Battery, gas sensing material and preparation method therefor, sensor, and electric device

Abstract

The present application discloses a gas sensing material and a preparation method therefor, a sensor, a battery, and an electric device. The gas sensing material is a metal organic framework (MOF) having a one-dimensional nanostructure, and a gas response mechanism of the gas sensing material is transfer of coordination electrons. By means of the described method, the present application can achieve detection of target gas in an oxygen-free environment, and can achieve detection of gas generated in the battery. Furthermore, the gas detection sensitivity and selectivity can be improved, the gas response time can be shortened, and the gas detection limit can be lowered.

Description

Battery, gas sensing material and preparation method thereof, sensor, and electrical equipment

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to Chinese patent application No. 202311641758.9, filed on November 30, 2023, entitled “Gas Sensing Materials, Preparation Methods Thereof, Sensors, Batteries and Electrical Equipment,” the entire contents of which are incorporated herein by reference. Technical Field

[0003] The present application relates to the field of new energy technology, and in particular to batteries, gas sensing materials and preparation methods thereof, sensors, and electrical equipment. Background Art

[0004] As global energy and environmental problems continue to intensify, new energy, as one of the areas of sustainable development, is developing rapidly. Batteries are being used more and more widely as a new energy source. Among them, the problem of battery gas production has always been a concern. The gas produced by the battery can easily cause safety problems. By detecting the gas situation inside the battery, timely warnings can be given. The existing gas sensing principle requires oxygen, which limits its application in detecting gas under anaerobic conditions. However, the environment inside the battery cell is anaerobic, so there is an urgent need to develop new materials and sensors that can respond to gas under non-oxygen conditions. The above statements are only used to provide background technical information related to this application and do not necessarily constitute prior art.

[0005] Summary of the Invention

[0006] The main technical problem solved by this application is to provide a battery, a gas sensing material and a preparation method thereof, a sensor, and an electrical device. The gas sensing material can respond to gas under non-oxygen conditions and can detect gas production in the battery.

[0007] To solve the above technical problems, the present application adopts a technical solution: providing a battery, the battery including a gas sensor, the gas sensor including a gas sensing material, the gas sensing material including a metal-organic framework material, the metal-organic framework material including a one-dimensional nanomaterial, the one-dimensional nanomaterial having nanoscale dimensions in at least two dimensions, the nanoscale being 0.1nm-100nm. When the metal-organic framework material is used as a gas-sensitive material, its response mechanism is the transfer of coordinated electrons, which is independent of oxygen. Therefore, it can achieve gas response under non-oxygen conditions, thereby enabling the detection of gas production within the battery.

[0008] Furthermore, the one-dimensional nanostructure gives the metal-organic framework material a higher surface area to volume ratio, providing a large number of adsorption sites for gas molecules, thereby improving the sensing sensitivity; at the same time, the diffusion rate of gas on the one-dimensional nanostructure is significantly faster, resulting in a shorter response time.

[0009] In one embodiment, the metal-organic framework material comprises nanoribbons having a thickness of 1-10 nm and a width of 10-100 nm. This arrangement significantly enhances the conductivity of the metal-organic framework material, while also significantly varying its resistance with gas adsorption, thereby effectively improving the sensitivity and speed of gas response.

[0010] In one embodiment, the metal-organic framework material comprises nanoribbons having a thickness of 3-8 nm and a width of 15-70 nm. This arrangement significantly enhances the conductivity of the metal-organic framework material, while also significantly varying its resistance with gas adsorption, thereby effectively improving the sensitivity and speed of gas response.

[0011] In one embodiment, the metal-organic framework material comprises a complex of a metal ion and an organic ligand, wherein the metal element comprises one or more of copper, nickel, cobalt, zinc, and iron. This arrangement improves the stability of the metal-organic framework material, while the metal ions can serve as gas adsorption sites, improving sensitivity and selectivity for the adsorbed gas.

[0012] In one embodiment, the organic ligand comprises a structure represented by formula (1):

[0013] Wherein, R1 and R2 are hydroxyl, amino or thiol, which are favorable for forming coordination bonds with metal ions and causing the metal organic framework material to grow in a ribbon shape.

[0014] In one embodiment, the organic ligand includes 1,5-diamino-4,8-dihydroxyanthraquinone. 1,5-Diamino-4,8-dihydroxyanthraquinone is an anthraquinone compound containing amino and hydroxyl substituents. Through these substituents, it can form stable coordination bonds with metal ions, thereby constructing metal-organic frameworks. This arrangement creates efficient charge transfer pathways between the metal ions and the organic ligands, contributing to a small band gap and high charge mobility. Furthermore, it can form π-d conjugated planes and π-π stacking, providing planar conductive paths and improving the conductivity of the metal-organic framework.

[0015] In one embodiment, the gas sensing material is responsive to one or more of carbon monoxide, ammonia, hydrogen sulfide, and nitrogen dioxide. While being responsive to multiple gases, the gas sensing material also has a certain degree of selectivity.

[0016] To address the aforementioned technical issues, another technical solution employed in this application is to provide a gas sensing material comprising a metal-organic framework (MOF) material, which includes a one-dimensional nanomaterial having nanoscale dimensions in at least two dimensions, with the nanoscale ranging from 0.1 nm to 100 nm. When used as a gas-sensing material, the MOF material exhibits a response mechanism based on the transfer of coordinated electrons and is independent of oxygen, enabling gas response in non-oxygen conditions.

[0017] To address the above technical issues, another technical solution adopted in this application is to provide a method for preparing a gas sensing material, comprising: providing a metal ion solution and an organic ligand solution; allowing the metal ion solution and the organic ligand solution to react with each other to obtain a metal-organic framework material, wherein the metal-organic framework material includes a one-dimensional nanomaterial, wherein the one-dimensional nanomaterial has nanoscale dimensions in at least two dimensions, and the nanoscale is 0.1nm-100nm. The one-dimensional nanostructure gives the metal-organic framework material a higher surface area to volume ratio, providing a large number of adsorption sites for gas molecules, thereby improving sensing sensitivity; at the same time, the diffusion rate of gas on the one-dimensional nanostructure is significantly faster, resulting in a shorter response time.

[0018] In one embodiment, allowing the metal ion solution and the organic ligand solution to react with each other includes uniformly mixing the metal ion solution and then allowing the mixture to react to form a metal-organic framework material. This configuration allows for the microstructure of the resulting metal-organic framework material to be controlled to form a one-dimensional nanostructure.

[0019] In one embodiment, the reaction is allowed to stand for 8-15 hours and / or at a temperature of 70-95° C. By regulating the reaction time and temperature of the reaction system, the yield and microstructure of the resulting metal-organic framework material can be controlled, thereby facilitating the regulation of gas sensing performance.

[0020] In one embodiment, uniformly mixing the metal ion solution and the organic ligand solution includes: adding the metal ion solution dropwise to the organic ligand solution and mixing; the metal ion solution is added at a rate of 1-20 seconds per drop. This arrangement allows the metal ions to be more evenly dispersed in the organic ligand solution.

[0021] In one embodiment, a base, such as ammonia, is added to the mixture of the metal ion solution and the organic ligand solution. This configuration facilitates the deprotonation of the metal ions and the dissociation of the organic ligands, thereby controlling the growth rate of the metal-organic framework material.

[0022] In one embodiment, allowing a metal ion solution to react with an organic ligand solution includes placing the metal ion solution and the organic ligand solution in the same container, wherein the metal ion solution and the organic ligand solution are immiscible, and utilizing an interfacial reaction to produce a metal-organic framework material. By regulating the interaction of reactants at the interface, the morphology and structure of the metal-organic framework material can be controlled, thereby adjusting the sensitivity of the sensing material.

[0023] In one embodiment, the organic ligand solution includes a 1,5-diamino-4,8-dihydroxyanthraquinone solution, the metal ion solution includes a divalent copper ion solution, and the molar ratio of 1,5-diamino-4,8-dihydroxyanthraquinone to divalent copper ions is 1:(2-8). This arrangement allows for an excess of copper ions in the reaction, which can promote the reaction toward the forward direction of generating reactants, thereby increasing the yield of the metal-organic framework material.

[0024] In one embodiment, the organic ligand solution includes a 1,5-diamino-4,8-dihydroxyanthraquinone solution, the metal ion solution includes a divalent copper ion solution, and the molar ratio of 1,5-diamino-4,8-dihydroxyanthraquinone to divalent copper ions is 1:(4-6). This arrangement allows for an excess of copper ions in the reaction, which can promote the reaction toward the forward direction of generating reactants, thereby increasing the yield of the metal-organic framework material.

[0025] In one embodiment, the solvent of the organic ligand solution includes one or more of methanol, ethanol, acetone, tetrahydrofuran, N,N-dimethylformamide, dimethyl sulfoxide, and dichloromethane. By selecting different solvents, different methods can be selected for preparing metal-organic framework materials. Furthermore, the crystallinity, pore structure, pore environment, and morphology of the metal-organic framework materials can be manipulated, and further, the selectivity, response value, and sensitivity to gases can be adjusted.

