WO2025112779A1 - 电池、气体传感材料及其制备方法、传感器、用电设备 - Google Patents

电池、气体传感材料及其制备方法、传感器、用电设备 Download PDF

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WO2025112779A1
WO2025112779A1 PCT/CN2024/117564 CN2024117564W WO2025112779A1 WO 2025112779 A1 WO2025112779 A1 WO 2025112779A1 CN 2024117564 W CN2024117564 W CN 2024117564W WO 2025112779 A1 WO2025112779 A1 WO 2025112779A1
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gas
metal
solution
gas sensing
organic framework
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French (fr)
Inventor
吴凯
张继君
杨志
王少飞
刘学
胡南滔
曾敏
杨建华
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Contemporary Amperex Technology Co Ltd
Shanghai Jiao Tong University
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Contemporary Amperex Technology Co Ltd
Shanghai Jiao Tong University
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
    • G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
    • G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
    • G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
    • G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte

Definitions

  • 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.
  • the main technical problem solved by the present 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.
  • a technical solution adopted by the present application is: to provide a battery, the battery 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 size of the one-dimensional nanomaterial in at least two dimensions is nanoscale, and the nanoscale is 0.1nm-100nm.
  • 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, so that it can achieve gas response under non-oxygen conditions, thereby enabling the detection of gas production in the battery.
  • 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 gas on the one-dimensional nanostructure is significantly faster, resulting in a shorter response time.
  • the metal organic framework material includes a nanobelt material, the thickness of the nanobelt material is 1-10nm; the width of the nanobelt is 10-100nm.
  • the metal organic framework material includes a nanobelt material, the thickness of the nanobelt material is 3-8nm; the width of the nanobelt is 15-70nm.
  • the metal organic framework material includes a complex of metal ions and organic ligands
  • the metal element includes one or more of copper, nickel, cobalt, zinc, and iron. This configuration is conducive to improving the stability of the metal organic framework material, and the metal ions can serve as gas adsorption sites to improve the sensitivity and selectivity of the adsorbed gas.
  • the organic ligand comprises a structure represented by formula (1):
  • R 1 and R 2 are hydroxyl, amino or thiol, which is conducive to forming coordination bonds with metal ions and making the metal organic framework material grow in a ribbon shape.
  • 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, which can form a stable coordination bond with metal ions through the substituents, thereby constructing a metal organic framework material.
  • the coordination bond formed by the metal ion and the organic ligand can establish an effective charge transfer path, which is conducive to the generation of a small band gap and high charge mobility; in addition, a ⁇ -d conjugated plane and a ⁇ - ⁇ stacking can be formed, thereby providing a conductive path on the plane and improving the conductivity of the metal organic framework material.
  • the gas sensing material responds to one or more of carbon monoxide, ammonia, hydrogen sulfide, and nitrogen dioxide. While responding to multiple gases, the gas sensing material also has a certain selectivity.
  • the gas sensing material includes a metal organic framework material
  • the metal organic framework material includes a one-dimensional nanomaterial
  • the size of the one-dimensional nanomaterial in at least two dimensions is nanoscale
  • the nanoscale is 0.1nm-100nm.
  • another technical solution adopted by the present application is: to provide a method for preparing a gas sensing material, the method for preparing a gas sensing material comprising: providing a metal ion solution and an organic ligand solution; allowing the metal ion solution to react with the organic ligand solution to obtain a metal organic framework material, the metal organic framework material comprising a one-dimensional nanomaterial, the one-dimensional nanomaterial having a nanoscale size in at least two dimensions, the nanoscale being 0.1nm-100nm.
  • the metal ion solution and the organic ligand solution are combined and reacted, comprising: uniformly mixing the metal ion solution and the organic ligand solution, and then standing to react to obtain a metal organic framework material.
  • the microstructure of the obtained metal organic framework material can be regulated to obtain a one-dimensional nanostructure.
  • the static reaction time is 8-15 hours; and/or the static reaction temperature is 70-95° C.
  • uniformly mixing the metal ion solution with the organic ligand solution comprises: dropping the metal ion solution into the organic ligand solution and mixing; the metal ion solution is added at a rate of 1-20 seconds per drop. This arrangement enables the metal ions to be more uniformly dispersed in the organic ligand solution.
