certain embodiments, in the disclosed method, waste plastics (e.g., polyethylene terephthalate (PET) from PET bottles) can be consumed (e.g., depolymerized) to produce the disclosed compositions. In certain embodiments, this method does not use environmentally harmful and / or expensive chemicals commonly used in the production of battery anode materials. On the other hand, in certain embodiments, the disclosed method can use relatively inexpensive, abundant, and safe reagents (e.g., SnCl2, =LiCl)=, =KCl)=) that have little or no carcinogenic or genotoxicity. Without being bound by theory, in certain embodiments, in some of the disclosed methods, conversion of SnCl2 to SnO2 may release chlorine gas. The generated chlorine can be used for one or more industrial applications (e.g., drinking water treatment).

[0012] In certain embodiments, in the disclosed method, a composition of an organic compound having a nanostructure (e.g., terephthalic acid) can be prepared. Without being bound by theory, in certain embodiments, the compound prepared by the disclosed method may have a dark (e.g., black) appearance due to unique light-matter interactions with the nanostructured organic compound (e.g., nanostructured terephthalic acid). And this light-matter interaction property does not exist in other (i.e., non-nanostructured) organic compounds.

[0013] In certain embodiments, in the disclosed method, it can be used to separate plastic compositions by selectively depolymerizing a portion of the plastic composition in the mixed plastics. For example, these methods can decompose the depolymerizable polymer (e.g., PET) without depolymerizing the non-depolymerizable plastics (e.g., high-density polyethylene (HDPE)) in the composition, thereby separating the depolymerizable polymer from the non-depolymerizable polymer of the polymer.

[0014] In one embodiment, the disclosed composition exhibits a faster reaction rate compared to other organic compounds (e.g., commercially available terephthalic acid that does not contain nanostructures and / or nanocrystals). Based on this, the disclosed composition (e.g., disodium terephthalate (Na2TP, Na2C8H4O4) and dilithium terephthalate (Li2TP, Na2C8H4O4)) can be used to manufacture materials. Different from other raw materials of terephthalic acid, polymers such as poly(succinic acid-terephthalate) (PBAT) and PET, and / or photosensitive nanoparticles are used as electrodes for sodium-ion batteries and lithium-ion batteries, respectively.

[0015] In one embodiment, in the disclosed method, waste PET can be depolymerized into pure nanostructured terephthalic acid (TPA) at atmospheric pressure without generating other types of monomers such as ethylene glycol.

[0016] Commercially available TPA is intensively used in many fields, such as the detection of hydroxyl radicals in solution, the preparation of 2-hydroxyterephthalic acid for biomedical cancer treatment and water treatment, the preparation of metal-organic frameworks and photosensitive nanoparticles for biomedical imaging, the preparation of various polymers such as poly(succinic acid-terephthalate) (PBAT) and PET, and the preparation of electrode materials for metal-ion batteries. For example, there are disodium terephthalate (Na2TP, Na2C8H4O4) and dilithium terephthalate (Li2TP, Na2C8H4O4), which are used as electrode materials for sodium-ion batteries and lithium-ion batteries, respectively.

[0017] In one embodiment, the present disclosure not only provides a relatively simple, rapid, and sustainable method for depolymerizing PET into TPA, but also provides a method for preparing nanostructured TPA. Different from commercially available TPA, nanostructured TPA has unique micro-morphological features that enable the use of TPA materials in various scenarios, while simultaneously improving the kinetics of these processes. By replacing commercially available TPA with nanostructured TPA in the production of various materials, a relatively rapid, simple, and efficient solution can be achieved, resulting in economic and technical advantages. This reduces the greenhouse gas emissions from the production of TPA raw materials.

[0018] In one embodiment, in the disclosed method, plastics can be depolymerized into nanostructured and / or nanocrystalline monomers, related compounds, and compositions, which are known to have novel and / or various potential applications. These applications include the preparation of electrode materials and / or electrolyte materials and / or other functional and / or structural components for energy generation and storage devices, the preparation of reagents for water purification, templates for the preparation of other nanostructured materials that can be used in energy / environmental protection / biomedical and / or structural materials, and the preparation of compositions with enhanced mechanical and / or physical properties.

[0019] In one embodiment, the disclosed method can provide a relatively simple and rapid depolymerization of PET into two or more monomers, where one monomer (e.g., TPA) becomes a condensation compound during the process and the other monomers are in the gas phase and leave the reactor during the reaction. This can reduce the subsequent purification steps for separating the mixed monomers, which are commonly used in current chemical depolymerization technologies (although not completely avoided). Thus, in one embodiment, the disclosed method can reduce the economic cost and process complexity of monomer synthesis.

[0020] In one embodiment, relatively low-cost and relatively easily available materials are disclosed that are applicable to the sustainable development of current and future emerging technologies, such as green energy production / storage and compositions.

[0021] In one aspect, a composition is disclosed that includes the following. Chemical formula C x O y H z A nanostructured organic compound composed of a plurality of molecules having the formula, where x ranges from 2 to 12, y ranges from 2 to 8, and z ranges from 2 to 14.

[0022] In one embodiment, a composition is provided that includes an organic compound and a metal-organic framework embedded in the organic compound.

[0023] In one aspect, a composition is disclosed that includes the following. A type of organic compound, where the organic compound is at least partially crystalline, and a crystalline metal oxide dispersed in the organic compound.

[0024] In one aspect, a composition is disclosed that includes the following. A silicon-containing material, a polymer made from imide monomers, where a part of the imide monomers is in a crosslinked form, and a part of the material and a part of the polymer are bonded to each other by hydrogen bonds.

[0025] In one aspect, a composition is disclosed that includes the following. A polymer, an organic compound composed of a plurality of molecules having the chemical formula C x O y H z where the organic compound is crystalline, and in the formula, x ranges from 2 to 12, y ranges from 2 to 8, and z ranges from 2 to 14. In one embodiment, the organic compound is a nanocrystal.

[0026] In one embodiment, the crystalline domain size of the composition ranges from 1 nm to 100 nm. In one embodiment, the crystalline domain size of the composition ranges from 20 nm to 80 nm. In one embodiment, the crystalline domain size of the composition ranges from 30 nm to 70 nm.

[0027] In one embodiment, the components of the composition have at least one dimension size of less than 100 nm. In one embodiment, the components of the composition have at least one dimension size of less than 50 nm. In one embodiment, the components of the composition have at least one dimension size of less than 10 nm. In one embodiment, the organic compound having a nanostructure has at least one dimension size of less than 2 nm.

[0028] In one embodiment, the composition further comprises at least one selected from the group consisting of metal oxides, metals, metal organic frameworks, silicon-containing substances, and graphene-containing materials selected for embedding in the nanostructured organic compound.

[0029] In one embodiment, the composition further comprises a crystalline metal oxide embedded in the nanostructured organic compound.

[0030] In one embodiment, there were diffraction (XRD) peaks in the X-ray diffraction test results of the composition. In one embodiment, the 2θ (±0.2°) values of the XRD pattern of the composition included at least one selected from 16.99°, 24.83°, and 27.54°. In one embodiment, the XRD pattern of the composition included at least two peaks (2θ, ±0.2°) selected from 16.99°, 24.83°, and 27.54°. In one embodiment, the 2θ (±0.2°) values of the XRD pattern of the composition were 16.99°, 24.83°, and 27.54°. In one embodiment, the composition has an XRD pattern of characteristic peaks as shown in FIG. 36d.

[0031] In one embodiment, the crystalline metal oxide is uniformly dispersed in the organic compound. In one embodiment, in the internal region of the composition, there is a first concentration of the crystalline metal oxide. In the surface region of the composition, the composition has a second concentration of the crystalline metal oxide, and / or the first concentration is greater than the second concentration. In one embodiment, the first concentration in the internal region of the composition ranges from 1 wt.% to 95 wt.%. In one embodiment, the first concentration in the internal region of the composition ranges from 5 wt.% to 80 wt.%. In one embodiment, the first concentration in the internal region of the composition ranges from 10 wt.% to 70 wt.%. In one embodiment, the first concentration in the surface region of the composition ranges from 0.1 wt.% to 80 wt.%. In one embodiment, the first concentration in the surface region of the composition ranges from 1 wt.% to 70 wt.%. In one embodiment, the first concentration in the surface region of the composition ranges from 5 wt.% to 60 wt.%. In one embodiment, the organic compound and the crystalline metal oxide are bonded by a hydrogen bond.

[0032] In one embodiment, the composition contains nanoparticles with a size of 1 nm to 200 nm. In one embodiment, the composition consists of nanoparticles having a size of 1 nm to 100 nm, for example, 0.01 μm to 100 μm.

[0033] In one embodiment, the composition particles have a particle size of 10 μm to 100 μm, for example, 1 nm to 200 nm. In one embodiment, the particles consist of sheet-like particles having a size of 1 nm to 1 μm, for example, 10 nm to 500 nm.

[0034] In one embodiment, the organic compound contains an amorphous phase. In one embodiment, a part of the components of the organic compound has a crystal structure. In one embodiment, the organic compound is crystalline. In one embodiment, the organic compound has a nanostructure.

[0035] In one embodiment, the organic compound has the molecular formula C x O y H zIt has. In certain embodiments, in the formula, x ranges from 2 to 12, y ranges from 2 to 8, and z ranges from 2 to 14. In certain embodiments, x is 8, y ranges from 4 to 6, and z is 4.

[0036] In certain embodiments, the organic compound includes terephthalic acid, terephthalic acid ester, dimethyl terephthalate, bis(2-hydroxyethyl) terephthalate, ethylene glycol, phthalic acid, protocatechuic acid, and / or isophthalic acid. In certain embodiments, the organic compound includes terephthalic acid. In certain embodiments, the organic compound includes an orthorhombic system.

[0037] In certain embodiments, the composition contains 1 wt.% to 99 wt.% of the organic compound, for example, 5 wt.% to 95 wt.%, or 10 wt.% to 90 wt.%.

[0038] In certain embodiments, the crystalline metal oxide includes crystalline metal oxide nanoparticles. In certain embodiments, the composition contains 1 wt.% to 95 wt.% of the crystalline metal oxide, for example, 5 wt.% to 90 wt.%, or 10 wt.% to 85 wt.% of the crystalline metal oxide.

[0039] In certain embodiments, the particle size of the crystalline metal oxide is 1 nm to 100 nm, for example, 1 nm to 50 nm, 1 nm to 10 nm, or 1 nm to 5 nm.

[0040] In certain embodiments, the crystalline metal oxide includes tin(IV) oxide (SnO2), tin(II) oxide (SnO), zinc oxide (ZnO), zinc peroxide (ZnO2), calcium oxide, lithium oxide, potassium oxide, lead oxide, and / or iron oxide. In certain embodiments, the crystalline metal oxide includes tin(IV) oxide (SnO2), etc. In certain embodiments, the crystalline metal oxide has a tetragonal system.

[0041] In one embodiment, the X-ray diffraction (XRD) pattern of the organic compound has diffraction peaks, and the crystalline metal oxide has XRD peaks. In one embodiment, the 2θ (±0.2°) values of the XRD peaks of the organic compound consist of at least one value among 17.41°, 25.21°, and 27.95°.

[0042] In one embodiment, the 2θ (±0.2°) values of the XRD pattern of the organic compound included at least two peaks selected from 17.41°, 25.21°, and 27.95°. In one embodiment, the 2θ (±0.2°) values of the XRD peaks of the organic compound were 17.41°, 25.21°, and 27.95°. In one embodiment, the 2θ (±0.2°) values of the XRD peaks of the crystalline metal oxide included at least one among 26.60°, 33.90°, 37.97°, 39.00°, 51.81°, 54.79°, 57.87°, 61.92°, 64.79°, 66.01°, 71.33°, 78.76°, 81.19°, 83.78°, and 87.29°. In one embodiment, the 2θ (±0.2°) values of the XRD pattern of the crystalline metal oxide included at least two from 26.60°, 33.90°, 37.97°, 39.00°, 51.81°, 54.79°, 57.87°, 61.92°, 64.79°, 66.01°, 71.33°, 78.76°, 81.19°, 83.78°, and 87.29°. In one embodiment, the 2θ (±0.2°) values of the XRD peaks of the crystalline metal oxide included at least three from 26.60°, 33.90°, 37.97°, 39.00°, 51.81°, 54.79°, 57.87°, 61.92°, 64.79°, 66.01°, 71.33°, 78.76°, 81.19°, 83.78°, and 87.29°. In one embodiment, the 2θ (±0.2°) values of the XRD peaks of the crystalline metal oxide included at least four from 26.60°, 33.90°, 37.97°, 39.00°, 51.81°, 54.79°, 57.87°, 61.92°, 64.79°, 66.01°, 71.33°, 78.76°, 81.19°, 83.78°, and 87.29°. In one embodiment, the XRD pattern of the composition having characteristic peaks is shown in FIG. 6c.

[0043] In certain embodiments, the composition has at least one endothermic peak having a maximum temperature of 328 °C, 461 °C, or 528 °C (±3 °C) according to a differential scanning calorimetry (DSC) thermogram. In certain embodiments, according to the DSC thermogram, the composition has at least two endothermic peaks having a maximum temperature of 328 °C, 461 °C, and 528 °C (±3 °C). In certain embodiments, according to the DSC thermogram, the composition has an endothermic peak with a maximum temperature (±3 °C) that includes 328 °C, 461 °C, and 528 °C. In certain embodiments, the composition has a DSC thermogram as shown in FIG. 11.

[0044] In certain embodiments, the composition has a thermogravimetric analysis (TGA) spectrum as shown in FIG. 11. In certain embodiments, the composition essentially has an X-ray photoelectron spectroscopy (XPS) spectrogram as shown in FIG. 15e.

[0045] In certain embodiments, the specific surface area of the composition is 10 square meters per gram (m 2 g -1 ) to 50 m 2 g -1 , for example 15 m 2 g -1 to 30 m 2 g -1 , or 17 m 2 g -1 to 21 m 2 g -1 .

[0046] In certain embodiments, the electrical conductivity of the composition is in the range of 5 Siemens per meter (S m -1 ) to 5000 S m -1 (6.3 MPa), for example 100 S m -1 to 1500 S m -1 at 6.3 MPa, or 400 S m -1 to 600 S m -1 at 6.3 MPa.

[0047] In one embodiment, the composition consists of a silicon-containing substance. In one embodiment, the silicon-containing substance is embedded in the organic compound. In one embodiment, the composition contains 0.1 wt% to 95 wt% of the silicon-containing substance, such as 5 wt.% to 90 wt.% of the silicon-containing substance, or 10 wt.% to 85 wt.% of the silicon-containing substance. In one embodiment, the silicon-containing substance contains silicon. In one embodiment, the silicon-containing substance contains silicon particles. In one embodiment, the silicone nanomaterial has a particle size in the range of 1 nanometer (nm) to 1000 nm, such as 1 nm to 500 nm, 1 nm to 20 nm, or 1 nm to 5 nm.

[0048] In one embodiment, the composition contains graphene nanosheets. In one embodiment, the graphene nanosheets cover at least a portion of the crystalline metal oxide. In one embodiment, the composition contains 0.1 wt.% to 50 wt.% of the graphene nanosheets, such as 5 wt.% to 45 wt.% of the graphene nanosheets, or 10 wt.% to 40 wt.% of the graphene nanosheets. In one embodiment, the graphene nanosheets contain sheets having a sheet size of 1 nm to 5 μm, such as 50 nm to 5 μm, or 100 nm to 1 μm. In one embodiment, the graphene nanosheets contain 1 layer to 100 layers, such as 1 layer to 50 layers, or 1 layer to 10 layers. In one embodiment, the graphene nanosheets contain at least 90%, such as at least 95% carbon. In one embodiment, the graphene nanosheets contain functional groups on their surface. In one embodiment, the functional groups consist of hydroxyl groups, carbonyl groups, carboxyl groups, and / or amino groups. In one embodiment, the composition further contains a silicon-containing substance, and the graphene nanosheets cover at least a portion of the silicon-containing substance.

[0049] In one embodiment, the composition contains a metal-organic structure embedded in the organic compound. In one embodiment, the metal-organic structure is partially crystalline. In one embodiment, the metal-organic framework is a crystal structure. In one embodiment, the metal-organic framework is a nanostructure.

[0050] In one embodiment, the metal-organic framework contains the organic compound and the metal. In one embodiment, the metal is Zn, Fe, Cu, Al, Zr, Cr, Co, Li, Na, or K. In one embodiment, the metal is Zn.

[0051] In one embodiment, the metal-organic framework has the molecular formula MC x H y O z ·nH2O, where M is a metal and n is in the range of 0 to 5 (for example, 0, 1, 2, or 3.5). In one embodiment, the metal-organic framework has the molecular formula MC x H y O z ·3.5H2O, where M is a metal. In one embodiment, the metal-organic framework has the molecular formula MC x H y O z and M is a metal. In one embodiment, x is in the range of 2 to 12, y is in the range of 2 to 8, and z is in the range of 2 to 14. In one embodiment, x is 8, y is 4, and z is 4. In one embodiment, the metal-organic framework contains terephthalic acid ester.

[0052] In one embodiment, the particle size of the composition is 500 nm to 700 μm. In one embodiment, the particles have the size of sheet-like particles in the range of 10 nm to 10 μm. In one embodiment, the thickness of the sheet-like particles is 1 nm to 10 nm. In one embodiment, the sheet-like particles contain nanoparticles with a size in the range of 1 nm to 60 nm. In one embodiment, the particles contain aggregated nanoparticles with a size in the range of 1 nm to 60 nm. In one embodiment, the particles contain metal-organic framework crystals with a size in the range of 10 nm to 10 μm. In one embodiment, the metal-organic framework has an average crystal domain size of 30 nm to 60 nm.

[0053] In one embodiment, the 2θ (±0.2°) values of the XRD peaks of the composition include at least one peak from 11.75°, 14.74°, 16.60°, and 16.98°. In one embodiment, the 2θ (±0.2°) values of the XRD peaks of the composition include at least two from 11.75°, 14.74°, 16.60°, and 16.98°. In one embodiment, the 2θ (±0.2°) values of the XRD peaks of the composition include 11.75°, 14.74°, 16.60°, and 16.98°. In one embodiment, the composition has an XRD spectrum of characteristic peaks as shown in FIG. 60a.

[0054] In one embodiment, the 2θ (±0.2°) values of the XRD peaks of the composition include at least one peak from 9.89°, 19.33°, 25.27°, and 40.11°. In one embodiment, the XRD peaks of the composition have 2θ (±0.2°) values that include at least two of 9.89°, 19.33°, 25.27°, and 40.11°. In one embodiment, the 2θ (±0.2°) values of the XRD peaks of the composition include 9.89°, 19.33°, 25.27°, and 40.11°.

[0055] In one embodiment, the 2θ (±0.2°) values of the XRD peaks of the composition include at least one from 17.45°, 25.27°, 28.017°, and 42.99°. In one embodiment, the 2θ (±0.2°) values of the XRD peaks of the composition include at least two of 17.45°, 25.27°, 28.017°, and 42.99°. In one embodiment, the 2θ (±0.2°) values of the XRD peaks of the composition include 17.45°, 25.27°, 28.017°, and 42.99°. In one embodiment, the XRD spectrum of the composition having characteristic peaks is shown in FIG. 60b.

[0056] In one embodiment, the composition contains a tin-containing component selected from metallic tin, tin chloride, tin chloride hydroxide, tin hydroxide, and tin chloride hydroxide (e.g., the molecular formula Sn 21 Cl 16 (OH) 14It further contains O6). In certain embodiments, the tin-containing component contains particles having a size of 1 nm to 100 nm. In certain embodiments, the tin-containing component is at least partially crystalline. In certain embodiments, the tin-containing component is crystalline. In certain embodiments, the tin-containing component has a nanostructure.

[0057] In certain embodiments, the composition is a dark-colored powder. In certain embodiments, the composition is a black powder.

[0058] In certain embodiments, the composition has an absorbance of at least 1 a.u. (e.g., at least 1.5 a.u.) at 242 nm at a concentration of 0.5 g / L. In certain embodiments, the composition has an absorbance of at least 0.4 a.u. at 450 nm at a concentration of 0.5 g / L.

[0059] In certain embodiments, the composition has an absorbance of at least 0.4 a.u. at 500 nm at a concentration of 0.5 g / L. In certain embodiments, the composition has an absorbance of at least 0.5 a.u. at 317 nm at a concentration of 0.5 g / L.

[0060] In certain embodiments, the composition further contains a metal embedded in the organic compound. In certain embodiments, the metal is selected from Na, Li, K, and Zn. In certain embodiments, the composition is selected from Na2C8H4O4, Li2C8H4O4, K2C8H4O4, or ZnC8H6O4.

[0061] In certain embodiments, the composition contains a nanostructured organic compound. In certain embodiments, the composition contains nanostructured terephthalic acid.

[0062] On the one hand, the present disclosure provides an electrode based on the composition of the present disclosure. In certain embodiments, the composition further comprises at least one component selected from conductive carbon, copper binder, and graphene nanosheets. In certain embodiments, the binder is made of polyimide.

[0063] In certain embodiments, the electrode has a lithium ion discharge capacity of 10 milliamperes per gram (mAh g -1 ) to 1500 mAh g -1 after 500 cycles at a current density of 200 mA g -1 (e.g., 100 mAh g -1 to 1000 mAh g -1 , 200 mAh g -1 to 800 mAh g -1 ).

[0064] In certain embodiments, the Coulomb efficiency of the electrode is 70 - 120% (e.g., 80 - 110%, 90 - 100%) after 500 cycles.

[0065] In certain embodiments, the electrolyte resistance of the half - cell assembled from the electrode material increases to 1.0 Ω - 6.0 Ω (e.g., 2.0 Ω - 5.0 Ω, 3.0 Ω - 4.0 Ω) after 150 cycles.

[0066] In certain embodiments, the electrolyte resistance of the half - cell assembled from the electrode material increases to 2.0 Ω - 8.0 Ω (e.g., 2.0 Ω - 7.0 Ω, 3.0 Ω - 6.0 Ω) after 300 cycles.

[0067] In certain embodiments, the lithium ion diffusion rate of the electrode after 300 cycles is in the range of 10 -11 cm 2 s -1 to 9×10 -9 cm 2 s -1 (e.g., 5×10 -11 cm 2 s -1 to 5×10 -9 cm 2 s -1 to 5×10 -11cm 2 s -1 ~10 -9 cm 2 s -1 )。In one embodiment, the lithium ion diffusion rate of the electrode after 300 cycles was 2×10 -11 cm 2 s -1 ~10 -8 cm 2 s -1 (e.g., 7×10 -11 cm 2 s -1 ~7×10 -9 cm 2 s -1 、10 -10 cm 2 s -1 ~9×10 -9 cm 2 s -1 ).

[0068] In one embodiment, after the electrode was cycled 10 times at a current density of 100 mA g -1 , it had a lithium ion discharge capacity of 300 mAh g -1 ~1500 mAh g -1 . In one embodiment, the lithium ion discharge capacity was in the range of 200 mAh g -1 ~1500 mAh g -1 after the electrode was cycled 30 times at a current density of 500 mA g -1 . In one embodiment, the lithium ion discharge capacity was in the range of 200 mAh g -1 ~1500 mAh g -1 after the electrode was cycled 50 times at a current density of 1000 mA g -1 . In one embodiment, after the electrode was cycled 60 times at a current density of 5000 mA g -1 , the discharge capacity of lithium ions increased to 50 mAh g -1 ~1300 mAh g -1 .

[0069] In one embodiment, Na ions are embedded in the electrode at a voltage of 0.1V to 0.9V (vs Na / Na+). In one embodiment, the embedding of Na ions into the electrode occurs at a voltage of 0.15V to 0.8V (vs Na / Na+). In one embodiment, the embedding of Na+ ions into the electrode occurs at a voltage of 0.17V to 0.3V (vs Na / Na+).

[0070] In one embodiment, the voltage at which Na ions desorb from the electrode is in the range of 0.3V to 0.7V (vs Na / Na+). In one embodiment, the voltage at which Na+ ions desorb from the electrode is in the range of 0.4V to 0.6V (vs Na / Na+).

[0071] In one embodiment, the electrode has a lithium ion discharge capacity of 100 mAh g -1 ~1800 mAh g -1 after 500 cycles.

[0072] In one embodiment, the lithium ion discharge capacity of this electrode ranges from 100 milliamperes per hour (mAh) per gram of crystalline metal oxide to 1800 mAh after 500 cycles. In one embodiment, the electrode has a lithium ion discharge capacity after 500 cycles in the range of 200 mAh to 1800 mAh per gram of crystalline metal oxide. In one embodiment, the electrode is in the range of 500 mAh per gram of crystalline metal oxide to 1800 mAh per gram of crystalline metal oxide lithium ion discharge capacity after 500 cycles.

[0073] In one aspect, the present disclosure provides a battery including an electrode according to the present disclosure. In one embodiment, the electrode is an anode. In one embodiment, the battery also includes a cathode. In one embodiment, the battery further includes an electrolyte between the anode and the cathode. In one embodiment, there is an electrical connection between the anode and the cathode. In one embodiment, the battery is a lithium ion battery, a sodium ion battery, a calcium ion battery, or a potassium ion battery.

[0074] In one aspect, according to the present disclosure, the present disclosure provides a vehicle including a battery. In one aspect, the present disclosure provides a structure including a battery according to the disclosure.

[0075] In one aspect, the present disclosure provides a power - generating system. Here, the system is configured to be coupled to a battery according to the disclosure. In one embodiment, the system includes a system capable of generating electricity from electromagnetic radiation, a system capable of generating electricity from the rotation of a turbine, and / or a system capable of generating electricity from a combustion reaction. In one embodiment, the system includes at least one selected from solar power generation, wind turbines, hydroelectric power units, hydroelectric power plants, nuclear power plants, coal - fired power plants, oil - fired power plants, and gas - fired power plants. In one embodiment, the battery is used to store the electric power generated by the system.

[0076] In one embodiment, the composition consists of a transition metal disulfide. In one embodiment, the transition metal disulfide has the molecular formula MX2. In one embodiment, M is a transition metal atom and X is a chalcogen atom. In one embodiment, M includes Mo or W. In one embodiment, the chalcogen atom consists of an element from the group consisting of S, Se, and Te. In one embodiment, the transition metal dichalcogenide consists of a two - dimensional transition metal dichalcogenide. In one embodiment, the transition metal dichalcogenide is encapsulated in an organic compound. In one embodiment, the composition consists of a crystalline metal oxide and the transition metal dichalcogenide is embedded in the crystalline metal oxide.

[0077] In one embodiment, the composition consists of a material containing a polymer and a silicone. In one embodiment, the polymer is made from monomers, and at least a portion of the monomers are cross-linked to each other. In one embodiment, the monomers consist of imide monomers. In one embodiment, a portion of the material and a portion of the polymer are bonded by hydrogen bonds. In one embodiment, the material consists of silicon particles embedded in an organic compound. In one embodiment, the material consists of silicon particles. In one embodiment, the silicon particles can have a size in the range of 1 nm to 5 μm, 10 nm to 1 μm, 20 nm to 500 nm, and 20 nm to 200 nm. In one embodiment, the organic compound crystals are nanostructures and nanocrystals. In one embodiment, based on the mass of silicon in the material, the specific capacity of lithium ions for storing electrical energy is 1000 mAh / g at a current density of 200 mA / g and becomes 3500 mAh / g after 30 cycles. In one embodiment, a hybrid assembled lithium-ion battery charged at a current density of 200 mA / g has a specific energy density in the range of 3000 Wh kg -1 ~8000 Wh kg -1 . In one embodiment, the composition has a lithium-ion diffusion impedance of 10 Ω to 60 Ω and may be 20 Ω to 40 Ω. In one embodiment, the infrared spectrum of the polymer has a peak at 1723 cm -1 and / or a peak at 1362 cm -1 . In one embodiment, the IR spectrum of the composition does not have a peak at 3739 cm -1 . In one embodiment, the polymer is a polyimide.

[0078] In one aspect, the present disclosure provides a method comprising: treating a mixture raw material based on the present disclosure to form a first solution constituting a first solution to contaminants; and reducing the concentration of contaminants in the first solution to form a second solution, wherein the second solution has a lower concentration of contaminants than the concentration of contaminants in the first solution. In certain embodiments, at least a portion of the contaminants in the first solution is adsorbed on the surface of the composition. In certain embodiments, the composition photocatalytically decomposes at least a portion of the contaminants in the first solution.

[0079] In certain embodiments, reducing the concentration of contaminants in the first solution further comprises exposing the first solution to visible light. In certain embodiments, the contaminants are compounds selected from the group consisting of hydrocarbons, azo dyes, and xanthate-based compounds.

[0080] In one aspect, the present disclosure provides a method comprising: heating a mixture comprising a first polymer, a second polymer, and a depolymerizing agent to a first temperature; depolymerizing the first polymer to form an organic compound; and forming a composition comprising the organic compound, wherein the second polymer is not substantially depolymerized. In certain embodiments, the first polymer is a polymer that can be depolymerized in the presence of water. In certain embodiments, the first polymer comprises polyethylene terephthalate (PET), polystyrene, polyvinyl chloride, nylon, polyurethane, phenolic resin, and / or epoxy resin. In certain embodiments, the second polymer consists of polyethylene and / or polypropylene. In certain embodiments, the method further comprises isolating the composition from the second polymer.

[0081] In one aspect, the present disclosure provides a method comprising: heating a mixture of reactants to a first temperature. A nanocrystalline organic compound composition is formed, and the reactants consist of a polymer and a depolymerizing agent. In certain embodiments, the reactants further comprise a salt, and the composition is heated such that the salt melts.

[0082] In one aspect, the present disclosure provides a method comprising: heating a composition of reactants to a first temperature; forming a composition of an organic compound and a crystalline metal oxide, wherein a part of the organic compound is in a crystalline state; the reactants consisting of a salt, a polymer, and a depolymerizing agent; heating the salt to form a molten salt.