[0026] In one embodiment, the metal ion solution includes a divalent copper salt solution, wherein the divalent copper salt includes at least one of copper acetate monohydrate, copper sulfate pentahydrate, and copper chloride dihydrate. By selecting different anions, the micromorphology, pore structure, and pore size of the metal-organic framework material can be manipulated, further adjusting the material's gas sensing performance.

[0027] To solve the above technical problems, another technical solution adopted in this application is to provide a gas sensor comprising the above gas sensing material, or a gas sensing material produced by any of the above methods. Through the above arrangement, a highly sensitive response to the target gas can be achieved.

[0028] To solve the above technical problems, another technical solution adopted by the present application is to provide an electrical device comprising the above battery. The electrical device has at least the same advantages as the battery.

[0029] The above description is only an overview of the technical solution of the present application. In order to more clearly understand the technical means of the present application, it can be implemented in accordance with the contents of the specification. In order to make the above and other purposes, features and advantages of the present application more obvious and easy to understand, the specific implementation methods of the present application are listed below. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the following briefly introduces the drawings required for use in the description of the embodiments. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without any creative work.

[0031] FIG1 is a transmission electron microscope (TEM) image of a metal organic framework material according to one or more embodiments;

[0032] FIG2 is a schematic diagram of a method for preparing a gas sensing material according to one or more embodiments;

[0033] FIG3 is a schematic diagram of a method for preparing a gas sensing material according to one or more embodiments;

[0034] FIG4 is a schematic diagram of an exploded structure of a battery according to one or more embodiments;

[0035] FIG5 is a schematic diagram of an exploded structure of a battery cell according to one or more embodiments;

[0036] FIG6 is a schematic structural diagram of an electric device according to one or more embodiments.

[0037] FIG7 is a schematic diagram of a gas sensing performance test according to one or more embodiments;

[0038] FIG8 is an X-ray diffraction pattern (XRD) of a gas sensing material DDA-Cu according to one or more embodiments;

[0039] 9 is an X-ray energy dispersive spectrometry (EDS) image of a gas sensing material DDA-Cu according to one or more embodiments;

[0040] FIG10 is a scanning electron microscope (SEM) image of the gas sensing material DDA-Cu-1 obtained in Example 1;

[0041] FIG11 is a scanning electron microscope (SEM) image of the gas sensing material DDA-Cu-2 obtained in Example 2;

[0042] FIG12 is a scanning electron microscope (SEM) image of the gas sensing material DDA-Cu-3 obtained in Example 3;

[0043] FIG13 is a schematic diagram illustrating gas response of a gas sensing material DDA-Cu according to one or more embodiments;

[0044] FIG14 is a schematic diagram illustrating gas response of the gas sensing material DDA-Co according to one or more embodiments;

[0045] FIG15 is a schematic diagram illustrating gas response of a gas sensing material DDA-Ni according to one or more embodiments;

[0046] FIG16 is a schematic diagram illustrating gas response of the gas sensing material DDA-Cu according to one or more embodiments;

[0047] FIG17 is a schematic diagram illustrating gas response of the gas sensing material DDA-Cu according to one or more embodiments;

[0048] FIG18 is a schematic diagram illustrating gas response of the gas sensing material DDA-Cu according to one or more embodiments;

[0049] In the attached figure:

[0050] 1000, vehicle; 300, motor; 200, controller; 100, battery; 10, housing; 11, first part; 12, second part; 20, battery cell; 21, end cap; 21a, electrode terminal; 22, housing; 23, electrode assembly. DETAILED DESCRIPTION

[0051] In order to make the purpose, technical solution and effect of this application clearer and more specific, the following embodiments of the technical solution of this application will be described in detail with reference to the accompanying drawings. The following embodiments are only used to more clearly illustrate the technical solution of this application and are therefore only examples and are not intended to limit the scope of protection of this application.

[0052] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this application belongs; the terms used herein are only for the purpose of describing specific embodiments and are not intended to limit this application; the terms "including" and "having" and any variations thereof in the specification and claims of this application and the above-mentioned figure descriptions are intended to cover non-exclusive inclusions.

[0053] In the description of the embodiments of the present application, the technical terms "first" and "second" are used only to distinguish different objects and should not be understood as indicating or implying relative importance or implicitly indicating the quantity, specific order, or primary and secondary relationship of the indicated technical features. In the description of the embodiments of the present application, the term "multiple" refers to more than two (including two), similarly, "multiple groups" refers to more than two (including two), and "multiple pieces" refers to more than two (including two), unless otherwise clearly and specifically defined.

[0054] References herein to "embodiments" mean that a particular feature, structure, or characteristic described in connection with the embodiments may be included in at least one embodiment of the present application. The appearance of this phrase in various places in the specification does not necessarily refer to the same embodiment, nor does it constitute an independent or alternative embodiment that is mutually exclusive of other embodiments. It is understood, both explicitly and implicitly, by those skilled in the art that the embodiments described herein may be combined with other embodiments.

[0055] In the description of the embodiments of this application, the term "and / or" is simply a description of the association relationship between associated objects, indicating that three relationships can exist. For example, A and / or B can represent the following three situations: A exists alone, A and B exist simultaneously, and B exists alone. In addition, the character " / " in this document generally indicates that the associated objects are in an "or" relationship.

[0056] Amounts, ratios, and other numerical values ​​are presented herein in a range format. It should be understood that such range format is used for convenience and brevity and should be interpreted flexibly to include not only the values ​​explicitly specified as range limits, but also all individual values ​​or sub-ranges encompassed within the range, as if each value and sub-range were explicitly specified.

[0057] If not otherwise specified, all steps of the present application may be performed sequentially, randomly, or in parallel, preferably sequentially. For example, the method includes steps (a) and (b), indicating that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially, or may include steps (a) and (b) performed simultaneously in parallel. For example, the method may further include step (c), indicating that step (c) may be added to the method in any order, for example, the method may include steps (a), (b), and (c), or may include steps (a), (c), and (b), or may include steps (c), (a), and (b), etc.

[0058] Due to their various superior properties, power batteries have been widely used in people's lives, new energy vehicles, and energy storage industries. New energy vehicles and electrochemical energy storage are the areas where power batteries are most widely used. The future development goals of batteries are high energy density, high safety, long life, and low cost. During the charging or discharging process of the battery, the electrochemical reaction causes material conversion and gas release, which will generate gas.

[0059] During charging, batteries convert external electrical energy into chemical energy for storage, and some side reactions can also generate gases. For example, in lead-acid batteries, the side reaction of water electrolysis during charging produces oxygen and hydrogen gases. During discharge, the chemical energy in the battery is converted into electrical energy, and some reactions can also generate gases. For example, during discharge, lithium-ion batteries may experience oxidation of the lithium metal, producing harmful gases such as carbon fluoride.

[0060] In addition, batteries may generate gas during use due to overcharging, over-discharging, internal faults, or improper operation. In such cases, the chemical reaction within the battery may become uncontrolled, resulting in violent gas release and even thermal runaway.

[0061] Battery thermal runaway is a crucial area of ​​battery safety research. It is a chain reaction phenomenon triggered by various factors. The battery packs of new energy vehicles are typically sealed and operate in an oxygen-free environment during normal operation. If thermal runaway occurs, the battery pack will release characteristic gases. These gases include carbon dioxide, carbon monoxide, hydrogen, ethylene, methane, ethane, and propylene. Detecting these characteristic gases can provide early warnings and enable timely action, minimizing damage to life and property. Currently, chemiresistor sensors hold promise for battery thermal runaway detection. They rely on changes in conductivity when the sensing material interacts with the characteristic gases, offering advantages such as simplicity, versatility, low power consumption, and cost-effectiveness. However, existing metal oxide sensors require oxygen, limiting their application in detecting gases generated during battery thermal runaway under oxygen-free conditions. However, the oxygen-free environment within a battery cell necessitates the development of new materials and sensors that can operate stably and accurately under oxygen-free conditions.

[0062] In order to achieve highly sensitive detection of characteristic gases of battery thermal runaway in an oxygen-free environment, studies have found that metal-organic frameworks (MOFs) have tunable surface properties and chemical reactivity, and can be used as gas sensing materials. Specifically, metal organic frameworks (MOFs) are typical porous crystalline materials constructed by orderly splicing organic connectors between metal nodes. The unique skeleton and pore structure characteristics of MOFs materials determine their unique characteristics such as large specific surface area, high porosity and chemical tunability. The large specific surface area and tunable porous structure of MOFs materials can provide a large number of sites for gas adsorption. After the gas molecules are adsorbed, the formation or breaking of coordination bonds will occur, causing electron transfer, thereby changing the electrical properties of MOFs materials and achieving response to the adsorbed gas. That is, when MOFs materials are used as gas-sensitive materials, their response mechanism is the transfer of coordinated electrons. Based on this principle, MOFs materials can achieve gas response even under oxygen-free conditions, expanding their application scenarios as gas sensing materials.

[0063] In the present application, a battery is provided, which includes a gas sensor, the gas sensor includes a gas sensing material, the gas sensing material includes a metal-organic framework material, the metal-organic framework material includes a one-dimensional nanomaterial, and the one-dimensional nanomaterial has a size of nanoscale in at least two dimensions, and the nanoscale is 0.1nm-100nm.

