Gas sensing material and preparation method thereof, sensor, battery and electric equipment

Abstract

The invention discloses a gas sensing material and a preparation method thereof, a sensor, a battery and electric equipment. Wherein the gas sensing material is a metal organic framework material (MOFs) with a one-dimensional nano structure, and the gas response mechanism of the gas sensing material is transfer of coordination electrons. Through the mode, the detection of the target gas in the oxygen-free environment can be realized, and the detection of the gas produced in the battery can be realized. Furthermore, the sensitivity and selectivity of gas detection can be improved, the gas response time is shortened, and the gas detection limit is reduced.

Description

Technical Field

[0001] This application relates to the field of new energy technologies, and particularly to gas sensing materials and their preparation methods, sensors, batteries, and electrical equipment. Background Art

[0002] With the continuous exacerbation of global energy and environmental problems, new energy, as one of the fields of sustainable development, is developing rapidly. Batteries are being applied more and more widely as a new energy source. Among them, the problem of gas production in batteries has always been a concern. The gas generated by the battery is likely to cause safety problems. By detecting the gas situation in the battery, early warnings can be given in a timely manner. Existing gas sensing principles require oxygen, which limits their application in detecting gases under anaerobic conditions. However, the inside of the battery monomer is an anaerobic environment. Therefore, there is an urgent need to develop new materials and sensors that can respond to gases 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. Summary of the Invention

[0003] The main technical problem to be solved by this application is to provide a gas sensing material and its preparation method, a sensor, a battery, and an electrical equipment, wherein the gas sensing material can respond to gases under non-oxygen conditions.

[0004] To solve the above technical problem, a technical solution adopted by this application is: to provide a gas sensing material, the gas sensing material includes a metal-organic framework material, the metal-organic framework material includes one-dimensional nanomaterials, and the one-dimensional nanomaterials have dimensions at the nanoscale in at least two dimensions, and the nanoscale is 0.1 nm - 100 nm. When the metal-organic framework material is used as a gas sensitive material, its response mechanism is the transfer of coordination electrons and does not depend on oxygen. Therefore, gas response under non-oxygen conditions can be achieved.

[0005] Furthermore, the one-dimensional nanostructure enables the metal-organic framework material to have a higher surface area to volume ratio, provides 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, making the response time shorter.

[0006] In one embodiment, the metal-organic framework material includes nanoribbon materials, the thickness of the nanoribbon materials is 1 - 10 nm, and can be 3 - 8 nm; the width of the nanoribbon is 10 - 100 nm, and can be 15 - 70 nm. Through this setting, the conductivity of the metal-organic framework material is significantly improved, and the resistance significantly changes with the change of gas adsorption. Therefore, the sensitivity and speed of gas response can be effectively improved.

[0007] In one embodiment, the metal-organic framework material comprises a complex of metal ions and organic ligands, and the metal elements include one or more of copper, nickel, cobalt, zinc, and iron. With this arrangement, it is beneficial to improve the stability of the metal-organic framework material. At the same time, the metal ions can serve as adsorption sites for gases, improving the sensitivity and selectivity to adsorbed gases.

[0008] In one embodiment, the organic ligand comprises the structure shown in formula (1):

[0009] Wherein, R 1 、R 2 is a hydroxyl group, an amino group, or a mercapto group. This is beneficial for forming coordination bonds with metal ions and enabling the metal-organic framework material to grow in a belt-like manner.

[0010] In one embodiment, the organic ligand comprises 1,5-diamino-4,8-dihydroxyanthraquinone. 1,5-diamino-4,8-dihydroxyanthraquinone is an anthraquinone compound containing amino and hydroxyl substituents, which can form stable coordination bonds with metal ions through the substituents, thereby constructing the metal-organic framework material. With this arrangement, the coordination bonds formed between the metal ions and the organic ligands can establish an effective charge transport pathway, which is beneficial for generating a small bandgap and high charge mobility; in addition, it can form a π-d conjugated plane and π-π stacking, thereby providing a conductive path on the plane and improving the conductivity of the metal-organic framework material.

[0011] In one embodiment, the response gases of the gas sensing material include 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 selectivity.

[0012] To solve the above technical problems, another technical solution adopted in this application is: to provide a preparation method of a gas sensing material, the preparation method of the gas sensing material comprising: providing a metal ion solution and an organic ligand solution; making the metal ion solution and the organic ligand solution undergo a binding reaction to obtain a metal-organic framework material, the metal-organic framework material comprising one-dimensional nanomaterials, and the one-dimensional nanomaterials having dimensions at the nanoscale in at least two dimensions, the nanoscale being 0.1 nm - 100 nm. The one-dimensional nanostructure enables the metal-organic framework material to have 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 gases on the one-dimensional nanostructure is significantly faster, resulting in a shorter response time.

[0013] In one embodiment, the reaction of combining a metal ion solution with an organic ligand solution includes: after uniformly mixing the metal ion solution and the organic ligand solution, allowing the reaction to stand to obtain a metal-organic framework material. Through this setting, the microstructure of the obtained metal-organic framework material can be regulated to obtain a one-dimensional nanostructure.

[0014] In one embodiment, the time for the standing reaction is 8 - 15 h; and / or the temperature for the standing reaction is 70 - 95 °C. By regulating the reaction time and temperature of the reaction system, the yield and microstructure of the finally formed metal-organic framework material can be regulated, which is conducive to regulating the gas sensing performance.

[0015] In one embodiment, uniformly mixing the metal ion solution and the organic ligand solution includes: dropping the metal ion solution into the organic ligand solution for mixing; optionally, the dropping rate of the metal ion solution is 1 - 20 seconds per drop. Through this setting, the metal ions can be more uniformly dispersed in the organic ligand solution.

[0016] In one embodiment, an alkali is added to the mixture of the metal ion solution and the organic ligand solution, and optionally, ammonia water is added. Through this setting, it is beneficial to the deprotonation of metal ions and the dissociation of organic ligands, and the growth rate of the metal-organic framework material can be controlled.

[0017] In one embodiment, the reaction of combining a metal ion solution with an organic ligand solution includes: placing the metal ion solution and the organic ligand solution in the same container. The metal ion solution and the organic ligand solution are immiscible, and a metal-organic framework material is prepared by using an interfacial reaction. By adjusting the interaction between the reactants at the interface, the morphology and structure of the metal-organic framework material can be controlled, and further, the sensitivity of the sensing material can be regulated.

[0018] In one embodiment, the organic ligand solution includes a 1,5-diamino-4,8-dihydroxyanthraquinone solution, and the metal ion solution includes a divalent copper ion solution. The molar ratio of 1,5-diamino-4,8-dihydroxyanthraquinone to divalent copper ions is 1:(2 - 8); it can be optionally 1:(4 - 6). Through this setting, the copper ions are in excess in the reaction, which can promote the forward reaction to generate reactants and is beneficial to improving the yield of the metal-organic framework material.

[0019] 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 to prepare the metal-organic framework material. At the same time, the crystallinity, pore structure, pore environment, morphology, etc. of the metal-organic framework material can be regulated, and further, the selectivity, response value, sensitivity, etc. to gases can be regulated.

[0020] In one embodiment, 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. By selecting different anions, the microscopic morphology, pore structure, and pore size of the metal-organic framework material can be regulated, and further the gas sensing performance of the material can be regulated.

[0021] To solve the above technical problems, another technical solution adopted by this application is: to provide a gas sensor, which includes the gas sensing material of any one of the above; or includes the gas sensing material prepared by the method of any one of the above. Through the above settings, a high-sensitivity response to the target gas can be achieved.

[0022] To solve the above technical problems, another technical solution adopted by this application is: to provide a battery, which includes the gas sensor of any one of the above. Through the above settings, the detection of gas production in the battery can be achieved.

[0023] To solve the above technical problems, another technical solution adopted by this application is: to provide an electrical device, which includes the above battery. The electrical device has at least the same advantages as the battery.

[0024] The above description is only an overview of the technical solution of this application. In order to be able to understand the technical means of this application more clearly, it can be implemented according to the content of the specification. And in order to make the above and other purposes, features, and advantages of this application more obvious and understandable, the specific embodiments of this application are specifically given below. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] In order to more clearly illustrate the technical solutions in the embodiments of this application, the drawings required for the description of the embodiments will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of this application. For those of ordinary skill in the art, without creative efforts, other drawings can be obtained based on these drawings.