[0083] In one aspect, the present disclosure provides a method for preparing a composition, the method including heating a mixture containing the polymer to a temperature of 150 °C to 400 °C. In one embodiment, the method includes heating for a period of 1 second to 5 hours. In one embodiment, the heating is performed in an inert or nitrogen atmosphere. In one embodiment, the atmosphere contains 0.1 to 99.9% hydrogen.

[0084] In one embodiment, when the mixture is heated, the polymer depolymerizes to obtain monomers, and the monomers form an organic compound. The reactants contain 1 wt.% (wt.%) to 99 wt.% of the polymer.

[0085] In one embodiment, the reactants contain 5 wt.% to 95 wt.% (e.g., wt.% to 90 wt.%) of the polymer.

[0086] In one embodiment, examples of the polymer include polyethylene terephthalate (PET), poly(acrylonitrile), poly(6-aminohexanoic acid), polycaprolactam, nylon, polyether ether ketone (PEEK), poly(ethylene) (PE), poly(hexamethylene hexane amide), poly(methyl methacrylate), poly(methylene oxide), poly(4-methylpentene), poly(propylene), poly(styrene), poly(trans-1,4-butadiene), poly(vinyl alcohol), poly(vinyl chloride) (PVC), poly(vinyl fluoride), poly(vinylidene chloride), and / or poly(vinylidene fluoride).

[0087] In one embodiment, the polymer consists of polyethylene terephthalate (PET). In one embodiment, the polymer is derived from waste plastic.

[0088] In one embodiment, the difference in melting temperature between the polymer and the depolymerizing agent is less than 100 °C (for example, less than 75 °C, less than 50 °C).

[0089] In one embodiment, the reactant contains 1 wt.% to 95 wt.% (for example, 5 wt.% to 90 wt.%, 10 wt.% to 85 wt.%) of the depolymerizing agent.

[0090] In one embodiment, the depolymerizing agent consists of inorganic salts. In one embodiment, the inorganic salts consist of the same metal as the metal oxide. In one embodiment, the inorganic salt undergoes an oxidation reaction during heating.

[0091] In one embodiment, the depolymerizing agent includes tin(II) chloride (SnCl2), zinc chloride (ZnCl2), calcium chloride (CaCl2), lead chloride (PbCl2), sodium chloride (NaCl), potassium chloride (KCl), and / or ferric chloride (FeCl2). In one embodiment, the depolymerizing agent contains tin(II) chloride (SnCl2). In one embodiment, the depolymerizing agent contains zinc chloride (ZnCl2).

[0092] In one embodiment, the depolymerizing agent contains an ionic liquid. In one embodiment, the ionic liquid consists of [bmpy][Tf2N] and [BMIM][Tf2N] and / or an imidazolium ionic liquid. In one embodiment, the ionic liquid contains 1-octyl-3-methyl-imidazolium ([OMIM]), 1-methyl-imidazolium ([MIM]), 1-ethyl-3-methyl-imidazolium ([EMIM]), 1-octyl-3-methyl-imidazolium ([EMIM]), 3-dimethylimidazolium ([M13IM]), 1-(2-hydroxyethyl)-3-methylimidazolium ([HOEMIm]), 1-ethyl-2,3-dimethylimidazolium ([EMMIM]), 1-butyl-3-methylimidazolium ([BMIM]), 1-hexyl-3-methylimidazolium ([HMIM]), 1,2,3-trimethylimidazolium ([MMMIM]), 1-decyl-3-methylimidazolium ([DMIM]), 1-allyl-3-butylimidazolium ([ABIM]), 1,2-dimethylimidazolium ([M 12 IM]), 1-butyl-2,3-dimethylimidazolium ([BMMIM]), 1-allyl-3-methylammonium imidazolium ([AMIM]), 1-allyl-3-vinylimidazolium ammonium ([AVIM]), tetradecyltrihexylphosphine ([P 66614 )), N-ethylpyridine ([EPy]), and N-butylpyridine ([BPy]). In one embodiment, the ionic liquid is selected from bis(trifluoromethylsulfonyl)imide ([Tf2N]), bromide ([Br]), dicyanamide ([DCA]), hexafluorophosphate ([PF6]), perchlorate ([ClO4]), toluenesulfonate ([TS]), acetate ([Ac]), chloride ([Cl]), glycinate ([Gly]), iodide ([I]), trifluoromethanesulfonate ([TFO]), sulfite ([Pro]), alanine hydrochloride ([Ala]), lysine hydrochloride ([Lys]), dihydrogen phosphate ([H2PO4]), nitrate ([NO3]), serine hydrochloride ([Ser]), glutamate hydrochloride ([Glu]), hydrogen sulfate ([H2SO4]), tetrafluoroborate ([BF4]).

[0093] In one embodiment, in one embodiment, the salt consists of a chloride salt. In one embodiment, the molten salt contains LiCl and / or KCl. In one example, the salt contains LiCl and KCl. In one embodiment, the salt contains 40 wt.% LiCl to 80 wt.% LiCl (for example, 50 wt.% LiCl to 70 wt.%, 55 wt.% LiCl to 65 wt.%). In one embodiment, the salt contains 20 wt.% to 70 wt.% of KCl (for example, 30 wt.% to 55 wt.% of KCl, 35 wt.% to 40 wt.% of KCl).

[0094] In one embodiment, the salt has a melting point of 250°C to 700°C (for example, 300°C to 600°C, 320°C to 500°C).

[0095] In one example, the heating is carried out in an atmosphere of one of air, nitrogen, argon, and hydrogen. In one example, the heating is carried out under an inert atmosphere.

[0096] In one example, the heating is carried out under an argon atmosphere. In one example, the heating is carried out under an atmosphere of argon and hydrogen. In one example, the heating is carried out in a gas composition containing argon and 1% to 99% hydrogen.

[0097] In one example, the heating is carried out at a temperature above the melting point of the polymer and the melting point of the depolymerizing agent. In one example, the heating is carried out at a temperature above the melting point of the polymer, the melting point of the molten salt, and the melting point of the depolymerizing agent. In one example, the heating is carried out at a temperature below the carbonization temperature of the polymer and the decomposition temperature of the organic compound.

[0098] In one example, the first temperature range is 200°C to 600°C. In one example, the first temperature is at most 600°C. In one example, the first temperature range is 200°C to 450°C.

[0099] In one embodiment, the first temperature is at least 250 °C. In one embodiment, the first temperature is at least 300 °C.

[0100] In one embodiment, the first temperature is at most 500 °C. In one embodiment, the first temperature is at most 400 °C. In one embodiment, the first temperature is at most 310 °C.

[0101] In one embodiment, the composition is maintained at the first temperature for 0.01 minutes to 120 minutes (e.g., 1 minute to 60 minutes, 5 minutes to 30 minutes, 1 second).

[0102] In one embodiment, the heating rate of the composition is 1 °C / min -1 ~100 °C / min -1 in the range of (e.g., 2 °C / min -1 ~50 °C / min -1 , 3 °C / min -1 ~20 °C / min -1 ).

[0103] In one embodiment, the method further comprises further contacting the composition with a solvent. In one embodiment, the solvent comprises at least one selected from an aqueous solution, an alkaline aqueous solution, an acidic aqueous solution, and a polar organic liquid. In one embodiment, the pH of the solvent is 0.1 to 7 (e.g., 1 to 6, 2 to 5). In one embodiment, the solvent comprises an acid selected from hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid. In one embodiment, the acid concentration in the solvent is in the range of 1 vol.% to 98 vol.% (e.g., 2 vol.% to 95 vol.%, 5 vol.% to 90 vol.%). In one embodiment, the pH of the solvent is 7 to 14 (e.g., 8 to 13, 9 to 12). In one embodiment, the solvent comprises a hydroxide. In one embodiment, the hydroxide includes sodium hydroxide and potassium hydroxide. In one embodiment, the polar organic liquid includes ethanol.

[0104] In certain embodiments, the composition comprises a depolymerizing agent, and the composition is contacted with a solvent to remove at least a portion of the depolymerizing agent. In certain embodiments, the composition comprises a depolymerizing agent, and when the composition is contacted with a solvent, a portion of the depolymerizing agent is hydrolyzed.

[0105] In certain examples, the depolymerizing agent consists of SnCl2, SnCl2 is hydrolyzed to form a second product consisting of elemental tin, chlorine, hydrogen, and oxygen, and is contacted to form a second material product consisting of the composition and the organic compounds dispersed in the composition. In certain examples, the second material consists of oxides, chlorides, and hydroxides. In certain examples, the chemical composition of the second material is Sn 21 C l16 (OH) 14O6 In certain examples, the second material portion is in a crystalline phase.

[0106] In certain examples, the method further includes separating the composition from the solvent. In certain examples, the separation methods include vacuum filtration and centrifugation. In certain examples, the method further includes drying the separated composition. In certain examples, the composition is dried in one of air, an inert atmosphere, or a vacuum atmosphere. In certain embodiments, the composition is dried at a temperature of -196°C to 100°C (e.g., -196°C to 0°C, 20°C to 100°C).

[0107] In certain embodiments, the solvent contains a precursor of a silicon-containing substance, and the silicon-containing substance is introduced into the composition by contacting the composition with the solvent.

[0108] In certain examples, the composition also contains a precursor of a silicon-containing substance, and the composition further contains the silicon-containing substance.

[0109] In certain embodiments, the reactant contains 0.1 wt.% to 98 wt.% (e.g., 5 wt.% to 90 wt.%, 10 wt.% to 85 wt.%) of the silicon-containing substance precursor.

[0110] In one embodiment, the silicon-containing material precursor is a nanostructured particle. In one embodiment, the silicon-containing material precursor comprises elemental silicon, Ca2Si, Ca5Si3, CaSi, Ca3Si4, CaSi2, and / or Mg2Si.

[0111] In one embodiment, the silicon-containing material precursor has a particle size in the range of 1 nm to 1000 nm (e.g., 1 nm to 500 nm, 1 nm to 20 nm, 1 nm to 5 nm). In one embodiment, the silicon-containing material precursor contains surface functional groups.

[0112] In one embodiment, the method further includes ball-milling the silicon-containing material precursor. In one embodiment, the silicon-containing precursor is ball-milled in the presence of a solvent. In one embodiment, the solvent includes normal hexane. In one embodiment, the solvent contains graphene nanosheets, and the composition is contacted with the solvent to introduce the graphene nanosheets into the composition.

[0113] In certain embodiments, the pre-reaction composition further comprises graphene nanosheets, and the composition product further comprises graphene nanosheets. In certain embodiments, the composition comprises 0.1 wt.% to 80 wt.% (e.g., 2 wt.% to 45 wt.%, 5 wt.% to 40 wt.%) of graphene nanosheets. In certain embodiments, the size of the graphene nanoflakes ranges from 1 nm to 5 μm (e.g., 50 nm to 5 μm, 100 nm to 1 μm). In certain embodiments, the number of layers of the graphene nanosheets ranges from 1 to 100 (e.g., 1 to 50, 1 to 10). In certain embodiments, the graphene nanosheets have a carbon purity of at least 90% (e.g., at least 95%). In certain embodiments, the surface of the graphene nanosheets contains functional groups. In certain embodiments, the functional groups include hydroxyl groups, carbonyl groups, carboxyl groups, and / or amino groups. In certain embodiments, the graphene nanosheets are produced by cathodic electrochemical exfoliation of graphite electrodes. In certain embodiments, the cathodic electrochemical exfoliation is carried out in a salt. In certain embodiments, the salt comprises at least one component selected from lithium chloride and sodium chloride. In certain embodiments, the cathodic electrochemical exfoliation is carried out at a temperature of 500 °C to 900 °C.

[0114] In certain embodiments, the organic compound comprises an amorphous phase component. In certain embodiments, the organic compound is in a crystalline phase.

[0115] In certain embodiments, the organic compound is nanostructured. In certain embodiments, the organic compound has the molecular formula C x O y H z where x ranges from 2 to 12, y ranges from 2 to 8, and z ranges from 2 to 14. In certain embodiments, x is 8, y ranges from 4 to 6, and z is 4.

[0116] In one embodiment, the organic compound includes terephthalic acid, terephthalic acid ester, dimethyl terephthalate, di(2-hydroxyethyl) terephthalate, ethylene glycol, phthalic acid, protocatechuic acid and / or isophthalic acid. In one example, the organic compound includes terephthalic acid. In one embodiment, the terephthalic acid is nanostructured and has at least one dimension with a dimension of less than 100 nm.

[0117] In one example, the heating is carried out in a pressure range of 0.01 to 100 atmospheres (for example, 0.1 to 10 atmospheres, 0.5 to 5 atmospheres, 0.8 to 1.5 atmospheres). In one example, the heating is carried out at atmospheric pressure.

[0118] In one example, the method further includes forming a suspension including the composition and graphene nanosheets, sonicating the suspension, and recovering a product from the suspension. Here, the product includes the composition and the graphene nanosheets. In one example, the suspension further includes an acid. In one example, the product includes 50 wt.% to 99.9 wt.% of the composition. In one example, the product includes 0.1 wt.% to 50 wt.% of graphene nanosheets.

[0119] In one example, the reactant further includes water. In one embodiment, at least a part of the depolymerizing agent is hydrated.

[0120] In one embodiment, the depolymerizing agent is hydrated. In one example, the depolymerizing agent includes 0.1 wt.% to 20 wt.% of water.

[0121] In one example, the method further includes removing at least a part of the composition and adding an additional polymer.

[0122] In one embodiment, the composition includes a metal-organic framework embedded within the organic compound. In one embodiment, the metal-organic framework includes the organic compound and the metal.

[0123] In one embodiment, the metal is selected from Zn, Fe, Cu, Al, Zr, Cr, Co, Li, Na, and K. In one embodiment, the metal is Zn.

[0124] In one embodiment, the metal-organic framework has the molecular formula MC x H y O z ·nH2O, where M is a metal and n ranges from 0 to 5 (e.g., 0, 1, 2, or 3.5).

[0125] In one embodiment, the metal-organic framework has the molecular formula MC x H y O z -3.5H2O, where M is a metal.

[0126] In one embodiment, the molecular formula of the metal-organic framework is MC x H y O z where M is a metal. In one embodiment, x ranges from 2 to 12, y ranges from 2 to 8, and z ranges from 2 to 14. In one embodiment, x is 8, y is 4, and z is 4. In one embodiment, the metal-organic framework includes terephthalate.

[0127] In one embodiment, the metal-organic framework contains water of hydration, and the method further includes heating the composition to a second temperature, where the heating removes at least a portion of the water of hydration from the metal-organic framework. In one embodiment, the metal-organic structure contains a first crystal structure before being heated to the second temperature, and the metal-organic structure contains a second crystal structure after being heated to the second temperature, and the second crystal structure is different from the first crystal structure. In one embodiment, the second temperature is from 50 °C to 400 °C. In one embodiment, the composition is maintained at the second temperature for from 1 millisecond to 10 hours. In one embodiment, the method further includes cooling the composition after heating the composition. In one embodiment, the cooling is performed in the same atmosphere as the heating.

[0128] In one embodiment, the reactants do not include acids, bases, and enzymes. In one embodiment, the method does not have a separation step.

[0129] In one embodiment, a second organic compound is formed by heating, and the second organic compound completely evaporates. In one embodiment, the second organic compound is ethylene glycol.

[0130] In one embodiment, the composition consists of a nanostructured organic compound. In one embodiment, the composition consists of nanostructured terephthalic acid.

[0131] In one embodiment, the method further includes reacting the composition with a metal hydroxide to form a composition containing a hydroxide and a metal product, and the reaction time is at most 18 hours. In one embodiment, the product contains the formula Na2C8H4O4, Li2C8H4O4, K2C8H4O4, or ZnC8H6O4.

[0132] In one embodiment, the reaction time is at most 12 hours (e.g., at most 6 hours). In one embodiment, the hydroxide is selected from NaOH, LiOH, KOH, and Zn(OH)2.

[0133] In one embodiment, the reactants and the composition include transition metal dichalcogenides. In one embodiment, the chemical formula of the transition metal dichalcogenide is MX2, where M is a transition metal atom and X is a chalcogen atom. In one embodiment, M includes Mo or W. In one embodiment, the chalcogen atoms include S, Se, and Te. In one embodiment, the transition metal dichalcogenides include two-dimensional transition metal dichalcogenides. In one embodiment, the transition metal dichalcogenide is embedded in an organic compound. In one embodiment, the composition consists of a crystalline metal oxide, and the transition metal disulfide is embedded in the crystalline metal oxide.

Brief Description of the Drawings

[0134]

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DETAILED DESCRIPTION OF THE INVENTION

[0135] Detailed description Composition In one embodiment, the compositions of the present disclosure can include nanostructured organic compounds composed of multiple molecules. When including one or more components having nanoscale dimensions (e.g., 1 nm to 100 nm), the composition is said to be nanostructured. In one embodiment, the components of the composition (e.g., the nanostructured organic compound) have at least one dimension less than 100 (e.g., less than 95, less than 90, less than 85, less than 80, less than 75, less than 70, less than 65, less than 60, less than 55, less than 50, less than 45, less than 40, less than 35, less than 30, less than 25, less than 20, less than 15, less than 10, less than 5, less than 4, less than 3, less than 2, less than 1) nm. Generally, organic compounds contain carbon, oxygen, and hydrogen (see the following discussions and examples). Generally, organic compounds have the formula C x O y H zIt has. In certain embodiments, x is from 2 to 12 (e.g., 2 to 3, 2 to 4, 2 to 5, 2 to 6, 2 to 7, 2 to 8, 2 to 9, 2 to 10, 2 to 11, 3 to 4, 3 to 5, 3 to 6, 3 to 7, 3 to 8, 3 to 9, 3 to 10, 3 to 11, 3 to 12, 4 to 5, 4 to 6, 4 to 7, 4 to 8, 4 to 9, 4 to 10, 4 to 11, 4 to 12, 5 to 6, 5 to 7, 5 to 8, 5 to 9, 5 to 10, 5 to 11, 5 to 12, 6 to 7, 6 to 8, 6 to 9, 6 to 10, 6 to 11, 6 to 12, 7 to 8, 7 to 9, 7 to 10, 7 to 11, 7 to 12, 8 to 9, 8 to 10, 8 to 11, 8 to 12, 9 to 10, 9 to 11, 9 to 12, 10 to 11, 10 to 12, 11 to 12, 11 to 12, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12). In certain embodiments, y is from 2 to 8 (e.g., 2 to 3, 2 to 4, 2 to 5, 2 to 6, 2 to 7, 3 to 4, 3 to 5, 3 to 6, 3 to 7, 3 to 8, 4 to 5, 4 to 6, 4 to 7, 4 to 8, 5 to 6, 5 to 7, 5 to 8, 6 to 7, 6 to 8, 7 to 8, 2, 3, 4, 5, 6, 7, 8). In certain embodiments, z is from 2 to 14 (e.g., 2 to 3, 2 to 4, 2 to 5, 2 to 6, 2 to 7, 2 to 8, 2 to 9, 2 to 10, 2 to 11, 2 to 12, 2 to 13, 3 to 4, 3 to 5, 3 to 6, 3 to 7, 3 to 8, 3 to 9, 3 to 10, 3 to 11, 3 to 12, 3 to 13, 3 to 14, 4 to 5, 4 to 6, 4 to 7, 4 to 8, 4 to 9, 4 to 10, 4 to 11, 4 to 12, 4 to 13, 4 to 14, 5 to 6, 5 to 7, 5 to 8, 5 to 9, 5 to 10, 5 to 11, 5 to 12, 5 to 13, 5 to 14, 6 to 7, 6 to 8, 6 to 9, 6 to 10, 6 to 11, 6 to 12, 6 to 13, 6 to 14, 7 to 8, 7 to 9, 7 to 10, 7 to 11, 7 to 12, 7 to 13, 7 to 14, 8 to 9, 8 to 10, 8 to 11, 8 to 12, 8 to 13, 8 to 14, 9 to 10, 9 to 11, 9 to 12, 9 to 13, 9 to 14, 10 to 11, 10 to 12, 10 to 13, 10 to 14, 11 to 12, 11 to 13, 11 to 14, 12 to 13, 12 to 14, 13 to 14, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12).

[0136] In certain embodiments, the composition includes nanostructured terephthalic acid. Without being bound by theory, nanostructured terephthalic acid is different from other forms of terephthalic acid due to its unique nanostructured morphology (see the following discussion and examples).

[0137] In certain embodiments, the composition comprises a nanostructured organic compound. In certain embodiments, the composition consists of nanostructured terephthalic acid.

[0138] In certain embodiments, the composition is nanostructured and nanocrystalline. When the crystalline domain size of the composition is less than 100 nm (e.g., less than 95, less than 90, less than 85, less than 80, less than 75, less than 70, less than 65, less than 60, less than 55, less than 50, less than 45, less than 40, less than 35, less than 30, less than 25, less than 20, less than 15, less than 10, less than 5, less than 4, less than 3, less than 2, less than 1) nm. In certain embodiments, the organic compound is in a nanocrystalline phase.

[0139] In certain embodiments, the composition consists of a metal oxide, a metal, a metal organic structure, a silicon-containing material, and / or a graphene-containing material embedded in a nanostructured organic compound (see the following discussion).

[0140] FIG. 1 illustrates one embodiment of the disclosed composition 1000. The composition 1000 consists of an at least partially crystallized organic compound (e.g., terephthalic acid) 1100 and a crystalline metal oxide (e.g., tin oxide (SnO2) 1200) dispersed in the organic compound 1100. In certain embodiments, the composition 1000 is a nanostructure and / or a nanocrystalline phase.

[0141] Typically, the organic compound (e.g., nanostructured organic compound, organic compound 1100) has the chemical formula C x O y H zIt has. In certain embodiments, x is from 2 to 12 (e.g., 2 - 3, 2 - 4, 2 - 5, 2 - 6, 2 - 7, 2 - 8, 2 - 9, 2 - 10, 2 - 11, 3 - 4, 3 - 5, 3 - 6, 3 - 7, 3 - 8, 3 - 9, 3 - 10, 3 - 11, 3 - 12, 4 - 5, 4 - 6, 4 - 7, 4 - 8, 4 - 9, 4 - 10, 4 - 11, 4 - 12, 5 - 6, 5 - 7, 5 - 8, 5 - 9, 5 - 10, 5 - 11, 5 - 12, 6 - 7, 6 - 8, 6 - 9, 6 - 10, 6 - 11, 6 - 12, 7 - 8, 7 - 9, 7 - 10, 7 - 11, 7 - 12, 8 - 9, 8 - 10, 8 - 11, 8 - 12, 9 - 10, 9 - 11, 9 - 12, 10 - 11, 10 - 12, 11 - 12, 11 - 12, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12). In certain embodiments, y is from 2 to 8 (e.g., 2 - 3, 2 - 4, 2 - 5, 2 - 6, 2 - 7, 3 - 4, 3 - 5, 3 - 6, 3 - 7, 3 - 8, 4 - 5, 4 - 6, 4 - 7, 4 - 8, 5 - 6, 5 - 7, 5 - 8, 6 - 7, 6 - 8, 7 - 8, 2, 3, 4, 5, 6, 7, 8). In certain embodiments, z is from 2 to 14 (e.g., 2 - 3, 2 - 4, 2 - 5, 2 - 6, 2 - 7, 2 - 8, 2 - 9, 2 - 10, 2 - 11, 2 - 12, 2 - 13, 3 - 4, 3 - 5, 3 - 6, 3 - 7, 3 - 8, 3 - 9, 3 - 10, 3 - 11, 3 - 12, 3 - 13, 3 - 14, 4 - 5, 4 - 6, 4 - 7, 4 - 8, 4 - 9, 4 - 10, 4 - 11, 4 - 12, 4 - 13, 4 - 14, 5 - 6, 5 - 7, 5 - 8, 5 - 9, 5 - 10, 5 - 11, 5 - 12, 5 - 13, 5 - 14, 6 - 7, 6 - 8, 6 - 9, 6 - 10, 6 - 11, 6 - 12, 6 - 13, 6 - 14, 7 - 8, 7 - 9, 7 - 10, 7 - 11, 7 - 12, 7 - 13, 7 - 14, 8 - 9, 8 - 10, 8 - 11, 8 - 12, 8 - 13, 8 - 14, 9 - 10, 9 - 11, 9 - 12, 9 - 13, 9 - 14, 10 - 11, 10 - 12, 10 - 13, 10 - 14, 11 - 12, 11 - 13, 11 - 14, 12 - 13, 12 - 14, 13 - 14, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12).

[0142] Examples of organic compounds (e.g., nanostructured organic compounds, organic compound 1100) include terephthalic acid, terephthalate, dimethyl terephthalate, bis(2-hydroxyethyl) terephthalate, ethylene glycol, phthalic acid, phenolic carboxylic acid, isophthalic acid, and the like.

[0143] In one embodiment, the organic compound 1100 is in a partially crystalline phase, i.e., includes both an amorphous phase and a crystalline phase. In one embodiment, the organic compound 1100 is in a crystalline phase and does not include an amorphous phase.

[0144] In one embodiment, the organic compound 1100 has a nanostructure. Typically, in such embodiments, the organic compound 1100 forms nanoclusters having a size of at least 1 (e.g., at least 2, at least 5, at least 10, at least 20, at least 50) nm and / or at most 200 (e.g., at most 150, at most 100) nm.

[0145] In one embodiment, a composition according to the present disclosure (e.g., a nanostructured organic compound, composition 1000) includes at least one (e.g., at least two, at least three, at least four, at least five) individual organic compounds (see Examples 17 and 18). In one embodiment, at least a portion (e.g., all) of the sole organic compound is partially crystalline. In one embodiment, at least a portion (e.g., all) of the different organic compounds is crystalline. In one embodiment, at least a portion (e.g., all) of the different organic compounds is nanostructured.

[0146] In one embodiment, the composition 1000 includes at least 5 wt.% (e.g., at least 10, at least 15, at least 20, at least 25, at least 30, at least 35, at least 40, at least 45, at least 50) and / or at most 99 wt.% (e.g., at most 95, at most 90, at most 85, at most 80, at most 75, at most 70, at most 65, at most 60, at most 55, at most 50) of an organic compound (e.g., terephthalic acid) 1100.

[0147] Examples of the crystalline metal oxide 1200 include tin oxides (e.g., Sn(IV) oxide (SnO2), Sn(II) oxide (SnO)), zinc oxides (e.g., zinc oxide (ZnO), zinc peroxide (ZnO2)), calcium oxide, lithium oxide, potassium oxide, lead oxide, iron oxide, molybdenum oxide, cobalt oxide, chromium oxide, niobium oxide, manganese oxide, etc. In one embodiment, the crystalline metal oxide 1200 includes semiconductor metals such as germanium oxide and silicon oxide. In one embodiment, the crystalline metal oxide 1200 includes Sn, Fe, Mo, Co, Cr, Nb, Mn, Zn, Ge, and / or Si.

[0148] In one embodiment, the composition 1000 is at least 1 (e.g., at least 5, at least 10, at least 15, at least 20, at least 25, at least 30, at least 35, at least 40, at least 45, at least 50) wt% and / or at most 95 wt.% (e.g., at most 90, at most 85, at most 80, at most 75, at most 70, at most 65, at most 60, at most 55, at most 50) of the crystalline metal oxide (e.g., SnO2) 1200.

[0149] In one embodiment, the crystalline metal oxide 1200 forms nanoparticles. In such an embodiment, the size of the crystalline metal oxide 1200 nm is at least 1 nm (e.g., at least 2, at least 3, at least 4, at least 5) and / or at most 100 nm (e.g., at most 50, at most 20, at most 10, at most 5).

[0150] In one embodiment, the amount of the crystalline metal oxide 1200 in the internal region (inside the body) of the composition 1000 is greater than the amount of the crystalline metal oxide 1200 of the material 1000 on the surface. In such an embodiment, the amount (i.e., the main amount) of the crystalline metal oxide 1200 in the internal region of the composition 1000 is at least 1 wt% (e.g., at least 5, at least 10, at least 15, at least 20, at least 25, at least 30, at least 35, at least 40, at least 45, at least 50), and / or at least 95 wt% (e.g., at least 90, at most 85, at most 80, at most 75, at most 70, at most 60, at most 50). 80, at most 75, at most 70, at most 60, at most 50), and / or the amount of the crystalline metal oxide 1200 on the surface of the composition 1000 is at least 0.1 wt% (e.g., at least 0.5, at least 1, at least 2, at least 5, at least 10, at least 15, at least 20) and / or at most 80 wt% (e.g., at most 70, at most 60, at most 50). Without being bound by theory, the crystalline metal oxide (e.g., SnO2) 1200 particles are covered by a layer of the organic compound (e.g., terephthalic acid) 1100, and as a result, the crystalline metal oxide 1200 particles are doped with the native organic compound 1100, and thus, more of the crystalline metal oxide 1200 is present natively with respect to the surface of the composition 1000.

[0151] In one embodiment, the compositions of the present disclosure (e.g., compositions containing nanostructured organic compounds, Composition 1000) are at least 1 (e.g., at least 2, at least 3, at least 4, at least 5, at least 6, at least 7, at least 8, at least 9, at least 10, at least 15, at least 20, at least 25, at least 30, at least 35, at least 40, at least 45, at least 50, at least 55, at least 60, at least 65, at least 70, at least 75, at least 80, at least 85, at least 90, at least 95) nm and / or at most 100 (e.g., at most 95, at most 90, at most 85, at most 80, at most 75, at most 70, at most 65, at most 60, at most 55, at most 50, at most 45, at most 40, at most 35, at most 30, at most 25, at most 20, at most 15, at most 10, at most 9, at most 8, at most 7, at most 6, at most 5, at most 4, at most 3, at most 2) nm.