[0064] When metal-organic framework materials are used as gas-sensitive materials, their response mechanism is the transfer of coordinated electrons, which is independent of oxygen. Therefore, they can achieve gas response under non-oxygen conditions, thereby enabling the detection of gas production in the battery.

[0065] In one embodiment, metal-organic frameworks (MOFs) can be nanostructured materials. Nanostructures are structures with dimensions between molecular and micrometer scales; these materials typically have linear dimensions ranging from 0.1 to 100 nm. Nanostructures include one-dimensional, two-dimensional, and three-dimensional systems, and these units include nanoparticles, nanotubes, nanorods, nanowires, nanobelts, and nanometer-sized pores.

[0066] By creating nanostructures of metal-organic frameworks (MOFs), they can possess a large specific surface area, providing numerous sites for gas adsorption and improving the sensitivity of gas sensing materials. Further research has revealed that most MOFs have a two-dimensional nanostructure, known as two-dimensional nano-MOFs. Furthermore, some two-dimensional nano-MOFs fail to quickly release adsorbed gases, exhibiting irreversible response, making the gas sensor unreusable. Other two-dimensional nano-MOFs exhibit poor electrical conductivity, resulting in insufficient sensitivity.

[0067] Based on this, the present application provides a metal organic framework material (MOFs) with a one-dimensional nanostructure, that is, a one-dimensional nano MOFs material. A one-dimensional nano material refers to a material whose dimensions in two dimensions are nanoscale and whose dimensions in the third dimension exceed the nanoscale, and the nanoscale is defined as 0.1nm-100nm. For example, from the perspective of the three dimensions of length, width, and height (thickness), a one-dimensional nano MOFs material can be a material whose width and height (thickness) are nanoscale, but whose length is greater than the nanoscale; or a material whose width and length are nanoscale, but whose height (thickness) is greater than the nanoscale. One-dimensional nano MOFs materials have a higher specific surface area to volume ratio, which is conducive to the adsorption of gas molecules, thereby improving the sensing sensitivity; at the same time, the diffusion rate of gas molecules on the one-dimensional nanostructure is significantly faster, with a faster gas diffusion rate, which makes the response time shorter.

[0068] In some embodiments of the present application, the metal-organic framework material includes a nanobelt material, namely a nanobelt MOFs material. The thickness of the nanobelt material is 1-10 nm and the width is 10-100 nm. Please refer to Figures 1 and 10. Figure 1 is a transmission electron microscope (TEM) image of the metal-organic framework material according to one or more embodiments, and Figure 7 is a scanning electron microscope (SEM) image of the metal-organic framework material according to one or more embodiments. It can be observed from the image that the thickness of the nanobelt MOFs material is 1-10 nm and the width is 10-100 nm, while the length is relatively large, exceeding tens of nanometers and reaching the micron level. For example, the thickness can be 1 nm, 2 nm, 3 nm, 5 nm, 6 nm, 8 nm, 10 nm; the width can be 10 nm, 15 nm, 20 nm, 30 nm, 40 nm, 60 nm, 80 nm, 100 nm, etc.

[0069] In one embodiment, the metal-organic framework material comprises a nanoribbon material, wherein the thickness of the nanoribbon material is 3-8 nm and the width of the nanoribbon is 15-70 nm. For example, the thickness may be 3 nm, 5 nm, 6 nm, 8 nm, etc., and the width may be 15 nm, 20 nm, 30 nm, 40 nm, 60 nm, 70 nm, etc.

[0070] Thanks to the one-dimensional nanostructure, the nanobelt MOFs material in this application has a higher structural freedom than two-dimensional and three-dimensional metal organic framework materials, providing more opportunities for creating conductive paths, thereby significantly improving the conductivity of the material; the structure is stable and orderly, with a higher surface area to volume ratio, providing a wider site for the adsorption of gas molecules, and at the same time can accelerate the diffusion rate of gas on the sensing material, so that the resistance changes significantly with the change of gas adsorption, thereby effectively improving the sensitivity and speed of gas response.

[0071] In some embodiments of the present application, the metal-organic framework material chemically comprises a complex of a metal and an organic ligand, wherein the metal element comprises one or more of copper, nickel, cobalt, zinc, and iron. Specifically, the metal-organic framework material may be a complex of a metal ion and an organic ligand, wherein the metal ion comprises one or more of copper, nickel, cobalt, zinc, and iron ions.

[0072] Metal ions and organic ligands form complexes through coordination bonds. Metal ions can act as coordination centers, coordinating with multiple atoms on the organic ligands to form a relatively stable morphology, enhancing the stability of metal-organic frameworks. Furthermore, metal ions can serve as gas adsorption sites. Adsorbed gas molecules can cause the formation or breakage of coordination bonds, leading to electron transfer, which in turn alters the electrical and optical properties of MOFs and enhances their sensitivity and selectivity to adsorbed gases. Specifically, gas molecules can be linked to metal ions through coordination bonds, leading to electron transfer, thus achieving gas response.

[0073] In some embodiments of the present application, a metal-organic framework (MOF) material may contain only one type of metal ion; alternatively, multiple different types of metal ions may be present simultaneously, forming different coordination centers. Multiple metal ions may be present, forming multiple coordination centers. Different types of metal ions can impart selectivity to the MOF material's response to different gases. Gas selectivity can be enhanced by regulating the type and quantity of metal ions.

[0074] In some embodiments of the present application, the organic ligand includes 1,5-diamino-4,8-dihydroxy anthraquinone (DDA), which has the structural formula This is a ligand with an aromatic core and a centrosymmetric molecule. Specifically, DDA is an anthraquinone compound containing amino and hydroxyl substituents, and its molecular formula is C 14 H 10N2O4, with a molecular weight of 270.24, contains an anthraquinone nucleus with amino groups substituted at positions 1 and 5, and hydroxyl groups substituted at positions 4 and 8. A conjugated effect exists between the anthraquinone ring and the amino and hydroxyl groups. The amino, hydroxyl, and carbonyl groups in the molecule can act as coordinating atoms to form stable coordination bonds with a variety of metal ions, resulting in metal-organic frameworks (MOFs) with diverse structural properties and strong design flexibility. Furthermore, the aromatic anthraquinone ring can form π-π stacking interactions, enhancing the stability of MOFs. Finally, because 1,5-diamino-4,8-dihydroxyanthraquinone has a planar configuration, it can be easily expanded into a one-dimensional nanoribbon form through self-assembly.

[0075] The coordination bonds formed between metal ions and organic ligands in metal-organic frameworks (MOFs) coordinated with these ligands can establish effective charge transfer pathways. Active transition metal ions, in particular, have suitable atomic radii for better orbital overlap with the ligands, which is conducive to generating small band gaps and high charge mobility. Furthermore, organic ligands with aromatic rings can form π-d conjugated planes and π-π stacking, thereby providing conductive paths on the plane and improving the conductivity of the metal-organic frameworks. This can improve the response value and sensitivity of gas sensing.

[0076] In some embodiments of the present application, the organic ligand may also carry substituents such as carboxyl (COOH) and thiol (SH) that are easy to form coordination bonds; the organic ligand may also be other condensed polycyclic aromatic compounds as the parent nucleus, such as anthracene, phenanthrene and other macrocyclic compounds.

[0077] In some embodiments of the present application, the organic ligand comprises the following structure:

[0078] Wherein R1 and R2 are hydroxyl (OH), amino (NH2) or thiol (SH).

[0079] That is, the substituent on the anthraquinone ring can also be a thiol group. The parent core can also be expanded to a larger conjugated structure.

[0080] In some embodiments of the present application, a metal organic framework material is a complex formed by divalent copper ions and 1,5-diamino-4,8-dihydroxyanthraquinone (hereinafter referred to as DDA-Cu), and the structural formula of DDA-Cu is

[0081] According to the structural formula of DDA-Cu, the copper ions in DDA-Cu are coordinated to the center of three oxygen atoms and one nitrogen atom in the DDA ligand, resulting in a stable copper ion configuration. Furthermore, the copper ion d orbitals stack between layers, forming axial conductive pathways and improving the conductivity of the metal-organic framework. Furthermore, the use of metal ions to connect the basic structural units further enhances the axial conductivity of the MOF material. Furthermore, the formation of a large in-plane π bond system improves the in-plane conductivity, further enhancing the material's electrical performance. This, in turn, can improve the response and sensitivity of gas sensing.

[0082] Furthermore, due to the high degree of structural flatness restricted by the bimetallic sites, DDA-Cu grows linearly along the coordination nodes, forming a one-dimensional nanoribbon structure. The one-dimensional nanoribbons then stack to form a bulk material through non-bonded interactions. Nanomaterials based on one-dimensional building blocks offer more adsorption sites due to their high structural regularity, chemically modular edges, and tunable structure-activity relationships.

[0083] The one-dimensional nanobelt metal-organic framework material in this embodiment has multiple highly conjugated structural units with excellent conductivity, and at the same time has a higher structural freedom than two-dimensional and three-dimensional metal-organic framework materials, providing more opportunities for creating conductive paths, thereby significantly improving the conductivity of the material; the structure is stable and orderly, with a higher surface area to volume ratio, providing a wider field for the adsorption of gas molecules, and at the same time can accelerate the diffusion rate of gas on the sensing material, so that the resistance changes significantly with the change of gas adsorption, thereby effectively improving the sensitivity and speed of gas response.