[0026] Figure 1 It is a transmission electron microscope (TEM) image of a metal-organic framework material for one or more embodiments;

[0027] Figure 2 It is a schematic diagram of a method for preparing a gas sensing material according to one or more embodiments;

[0028] Figure 3 It is a schematic diagram of a method for preparing a gas sensing material according to one or more embodiments;

[0029] Figure 4 It is a schematic diagram of the exploded structure of a battery according to one or more embodiments;

[0030] Figure 5 Schematic diagram of the disassembly structure of a battery cell according to one or more embodiments;

[0031] Figure 6 Schematic diagram of the structure of an electrical device according to one or more embodiments.

[0032] Figure 7 Schematic diagram of the gas sensing performance test according to one or more embodiments;

[0033] Figure 8 X-ray diffraction pattern (XRD) of the gas sensing material DDA-Cu according to one or more embodiments;

[0034] Figure 9 X-ray energy dispersive spectroscopy image (EDS) of the gas sensing material DDA-Cu according to one or more embodiments;

[0035] Figure 10 Scanning electron microscope (SEM) image of the gas sensing material DDA-Cu-1 obtained in Example 1;

[0036] Figure 11 Scanning electron microscope (SEM) image of the gas sensing material DDA-Cu-2 obtained in Example 2;

[0037] Figure 12 Scanning electron microscope (SEM) image of the gas sensing material DDA-Cu-3 obtained in Example 3;

[0038] Figure 13 Schematic diagram of the gas response of the gas sensing material DDA-Cu according to one or more embodiments;

[0039] Figure 14 Schematic diagram of the gas response of the gas sensing material DDA-Co according to one or more embodiments;

[0040] Figure 15 Schematic diagram of the gas response of the gas sensing material DDA-Ni according to one or more embodiments;

[0041] Figure 16 Schematic diagram of the gas response of the gas sensing material DDA-Cu according to one or more embodiments;

[0042] Figure 17 Schematic diagram of the gas response of the gas sensing material DDA-Cu according to one or more embodiments;

[0043] Figure 18 Schematic diagram of the gas response of the gas sensing material DDA-Cu according to one or more embodiments;

[0044] In the accompanying drawings:

[0045] 1000, Vehicle; 300, Motor; 200, Controller; 100, Battery; 10, Box; 11, First Part; 12, Second Part; 20, Battery Cell; 21, End Cap; 21a, Electrode Terminal; 22, Housing; 23, Electrode Assembly. Detailed Embodiment

[0046] To make the purpose, technical solutions and effects of this application clearer and more definite, the following will describe in detail the embodiments of the technical solutions of this application with reference to the accompanying drawings. The following embodiments are only used to illustrate the technical solutions of this application more clearly, so they are only examples and cannot be used to limit the protection scope of this application.

[0047] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the technical field 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 drawings are intended to cover non-exclusive inclusion.

[0048] In the description of the embodiments of this application, technical terms such as "first" and "second" are only used to distinguish different objects and cannot be understood as indicating or implying relative importance or implicitly indicating the quantity, specific order or primary-secondary relationship of the indicated technical features. In the description of the embodiments of this application, the term "multiple" means two or more (including two). Similarly, "multiple groups" means two or more groups (including two groups), and "multiple pieces" means two or more pieces (including two pieces), unless otherwise specifically defined.

[0049] Referring to "embodiments" herein means that the specific features, structures or characteristics described in connection with the embodiments can be included in at least one embodiment of this application. The phrase appears in various places in the specification does not necessarily refer to the same embodiment, nor is it an independent or alternative embodiment mutually exclusive with other embodiments. Those skilled in the art explicitly and implicitly understand that the embodiments described herein can be combined with other embodiments.

[0050] In the description of the embodiments of this application, the term "and / or" is only a description of the association relationship of associated objects, indicating that there can be three relationships. For example, A and / or B can represent: A exists alone, A and B exist simultaneously, and B exists alone. In addition, the character " / " in this article generally represents an "or" relationship between the associated objects before and after.

[0051] In this document, quantities, ratios, and other numerical values are presented in range format. It should be understood that such range format is 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 subsumed within the stated range, as if each value and sub-range were explicitly specified.

[0052] Unless otherwise specified, all steps of this application can be carried out sequentially, randomly, or in parallel, and preferably sequentially. For example, the method includes steps (a) and (b), which means that the method can include steps (a) and (b) carried out sequentially, or steps (b) and (a) carried out sequentially, or steps (a) and (b) carried out in parallel simultaneously. For example, it is also mentioned that the method may further include step (c), which means that step (c) can be added to the method in any order. For example, the method can include steps (a), (b), and (c), or steps (a), (c), and (b), or steps (c), (a), and (b), etc.

[0053] Due to the various excellent properties of power batteries, they have been widely used in people's lives, new energy vehicles, energy storage, and other industries. New energy vehicles and electrochemical energy storage are the fields 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, due to the material transformation and gas release caused by electrochemical reactions, the battery will generate gas.

[0054] During the charging process, the battery converts external electrical energy into chemical energy for storage, and at the same time, there are also some side reactions that generate gas. For example, during charging, lead-acid batteries will undergo a side reaction of electrolytic water decomposition, resulting in the generation of oxygen and hydrogen gases. During the discharging process, the chemical energy in the battery is converted into electrical energy, and at the same time, there will also be some gas-generation reactions. For example, during the discharging process of lithium-ion batteries, an oxidation reaction of lithium metal may occur, generating some harmful gases such as fluorocarbon compounds.

[0055] In addition, the battery may generate gas during use due to overcharging, over-discharging, internal faults, or incorrect operations. In this case, the chemical reactions inside the battery may get out of control, releasing gas violently and even triggering the phenomenon of battery thermal runaway.

[0056] Battery thermal runaway is an important part of battery safety research. Battery thermal runaway is a chain reaction phenomenon triggered by various incentives. The battery packs of new energy vehicles are usually sealed and in an anaerobic environment during normal operation. If a battery pack experiences thermal runaway, some characteristic gases will be released. The characteristic gases of battery thermal runaway include carbon dioxide, carbon monoxide, hydrogen, ethylene, methane, ethane, propylene, etc. Detecting the characteristic gases of battery thermal runaway can provide early warning and timely take corresponding measures when thermal runaway occurs, reducing the damage to life and property safety. Currently, in the field of battery thermal runaway detection, chemiresistive sensors have a reliable application prospect. It relies on the change in conductivity when the sensing material interacts with the characteristic gas to achieve the detection purpose, and has the advantages of simplicity, universality, low power consumption, and high cost-effectiveness. However, existing metal oxide sensors require oxygen, which limits their application in detecting the gases generated by battery thermal runaway under anaerobic conditions. But the inside of the battery cell is an anaerobic environment. Therefore, there is an urgent need to develop new materials and sensors that can work stably under non-oxygen conditions and accurately detect the gases generated by battery thermal runaway.

[0057] To achieve highly sensitive detection of the characteristic gases of battery thermal runaway in an anaerobic environment, it has been found that metal-organic framework materials (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 linkers between metal nodes. The unique framework and pore structure characteristics of MOF materials determine that they have unique properties such as a large specific surface area, high porosity, and chemical tunability. The large specific surface area and adjustable porous structure of MOF materials can provide a large number of sites for gas adsorption. After adsorbing gas molecules, it will cause the formation or breakage of coordination bonds, resulting in electron transfer, thereby changing the electrical properties of MOF materials and achieving a response to the adsorbed gas. That is, when MOF materials are used as gas-sensitive materials, their response mechanism is the transfer of coordination electrons. Based on this principle, MOF materials can achieve gas response even under anaerobic conditions, expanding their application scenarios as gas sensing materials.

[0058] In this application, a gas sensing material is provided. The gas sensing material includes a metal-organic framework material, and the metal-organic framework material includes one-dimensional nanomaterials. The one-dimensional nanomaterials have dimensions at the nanoscale in at least two dimensions, and the nanoscale is 0.1 nm - 100 nm.

[0059] In one embodiment, the metal-organic framework material (MOFs) can be a material with a nanostructure. A nanostructure is the structure of an object with dimensions between the molecular and micron scales; the linear dimensions of these substances are generally in the range of 0.1 - 100 nm. Nanostructures include one-dimensional, two-dimensional, and three-dimensional systems, and these material units include nanoparticles, nanotubes, nanorods, nanowires, nanobelts, and nanoscale pores, etc.