  • a base is added to the mixture of the metal ion solution and the organic ligand solution, and the base includes aqueous ammonia. This configuration is beneficial to the deprotonation of the metal ions and the dissociation of the organic ligands, and the growth rate of the metal organic framework material can be controlled.
  • the metal ion solution and the organic ligand solution are combined and reacted, including: 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 utilizing the interface reaction to obtain the metal organic framework material.
  • the morphology and structure of the metal organic framework material can be controlled, thereby achieving the regulation of the sensitivity of the sensing material.
  • the organic ligand solution includes a 1,5-diamino-4,8-dihydroxyanthraquinone solution
  • 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).
  • the organic ligand solution includes a 1,5-diamino-4,8-dihydroxyanthraquinone solution
  • 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:(4-6).
  • the solvent of the organic ligand solution includes one or more of methanol, ethanol, acetone, tetrahydrofuran, N,N-dimethylformamide, dimethyl sulfoxide, and dichloromethane.
  • different methods can be selected to prepare metal organic framework materials, and the crystallinity, pore structure, pore environment, morphology, etc. of the metal organic framework materials can also be regulated, and the selectivity, response value, sensitivity, etc. to gas can be further regulated.
  • the metal ion solution includes a divalent copper salt solution
  • the divalent copper salt includes at least one of copper acetate monohydrate, copper sulfate pentahydrate, and copper chloride dihydrate.
  • another technical solution adopted by the present application is to provide a gas sensor, the sensor comprising the above gas sensing material; or comprising a gas sensing material prepared by any of the above methods.
  • an electric device comprising the above battery.
  • the electric device has at least the same advantages as the battery.
  • FIG1 is a transmission electron microscope (TEM) image of a metal organic framework material of one or more embodiments
  • FIG2 is a schematic diagram of a method for preparing a gas sensing material according to one or more embodiments
  • FIG3 is a schematic diagram of a method for preparing a gas sensing material according to one or more embodiments
  • FIG4 is a schematic diagram of an exploded structure of a battery according to one or more embodiments.
  • FIG5 is a schematic diagram of an exploded structure of a battery cell according to one or more embodiments.
  • FIG. 6 is a schematic diagram of the structure of an electric device according to one or more embodiments.
  • FIG7 is a schematic diagram of a gas sensing performance test according to one or more embodiments.
  • FIG8 is an X-ray diffraction pattern (XRD) of a gas sensing material DDA-Cu according to one or more embodiments;
  • FIG9 is an X-ray energy dispersive spectrometry (EDS) image of a gas sensing material DDA-Cu according to one or more embodiments;
  • FIG10 is a scanning electron microscope (SEM) image of the gas sensing material DDA-Cu-1 obtained in Example 1;
  • FIG11 is a scanning electron microscope (SEM) image of the gas sensing material DDA-Cu-2 obtained in Example 2;
  • FIG12 is a scanning electron microscope (SEM) image of the gas sensing material DDA-Cu-3 obtained in Example 3;
  • FIG13 is a schematic diagram of gas response of a gas sensing material DDA-Cu according to one or more embodiments
  • FIG14 is a schematic diagram of gas response of a gas sensing material DDA-Co according to one or more embodiments
  • FIG. 15 is a schematic diagram of gas response of a gas sensing material DDA-Ni according to one or more embodiments
  • FIG16 is a schematic diagram of gas response of a gas sensing material DDA-Cu according to one or more embodiments
  • FIG. 17 is a schematic diagram of gas response of a gas sensing material DDA-Cu according to one or more embodiments.
  • FIG. 18 is a schematic diagram of gas response of a gas sensing material DDA-Cu according to one or more embodiments
  • the technical terms “first”, “second”, etc. are only used to distinguish different objects, and cannot be understood as indicating or implying relative importance or implicitly indicating the number, specific order or primary and secondary relationship of the indicated technical features.
  • the term “multiple” refers to more than two (including two), and similarly, “multiple groups” refers to more than two (including two groups), and “multiple pieces” refers to more than two (including two pieces), unless otherwise clearly and specifically defined.
  • the term "and/or" is only a description of the association relationship of the associated objects, indicating that there may be three relationships.
  • a and/or B can represent: A exists alone, A and B exist at the same time, and B exists alone.
  • the character "/" in this article generally indicates that the associated objects before and after are in an "or" relationship.