[0084] In some embodiments, the gas sensing material responds to one or more of carbon monoxide, ammonia, hydrogen sulfide, and nitrogen dioxide. The gas sensing materials provided herein can respond to a variety of gases and exhibit a certain degree of selectivity. For details, please refer to the experimental examples below.

[0085] Some embodiments of the present application also provide a gas sensing material comprising a metal-organic framework material, wherein the metal-organic framework material comprises a one-dimensional nanomaterial, wherein the one-dimensional nanomaterial has nanoscale dimensions in at least two dimensions, with the nanoscale being 0.1 nm to 100 nm. When the metal-organic framework material is used as a gas-sensitive material, its response mechanism is the transfer of coordinated electrons, which is independent of oxygen and can therefore achieve gas response under non-oxygen conditions.

[0086] Some embodiments of the present application also provide a method for preparing a gas sensing material. The method specifically comprises: providing a metal ion solution and an organic ligand solution; and reacting the metal ion solution with the organic ligand solution to produce a metal-organic framework material. The resulting metal-organic framework material has a one-dimensional nanostructure, i.e., a one-dimensional nano-MOF material.

[0087] The metal ion solution is prepared by dissolving a metal salt in a solvent. The metal salt is the metal source of the metal-organic framework material and can be a transition metal salt: such as (Cu(NO3)2), zinc nitrate (Zn(NO3)2), cobalt nitrate (Co(NO3)2) and other inorganic salts of transition metals; transition metal organic complexes: such as copper acetate (Cu2(CH3COO)4), ferrous succinate, etc.; oxide precursors: such as transition metal oxides such as CuO and ZnO; metal-organic framework: some metal-organic framework materials can also serve as metal sources, releasing metal ions for further construction of the metal-organic framework structure; other materials: metal foil, salts, inorganic acids, etc. By selecting different metal salts to prepare the metal ion solution, the morphology, crystallization, etc. of the resulting metal-organic framework material can be controlled, and the morphology and crystallinity of the resulting metal-organic framework material can be controlled, and the gas sensing performance can be controlled. The solvent used for the metal ion solution can be deionized water, that is, the metal salt is dissolved in deionized water to prepare the metal ion solution. In other embodiments, the metal ion solution can also be prepared using an alcohol solvent.

[0088] The organic ligand solution is prepared by dissolving the organic ligand in a solvent. The solvent for the organic ligand solution includes one or more of methanol, ethanol, acetone, tetrahydrofuran, N,N-dimethylformamide, dimethyl sulfoxide, and dichloromethane. These solvents have different polarities and different solubilities for metal ions and products (MOFs) in the reaction system. By selecting different solvents, different methods can be selected to prepare MOFs materials. The crystallinity, pore structure, pore environment, and morphology of the MOFs material can also be manipulated to control its gas sensor performance, such as gas selectivity, response value, and sensitivity.

[0089] In some embodiments of the present application, a metal ion solution and an organic ligand solution may be reacted by combining based on a solvothermal method to obtain a metal-organic framework material.

[0090] Specifically, a metal ion solution and an organic ligand solution are uniformly mixed and then allowed to react to produce a metal-organic framework material. "Standing" means that the reaction solution is not subjected to any stirring or dispersion treatment during the reaction. Specifically, the solutions are first mixed, and stirring and dispersion may be performed during the mixing process, but no other stirring or other mixing treatments are performed during the reaction after mixing.

[0091] In some embodiments of the present application, the metal ion solution can be added dropwise to the organic ligand solution to mix the metal ion solution with the organic ligand solution. In one embodiment, the metal ion solution is added at a rate of 1-20 seconds per drop, for example, 1 second per drop, 5 seconds per drop, 10 seconds per drop, 15 seconds per drop, 20 seconds per drop, etc. Through this arrangement, the metal ions can be more evenly dispersed in the organic ligand solution. Furthermore, after the addition is complete, the mixed solution can also be ultrasonically treated to uniformly mix the mixed solution.

[0092] In some embodiments of the present application, the metal ion solution and the organic ligand solution are uniformly mixed and then allowed to react for 8-15 hours at a temperature of 70-95°C.

[0093] During the static reaction, the screw cap of the reaction vessel is not completely tightened, allowing oxygen to enter the reaction vessel and participate in the reaction. The reaction is carried out under heating conditions, and the heating temperature is 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, etc. The container can be placed in a constant temperature oven for heating. As the temperature increases, the reaction rate of the reaction system will accelerate, and thus the growth rate of the crystal will accelerate, and a higher yield can be achieved in the same reaction time. However, the heating temperature should not be too high to prevent the reaction rate from being too fast, resulting in too fast crystal growth and difficulty in maintaining a one-dimensional nanostructure. Furthermore, by controlling the heating temperature, the crystallinity of the product can be regulated, and then the gas response performance can be regulated. The reaction time is 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, etc., and is adjusted according to the reaction progress. As time goes on, the reaction will proceed more and more completely. Considering the time cost, in one embodiment, the reaction time can be 12h.

[0094] In some embodiments of the present application, a base may be added to the reaction mixture of the metal ion and the organic ligand to promote the reaction. The added base is a weak base, such as aqueous ammonia.

[0095] During the synthesis of metal-organic framework materials, the pH of the reaction system needs to be adjusted to a range suitable for crystal growth. The pH can be adjusted using an acid or base, referred to as a pH regulator, and includes concentrated ammonia, sodium hydroxide, triethylamine, ethylenediamine, tetrabutylammonium hydroxide, hydrochloric acid, oxalic acid, phosphoric acid, and the like. In one embodiment, the base includes ammonia. The functions of ammonia include: providing an alkaline environment that is conducive to the deprotonation of metal ions and the dissociation of organic ligands; regulating the pH value, thereby controlling the growth rate of the metal-organic framework material; improving solubility so that the metal salt and organic ligand are completely dissolved in the synthesis solvent; and accelerating the reaction and the coordination and cross-linking rate between the metal salt and the organic ligand.

[0096] After the reaction between the metal ion solution and the organic ligand solution is completed, the solution is naturally cooled to room temperature. This slow cooling rate favors crystal growth and the formation of relatively regular crystals. A precipitate forms in the reaction system, which is washed by alternating centrifugation with deionized water and ethanol, then dried in an oven at 60°C for 6 hours to produce the metal-organic framework (MOF) material. This washing process removes impurities from the MOF surface, including unreacted reactants and some impurity ions, without affecting subsequent performance testing.

[0097] In some embodiments of the present application, a metal ion solution and an organic ligand solution may be combined and reacted based on an interfacial growth reaction method to obtain a metal-organic framework material.

[0098] Specifically, metal ions and organic ligands are respectively dissolved in two immiscible solvents to obtain a metal ion solution and an organic ligand solution. The immiscible metal ion solution and the organic ligand solution are placed in the same container. Since the metal ion solution and the organic ligand solution are immiscible, they will be in a stratified state, causing the reaction system to produce a two-phase interface. The organic ligands and metal ions contact and react at the two-phase interface, causing the metal-organic framework crystals to grow at the two-phase interface. The two raw materials for preparing MOFs will diffuse with each other at the interface, and a MOFs membrane will be produced at the interface.

[0099] In some embodiments of the present application, the metal ion solution is an aqueous solution of a metal salt, and the organic ligand solution is a dichloromethane solution of the organic ligand. The organic ligand solution is in the lower layer, and the metal ion solution is in the upper layer. The metal ion solution and the organic ligand solution interact at the interface, assembling the organic ligand and metal ions into a metal-organic framework crystal with a specific structure through a stepwise growth process.

[0100] By regulating the interaction of reactants at the interface, the morphology and structure of metal-organic framework materials can be controlled, and the sensitivity of sensing materials can be regulated; the interfacial growth method facilitates the reconstruction of sensing materials and can achieve repeated assembly and reconstruction of sensing materials, thereby realizing the design and application of multifunctional sensors.

[0101] In some embodiments of the present application, a metal-organic framework material is a complex formed by the coordination of divalent copper ions and 1,5-diamino-4,8-dihydroxyanthraquinone (hereinafter referred to as DDA-Cu). The preparation method of DDA-Cu includes: reacting a 1,5-diamino-4,8-dihydroxyanthraquinone solution with a divalent copper ion solution. The reaction formula is:

[0102] As can be seen from the reaction formula, each DDA ligand needs to be coordinated with four times the equivalent of copper ions, and each copper ion is connected to two DDA ligands, so the theoretical feed ratio is DDA: copper ion = 1:2 (amount of substance). However, under actual working conditions, the synthesis and decomposition of metal-organic framework materials are reversible reactions. According to the theoretical feed ratio, the reaction cannot achieve a high yield, so the reactants need to be in excess to promote the reaction in the forward direction. Furthermore, in order to control costs, the concentration of relatively low-priced copper ions is increased to promote the reaction in the direction of metal-organic framework material formation.

[0103] In some embodiments of the present application, the molar ratio of DDA to divalent copper ions is 1:(2-8), for example, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, etc.

[0104] In one embodiment, the molar ratio of DDA to divalent copper ions is 1:(4-6), for example, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, etc.