[0060] By making the metal-organic framework material (MOFs) into a material with a nanostructure, it can have a large specific surface area, providing a large number of sites for gas adsorption and improving the sensitivity of the gas sensing material. Further research found that most of the metal-organic framework materials (MOFs) have a two-dimensional nanostructure, that is, two-dimensional nano-MOFs materials. And some two-dimensional nano-MOFs materials cannot release gas quickly after adsorption, that is, they have response irreversibility, resulting in the inability of the gas sensor to be reused; there are also some two-dimensional nano-MOFs materials with poor conductivity, resulting in insufficient sensitivity.

[0061] Based on this, the present application provides a metal-organic framework material (MOFs) with a one-dimensional nanostructure, that is, one-dimensional nano-MOFs material. One-dimensional nanomaterials refer to materials with dimensions on the nanoscale in two dimensions and dimensions exceeding the nanoscale in the third dimension, and the nanoscale is defined as 0.1 nm - 100 nm. For example, from the three dimensions of length, width, and height (thickness), the one-dimensional nano-MOFs material can be a material with a width and height (thickness) on the nanoscale but a length greater than the nanoscale; it can also be a material with a width and length on the nanoscale but a height (thickness) greater than the nanoscale. The one-dimensional nano-MOFs material has a higher specific surface area to volume ratio, which is beneficial 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, resulting in a shorter response time.

[0062] In some embodiments of the present application, the metal-organic framework material includes a nanobelt material, that is, a nanobelt MOFs material. Among them, the thickness of the nanobelt material is 1 - 10 nm, and the width is 10 - 100 nm. Please refer to Figure 1 and Figure 10 , Figure 1 are transmission electron microscope (TEM) images of the metal-organic framework material according to one or more embodiments, Figure 7Scanning electron microscope (SEM) image of a metal-organic framework material according to one or more embodiments. It can be observed from the image that the thickness of the nanobelt MOF material is 1-10 nm, the width is 10-100 nm, and the length is relatively large, exceeding dozens 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. Thanks to the one-dimensional nanostructure, the nanobelt MOF material in this application has a higher structural degree of freedom than two-dimensional and three-dimensional metal-organic framework materials, providing more opportunities to create conductive paths, significantly improving the conductivity of the material; the structure is stable and ordered, with a higher surface area to volume ratio, providing a broader site for the adsorption of gas molecules, and at the same time being able to accelerate the diffusion rate of gas on the sensing material, making the resistance change significantly with the change of gas adsorption, so the sensitivity and speed of gas response can be effectively improved.

[0063] In some embodiments of the present application, the metal-organic framework material includes a complex of a metal and an organic ligand in terms of chemical composition, and the metal elements include one or more of copper, nickel, cobalt, zinc, and iron. Among them, it can be a complex of metal ions and organic ligands, and the metal ions include one or more of copper ions, nickel ions, cobalt ions, zinc ions, and iron ions.

[0064] The metal ions and the organic ligands form a complex through coordination bonds. The metal ions can act as coordination centers and coordinate with multiple atoms on the organic ligands to form a relatively stable form, improving the stability of the metal-organic framework material. At the same time, the metal ions can act as adsorption sites for gases. The adsorbed gas molecules will cause the formation or breakage of coordination bonds, resulting in electron transfer, thereby changing the electrical and optical properties of the MOFs and realizing the sensitivity and selectivity to the adsorbed gas. Specifically, gas molecules can be connected to metal ions through coordination bonds and electron transfer occurs, thereby realizing the response to the gas.

[0065] In some embodiments of the present application, there can be only one type of metal ion in the metal-organic framework material (MOFs); there can also be multiple different types of metal ions at the same time, forming different coordination centers. There can be multiple metal ions, forming multiple coordination centers. Different types of metal ions can endow the metal-organic framework material with response selectivity to different gases, and the gas selectivity of the metal-organic framework material can be provided by regulating the type and quantity of the metal ions.

[0066] In some embodiments of the present application, the organic ligand includes 1,5-diamino-4,8-dihydroxy anthraquinone (DDA), and its structural formula is This is a ligand with an aromatic nucleus, and the molecule is centrosymmetric. Specifically, DDA is an anthraquinone compound containing amino and hydroxyl substituents, and its molecular formula is C 14 H 10 N 2 O 4 , with a molecular weight of 270.24. It contains an anthraquinone parent nucleus, and the 1st and 5th positions are substituted by amino groups, and the 4th and 8th positions are substituted by hydroxyl groups. There is a conjugation effect between the anthraquinone ring and the amino and hydroxyl groups. The amino, hydroxyl, and carbonyl groups in the molecule can act as coordination atoms to form stable coordination bonds with various metal ions, obtaining metal-organic framework materials with different structural properties, and having strong design flexibility. Furthermore, the aromatic anthraquinone ring can form π-π stacking interactions, enhancing the stability of MOFs. Finally, since 1,5-diamino-4,8-dihydroxy anthraquinone has a planar configuration, it is easy to expand into a one-dimensional nanoribbon form through self-assembly.

[0067] In the metal-organic framework material (MOFs) formed by coordinating with this ligand, the coordination bonds formed between metal ions and organic ligands can establish an effective charge transport pathway. Especially for active transition metal ions, they have appropriate atomic radii to obtain better orbital overlap with the ligand, which is beneficial to generating a small bandgap and high charge mobility. In addition, the organic ligand with an aromatic ring can also form a π-d conjugated plane and π-π stacking, thereby providing a conduction path on the plane, which is beneficial to improving the conductivity of the metal-organic framework material. Thus, the response value and sensitivity of gas sensing can be improved.

[0068] In some embodiments of the present application, the organic ligand can also carry substituents that are easy to form coordination bonds, such as carboxyl (COOH), mercapto (SH), etc.; the organic ligand can also be other condensed polycyclic aromatic compounds as the parent nucleus, such as macrocyclic planar compounds such as anthracene and phenanthrene.

[0069] In some embodiments of the present application, the organic ligand includes the following structure:

[0070] Where R 1 , R 2 are hydroxyl (OH), amino (NH 2 ), or mercapto (SH).

[0071] That is, the substituent on the anthraquinone ring can also be mercapto. The parent nucleus can also be extended to a larger conjugated structure.

[0072] In some embodiments of the present application, a metal-organic framework material is a complex formed by the coordination of divalent copper ions with 1,5-diamino-4,8-dihydroxyanthraquinone (hereinafter referred to as DDA-Cu). The structural formula of DDA-Cu is

[0073]

[0074] According to the structural formula of DDA-Cu, the copper ions in DDA-Cu are coordinated at the centers of three oxygen atoms and one nitrogen atom in the DDA ligand, making the copper ions in a stable form. At the same time, the d orbitals of the copper ions between layers are stacked to form an axial conduction path, improving the conductivity of the metal-organic framework material. In addition, using metal ions to connect the basic structural units can further increase the axial conductivity of the MOFs material. At the same time, due to the formation of a large π-bond system in the plane, the conductivity in the plane direction is improved, thereby further increasing the electrical properties of the material. Furthermore, the response value and sensitivity of gas sensing can be improved.

[0075] Furthermore, due to the high degree of restriction of the bimetallic sites on the structural flatness, DDA-Cu grows linearly along the coordination nodes to form a one-dimensional nanoribbon structure. The one-dimensional nanoribbons are stacked through non-bonding interactions to form a bulk material. Nanomaterials based on one-dimensional building blocks have highly regular structures, chemically modular edges, and tunable structure-activity relationships, and can provide more adsorption sites.

[0076] The one-dimensional nanoribbon metal-organic framework material in this embodiment has multiple highly conjugated structural units with excellent conductivity. At the same time, it has a higher structural freedom than two-dimensional and three-dimensional metal-organic framework materials, providing more opportunities for creating conduction paths, significantly improving the conductivity of the material; the structure is stable and orderly, with a higher surface area to volume ratio, providing a broader site for the adsorption of gas molecules, and at the same time being able to accelerate the diffusion rate of gas on the sensing material, making the resistance change significantly with the change of gas adsorption. Therefore, the sensitivity and speed of gas response can be effectively improved.

[0077] In some embodiments, the response gases of the gas sensing material include one or more of carbon monoxide, ammonia, hydrogen sulfide, and nitrogen dioxide. The gas sensing material provided by the present application can respond to multiple gases and has a certain selectivity. For specific details, please refer to the description of the experimental examples below.