[0152] The size of the compositions of the present disclosure (e.g., compositions containing nanostructured organic compounds, Composition 1000) ranges from 1 (e.g., at least 10, at least 20, at least 50, at least 100, at least 150) nm and / or at most 200 (e.g., at most 100, at most 50, at most 20, at most 10) nm.

[0153] The compositions of the present disclosure (e.g., compositions containing nanostructured organic compounds, Composition 1000) can be formed with a size of at least 0.01 (e.g., at least 0.1, at least 1, at least 5, at least 10, at least 50, at least 100) μm and / or at most 100 (e.g., at most 50, at most 10, at most 5, at most 1) μm. In certain embodiments, the particles include particles having a size range of at least 1 (e.g., at least 10, at least 20, at least 50, at least 100, at least 150) nm and / or at most 200 (e.g., at most 100, at most 50, at most 20, at most 10) nm. In certain embodiments, the particle diameter is 1 (e.g., at least 5, at least 10, at least 50, at least 100, at least 200, at least 500) nm and / or at most 1000 (e.g., at most 500, at most 200, at most 100, at most 50, at most 10, at most 5) nm of the sheet-like particles.

[0154] In certain embodiments, the compositions of the present disclosure (e.g., compositions containing nanostructured organic compounds, Composition 1000) have a specific surface area in the range of at least 10 (e.g., at least 15, at least 17, at least 20) square meters per gram (m 2 g -1 ) and / or at most 50 (e.g., at most 45, at most 40, at most 35, at most 30, at most 25, at most 21, at most 20) m 2 g -1 . The measurement of the specific surface area is described in detail in Example 8.

[0155] In certain embodiments, the disclosed compositions (e.g., compositions containing nanostructured organic compounds, Composition 1000) have a bulk electrical conductivity in the range of at least 5 (e.g., at least 10, at least 20, at least 50, at least 100, at least 150, at least 200, at least 250, at least 300, at least 350, at least 40, at least 500) S m -1 at a pressure of 6.3 MPa. And / or at most 5000 S m -1(For example, up to 4000, up to 3000, up to 2000, up to 1500, up to 1000, up to 900, up to 800, up to 700, up to 600, up to 500). The measurement of the bulk electrical conductivity will be described in detail in Example 10 below. Without being restricted by theoretical values, the relatively high electrical conductivity of Composition 1000 is due to the presence of crystalline metal oxide (e.g., SnO2) 1200 particles. For example, although crystalline metal oxide (e.g., SnO2) 1200 is a semiconductor, it exhibits metallic conductivity for various reasons such as the presence of oxygen vacancies.

[0156] Figure 2 shows an example of Composition 2000 of the present disclosure. In addition to the components of Composition 1000 in Figure 1, Composition 2000 includes a silicon-containing substance 2300 and a graphene nanosheet 2400 dispersed in an organic compound 1100. Without being bound by theory, the silicon-containing substance 2300 is embedded in the organic compound 1100.

[0157] In one example, the nanostructured organic compound (e.g., nanostructured terephthalic acid) includes a silicon-containing substance dispersed in the nanostructured organic compound and a graphene nanosheet.

[0158] In one example, the composition according to the present disclosure (e.g., nanostructured organic compound, Composition 2000) includes at least 0.1 (e.g., at least 0.5, at least 1, at least 5, at least 10) wt.% and / or at most 95 (e.g., at most 90, at most 85) wt.% of the silicon-containing substance 2300. In one example, the silicon-containing substance 2300 is monomeric silicon. In one example, the silicon-containing substance 2300 is silicon nanoparticles. In one example, the silicon-containing substance 2300 has a size in the range of at least 1 (e.g., at least 2, at least 3, at least 4, at least 5) nm and / or at most 1000 (e.g., at most 500, at most 200, at most 100, at most 50, at most 20, at most 10, at most 5) nm.

[0159] In certain embodiments, the compositions according to the present disclosure (e.g., nanostructured organic compounds, Composition 2000) include at least 0.1 (e.g., at least 0.5, at least 1, at least 5, at least 10) wt.% and / or at most 50 (e.g., at most 45, at most 40) wt.% of graphene nanosheets 2400. In certain embodiments, the graphene nanosheets 2400 consist of sheets having a thickness of at least 1 (e.g., at least 2, at least 5, at least 10, at least 20, at least 50, at least 100) nm and / or at most 5 (e.g., at most 4, at most 3, at most 2, at most 1) μm. In certain embodiments, the graphene nanosheets 2400 have at least 1 layer (e.g., at least 2 layers, at least 3 layers, at least 4 layers, at least 5 layers) and / or at most 100 layers (e.g., at most 90 layers, at most 80 layers, at most 70 layers, at most 60 layers, at most 50 layers, at most 40 layers, at most 30 layers, at most 20 layers, at most 10 layers). In certain embodiments, the graphene nanosheets 2400 have a carbon purity of at least 90% (e.g., at least 91, at least 92, at least 93, at least 94, at least 95). In certain embodiments, the graphene nanosheets 2400 include functional groups (e.g., hydroxyl groups, carbonyl groups, carboxyl groups, and / or amino groups) on their surfaces.

[0160] In certain embodiments, the graphene nanosheets 2400 cover at least a portion of the crystalline metal oxides 1200 and / or the silicon-containing materials 2300.

[0161] FIG. 2 shows an example. In certain embodiments, Composition 2000 includes a silicon-containing material 2300 in addition to the organic compound 1100 and the crystalline metal oxide 1200, but does not include graphene nanosheets 2400. Further, in certain embodiments, Composition 2000 includes graphene nanosheets 2400 in addition to the organic compound 1100 and the crystalline metal oxide 1200, but does not include a silicon-containing material 2300.

[0162] The disclosed composition can include an organic compound and a metal-organic structure embedded in the organic compound. In certain embodiments, the organic compound is partially crystalline. In certain embodiments, the organic compound is crystalline. In certain embodiments, the organic compound is nanostructured. In certain embodiments, the metal-organic structure is at least partially crystalline. In certain embodiments, the metal-organic structure is crystalline. In certain embodiments, the metal-organic structure has a nanostructure. In certain embodiments, the metal-organic structure is a nanocrystal.

[0163] In certain embodiments, the compositions of the present disclosure (e.g., nanostructured organic compounds, Composition 1000, Composition 2000) can include a metal-organic structure embedded in an organic compound. In certain embodiments, the metal-organic structure consists of the organic compound and the metal.

[0164] In certain embodiments, the chemical formula of the metal-organic structure is MC x H y O z `nH2O, where M is a metal and n ranges from 0 to 5. In certain embodiments, n is 0, 1, 2, or 3.5. In certain embodiments, the metal-organic structure has the chemical formula MC x H y O z ·3.5H2O. In certain embodiments, the metal-organic structure molecules have the general formula MC x H y O z having.

[0165] In one embodiment, x is from 2 to 12 (e.g., 2 to 3, 2 to 4, 2 to 5, 2 to 6, 2 to 7, 2 to 8, 2 to 9, 2 to 10, 2 to 11, 3 to 4, 3 to 5, 3 to 6, 3 to 7, 3 to 8, 3 to 9, 3 to 10, 3 to 11, 3 to 12, 4 to 5, 4 to 6, 4 to 7, 4 to 8, 4 to 9, 4 to 10, 4 to 11, 4 to 12, 5 to 6, 5 to 7, 5 to 8, 5 to 9, 5 to 10, 5 to 11, 5 to 12, 6 to 7, 6 to 8, 6 to 9, 6 to 10, 6 to 11, 6 to 12, 7 to 8, 7 to 9, 7 to 10, 7 to 11, 7 to 12, 8 to 9, 8 to 10, 8 to 11, 8 to 12, 9 to 10, 9 to 11, 9 to 12, 10 to 11, 10 to 12, 11 to 12, 11 to 12, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12). In one embodiment, y is from 2 to 8 (e.g., 2 to 3, 2 to 4, 2 to 5, 2 to 6, 2 to 7, 3 to 4, 3 to 5, 3 to 6, 3 to 7, 3 to 8, 4 to 5, 4 to 6, 4 to 7, 4 to 8, 5 to 6, 5 to 7, 5 to 8, 6 to 7, 6 to 8, 7 to 8, 2, 3, 4, 5, 6, 7, 8). In one embodiment, z is from 2 to 14 (e.g., 2 to 3, 2 to 4, 2 to 5, 2 to 6, 2 to 7, 2 to 8, 2 to 9, 2 to 10, 2 to 11, 2 to 12, 2 to 13, 3 to 4, 3 to 5, 3 to 6, 3 to 7, 3 to 8, 3 to 9, 3 to 10, 3 to 11, 3 to 12, 3 to 13, 3 to 14, 4 to 5, 4 to 6, 4 to 7, 4 to 8, 4 to 9, 4 to 10, 4 to 11, 4 to 12, 4 to 13, 4 to 14, 5 to 6, 5 to 7, 5 to 8, 5 to 9, 5 to 10, 5 to 11, 5 to 12, 5 to 13, 5 to 14, 6 to 7, 6 to 8, 6 to 9, 6 to 10, 6 to 11, 6 to 12, 6 to 13, 6 to 14, 7 to 8, 7 to 9, 7 to 10, 7 to 11, 7 to 12, 7 to 13, 7 to 14, 8 to 9, 8 to 10, 8 to 11, 8 to 12, 8 to 13, 8 to 14, 9 to 10, 9 to 11, 9 to 12, 9 to 13, 9 to 14, 10 to 11, 10 to 12, 10 to 13, 10 to 14, 11 to 12, 11 to 13, 11 to 14, 12 to 13, 12 to 14, 13 to 14, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12).

[0166] The metal includes Zn, Fe, Cu, Al, Zr, Cr, Co, Li, Na, K. In one embodiment, the particle size of the generated composition is at least 0.5 (e.g., at least 1, at least 5, at least 10, at least 15, at least 20, at least 30, at least 40, at least 50, at least 60, at least 70, at least 80, at least 90, at least 100, at least 150, at least 200, at least 250, at least 300, at least 350, at least 400, at least 450, at least 500, at least 550) μm and / or at most 600 (e.g., at most 550, at most 500, at most 450, at most 400, at most 350, at most 300, at most 250, at most 200, at most 150, at most 100, at most 90, at most 80, at most 70, at most 60, at most 50, at most 40, at most 30, at most 20, at most 15, at most 10, at most 5, at most 1) μm. In one embodiment, the particle size range includes sheet-like particles having a minimum of 10 (e.g., at least 20, at least 50, at least 100, at least 500, at least 1000, at least 5000) nm and / or at most 10000 (e.g., at most 5000, at most 1000, at most 500, at most 20) nm. In one embodiment, the sheet-like particles have a thickness of at least 1 (e.g., at least 2, at least 3, at least 4, at least 5, at least 6, at least 7, at least 8, at least 9) nm and / or at most 10 (e.g., at most 9, at most 8, at most 7, at most 6, at most 5, at most 4, at most 3, at most 2) nm. In one embodiment, the sheet-like particle size includes at least 1 (e.g., at least 2, at least 3, at least 4, at least 5, at least 6, at least 7, at least 8, at least 9, at least 10, at least 15, at least 20, at least 25, at least 30, at least 35, at least 40, at least 45, at least 50, at least 55) nm and / or at most 60 (e.g., at most 55, at most 50, at most 45, at most 40, at most 35, at most 30, at most 25, at most 20, at most 15, at most 10, at most 9, at most 8, at most 7, at most 6, at most 5, at most 4, at most 3, at most 2) nm.In one embodiment, the particles are at least 1 (e.g., at least 2, at least 3, at least 4, at least 5, at least 6, at least 7, at least 8, at least 9, at least 10, at least 15, at least 20, at least 25, at least 30, at least 35, at least 40, at least 45, at least 50, at least 55) nm and / or at most 60 (e.g., at most 55, at most 50, at most 45, at most 40, at most 35, at most 30, at most 25, at most 20, at most 15, at most 10, at most 9, at most 8, at most 7, at most 6, at most 5, at most 4, at most 3, at most 2) nm. In one embodiment, the particle size range includes metal-organic framework crystals of at least 10 (e.g., at least 50, at least 100, at least 500, at least 1000, at least 5000) nm and / or at most 10000 (e.g., at most 5000, at most 1000, at most 500, at most 100, at most 50) nm.

[0167] In one embodiment, the crystalline domain size of the metal-organic framework is in the range of at least 30 (e.g., at least 35, at least 40, at least 45, at least 50, at least 55) nm and / or at most 60 (e.g., at least 55, at least 50, at least 45, at least 40, at least 35) nm.

[0168] In one embodiment, the disclosed compositions (e.g., nanostructured organic compounds, Composition 1000, Composition 2000) may contain a tin-containing component. Examples of tin-containing components include metallic tin, tin chloride, tin chloride hydroxide, tin hydroxide, tin chloride hydroxide, etc. In one embodiment, tin chloride hydroxide has the molecular formula Sn 21 Cl 16 (OH) 14 O6. Without being bound by theory, when hydrolyzing SnCl in the solvent contact step (see the following discussion), for example, by washing with distilled water, oxides, chlorides, and hydroxides may be formed as shown in the following reaction.

[0169] [Chemistry]

[0170] Since oxides, chlorides, and hydroxides have relatively low solubility in water, they remain in the organic compound (e.g., the nanostructure of terephthalic acid) even after washing and filtration.

[0171] In certain embodiments, at least a portion of the tin-containing component is crystalline. In certain embodiments, the tin-containing component is crystalline. In certain embodiments, the tin-containing component has a nanostructure. In certain embodiments, the tin-containing member has a size of at least 1 (e.g., at least 2, at least 3, at least 4, at least 5, at least 6, at least 7, at least 8, at least 9, at least 10, at least 15, at least 20, at least 25, at least 30, at least 35, at least 40, at least 45, at least 50, at least 55, at least 60, at least 65, at least 70, at least 75, at least 80, at least 85, at least 90, at least 95) nm and / or a maximum of 100 (e.g., maximum 95, maximum 90, maximum 85, maximum 80, maximum 75, maximum 70, maximum 65, maximum 60, maximum 55, maximum 50, maximum 45, maximum 40, maximum 35, maximum 30, maximum 25, maximum 20, maximum 15, maximum 10, maximum 9, maximum 8, maximum 7, maximum 6, maximum 5, maximum 4, maximum 3, maximum 2) nm.

[0172] In certain embodiments, the disclosed compositions (e.g., nanostructured organic compounds, Composition 1000, Composition 2000) can contain metals. Examples of metals include Sn, Zn, Fe, Cu, Ni, Cr, Al, Co, etc.

[0173] In certain embodiments, the disclosed compositions (e.g., compositions 1000 and 2000 of nanostructured organic compounds) have an absorbance of at least 1 (e.g., at least 1.1, at least 1.2, at least 1.3, at least 1.4, at least 1.5, at least 1.6, at least 1.7, at least 1.8, at least 1.9) a.u. at 242 nm at a concentration of 0.5 g / L and / or a maximum absorbance of 2 (e.g., maximum 1.9, maximum 1.8, maximum 1.7, maximum 1.6, maximum 1.5, maximum 1.4, maximum 1.3, maximum 1.2, maximum 1.1) a.u. In certain embodiments, the disclosed compositions (e.g., compositions 1000 and 2000 of nanostructured organic compounds) have an absorbance of at least 0.1 a.u. (e.g., at least 0.2, at least 0.3, at least 0.4, at least 0.5, at least 0.6, at least 0.7) and / or a maximum absorbance of 0.8 a.u. (e.g., maximum 0.7, maximum 0.6, maximum 0.5, maximum 0.4, maximum 0.3, maximum 0.2), and the absorbance is measured at 450 nm at a concentration of 0.5 g / L. In certain embodiments, the disclosed compositions (e.g., compositions 1000 and 2000 of nanostructured organic compounds) have an absorbance of at least 0.1 a.u. (e.g., at least 0.2, at least 0.3, at least 0.4, at least 0.5, at least 0.6, at least 0.7) and / or a maximum absorbance of 0.8 a.u. (e.g., maximum 0.7, maximum 0.6, maximum 0.5, maximum 0.4, maximum 0.3, maximum 0.2), and the absorbance is measured at 500 nm at a concentration of 0.5 g / L. In certain embodiments, the disclosed compositions (e.g., compositions 1000 and 2000 of nanostructured organic compounds) have an absorbance of at least 0.1 a.u. (e.g., at least 0.2, at least 0.3, at least 0.4, at least 0.5, at least 0.6, at least 0.7) and / or a maximum absorbance of 0.8 a.u. (e.g., maximum 0.7, maximum 0.6, maximum 0.5, maximum 0.4, maximum 0.3, maximum 0.2), and the absorbance is measured at 317 nm at a concentration of 0.5 g / L.

[0174] In certain embodiments, the disclosed composite (e.g., a composite comprising at least partially a crystalline organic compound metal oxide, molecular formula C x O y Hz A composite comprising a nanostructured organic compound composed of a plurality of molecules having; a composite in which an organic compound and a metal-organic framework are embedded; or a composite comprising an organic compound and a crystalline metal oxide) further comprises a transition metal disulfide. The group of this transition metal disulfide includes compounds having the empirical formula MX2, where M is a transition metal atom (e.g., Mo or W) and X is a chalcogen atom (e.g., S, Se, or Te). Without being bound by theory, in one embodiment, it has a molten salt (see the following discussion) that prevents oxidation at temperatures above 300°C at which the transition metal disulfide normally undergoes an oxidation reaction. In one embodiment, the transition metal disulfide is a two-dimensional transition metal disulfide. In one embodiment, the transition metal disulfide is embedded in the organic compound and / or metal oxide (if present), and without being bound by theory, it is thought to enhance the structural integrity and electrical conductivity of the composition. Without being bound by theory, for example, it is possible to increase the kinetic reaction rate of metal ions when inserting and extracting metal ions into and from an electrode comprising the composition. In one embodiment, the presence of one or more transition metal disulfides in the subject matter according to the present disclosure can increase the rate capability of the resulting electrodes for use in metal ion secondary batteries such as electrodes of lithium ion batteries, sodium ion batteries, and potassium ion batteries (see the following discussion).

[0175] Electrodes and energy storage devices As shown in the schematic diagram of FIG. 3, the composition 1000 can be used for manufacturing an electrode 3000 such as an anode. FIG. 3 shows an example. In one example, the electrode 3000 is composed of a composition including an organic compound embedded in an organic compound and a metal organic structure in addition to the composition 2000, the nanostructured organic compound, and / or the composition 1000. In one example, in addition to the composition 1000, the composition 2000, the nanostructured organic compound, and / or the composition composed of the organic compound and the organic compound embedded in the metal organic structure, the electrode 3000 includes a binder (e.g., polyvinylidene fluoride (PVDF), styrene butadiene rubber (SBR), carboxymethyl cellulose (CMC), polyacrylic acid (PAA), polyvinyl alcohol (PVA), polyglutamic acid (PGA), sodium alginate (SA), chitosan (CS), polyacrylonitrile (PAN), polyimide (PI), gum), a solvent (e.g., N-methyl-2-pyrrolidone (NMP), water), conductive carbon, copper foil, and / or graphene nanosheet. Similarly, correspondingly, the electrode 3000 can be composed of one or more additional compositions as appropriate.

[0176] Generally, the electrode 3000 can be used for an energy storage device such as a battery or a supercapacitor. As an example, FIG. 4 shows a single cell of a battery 4000 including the electrode 3000 as an anode, a cathode 4100, an electrolyte 4200, and a separator 4300 between the anode 3000 and the cathode 4100. The described battery 4000 system also includes an electric wire 4500 connecting the anode 3000 and the cathode 4100 and a load 4600. The battery 4000 includes various batteries. Application examples of the battery include a lithium ion battery, a sodium ion battery, a calcium ion battery, a potassium ion battery, and the like.

[0177] Without being constrained by theoretical values, a crystalline metal oxide (e.g., SnO2) 1200 can be used as the active material of the electrode 3000. Further, without being bound by theoretical values, the presence of an organic compound (e.g., terephthalic acid) 1100 is considered to reduce (e.g., prevent) the decomposition of the crystalline metal oxide (e.g., SnO2) 1200 with respect to the organic compound (e.g., terephthalic acid) 1100. The organic compound (e.g., terephthalic acid) 1100 supports the integrity of the electrode 3000, reduces (e.g., prevents) the deterioration of the crystalline metal oxide (e.g., SnO2) 1200, and / or can maintain good contact between the particles of the crystalline metal oxide (e.g., SnO2) 1200 and the integrity of the electrode. Without being bound by theoretical values, these properties are considered to result at least in part from hydrogen bond interactions between the crystalline metal oxide 1200 and the organic compound 1100 (e.g., hydrogen bond interactions between the oxygen of SnO2 and the hydrogen of terephthalic acid).

[0178] Without being constrained by theoretical values, the disclosed compositions (e.g., composition 1000 and / or composition 2000) can have desirable properties resulting from a uniform distribution of a crystalline metal oxide that provides a lower charge transfer resistance (e.g., SnO2) 1200 within the particles of an organic compound (e.g., terephthalic acid) 1100 matrix, such as when in the form of an electrode 3000.

[0179] In one embodiment, the electrode 3000 has a discharge capacity of at least 10 (for "Li-ion") (e.g., at least 20, at least 50, at least 100, at least 150, at least 200, at least 250, at least 300, at least 350, at least 400, at least 450, at least 500) milliampere-hours per gram (mAh g -1 ) and / or a specific capacity of up to 1500 mAh g -1 (e.g., 200 mA g -1After 500 cycles at a current density of, up to 1400, 1300, 1200, 1100, 1000, 950, 900, 850, 800, 750, 700, 650, 600, 550, 500 mAh g -1 ) It has. In certain embodiments, the electrode has a lithium ion discharge capacity of at least 100 (e.g., 200, at least 500) milliampere hours (mAh) per gram of crystalline metal oxide to a maximum of 1800 (e.g., maximum 1700, maximum 1600) mAh per gram of crystalline metal oxide after 500 cycles. The measurement of the lithium ion discharge capacity is described in Example 11.

[0180] In certain embodiments, electrode 3000 is at 100 mA g -1 After 10 cycles at a current density of, at least 300 (e.g., at least 400, at least 500, at least 600, at least 700, at least 800, at least 900, at least 1000) mAh g -1 and / or up to 1500 mAh g -1 (e.g., maximum 1400, maximum 1300, maximum 1200, maximum 1100, maximum 1000). In certain embodiments, electrode 3000 is at 500 mA g -1 After 30 cycles at a current density of, at least 200 (e.g., at least 300, at least 400, at least 500, at least 600, at least 700, at least 800, at least 900, at least 1000) mAh g -1 and / or up to 1500 mAh g -1 (e.g., maximum 1400, maximum 1300, maximum 1200, maximum 1000) specific capacity. In certain embodiments, electrode 3000 is at 1000 mA g -1 After 50 cycles at a current density of, at least 200 (e.g., at least 300, at least 400, at least 500, at least 600, at least 700, at least 800, at least 900, at least 1000) mAh g -1 and / or up to 1500 (e.g., maximum 1400, maximum 1300, maximum 1200, maximum 1000) mAh g-1 has a specific capacity. In certain embodiments, electrode 3000 has a specific capacity of at least 50 (e.g., at least 100, at least 200, at least 300, at least 400, at least 500, at least 600, at least 700, at least 800, at least 900, at least 1000) mAh g -1 after 60 cycles at a current density of 1100 mA g -1 and / or a maximum of 1300 (e.g., maximum 1200, maximum 1000) mAh g -1 In certain embodiments, the electrode has a specific capacity of at least 100 mAh g -1 (e.g., at least 200, at least 300, at least 400, at least 500, at least 600, at least 700, at least 800, at least 900, at least 1000, at least 1100, at least 1200, at least 1300, at least 1400, at least 1500, at least 1600, at least 1700) and / or at most 1800 mAh per gram (e.g., maximum 1700, maximum 1600, maximum 1500, maximum 1400, maximum 1300, maximum 1200, maximum 1100, maximum 1000, maximum 900, maximum 800, maximum 700, maximum 600, maximum 500, maximum 400, maximum 300, maximum 200) of lithium ion discharge capacity mAh g -1 In certain embodiments, the electrode has a Coulombic efficiency of at least 70 (e.g., at least 75, at least 80, at least 85, at least 90, at least 95) and / or a maximum of 120 (e.g., maximum 115, maximum 100, maximum 105, maximum 100) % after 500 cycles. Measurement of the Coulombic efficiency is described in Example 11 below.

[0181] Without being bound by theory, the lithium ion discharge ability of electrode 3000 is at least partially due to the relatively small average size of the crystalline metal oxide (e.g., SnO2) 1200 particles and the presence of the organic compound (e.g., terephthalic acid) 1100 that affects the performance of the electrode, as described above.

[0182] ​

[0183] Without being restricted by the theoretical value, the reactions occurring during the lithiation - delithiation cycle are as follows:

[0184]

Chemical formula

[0185] In one embodiment, a half - cell composed of the electrode 3000 and the electrolyte increases the electrolyte resistance by at least 1.0 (e.g., at least 1.5, at least 2.0, at least 2.5, at least 3.0, at least 4.0) Ω and / or at most 6.0 Ω (e.g., at most 5.5, at most 5.0, at most 4.5, at most 4.0, at most 3.5, at most 3.0) after 150 cycles. In one embodiment, a half - cell composed of the electrode 3000 and the electrolyte increases the resistance by at least 2.0 (e.g., at least 2.5, at least 3.0, at least 3.5, at least 4.0) Ω and / or at most 8.0 (e.g., at most 7.5, at most 7.0, at most 6.5, at most 6.0, at most 5.5, at most 5.0, at most 4.5, at most 4.0, at most 3.5, at most 3.0) Ω after 300 charge - discharge cycles. The measurement of the electrolyte resistance is described in Example 11 below.

[0186] In one embodiment, the electrode 3000 is at least 10 -11 (e.g., at least 2×10 -11 , at least 3×10 -11 , at least 4×10 -11 , at least 5×10 -11 -11 , at least 6×10 -11 , at least 7×10 -11 , at least 8×10 -11 , at least 9×10 -11 ) cm 2 s -1 and / or at most 9×10 -9 (e.g., after 150 cycles, at most 8 × 10 -9 , at most 7 × 10 -9 , at most 6 × 10 -9 , at most 5 × 10-9 , maximum 4 × 10 -9 , maximum 3 × 10 -9 , maximum 2 × 10 -9 , maximum 10 -9 ) cm 2 s -1 and has. In one embodiment, the electrode 3000 is at least 2×10 -11 cm 2 s -1 (e.g., at least 3×10 -11 , at least 4×10 -11 , at least 5×10 -11 , at least 6×10 -11 , at least 7×10 -11 , at least 8×10 -11 , at least 9×10 -11 , at least 10 -10 ) and / or maximum 10 -8 (e.g., after 300 cycles, maximum 9×10 -9 , maximum 8×10 -9 , maximum 7×10 -9 , maximum 6×10 -9 , maximum 5×10 -9 , maximum 4×10 -9 , maximum 3×10 -9 , maximum 2×10 -9 , maximum 10 -9 ) cm2s-1 lithium ion diffusion rate. The measurement of the lithium ion diffusion rate is described in Example 11 below.

[0187] Without being restricted by theoretical values, the improvement in the lithium ion diffusion rate of the electrode 3000 is attributed to the form of the composition 1000 and / or 2000 in which particles of the crystalline metal oxide (e.g., SnO2) 1200 are embedded in the organic compound (e.g., terephthalic acid) 1100. Since the organic compound (such as terephthalic acid) 1100 in the electrode 3000 can effectively form an ion transport channel, it can exhibit better ion electrical conductivity and healing ability. The organic compound (such as terephthalic acid) 1100 matrix can efficiently cope with the volume change caused by the lithiation / delithiation of the crystalline metal oxide (such as SnO2) 1200 during long-term cycling, which is promoted by the formation of hydrogen bonds between the two components and the promotion of the lithium ion diffusion rate.

[0188] Without being restricted by theoretical values, the lithium ion diffusion rate in the cycling electrode containing the composition 1000 and / or 2000 increases compared to the non-cycling electrode containing the composition 1000 and / or 2000. This is because, due to the volume change associated with cycling, the crystalline metal oxide (e.g., SnO2) is pulverized, the 1200 particles are converted to smaller particle sizes, and then the organic compound matrix 1100 rearranges the fine particles to form new hydrogen bonds between the fine crystalline metal oxide (e.g., SnO2) 1200 particles and the organic compound (e.g., terephthalic acid) 1100. These interactions and structural reconstructions lead to an increase in the surface area of the active material, a shortening of the lithium ion diffusion distance, and / or a promotion of electron and lithium ion Li+ transport at the active material / electrolyte interface.

[0189] In one embodiment, the sodium ions (referred to as "Na ions") at the electrode 3000 are at a voltage of at least 0.1 (e.g., at least 0.11, at least 0.12, at least 0.13, at least 0.14, at least 0.15, at least 0.16, at least 0.17, at least 0.18, at least 0.19, at least 0.2, at least 0.25, at least 0.3, at least 0.35, at least 0.4, at least 0.45, at least 0.5, at least 0.55, at least 0.6, at least 0.65, at least 0.7, at least 0.75, at least 0.8, at least 0.85) V and / or at most 0.9 (e.g., at most 0.85, at most 0.8, at most 0.75, at most 0.7, at most 0.65, at most 0.6, at most 0.55, at most 0.5, at most 0.45, at most 0.4, at most 0.35, at most 0.3, at most 0.25, at most 0.2, at most 0.15) V. The voltage of the sodium ions (referred to as "Na ions") extracted from the electrode 3000 is at a voltage of at least 0.3 (e.g., at least 0.4, at least 0.5, at least 0.6) V and / or at most 0.7 (e.g., at most 0.6, at most 0.5, at most 0.4) V.