[0105] As the amount of copper ion increases, the reaction proceeds more and more completely. By adjusting the feed ratio, the morphology and crystallinity of the resulting product, and thus the gas response performance, can also be controlled.

[0106] In some embodiments of the present application, the metal ion solution includes a divalent copper salt solution, wherein the divalent copper salt includes at least one of copper acetate monohydrate, copper sulfate pentahydrate, and copper chloride dihydrate. By selecting different anions, the micromorphology, pore structure, and pore size of the metal-organic framework material can be manipulated, further adjusting the material's gas sensing performance.

[0107] In some embodiments of the present application, the solvent for the DDA ligand includes one or more of methanol, ethanol, acetone, tetrahydrofuran, dimethyl sulfoxide, N,N-dimethylformamide, and dichloromethane. By selecting different solvents, the micromorphology, pore structure, and pore size of the metal-organic framework material can be manipulated, further adjusting the material's gas sensing performance.

[0108] Referring to Figure 2, which is a schematic diagram of a method for preparing a gas sensing material according to one or more embodiments, a divalent copper ion solution and a DDA ligand solution can be reacted together using a solvothermal method to obtain a metal organic framework material.

[0109] Specifically, a divalent copper ion solution and a DDA ligand solution were mixed, placed in a screw-capped glass bottle with the cap slightly loosened, and incubated at 95°C for 12 hours. After the reaction, the solution was allowed to cool naturally to room temperature. The resulting black precipitate was washed by alternating centrifugation with deionized water and ethanol at a speed of 8000 rpm for 10 minutes. The product was then dried in a 60°C oven for 6 hours.

[0110] Referring to Figure 3, which is a schematic diagram of a method for preparing a gas sensing material according to one or more embodiments, a divalent copper ion solution and a DDA ligand solution can be combined and reacted based on an interfacial reaction growth method to obtain a metal organic framework material.

[0111] Specifically, the DDA ligand is dissolved in dichloromethane, and an aqueous solution of divalent copper ions is added to a container containing the DDA ligand solution. The two solutions are separated and allowed to react for one week, and a MOFs film grows at the interface.

[0112] In some embodiments of the present application, a gas sensor is further provided, which includes any of the above-mentioned gas sensing materials; or includes a gas sensing material prepared using any of the above-mentioned methods.

[0113] Specifically, one-dimensional nano-MOFs material is used as a gas sensing material. This material responds to the sensing gas based on the principle of coordinated electron transfer and can respond to gas under anaerobic conditions. A gas sensor that can respond quickly to gas under anaerobic conditions and has high detection sensitivity is prepared.

[0114] In some embodiments of the present application, the gas sensor provided by the present application can be used to detect gas inside a battery.

[0115] Please refer to Figure 4, which is a schematic diagram of an exploded structure of a battery according to one or more embodiments. Battery 100 includes a housing 10 and battery cells 20, with battery cells 20 housed within housing 10. Housing 10 provides storage space for battery cells 20 and can have various structures. In some embodiments, housing 10 can include a first portion 11 and a second portion 12, which overlap each other and together define a storage space for battery cells 20. Second portion 12 can be a hollow structure with one end open. First portion 11 can be a plate-like structure, overlapping the open side of second portion 12, so that the first and second portions 11 and 12 together define a storage space. Alternatively, first portion 11 and second portion 12 can each be a hollow structure with one end open, with the open side of first portion 11 overlapping the open side of second portion 12. Housing 10 formed by first portion 11 and second portion 12 can have various shapes, such as a cylinder or a rectangular parallelepiped. The gas sensor may be installed inside the box 10 .

[0116] In the battery 100, there may be multiple battery cells 20, and the multiple battery cells 20 may be connected in series, in parallel, or in a hybrid connection. A hybrid connection refers to a combination of series and parallel connections among the multiple battery cells 20. The multiple battery cells 20 may be directly connected in series, in parallel, or in a hybrid connection, and then the entire battery cell 20 may be housed within the housing 10. Alternatively, the battery 100 may be constructed by first connecting multiple battery cells 20 in series, in parallel, or in a hybrid connection to form a battery module, which is then connected in series, in parallel, or in a hybrid connection to form a complete battery module, and then housed within the housing 10. The battery 100 may also include other structures, such as a busbar assembly for electrically connecting the multiple battery cells 20.

[0117] Each battery cell 20 may be a secondary battery or a primary battery, and may also be a lithium-sulfur battery, a sodium-ion battery, or a magnesium-ion battery, but is not limited thereto. The battery cell 20 may be cylindrical, flat, rectangular, or in other shapes.

[0118] Please refer to Figure 5, which is a schematic diagram of the exploded structure of a battery cell according to one or more embodiments. A battery cell 20 is the smallest unit that makes up a battery. As shown in Figure 5, a battery cell 20 includes an end cap 21, a housing 22, an electrode assembly 23, and other functional components.

[0119] The end cap 21 refers to a component that covers the opening of the shell 22 to isolate the internal environment of the battery cell 20 from the external environment. Without limitation, the shape of the end cap 21 can be adapted to the shape of the shell 22 to match the shell 22. In one embodiment, the end cap 21 can be made of a material with a certain hardness and strength (such as an aluminum alloy). In this way, the end cap 21 is not easily deformed when squeezed or collided, so that the battery cell 20 can have a higher structural strength and improved safety performance. Functional components such as electrode terminals 21a can be provided on the end cap 21. The electrode terminal 21a can be used to electrically connect to the electrode assembly 23 for outputting or inputting electrical energy of the battery cell 20. In some embodiments, the end cap 21 can also be provided with a pressure relief mechanism for releasing internal pressure when the internal pressure or temperature of the battery cell 20 reaches a threshold. The material of the end cap 21 can also be various, including but not limited to copper, iron, aluminum, stainless steel, aluminum alloy, plastic, etc. In some embodiments, an insulating member may be provided inside the end cap 21 to isolate the electrical connection components in the housing 22 from the end cap 21 to reduce the risk of short circuit. For example, the insulating member may be made of plastic, rubber, or the like.

[0120] The housing 22 is a component that cooperates with the end cap 21 to form the internal environment of the battery cell 20, wherein the formed internal environment can be used to accommodate the electrode assembly 23, electrolyte, and other components. The housing 22 and the end cap 21 can be independent components. An opening can be provided in the housing 22, and the end cap 21 is closed at the opening to form the internal environment of the battery cell 20. The end cap 21 and the housing 22 can also be integrated. Specifically, the end cap 21 and the housing 22 can form a common connection surface before other components are inserted into the housing. When the interior of the housing 22 needs to be encapsulated, the end cap 21 is closed to the housing 22. The housing 22 can be of various shapes and sizes, such as a rectangular parallelepiped, a cylindrical shape, a hexagonal prism, etc. Specifically, the shape of the housing 22 can be determined according to the specific shape and size of the electrode assembly 23. The housing 22 can be made of various materials, including but not limited to copper, iron, aluminum, stainless steel, aluminum alloy, plastic, etc.

[0121] The electrode assembly 23 is a component in the battery cell 100 where electrochemical reactions occur. One or more electrode assemblies 23 may be contained in the housing 22. The electrode assembly 23 is mainly formed by winding or stacking positive and negative electrode sheets, and a separator is usually provided between the positive and negative electrode sheets. The parts of the positive and negative electrode sheets with active materials constitute the main body of the electrode assembly, and the parts of the positive and negative electrode sheets without active materials each constitute a tab 23a. The positive and negative electrode tabs may be located together at one end of the main body or respectively at both ends of the main body. During the charge and discharge process of the battery, the positive active material and the negative active material react with the electrolyte, and the tabs 23a connect the electrode terminals to form a current loop.

[0122] In one embodiment, the positive electrode sheet includes a current collector and a positive active layer disposed on the current collector.

[0123] The positive electrode active layer includes a positive electrode active material, and the positive electrode active material may include at least one of the following materials: lithium-containing phosphates with an olivine structure, lithium transition metal oxides, and their respective modified compounds. However, the present application is not limited to these materials, and other traditional materials that can be used as positive electrode active materials for batteries may also be used. These positive electrode active materials may be used alone or in combination of two or more. Examples of lithium transition metal oxides may include, but are not limited to, lithium cobalt oxide (such as LiCoO2), lithium nickel oxide (such as LiNiO2), lithium manganese oxide (such as LiMnO2, LiMn2O4), lithium nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide (such as LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O2 (also referred to as NCM 333 ), LiNi 0.5 Co 0.2 Mn 0.3 O2 (also referred to as NCM 523 ), LiNi 0.5 Co 0.25 Mn 0.25 O2 (also referred to as NCM 211 ), LiNi 0.6 Co 0.2 Mn 0.2 O2 (also referred to as NCM 622 ), LiNi 0.8 Co 0.1 Mn 0.1 O2 (also referred to as NCM 811 ), lithium nickel cobalt aluminum oxide (such as LiNi 0.85 Co 0.15 Al 0.05 O2) and its modified compounds. Examples of olivine-structured lithium-containing phosphates may include, but are not limited to, at least one of lithium iron phosphate (such as LiFePO4 (also referred to as LFP)), a composite material of lithium iron phosphate and carbon, lithium manganese phosphate (such as LiMnPO4), a composite material of lithium manganese phosphate and carbon, lithium iron manganese phosphate, and a composite material of lithium iron manganese phosphate and carbon.