[0078] In some embodiments of the present application, a preparation method of a gas sensing material is further provided. The preparation method of the gas sensing material specifically includes: providing a metal ion solution and an organic ligand solution; combining and reacting the metal ion solution with the organic ligand solution to obtain a metal-organic framework material. The obtained metal-organic framework material has a one-dimensional nanostructure, that is, a one-dimensional nano-MOFs material.

[0079] Among them, 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(NO 3 ) 2 ), zinc nitrate (Zn(NO 3 ) 2 ), cobalt nitrate (Co(NO 3 ) 2 ) and other inorganic salts of transition metals; transition metal organic complexes, such as copper acetate (Cu 2 (CH 3 COO) 4 ), ferrous succinate, etc.; oxide precursors, such as CuO, ZnO and other transition metal oxides; metal-organic frameworks: some metal-organic framework materials can also be used as metal sources to release metal ions for continuing to construct the metal-organic framework structure; other materials: metal foils, salts, inorganic acids, etc. By selecting different metal salts to prepare the metal ion solution, the morphology, crystallization, etc. of the obtained metal-organic framework material can be regulated, and then the morphology and crystallinity of the obtained metal-organic framework material can be regulated, and further the gas sensing performance can be regulated. The solvent used in 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, an alcohol solvent can also be used to prepare the metal ion solution.

[0080] The organic ligand solution is prepared by dissolving an organic ligand in a solvent. The solvents of the organic ligand solution include 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 materials) in the reaction system. By selecting different solvents, different methods can be selected to prepare MOFs materials, and at the same time, the crystallinity, pore structure, pore environment, morphology, etc. of MOFs materials can be regulated to regulate their performance as gas sensors, such as regulating the selectivity to gases, regulating the response value, sensitivity, etc.

[0081] In some embodiments of the present application, the metal ion solution and the organic ligand solution can be combined and reacted based on the solvothermal method to obtain a metal-organic framework material.

[0082] Specifically, after the metal ion solution and the organic ligand solution are uniformly mixed, they are allowed to stand and react to obtain a metal-organic framework material. Among them, standing and reacting means that the reaction solution system is not stirred, dispersed, etc. during the reaction process. That is, the solutions are first mixed, and stirring, dispersion and other operations can be performed during mixing, but no other mixing operations such as stirring are performed during the reaction after mixing.

[0083] In some embodiments of the present application, the metal ion solution may be dropped into the organic ligand solution to mix the metal ion solution and the organic ligand solution. Optionally, the dropping rate of the metal ion solution is 1 - 20 seconds per drop, for example, it can be 1 second per drop, 5 seconds per drop, 10 seconds per drop, 15 seconds per drop, 20 seconds per drop, etc. Through this setting, the metal ions can be more evenly dispersed in the organic ligand solution. Further, after the dropping is completed, the mixture can be ultrasonically treated to make it mix evenly.

[0084] In some embodiments of the present application, after the metal ion solution and the organic ligand solution are evenly mixed, they are allowed to stand and react, and the standing reaction time is 8 - 15 h; the temperature of the standing reaction is 70 - 95 °C.

[0085] Among them, during the standing reaction, the screw cap of the reaction vessel is not completely tightened, so that oxygen can 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 increase, so the crystal growth rate will increase, 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 the one-dimensional nanostructure. Further, by controlling the heating temperature, the crystallinity of the product can be regulated, and thus the gas response performance can be regulated. The reaction time is 8 h, 9 h, 10 h, 11 h, 12 h, 13 h, 14 h, 15 h, etc., and is specifically adjusted according to the reaction progress. As the time extends, the reaction will proceed more and more completely. Considering the time cost, preferably, the reaction time can be 12 h.

[0086] In some embodiments of the present application, a base can also 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, for example, it can be ammonia water.

[0087] Among them, during the synthesis process of the metal-organic framework material, it is necessary to adjust the pH value of the reaction system to the range suitable for crystal growth. The pH value can be adjusted by using an acid or a base, which is called a pH value regulator, including: concentrated ammonia water, sodium hydroxide, triethylamine, ethylenediamine, tetrabutylammonium hydroxide, hydrochloric acid, oxalic acid, phosphoric acid, etc. Optionally, concentrated ammonia water can be added in the solution of the present application. The functions of concentrated ammonia water include: providing an alkaline environment, which is beneficial to the deprotonation of metal ions and the dissociation of organic ligands; adjusting the pH value, thereby controlling the growth rate of the metal-organic framework material; improving solubility, making the metal salt and the organic ligand completely dissolve in the synthesis solvent; accelerating the reaction, accelerating the coordination cross-linking rate between the metal salt and the organic ligand.

[0088] After the reaction between the metal ion solution and the organic ligand solution is completed, it is naturally cooled to room temperature. The cooling rate during natural cooling is not high, which is beneficial to the growth of crystals and can form relatively regular crystals. There is precipitation in the reaction system. The obtained precipitate is alternately centrifuged and washed with deionized water and ethanol, and then dried in an oven to obtain the product metal-organic framework material. The drying temperature is 60 °C and the drying time is 6 h. The washing process can remove impurities on the surface of the metal-organic framework material, including unreacted reactants and some impurity ions, etc., and will not affect the subsequent performance tests.

[0089] In some embodiments of the present application, a metal-organic framework material can be obtained by combining and reacting a metal ion solution and an organic ligand solution based on the interfacial growth reaction method.

[0090] Specifically, the metal ions and the organic ligand are respectively dissolved in two immiscible solvents to obtain a metal ion solution and an organic ligand solution. The immiscible metal ion solution and organic ligand solution are placed in the same container. Since the metal ion solution and the organic ligand solution are immiscible, they will present a layered state, causing a two-phase interface to be generated in the reaction system. The organic ligand and the metal ions come into contact and react at the two-phase interface, enabling the growth of metal-organic framework crystals at the two-phase interface. The two raw materials for preparing MOFs will diffuse into each other at the interface, and a MOF film will be produced at the interface.

[0091] 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 with each other at the interface, and the organic ligand and the metal ions are assembled into metal-organic framework crystals with a specific structure through a step-by-step growth method.

[0092] By adjusting the interaction between the reactants at the interface, the morphology and structure of the metal-organic framework material can be controlled, and the sensitivity of the sensing material can be regulated; the interfacial growth method provides convenience for the reconstruction of the sensing material, enabling the repeated assembly and reconstruction of the sensing material, and thus the design and application of multifunctional sensors can be realized.

[0093] 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: combining and reacting a 1,5-diamino-4,8-dihydroxyanthraquinone solution with a divalent copper ion solution. The reaction formula is:

[0094]

[0095] As can be seen from the reaction formula, each DDA ligand needs to coordinate with four equivalents of copper ions, and each copper ion is connected to two DDA ligands. Therefore, the theoretical feed ratio is DDA:copper ions = 1:2 (in terms of amount of substance). However, under actual working conditions, the synthesis and decomposition of metal-organic framework materials are reversible reactions. Reacting according to the theoretical feed ratio cannot achieve a high yield. Therefore, it is necessary to make the reactants in excess to promote the reaction to proceed in the forward direction. Further, in order to control costs, the concentration of copper ions with relatively low price is increased to promote the reaction to proceed in the direction of forming metal-organic framework materials.

[0096] In some embodiments of the present application, the molar ratio of DDA to divalent copper ions is 1:(2 - 8). For example, it can be 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, etc. As the amount of copper ions increases, the reaction proceeds more and more completely. At the same time, by regulating the feed ratio, the morphology and crystallinity of the obtained product can also be regulated, and then the gas response performance can be regulated.

[0097] In some embodiments of the present application, 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. By selecting different anions, the microscopic morphology, pore structure, and pore size of the metal-organic framework material can be regulated, and further the gas sensing performance of the material can be regulated.

[0098] In some embodiments of the present application, the solvent of the DDA ligand includes one or more of methanol, ethanol, acetone, tetrahydrofuran, dimethyl sulfoxide, N,N-dimethylformamide, and dichloromethane. By selecting different solvents, the microscopic morphology, pore structure, and pore size of the metal-organic framework material can be regulated, and further the gas sensing performance of the material can be regulated.