  • 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 be steps (a) and (b) performed simultaneously in parallel.
  • the method may also 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.
  • the battery converts external electrical energy into chemical energy for storage, and some side reactions also produce gas.
  • the side reaction of water decomposition occurs, resulting in the production of oxygen and hydrogen gases.
  • the chemical energy in the battery is converted into electrical energy, and some gas-producing reactions also occur.
  • the oxidation reaction of lithium metal may occur, producing some harmful gases such as carbon fluoride compounds.
  • the battery may generate gas during use due to overcharge, overdischarge, internal fault or improper operation.
  • the chemical reaction in the battery may be uncontrolled, violently releasing gas and even causing thermal runaway of the battery.
  • Battery thermal runaway is an important part of battery safety research. Battery thermal runaway is a chain reaction phenomenon caused by various factors. The battery pack of new energy vehicles is usually sealed and is an oxygen-free environment in normal operation. If the battery pack has thermal runaway, some characteristic gases will be released.
  • the characteristic gases of battery thermal runaway include carbon dioxide, carbon monoxide, hydrogen, ethylene, methane, ethane and propylene. Detecting the characteristic gases of battery thermal runaway can give early warnings and take corresponding measures in time when thermal runaway occurs, reducing the damage to life and property safety.
  • chemical resistance sensors have reliable application prospects. They rely on the change of conductivity when the sensing material interacts with the characteristic gas to achieve the detection purpose.
  • the existing metal oxide sensors require oxygen, which limits their application in detecting the gas generated by battery thermal runaway under oxygen-free conditions.
  • the battery cell is an oxygen-free environment. Therefore, it is urgent to develop new materials and sensors that can work stably under non-oxygen conditions and accurately detect the gas generated by battery thermal runaway.
  • metal organic framework materials have adjustable surface properties and chemical reactivity, and can be used as gas sensing materials.
  • metal organic framework materials 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 that they have unique characteristics such as large specific surface area, high porosity and chemical adjustability.
  • the large specific surface area and adjustable porous structure of MOFs materials can provide a large number of sites for gas adsorption.
  • MOFs materials After the gas molecules are adsorbed, the formation or breakage of coordination bonds will occur, causing electron transfer, thereby changing the electrical properties of MOFs materials and achieving response to adsorbed gases. 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.
  • a battery in the present application, 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.
  • metal-organic framework materials 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.
  • the metal organic framework material can be a material with a nanostructure.
  • Nanostructure is the structure of an object with a size between the molecular and micrometer scales; the linear dimensions of these substances are generally in the range of 0.1-100nm.
  • Nanostructures include one-dimensional, two-dimensional, and three-dimensional systems, and these material units include nanoparticles, nanotubes, nanorods, nanowires, nanobelts, and nano-sized holes.
  • metal organic framework materials By making metal organic framework materials (MOFs) into nanostructured materials, they can have a large specific surface area, provide a large number of sites for gas adsorption, and improve the sensitivity of gas sensing materials. Further research has found that most 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 the gas quickly after adsorbing it, that is, they have irreversible response, which makes the gas sensor unable to be reused; some two-dimensional nano MOFs materials have poor conductivity, resulting in insufficient sensitivity.
  • a metal organic framework material with a one-dimensional nanostructure, that is, a one-dimensional nano MOFs material.
  • a one-dimensional nano material refers to a material whose size in two dimensions is nanoscale and whose size in the third dimension exceeds the nanoscale, and the nanoscale is defined as 0.1nm-100nm.
  • 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; it can also be 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, so that the response time is shorter.
  • the metal organic framework material includes a nanobelt material, that is, a nanobelt MOFs material.
  • the thickness of the nanobelt material is 1-10nm and the width is 10-100nm.
  • Figure 1 is a transmission electron microscope (TEM) image of a metal organic framework material according to one or more embodiments
  • Figure 7 is a scanning 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 MOFs material is 1-10nm, the width is 10-100nm, and the length is relatively large, exceeding tens of nanometers, and can reach the micron level.
  • the thickness can be 1nm, 2nm, 3nm, 5nm, 6nm, 8nm, 10nm; the width can be 10nm, 15nm, 20nm, 30nm, 40nm, 60nm, 80nm, 100nm, etc.