[0190] In one embodiment, the binder consists of PI. Without being bound by theory, the electrode including the disclosed composition with SiNP, PI, and heat treatment of the electrode may provide an electrode with improved electrochemical performance. The heat treatment may consist of heating to a temperature of at least 150 (e.g., at least 200, at least 250) °C and / or up to 400 °C (e.g., at most 350, at most 300, at most 250, at most 200) °C in an inert gas atmosphere containing H2. Without being bound by theory, the hydrogen bond between PI and oxygen on the SiNP surface can reduce (e.g., suppress) the disintegration of the electrode caused by the expansion and contraction of SiNP. Without being bound by theory, when a charge transfer composition structure is formed within the PI chain during the heat treatment process, the toughness of the electrode is improved. In one embodiment, the improved electrochemical performance includes the stabilization of the increased lithium ion specific capacity during the insertion and extraction of lithium ions over a number of cycles compared to certain other electrode materials.

[0191] In one embodiment, by heat-treating a disclosed electrode containing Si (e.g., Si nanoparticles, the Si-containing composition of the present disclosure) with PI as a binder (referred to as "Si@PI" in the text), a charge transfer composition (CTC) structure can be generated. Without being bound by theory, this CTC structure can improve the electrochemical lithium storage performance of the electrode by forming a dense structure with reduced charge transfer impedance. Similarly, the cycling performance of the silicon negative electrode can be significantly improved without being bound by theory. For example, in one embodiment, an electrode containing Si with PI heat-treated at 350°C as a binder (Si@PI-350) has a charge transfer impedance of 37.67 Ω and a reversible Li+ storage capacity of 2334 mAh g -1 after 30 cycles at a current density of 200 mA g -1 , while the pristine (non-heat-treated) Si@PI electrode shows a charge transfer impedance of 130.4 Ω and a relatively low Li+ storage capacity of 737 mAh g -1 . At a high current density of 2000 mA g -1 , the specific capacity of Si@PI-350 (1001 mAh g -1 ) is much higher than that of Si@PI (455 mAh g -1 ), indicating the high efficiency of the CTC structure formed during the heat treatment process. In one embodiment, the Si@PI electrode heat treatment step may significantly affect the lithium ion insertion / extraction cycling performance of SiNP.

[0192] In one embodiment, the electrode of the present disclosure includes silicon particles and a polymer binder containing an imide monomer. In one embodiment, the electrode of the present disclosure includes SiNP and PI. For example, such an electrode can be used as the anode of a metal ion battery such as a lithium ion battery, a sodium ion battery, or a potassium ion battery.

[0193] In one embodiment, the polymer (e.g., PI) contains imide groups (-CO-N-CO-) on its main molecular chain. In one embodiment, the PI material is a thermoplastic polymer. In one embodiment, the PI material is formed by polycondensation and imidization of 1-(4-aminophenyl)-1,3,3-trimethyl-2H-indene-5-amine (DAPI) and benzophenone-3,3',4,4'-tetracarboxylic dianhydride (BTDA).

[0194] In one embodiment, the Si particles have a particle size of at least 1 (e.g., at least 5, at least 10, at least 50, at least 100, at least 200, at least 400, at least 700, at least 1,000, at least 3,000, at least 5,000) nm and / or a maximum of 5,000 (e.g., maximum 3,000, maximum 1,000, maximum 700, maximum 400, maximum 200, maximum 100, maximum 50, maximum 10, maximum 5) nm. In one embodiment, the surface of the silicon particles is partially oxidized to SiO x(x = 0.1 to 2.0) is formed. In certain embodiments, the imide monomer-containing silicon particles and the polymer are mixed with other additives such as conductive carbon. In certain embodiments, the imide monomer-containing silicon particles and the polymer are mixed with other additives such as conductive carbon and at least partially crystalline organic compounds (e.g., crystalline organic compounds). In certain embodiments, the partially crystallized organic compound is terephthalic acid. In certain embodiments, the Si particles are embedded in the crystalline organic compound. In certain embodiments, the composition is heat-treated at a target temperature for a certain period of time under an inert atmosphere. In certain embodiments, the target temperature is at least 140 (e.g., at least 15, at least 160, at least 180, at least 200, at least 230, at least 250, at least 280, at least 300, at least 318, at least 350, at least 400) °C and / or at most 400 (e.g., at most 350, at most 318, at most 300, at most 280, at most 250, at most 230, at most 200, at most 180, at most 160, at most 150) °C. In certain embodiments, the heating is carried out at the target temperature for at least 1 second (e.g., at least 5 seconds, at least 10 seconds, at least 10 minutes, at least 30 minutes, at least 1 hour, at least 5 hours) and / or at most 10 hours (e.g., at most 5 hours, at most 1 hour, at most 30 minutes, at most 10 minutes, at most 10 seconds, at most 5 seconds). In certain embodiments, the heating atmosphere contains hydrogen at a volume ratio of at least 0.1 vol.% and / or at most 100.0 vol.%. In certain embodiments, the heating atmosphere contains, in addition to hydrogen, argon, nitrogen and / or helium at a volume ratio of at least 0.1 vol.% and / or at most 99.9 vol.%.

[0195] Without being bound by theory, a hydrogen bond is formed between the polymer and the oxide present on the surface of the Si particles by the heat treatment process, so that the stability of metal ions during the embedding and peeling cycles can be improved compared to certain other types of electrodes. Further, without being bound by theory, a charge transfer composition is formed within the polymer chain by the heat treatment process, so that the stability of metal ions during the embedding and peeling cycles can be improved compared to certain other types of electrodes. Thus, the improvement in the cycle stability of the electrode is related to the cross-linking of the PI polymer.

[0196] In one embodiment, in the presence of a nanostructured organic compound, PI reacts with the nanostructured organic compound during the heat treatment process to form crystals of an organic compound having an XRD pattern different from the XRD patterns of PI and the nanostructured organic compound. In one embodiment, the reaction occurs at a temperature in the range of 250 to 400 °C.

[0197] Without being bound by theory, in one embodiment, the interaction between the polymer and the at least partially crystalline organic compound improves the toughness of the electrode compared to other specific electrodes.

[0198] In certain embodiments, the electrode is formed from a composition comprising Si particles and a binder. In certain embodiments, the Si particles are doped with the compositions of the present disclosure (e.g., Composition 2000). In certain embodiments, the binder is a polymer comprising an imide monomer, and the binder is at least 0.1 (e.g., at least 1, at least 5, at least 10, at least 15, at least 20, at least 25, at least 305) wt.% and / or at most 40 (e.g., at most 35, at most 30, at most 25, at most 20, at most 15, at most 10, at most 5) wt.%. In certain embodiments, the silicon particles are at least 5 (e.g., at least 10, at least 15, at least 20, at least 25, at least 30, at least 35, at least 40, at least 45, at least 50, at least 55, at least 60, at least 65, at least 70, at least 75, at least 80), at least 85, at least 90) wt.% and / or at most 95 (e.g., at most 90, at most 85, at most 80, at most 75, at most 70, at most 65, at most 60, at most 55, at most 50, at most 45, at most 40, at most 35, at most 30, at most 25, at most 20, at most 15, at most 10) wt.%. In certain embodiments, the organic compound (e.g., terephthalic acid) occupies at least 0.1 (e.g., at least 1, at least 5, at least 10, at least 15, at least 20, at least 25, at least 30, at least 35, at least 40, at least 45, at least 50, at least 55, at least 60, at least 65, at least 70, at least 75, at least 80, at least 85, at least 90) wt.% and / or at most 95 (e.g., at most 90, at most 85, at most 80, at most 75, at most 70, at most 65, at most 60, at most 55, at most 50, at most 45, at most 40, at most 35, at most 30, at most 25, at most 20, at most 15, at most 10, at most 5, at most 1) wt.%.

[0199] In one embodiment, PI is insoluble in polar solvents such as NMP after heat treatment. In one embodiment, the electrode is manufactured by mixing a material including silicon particles, PI, and conductive carbon, and the composition is heat-treated at a temperature of at least 200 (e.g., at least 250, at least 300, at least 350) °C and / or a maximum of 400 (e.g., maximum 350, maximum 300, maximum 250) °C. In one embodiment, the electrode has a lithium storage specific capacity of at least 700 (e.g., maximum 1000, maximum 1500, maximum 2000, maximum 2500) mAh g -1 and / or a maximum of 3000 (e.g., maximum 2500, maximum 2000, maximum 1500, maximum 1000) mAh g -1 after 100 lithium ion insertion / removal cycles. In one embodiment, the lithium ion diffusion impedance (Rs) of the electrode obtained after heat treatment is greater than the lithium ion diffusion impedance (Rs) of the initial electrode before heat treatment. In one embodiment, the composition is heat-treated at 350 °C, and the charge transfer resistance of the electrode decreases from 130.4 Ω to 37.7 Ω. In one embodiment, the electrode is fabricated by heat-treating a composition including a metal ion active material such as Si particles and a polymer containing an imide monomer. This mixture is heat-treated at a maximum temperature of 150 - 400 °C for 1 second - 10 hours. The electrode made of the composition has a metal ion diffusion impedance (Rs) of at least 10 (e.g., at least 20, at least 30, at least 40, at least 50) Ω and / or a maximum of 60 (e.g., at most 50, at most 40, at most 30, at most 20) Ω.

[0200] Purification of water The compositions of the present disclosure (e.g., nanostructured organic compounds, Composition 1000, or Composition 2000) can be used for water purification (see, e.g., Example 19). In certain embodiments, the composition consists of SnO and / or Sn. SnO and / or Sn may be crystalline. The compositions of the present disclosure can reduce the concentration of contaminants (e.g., organic contaminants) in an aqueous solution. Without being bound by theory, contaminants can be adsorbed onto the surface of the composition. Further, without being bound by theory, this composition can photocatalytically decompose contaminants under visible light exposure (e.g., excitation at 400 - 650 nm). Examples of contaminant uses include azo dyes such as methyl yellow, methyl orange, methyl red, congo red, alizarin yellow, methyl blue, methylene blue, rhodamine, and hydrocarbons such as compounds based on xanthate esters such as potassium ethylxanthate, sodium isopropylxanthate, sodium isobutylxanthate, sodium butylxanthate, butylxanthate ester. Hydrocarbons include compositions of recovered petroleum or natural gas, compositions of crude oil, alkanes (e.g., methane, ethane, propane, butane, pentane, hexane), olefins, alkynes, halogen compounds, and / or aromatic compounds (e.g., benzene, toluene, xylene).

[0201] In certain embodiments, the composition of the present disclosure has an adsorption capacity of at least 5 (e.g., at least 10, at least 15, at least 20, at least 25) mg / g and / or at most 30 (e.g., at most 25, at most 20, at most 15, at most 10) mg / g as defined by formula (12) of Example 19. In certain embodiments, the composition of the present disclosure has an organic compound removal performance of at least 1 (e.g., at least 2, at least 3, at least 4, at least 5, at least 6, at least 7, at least 8, at least 9) mg / (g×h) and / or at most 10 (e.g., up to 9, up to 8, up to 7, up to 6, up to 5, up to 4, up to 3, up to 2 under light conditions) mg / (g×h) as defined by formula (13) of Example 19.

[0202] Depolymerization of polymers and synthesis of compounds Figure 5a shows a synthesis scheme of nanostructured terephthalic acid. A mixture containing the reactants polyethylene terephthalate (PET) and tin dichloride (SnCl2) forms nanostructured terephthalic acid by heating. The polymer (PET) produces terephthalic acid by depolymerization. In some examples, the reactants further contain salts, and heating the mixture results in a molten salt.

[0203] Figure 5b shows a reaction scheme for synthesizing compound 1000 containing terephthalic acid and SnO2. A mixture containing the reactants polyethylene terephthalate (PET), tin dichloride (SnCl2), and KCl-LiCl forms compound 1000 (terephthalic acid + SnO2) by heating. The polymer (PET) produces terephthalic acid by depolymerization and forms organic compound 1100 in compound 1000.

[0204] Without being limited to theory, PET depolymerizes in the presence of SnCl2 to produce terephthalic acid, and SnCl2 functions as a depolymerizing agent. In the solid phase, SnCl2 exists as a polymer chain. When melted, SnCl2 maintains its polymeric structure (SnCl2)n, where Sn 2+ is three-coordinate. Further increasing the temperature can reduce the degree of polymerization and lower the viscosity. Without being bound by theory, PET and SnCl2 melt at about 250 °C to form two types of polymer melts. When the temperature is raised to 350 °C, free Sn 2+ and Cl - are generated, which may break the chains of PET to produce terephthalic acid.

[0205] Typically, the reactants contain a polymer (e.g., PET) and a depolymerizing agent (e.g., SnCl2SnCl2). In some embodiments, the reactants further contain a molten salt (e.g., LiCl-KCl). Without being limited by theory, heating the mixture causes the salt to become a molten salt.

[0206] In some embodiments, the depolymerization reaction of the polymer can produce a first organic compound (e.g., terephthalic acid) and a second organic compound having a lower boiling point than the first organic compound (e.g., ethylene glycol). Without wishing to be bound by theory, incorporating the first organic compound into the products of the present disclosure (e.g., nanostructured organic compounds, the organic compound 1100 in composites 1000 or 2000) allows the second organic compound to be separated relatively easily, for example, by evaporating the second organic compound. In some examples, the second organic compound completes evaporation during its formation process. In such examples, the second organic compound can solidify and be collected as a liquid.

[0207] Without being bound by theory, water associated with the depolymerizing agent (e.g., SnCl2ZnCl2SnCl2), ZnCl2) plays a role in the depolymerization of the polymer, as shown in reaction (3):

[0208]

Chemical formula

[0209] The hydrated SnCl2 melts at about 258 °C, and the SnCl2 retains at least a portion (e.g., most) of the water content (see Example 22). In certain embodiments, at least a portion (e.g., all) of the depolymerizing agent is hydrated. In certain embodiments, at least a portion (e.g., all) of the depolymerizing agent remains hydrated until the depolymerizing agent serves to depolymerize the polymer. In certain embodiments, the depolymerizing agent contains at least 0.1 (e.g., at least 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.5, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19) wt.% of water and / or up to 20 (e.g., up to 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1.5, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2) wt.% of water. Without being bound by theory, the hydration of reactants such as the depolymerizing agent may be due to moisture in the atmosphere. In certain embodiments, at least a portion (e.g., all) of the depolymerizing agent absorbs moisture from the environment such as the ambient atmosphere.

[0210] In certain embodiments, the reactants contain at least 1 (e.g., at least 2, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50) wt.% and / or up to 95 (e.g., up to 90, 85, 80, 75, 70, 65, 60, 55, 50) wt.% of the depolymerizing agent.

[0211] In some embodiments, the depolymerizing agent is an inorganic salt. Examples of applications of inorganic salts include tin(II) chloride (SnCl2), zinc chloride (ZnCl2), calcium chloride (CaCl2), lead chloride (PbCl2), sodium chloride (NaCl), potassium chloride (KCl), iron(II) chloride (FeCl2).

[0212] In certain examples, the inorganic salt contains the metal of the crystalline metal oxide 1200. In certain examples, the inorganic salt undergoes an oxidation reaction during heating. For example, SnCl2 oxidizes upon reaction with oxygen in the atmosphere to produce SnO2.

[0213] Unless limited by theory, the phase transition reaction of nanoparticles from SnCl2 to SnO2 is as follows.

[0214]

Chemical formula

[0215] O2 is consumed to form SnO2, and Cl2 gas product is released.

[0216] Generally, the melting point of the depolymerizer is close to that of the polymer material. In one embodiment, the difference in melting point between the polymer and the depolymerizer is less than 100 °C (e.g., less than 95 °C, less than 90 °C, less than 85 °C, less than 80 °C, less than 75 °C, less than 70 °C, less than 65 °C, less than 60 °C, less than 55 °C, less than 50 °C).

[0217] Generally, the polymer (e.g., PET) decomposes to form an organic compound (e.g., terephthalic acid). In some embodiments, the reactant comprises at least 1 (e.g., at least 2, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50) wt.% and / or up to 99 (e.g., up to 95, 90, at least 85, 80, 75, 70, 65, 60, 55, 50) wt.% of the polymer. Examples of the polymer include polyethylene terephthalate (PET), polyacrylonitrile, poly(6-aminocaproic acid), poly(caprolactam), nylon, polyetheretherketone (PEEK), polyethylene (PE), polyhexamethylene adipate, polymethyl methacrylate, polyoxyethylene, poly(4-methylpentene), polypropylene, polystyrene, poly(trans-1,4-butadiene), polyvinyl alcohol, polyvinyl chloride (PVC), polyvinyl fluoride, polyvinylidene chloride, and polyvinylidene fluoride, etc. In some embodiments, the polymer is derived from waste plastics.

[0218] Without being bound by theory, it is believed that organic compounds (e.g., terephthalic acid) can sublime and / or decompose at relatively high temperatures (e.g., 500 °C or higher, 600 °C or higher, 700 °C or higher, 800 °C or higher). Without being subject to theoretical constraints, the phase transition reaction is as follows.

[0219]

Chemical formula

[0220] In some embodiments, the salt includes a chloride molten salt (e.g., LiCl and / or KCl). In some embodiments, the salt includes at least 40 (e.g., at least 45, 50, 55, 60) wt.% and / or up to 80 (e.g., 75, up to 70, 65, 60, 55, 50) wt.% of LiCl. In some embodiments, the molten salt includes at least 20 (e.g., at least 25, 30, 35, 40, 45, 50) wt.% and / or up to 70 (e.g., up to 65, 60, 55, 50, 45, 40) wt.% of KCl. In some embodiments, the salt includes at least 40 (e.g., at least 45, 50, 55, 60) wt.% and / or up to 80 (e.g., 75, up to 70, 65, 60, 55, 50) wt.% of LiCl and / or at least 20 (e.g., at least 25, 30, 35, 40, 45, 50) wt.% and / or up to 70 (e.g., up to 65, 60, 55, 50, 45, 40) wt.% of KCl. In some embodiments, the salt includes a eutectic molten mixture of LiCl-KCl. In some embodiments, the melting point of the salt is at least 250 °C (e.g., at least 300 °C, 320 °C) and / or up to 700 °C (e.g., up to 650 °C, 600 °C, 550 °C, 500 °C).

[0221] Unconstrained by theory, the salt (e.g., a eutectic mixture of KCl - LiCl) provides an ionic environment that enhances the formation of partially crystalline (e.g., crystallized) organic compound (e.g., terephthalic acid) monomers, plays an important role in the formation of porosity within the resulting composite, and also supports the phase transition of a depolymerizing agent to a crystalline metal oxide (e.g., SnO2 particles from molten SnCl2), resulting in the formation of at least partially crystalline organic compound (e.g., terephthalic acid) in which the crystalline metal oxide (e.g., SnO2) is distributed.

[0222] Generally, the reactions of the present disclosure (e.g., the reactions shown in FIGS. 5a - c) can be carried out in any suitable atmosphere. In some embodiments, the reactions of the present disclosure (e.g., the reactions of FIGS. 5a - c) are carried out in an oxygen-containing atmosphere (e.g., air). In some embodiments, the atmosphere contains at least 1% (e.g., at least 2%, 5%, 10%, 15%, 20%, 21%) vol. % of oxygen. In some embodiments, the reactions of the present disclosure (e.g., the reactions shown in FIGS. 5a - c) are carried out under an inert atmosphere (e.g., argon atmosphere, nitrogen atmosphere) and / or hydrogen gas (as described in Examples 14, 17, and 18 below). In some embodiments, the disclosed reactions (e.g., the reactions of FIGS. 5a - c) are carried out in an atmosphere containing argon gas and at least 1 (e.g., at least 2, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95) vol. % and / or up to 99 (e.g., up to 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 4, 2) vol. % of hydrogen.

[0223] Without being limited by theory, by performing the reaction under an inert atmosphere and / or hydrogen gas, oxidation of SnCl2 to SnO2 by oxygen gas in the atmosphere is reduced (e.g., prevented), and a composite without SnO2, or a composite with less SnO2 compared to a reaction performed in the presence of oxygen, or an oxide with less oxygen content can be formed. In such embodiments, the composite may contain SnO and / or Sn in addition to, or instead of, SnO2. Without being bound by theory, by performing the reaction under an inert atmosphere and / or hydrogen gas, the organic compound products formed by depolymerization of the polymer can be changed. Generally, the mixture is heated above the melting point of the polymer, the melting point of the salt, the melting point of the depolymerizing agent, and / or below the carbonization temperature of the polymer and the decomposition temperature of the organic compound. In certain embodiments, the mixture is heated to at least 250 °C (e.g., at least 300 °C, 310 °C, 350 °C, 400 °C, 450 °C, 500 °C) and / or up to 600 °C (e.g., up to 550 °C, 500 °C, 450 °C, 400 °C, 350 °C, 310 °C, 300 °C). In some embodiments, the mixture is maintained at the maximum temperature for at least 0.01 (e.g., at least 0.017, 0.1, 1, 5, 10, 20, 30, 40, 50, 60) minutes and / or up to 120 (e.g., up to 110, 100, 90, 80, 70, 60, 50, 40, 30, 20, 10) minutes. In some embodiments, the mixture is maintained at the maximum temperature for 1 second. In some embodiments, the mixture is heated at a rate of at least 1 (e.g., at least 2, 3, 4, 5, 10, 15, 20, 30, 40, 50) °C min -1 and / or up to 100 (e.g., up to 90, 80, 70, 60, 50, 40, 30, 20, 10, 5) °C min -1 .

[0224] In some embodiments, the reaction process of the present disclosure (e.g., the reaction shown in FIGS. (5a - c)) includes cooling the mixture after heating the mixture. In some embodiments, both the cooling step and the heating step are performed in the same atmosphere (see the above discussion).

[0225] Generally, the reactions of the present disclosure (e.g., the reactions shown in FIGS. 5a - c) can be carried out at any suitable pressure. In certain embodiments, the reactions of the present disclosure (e.g., the reactions shown in FIGS. 5a - c) are carried out at at least 0.01 (e.g., at least 0.05, 0.1, 0.2, 0.25, 0.3, 0.4, 0.6, 0.7, 0.75, 0.8, 0.9, 1, 1.5, 2, 5, 10, 15, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 90, 100, 110, 120, 130, 140, 150, 160, 180, 190, 220, 210, 230, 250, 260, 270, 280, 290, 310, 320, 330, 350, 450, 550, 600, 650, 700, 750, 800, 950, 1000, 1150, 1250, 1300, 1450, 1500, 1650, 1750, 1850, 1950, 2000, 2500, 3500, 450, 550, 60, 650, 70, 750, 800, 1..., 85, 90, 95) atm and / or up to 100 (e.g., up to 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 2, 1, 0.9, 0.8, 0.75, 0.7, 0.6, 0.5, 0.4, 0.3, 0.25, 0.2, 0.1, 0.05) atm.

[0226] In certain examples, the reactions of the present disclosure (e.g., the reactions shown in FIGS. 5a - c) were carried out at atmospheric pressure. In some examples, the reactants and / or complexes are in contact with a solvent during synthesis. In some examples, the solvent is an aqueous solution (e.g., an alkaline aqueous solution, an acidic aqueous solution) and / or contains a polar organic liquid. In some examples, the polar organic liquid is an alcohol (e.g., methanol, ethanol, propanol, butanol).

[0227] In some embodiments, the pH of the solvent is at least 0 (e.g., at least 0.1, 1, 2, 3, 4, 5, 6) and / or at most 7 (e.g., at most 6, 5, 4, 3, 2, 1). In some embodiments, the solvent contains hydrochloric acid, sulfuric acid, nitric acid, and / or phosphoric acid. In some embodiments, the solvent contains at least 1 (e.g., at least 2, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90) volume (vol. %) and / or at most 98 (e.g., at most 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5) vol. % of an acid.

[0228] In some embodiments, the pH of the solvent is at least 7 (e.g., at least 8, 9, 10, 11, 12, 13), and / or at most 14 (e.g., at most 13, 12, 11, 10, 9, 8). In some embodiments, the solvent contains hydroxides (e.g., sodium hydroxide, potassium hydroxide). In some embodiments, the solvent contains at least 1 (e.g., at least 2, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90) vol. % and / or at most 98 (e.g., at most 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5) vol. % of an acid.

[0229] In certain embodiments, the complex of the present disclosure (e.g., nanostructured organic compound, complex 1000, complex 2000) contains a depolymerizing agent, and at least a part of the depolymerizing agent can be removed by contacting the complex with a solvent (e.g., acidic water, a leaching agent such as HCl, H2SO4, or HNO3). In certain embodiments, the complex of the present disclosure (e.g., nanostructured organic compound, complex 1000, complex 2000) contains a depolymerizing agent, and at least a part of the depolymerizing agent can be hydrolyzed by contacting the complex with a solvent.

[0230] In some embodiments, the depolymerizing agent is SnCl2, and the hydrolysis of SnCl2 forms a second material having tin, chlorine, hydrogen, and oxygen, where the second material is dispersed in the composite organic compound. In some embodiments, the second material is tin oxide, chloride, hydroxide. In some embodiments, the stoichiometry of the second material is Sn 21 C l16 (OH) 14 O6. In some embodiments, the second material at least partially crystallizes (e.g., crystallizes).

[0231] In some embodiments, contacting the composite with a solvent (e.g., a leaching agent such as acidic water, hydrochloric acid, sulfuric acid, nitric acid) removes the Sn-containing material (e.g., SnO2, SnO, Sn, SnCl2) from the composite. In some embodiments, a composite containing Si, SnO2, and terephthalic acid (e.g., Example 15) can be contacted with a solvent (e.g., sulfuric acid, hydrochloric acid) to remove SnO2. Without theoretical limitation, the hydrolysis reaction (1) can be avoided (see the above discussion).

[0232] In embodiments using a solvent, the method may include separating the composite from the solvent and / or drying the composite. Separation methods are known in the art and include vacuum filtration, centrifugation, etc. In some embodiments, the composite is dried in air, an inert atmosphere, or under vacuum. In one embodiment, the composite is dried at a temperature of at least -196 (e.g., -100, -50, 0, 20) °C and / or a maximum of 100 (e.g., a maximum of 50, 20, 0) °C.

[0233] As described above, in some embodiments, the composite includes a silicon-containing material and / or a graphene nanosheet. In some embodiments, the mixture includes a precursor of the silicon-containing material, and the resulting composite contains the silicon-containing material. In some embodiments, the mixture includes a graphene nanosheet, and the resulting composite contains the graphene nanosheet. In some embodiments, the solvent includes a precursor of the silicon-containing material, and the resulting composite includes the silicon-containing material. In some embodiments, the solvent includes a graphene nanosheet, and the resulting composite includes the graphene nanosheet.

[0234] In certain embodiments, the reactant includes at least 0.1 (e.g., at least 0.2, 0.5, 1, 2, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50) wt.% and / or at most 98 (e.g., at most 95, 90, 85, 80, 75, 70, 65, 60, 55, 50) wt.% of a silicon-containing precursor. Examples of the precursor of the silicon-containing material include elemental silicon, Ca2Si, Ca5Si3, CaSi, Ca3Si4, CaSi2, Mg2Si, etc. In certain embodiments, the silicon-containing material precursor includes nanoparticles. In certain embodiments, the particle size of the silicon-containing material precursor is at least 1 (e.g., at least 2, 3, 4, 5) nm and / or at most 1000 (e.g., at most 500, 200, 100, 50, 20, 10, 5) nm.

[0235] In some embodiments, the precursor of the silicon-containing material is ball milled. In some embodiments, the precursor of the silicon-containing material is ball milled after being mixed with a solvent. In some embodiments, the solvent is n-hexane. Without being bound by theory, the solvent (e.g., n-hexane) is thought to prevent oxidation of the silicon particles during ball milling. Further, without being bound by theory, the solvent (e.g., n-hexane) can functionalize the silicon surface during mechanical ball milling, whereby the final composite is thought to obtain desired properties.

[0236] In certain embodiments, the reactant comprises at least 0.1 (e.g., at least 0.2, 0.5, 1, 2, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50) wt.% and / or at most 80 (e.g., at most 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5) wt.% of graphene nanosheets. In certain embodiments, the graphene nanosheets have a sheet size of at least 1 (e.g., at least 2, 5, 10, 20, 50, 100) nm and / or at most 5 (e.g., at most 4, 3, 2, 1) μm.

[0237] In certain embodiments, the graphene nanosheets have a graphene structure of at least 1 (e.g., at least 2, 3, 4, 5) layers and / or at most 100 (e.g., at most 90, 80, 70, 60, 50, 40, 30, 20, 10) layers. In certain examples, the carbon purity of the graphene nanosheets is at least 90% (e.g., at least 91%, 92%, 93%, 94%, 95%). In certain examples, the surface of the graphene nanosheets contains functional groups (e.g., hydroxyl groups, carbonyl groups, carboxyl groups and / or amino groups).

[0238] In some embodiments, the graphene nanosheets are produced by cathodic electrochemical exfoliation of a graphite electrode. In some embodiments, the cathodic electrochemical exfoliation is performed in a molten salt (e.g., lithium chloride and / or sodium chloride). In some embodiments, the cathodic electrochemical exfoliation is performed at a temperature of at least 500 (e.g., at least 600, 700, 800) °C and / or at most 900 (e.g., at most 800, 700, 600) °C.

[0239] In certain embodiments, the graphene nanosheet can be introduced into the composite of the present disclosure by forming a suspension using the composite and the graphene nanosheet and subjecting the suspension to ultrasonic treatment to form a product containing the composite and the graphene nanosheet. In certain embodiments, the suspension contains an acid. In certain embodiments, the product contains at least 50 (e.g., at least 55, 60, 65, 70, 75, 80, 85, 90, 95, 99, 99.5) wt.% and / or up to 99.9 (e.g., up to 99.5, 99, 90, 85, 80, 75, 70, 65, 60, 55) wt.% of the composite. In certain examples, the product contains at least 0.1 (e.g., at least 0.2, 0.5, 1, 2, 5, 10, 15, 20, 25, 30, 35, 40, 45) wt.% and / or up to 50 (e.g., up to 45, 40, 35, 30, 25, 20, 15, 10, 5, 2, 1) wt.% of the graphene nanosheet.