[0099] Please refer to Figure 2 , Figure 2 which is a schematic diagram of a method for preparing a gas sensing material according to one or more embodiments. The divalent copper ion solution can be combined with the DDA ligand solution to react based on the solvothermal method to obtain a metal-organic framework material.

[0100] Specifically, the divalent copper ion solution and the DDA ligand solution are mixed, and the mixed solution is placed in a screw-cap glass bottle. The screw of the glass bottle is slightly loosened and placed, and it is kept warm at 95 °C for 12 h; after the reaction is completed, it is allowed to cool naturally to room temperature. The obtained black precipitate is alternately centrifuged and washed with deionized water and ethanol. The centrifugation speed for centrifugation and washing is 8000 rpm, and the time for centrifugation and washing is 10 min. Then it is dried in an oven at 60 °C for 6 h to obtain the product.

[0101] Please refer to Figure 3 , Figure 3Schematic diagram of a preparation method of a gas sensing material according to one or more embodiments. A divalent copper ion solution can be combined and reacted with a DDA ligand solution based on the interfacial reaction growth method to obtain a metal-organic framework material.

[0102] 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 layered and allowed to stand and react for one week, and a MOFs thin film grows at the interface.

[0103] In some embodiments of the present application, a gas sensor is further provided. The gas sensor includes the gas sensing material of any one of the above; or includes the gas sensing material prepared by using the method of any one of the above.

[0104] Specifically, a one-dimensional nano MOFs material is used as the gas sensing material. This material realizes the response to the sensing gas based on the principle of coordination electron transfer, can realize gas response under anaerobic conditions, and a gas sensor that can quickly respond to gas and has high detection sensitivity under anaerobic conditions is prepared.

[0105] In some embodiments of the present application, the gas sensor provided by the present application can be used for detecting the gas inside the battery. That is, the present application provides a battery, and the battery includes the gas sensor of the above embodiment.

[0106] Please refer to Figure 4 , Figure 4 For the exploded structural schematic diagram of a battery according to one or more embodiments. The battery 100 includes a box body 10 and battery cells 20, and the battery cells 20 are accommodated in the box body 10. Among them, the box body 10 is used to provide an accommodation space for the battery cells 20, and the box body 10 can adopt various structures. In some embodiments, the box body 10 can include a first part 11 and a second part 12, the first part 11 and the second part 12 are covered with each other, and the first part 11 and the second part 12 jointly define an accommodation space for accommodating the battery cells 20. The second part 12 can be a hollow structure with one end open, the first part 11 can be a plate-like structure, and the first part 11 is covered on the open side of the second part 12 so that the first part 11 and the second part 12 jointly define an accommodation space; the first part 11 and the second part 12 can also both be hollow structures with one side open, and the open side of the first part 11 is covered on the open side of the second part 12. Of course, the box body 10 formed by the first part 11 and the second part 12 can be various shapes, for example, a cylinder, a cuboid, etc. The gas sensor can be installed inside the box body 10.

[0107] In battery 100, there may be multiple battery cells 20. The multiple battery cells 20 can be connected in series, parallel, or in a combined series-parallel connection. A combined series-parallel connection means that among the multiple battery cells 20, there are both series and parallel connections. The multiple battery cells 20 can be directly connected in series, parallel, or in a combined series-parallel connection, and then the whole formed by the multiple battery cells 20 is accommodated in the box 10. Of course, battery 100 can also be such that multiple battery cells 20 are first connected in series, parallel, or in a combined series-parallel connection to form a battery module, and then multiple battery modules are connected in series, parallel, or in a combined series-parallel connection to form a whole and are accommodated in the box 10. Battery 100 can also include other structures. For example, the battery 100 can also include a busbar component for realizing the electrical connection between the multiple battery cells 20.

[0108] Among them, each battery cell 20 can be a secondary battery or a primary battery; it can also be a lithium-sulfur battery, a sodium-ion battery, or a magnesium-ion battery, but is not limited thereto. The battery cell 20 can be in the shape of a cylinder, a flat body, a cuboid, or other shapes, etc.

[0109] Please refer to Figure 5 , Figure 5 , which is a schematic exploded view of a battery cell according to one or more embodiments. A battery cell 20 refers to the smallest unit that makes up a battery. As Figure 5 , the battery cell 20 includes an end cap 21, a housing 22, an electrode assembly 23, and other functional components.

[0110] The end cap 21 refers to a component that covers the opening of the housing 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 housing 22 to cooperate with the housing 22. Optionally, the end cap 21 can be made of a material with a certain hardness and strength (such as aluminum alloy). In this way, the end cap 21 is not easily deformed when subjected to extrusion and collision, enabling the battery cell 20 to have higher structural strength and the safety performance can also be improved. Functional components such as electrode terminals 21a can be provided on the end cap 21. The electrode terminals 21a can be used for electrically connecting to the electrode assembly 23 to output or input the electrical energy of the battery cell 20. In some embodiments, a pressure relief mechanism for releasing the internal pressure when the internal pressure or temperature of the battery cell 20 reaches a threshold can also be provided on the end cap 21. The material of the end cap 21 can also be various, such as copper, iron, aluminum, stainless steel, aluminum alloy, plastic, etc. The embodiments of the present application do not make special restrictions on this. In some embodiments, an insulating member can also be provided on the inner side of the end cap 21. The insulating member can be used to isolate the electrical connection components in the housing 22 from the end cap 21 to reduce the risk of short circuit. Exemplarily, the insulating member can be plastic, rubber, etc.

[0111] The housing 22 is a component for cooperating with the end cap 21 to form the internal environment of the battery cell 20. Among them, the formed internal environment can be used to accommodate the electrode assembly 23, the electrolyte, and other components. The housing 22 and the end cap 21 can be independent components. An opening can be provided on the housing 22, and the end cap 21 is covered at the opening to form the internal environment of the battery cell 20. Without limitation, the end cap 21 and the housing 22 can also be integrated. Specifically, the end cap 21 and the housing 22 can first form a common connection surface before other components are put into the housing. When it is necessary to encapsulate the interior of the housing 22, the end cap 21 is then covered on the housing 22. The housing 22 can be of various shapes and sizes, such as cuboid, cylindrical, 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 material of the housing 22 can be various, such as copper, iron, aluminum, stainless steel, aluminum alloy, plastic, etc. The embodiments of the present application do not make special restrictions on this.

[0112] The electrode assembly 23 is a component in the battery cell 100 where an electrochemical reaction occurs. The housing 22 can contain one or more electrode assemblies 23. The electrode assembly 23 is mainly formed by winding or laminating a positive electrode sheet and a negative electrode sheet, and a separator is usually provided between the positive electrode sheet and the negative electrode sheet. The parts of the positive electrode sheet and the negative electrode sheet with active substances constitute the main body of the electrode assembly, and the parts of the positive electrode sheet and the negative electrode sheet without active substances respectively constitute the electrode tabs 23a. The positive electrode tab and the negative electrode tab can be located at one end of the main body together or at both ends of the main body respectively. During the charging and discharging process of the battery, the positive electrode active substance and the negative electrode active substance react with the electrolyte, and the electrode tabs 23a are connected to the electrode terminals to form a current loop.

[0113] In one embodiment, the positive electrode sheet includes a current collector and a positive electrode active layer provided on the current collector.

[0114] The positive electrode active layer includes a positive electrode active material, and the positive electrode active material can include at least one of the following materials: lithium phosphate 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 conventional materials that can be used as battery positive electrode active materials can also be used. These positive electrode active materials can be used alone or in combination of two or more. Among them, examples of lithium transition metal oxides can include but are not limited to lithium cobalt oxide (such as LiCoO 2 ), lithium nickel oxide (such as LiNiO 2 ), lithium manganese oxide (such as LiMnO 2 , LiMn 2 O 4 ), lithium nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide (such as LiNi 1 / 3 Co 1 / 3Mn 1 / 3 O 2 (which can also be abbreviated as NCM 333 )、LiNi 0.5 Co 0.2 Mn 0.3 O 2 (which can also be abbreviated as NCM 523 )、LiNi 0.5 Co 0.25 Mn 0.25 O 2 (which can also be abbreviated as NCM 211 )、LiNi 0.6 Co 0.2 Mn 0.2 O 2 (which can also be abbreviated as NCM 622 )、LiNi 0.8 Co 0.1 Mn 0.1 O 2 (which can also be abbreviated as NCM 811 )、lithium nickel cobalt aluminum oxide (such as LiNi 0.85 Co 0.15 Al 0.05 O 2 ) and at least one of its modified compounds, etc. Examples of olivine-structured lithium-containing phosphates may include, but are not limited to, lithium iron phosphate (such as LiFePO 4 (which can also be abbreviated as LFP)), composite materials of lithium iron phosphate and carbon, lithium manganese phosphate (such as LiMnPO 4 ), composite materials of lithium manganese phosphate and carbon, lithium manganese iron phosphate, and composite materials of lithium manganese iron phosphate and carbon.