[0124] In one embodiment, the positive electrode active layer also includes a conductive agent, thereby giving the electrode conductivity. The positive electrode conductive material may include any conductive material as long as it does not cause chemical changes. Non-limiting examples of positive electrode conductive materials include carbon-based materials (e.g., natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, carbon fiber, etc.), metal-based materials (e.g., metal powder, metal fiber, etc., including, for example, copper, nickel, aluminum, silver, etc.), conductive polymers (e.g., polyphenylene derivatives) and mixtures thereof. In one embodiment, the conductive agent includes one or more of conductive carbon black, conductive graphite, carbon fiber, carbon nanotubes, graphene, Ketjen black and acetylene black.

[0125] In one embodiment, the positive electrode active layer further includes a binder to improve the adhesion stability of the active layer and reduce the probability of powder loss. The binder can be one or more of styrene-butadiene rubber (SBR), water-based acrylic resin, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), ethylene-vinyl acetate copolymer (EVA), polyacrylic acid (PAA), carboxymethyl cellulose (CMC), polyvinyl alcohol (PVA), and polyvinyl butyral (PVB). In one embodiment, the binder includes one or more of polyvinylidene fluoride, polytetrafluoroethylene, acrylate, and polyurethane.

[0126] In one embodiment, the positive electrode active layer further includes other optional additives, which may be thickening and dispersing agents (such as sodium carboxymethyl cellulose CMC-Na) and PTC thermistor materials.

[0127] In some embodiments, the negative electrode sheet includes a current collector and a negative active layer disposed on the current collector.

[0128] The negative electrode active layer includes a negative electrode active material, which includes but is not limited to carbon-based negative electrode materials, silicon-based negative electrode materials, tin-based negative electrode materials, lithium titanate negative electrode materials, metallic lithium negative electrode materials, etc.; specifically includes but is not limited to graphite materials, silicon-carbon materials, graphite-silicon oxide materials, nano-silicon materials, silicon oxide materials and tin-based materials; more specifically includes natural graphite, artificial graphite, mesophase microcarbon beads (abbreviated as MCMB), hard carbon, soft carbon, silicon, silicon-carbon composites, Li-Sn alloys, Li-Sn-O alloys, Sn, SnO, SnO2, spinel structured lithiated TiO2-Li4Ti5O 12 , one or more of Li-Al alloys.

[0129] In some embodiments, the negative electrode active layer may further include a binder, a conductive agent, and other optional additives. As an example, the conductive agent may be one or more of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, Super P (SP), graphene, and carbon nanofibers. As an example, the binder may be one or more of styrene-butadiene rubber (SBR), water-based acrylic resin, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), ethylene-vinyl acetate copolymer (EVA), polyacrylic acid (PAA), carboxymethyl cellulose (CMC), polyvinyl alcohol (PVA), and polyvinyl butyral (PVB). As an example, other optional additives may be thickening and dispersing agents (e.g., sodium carboxymethyl cellulose CMC-Na) and PTC thermistor materials.

[0130] In some embodiments, the material of the separator can be selected from at least one of glass fiber, non-woven fabric, polyethylene, polypropylene, and polyvinylidene fluoride. The separator can be a single-layer film or a multi-layer composite film, without particular limitation. When the separator is a multi-layer composite film, the materials of each layer can be the same or different, without particular limitation.

[0131] In one embodiment, the electrolyte includes one or more of carbonate solvents and ether solvents.

[0132] Carbonates are generally small molecule cyclic or chain carbonates; including but not limited to one or more of ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, methylpropyl carbonate, dipropyl carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and fluorocarbonates; and may also be at least one ester solvent selected from γ-butyrolactone, dimethyl sulfite, ethyl acetate, methyl acetate, methyl butyrate, ethyl butyrate, methyl propionate, ethyl propionate, propyl acetate, and fluorocarboxylic acid esters.

[0133] Ether solvents include, but are not limited to, one or more of dimethyl ether, diethyl ether, tetrahydrofuran, methyltetrahydrofuran, ethylene oxide, 1,3-dioxolane, fluoroether, DME (ethylene glycol dimethyl ether), DEE (ethylene glycol diethyl ether), DEGDME (diethylene glycol dimethyl ether), TRGDME (triethylene glycol dimethyl ether), TEGDME (tetraethylene glycol dimethyl ether), dipropyl ether and dibutyl ether.

[0134] In other embodiments, the electrolyte may also include any one or a mixture of several of an amine solvent, a sulfone solvent, and a nitrile solvent. The amine solvent includes at least one of N-methylacetamide, N-methylformamide, dimethylformamide, and diethylformamide. The sulfone solvent includes at least one of dimethyl sulfoxide, cyclopentane sulfone, diphenyl sulfoxide, thionyl chloride, and dipropyl sulfone. The nitrile solvent includes at least one of acetonitrile, succinonitrile, adiponitrile, and glutaronitrile. The electrolyte is preferably a high-voltage resistant electrolyte, which has reduced acidity under high voltage, can facilitate the transmission of active ions, significantly reduce side reactions on the electrode surface, and improve battery stability.

[0135] In some embodiments, the electrolyte further includes an electrolyte salt, which can be selected from at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bis(fluorosulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, lithium trifluoromethanesulfonate, lithium difluorophosphate, lithium difluorooxalatoborate, lithium dioxalatoborate, lithium difluorodioxalatophosphate, and lithium tetrafluorooxalatophosphate.

[0136] In some embodiments, the electrolyte further includes additives. For example, the additives may include negative electrode film-forming additives, positive electrode film-forming additives, and additives that can improve certain battery properties, such as additives that improve battery overcharge performance, and additives that improve battery high or low temperature performance.

[0137] The battery disclosed in the embodiments of the present application can be used in various energy storage systems that use batteries as power sources or use batteries as energy storage elements. That is, the present application provides an electric device, and the electric device includes the battery of the above embodiment. In some embodiments, the electric device of the present application can be used for, but not limited to, laptop computers, pen-input computers, mobile computers, e-book players, portable phones, portable fax machines, portable copiers, portable printers, head-mounted stereo headphones, video recorders, LCD TVs, portable cleaners, portable CD players, mini discs, transceivers, electronic notepads, calculators, memory cards, portable recorders, radios, backup power supplies, motors, cars, motorcycles, power-assisted bicycles, bicycles, ships, spacecraft, lighting fixtures, toys, game consoles, clocks, power tools, flashlights, cameras, large household batteries and lithium-ion capacitors, etc.

[0138] Electrical equipment can choose battery cells, battery modules or battery packs according to its usage requirements.

[0139] Please refer to Figure 6, which is a schematic structural diagram of a vehicle according to one or more embodiments. The vehicle 1000 can be a fuel vehicle, a gas vehicle or a new energy vehicle. The new energy vehicle can be a pure electric vehicle, a hybrid vehicle or an extended-range vehicle, etc. A battery 100 is provided inside the vehicle 1000, and the battery 100 can be provided at the bottom, head or tail of the vehicle 1000. The battery 100 can be used to power the vehicle 1000. For example, the battery 100 can serve as an operating power source for the vehicle 1000. The vehicle 1000 may also include a controller 200 and a motor 300. The controller 200 is used to control the battery 100 to power the motor 300, for example, for starting, navigating and driving the vehicle 1000.

[0140] In some embodiments of the present application, the battery 100 can serve not only as an operating power source for the vehicle 1000, but also as a driving power source for the vehicle 1000, replacing or partially replacing fuel or natural gas to provide driving power for the vehicle 1000.

[0141] In order to make the technical problems, technical solutions and beneficial effects solved by the embodiments of the present application clearer, the following will be further described in detail with reference to the embodiments and drawings. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. The following description of at least one exemplary embodiment is actually only illustrative and is in no way intended to limit the present application and its applications. Based on the embodiments in this application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of this application.

[0142] 1. Preparation of gas sensing materials

[0143] Example 1

[0144] 1. Weigh 13.61 mg (0.05 mmol) of DDA ligand and 40.00 mg (0.20 mmol) of copper acetate monohydrate.

[0145] 2. Dissolve 13.61 mg of DDA ligand in 0.5 mL of N,N-dimethylformamide (DMF) and sonicate for 5 min to dissolve the organic ligand to obtain a DDA ligand solution. Dissolve 40.00 mg of copper acetate monohydrate in 1.5 mL of deionized water and stir thoroughly to dissolve it to obtain a divalent copper ion solution.

[0146] 3. Add the divalent copper ion solution to the DDA ligand solution and mix thoroughly. Slowly add the copper acetate solution to the DDA ligand solution at a rate of 1-20 seconds per drop. Then, add 0.2 mL of 14.0 mol / L concentrated ammonia to the mixed solution. Ultrasonicate the solution for 10 minutes to ensure uniform mixing.

[0147] 4. Place the mixed solution in a 20 mL screw-capped glass bottle, loosen the cap slightly, and keep warm at 85°C for 12 h.

[0148] 5. After the reaction, the mixed solution was allowed to cool naturally to room temperature. The resulting black precipitate was washed by alternating centrifugation with deionized water and ethanol at a speed of 8000 rpm for 10 minutes. The mixture was then dried in a 60°C oven for 6 hours to obtain the nanobelt MOF material DDA-Cu-1.