[0240] Figure 5c shows a reaction scheme for synthesizing the composite of the present disclosure containing a metal-organic framework (see the above discussion). A mixture containing polyethylene terephthalate (PET) and ZnCl2 as reactants is heated to depolymerize PET to form terephthalic acid (C8H6O4). Terephthalic acid (C8H6O4) and ZnCl2 form zinc terephthalate (ZnC8H4O4) and HCl. HCl can be removed from zinc terephthalate (ZnC8H4O4). In the reaction shown in Figure 5c, the formed zinc terephthalate (ZnC8H4O4) is a zinc-based metal-organic framework. Zinc terephthalate (ZnC8H4O4) is embedded in an organic compound (see the above discussion). In some embodiments, zinc terephthalate is hydrated. In some embodiments, the molecular formula of zinc terephthalate is Zn C8H4O4·nH2O, where n ranges from 0 to 5. In some embodiments, n is 0, 1, 2 or 3.5.

[0241] In some embodiments, zinc hydroxide chloride is used as the depolymerizing agent. Without being bound by theory, zinc hydroxide chloride can decompose upon heating to form ZnCl2.

[0242] In certain embodiments, the composite of the present disclosure has a metal-organic framework containing water of hydration, and by heating the composite to a second temperature, at least a portion of the water of hydration is removed from the metal-organic framework. In certain embodiments, the metal-organic framework has a first crystal structure prior to heating to the second temperature and has a second crystal structure different from the first crystal structure after heating to the second temperature (see Example 32). In certain embodiments, the second temperature is at least 50 (e.g., at least 100, 150, 200, 250, 300, 350) °C and / or at most 400 (e.g., at most 350, 300, 250, 200, 150, 100) °C. In certain embodiments, the composite is held at the second temperature for at least 1 millisecond (e.g., at least 0.1 second, 1 second, 10 seconds, 1 minute, 10 minutes, 1 hour) and / or at most 10 hours (e.g., at most 1 hour, 10 minutes, 1 minute, 10 seconds, at most 1 second).

[0243] In some embodiments, at least a portion of the composite (e.g., nanostructured terephthalic acid, terephthalic acid + SnO2) can be removed by the reactions shown in FIGS. 5a and 5b, and an additional polymer (e.g., PET) can be added.

[0244] Further, in some embodiments, the method of the present disclosure includes preparing Na2TP (Na2C8H4O4), Li2TP (Li2C8H4O4), K2TP (K2C8H4O4), or ZnTP (ZnC8H6O4) from the compounds of the present disclosure. For example, Na2TP can be produced by an acid-base reaction:

[0245]

Chemical formula

[0246] Without theoretical constraints, the compounds of the present disclosure cause the above reactions to occur at a faster kinetic rate compared to certain other organic compounds (e.g., commercial terephthalic acid that is non-nanostructured and / or nanocrystalline). The greater reaction rate of nanostructured organic compounds (e.g., terephthalic acid) may be related to their nanoscale size and nanocrystalline structure, which enables the material to react at a greater rate compared to certain other organic compounds (e.g., commercial terephthalic acid that is non-nanostructured and / or nanocrystalline). Rapid production of functional materials such as Na2TP can reduce manufacturing costs and facilitate applications such as the negative electrode of Na-ion batteries.

[0247] Without theoretical constraints, compounds such as Li2TP (Li2C8H4O4), K2TP (K2C8H4O4), ZnTP (Zn C8H6O4) can be produced by treating nanostructured organic compounds (e.g., nanostructured terephthalic acid) with appropriate solutions (e.g., LiOH, KOH, Zn(OH)2 solutions) for a relatively short reaction time. These compounds can be used respectively as electrodes for metal-ion batteries such as lithium-ion batteries, potassium-ion batteries, and zinc-ion batteries.

[0248] In some embodiments, reaction (15) operates for a maximum of 18 (e.g., maximum 16, 14, 12, 10, 8, 6, 5, 4, 3, 2, 1) hours.

[0249] Plastic separation A reaction scheme is shown in Figure 5d. By heating a mixture containing the reactants polyethylene terephthalate (PET), SnCl2, and HDPE, nanostructured terephthalic acid is formed. The polymer (PET) depolymerizes to form terephthalic acid, and HDPE does not depolymerize. HDPE can melt and sink to the bottom of the container, so HDPE can be separated from nanostructured terephthalic acid relatively easily. Without theoretical constraints, the crystal structure of HDPE is not affected by heating with a depolymerizing agent such as SnCl2 (see Example 34).

[0250] In the reaction shown in Fig. 5d, SnCl2 is used as the depolymerizing agent, but any of the depolymerizing agents of the present disclosure may be used. Similarly, in the reaction shown in Fig. 5d, nanostructured terephthalic acid is formed, but any composite of the present disclosure can be prepared using appropriate reagents and reaction conditions.

[0251] Without theoretical constraints, crystalline polymers are difficult to decompose due to their highly ordered structure and strong intermolecular forces, while semi-crystalline or amorphous polymers can be decomposed more efficiently due to their lower degree of structural order. Also, polymers with relatively high thermal stability (such as polyimides) may not be efficiently depolymerized.

[0252] Examples of depolymerizable polymers include, in addition to PET, polystyrene, polyvinyl chloride, nylon, polyurethane, phenolic resin, epoxy resin, etc.

[0253] Examples of non-depolymerizable (e.g., highly crystalline) polymers other than HDPE include polyethylene and polypropylene.

Examples

[0254] Examples Example 1 - Synthesis Polyethylene terephthalate (PET) was cut into pieces of about 10×5 mm with scissors. 20 g of PET pieces were placed in an alumina crucible with an inner diameter of about 5 mm and a height of about 100 mm. 10.10 g of SnCl2 (99.9%, Aladdin), 27.54 g of KCl (99.9%, Aladdin), and 23.06 g of LiCl (98%, Aladdin) were added to the crucible. LiCl-KCl binary eutectic molten salt (KCl: 54.8 wt. % - 45.2 wt. % LiCl), melting point is about 360 °C. The mixed molten salt was heated from room temperature to the target temperatures of 500 °C, 600 °C, 700 °C, 800 °C (denoted as PDN-500, -600, -700, -800 respectively) at a heating rate of 5 °C min -1 and held for 20 minutes. Then, the resistance furnace was heated at 5 °C min -1It was cooled to room temperature at a speed of . The sample was washed with deionized water, vacuum filtered, and dried at about 100 °C for 2 hours.

[0255] Example 2 - X-ray diffraction measurement The X-ray diffraction pattern of the sample was measured in the range of 10 - 90° (2θ) using a powder diffractometer (Panalytical X'pert Pro) with a Cu Kα radiation source (λ = 0.1542 nm). PET was heated at 300 °C and 350 °C for 20 minutes using SnCl2, and then the sample was washed and filtered.

[0256] Figures 6a - c show the X-ray diffraction patterns of PET heat-treated with LiCl-KCl (PET+(LiCl-KCl) / 500 °C), PET heat-treated with SnCl2 up to 350 °C (PET+SnCl2 / 350 °C), and PDN-500 (PET heat-treated with SnCl2 and LiCl-KCl as described in Example 1, target temperature 500 °C) (PET+(SnCl2-LiCL-KCl) / 500 °C), respectively. Figures 6d - f show the XRD patterns of commercial terephthalic acid (C8H6O4) and the standard diffraction patterns of SnO2 and terephthalic acid, respectively.

[0257] (PET+SnCl2SnCl2 / 350 °C)'s XRD pattern showed the formation of terephthalic acid. The XRD pattern of PET heat-treated with SnCl2 at 350 °C showed evidence of the formation of terephthalic acid.

[0258] For PDN-500 (PET + (SnCl2 - LiCL - KCl) / 500℃), diffraction peaks appeared at 2θ values of about 26.60°, 33.90°, 37.97°, 39.00°, 51.81°, 54.79°, 57.87°, 61.92°, 64.79°, 66.01°, 71.33°, 78.76°, 81.19°, 83.78°, 87.29°. These were indexed to the diffraction crystal planes of tetragonal SnO2 in the standard card (JCPDS≠01 - 070 - 4177), namely (110), (101), (200), (111), (211), (220), (002), (310), (112), (301), (202), (321), (400), (222), (330). In addition to SnO2, the presence of terephthalic acid (C8H6O4, JCPDS≠031 - 1916) with a different crystal structure was also confirmed in the diffraction pattern. The diffraction peaks observed at 2θ = 17.41°, 25.21°, 27.95° were attributed to the (110), (0 - 10), (200) diffraction crystal planes of terephthalic acid. For comparison, the XRD pattern of commercial terephthalic acid (C8H6O4, Shanghai Macklin, 400 - 623 - 8666, 99%) is also shown in Figure 6, confirming that terephthalic acid was produced by the molten salt method.

[0259] Figure 7 shows (a) the XRD pattern of PDN-500 (as described in Example 1, where PET was heat-treated with SnCl2 and LiCl - KCl to a target temperature of 500℃ (PET + (SnCl2 - LiCL - KCl) / 500℃)), and (b) commercially available micron-sized terephthalic acid (C8H6O4, Shanghai Macklin, 400 - 623 - 8666, 99%). Figure 7 further confirmed that terephthalic acid was formed by the method described in Example 1.

[0260] Example 3 - Influence of temperature Figure 8a shows the X-ray diffraction patterns of PDN-500, -600, -700, -800 (compounds synthesized from PET, SnCl2, and LiCl-KCl as described in Example 1, with target temperatures of 500, 600, 700, and 800 °C) in the range of 10 to 90°. Figure 8b shows the high-resolution XRD patterns of the samples in the scanning range of 14 to 30°. Figure 8c shows the high-resolution XRD patterns of the samples in the 2θ range of 60 to 68°. Figure 8a also includes the JCPDS standard card.

[0261] Figures 8a and 8b showed that X-ray peaks corresponding to SnO2 could be observed in all samples. However, for the samples prepared at target temperatures of 600, 700, and 800 °C, no peaks of terephthalic acid were present.

[0262] Figure 8a further showed the possibility of the existence of graphite carbon with a hexagonal crystal structure (JCPDS #00-025-0284). The (002) crystal plane of the carbon phase had a maximum peak at a 2θ value of 26.603°, which overlapped with the strongest peak of the SnO2 phase corresponding to the (110) crystal plane at 2θ = 26.597°.

[0263] Figure 8c showed the shoulders of the SnO2 diffraction peaks on the high-angle side due to the Kα1 / Kα2 XRD peak splitting caused by the copper-based X-ray tube used in the XRD instrument. This X-ray tube generates radiation with wavelengths of 0.1541 nm (Kα1 line) and 0.1544 nm (Kα2 line). The well-separated double peaks in Figure 8c are considered to be due to the growth of the SnO2 microcrystals into faceted crystals, resulting in a highly crystalline SnO2 phase formed at high temperatures.

[0264] The XRD data showed that PET in the binary eutectic melt LiCl-KCl and SnCl2 was converted to at least partially crystalline terephthalic acid and SnO2 at a temperature of 500 °C, and to carbon and SnO2 at temperatures of 600, 700, and 800 °C.

[0265] Example 4 - Raman property evaluation The Raman spectra were recorded using a Jobin-Yvon LabRam HR800 spectrometer equipped with a 488 nm laser source.

[0266] Figure 9 shows the Raman spectra of PDN-500, -600, -700, and -800 (compounds synthesized from PET, SnCl2, and LiCl-KCl at target temperatures of 500, 600, 700, and 800 °C as described in Example 1).

[0267] The Raman D spectral peaks in the range of 1337 - 1361 cm -1 and the G spectral peaks in the range of 1591 - 1594 cm -1 confirmed the presence of defective graphite. The G band observed in the spectrum is a Raman characteristic of sp2 carbon and corresponds to graphite defects. The intensity ratio of the D band to the G band (ID / IG) is an indicator of the degree of graphite defects. As shown in Figure 9, the ID / IG ratio increases with increasing temperature, indicating the occurrence and evolution of disorder in the product structure.

[0268] Example 5 - FTIR property evaluation Fourier transform infrared (FTIR) spectroscopic analysis was performed in the wavelength range of 400 - 4000 cm -1 using a VERTEX 70 spectrometer. Figure 10 shows the FTIR spectra of PDN-500 and -800 (compounds synthesized from PET, SnCl2, and LiCl-KCl at target temperatures of 500 °C and 800 °C as described in Example 1).

[0269] In the spectrum of PDN-800, there are SnO2 frame vibrations and Sn-O stretching at 636 cm -1 and 918 cm -1 respectively. The O-H stretching signals are present at 1201, 1603, and 3454 cm -1 and are due to adsorbed water molecules.

[0270] In the spectrum of PDN-500, there are Sn-O stretching at 551, 571, and 681 cm -1 and Sn-O stretching at 785 cm -1There is Sn-O-Sn vibration. The spectrum also includes a broad band corresponding to O-H stretching at 3468 cm -1 . The spectrum of PDN-500 also includes the FTIR characteristic peaks of terephthalic acid. The peak at 1697 cm -1 is due to the asymmetric stretching vibration of the carbonyl group (C=O), and the peaks at 1419 cm -1 , 1298 cm -1 , 947 cm -1 , and 735 cm -1 are due to C=C stretching, C-C stretching, O-H bending, and out-of-plane aromatic ring bending, respectively, and are commonly seen in the FTIR spectrum of terephthalic acid. The other FTIR peaks at 1022, 1846, 1971, 2557, 2673, 2891, 2907, 2993, and 3072 cm -1 also correspond to terephthalic acid. The observed FTIR peaks at 889 and 1128 cm -1 are classified as hydrogen bonds between the oxygen of SnO2 and the hydrogen of terephthalate (Sn-O-H). Table 1 summarizes the peaks observed in the FTIR spectrum.

[0271]

Table 1

[0272] The FTIR results showed the presence of terephthalic acid and SnO2 in the sample prepared at the target temperature of 500 °C.

[0273] Example 6 - Thermal analysis An SDT Q600 thermal analyzer equipped with an alumina crucible was used for differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA).

[0274] Generally, the thermogram of terephthalic acid has an endothermic peak at a temperature of 300 - 400 °C corresponding to the partial sublimation of the reactant, and then the remaining material decomposes without melting at high temperature. The decomposition process is an exothermic reaction, and a gas phase (benzene, biphenyl, toluene, hydrogen, carbon monoxide) and residual carbon are formed.

[0275] Approximately 8 mg of PDN-500 (a compound synthesized from PET, SnCl2, and LiCl-KCl at a target temperature of 500 °C as described in Example 1) was analyzed by DSC and TGA techniques at an air flow rate of 100 mL min -1 and the results are shown in Figure 11.

[0276] The TGA curve shows a 4.4% mass loss during heating from room temperature to 250 °C, which corresponds to the removal of surface hydroxyl groups and / or adsorbed water. The TGA curve shows a sharp 42.1% mass loss in the temperature range of 250 - 335 °C, and the DSC curve shows an endothermic peak at 328 °C. This endothermic peak corresponds to the partial sublimation of terephthalic acid. The TGA curve shows that further heating in the temperature range of 334 - 465 °C results in a 15.1% mass loss, and an exothermic peak appears at 461 °C in the DSC thermal imaging device. This peak is thought to be due to the decomposition of residual terephthalic acid into gaseous by-products and residual carbon. The residual carbon is oxidized at high temperature, corresponding to an 11.3% mass loss, as evidenced by the exothermic peak with a maximum value in the TGA curve in the temperature range of 462 - 573 °C. The remaining 27.1% of the mass is stable even after heating to 900 °C and corresponds to SnO2 in the sample. When the initial moisture content is 4.4%, the SnO2 content of the sample is estimated to be 28.3 wt. %. The results of the thermal analysis showed the presence of terephthalic acid and SnO2 in the sample.

[0277] Example 7 - Microstructure property evaluation The evaluation of the fine morphological characteristics was carried out using a scanning electron microscope (SEM, Ultra-Plus ZEISS) and a transmission electron microscope (TEM, Tecnai F20).

[0278] Figures 12a and 12b show SEM micrographs of PDN-500 (a compound synthesized from PET, SnCl2, and LiCl-KCl at a target temperature of 500 °C as described in Example 1). The micrographs show that this compound contains nanostructured clusters with a total size of less than 2 μm. Based on the XRD pattern of Example 2, these clusters mainly contain terephthalic acid and SnO2.

[0279] Figures 12c and 12d show SEM micrographs of PDN-800 (a compound synthesized from PET, SnCl2, and LiCl-KCl at a target temperature of 800 °C as described in Example 1). The PDN-800 sample has a different morphology from the PDN-500 sample and has large SnO2 faceted crystals with a size of 10 μm. A large number of SnO2 particles maintain a submicron size.

[0280] Figure 13a shows the EDS spectrum of PDN-500. The relatively uniform distribution of C, O, and Sn indicates the formation of a hybrid structure of SnO2 and terephthalic acid. EDS could not detect hydrogen.

[0281] Figure 13b shows the EDS spectrum of PDN-800. The SEM micrograph of Figure 12d and the EDS spectrum of Figure 13b show that SnO2 with a size of about 600 nm is present in the carbon substrate formed by the carbonization of terephthalic acid.

[0282] Figures 14a-d show the TEM analysis of PDN-500. Figure 14a shows SnO2 nanoparticles with a size of less than 5 nm. Figure 14b shows the fast Fourier transform (FFT) plot recorded in Figure 14a. In Figure 14b, rings corresponding to the tetragonal SnO2 crystal phase were observed. Figure 14c shows a high-magnification TEM micrograph of a nanocrystal with a length of 4.23 nm. The FFT recorded for this nanocrystal is shown in Figure 14d, indicating the presence of spots on the crystal plane with an interlayer spacing of 0.33 nm corresponding to the (110) SnO2 characteristics. Since terephthalic acid is unstable under a high-voltage electron beam, property evaluation by TEM is not possible.

[0283] Example 8 - Surface area property evaluation The specific surface area of the sample was measured using the Brunauer-Emmett-Teller (BET) method. The BET specific surface area of PDN-500 was 19.2 m 2 g -1 and was measured.

[0284] Example 9 - XPS property evaluation As described in Example 1 (PDN-500), at 500 °C, the products synthesized from PET and molten LiCl-KCl and from PET, SnCl2 and LiCl-KCl were measured by X-ray photoelectron spectroscopy (XPS, ESCALAB250, Thermo Fisher Scientific).

[0285] Figures 15a-c show the XPS spectra of the PET + LiCl-KCl sample. The spectral results in Figure 15a show the presence of C and O elements in the sample. As shown in Figure 15b, the C1s fine spectrum is dominated by a peak at 284.1 eV, indicating the presence of graphitic carbon with C-C bonds in the sample. The two broad peaks centered at 285.4 and 288.4 eV respectively show lattice defects caused by the random orientation of dangling bonds related to carbon atoms and defective carbon. The XPS test results are consistent with the XRD results of Example 2, further confirming that the PET + LiCl-KCl sample contains amorphous carbon. Curve fitting related to the O 1s peak of the sample XPS spectrum (Figure 15c) shows the presence of three types of surface oxygen bonds: C=O (530.3 eV), C-O, carbonyl (532.5 eV), C-OH, and O-C=O (533.4 eV). The amount of surface oxygen in the sample is 16.49 atomic percent (at%), which corresponds to the atomic percent of amorphous carbon.

[0286] Figures 15e - h show the XPS spectra of the PDN - 500 sample. Compared with Figure 15a, the spectrum in Figure 15e contains an Sn peak and a much lower carbon - oxygen ratio due to the formation of terephthalic acid and SnO₂. Figure 15f shows the C1s spectrum of PDN - 500, and its peak can be divided into four peaks at 284.2, 284.9, 286.3, and 288.5 eV corresponding to four different types of non - equivalent carbon atoms observed in terephthalic acid, corresponding to the excitation of phenyl carbon into the π* molecular orbital. Fitting the important O 1s fine spectrum shown in Figure 15g gives three peaks located at 530.6, 531.6, and 532.7 eV, corresponding to O - Sn, C - O - Sn, and chemisorbed oxygen, respectively. The peak at 532.7 eV is thought to be due to the excitation of the carbonyl bond of terephthalic acid. The Sn 3d spectrum of the sample is shown in Figure 15h, with peaks at 486.7 eV and 486.7 eV, corresponding to Sn 3d 5 / 2 and Sn 3d 3 / 2 indicating their presence. These peaks correspond to the characteristics of Sn4 + and indicate the formation of SnO₂, which is consistent with the XRD results of Example 2. The Sn content on the sample surface is 6.71 at%. Figure 15d shows the elemental analysis results of each sample.

[0287] Example 10 - Bulk electrical conductivity The room-temperature electrical conductivity was measured by a four-probe system (DCY-3F, Hunan Zhenhua Analysis Co., Ltd.) equipped with a bench-top unidirectional hydraulic press. A copper piston (D = 20.05 mm, H = 85.36 mm) was attached to a copper holder, and a 2.0 g sample was compressed in an acrylic tube (ID = 20.05 mm, H = 45.37 mm) at various pressure values. The measurements were performed using the hydraulic press at different pressure values (up to 6 MPa). Different current values in the range of 0.10 - 0.30 A were passed between the copper piston and the holder at different pressures, and the corresponding potentials were recorded at 20 °C using the four-probe DC method. The voltage resolution and current resolution of the control system display were 0.1 mV and 0.1 mA, respectively. The powder density can be calculated by applying various pressures to the sample. The resistance can be calculated from the slope of the V-I curve. The resistivity (ρ) of the sample is calculated as follows.

[0288] [Number]

[0289] Here, R is the resistance obtained from the slope of the voltage vs. current, S is the cross-sectional area of the sample particles (D = 2 cm), and h is the height of the sample. By taking the reciprocal of the resistivity of the sample, the electrical conductivity (σ) can be calculated as follows.

[0290] [Number]

[0291] To measure the electrical conductivity, PDN-500 and synthetic graphite powder (G) were thoroughly mixed at a mass ratio of 25:75, and the resulting mixture was used for the measurement of electrical conductivity. In the measurement, a 2.0 g sample (G or G + PDN-500 mixture) was fed into the cavity of the electrical conductivity measuring device, and the electrical conductivities of G (C G ) and the G + PDN-500 mixture (C G+PDN-500 ) were measured under different pressures. Due to the presence of graphite powder, PDN-500 (CPDN-500 )'s bulk electrical conductivity can be measured, and the results are shown in Figure 16.

[0292]

Number

[0293] As observed in Figure 16, the bulk electrical conductivity of PDN-500 increases as the applied pressure increases, from 74.8 S / m at a pressure of 2.7 MPa -1 to 447.3 S / m at 6.3 MPa. -1 The bulk density of PDN-500 was calculated by measuring the height (and thus the volume) of the compressed powder, taking into account that the cross-sectional area value and mass value of the compressed powder were constant during the uniaxial compression test. The bulk density of PDN-500 is 1.2 g / cm -3 , and the pressure is 6.3 MPa.

[0294] Example 11 - Lithium ion storage performance and electrochemical property evaluation A slurry suspension was prepared by applying NMP solvent using a prepared sample (80 wt.%) mixed with conductive carbon (C65, 10 wt.%) and PVDF binder (10 wt.%). The slurry suspension was coated on a copper foil and vacuum dried at 100 °C overnight. Next, the copper foil containing the active material was cut into disks with a diameter of 1.2 cm, and a CR2025 half-cell was assembled. In this electrochemical cell, the coated copper foil functioned as the working electrode, and the lithium sheet was used as both the reference electrode and the counter electrode. At the same time, a glass microfiber separator (Whatman, 1823025) was placed between the above electrodes to prevent physical contact between the positive and negative electrodes that could cause a short circuit, and at the same time promote the transport of ions in the cell. The cell assembly was carried out in a gas control glove box (Mikrouna) filled with high-purity argon gas with an O2 and H2O content of less than 0.1 ppm. The mass loading of the active material was 1.3 mg cm-2. Using the same mass loading, the constant current charge-discharge cycle performance was evaluated and also used for cyclic voltammetry testing. The electrolyte was LiPF6 (1 M) dissolved in a solvent of ethylene carbonate (EC), dimethyl carbonate (DMC), and ethyl methyl carbonate (EMC) (volume ratio 1:1:1). The button cell was fabricated using a sealing machine (YLJ-24T, MTI). After stabilizing the half-cell at room temperature for 10 hours, it was connected to a battery test system (Land CT2001A), and charge-discharge cycle tests were performed at a constant and variable current density in the voltage range of 0.01~3.0 V (vs Li + / Li). Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) tests were performed using a CHI-660E electrochemical workstation.

[0295] The lithium ion storage performance of PDN-500, PDN-600, PDN-700, and PDN-800 was continuously evaluated through constant current charge-discharge experiments and cyclic voltammetry tests in the voltage range of 0.01~3 V (vs Li+ / Li) for 500 cycles.

[0296] Figure 17a shows a current density of 200 mA g-1 Shows the discharge capacity values during the lithium-ion insertion / extraction cycles of PDN-500, -600, -700, and -800. PDN-500 shows a discharge capacity of 498 mAh g after 500 cycles -1 and PDN-600 (169 mAh g -1 , 428 cycles), PDN-700 (138 mAh g -1 , 360 cycles), and PDN-800 (125 mAh g -1 and 500 cycles) is much larger.

[0297] Figure 17b shows the Coulombic efficiency of the electrode made of PDN-500 at a current density of 200 mA g-1. The capacity values of the first discharge / charge cycle are 1183 / 545 mAh g -1 and the corresponding Coulombic efficiency was 46.1%. The capacity loss is mainly due to the irreversible decomposition of the electrolyte at the electrode surface, and a solid electrolyte interface (SEI) is formed. In the second discharge / charge cycle, a specific capacity value of 612 / 535 mAh g -1 and a high Coulombic efficiency of 87.5% were obtained, indicating that the interaction between the electrolyte and the electrode was limited during the second cycle. In the third discharge / charge, the specific capacity value was 572 / 524 mAh g -1 and the Coulombic efficiency was 91.5%. The Coulombic efficiency increased gradually with the cycles and reached 97.3% after 22 cycles and 99.2% after 78 cycles. The Coulombic efficiency fluctuated slightly, corresponding to a discharge / charge specific capacity value of 498 / 492 mAh g recorded after 500 cycles -1 and a Coulombic efficiency of 98.8%.

[0298] As shown in Figure 17g, the lithium-ion storage specific capacity of waste plastic-derived PDN-500 was measured at a current density of 100 - 2000 mA g -1 . At current densities of 100, 200, 500, 1000, and 2000 mA g -1 , the electrodes had specific capacities of 605.7 (10 cycles), 527.2 (20 cycles), 449.4 (30 cycles), 363.3 (40 cycles), and 260.5 (50 cycles) mAh g -1has a reversible specific capacity. Subsequently, the current density is restored to 100 mA g -1 and a reversible specific capacity of 628 mAh g -1 is recorded at 70 cycles. This result confirms that the PDN-500 electrode has ideal rate performance even at current densities up to 2000 mA g -1 .

[0299] As shown in Fig. 17c, the lithium-ion storage specific capacity of the PDN-500 electrode was measured at current densities of 100 - 5000 mA g -1 . After cycling at different current densities of 100, 200, 500, 1000, 2000 mA g -1 , the specific capacity of the electrode was 101.3 mAh g -1 at 5000 mA g -1 after 60 cycles. After returning the current density to 100 mA g -1 , the reversible specific capacity recorded at 70 cycles was 436.8 mAh g -1 , which was lower than the value of 600.7 mAh g -1 recorded at 10 cycles at the same current density. Even after 70 cycles and high current density of 5000 mA g -1 , the specific capacity was relatively high at 436.8 mAh g -1 , indicating that this material has relatively high lithium storage rate performance at current densities up to 5000 mA g -1 .

[0300] The cyclic voltammetry (CV) curves of PDN-500 recorded at different cycles are shown in Fig. 17d. The peaks observed in the CV curves represent the electrochemical reactions involved during the cycling of the cell. During the first cathodic scan, a peak at 1.7 V (vs Li / Li + ) was detected, but this peak did not appear in subsequent cycles. This peak is thought to be due to the SEI layer formed by the reduction reaction of the solvent (EC-DEC-DMC) on the electrode (Reaction (8)).

[0301]

Chemical formula

[0302] A stable SEI layer is required for the long cycle ability of the electrode. Furthermore, the cathodic peaks observed near 0.83 and 0.22 V are due to the formation of Li-Sn intermetallic compounds as shown in reaction (2b) by the phase transition from SnO2 to Sn, reaction (2a), and the alloying reaction of lithium and tin. During the first anodic cycle, the oxidation peak at about 0.54 V is considered to be due to the dealloying reaction of LixSn (2b). As shown in reaction (2a), the anodic peaks near 0.97 V and 1.24 V correspond to the reversible phase transition from Sn to SnO2.

[0303] As shown in Fig. 17d, the difference between the two cycles and the first cycle of the cathode is that there is no obvious cathodic peak near 1.7 V in the two cycles, which indicates that the stability of the SEI layer formed in the first cycle is relatively excellent. Furthermore, peaks related to the reduction and oxidation of tin compounds were observed in the CV patterns recorded in subsequent cycles, demonstrating the reversibility of the lithiation / delithiation of SnO2 nanocrystals embedded in terephthalic acid. In this case, terephthalic acid functions as a carrier to adjust and adapt to the volume change during electrochemical reactions (2a) and (2b), ensuring the cycle stability of the electrode.