[0115] In one embodiment, the positive electrode active layer further includes a conductive agent to impart conductivity to the electrode. The positive electrode conductive material can include any conductive material as long as it does not cause chemical changes. Non-limiting examples of the positive electrode conductive material 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. Optionally, the conductive agent includes one or more of conductive carbon black, conductive graphite, carbon fiber, carbon nanotube, graphene, Ketjen black, and acetylene black.

[0116] 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 falling off. 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). Optionally, the binder includes one or more of polyvinylidene fluoride, polytetrafluoroethylene, acrylate, and polyurethane.

[0117] In one embodiment, the positive electrode active layer further includes other optional additives, and the other optional additives can be thickening and dispersing agents (such as sodium carboxymethyl cellulose CMC-Na), PTC thermistor materials.

[0118] In some embodiments, the negative electrode sheet includes a current collector and a negative electrode active layer provided on the current collector.

[0119] The negative electrode active layer includes a negative electrode active material, and the negative electrode active material 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 including but not limited to graphite materials, silicon-carbon materials, graphite-silicon monoxide materials, nano-silicon materials, silicon monoxide materials, and tin-based materials; more specifically including natural graphite, artificial graphite, mesocarbon microbeads (abbreviated as MCMB), hard carbon, soft carbon, silicon, silicon-carbon composites, Li-Sn alloys, Li-Sn-O alloys, Sn, SnO, SnO 2 spinel-structured lithiated TiO 2 -Li 4 Ti 5 O 12 and one or more of Li-Al alloys.

[0120] 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 (such as sodium carboxymethyl cellulose CMC-Na), PTC thermistor materials.

[0121] In some embodiments, the material of the separator may be selected from at least one of glass fiber, non-woven fabric, polyethylene, polypropylene, and polyvinylidene fluoride. The separator may 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 may be the same or different, without particular limitation.

[0122] In one embodiment, the electrolyte includes one or more of carbonate solvents and ether solvents.

[0123] Carbonates are usually small-molecule cyclic or chain carbonates; including but not limited to one or more of ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, methyl propyl carbonate, dipropyl carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, and fluorinated carbonates; it may also be at least one ester solvent of γ-butyrolactone, dimethyl sulfite, ethyl acetate, methyl acetate, methyl butyrate, ethyl butyrate, methyl propionate, ethyl propionate, propyl acetate, and fluorinated carboxylate.

[0124] Ether solvents include but are not limited to one or more of dimethyl ether, diethyl ether, tetrahydrofuran, methyl tetrahydrofuran, ethylene oxide, 1,3-dioxolane, fluorinated ether, 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.

[0125] In other embodiments, the electrolyte may further include any one or a mixture of amine solvents, sulfone solvents, and nitrile solvents. The amine solvents include at least one of N-methylacetamide, N-methylformamide, dimethylformamide, and diethylformamide. The sulfone solvents include at least one of dimethyl sulfoxide, sulfolane, diphenyl sulfoxide, thionyl chloride, and dipropyl sulfone. The nitrile solvents include at least one of acetonitrile, succinonitrile, adiponitrile, and glutaronitrile. The electrolyte is preferably a high-voltage-resistant electrolyte, whose acidity weakens under high voltage, which is beneficial to the transport of active ions, significantly reduces side reactions on the electrode surface, and improves battery stability.

[0126] In some embodiments, the electrolyte further includes an electrolyte salt, and the electrolyte salt may 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 difluoro(oxalato)borate, lithium bis(oxalato)borate, lithium difluoro bis(oxalato)phosphate, and lithium tetrafluoro(oxalato)phosphate.

[0127] In some embodiments, the electrolyte may optionally further include additives. For example, the additives may include negative electrode film-forming additives, positive electrode film-forming additives, and may also include additives that can improve certain battery performances, such as additives for improving the overcharge performance of the battery, additives for improving the high-temperature or low-temperature performance of the battery, etc.

[0128] The battery disclosed in the embodiments of the present application can be used in electrical devices using the battery as a power source or various energy storage systems using the battery as an energy storage element. That is, the present application provides an electrical device, and the electrical device includes the battery of the above embodiments. In some embodiments, the electrical device of the present application can be used in, but is 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, liquid crystal TVs, portable cleaners, portable CD players, mini-discs, transceivers, electronic notebooks, calculators, memory cards, portable recorders, radios, backup power supplies, motors, automobiles, motorcycles, power-assisted bicycles, bicycles, ships, spacecrafts, lighting appliances, toys, game consoles, clocks, power tools, flashlights, cameras, large household storage batteries, and lithium-ion capacitors, etc.

[0129] The electrical device can select battery cells, battery modules, or battery packs according to its usage requirements.

[0130] Please refer to Figure 6 , Figure 6Schematic 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, an extended-range vehicle, etc. A battery 100 is disposed inside the vehicle 1000. The battery 100 can be disposed at the bottom, the head, or the tail of the vehicle 1000. The battery 100 can be used for power supply of the vehicle 1000. For example, the battery 100 can serve as the operating power source of the vehicle 1000. The vehicle 1000 can further include a controller 200 and a motor 300. The controller 200 is used to control the battery 100 to supply power to the motor 300. For example, it is used for the working power requirements during the start, navigation, and driving of the vehicle 1000.

[0131] In some embodiments of the present application, the battery 100 can not only serve as the operating power source of the vehicle 1000, but also serve as the driving power source of the vehicle 1000, replacing or partially replacing fuel or natural gas to provide driving power for the vehicle 1000.

[0132] 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 in conjunction with the embodiments and the 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 in no way constitutes a limitation to the present application and its application. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present application.

[0133] I. Preparation of Gas Sensing Materials

[0134] Example 1

[0135] 1. Weigh 13.61 mg (0.05 mmol) of DDA ligand and 40.00 mg (0.20 mmol) of copper acetate monohydrate.

[0136] 2. Dissolve 13.61 mg of DDA ligand in 0.5 mL of N,N-dimethylformamide (DMF), and use an ultrasonic machine to ultrasonicate for 5 min to dissolve the organic ligand, obtaining a DDA ligand solution; dissolve 40.00 mg of copper acetate monohydrate in 1.5 mL of deionized water, and stir well to dissolve it, obtaining a divalent copper ion solution.

[0137] 3. Add the divalent copper ion solution to the DDA ligand solution and mix well. The copper acetate solution can be slowly dropped into 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 water to the above mixed solution; use an ultrasonic machine to ultrasonicate for 10 min to make the mixed solution mix evenly.

[0138] 4. Place the mixed solution in a 20 mL screw-cap glass bottle. Loosen the screw cap of the glass bottle slightly and keep it at 85 °C for 12 h.

[0139] 5. After the reaction is completed, let the mixed solution cool naturally to room temperature. Wash the obtained black precipitate by centrifugation alternately with deionized water and ethanol. The centrifugation speed for washing is 8000 rpm, and the centrifugation time for washing is 10 min. Then dry it in an oven at 60 °C for 6 h to obtain the nanobelt MOFs material DDA-Cu-1.

[0140] Example 2-3

[0141] On the basis of Example 1, change the preparation of the metal ion solution. The difference is that the metal copper salt is replaced with copper sulfate pentahydrate and copper chloride dihydrate respectively to obtain the nanobelt MOFs materials DDA-Cu-2 and DDA-Cu-3. The specific reaction conditions are shown in Table 1, and Table 1 lists the reactants, feeding ratios, reaction system solvents, and reaction system temperatures of each example.

[0142] Example 4-9

[0143] On the basis of Example 1, change the feeding ratio of the DDA ligand to the divalent copper ion. The difference is that the feeding ratio is adjusted from 1:4 to 1:2, 1:3, 1:5, 1:6, 1:7, 1:8 respectively to obtain the nanobelt MOFs materials DDA-Cu-4 to DDA-Cu-9. The specific reaction conditions are shown in Table 1.