[0149] Example 2-3

[0150] The metal ion solution preparation was modified based on Example 1, with the copper salts being replaced with copper sulfate pentahydrate and copper chloride dihydrate, respectively, to produce the nanobelt MOF materials DDA-Cu-2 and DDA-Cu-3. Specific reaction conditions are detailed in Table 1, which lists the reactants, feed ratios, reaction system solvents, and reaction system temperatures for each example.

[0151] Examples 4-9

[0152] On the basis of Example 1, the feed ratio of DDA ligand to divalent copper ions was changed. The difference was that the feed ratio was adjusted from 1:4 to 1:2, 1:3, 1:5, 1:6, 1:7, and 1:8, respectively, to prepare nanobelt MOFs materials DDA-Cu-4 to DDA-Cu-9. The specific reaction conditions are detailed in Table 1.

[0153] Examples 10-14

[0154] The solvent of the reaction system was changed on the basis of Example 1. The difference was that the solvent was replaced with methanol, ethanol, acetone, tetrahydrofuran and dimethyl sulfoxide, respectively, to prepare nanobelt MOFs materials DDA-Cu-10 to DDA-Cu-14. The specific reaction conditions are detailed in Table 1.

[0155] Examples 15-19

[0156] The temperature of the reaction system was changed on the basis of Example 1. The difference was that the temperature was adjusted from 85°C to 70°C, 75°C, 80°C, 90°C, and 95°C, respectively, to obtain nanobelt MOFs materials DDA-Cu-15 to DDA-Cu-19. The specific reaction conditions are detailed in Table 1.

[0157] Examples 20-21

[0158] The type of metal salt was changed on the basis of Example 1. The difference was that copper acetate monohydrate was replaced by cobalt acetate tetrahydrate and nickel acetate tetrahydrate, respectively, to prepare nanobelt MOFs materials DDA-Co and DDA-Ni. The specific reaction conditions are detailed in Table 1.

[0159] 2. Testing of Gas Sensing Materials

[0160] (1) Transmission electron microscopy (TEM)

[0161] Referring to JY / T 0581-2020 General Rules for Transmission Electron Microscopy Analysis Methods, the electron beam was used to penetrate the sample to measure the TEM image of the metal-organic framework material.

[0162] (2) X-ray diffraction (XRD)

[0163] The X-ray diffraction patterns of the metal-organic framework materials were measured using CuKα1 radiation in accordance with JIS K 0131-1996, General Rules for X-ray Diffraction Analysis.

[0164] (3) Scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS)

[0165] Referring to JY / T010-1996 General Rules for Analytical Scanning Electron Microscopy, the sample surface was scanned with an electron beam to measure the SEM image of the metal-organic framework material and simultaneously obtain the energy spectrum of the metal-organic framework material.

[0166] 3. Preparation of gas sensors

[0167] The gas sensing material was dispersed in ethanol at a concentration of 10 mg / L and treated with 40 kHz ultrasonic waves for 10 minutes to ensure uniform dispersion of the composite material. Gold electrodes were fabricated using micromachining, with a spacing of 800 μm between the positive and negative electrodes and 300 μm between adjacent electrodes. Five μL of the dispersion was dripped onto the interdigitated electrodes and dried under vacuum at 60°C for 1 hour to produce the gas sensor.

[0168] 4. Gas Sensing Performance Test

[0169] Please refer to Figure 7, which is a schematic diagram of the gas sensing performance test according to one or more embodiments. The gas sensor is placed in the test chamber, and the target gas is introduced by static gas distribution at room temperature. A constant operating voltage of 500mV is applied between the sensor electrodes, and the resistance change of the sensor in the inert gas and target gas environment is detected by Agilent 4156C semiconductor parameter analyzer. Before the target gas is introduced, dry compressed nitrogen (MFC3) is used to purge the chamber to stabilize the baseline signal, and compressed nitrogen (MFC2) is used as a carrier gas to dilute the target gas, and the target gas is controlled by a mass flow controller (MFC1). The resistance difference between the sensor in dry nitrogen and the target gas is related to the resistance ratio in dry nitrogen (|R a -R g | / R a× 100%) is the response value of the device to the target gas, and the response and recovery time are defined by reaching 90% saturation of the response and recovery curves.

[0170] Table 1 Reaction parameters and performance parameters of each embodiment

[0171] Note: DDA:A n+ The DDA ligand and the metal ion (A n+ ) of the substance ratio; the response value is the response value of the metal organic framework material to a concentration of 50ppm CO; the recovery time is the recovery time of the metal organic framework material to a concentration of 50ppm CO.

[0172] Please refer to Figure 1 and Figure 10. It can be observed from the TEM images and SEM images that DDA-Cu-1 has a nanostructure, specifically in the form of nanobelts. The thicknesses of different nanobelts range from 2.5 nm, 3.0 nm, 6.2 nm, and 8.2 nm, and the widths range from 19.0 nm, 32.4 nm, 66.7 nm, and 95.8 nm.

[0173] Please refer to Figure 8, which shows an X-ray diffraction pattern of the gas sensing material DDA-Cu according to one or more embodiments. As shown in the figure, the XRD diffraction peak positions of DDA-Cu-1 are substantially consistent with those simulated from single crystal data obtained using Materials Studio software. Diffraction peaks corresponding to the (001), (100), and (010) crystal planes are observed, and the peaks are relatively sharp, indicating that the experimental sample has a relatively ordered crystal structure, a relatively regular arrangement of atoms within the crystal, and a high purity without excessive crystal defects or impurities.

[0174] Please refer to Figure 9, which shows an X-ray energy dispersive spectrometry (EDS) image of the DDA-Cu gas sensing material according to one or more embodiments. As shown, oxygen (O), nitrogen (N), and copper (Cu) are uniformly distributed throughout the gas sensing material.

[0175] Please refer to Figures 10 to 12. Figure 10 shows a scanning electron microscope (SEM) image of the gas sensing material DDA-Cu-1 obtained in Example 1, Figure 11 shows a scanning electron microscope (SEM) image of the gas sensing material DDA-Cu-2 obtained in Example 2, and Figure 12 shows a scanning electron microscope (SEM) image of the gas sensing material DDA-Cu-3 obtained in Example 3. As shown in the figures, the gas sensing materials prepared using different metal salts exhibit different microscopic morphologies. DDA-Cu-1 and DDA-Cu-3 exhibit nanoribbons and nanosheets, while DDA-Cu-2 exhibits needle-like crystals. However, all three exhibit nanostructures. By selecting different copper salts to prepare the metal ions, the micromorphology of the metal-organic framework can be manipulated.

[0176] Refer to Table 1. The gas response data for DDA-Cu-1, DDA-Cu-2, and DDA-Cu-3 differ somewhat. DDA-Cu-3 exhibits a higher response to CO than DDA-Cu-1 and DDA-Cu-2, but also exhibits a longer recovery time. Therefore, the response and recovery properties of metal-organic frameworks in gas sensing can be tuned by adjusting the type of anion in the metal salt.

[0177] In Examples 1 and 4-9, the sensing performance of the Cu-DDA gas sensing material for 50ppm carbon monoxide gas is shown when the feed ratio is 1:2-1:8. As the amount of copper ion substance increases, the reaction proceeds more and more completely, and the sensing performance of the Cu-DDA gas sensing material for 50ppm carbon monoxide gas is also improved, specifically manifested in that the response value becomes larger and the recovery time decreases. However, when the feed ratio exceeds 1:4, the improvement in sensing performance is no longer obvious. Therefore, considering the cost of raw materials, in one embodiment, the feed ratio is 1,5-diamino-4,8-dihydroxyanthraquinone: copper ion = 1:4 (amount of substance), which can not only improve the gas sensing performance of the product, but also save raw materials.

[0178] In Examples 1, 10-14, the sensing performance of the Cu-DDA gas sensing material to 50ppm carbon monoxide gas is demonstrated when the solvents of the reaction system are different. Different solvents have different polarities. The polarity of the solvent can affect the interaction and reaction rate between the ligand and the metal ion, and also affect the pore structure and the intrapore environment of the metal organic framework material, further affecting the gas sensing performance of the metal organic framework material. When the solvents are different, the gas response values ​​of the metal organic framework material are different, among which dimethyl sulfoxide has a higher polarity and can effectively interact with the hydrogen bond acceptor and donor groups of DDA. Therefore, DDA can be dissolved more thoroughly. At this time, the response value of the Cu-DDA metal organic framework material to carbon monoxide is high and the recovery time is also short.

[0179] In Examples 1, 15-19, the sensing performance of the Cu-DDA gas sensing material to 50ppm carbon monoxide gas is demonstrated when the temperature of the reaction system is 70°C-95°C. As the temperature increases, the reaction rate of the reaction system will accelerate, so the growth rate of the crystal will accelerate, and a higher yield can be achieved in the same reaction time. By regulating the temperature of the reaction system, the yield of the gas sensing material finally generated is higher, and therefore the gas sensing performance is better. As the static reaction temperature increases, the reaction proceeds more and more completely, the response value to carbon monoxide gas increases, and the recovery time decreases. However, after the temperature exceeds 85°C, the improvement in gas sensing performance is no longer obvious. In one embodiment, the temperature can be set to 85°C, at which time the sensing performance of the Cu-DDA metal organic framework material is better, and energy is not wasted.