[0304] Electrochemical impedance spectroscopy (EIS) measurements were performed using PDN-500 electrodes before cycling at a constant current density of 200 mA g -1 in 150 and 300 constant current discharge / charge cycles. Fig. 17e shows the electrochemical impedance spectrum recorded at an amplitude of 5 mV in the frequency range of 10 mHz to 100 kHz, together with the equivalent circuit of the Nyquist plot. The impedance spectrum becomes semi-circular in the high-frequency region and a sloping straight line in the low-frequency region. The electrochemical behavior of PDN-500 in the high-frequency region represents the migration resistance (R f ) of lithium ions through the SEI film, and the electrochemical behavior in the mid-frequency region represents the charge transfer resistance (R ct) is caused by. On the other hand, the low-frequency impedance of the electrode is the Warburg impedance (Z w ) caused by. The equivalent circuit shown in Fig. 17e also includes a constant phase element (CPE) to simulate the operation of a non-ideal capacitor. From the impedance spectrum, it can be observed that the diameter of the semi-circular arc obtained after 150 cycles is smaller than that of the new electrode, and a decrease in R ct during cycling was confirmed. The decrease in the cell resistance is considered to be due to the rearrangement of SnO2 nanoparticles in the terephthalic acid matrix during cycling.

[0305] Table 2 shows the electrochemical parameters derived from the EIS spectra of Figs. 17e and 17f. Based on the measured values, the lithium ion diffusion coefficient was calculated using Equation (9), and the results are shown in Table 2.

[0306]

Equation

[0307] Here, R is the gas constant (8.314 J mol-1 K-1), T is the temperature (298K), A is the surface area of the electrode (~1.13 cm2), n is the number of moles of electrons transferred (1 in the case of lithium), F is the Faraday constant (96,485 C mol -1 ), C is the lithium ion concentration obtained from the tap density of the active material, σ is the Warburg coefficient determined by the slope of the actual Z and ω -1 / 2, as shown in Fig. 17e.

[0308]

Table 2

[0309] As seen in Table 2, the electrolyte resistance (R e ) slightly increased from 3.47 Ω for the non-cycled electrode to 3.58 Ω after 150 cycles. After 300 cycles, the value significantly increased to 5.40 Ω. On the other hand, the charge transfer resistance (R ct) significantly decreased from 34.06 Ω to 22.83 Ω after 150 cycles. After 300 cycles, the value slightly increased to 25.54 Ω. Furthermore, the resistance (R f ) of the SEI film slightly increased from 6.41 Ω to 8.81 Ω after 150 cycles and further increased to 15.21 Ω after 300 cycles. The Warburg coefficient σ was determined from the slope of the actual impedance and the reciprocal of the square root of the angular frequency (Figure 17f). The value decreased from 600.30 s -1 / 2 for the non-cycled electrode to 283.44 s -1 / 2 and 108.83 s -1 / 2 for the 150-cycle and 300-cycle electrodes, respectively. As shown in Table 2, the smaller the value of the Warburg coefficient, the higher the value of the ion diffusion coefficient (D Li ). After 150 cycles, the lithium diffusion coefficient increased from the initial value of 2.80×10 -11 to 1.26×10 -10 cm 2 S -1 .

[0310] Figure 18 shows the extended cycle performance of the electrodes prepared from the sample (PET + (SnCl2-LiCl-KCl) / 500 °C) based on the mass of SnO2 (oxidized phase) of the electrodes measured at a current density of 200 mA g. The thermal analysis of PDN-500 in Example 6 confirmed that PDN-500 contains about 28.3 wt.% of SnO2. The capacity of the SnO2 component of the electrodes can be determined based on the specific capacity of terephthalic acid (14 mAh g -1 ) and the conductive carbon (184 mAh g -1 ) used in the manufacture of the electrodes. Therefore, the capacity of the electrodes was converted to 1657 mAh per 1 g of SnO2, which is almost the same as the theoretical capacity of SnO2, indicating that when SnO2 nanocrystals are incorporated into the terephthalic acid matrix, they have the maximum specific capacity even after 500 cycles.

[0311] Example 12 - Morphological property evaluation of electrodes after cycling The morphological characteristics of the electrodes after cycling in Example 11 were evaluated using the method of Example 7.

[0312] Figure 19a shows the SEM micrograph of the PDN-500 electrode after 200 Li insertion / extraction cycles. The absence of obvious cracks indicates the structural integrity of the material during the cycles.

[0313] Figure 19b shows the TEM micrograph of the PDN-500 electrode. Fine SnO2 particles are dispersed in the terephthalic acid matrix. Although holes are present, the material maintains its structural integrity. Since the SnO2 particles are completely covered by the matrix, the integrity of the electrode is improved.

[0314] Figures 19a and 19b confirm that the presence of terephthalic acid in PDN-500 can effectively prevent the decomposition of the electrode material during long-term cell cycling.

[0315] Example 13 - Pseudo-capacity performance To evaluate the contribution of pseudocapacitive lithium storage to the PDN-500 cycling performance, as described in Example 11, cyclic voltammetry measurements were performed on the cell at different scan rates of 0.2, 0.4, 0.6, 0.8, and 1.0 mV s -1 after 100 cycles, and the results are shown in Figure 20a. In the CV curve, two anodic peaks corresponding to the delithiation process of the electrode can be detected. As the scan rate increases from 0.2 mV s -1 to 1.0 mV s -1 , these peaks shift to higher potential values, indicating that ion diffusion is controlled. Furthermore, as the scan rate increases, the peak intensity increases. The current intensity (i) and the scan rate (v) are related by Equation (10) and its logarithmic form Equation (11).

[0316]

Equation

[0317] Here, a and b are dimensionless variables. In the case of a redox reaction controlled by a semi-infinite diffusion control process, the value of b is close to 0.5, and in the case of a capacitive process, the value is close to 1. By plotting the logarithmic peak current against the logarithmic scan rate (Figure 20b), the b values of peaks 1 and 2 in Figure 20a were calculated to be 0.65 and 0.75, respectively. Since 0.65 is close to 0.5, the reaction occurring at peak 1 is mainly controlled by a diffusion-based process, except for the limited contribution of the capacitive charge accumulation process. The b value of peak 2 is 0.75, corresponding to the capacitive contribution, but there is also a contribution from limited diffusion behavior. Based on the obtained results, Figure 20c shows the relative contributions of the capacitive process and the diffusion control process at different scan rates, indicating that the pseudo-capacitive contribution gradually increases with the increase in the scan rate. Figure 20d shows the capacitive contribution to the total current at 1.0 mV s -1 to the total current at 1.0 mV s.

[0318] Example 14 - Oxygen-free synthesis A PET plastic sheet (10 g, polymer material) was mixed with SnCl2 (5.05 g, depolymerizing agent), as well as KCl (13.79 g) and LiCl (11.53 g). The mixture was heated to 500 °C at a heating rate of 10 °C min -1 and held at the maximum temperature for 10 minutes, and then the temperature was lowered to room temperature. The heat treatment process was carried out in a tubular furnace under a gas flow of Ar (95%) and H2 (5%). Then, the obtained material was washed with deionized water, and the obtained suspension was vacuum filtered through a polymer filter paper to collect the filtration product, which was then dried at 100 °C for several hours.

[0319] The XRD pattern of the obtained product is shown in Figure 21, and the XRD pattern confirmed the presence of terephthalic acid (C6H8O6). During the heat treatment, phases such as SnO2, SnO, and Sn may be generated by the depolymerizing agent (SnCl2).

[0320] The TEM micrograph of the organic compound is shown in Figure 22. The TEM micrograph shows the nanostructural characteristics of the material, and particles with sizes of 18 nm and 3 nm were observed.

[0321] Example 15 - Silicon-containing materials Using a planetary ball mill, silicon particles (21.7 g) with a size of less than 500 μm, zirconia balls (diameter 15 mm, 650 g), and n - hexane were ball - milled at a rotational speed of 300 rpm for 50 hours.

[0322] The SEM micrograph of the silicon raw material is shown in Fig. 23. After ball - milling, the ball - milled Si was dried to remove n - hexane. Fig. 24 shows the SEM micrograph of the obtained silicon, and it was confirmed that the particle size of the ball - milled silicon was reduced to about 50 nm - 700 nm.

[0323] The obtained SiNP (2 g) was mixed with PET particles (4 g) and SnCl2 (4 g). The mixture was put into an alumina crucible, and then the crucible was placed in a muffle furnace. In an air atmosphere, it was heated to 500 °C at a heating rate of 10 °C / min and held at that temperature for 5 minutes. Then, the muffle furnace was cooled to room temperature, and the obtained material was washed with deionized water, vacuum - filtered, and dried.

[0324] The XRD pattern of the product is shown in Fig. 25, and the presence of terephthalic acid (C5H6O4) could be confirmed. Furthermore, Fig. 25 also showed the presence of Si and SnO2.

[0325] The SEM morphology of the obtained product is shown in Figs. 26a and 26b. In this micrograph, terephthalic acid polymerized SiNP (particle size about 50 - 700 nm) to form a Si / SnO2 / terephthalic acid nanostructured composite material with a particle size exceeding 10 μm.

[0326] Example 16 - Comparison between nanostructured terephthalic acid and commercially available terephthalic acid By Example 1, PET can be nanostructured using SnCl2 as a depolymerizing agent in the presence of LiCl-KCl. This nanostructured material was characterized as a mixture of nanosized terephthalic acid (C8H6O4) structures and SnO2 crystals. As a control for the Example 1 material, the properties of micron-sized terephthalic acid powder (Shanghai Macklin Biochemical Co., 400-623-8666, 99%) were evaluated. Figure 6d shows the XRD pattern of commercially available terephthalic acid, confirming that the commercially available terephthalic acid has a crystalline structure. Figures 27a-d show the SEM morphology of the material, confirming that the particle size ranges from 10 to 100 μm. Figures 28a and 28b show the powders of PDN-500 (PET+(SnCl2-LiCl-KCl) / 500 °C) and commercially available terephthalic acid, respectively. By heat-treating PET in a molten salt environment, terephthalic acid with the same crystalline structure as commercially available terephthalic acid is formed, but the morphology, microstructure, and color are significantly different from those of commercially available terephthalic acid. As shown in Figures 28a and 28b, respectively, PDN-500 is dark in color, while commercially available terephthalic acid is white. Considering the white color of the SnO2 nanoparticles, the dark appearance of this nanostructured material may be due to the black color of the terephthalic acid therein. Since commercially available terephthalic acid is a white crystalline solid, the black appearance of the terephthalic acid in PDN-500 may be related to the nanostructured nature of the material.

[0327] Example 17 - Heat treatment of PET, SnCl 2 , Li-KCL in Ar atmosphere 60 g of PET flakes were mixed with 184 g of SnCl2, 46.4 g of LiCl, and 54.9 g of KCl. The mixture was placed in an alumina crucible (H = 10 cm, D = 7.5 cm), the crucible was covered with an alumina lid, and placed in a stainless steel reactor equipped with a gas inlet / outlet. In an electric furnace, the reactor was heated to 445 °C at an average heating rate of 5 °C min -1 under an argon stream, and the material temperature in the crucible was measured with a thermocouple pre-mounted in the furnace. After reaching the maximum temperature, heating was stopped and the reactor was naturally cooled to room temperature.

[0328] Figures 29a to 29d show photographs of alumina crucibles filled with waste PET, crushed PET, and PET + SnCl2 before and after heat treatment at 445 °C respectively. The product obtained after heat treatment was observed to be much larger than the initial materials, indicating that the product had a porous structure. The porous product could be easily separated from the crucible. Since the apparent density of the salt was higher than that of the porous product, the salt mainly adhered to the bottom of the crucible during the molten salt process. As shown in Figures 29e - f, there was a solidified salt field at the bottom of the crucible. The results showed that SnCl2 - LiCl - KCl could be separated from the porous product based on its density, and the product could be easily collected without the need to wash the salt mixture.

[0329] Based on these experimental results, the depolymerization of PET occurred at the interface between the salt and PET, and the depolymerized organic compounds moved towards the upper part of the reactor. Therefore, at the end of the process, the organic compounds were mainly located at the upper part of the reactor, the molten salt was located at the bottom of the reactor, and the separation process was greatly simplified.

[0330] The material obtained at the upper part of the crucible was washed with water to remove the residual salt trapped in its porous structure, and the obtained material was dried at 80 °C for 2 hours. Figure 30 shows the XRD pattern of the obtained material. It was observed that this product contained various crystalline organic compounds such as phthalic acid (C8H6O4) with a monoclinic crystal structure (ICDD: 00 - 037 - 1919), terephthalic acid, and protocatechuic acid (C7H6O4; ICDD: 00 - 008 - 056) in addition to basic tin chloride. Basic tin chloride may be formed by the hydrolysis of residual SnCl2 during the washing step.

[0331] Example 18 - PET, SnCl in Ar+H 2 atmosphere 2 , Li-KCL heat treatment A mixture containing 13.79 g of KCl, 11.53 g of LiCl, 5.05 g of SnCl2, and 10 g of plastic pieces was placed in an alumina crucible, and the crucible was placed in a tubular furnace equipped with an alumina tube. Ar-5% H2 gas was flowed through the pipeline. The temperature was raised to 90 °C (for 8 hours), and then raised to 500 °C at a heating rate of 10 °C min -1 −1. The sample was held at 500 °C for 10 minutes and then cooled to room temperature. The heat treatment was carried out in an Ar-5%H2 atmosphere. The obtained product was washed with deionized water and then vacuum filtered using a polymer filter paper. The product was dried at 100 °C for 24 hours. As shown in Figure 31, the XRD pattern of the product was measured by Cu-Kα (λ = 0.1542 nm). In this spectrum, organic crystalline compounds such as isophthalic acid (C8H6O4, ICDD: 00-037-1920) and phthalic acid (C8H6O4, ICDD: 00-037-1919) with a monoclinic crystal structure can be identified. Furthermore, SnO (ICCD: 01-085-0712) and metallic Sn (ICCD: 00-004-0673) are also present.

[0332] Figures 32a - c show TEM micrographs of the product obtained by heating the mixture in Ar-5%H2 followed by washing and drying. Figure 32a shows a bright-field TEM micrograph of a crystalline organic compound containing particles composed of aggregates of nanoparticles with sizes in the range of 1 - 100 nm. Nanoparticles with sizes of 2, 12, and 68 nm can be observed in the micrograph. Figure 32b shows SnO nanoparticles with a size of 3.8 nm embedded in the organic compound. Figure 32c is the fast Fourier transform spectrum of the SnO nanoparticles, corresponding to the (101) crystal plane spots of SnO with a tetragonal crystal structure.

[0333] Example 19 - Purification of water The product of Example 18 contains a crystalline organic compound, SnO and Sn, and this product is used as an adsorbent / photocatalyst for removing organic dyes from an aqueous solution. The photocatalytic properties and adsorption properties of the product were tested at room temperature in a sealed metal box. 0.1 g of the product was added to 100 mL of a methyl orange (MO) or methylene blue (MB) solution (concentration 50 mg / L). The suspension was magnetically stirred for various times in the dark with an LED light source module having a fixed wavelength of 450 nm in the visible light region. The reaction temperature was maintained at 20 °C using a water-cooled jacket. 2 mL was extracted at specific intervals, filtered and transferred to a cuvette, and the property evaluation was carried out using an ultraviolet-visible spectrophotometer.

[0334] Based on the obtained absorption peaks, the concentration of the dye solution can be calculated by comparing the absorption spectrum with the standard curve. The value of the adsorption capacity can be calculated by Equation (12).

[0335]

Number

[0336] Here, qe is the adsorption capacity at equilibrium, m (g) is the mass of the adsorbent, and V is the volume of the dye solution. C0 and Ce are the initial concentration and equilibrium concentration of the dye solution, respectively. The value of the removal performance (by adsorption or photocatalytic decomposition) of the organic compound at a predetermined time (t) can be evaluated according to Equation (13).

[0337]

Number

[0338] Here, Ct is the dye concentration in the solution at a predetermined time (t). The dye removal performance of this product is shown in FIGS. 33a-b. As shown in the figure, the adsorption of the dye onto the adsorbent reached equilibrium after 30 minutes. The adsorption performance of this product for organic dyes is in the range of 12-21 mg g at room temperature -1 but is 25 mg g at a high temperature of 40 °C -1It may increase up to. In the case of MO, after 7 hours of LED irradiation (450 nm), the dye was completely removed from the solution. In the case of MB, this period is 20 hours. Contrary to theory, in this example, the SnO nanocrystals embedded in the organic compound are involved in the visible-light photocatalytic properties of this nanocomposite.

[0339] Example 20 - Electrochemical property evaluation The product of Example 18 was mixed with conductive carbon (C45) and a PAA-CMC (1:1, weight ratio) binder at a mass ratio of 7:1:1. The mixture was pulverized into a uniform slurry in deionized water, coated on a copper foil, and dried to form an electrode with a load of about 1.5 mg cm -2 The prepared electrode was assembled into a CR2025 half-cell using a lithium sheet as the reference electrode / counter electrode and LB-010 as the electrolyte. Figure 34 shows the lithium-ion storage performance of the electrode after 140 cycles at a current density of 100 mA g -1 and the reversible capacity is 707 mAh g -1 .

[0340] This result indicates that the product of Example 18 containing the crystalline organic compound, SnO, and Sn can be used as an anode such as in a lithium-ion battery. This result also shows that the organic compound can effectively affect the electrochemical properties of the metal oxide and maintain the lithium-ion storage capacity for at least 140 cycles. The organic compound here is presumed to be able to maintain the lithium-ion, sodium-ion, or potassium-ion storage capacity of the metal oxide or semimetal oxide during cell cycling.

[0341] Example 21 - Conversion of PET to nanostructured terephthalic acid using inorganic salts PET mineral water bottles were cut into fine chips, and 138.5 g of PET chips were placed in an alumina crucible. Next, 226.3 grams of anhydrous SnCl2 (Sigma, 208256, reagent purity 98%) were added to the crucible. The crucible was placed in a vertical furnace and partially covered with an alumina lid. The furnace was heated while recording the temperature inside the crucible using a thermocouple protected by alumina placed inside the crucible. A schematic diagram of the apparatus is shown in Fig. 35a. It was heated in air for 151 minutes up to a maximum temperature of 303 °C, and then the furnace was cooled to room temperature. After the heat treatment, the contents of the alumina crucible were washed with 700 ml of acidic water (HCl - 27%). This acidic water can dissolve the SnCl2 salt but does not cause hydrolysis (SnCl2 interacts with the aqueous solvent to form insoluble oxides). Next, the suspension was vacuum filtered, and the product was dried at 100 °C for 2 hours.

[0342] Fig. 35b shows the temperature - time curve of the mixture heated from room temperature to a maximum temperature of 303 °C over 151 minutes. The curve shows two inclined lines corresponding to the heating of the material from 0 minutes (26 °C) to 55 minutes (114 °C) and from 55 minutes to 95 minutes (257 °C). Thereafter, the curve shows a horizontal line from 95 minutes to 106 minutes (259 °C). Fig. 35c shows the isotherm at a higher time resolution. The average temperature of this part was calculated to be 258.6 °C. This horizontal part of temperature and time is usually observed during phase - change events such as melting. After that, from 106 minutes to 151 minutes, there is another inclined line with a much smaller slope than the first part, where the maximum temperature (303 °C) was recorded. After that, the power of the furnace was turned off to let the temperature drop to room temperature.

[0343] The phase transformations occurring during the heat treatment can be observed from the XRD patterns in Figs. 36a - d. Fig. 36a shows the XRD pattern of the plastic material chips, where the broad peak centered at 2θ ≈ 25.4° has irregular non - orthorhombic crystals (C 10An organic polymer material corresponding to the (100) reflection of polyethylene terephthalate (PET) with the formula (C8H8O4)n was heated to 260 °C and held overnight, then cooled to room temperature. Figure 36b shows the XRD pattern of the resulting heat-treated product, indicating the presence of an amorphous structure of crystalline PET (ICDD #00-049-2301). The strongest peak observed at 2θ ≈ 26.0 is related to the (100) reflection, and compared to the original PET, this reflection is shifted to a larger angle, confirming the crystallization process.

[0344] The XRD pattern of the nominal anhydrous SnCl2 used in this example is shown in Figure 36c. The raw material is mainly tin(II) chloride hydrate SnCl2·H2O with a monoclinic crystal structure (ICDD #01-077-0053), and it was also observed to contain orthorhombic tin(II) chloride SnCl2 (ICDD #01-072-0137). Quantitative analysis of the XRD pattern showed that the ratio of SnCl2·H2O is about 59 wt.% SnCl2 and SnCl2 is 41 wt.%, confirming that there is about 11 wt.% water of hydration in this sample. Water absorption by the sample may be caused by moisture in the atmosphere during sample processing. A sample obtained by heat-treating nominal anhydrous SnCl2 (including water of hydration) and PET up to a maximum temperature of 303 °C is shown in Figure 36d. This spectrum contains terephthalic acid C8H6O4 with a non-orthorhombic crystal structure (ICDD #00-022-1941).

[0345] Example 22 - Thermal phase change analysis 1.046 mg of PET and 38.401 mg of SnCl2 were mixed, and the mixture was placed in an alumina crucible, followed by measuring the DSC curve and TGA curve of the mixture at an air flow rate of 100 mL min -1 -1 and a heating rate of 10 °C min-1. The thermodynamic results of this mixture, PET, and SnCl2 measured separately under the same conditions are shown in Figures 37a - f.

[0346] Figure 37a shows the DSC curve of PET recorded at 50 - 350 °C. The endothermic peak observed at 251.3 °C is related to the melting of the material. After heating PET to 350 °C, no additional peaks are present. This is confirmed by the TGA results shown in Figure 37d, and the total mass losses at 250, 270, and 350 °C are 0.73%, 1.06%, and 1.47% respectively. The slight mass loss observed is related to the gradual evaporation of surface organic contaminants and moisture. This result is further confirmed by the X-ray diffraction pattern in Figure 36b, and no phase transition is observed when PET is heated at 260 °C overnight.

[0347] Figure 37b shows the DSC curve of nominally anhydrous SnCl2 (Figure 36c) containing approximately 11 wt.% moisture from the environment. The DSC curve shows only an obvious endothermic peak at 259.1 °C related to the melting of SnCl2. As shown in Figure 37e, the TGA curve of the sample confirmed that the mass losses at 250, 270, and 350 °C are 0.61%, 0.89%, and 1.47% respectively. Based on the observations, it can be concluded that SnCl2 absorbs moisture and can retain a significant portion of its water of hydration at relatively high temperatures even after melting.

[0348] Figure 37c shows the DSC curve recorded for a mixture of PET (11.046 mg) and SnCl2 (38.401 mg). The endothermic peak observed at 258.2 °C is due to the eutectic melting of PET and SnCl2, which is consistent with the isothermal phenomenon at 258.6 °C in Figure 35c. Figure 37f shows the TGA curve of the PET + SnCl2 mixture, with mass losses of 1.49%, 2.56%, and 23.23% at 250, 270, and 350 °C respectively. Considering that approximately 11 wt.% water of hydration is present in SnCl2, the total amount of water of hydration derived from SnCl2·H2O in the salt is estimated to be approximately 8.5 wt.% (4.224 mg). Therefore, at 250 °C just before eutectic melting, there may be approximately 7 wt.% water of hydration present in the PET + SnCl2 mixture.

[0349] On the premise of not adhering to theory, it is speculated that moisture causes the depolymerization of PET. According to the possible reaction (3) (see the above discussion), hydrated SnCl2 and PET eutectic at about 258 °C, but hydrated SnCl2 retains most of its moisture. At about 290 - 320 °C, PET depolymerizes into the monomers terephthalic acid (C8H6O4) and ethylene glycol ((CH2OH)2) due to the moisture in the melt, and the latter evaporates together with the remaining moisture. The endothermic peak with a maximum value at 314.9 °C in the DSC curve of Figure 37c also confirmed this process. The 15 wt.% mass loss (Figure 37f) observed in the temperature range of 290 - 320 °C corresponds to the evaporation of ethylene glycol and residual moisture, leaving solid PET and molten SnCl2. The above mechanism was confirmed by the XRD pattern (Figure 36d) of the product obtained by heating PET + SnCl2SnCl2. The peak values are shown in Table 3.

[0350]

Table 3

[0351] The peaks with 2θ values of 16.99, 24.54, and 29.31 have full width at half maximum (FWHM, 2θ) values of 0.1496, 0.1309, and 0.1870 respectively. Using these values, the average crystal size of various crystal orientations is calculated according to the Scherer equation.

[0352]

Equation

[0353] Here, k is the Scherer constant (K = 0.9), λ is the wavelength of X-rays (1.54 Å), β is the FWHM of the diffraction peak (unit: radian), and θ is the diffraction angle. Therefore, in the diffraction pattern of Figure 36d, the average crystal sizes of the peaks located at 2θ values of 16.99, 24.54, and 29.31 were calculated to be 53.6 nm, 62.1 nm, and 43.5 nm respectively.

[0354] Example 23 - Microstructure property evaluation of terephthalic acid produced from waste plastics Figures 38a - c show SEM (FEI Nova Nano - SEM) photographs of terephthalic acid produced by heat - treating PET and nominally anhydrous SnCl₂ at 303 °C (Example 21). Figure 38a shows aggregated particles with a total size of 26 μm. As shown in the micrograph, such aggregated particles usually contain nanoscale entities with sizes less than 200 nm. Other morphologies observed in the terephthalic acid product are shown in Figures 38b and 38c. Figure 38b shows a flake - like morphology, with an overall size usually less than about 1 μm, for example 411 nm. The sheet - like particles may contain nanoscale entities with dimensions less than 50 nm, for example 27 nm. The presence of aggregated nanostructured particles is also confirmed in Figure 38b, with an entity of particle size 38 nm highlighted. Figure 38c shows aggregated nanoparticles at a higher resolution. From this micrograph, terephthalic acid nanoparticles smaller than 100 nm, such as 53 nm and 57 nm, were measured. The fine structure of the prepared terephthalic acid is different from existing terephthalic acid materials. Figures 39a - b show SEM micrographs of commercially available crystalline terephthalic acid (Merck, 8.00762, purity ≥ 98%). As shown in Figure 39a, terephthalic acid particles are usually much larger than 1 μm and can reach sizes of hundreds of microns, such as 332 μm. Figure 39b shows a high - magnification micrograph, revealing that, unlike the terephthalic acid material produced by depolymerization of PET and SnCl₂ (Figures 38a - c), the particles are not porous.

[0355] Terephthalic acid obtained by depolymerizing PET and SnCl₂ is different from commercially available terephthalic acid samples. The former has a unique nanostructured form and is also different from the terephthalic acid reported in the literature.

[0356] Example 24 - Electrochemical properties of nanostructured terephthalic acid The terephthalic acid produced by depolymerizing waste PET using SnCl2 (Example 21, Figures 38a - c) was uniformly mixed with conductive carbon (C45) and PVDF binder in a mass ratio of 60:30:10 using NMP as a solvent. Next, the resulting slurry was coated onto a copper foil using a scraper and dried in a vacuum oven at 80 °C for 12 hours to obtain an electrode sheet with a loading of more than 1.5 mg cm -2 . Then, a coin - type half - cell (CR 2032) was assembled using metallic sodium as the counter electrode, a 1.0 M NaCF3SO3 solution in diethylene glycol dimethyl ether as the electrolyte, and glass microfiber (Whatman, 1823025) as the separator. The cell was stabilized at room temperature for 10 hours before measurement in a battery test system, and Na - ion insertion / extraction cycles were performed at a constant current density of 30 mA / g in a voltage range of 0.01 - 3.0 V vs Na / Na + . The constant - current discharge - charge curves of the first and second cycles are shown in Figures 40a and 40b, respectively. During the first discharge cycle, a plateau of about 0.26 V vs Na / Na + (0.23 - 0.33 V vs Na / Na + ) appeared, and it was confirmed that a plateau of 0.5 V vs Na / Na + (0.45 - 0.55 V) appeared during the charge process. Similarly, during the discharge process of the second cycle, a plateau of 0.28 V vs Na / Na + (0.25 - 0.35 V vs Na / Na + ) appeared, and it was confirmed that a plateau of 0.5 V vs Na / Na+(0.45 - 0.55 V vs Na / Na + ) appeared during the charge process. The plateau observed in the second discharge / charge was repeated in subsequent lithium - ion insertion / extraction cycles and maintained at 100, 500, 1000, and 5000 cycles. The sodium - ion storage capacity obtained during the second discharge was 209.1 mAh g -1 .

[0357] During the discharge / charge process, the existing 0.28 / 0.5 V vs Na / Na + platform is very beneficial for the storage of Na ions. This improves safety and avoids the deposition of sodium on the electrode surface at a voltage close to 0 V vs Na / Na + . When using the nanostructured terephthalate as the anode material, this value is also relatively small, ensuring a high energy density of the battery.

[0358] This result indicates that the intercalation / extraction of Na ions from the electrode made of nanostructured terephthalic acid occurs at 0.28 / 0.5 V vs Na / Na + , bringing safety and high efficiency to the battery using nanostructured terephthalic acid as the negative electrode material. This result shows that nanostructured terephthalic acid can be used as an electrode for metal ion batteries such as the negative electrode of lithium-ion batteries, sodium-ion batteries, and potassium-ion batteries.

[0359] Example 25 - Conversion of PET containing oxide phase or hydroxide phase to nanostructured terephthalic acid using inorganic salts A PET plastic sheet (20.1 g) made from a cut waste water bottle and nominally anhydrous SnCl2 (142.0 g) were mixed and the mixture was placed in an alumina crucible. The crucible containing the mixture (162.1 g) was placed in an airtight reactor, and the reactor was placed in a vertical resistance furnace. The temperature inside the crucible was measured with a thermocouple protected by alumina placed inside the mixture. While flowing Ar gas (60 mL min -1 ), the furnace was heated from room temperature to a maximum temperature of 333 °C. The temperature inside the crucible rose from 23 °C to a maximum temperature of 312 °C in 137 minutes. Before turning off the power of the furnace, it was maintained at the maximum temperature for 13 minutes. After cooling the furnace to room temperature, the material inside the crucible was weighed as 148.3 g. The weight loss (13.8 g) mainly corresponds to the evaporation of ethylene glycol and the residual moisture in the melt when converting PET to nanostructured terephthalic acid. As shown in reaction (3), converting PET to terephthalic acid with the water of hydration (moisture) in the salt, combined with the loss of ethylene glycol, results in a mass loss of 13.54%.