[0144] Example 10-14

[0145] On the basis of Example 1, change the solvent of the reaction system. The difference is that the solvent is replaced with methanol, ethanol, acetone, tetrahydrofuran, and dimethyl sulfoxide respectively to obtain the nanobelt MOFs materials DDA-Cu-10 to DDA-Cu-14. The specific reaction conditions are shown in Table 1.

[0146] Example 15-19

[0147] On the basis of Example 1, change the temperature of the reaction system. The difference is that the temperature is adjusted from 85 °C to 70 °C, 75 °C, 80 °C, 90 °C, 95 °C respectively to obtain the nanobelt MOFs materials DDA-Cu-15 to DDA-Cu-19. The specific reaction conditions are shown in Table 1.

[0148] Example 20-21

[0149] On the basis of Example 1, change the type of metal salt. The difference is that copper acetate monohydrate is replaced with cobalt acetate tetrahydrate and nickel acetate tetrahydrate respectively to obtain the nanobelt MOFs materials DDA-Co and DDA-Ni. The specific reaction conditions are shown in Table 1.

[0150] II. Testing of Gas Sensing Materials

[0151] (1) Transmission Electron Microscopy (TEM)

[0152] Refer to the General Rules for Transmission Electron Microscopy Analysis Method JY / T 0581 - 2020. Use an electron beam to penetrate the sample to measure the TEM image of the metal - organic framework material.

[0153] (2) X - ray Diffraction (XRD)

[0154] Refer to the General Rules for X - ray Diffraction Analysis Method JIS K 0131 - 1996. Use CuKα1 ray to measure the X - ray diffraction pattern of the metal - organic framework material.

[0155] (3) Scanning Electron Microscopy (SEM) and Energy - Dispersive X - ray Spectroscopy (EDS)

[0156] Refer to the General Rules for Analytical Scanning Electron Microscopy Method JY / T010 - 1996. Use an electron beam to scan the surface of the sample to measure the SEM image of the metal - organic framework material and obtain the energy - dispersive spectrum of the metal - organic framework material at the same time.

[0157] III. Preparation of Gas Sensors

[0158] Disperse the gas sensing material in ethanol at a concentration of 10 mg / L and ultrasonically treat it for 10 min at 40 KHz to make the composite material evenly dispersed in ethanol. Use a micro - machining process to prepare gold electrodes, control the distance between the positive and negative electrodes to be 800 μm, and the distance between adjacent electrodes to be 300 μm. Take 5 μL of the above - mentioned dispersion and drop it on the interdigital electrodes, and dry it in a vacuum at 60 °C for 1 h to obtain the gas sensor.

[0159] IV. Gas Sensing Performance Testing

[0160] Please refer to Figure 7 , Figure 7 , which is a schematic diagram of the gas sensing performance testing according to one or more embodiments. Place the gas sensor in the test chamber. Under room - temperature conditions, introduce the target gas in a static gas - mixing manner, apply a constant working voltage of 500 mV between the sensor electrodes, and detect the resistance change of the sensor in an inert gas and target gas environment through an Agilent 4156C semiconductor parameter analyzer. Among them, before introducing the target gas, use dry compressed nitrogen (MFC3) to purify the chamber to stabilize the baseline signal, use compressed nitrogen (MFC2) as the carrier gas to dilute the target gas, and the target gas is controlled by a mass flow controller (MFC1). The difference between the resistance of the sensor in dry nitrogen and in the target gas and the ratio of the resistance in dry nitrogen (|R a -R g | / Ra × 100%) is the response value of the device to the target gas, and the response and recovery times are defined by reaching 90% saturation of the response and recovery curves.

[0161] Table 1 Reaction parameters and performance parameters of each example

[0162]

[0163] Note: DDA:A n+ is the molar ratio of the DDA ligand to the metal ion (A n+ ); the response value is the response value of the metal-organic framework material to CO with a concentration of 50 ppm; the recovery time is the recovery time of the metal-organic framework material to CO with a concentration of 50 ppm.

[0164] Please refer to Figure 1 and Figure 10 . It can be observed from the TEM image and SEM image that DDA-Cu-1 has a nanostructure, specifically in the form of nanoribbons. The thicknesses of different nanoribbons are 2.5 nm, 3.0 nm, 6.2 nm, 8.2 nm, etc., and the widths are 19.0 nm, 32.4 nm, 66.7 nm, 95.8 nm, etc.

[0165] Please refer to Figure 8 , Figure 8 is the 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 basically the same as those simulated from the single crystal data obtained by Materials Studio software. The diffraction peaks corresponding to the (001), (100), and (010) crystal planes can be observed, and the peak shapes are relatively sharp, indicating that the crystal structure of the experimental sample is relatively ordered, the atomic arrangement inside the crystal is relatively regular, there are not too many crystal defects or impurities, and the purity is relatively high.

[0166] Please continue to refer to Figure 9 , Figure 9 is the X-ray energy spectrum analysis (EDS) image of the gas sensing material DDA-Cu according to one or more embodiments. As shown in the figure, in the gas sensing material, oxygen element (O), nitrogen element (N), and copper element (Cu) are uniformly distributed in the gas sensing material.

[0167] Please refer to Figures 10 to 12 , Figure 10 is the scanning electron microscope (SEM) image of the gas sensing material DDA-Cu-1 obtained in Example 1, Figure 11 is the scanning electron microscope (SEM) image of the gas sensing material DDA-Cu-2 obtained in Example 2, Figure 12SEM image of the gas sensing material DDA-Cu-3 obtained in Example 3. As shown in the figure, the gas sensing materials prepared from different metal salts also have different micro-morphologies. DDA-Cu-1 and DDA-Cu-3 are in the form of nanobelts and nanosheets, while DDA-Cu-2 is in the form of needle-like crystals. However, all three are nanostructures. By selecting different copper salts to prepare metal ions, the micro-morphology of the metal-organic framework material can be regulated.

[0168] Please refer to Table 1 for combination. There are certain differences in the response data of DDA-Cu-1, DDA-Cu-2, and DDA-Cu-3 to gases. Compared with DDA-Cu-1 and DDA-Cu-2, DDA-Cu-3 has a higher response value to CO, but the recovery time is also prolonged. Therefore, by adjusting the types of anions in the metal salt, the response and recovery performance of the metal-organic framework material in gas sensing can be regulated.

[0169] In Examples 1, 4-9, the gas sensing performance of the Cu-DDA gas sensing material to 50 ppm carbon monoxide gas was demonstrated when the feeding ratio was 1:2 - 1:8. As the amount of copper ions increased, the reaction proceeded more completely, and the gas sensing performance of the Cu-DDA gas sensing material to 50 ppm carbon monoxide gas was also improved accordingly, specifically manifested as an increase in the response value and a decrease in the recovery time. However, when the feeding ratio exceeded 1:4, the improvement in the gas sensing performance was no longer obvious. Therefore, considering the raw material cost, preferably, the feeding ratio of 1,5-diamino-4,8-dihydroxyanthraquinone:copper ions = 1:4 (amount of substance), at this time, both the gas sensing performance of the product can be improved and the raw materials can be saved.

[0170] In Examples 1, 10-14, the gas sensing performance of the Cu-DDA gas sensing material to 50 ppm carbon monoxide gas was demonstrated when the solvents in the reaction system were different. The polarities of different solvents are different. The polarity of the solvent can affect the interaction and reaction rate between the ligand and metal ions, and also affect the pore structure and the environment inside the pores 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 materials are different. Among them, dimethyl sulfoxide has a relatively high 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 Cu-DDA metal-organic framework material has a high response value to carbon monoxide and a short recovery time.

[0171] In Examples 1, 15 - 19, the gas sensing performance of the Cu - DDA gas sensing material to 50 ppm carbon monoxide gas was demonstrated when the reaction system temperature was 70°C - 95°C. As the temperature increased, the reaction rate of the reaction system would accelerate, so the crystal growth rate would accelerate, and a higher yield could be achieved in the same reaction time. By regulating the temperature of the reaction system, the yield of the finally generated gas sensing material was higher, so it was more excellent in gas sensing performance. As the static reaction temperature increased, the reaction proceeded more and more completely, the response value to carbon monoxide gas increased, and the recovery time decreased. However, when the temperature exceeded 85°C, the improvement of gas sensing performance was no longer obvious. Preferably, the temperature can be set to 85°C. At this time, the Cu - DDA metal - organic framework material has good sensing performance and does not waste energy.