[0180] Examples 1, 20, and 21 demonstrate the sensing performance of the prepared gas sensing materials for 50 ppm carbon monoxide gas when the metal salts are copper acetate monohydrate, cobalt acetate tetrahydrate, and nickel acetate tetrahydrate, respectively. While the gas response values ​​are higher when the metal ions are cobalt and nickel, they cannot be restored. Therefore, copper ions can be selected as the metal ion for carbon monoxide gas detection in gas sensing materials, depending on the application requirements.

[0181] Please refer to Figures 13 to 15. Figure 13 is a schematic diagram of the gas response of the gas sensing material DDA-Cu according to one or more embodiments, Figure 14 is a schematic diagram of the gas response of the gas sensing material DDA-Co according to one or more embodiments, and Figure 15 is a schematic diagram of the gas response of the gas sensing material DDA-Ni according to one or more embodiments. The responses of different gas sensing materials to 50 ppm concentrations of carbon monoxide (CO), ammonia (NH3), and hydrogen sulfide (H2S) were tested. It was found that DDA-Cu, DDA-Co, and DDA-Ni all exhibited certain response characteristics to carbon monoxide (CO), ammonia (NH3), and hydrogen sulfide (H2S), and can be used as gas sensors to detect these gases. However, the response values ​​achieved for different gases vary, and the appropriate gas sensing material can be selected based on actual conditions.

[0182] Please refer to Figure 16, which illustrates the gas response of the DDA-Cu gas sensing material according to one or more embodiments. Furthermore, the response of the sensor based on the DDA-Cu-1 gas sensing material prepared in Example 1 to 50 ppm of various gases was tested at room temperature. The results are shown in Figure 16. As can be seen, the DDA-Cu-1 gas sensing material exhibits a response of approximately 9% to carbon monoxide, over 15% to ammonia, and over 20% to hydrogen sulfide. Meanwhile, the response to the other five gases did not exceed 5%, demonstrating that DDA-Cu-1 exhibits good gas selectivity.

[0183] Please refer to Figures 17 and 18. Figure 17 is a schematic diagram of the gas response of the DDA-Cu gas sensing material according to one or more embodiments, and Figure 18 is a schematic diagram of the gas response of the DDA-Cu gas sensing material according to one or more embodiments. The response of the sensor based on the DDA-Cu-1 gas sensing material prepared in Example 1 to carbon monoxide concentrations ranging from 10 ppm to 80 ppm was tested at room temperature. In the figure, the horizontal axis represents the acquisition time, and the vertical axis represents the response value. As can be seen from the figure, the DDA-Cu-1-based sensor prepared in the above example achieved a response value of 8.8% to 80 ppm of carbon monoxide. The lowest detectable carbon monoxide concentration reached 10 ppm, corresponding to a response value of 1.1%. As the carbon monoxide concentration increased, the sensor's response to the gas also increased, with response values ​​of 1.1%, 2.0%, 3.7%, and 8.8% to 10, 20, 40, and 80 ppm of carbon monoxide, respectively. This demonstrates that the gas sensing material provided in this application exhibits a more sensitive gas response and a lower detection limit.

[0184] Furthermore, the cyclic response performance of the sensor based on the DDA-Cu-1 gas sensing material prepared in Example 1 to 50 ppm carbon monoxide was tested at room temperature. In the figure, the horizontal axis represents acquisition time, and the vertical axis represents response value. The sensor's response time to the gas is approximately 400 seconds, and its recovery time is also around 400 seconds, indicating a more sensitive response. Furthermore, after six response-recovery cycles, the sensor's response value remained above 3.8%, and the response time remained essentially unchanged, demonstrating that the sensor prepared in the aforementioned example has excellent cyclic stability.

[0185] In the above examples, the gas sensing materials provided by this application can be used to detect gas production within batteries, and exhibit good response sensitivity and selectivity to gases. Furthermore, the gas sensing materials described above are tested at room temperature, which is more moderate than existing materials that require high temperatures to detect gas, and thus has a wider range of applications.

[0186] The above description is only an implementation method of the present application and does not limit the patent scope of the present application. Any equivalent structure or equivalent process transformation made using the contents of the description and drawings of this application, or directly or indirectly applied in other related technical fields, are also included in the patent protection scope of the present application.

Claims

1. A battery, wherein: Including gas sensors; The gas sensor comprises a gas sensing material, the gas sensing material comprises a metal organic framework material, the metal organic framework material comprises a one-dimensional nano material, the one-dimensional nano material has a nanoscale size in at least two dimensions, and the nanoscale is 0.1-100 nm.

2. The battery according to claim 1, wherein The metal organic framework material comprises a nanobelt material, the thickness of the nanobelt material is 1-10 nm, and the width of the nanobelt is 10-100 nm.

3. The battery according to claim 1 or 2, wherein: The metal organic framework material comprises a nanobelt material, the thickness of the nanobelt material is 3-8 nm, and the width of the nanobelt is 15-70 nm.

4. The battery according to any one of claims 1 to 3, wherein: The metal organic framework material includes a complex of a metal and an organic ligand, and the metal includes one or more of copper, nickel, cobalt, zinc, and iron.

5. The battery according to any one of claims 1 to 4, wherein: The organic ligand comprises a structure shown in formula (1): Wherein, R1 and R2 include any one of hydroxyl, amino or thiol.

6. The battery according to any one of claims 1 to 5, wherein: The organic ligand includes 1,5-diamino-4,8-dihydroxyanthraquinone.

7. The battery according to any one of claims 1 to 6, wherein: The response gas of the gas sensing material includes one or more of carbon monoxide, ammonia, hydrogen sulfide, and nitrogen dioxide.

8. A gas sensing material, wherein: include: A metal organic framework material, wherein the metal organic framework material comprises a one-dimensional nano material, wherein the size of the one-dimensional nano material in at least two dimensions is nanoscale, and the nanoscale is 0.1-100 nm.

9. A method for preparing a gas sensing material, wherein: include: providing a metal ion solution and an organic ligand solution; The metal ion solution and the organic ligand solution are combined and reacted to obtain a metal organic framework material, wherein the metal organic framework material comprises a one-dimensional nanomaterial, wherein the size of the one-dimensional nanomaterial in at least two dimensions is nanoscale, and the nanoscale is 0.1nm-100nm.

10. The method for preparing a gas sensing material according to claim 9, wherein: The step of combining the metal ion solution with the organic ligand solution comprises: The metal ion solution and the organic ligand solution are uniformly mixed and allowed to stand for reaction to obtain the metal organic framework material.

11. The method for preparing a gas sensing material according to claim 10, wherein: The static reaction time is 8-15h; and / or The temperature of the static reaction is 70-95°C.

12. The method for preparing a gas sensing material according to claim 10 or 11, wherein: The step of uniformly mixing the metal ion solution and the organic ligand solution comprises: Adding the metal ion solution dropwise into the organic ligand solution and mixing; The metal ion solution is added at a dropping speed of 1-20 seconds per drop.

13. The method for preparing a gas sensing material according to any one of claims 10 to 12, wherein: Also includes: adding a base to the mixed solution of the metal ion solution and the organic ligand solution; The base includes aqueous ammonia.

14. The method for preparing a gas sensing material according to claim 9, wherein: The step of combining the metal ion solution with the organic ligand solution comprises: The metal ion solution and the organic ligand solution are placed in the same container. The metal ion solution and the organic ligand solution are immiscible. The metal organic framework material is prepared by utilizing interface reaction.

15. The method for preparing a gas sensing material according to any one of claims 9 to 14, wherein: The organic ligand solution includes a 1,5-diamino-4,8-dihydroxyanthraquinone solution, the metal ion solution includes a divalent copper ion solution, and the molar ratio of the 1,5-diamino-4,8-dihydroxyanthraquinone to the divalent copper ion is 1:(2-8).

16. The method for preparing a gas sensing material according to any one of claims 9 to 15, wherein: The organic ligand solution includes a 1,5-diamino-4,8-dihydroxyanthraquinone solution, the metal ion solution includes a divalent copper ion solution, and the molar ratio of the 1,5-diamino-4,8-dihydroxyanthraquinone to the divalent copper ion is 1:(4-6).

17. The method for preparing a gas sensing material according to any one of claims 9 to 16, wherein: The solvent of the organic ligand solution includes one or more of methanol, ethanol, acetone, tetrahydrofuran, N,N-dimethylformamide, dimethyl sulfoxide, and dichloromethane.

18. The method for preparing a gas sensing material according to any one of claims 9 to 17, wherein: The metal ion solution includes a divalent copper salt solution, and the divalent copper salt includes at least one of copper acetate monohydrate, copper sulfate pentahydrate, and copper chloride dihydrate.

19. A gas sensor, wherein: The method comprises the gas sensing material as claimed in claim 8; or comprises the gas sensing material prepared by the method as claimed in any one of claims 9 to 18.

20. An electrical device, wherein: A battery comprising any one of claims 1 to 7.

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