[0360] From 20.1 g of PET, 17.3 g of terephthalic acid is produced, resulting in a mass loss of approximately 2.8 g. The other approximately 11 g mass loss is thought to be due to the evaporation of the remaining water of hydration during depolymerization. Based on these calculations, it is expected that approximately 85 g of nanostructured terephthalic acid can be produced from 142 g of SnCl2 at about 300 °C.

[0361] The materials obtained by heat treatment of PET and SnCl2 were washed with distilled water (pH about 7), and the resulting suspension was filtered. The product was dried at 80 °C for 2 hours and then subjected to X-ray diffraction analysis. The obtained spectrum is shown in Figure 41, where the terephthalic acid monomer C8H6O4 with a triclinic crystal structure (ICDD # 00-021-1919) is dominated by, and the rhombohedral crystal structure of Sn 21 C l16 (OH) 14 O6 (ICDD # 00-035-0907) is supplemented by. Sn 21 C l16 (OH) 14 The formation of O6 may be related to the hydrolysis of SnCl2 during washing with distilled water (as shown in reaction (1)).

[0362] Sn 21 C l16 (OH) 14 Since SnC(OH)O6 has low solubility in water, it remained in the terephthalic acid nanostructure after washing and filtration.

[0363] Example 26 - Preparation of SiNP-embedded organic compounds by heat treatment of PET with SnCl 2 in the presence of Si 6 g of SiNP (Sigma Aldrich, 633097) with a nominal particle size of less than 100 nm and having a spherical morphology were mixed with 20 g of waste PET plastic bottles (cut into small pieces several centimeters in length) and 159.6 g of SnCl2 powder (Sigma Aldrich, 208256). The mixture was placed in an alumina crucible. The crucible was placed in an Inconel airtight reactor equipped with a gas inlet / outlet. The reactor was placed in a resistance furnace and heated from room temperature to a maximum temperature of 284 °C under an Ar-5%H2 gas stream and then held for 5 minutes. Thereafter, the temperature was lowered to room temperature, and 1 g of the obtained product was washed with dilute hydrochloric acid (10%) to remove residual salts and then dried at 100 °C for 2 hours under an Ar-5%H2 gas stream. The obtained sample was measured using an electron microscope. Figure 42 shows the SEM micrograph of this product, confirming the presence of a porous morphology due to SiNP embedded in terephthalic acid. Figure 43 shows a high-magnification SEM photograph, confirming the presence of spherical SiNP in the terephthalic acid matrix. Two SiNP with diameters of 84 nm and 106 nm are highlighted in the micrograph.

[0364] Example 27 - Electrochemical properties of an organic compound embedded with SiNP 12.21 g of the product (Example 26) obtained by heating the mixture of PET, SnCl2 and SiNP to 284 °C and 2.05 g of graphene nanosheets were added to 400 mL of concentrated sulfuric acid, the suspension was sonicated for 20 minutes and then magnetically stirred for 20 minutes. The suspension was filtered, the product was washed with deionized water and dried at 180 °C for 5 hours under an Ar-5%H2 gas stream. The XRD pattern of the obtained product is shown in Figure 44. It can be observed that the obtained product contains terephthalic acid (ICCD: 00-021-1919), elemental silicon (ICCD: 01-089-2749) and graphite carbon (ICCD: 01-075-2078). EDS analysis of the sample revealed the presence of silicon (about 28 wt. %) in the sample.

[0365] The obtained material is used for manufacturing the anode of a lithium-ion battery. PI powder was added to 400 μL of NMP and stirred. Next, a sample containing silicon, terephthalic acid, and graphene (Figure 44) was added to the PI solution. After subjecting the mixture to ultrasonic treatment, it was magnetically stirred for 10 hours to obtain a uniform slurry. The obtained uniform slurry was coated on a copper foil, dried at room temperature for 10 minutes, and then dried under reduced pressure at 100 °C for 2 hours to remove NMP. After drying, the electrode was heated in a tubular furnace under an Ar-4%H2 gas stream at a heating rate of 2 °C min -1 to 250 °C and held at 250 °C for 2 hours. Next, the temperature was lowered to room temperature under the same gas stream. A coin cell CR 2025 half-cell was assembled using the obtained electrode. In this case, metallic lithium was used as the counter electrode and the reference electrode. 1.0 M LiPF6 dissolved in EC:DEC:EMC (1:1:1 wt. %) and a Celgard 2400 polypropylene film were used as the electrolyte and the separator, respectively. After equilibrating the cell at room temperature for 10 hours, a constant current test was performed at a constant current density of 100 mA / g between 0.01 and 3.0 V vs Li / Li+. The general cycle performance of the electrode is shown in Figure 45. After performing 130 cycles of lithium ion insertion and extraction, a reversible capacity of 1285 mAh / g can be observed. This capacity was calculated based on the total mass of silicon / terephthalic acid / graphene.

[0366] This result indicates that a material in which SiNP is embedded in a crystalline organic compound can be used as the anode of a metal ion battery such as a lithium-ion battery.

[0367] Example 28 - Conversion of waste plastic into an organic compound embedded with a zinc metal-organic framework 16.1 g of ZnCl2 (Sigma, 98%) was mixed with small pieces of waste PET material (11.5 g). The mixture (27.6 g) was placed in an alumina crucible, and the crucible was placed in an airtight steel reactor. The latter was placed in a vertical furnace. While flowing an Ar gas stream (60 mL / min) through the reactor, the reactor was heated. The temperature inside the crucible (measured using a thermocouple protected by alumina) was increased at 7 °C min -1It was heated from room temperature to 373 °C at a heating rate of. Next, the power supply of the furnace was turned off, and the temperature was cooled to room temperature. The obtained product (21.4 g) was washed with distilled water to dissolve the salt, and then filtered. The obtained product was dried at 80 °C for 2 hours and then subjected to property evaluation.

[0368] Figure 46 shows the X-ray diffraction pattern of the product, and the presence of zinc terephthalate hydrate (ZnC8H4O4·3.5H2O, or ZnTP·3.5 H2O, ICDD: 00-038-1777) was confirmed as the main phase. Figure 46 shows that, in addition to the zinc metal-organic structure, there are XRD peaks related to the organic compound having the general formula C x H y O z This indicates that there are. Table 4 reports the values of 2θ, FWHM, and intensity related to ZnC8H4O4·3.5 H2O and the observed organic compound.

[0369]

Table 4

[0370] Example 29 - Conversion of waste plastic into a metal-organic framework 8.47 mg of PET flakes were mixed with 30.51 g of dried nominal ZnCl2, and the mixture (38.98 mg) was placed in an alumina crucible. The crucible was placed in a thermal analyzer, and the Ar flow rate was 100 mL min -1 , and the heating rate was 20 °C min -1 It was heated to 1200 °C at. Figures 47 and 48 show the recorded TGA curve and DSC curve, respectively.

[0371] According to the TGA curve in Figure 47, the mass loss when heated to 170 °C was 0.35%, and an endothermic peak appeared at 110 °C (Figure 48). This reaction is related to the evaporation of unhydrated water from the material. The second endothermic peak was observed at 195 °C, which is related to the glass transition reaction. This reaction was accompanied by further evaporation of moisture (1.41%) in the temperature range of 170 - 227 °C. The third endothermic peak (235 °C, Figure 48) was accompanied by a mass loss of 1.85% in the temperature range of 227 - 248 °C. This reaction may be related to the evaporation of the hydrated water of ZnCl₂. The dehydration of ZnCl₂ provides moisture for the depolymerization of PET. The depolymerization reaction may be accompanied by an exothermic reaction that peaks at 287 °C, which involves the evaporation of depolymerization by-products (such as ethylene glycol) and residual moisture, resulting in a mass loss of 3.99 wt.% in the temperature range of 248 - 316 °C. Here, according to the DSC curve in Figure 48, an endothermic reaction occurs at 321 °C, which is presumed to correspond to the formation of zinc terephthalate by the melting of dehydrated ZnCl₂ and the reaction of the monomers (such as terephthalic acid, TPA) formed by the depolymerization of PET with the molten ZnCl₂ (see Figure 5c).

[0372] As can be seen from the TGA plot in Figure 47, a mass loss of 3.92 wt.% was observed in the range of 316 - 416 °C. This may be related to the stepwise removal of HCl from the system. From 416 °C to about 800 °C, a substantial mass loss of 78.26% occurred. This may be related to the decomposition of the zinc metal-organic framework, residual organics (terephthalic acid + terephthalate), and the evaporation of molten ZnCl₂. The remaining mass was relatively stable even at high temperatures, and an amount of 9.0 g was obtained at the end of the heat treatment at 1200 °C. When the remaining material was analyzed by XRD (Figure 49), it was found to be ZnO (ICSD: 01-079-0207) with a hexagonal crystal structure.

[0373] Example 30 - Morphological property evaluation of an organic compound embedded in a zinc metal-organic framework Figure 50 shows a backscattered electron micrograph of the product of Example 28, indicating the presence of crystals with sizes substantially from 1 μm to less than a few microns embedded in the organic compound.

[0374] As shown in FIGS. 51a-c, by energy-dispersive X-ray spectroscopy (EDS) of the zinc metal-organic framework crystal and the organic compound, it is confirmed that main elements such as C, Zn, and O are present in the metal-organic framework of zinc, and C and O are present in the organic compound. Since hydrogen element cannot be detected by EDS, there is no hydrogen element. A small amount of Cl is present in the sample, which may be the residue of ZnCl2 used in the product preparation process. Furthermore, the EDS elemental mapping analysis of the backscattered electron micrograph is shown in FIG. 52. It can be seen that the concentration of zinc in the zinc metal-organic framework crystal is much higher. The zinc metal-organic crystals have various sizes and shapes. FIG. 53b shows the size distribution histogram of more than 100 crystals. It can be seen that the size of the crystals is usually less than 20 μm, and the size of most crystals is 1-4 μm. Crystals in the range of about 10 nm to 1 μm also exist slightly.

[0375] FIGS. 54a-d show the backscattered electron micrographs of the zinc metal-organic framework embedded in the organic compound (the product of Example 28), highlighting some morphological features of the nanocrystals. As can be seen from FIG. 54a, the total size of the organic compound embedded in the zinc metal-organic framework is at most several hundred microns, such as 700 μm, 500 μm, and 400 μm. According to FIG. 54b, the total size of the zinc metal-organic framework embedded in the organic compound particles is at least 50 μm, 40 μm, 30 μm, 20 μm, 10 μm, 8 μm, 5 μm, 2 μm, 1 μm or 500 nm. According to FIGS. 54c and 54d, the zinc metal-organic framework crystals are faceted crystals, and these crystals are embedded in the organic compound. The size of the faceted zinc metal-organic framework crystals is in the range of 50 nm to 10 μm.

[0376] Figures 55a-d show secondary electron scanning electron micrographs of zinc metal-organic frameworks embedded in an organic compound (the product of Example 28), highlighting some of the morphological features of the organic compound. According to Figures 55a and 55b, the product contains particles with a total size greater than 600 μm and less than 10 μm. These particles contain zinc metal-organic crystals embedded in the organic compound. The shape of the zinc metal-organic framework crystals is highlighted in Figures 55c and 55d. These figures show the presence of faceted crystals with square, rectangular, pentagonal, or hexagonal surfaces. Most of the crystals were embedded in the organic compound, but isolated zinc metal-organic framework crystals were also detected.

[0377] According to the micrographs of Figures 55a-d, in addition to metal-organic framework crystals, two other morphologies, sheet-like particles and aggregated nanoparticles, were also observed. The sheet-like particles of the organic compound can be observed in Figures 55c and 55d. The lateral dimension of the sheet-like particles varies from 100 nm to several microns (such as 10 μm). The thickness of the sheet-like particles is about 1-10 nm.

[0378] The morphological features of the zinc metal-organic framework embedded in the organic compound product were further understood by transmission electron microscopy (TEM, Tecnai F20, 200 kV). Figure 56 shows a low-magnification TEM micrograph of this product featuring zinc terephthalate hydrate (ZnC8H4O4·XH2O) embedded in the organic compound. There is an obvious difference between the woven sheet-like particles and the aggregated nanoparticles. In Figure 56, two woven sheet-like particles with dimensions of 750 nm × 1.1 μm and 484 nm × 584 nm can be observed. As shown in the high-magnification TEM micrograph of the sheet-like particles in Figure 57a, the surface of the sheet-like particles is woven / modified with nanoparticles.

[0379] As shown in Fig. 57a, the surface of the sheet-like particles is composed of nanoparticles of various sizes and shapes, mainly hemispherical and worm-like nanoparticles. Fig. 57b shows a histogram of the size distribution obtained by recording the sizes of more than 100 nanoparticles present on the surface of the sheet-like particles in Fig. 57a. The size ranges of the surface nanoparticles are 0 - 4 nm (5%), 5 - 9 nm (38%), 10 - 14 nm (37%), 15 - 19 nm (7%), 20 - 24 nm (6%), 25 - 29 nm (2%), and 30 - 60 nm (8%).

[0380] Fig. 58a shows a TEM image of the prepared zinc metal-organic framework embedded in an organic compound, showing micron-sized particles containing aggregated nanoparticles. It can be observed that nanoparticles of various sizes are aggregated to form micron-sized particles. Fig. 58b shows a size distribution histogram obtained by recording the sizes of more than 60 nanoparticles present in the micrograph of Fig. 58a. The size ranges of the nanoparticles are 5 - 9 nm (38%), 10 - 14 nm (22%), 15 - 19 nm (10%), 20 - 24 nm (3%), 25 - 29 nm (4%), and 30 - 60 nm (3%).

[0381] Example 31 - Lithium ion storage performance of an organic compound embedded in a zinc metal-organic framework Electrodes were fabricated using Zn C8H4O4·3.5H2O (described in Examples 28 and 30) embedded in CXHyOz. ZnC8H4O4·3.5H2O-embedded C x H y O z material, PVDF binder (in NMP), and conductive carbon (Super P) were thoroughly mixed in a ratio of (6:3:1) to form a uniform suspension, which was coated on copper foil and left at 80 °C for 10 hours to remove NMP. Finally, a loading of 1.5 mg cm -2A CR2025 button cell was assembled using the above electrodes, with metallic lithium as counter and reference electrodes, 1.0 M LiPF6EC:DEC:EMC (1:1:1 wt. %) solution and Celgard 2400 polypropylene film as electrolyte and separator, respectively. The cycling performance was measured at a current density of 100 mA / g in the potential range of 0.01-3 V vs Li / Li+. The results are shown in Figure 59. It has a high reversible specific capacity of 326.3 mAh / g after 156 lithium ion implantation and extraction cycles.

[0382] Example 32 - ZnC embedded in an organic compound 8 H 4 O 4 ·3.5H 2 Heat treatment of O Organic compounds (C x H y O z ) embedded in ZnC8H4O4 3.5H2OC x H y O z () is converted to heat-treated zinc terephthalate (Zn-TP) embedded in terephthalic acid (TPA) through a heat treatment process. x H y O z ZnC8H4O4·3.5H2O embedded in ZnC8H4O4·3.5H2O was heated at 150 °C under Ar for 2 h. The XRD patterns of the heat-treated sample compared to the XRD pattern of the original sample are shown in Figure 60a-b. The original XRD sample is shown in Figure 60a, and the XRD heat-treated sample in Figure 60b. This heat-treated material contains zinc terephthalate (Zn-TP) and terephthalic acid (TPA) produced by heat treatment. The XRD pattern data of zinc terephthalate (Zn-TP) is provided by the single crystal compound calculated in the following literature: [M. Nakhaei et al., Antibacterial activity of three zinc terephthalate MOFs and its relationship to structural features, Inorganica Chimica Acta 522 (2021) 120353].

[0383] In Fig. 60a, the FWHM of the diffraction peak with a 2θ value of 11.75° is 0.150°, and the crystal size is 53.2 nm. When the 2θ value is 16.592°, the FWHM of the diffraction peak is 0.187°, and the crystal size is 42.9 nm. When the 2θ value is 35.202°, the FWHM of the diffraction peak is 0.228°, and the crystal size is 36.5 nm.

[0384] In Fig. 60b, the FWHM (2θ, degrees) of the peaks at 9.89, 19.33, 25.27, and 40.11 degrees are 0.1299, 0.1948, 0.1624, and 0.2922, respectively. The average particle sizes associated with these peaks were calculated to be 61.4 nm, 41.3 nm, 50.1 nm, and 28.9 nm. The peak values are shown in Table 5.

[0385]

Table 5-1

[0386]

Table 5-2

[0387] Example 33 - Metal ion storage performance of zinc terephthalate (Zn-TP) after heat treatment embedded in terephthalic acid (TPA) To observe the sodium ion storage characteristics, an electrode made of heat-treated Zn-TP embedded in terephthalic acid (described in Example 31) was used as the active material. Therefore, NMP was used as the solvent, and conductive carbon (C45) and a PVDF binder with a mass ratio of 6:3:1 to the active material were mixed. Next, the obtained suspension was spread on copper foil using a 200 μm doctor blade and dried in a vacuum oven at 80°C for 12 hours. The electrode loading was approximately 1.5 mg cm -2It is as follows. Using metallic sodium as the counter / reference electrode, a 1.0 M NaCF3SO3 solution in diethylene glycol dimethyl ether as the electrolyte, and a glass microfiber (Whatman, 1823025) as the separator, a coin-type half-cell (CR 2032) was assembled. The half-cell was assembled in a glove box and placed in high-purity argon with an O2 and H2O content of 0.1 ppm or less. After stabilizing the cell at room temperature for 10 hours, it was tested in a cell test system at a constant current of 30 mA g-1 in the voltage range of 0.01 - 3.0 V vs Na / Na + and measured. The constant current charge and discharge curves were recorded at a current density of 30 mA / g. The first four cycle discharge / charge curves are shown in Figs. 61a - d respectively. The first discharge curve shows a plateau between 0.8 V and 0.25 V vs Na / Na + , and a plateau can be observed at about 0.3 V in the subsequent discharge curves. On the other hand, as a characteristic of the charge curve, there is a plateau between 0.5 V vs Na / Na + . There is a plateau at 0.25 V and 0.3 V vs Na / Na + near Na / Na + , which is much higher than 0.0 V, and can avoid the formation of metallic Na on the electrode surface, thus improving the safety of the electrode. Also, the charge plateau at about 0.5 V vs Na / Na + is low enough to ensure the high energy density of the battery with Zn-TP embedded in terephthalic acid as the negative electrode active material. Fig. 62 shows the cycling performance of the electrode recorded at 30 mA g - -1, where there is a reversible capacity of 200 mAh / g after 10 sodium ion insertion / desorption cycles.

[0388] The lithium-ion storage performance of Zn-TP embedded in heat-treated terephthalic acid was also investigated. Using NMP as the solvent, Zn-TP embedded in terephthalic acid was mixed with a PVDF binder and conductive carbon (Super P) (6:1:3). The prepared suspension was coated on copper foil and dried at 80 °C for 10 h under vacuum. As described in the previous example, coin cells were assembled using Li as the counter / reference electrode and a solution of 1.0 M LiPF6 in EC:DEC:EMC (1:1:1 wt. %) as the electrolyte. An electrode with a loading of approximately 1.5 mg cm -2 was cycled at a current density of 100 mA g + within a potential window of 0.01–3 V vs Li / Li -1 . Figure 63 shows the cycling performance of the electrode. After 23 lithium-ion insertion and extraction cycles, it exhibits a stable reversible capacity of 252 mAh g−1.

[0389] As a result, it was found that the heat-treated Zn-TP (obtained in Example 31) embedded in the terephthalic acid product can be used as the anode of a metal-ion battery, such as the anode of a sodium-ion battery (SIB) or a lithium-ion battery (LIB).

[0390] Example 34 - Treatment of HDPE with SnCl 2 Example 35 - Measurement with an ultraviolet-visible spectrophotometer PET bottles made of HDPE are cut into pieces several centimeters in size. 30.0 g of HDPE chips and 140.0 g of SnCl2 are mixed, and the mixture (170.0 g) is placed in an alumina crucible. The crucible is heated to 337 °C in a vertical resistance furnace under an argon flow, with an average heating rate of 3 °C min−1, and the temperature inside the crucible is measured throughout the experimental process. After heating, the crucible is cooled to room temperature. The mass measurement of the heat-treated material is 168.0 g, and the mass loss is about 0.7%, which can be ignored and corresponds to the dehydration of the material during the heat treatment process. Figure 64a shows the untreated HPDE, and Figure 64b shows the heat-treated HDPE. As shown in Figure 64b, HDPE did not depolymerize during the heat treatment process and could be easily recovered from the container.

[0391] The X-ray diffraction patterns of HDPE before and after the heat treatment process are shown in Figures 65a and 65b, respectively. The XRD patterns indicate that the crystal structure of HDPE does not change during this process.

[0392] As a result, it was found that when a mixture of PET and HDPE was heated to a sufficiently high temperature with SnCl2, PET was depolymerized, HDPE melted during heating, sank to the bottom of the container, and a porous structure of terephthalic acid monomer produced by PET depolymerization remained at the top of the container.

[0393] Example 36 - Production of Na Figure 66a shows the ultraviolet-visible absorption spectra of nanostructured terephthalic acid (TPA) prepared by PET and SnCl2 heat treatment (described in Example 21) and commercially available terephthalic acid. The detection method for the samples is as follows. First, the sample is added to deionized water and ultrasonically washed for 10 minutes, and the absorption spectrum is measured with an ultraviolet-visible spectrophotometer (Thermo Scientific Evolution 220). At the time of detection, the concentration of TPA is controlled to 0.5 g L-1, and the absorption spectrum of pure water is first detected as the baseline. When actually detecting TPA, the absorbance of water is automatically subtracted as the baseline.

[0394] As can be seen in Figure 66a, both samples show peaks at approximately the same number of wavelengths, 242 nm for nanostructured terephthalic acid and 241 nm for commercially available terephthalic acid, indicating that the crystal structures of both compounds are the same.

[0395] Despite this similarity, the two compounds show a clear difference in absorbance. First, the absorbance of nanostructured terephthalic acid at 242 nm (1.840 au) is approximately 2.3 times higher than the absorbance of commercially available terephthalic acid at the absorption peak (0.815). Second, the absorbance of commercially available terephthalic acid approaches zero at wavelengths above 300 nm. In contrast, nanostructured terephthalic acid showed a relatively large absorbance at all wavelengths. For example, 0.5 g L -1At the concentration of, the following absorbance data are observed from Figure 66a: 450 nm (0.564 a.u.) and 500 nm (0.548 a.u.).

[0396] Furthermore, Figure 66b shows that nanostructured terephthalic acid exhibits an additional peak at 317 nm, which does not exist in commercially available terephthalic acid. Without being limited to theory, this peak is presumably due to the presence of nanopores on the surface of nanostructured terephthalic acid, thereby resulting in additional absorbance characteristics.

[0397] As shown in Figure 28a - b, the color of nanostructured terephthalic acid is much darker than the appearance of commercially available terephthalic acid and can be distinguished by the human eye.

[0398] TP using commercially available and nanostructured TPA 2 Example 37 - Silicon thermally denatured PI electrode for lithium ion storage 1.5 g of NaOH and 1.5 g of TPA (commercially available TPA or nanostructured TPA) were mixed with 60 mL of ethanol (purity ≥ 99.7%, 0.789 - 0.791 g mL-1 at 20°C), and then magnetically stirred for different times (6 hours, 12 hours, 18 hours, 24 hours). After completion, the mixture was centrifuged to recover the product, and then dispersed in ethanol and centrifuged again. The last step was repeated twice, and the obtained powder was dried at 150°C under vacuum for 1 hour.

[0399] The X-ray diffraction patterns of commercially available TPA, nanostructured TPA, and products obtained at different stirring times were examined. The apparatus was a PANalyco apparatus, the radiation source was Cu-Kα radiation (λ = 1.54 Å), the step size was 0.033°, the dwell time was 45 seconds, and the scan rate was 0.094 degrees / second.

[0400] As shown in Fig. 67a, all diffraction peaks of the nanostructured TPA are those of terephthalic acid (ICDD#00-021-1919) with a triclinic crystal structure, proving the successful preparation of the nanostructured TPA. Among the diffraction peaks, the peak 2θ values with higher intensity values are located at 17.517° (FWHM = 0.276°), 25.301 (FWHM = 0.276°), and 28.080° (FWHM = 0.335°).

[0401] Fig. 67b shows that the diffraction peaks of the commercially available TPA are those of terephthalic acid (ICDD#00-021-1919) with a triclinic crystal structure. The XRD peaks of the commercially available TPA can be observed at 2θ values of 17.483° (FWHM = 0.138°), 25.291° (FWHM = 0.197°), and 28.019° (FWHM = 0.157°). It can be observed that the FWHM value of the nanostructured TPA is much larger than that of the commercially available TPA. This indicates that the particle size of the nanostructured TPA is much smaller.

[0402] Figs. 67c - e show the commercial TPA after 6 hours, 12 hours, and 18 hours of treatment respectively, and the results show no structural changes, indicating that the kinetics of this process is relatively slow.

[0403] Since the reactivity of the nanostructured TPA with NaOH is much stronger than that of the commercial TPA, a treatment for 6 hours (or shorter) is sufficient to produce Na2TP.

[0404] Example 38 - Preparation of SnO The effect of the PI binder on the lithium storage performance of SiNP (particle size = 20 - 60 nm, ≥99.9%, Aladdin) was investigated by assembling half-cells. First, 10 mg of PI powder (PI, Mw = 50000 - 80000, Macklin) was mixed with 405 mg (400 μL) of NMP to form a homogeneous solution. Next, 10 mg of conductive carbon (Super P, ≥99.9%) and 80 mg of SiNP were added to the PI solution, and the mixture was sonicated for over 2 hours to achieve a homogeneous dispersion. Then, the dispersion was stirred for 3 hours, and the resulting suspension was coated onto copper foil. NMP was removed by drying at room temperature for 10 minutes and then at 100 °C under vacuum for 2 hours. After drying, the electrodes were heated in a tubular furnace under a gas flow of Ar - 4%H2 at different temperatures of 300 °C, 350 °C, and 400 °C at a heating rate of 2 °C min-1 and held at this temperature for 2 minutes. Then, the temperature was lowered to room temperature under the same air flow, and the resulting electrodes were used to assemble coin cells. Figure 68 shows a schematic diagram of the electrode manufacturing process.

[0405] As a control, electrodes were fabricated using PAA / CMC (1:1 mass ratio) as a binder in the same manner as described above, but without the high-temperature heat treatment process. Button cells (type 2025) were assembled in an argon-filled glove box, using polypropylene as a separator, 1 M lithium hexafluorophosphate (LiPF6) as an electrolyte lithium salt, and a mixture of ethylene carbonate (EC), diethyl carbonate (DEC), and methyl ethyl carbonate (EMC) (EC / DEC / DEC = 1:1:1 mass ratio) as an electrolyte solvent. In the assembled coin cells, a metallic lithium sheet functions as the reference electrode and the counter electrode. The X-ray diffraction (XRD) instrument is D8 ADVANCE, the measurement range is 2θ = 10~80°, and the X-ray source is Cu-Kα radiation (1.5405 Å). Fourier transform infrared (FTIR) tests were performed using a VERTEX70 instrument. A Thermo Scientific K-Alph instrument was used for the X-ray photoelectron spectroscopy (XPS) test. Ultraviolet-visible absorption spectroscopy was performed using an Evolution 220 instrument. Before studying the morphology of the cycle electrodes with a scanning electron microscope (SEM, ZEISS EVO18), the electrodes were immersed in dimethyl carbonate (DMC) overnight. The measurements of constant current charge and discharge were performed using a LAND battery test system at 0.01~3.0 V (25 °C). Cyclic voltammetry was used to study the electrochemical process on the electrodes, and the equipment was an electrochemical workstation (CHI 660 E, China), and the scanning rate was 0.1 mVs -1 and the voltage range was 0.01~3.0 V vs Li / Li + was used. Electrochemical impedance spectroscopy (EIS) measurements were performed using an alternating current with an amplitude of 5 mV and a frequency range of 100 kHz~10 MHz. At the OCV steady state, EIS data were measured using a CHI 660E electrochemical workstation.

[0406] The PI material used was 1-(4-aminophenyl)-1,3,3-trimethyl -A thermoplastic polymer consisting of condensation polymerization and imidization of 2H-indene-5-amine (DAPI) and benzophenone-3,3',4,4'-tetracarboxylic dianhydride (BTDA), which is soluble in NMP.

[0407] After heating the PI material to 350 °C and holding it for 2 hours, the PI material changed greatly from a pale yellow powder to a dark brown hard mass. Figures 69a and 69b show the photos of PI before and after heat treatment, respectively. As shown in Figure 69c, it was observed that the heat-treated PI (PI-350) became insoluble in polar solvents. This phenomenon is presumably due to the bonding and / or crystallization of the compound. To examine the change in the crystal structure of PI, the samples before heat treatment (PI) and after heat treatment (PI-350) were analyzed by X-ray diffraction. The obtained patterns are shown in Figure 70.

[0408] In the XRD pattern of PI before heat treatment, two broad diffraction peaks appeared at 2θ = 10~30° and 2θ = 40~50°, corresponding to the amorphous structure of PI, indicating the disordered arrangement of PI molecular chains. At the same time, these two broad peaks also appeared in the XRD pattern of PI-350, indicating that PI-350 has the same amorphous structure. Table 6 shows the physical properties of PI before and after heat treatment. In addition to the differences in appearance and NMP solubility, it can be seen that the mechanical hardness of PI-350 is much higher than that of PI. This means that the polymer chains of PI-350 are more densely packed and the intermolecular space is smaller. As will be described later, this property helps to improve the mechanical properties of the PI binder and reduce the problems caused by the volume expansion associated with the cycling of the Si electrode.