[0172] In Examples 1, 20 - 21, the gas sensing performance of the prepared gas sensing material to 50 ppm carbon monoxide gas was demonstrated when the metal salts were copper acetate monohydrate, cobalt acetate tetrahydrate, and nickel acetate tetrahydrate respectively. When the metal ions were cobalt and nickel, although the response value to the gas was large, it could not recover. Therefore, copper ions can be preferably selected as the metal ions for the gas sensing material to detect carbon monoxide gas according to application requirements.

[0173] Please refer to Figures 13 to 15 , Figure 13 FIG. is the gas response schematic diagram of the gas sensing material DDA - Cu according to one or more embodiments, Figure 14 FIG. is the gas response schematic diagram of the gas sensing material DDA - Co according to one or more embodiments, Figure 15 FIG. is the gas response schematic diagram of the gas sensing material DDA - Ni according to one or more embodiments. The response of different gas sensing materials to carbon monoxide (CO), ammonia (NH 3 ) and hydrogen sulfide (H 2 S) with a concentration of 50 ppm was tested respectively. It was detected that DDA - Cu, DDA - Co, and DDA - Ni all had certain response characteristics to carbon monoxide (CO), ammonia (NH 3 ) and hydrogen sulfide (H 2 S), and could be used as gas sensors to detect these gases. However, the response values that could be achieved for different gases were different, and a suitable gas sensing material could be selected according to the actual situation.

[0174] Please refer to Figure 16 , Figure 16 FIG. is the gas response schematic diagram of the gas sensing material DDA - Cu according to one or more embodiments. Further, at room temperature, the response of the sensor prepared from the DDA - Cu - 1 gas sensing material in Example 1 to 50 ppm of different gases was tested, and the results are as Figure 16As shown, it can be seen that the response value of the DDA-Cu-1 gas sensing material to carbon monoxide is about 9%, the response value to ammonia exceeds 15%, the response value to hydrogen sulfide exceeds 20%, and the response values to the other five gases do not exceed 5%. Therefore, DDA-Cu-1 exhibits good gas selectivity.

[0175] Please refer to Figure 17 and 18 , Figure 17 is a schematic diagram of the gas response of the gas sensing material DDA-Cu according to one or more embodiments. Figure 18 is a schematic diagram of the gas response of the gas sensing material DDA-Cu according to one or more embodiments. At room temperature, the response of the sensor prepared in Example 1 based on the DDA-Cu-1 gas sensing material to carbon monoxide with a concentration of 10 ppm - 80 ppm was tested. In the figure, the abscissa is the acquisition time and the ordinate is the response value. It can be seen from the figure that the response value of the DDA-Cu-1 based sensor prepared in the foregoing embodiment to 80 ppm carbon monoxide reached 8.8%. The lowest detectable carbon monoxide concentration reached 10 ppm, and the corresponding response value was 1.1%. As the carbon monoxide concentration increased, the response value of the sensor to the gas also increased, and the response values to 10, 20, 40, and 80 ppm carbon monoxide were 1.1%, 2.0%, 3.7%, and 8.8% respectively. It can be seen that the gas sensing material provided in this application has a more sensitive gas response and a low detection limit.

[0176] Furthermore, at room temperature, the cyclic response performance of the sensor prepared in Example 1 based on the DDA-Cu-1 gas sensing material to 50 ppm carbon monoxide was tested. In the figure, the abscissa is the acquisition time and the ordinate is the response value. The response time of the sensor to the gas is about 400 s, and the recovery time is also about 400 s, and the response is more sensitive. And after six response-recovery cycles, the response value of the sensor remained above 3.8%, and the response time remained basically unchanged, indicating that the sensor prepared in the foregoing embodiment has good cyclic stability.

[0177] In the above embodiments, the gas sensing material provided in this application has good response sensitivity and selectivity to gases. Furthermore, the above gas sensing test of the gas sensing material was carried out at room temperature. Compared with the existing materials that require high temperature for gas response, the conditions are milder and the application range is wider.

[0178] The above description is only the implementation manner of this application, and does not limit the patent scope of this application. Any equivalent structure or equivalent process transformation made by using the content of the specification and drawings of this application, or directly or indirectly applied in other related technical fields, shall be equally included in the patent protection scope of this application.

Claims

1. A gas sensing material, characterized in that, it comprises: a metal-organic framework material, the metal-organic framework material comprising one-dimensional nanomaterials, the one-dimensional nanomaterials having dimensions in at least two dimensions in the nanoscale range, the nanoscale range being 0.1 nm - 100 nm.

2. The gas sensing material according to claim 1, characterized in that, the metal-organic framework material comprises nanobelt materials, the nanobelt materials having a thickness of 1 - 10 nm, optionally 3 - 8 nm; the width of the nanobelts is 10 - 100 nm; optionally 15 - 70 nm.

3. The gas sensing material according to claim 1 or 2, characterized in that, the metal-organic framework material comprises a complex of a metal and an organic ligand, the metal comprising one or more of copper, nickel, cobalt, zinc, and iron.

4. The gas sensing material according to any one of claims 1 to 3, characterized in that, the organic ligand comprises the structure shown in formula (1): Among them, R 1 , R 2 includes any one of a hydroxyl group, an amino group or a mercapto group.

5. The gas sensing material according to any one of claims 1 to 4, characterized in that, the organic ligand comprises 1,5-diamino-4,8-dihydroxyanthraquinone.

6. The gas sensing material according to any one of claims 1 to 5, characterized in that, the response gases of the gas sensing material comprise one or more of carbon monoxide, ammonia, hydrogen sulfide, and nitrogen dioxide.

7. A method for preparing a gas sensing material, characterized in that, it comprises: providing a metal ion solution and an organic ligand solution; causing the metal ion solution and the organic ligand solution to undergo a binding reaction to obtain a metal-organic framework material, the metal-organic framework material comprising one-dimensional nanomaterials, the one-dimensional nanomaterials having dimensions in at least two dimensions in the nanoscale range, the nanoscale range being 0.1 nm - 100 nm.

8. The method for preparing a gas sensing material according to claim 7, characterized in that, the causing the metal ion solution and the organic ligand solution to undergo a binding reaction comprises: uniformly mixing the metal ion solution and the organic ligand solution, and then allowing the mixture to stand and react to obtain the metal-organic framework material.

9. The method for preparing a gas sensing material according to claim 8, characterized in that, the time for the standing reaction is 8 - 15 h; and / or the temperature for the standing reaction is 70 - 95 °C.

10. The method for preparing a gas sensing material according to claim 8 or 9, characterized in that, the uniformly mixing the metal ion solution and the organic ligand solution comprises: dropping the metal ion solution into the organic ligand solution for mixing; optionally, the dropping rate of the metal ion solution is 1 - 20 drops / second.

11. The method for preparing a gas sensing material according to any one of claims 8 to 10, characterized in that, it further comprises: adding an alkali to the mixture of the metal ion solution and the organic ligand solution; optionally, adding ammonia water to the mixture of the metal ion solution and the organic ligand solution.

12. The method for preparing a gas sensing material according to claim 7, characterized in that, the causing the metal ion solution and the organic ligand solution to undergo a binding reaction comprises: Place the metal ion solution and the organic ligand solution in the same container. The metal ion solution and the organic ligand solution are immiscible with each other, and the metal-organic framework material is prepared by using an interfacial reaction.

13. The method for preparing a gas sensing material according to any one of claims 7 to 12, characterized in that 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 the divalent copper ion is 1:(2 - 8); optionally 1:(4 - 6).

14. The method for preparing a gas sensing material according to any one of claims 7 to 13, characterized in that the solvent of the organic ligand solution includes one or more of methanol, ethanol, acetone, tetrahydrofuran, N,N-dimethylformamide, dimethyl sulfoxide, and dichloromethane.

15. The method for preparing a gas sensing material according to any one of claims 7 to 14, characterized in that 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.

16. A gas sensor, characterized in that it includes the gas sensing material according to any one of claims 1 to 6; or includes the gas sensing material prepared by using the method according to any one of claims 7 to 15.

17. A battery, characterized in that it includes the gas sensor according to claim 16.

18. An electrical device, characterized in that it includes the battery according to claim 17.

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