[0409]

Table 6

[0410] Not limited to theory, it is speculated here that the cross-linking between PI molecular chains generated by the heat treatment process may cause the formation of charge transfer complexes (CTCs), which in turn leads to the observed differences in the properties of the original PI and PI-350. From this, it is speculated that CTCs are formed by the electron transfer between electron-rich donor molecules and electron-deficient acceptor molecules (e.g., pentaerylimide rings and benzene rings). At the same time, after heat treatment, the molecular chains of PI approach each other very closely, and thus, as shown in Figure 71, it is speculated that p electrons can move through the electron donor and acceptor compartments of PI, and CTCs are formed between PI chains.

[0411] To prove that PI forms CTCs during the heat treatment process, FTIR spectral analysis was performed on the original PI and PI-350. The FTIR spectra of PI (Figures 72a and 72b) show bands around 1778 cm -1 which are the asymmetric stretching of the C=O imide group. The peak at 1730 cm -1 is due to the symmetric stretching of C=O of the imide group, and the peak at 1367 cm -1 is due to the C-N stretching of the imide group. These three peaks represent the stretching vibrations of the imide group, proving the presence of the PI material. Furthermore, the peak around 837 cm-1 is thought to be due to the vibration of the p-aryl unsaturated π bond of the benzene ring. The FTIR spectrum of PI-350 is shown in Figure 72a. Here, peaks corresponding to the symmetric C=O, asymmetric C=O, and C-N stretching of the imide group can be detected around 1778, 1723, and 1362 cm -1 respectively. The presence of these peaks indicates that the chemical structure of PI is not affected by the heat treatment process, and the thermal stability of PI is confirmed. The results show that the polymer structure of PI can be used as a binder for Si anodes because it is retained during the heat treatment process.

[0412] Comparing the FTIR spectra of PI and PI-350, the peaks related to the C=O bond and C-N bond of the imide group shift to lower wavenumbers. Not limited to theory, this red shift phenomenon is presumably caused by the interaction between intermolecular groups. In the case of the PI-350 sample, due to the influence of heat treatment, as shown in Fig. 71, it is presumed that the molecular chains are sufficiently close to each other by cross-linking to form a CTC structure. Therefore, after heat treatment, as shown in Fig. 72c, the peak related to the C=O bond of the imide group moves from 1730 cm -1 to 1723 cm -1 . Also, the peak related to the C-N bond of the imide group moves from 1367 cm -1 to 1362 cm-1. The FTIR results indicate that a CTC structure was formed between the molecular chains of PI during the heat treatment process, which can explain the observed differences in the properties between PI and PI-350 (Table 6). Due to the presence of the CTC structure, the packing density of the PI binder is improved, thereby imparting mechanical properties that can improve the electrochemical performance of the Si-PI electrode.

[0413] Fig. 73 shows the results of an ultraviolet-visible spectrophotometer above the PI / NMP solution and PI-350 / NMP. Both samples are colorless and transparent due to the dissolution of PI and the precipitation of PI-350 particles in NMP. No absorption was observed in the ultraviolet-visible spectrum of NMP. However, the ultraviolet-visible spectra of PI and PI-350 have broad absorption peaks at wavelengths of 229 nm and 271 nm, respectively. This peak is considered to be due to the conjugated carbonyl group C=O of the benzene ring on the PI molecular chain. Compared with PI, it can be observed that the absorption peak of PI-350 is narrower and shifted to a lower wavelength value. This may be related to the formation of CTC between the PI molecular chains. Therefore, it can be further confirmed that CTC resulting from cross-linking between PI molecular chains exists in PI-350.

[0414] PI materials with a rich carbonyl group (C=O) in the imide ring can form strong hydrogen bonds with SiNP by utilizing the hydroxyl groups (-OH) on the surface. Not limited to theory, this enables the PI binder to bind relatively firmly to SiNP, thereby forming a relatively strong electrode, and Li + It is speculated that the volume expansion that occurs during the embedding and extraction of may be alleviated.

[0415] Surface characterization of SiN, PI, SI-PI, and Si-PI-350 was performed using FTIR and XPS. As shown in FIGS. 74a and 74b, FTIR characterization was used to investigate the interaction between the Si active material and the PI binder. A schematic diagram of the hydrogen bond between SiNP and PI is shown in FIG. 74c. The FTIR spectra of Si-PI and Si-PI-350 are characterized by the presence of three characteristic peaks near 1778, 1730, and 1367 cm -1 . These peaks correspond to the asymmetric stretching of C=O and C in the imide, respectively. Symmetric stretching of Ring=O and CN. Due to the presence of the PI characteristic peak, the presence of PI was confirmed by the FTIR spectra of Si-PI and Si-PI-350. In the FTIR spectrum of SiNP, as shown in FIG. 74a, a stretching peak associated with the hydroxyl group (-OH) on the nanoparticle surface appears at a wave number of 3739 cm -1 . However, this peak does not exist in the FTIR spectrum of Si-PI-350 shown in FIG. 74a. Not limited to theory, it is speculated that the -OH group on Si interacts with the C=O group of PI to form a hydrogen bond. Furthermore, as shown in FIG. 74b, the stretching peak corresponding to the C=O group of the PI imide ring shifts from 1730 cm of the original PI -1 to 1722 cm of Si-PI -1 . The formation of a hydrogen bond may also cause a wavenumber red shift of 8 cm-1.

[0416] Not only in theory, it is speculated that the structure of the electrode is strengthened by the hydrogen bond between the Si active material surface and the binder, enabling the electrode to withstand the volume change during cycling. On the other hand, in the spectrum of Si-PI-350, a peak related to the vibration of -OH groups (not present in Si-PI), which may be due to the formation of hydroxy-functionalized CTC, reappeared at a wavenumber of 3739 cm -1 . As will be explained below, this strategy can improve the electrochemical performance of the electrode.

[0417] The effect of heat treatment on the electrochemical properties of electrodes made of SiNP and PI binder was evaluated. The electrodes were fabricated using SiNP and PI as the binder (Si@PI). Next, the electrodes were heat-treated at different temperatures of 300, 350, and 400 °C in an Ar-4%H2 flow to create Si@PI-300, Si@PI-350, and Si@PI-400 electrodes, respectively (see Figure 68). The lithium-ion storage performance of the electrodes was evaluated. The results are shown in Figures 75a-b. Figure 75a shows the cycling performance of the electrodes recorded at a current density of 200 mA g -1 . For comparison, the electrochemical performance of electrodes made of Si and PAA / CMC is also shown. Also, the rate capabilities of Si@PI-400, Si@PI-350, Si@PI-300, and Si@PI evaluated at current densities of 100, 200, 500, 1000, and 2000 mA g - −1 are shown in Figure 75b. In Figure 75b, for each cycling number, the order of the resulting specific capacities from the highest to the lowest is Si@PI-350, Si@PI-400, Si@PI-300, Si@PI. Table 7 summarizes the lithium-ion storage performance of the electrodes.

[0418] According to Figure 75a, the specific charge capacities of the Si@PI-400, Si@PI-350, Si@PI-300, Si@PI, and Si@PAA / CMC electrodes after 30 cycles are 1818, 2334, 1383, 737, and 182 mAh g -1It is recorded in []. It can be observed that the electrodes made using the PI binder showed significantly improved cycling performance compared to the electrodes made using the PAA / CMC binder. Not limited to theory, this improvement is considered to be due to the more favorable mechanical properties of the PI brought about by the benzene rings on the molecular chain, which enables the electrodes to maintain their integrity during cycling. Furthermore, it is clear that the electrochemical performance of Si@PI-350 is superior to that of other electrodes. For example, the initial discharge efficiency of the Si@PI-350 electrode (88.57%) is the highest among the electrodes, and all PI-containing electrodes maintain a discharge efficiency of over 95% in subsequent cycling. According to Figures 75a and b, the Si@PI-350 electrode shows a larger specific capacity and rate capability among the electrodes, which is attributed to the structural changes occurring during the heat treatment process, particularly the formation of an optimal CTC structure and hydrogen bonds between the PI and SiNP. Not limited to theory, these modifications can provide the electrodes with higher mechanical performance, accommodate the volume expansion / contraction involved in the lithium-ion insertion and extraction cycles, thereby providing greater electrode integrity during cycling.

[0419]

Table 7

[0420] As shown in Figures 75a-b and Table 7, by raising the heat treatment temperature to 350 °C, the cycling performance of the electrodes is gradually improved, and a peak in the electrochemical performance is recorded therein. The capacity of the Si@PI-350 electrode after 30 cycles at 200 mA g -1 is 2334 mAh g -1 . By further increasing the heat treatment temperature to 400 °C, the lithium-ion storage performance of the sample (Si@PI-400) decreases, which may be due to the damage of the CTC structure and hydrogen bonds at higher temperatures. Not limited to theory, as shown in Figure 75b, an appropriate CTC structure can provide the electrodes with relatively high toughness and improve their cycling stability and rate performance. It should be noted that at 2000 mA g -1After 25 cycles at a current density of, the reversible capacity of Si@PI-350 (900 mAh g -1 ) is larger than that of Si@PI-400 (713 mAh g-1), Si@PI-300 (569 mAh g-1), and Si@PI (338 mAh g-1). Even after reducing the current density to 100 mA g-1, Si-PI@350 still shows a high reversible capacity of 1898 mAh g-1 after 30 cycles, confirming the robustness of the heat-treated PI adhesive. Figure 76 shows the galvanostatic charge-discharge (GCD) curves of the Si@PI-350 electrode recorded at a constant current density of 200 mA g-1. In the first discharge cycle, a short plateau period can be observed around 1.23 V, which is due to the formation of the solid electrolyte interface (SEI) layer. The subsequent charge / discharge curves show excellent consistency, indicating the ideal cycling performance of the Si@PI-350 electrode.

[0421] In addition to the high-voltage plateau in the first discharge cycle, the galvanostatic charge-discharge (GCD) curves of the electrode also show the presence of a low-voltage broad plateau. This is considered to be due to the reactivity of Si NPs in the lithium-ion insertion and extraction events.

[0422] Electrochemical impedance spectroscopy (EIS) was performed in the frequency range of 0.01 - 1000000 Hz with an AC amplitude of 5 mV to further study the effect of heat treatment on the electrochemical resistance of the Si@PI electrode. The EIS curves of the Si@PI and Si@PI-350 electrodes are shown in Figure 77a, and the EIS curves of PI and PI-350 are shown in Figure 77b.

[0423] In the EIS curve, the semicircle observed in the high-frequency region may be related to the charge transfer resistance (Rct). Furthermore, the slope in the low-frequency region is considered to be due to the lithium ion diffusion resistance (Rs). The smaller the diameter of the semicircle, the smaller the electron transfer resistance. The resistance values extracted from FIGS. 77a and b are as shown in Table 8. According to this value, the small Rct value of the heat-treated sample is clear. This is mainly due to the formation of a charge transfer complex between PI and the main molecular chain of the hydrogen bond during the heat treatment process, and the close contact within the SiNP, conductive carbon, and PI binder.

[0424]

Table 8

[0425] Electron microscopy of Si@PI and Si@PI-350 before cycling and after 20 lithium ion insertion / extraction cycles further confirmed the denser morphology of the heat-treated samples. FIGS. 78a-d show the SEM micrographs of Si@PI before cycling, Si@PI-350 before cycling, Si@PI after lithium ion insertion / extraction after 20 cycles, and Si@PI-350 after lithium ion insertion / extraction after 20 cycles.

[0426] Cracks with a size of several microns are observed on the surface of the Si@PI electrode after cycling, but no obvious cracks are seen on the surface of the Si@Pi-350 electrode after cycling, and the structural integrity of the electrode is maintained.

[0427] By comparing the standard SHE reference of the half-cell with the reversible specific capacity and relative average charge potential of the electrode, the electrochemical properties of the anode in the specific energy density of Si@PI-350 were evaluated. The reversible specific capacity and average charging potential of Si@PI-350 (Li +Assuming that the specific capacities (with respect to Li) are 2334 mAh g-1 and 0.53 V respectively, the average electrode potential (with respect to SHE) value is 2.54 V. Based on the relative potential of metallic lithium (-3.04 V vs. SHE). Therefore, at the 30th cycle, the specific energy density of the Si@PI-350 anode was calculated to be 5858 Wh kg-1. As shown in the figure, after 30 cycles, the Si@PI-350 electrode exhibits very high specific capacities and energy densities of 2334 mAh g-1 and 5858 Wh kg-1 respectively, which are superior to those of other binders including sodium carboxymethyl cellulose (CMC), sodium hyaluronate-epichlorohydrin (SH-ECH), polyimide, okra gum, carboxymethyl cellulose-cationic polyacrylamide (CMC-CPAM), and PI with hydroxyl groups (PI-COOH). Compared with the complex synthesis methods commonly used in the preparation of binder systems, the preparation of the Si@PI-350 electrode system is relatively simple and easily scalable. The experimental results introduced here show that by performing a simple heat treatment step, the Li + insertion / extraction performance is significantly improved, thereby making the morphological structure of the electrode denser.

[0428] -MoS 2 -TPA nanostructure 2 Example 39 - Silicon thermally denatured polyimide TPA electrode for lithium ion storage 2.0 g of MoS2 was mixed with 20.0 g of clean waste PET flakes, 10.0 g of SnCl2 and 50 g of LiCl-KCl eutectic mixture. The mixture was transferred to an alumina crucible and heated in a resistance furnace at a heating rate of 5 °C min-1 to various temperatures in the range of 400 - 600 °C with a residence time of 20 minutes at the maximum temperature. Then, it was cooled to room temperature, and the obtained material was washed with deionized water to remove the soluble components of the product, and then dried at 100 °C for 2 hours.

[0429] Figure 79 shows the XRD pattern of the initial MoS2 and that the products obtained at different temperatures are combined with the standard XRD patterns of MoS2, terephthalic acid, and SnO2. It can be observed that the material prepared at 400 °C (Figure 79b) mainly contains MoS2 and terephthalic acid. When the temperature is raised to 450 °C (Figure 79c), the amount of terephthalic acid increases, and as a characteristic, the peaks of the organic compounds in this sample are relatively strong compared to the sample prepared at 400 °C. At 500 °C, as shown in Figure 79(d), in addition to MoS2 and terephthalic acid, diffraction peaks related to SnO2 are also observed. At 600 °C, as shown in Figure 79(e), the XRD peaks corresponding to terephthalic acid disappear.

[0430] MoS prepared at 500 °C 22 , SnO2, and a composite containing C8H6O4 were used to prepare an electrode for storing lithium ions and tested at various current densities in a voltage range of 0.01 - 3.0 V (vs Li + / Li). The electrode was fabricated using the composite, conductive carbon (C45), PVDF with a mass ratio of 7:2:1, and NMP as a solvent, and a mass loading of about 1.2 mg cm -2 was obtained. According to Figure 80, after cycling the electrode 10 times at a current density of 100 mA g -1 , the charge capacity was 570 mAh g -1 , after cycling 20 times at 200 mA g -1 , the charge capacity was 518 mAh g -1 , after cycling 30 times at 500 mA g -1 , the charge capacity was 416 mAh g -1 , after cycling 40 times at 1000 mA g -1 , the charge capacity was 309 mAh g -1 , after cycling 50 times at 2000 mA g -1 , the charge capacity was 183 mAh g -1 , after cycling 60 times at 5000 mA g -1 , the charge capacity was 55 mAh g -1 is. When the current density is 100 mA g -1After returning, the charge capacity recorded at the 71st time is 589 mAh g -1 This shows the high-rate capability and specific capacity of the electrode.

[0431] Other embodiments The procedure described in Example 27 was repeated, with the difference being that the mixture for producing the suspension for applying copper flakes was Si nanoparticles, polyimide, nanostructured TPA, conductive carbon with a mass ratio of 5:2:2:1, and heat treatment was carried out at a target temperature of 250 °C. The nanostructured TPA was obtained based on the process described in Example 21. Figure 81 shows the cycling performance of the electrode obtained in a half-cell coin cell configuration (2025 type) at a current density of 200 mAh g -1 and a cut-off voltage of 0.01 - 1.5 V with respect to lithium. The specific capacity values are determined based on the quality of the silicon material used in the electrode. The specific capacities of the first discharge and charge are 4836 mAh g -1 and 3225 mAh g -1 respectively, and the corresponding discharge efficiency is 66.7%. The specific capacities of the second discharge and charge are 3445 and 3253 mAh g -1 respectively, indicating a discharge efficiency of 94.4%. The third discharge capacity and the charged capacity are 3373 mAh g -1 and 3256 mAh g -1 respectively, indicating a discharge efficiency of 96.5%. Furthermore, the third discharge capacity and the charged capacity are 3373 mAh g -1 and 3256 mAh g -1 respectively, indicating a discharge efficiency of 96.5%. Furthermore, the discharge and charge capacity values at the 30th cycle are 3132 and 3078 mAh g -1 respectively, corresponding to a discharge efficiency of 98.3%. Considering the average charging voltage of 0.5 V, the specific energy density of the electrode at the 30th cycle was evaluated to be 7818 Wh kg-1.

[0432] ​ Although specific embodiments have been disclosed above, the present disclosure is not limited to such embodiments.

[0433] For example, in some embodiments, the depolymerizing agent can include an ionic liquid other than an inorganic salt or a substitute for an inorganic salt. Examples of ionic liquids include [bmpy][Tf2N], [BMIM][Tf2N], and imidazole ionic liquids. Examples of cations in ionic liquids include 1-octyl-3-methylimidazolium ([OMIM]), 1-methylimidazolium ([MIM]), 1-ethyl-3-methylimidazolium ([EMIM]), 1,3-dimethylimidazolium ([M13IM]), 1-(2-hydroxyethyl)-3-methylimidazolium ([HOEMIm]), 1-ethyl-2,3-dimethylimidazolium ([EMMIM]), 1-butyl-3-methylimidazolium ([BMIM]), 1-hexyl-3-methylimidazolium ([HMIM]), 1,2,3-trimethylimidazolium ([MMIM]), 1-decyl-3-methylimidazolium ([DMIM]), 1-allyl-3-butylimidazolium ([ABIM]), 1,2-dimethylimidazolium ammonium ([M12IM]), 1-butyl-2,3-dimethylimidazolium ([BMMIM]), 1-allyl-3-methylimidazolium ([AMIM]), 1-allyl-3-vinylimidazolium ammonium ([AVIM]), tetradecyltrihexylphosphine ([P66614]), N-ethylpyridine ([EPy]), N-butylpyridine ([BPy]). Examples of anions in ionic liquids include bis(trifluoromethylsulfonyl)imide ([Tf2N]), bromide ([Br]), dicyandiamide ([DCA]), hexafluorophosphate ([PF6]), perchlorate ([ClO4]), toluenesulfonate ([TS]), acetate ([Ac]), chloride ([Cl]), glycinate ([Gly]), iodide ([I]), trifluoromethanesulfonate ([TFO]), iminate ([Pro]), alaninate ([Ala]), lysinate ([Lys]), dihydrogen phosphate ([H2PO4]), nitrate ([NO3]), serine salt ([Ser]), glutamate ([Glu]), and bisulfate ([HSO4]) and tetrafluoroborate ([BF4]).

Claims

【Request Item 1】 Equation C x O y H z (In the formula, x ranges from 2 to 12, y is between 2 and 8, and z ranges from 2 to 14. A composition comprising a nanostructured organic compound containing multiple molecules having, The nanostructured organic compound has at least one dimension less than 100 nm, and A composition comprising the nanostructured organic compound selected from the group consisting of terephthalic acid, terephthalate, dimethyl terephthalate, bis(2-hydroxyethyl) terephthalate, ethylene glycol, phthalic acid, protocatechuic acid, and isophthalic acid.

2. (a) The organic compound is a nanocrystalline material; and / or (b) The composition comprises crystal domain sizes of 1 nm to 100 nm; and / or (c) The components of the composition have a maximum dimension of less than 100 nm in at least one dimension. The composition according to claim 1.

3. The composition according to claim 1, wherein the 2θ (±0.2 degrees) value of the XRD peak of the composition includes at least one selected from the group consisting of 16.99 degrees, 24.83 degrees, and 27.54 degrees.

4. The composition according to claim 1, further comprising a crystalline metal oxide embedded within the nanostructured organic compound.

5. (a) The crystalline metal oxide is uniformly distributed within the organic compound; or (b) The composition has a first concentration of crystalline metal oxide in the internal region of the composition, a second concentration of crystalline metal oxide in the surface region of the composition, and the first concentration is greater than the second concentration. The composition according to claim 4.

6. The composition according to claim 1, wherein the composition comprises nanoparticles having a size of 1 nm to 200 nm.

7. The composition according to claim 1, wherein the composition forms particles having a size of 0.01 μm to 100 μm.

8. (a) the organic compound comprises terephthalic acid; or (b) The composition comprises a nanostructured organic compound; or (c) The composition comprises nanostructured terephthalic acid, The composition according to claim 1.

9. (a) The composition comprises 1 wt.% to 99 wt.% of an organic compound; and / or (b) The crystalline metal oxide comprises crystalline metal oxide nanoparticles; and / or (c) The composition contains 1 wt.% to 95 wt.% of a crystalline metal oxide; and / or (d) The particle size of the crystalline metal oxide is 1 nm to 100 nm; and / or (e) The crystalline metal oxide comprises at least one selected from the group consisting of tin(IV) oxide (SnO₂), tin(II) oxide (SnO), zinc oxide (ZnO), zinc peroxide (ZnO₂), calcium oxide, lithium oxide, potassium oxide, lead oxide, and iron oxide; and / or (f) The 2θ (±0.2°) value of the XRD peak of the organic compound includes at least one selected from the group consisting of 17.41°, 25.21°, and 27.95°; and / or (g) The 2θ (±0.2°) value of the XRD peak of the crystalline metal oxide includes at least one selected from the group consisting of 26.60°, 33.90°, 37.97°, 39.00°, 51.81°, 54.79°, 57.87°, 61.92°, 64.79°, 66.01°, 71.33°, 78.76°, 81.19°, 83.78°, and 87.29°. The composition according to claim 4.

10. (a) The composition has at least one endothermic peak having the highest temperature (±3°C) selected from the group consisting of 328°C, 461°C, and 528°C as determined by differential scanning calorimetry (DSC) thermogram; and / or (b) The composition has a surface area of ​​10 square meters / g (m²g⁻¹) to 50 m²g⁻¹; and / or (c) The composition has a bulk electrical conductivity of 5 siemens / meter (S m⁻¹) to 5000 S m⁻¹ at 6.3 MPa. The composition according to claim 4.

11. The composition according to claim 1, further comprising a silicon-containing material.

12. (a) The silicon-containing material is embedded in the organic compound; and / or (b) The composition contains 0.1 wt.% to 95 wt.% of a silicon-containing material; and / or (c) The silicon-containing material contains elemental silicon; and / or (d) The silicon-containing material includes nanoparticles, The composition according to claim 11.

13. The composition according to claim 1, further comprising graphene nanosheets.

14. (a) The composition comprises 0.1 wt.% to 50 wt.% of graphene nanosheets; and / or (b) The graphene nanosheet comprises flakes having a flake size of 1 nm to 5 μm; and / or (c) The graphene nanosheets consist of 1 to 100 layers; and / or (d) The graphene nanosheet has a carbon purity of at least 90%; and / or (e) The graphene nanosheet contains functional groups on its surface, The composition according to claim 13.

15. The composition according to claim 14, wherein the functional group comprises at least one selected from the group consisting of a hydroxyl group, a carbonyl group, a carboxyl group, and an amino group.

16. The composition according to claim 1, further comprising a metal-organic structure embedded in the organic compound.

17. (a) The metal-organic structure comprises the organic compound and the metal; and / or (b) The metal is selected from the group consisting of Zn, Fe, Cu, Al, Zr, Cr, Co, Li, Na and K; and / or (c) The metal-organic structure has the formula MC x H y O z ・nH 2 O, where M is a metal and n is 0 to 5; and / or (d) The metal-organic structure has the formula MC x H y O z, where M is a metal; and / or (e) The organometallic structure contains a terephthalate ester; and / or (f) The average crystal domain size of the metal-organic structure is 30 nm to 60 nm; and / or (g) The 2θ (±0.2°) value of the XRD peak of the composition includes at least one selected from the group consisting of 11.75°, 14.74°, 16.60°, and 16.98°; and / or (h) The 2θ (±0.2°) value of the XRD peak of the composition includes at least one selected from the group consisting of 9.89°, 19.33°, 25.27°, and 40.11°; and / or (i) The 2θ (±0.2°) value of the XRD peak of the composition includes at least one selected from the group consisting of 17.45°, 25.27°, 28.017°, and 42.99°. The composition according to claim 16.

18. The composition according to claim 16, wherein the composition forms particles having a size of 500 nm to 700 μm.

19. (a) The particles include sheet-like particles having a size of 10 nm to 10 μm; and / or (b) The particles include aggregated nanoparticles having a size of 1 nm to 60 nm; and / or (c) The particles include metal-organic structure crystals having a size of 10 nm to 10 μm. The composition according to claim 18.

20. The composition according to claim 1, further comprising a tin-containing member selected from the group consisting of metallic tin, tin chloride, tin chloride hydrate, tin chloride hydroxide, and oxidized tin chloride hydroxide.

21. (a) The tin-containing member comprises particles having a size of 1 nm to 100 nm; and / or (b) The tin-containing member is at least partially crystalline; and / or (c) The tin-containing component has a nanostructure; and / or (d) The tin hydroxide oxidized by the tin hydroxide contains the formula Sn 21 Cl 16 (OH) 14 O 6, The composition according to claim 20.

22. The composition according to claim 1, wherein the composition has an absorbance of at least 1 a.u. at 242 nm at a concentration of 0.5 g / L.

23. An electrode comprising the composition according to any one of claims 1 to 22.

24. (a) The electrode further comprises at least one selected from the group consisting of conductive carbon, a binder, copper foil, and graphene nanosheets; and / or (b) The electrode has a Li-ion discharge capacity of 10 mAh / g (mAh g⁻¹) to 1500 mAh g⁻¹ after 500 cycles at a current density of 200 mA g⁻¹; and / or (c) The electrode has a Coulomb efficiency of 70% to 120% after 500 cycles; and / or (d) The electrolyte resistance of the half-cell made from the electrodes increases from 1.0 Ω to 6.0 Ω after 150 cycles; and / or (e) The electrolyte resistance of the half-cell made from the electrodes increases from 2.0 Ω to 8.0 Ω after 300 cycles; and / or (f) The lithium ion diffusion rate of the electrode is 10⁻¹¹ cm² s⁻¹ to 9 × 10⁻⁹ cm² s⁻¹ after 150 cycles; and / or (g) The lithium ion diffusion rate of the electrode is 2 × 10⁻¹¹ cm² s⁻¹ to 10⁻⁸ cm² s⁻¹ after 300 cycles; and / or (h) The electrode has a Li-ion discharge capacity of 300 mAh g⁻¹ to 1500 mAh g⁻¹ after 10 cycles at a current density of 100 mAh g⁻¹; and / or (i) The embedding of Na ions into the electrode occurs at a voltage of 0.1V to 0.9V (vs Na / Na+); and / or (j) Desorption of Na+ ions from the electrode occurs at a voltage of 0.3V to 0.7V (vs Na / Na+); and / or (k) The electrode has a Li-ion discharge capacity of 100 mAh g⁻¹ to 1800 mAh g⁻¹ after 500 cycles. The electrode according to claim 23.

25. The composition according to claim 1, further comprising a metal embedded in the organic compound.

26. (a) The metal is selected from the group consisting of Na, Li, K, and Zn; and / or (b) The composition comprises a molecular formula selected from the group consisting of Na₂C₄H₄O₄, Li₂C₄H₄O₄, K₂C₄H₄O₄, and ZnC₄H₆O. The composition according to claim 25.

27. The composition according to claim 1, wherein the composition comprises a transition metal dichalcogenide.

28. (a) The transition metal dichalcogenide has formula MX2, where M is a transition metal atom and X is a chalcogen atom; and / or (b) The transition metal dichalcogenide includes a two-dimensional transition metal dichalcogenide; and / or (c) The transition metal dichalcogenide is embedded in the organic compound; and / or (d) The composition comprises a crystalline metal oxide, and the transition metal dichalcogenide is embedded in the crystalline metal oxide. The composition according to claim 27.

29. The composition according to any one of claims 1 to 22 and 25 to 28, further comprising a polymer and a silicon-containing material.

30. (a) The polymer is made from monomers, and at least a portion of the monomers are crosslinked with each other; and / or (b) The monomer includes an imide monomer; and / or (c) A portion of the material and a portion of the polymer are bonded by hydrogen bonds; and / or (d) The material includes silicon particles embedded within the organic compound; and / or (d) The material contains silicon particles; and / or (f) The polymer comprises polyimide; and / or (g) The Li-ion energy storage capacity of the composition at a current density of 200 mA / g is such that, based on the mass of silicon elements in the material, the composition has a capacity of 1000 mAh / g to 3500 mAh / g after 30 cycles; and / or (h) The Li-ion energy storage process of the composition at a current density of 200 mA / g provides a specific energy density of 3000 Wh kg⁻¹ to 8000 Wh kg⁻¹ after 30 cycles; and / or (i) The lithium ion diffusion impedance of the composition is 10Ω to 60Ω; and / or (j) The infrared spectrum of the polymer has a peak at 1723 cm⁻¹ and / or a peak at 1362 cm⁻¹; and / or (k) The infrared spectrum of the composition does not have a peak at 3739 cm⁻¹; and / or (l) The polymer is polyimide, The composition according to claim 29.

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