  • the metal organic framework material includes a nanobelt material, the thickness of the nanobelt material is 3-8 nm, and the width of the nanobelt is 15-70 nm.
  • the thickness can be 3 nm, 5 nm, 6 nm, 8 nm, etc.
  • the width can be 15 nm, 20 nm, 30 nm, 40 nm, 60 nm, 70 nm, etc.
  • the nanoribbon MOFs material in this application has a higher structure than two-dimensional and three-dimensional metal organic framework materials.
  • the degree of freedom provides more opportunities for creating conductive paths, which significantly improves the conductivity of the material; the structure is stable and ordered, with a higher surface area to volume ratio, which provides a wider site for the adsorption of gas molecules and can accelerate the diffusion rate of gas on the sensing material, making the resistance change significantly with the change of gas adsorption, thereby effectively improving the sensitivity and speed of gas response.
  • the metal organic framework material includes a complex of a metal and an organic ligand in terms of chemical composition
  • the metal element includes one or more of copper, nickel, cobalt, zinc, and iron.
  • it can be a complex of a metal ion and an organic ligand, and the metal ion includes one or more of copper ions, nickel ions, cobalt ions, zinc ions, and iron ions.
  • Metal ions and organic ligands form complexes through coordination bonds.
  • Metal ions can act as coordination centers to coordinate with multiple atoms on organic ligands to form a more stable form, thereby improving the stability of metal organic framework materials.
  • metal ions can act as gas adsorption sites. Adsorbed gas molecules will cause the formation or breakage of coordination bonds, causing electron transfer, thereby changing the electrical and optical properties of MOFs and achieving sensitivity and selectivity to adsorbed gases.
  • gas molecules can be connected to metal ions through coordination bonds, and electron transfer occurs, thereby achieving response to gas.
  • metal organic framework material there may be only one type of metal ion in the metal organic framework material (MOFs); or there may be multiple different types of metal ions at the same time to form different coordination centers. There may be multiple metal ions to form multiple coordination centers. Different types of metal ions can give the metal organic framework material a selectivity in response to different gases, and the gas selectivity of the metal organic framework material can be provided by regulating the type and amount of metal ions.
  • 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.
  • DDA 1,5-diamino-4,8-dihydroxy anthraquinone
  • This is a ligand with an aromatic core and a centrosymmetric molecule.
  • DDA is an anthraquinone compound containing amino and hydroxyl substituents, with a molecular formula of C 14 H 10 N 2 O 4 and a molecular weight of 270.24. It contains an anthraquinone mother nucleus, with positions 1 and 5 substituted by amino groups, and positions 4 and 8 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 be used as coordinating atoms to form stable coordination bonds with a variety of metal ions to obtain metal organic framework materials with different structural properties, which have strong design flexibility. Furthermore, the aromatic anthraquinone ring can form ⁇ - ⁇ stacking interactions to enhance the stability of MOFs. Finally, since 1,5-diamino-4,8-dihydroxyanthraquinone is a planar configuration, it is easy to expand into a one-dimensional nanobelt form through self-assembly.
  • the coordination bonds formed by metal ions and organic ligands in the metal organic framework materials (MOFs) coordinated with the ligands can establish effective charge transfer pathways, especially active transition metal ions, which have suitable atomic radii to obtain better orbital overlap with ligands, which is conducive to the generation of small band gaps and high charge mobility; in addition, organic ligands with aromatic rings can also form ⁇ -d conjugated planes and ⁇ - ⁇ stacking, thereby providing conductive paths on the plane, which is conducive to the improvement of the conductivity of metal organic framework materials. Thereby, the response value and sensitivity of gas sensing can be improved.
  • 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 core, such as anthracene, phenanthrene and other macrocyclic compounds.
  • 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 core, such as anthracene, phenanthrene and other macrocyclic compounds.
  • the organic ligand comprises the following structure:
  • R 1 and R 2 are hydroxyl (OH), amino (NH 2 ) or thiol (SH).
  • the substituent on the anthraquinone ring can also be a thiol group.
  • the parent core can also be expanded to a larger conjugated structure.
  • 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), and the structural formula of DDA-Cu is
  • the copper ions in DDA-Cu are coordinated to the center of three oxygen atoms and one nitrogen atom in the DDA ligand, making the copper ions in a stable form.
  • the copper ion d orbitals between layers are stacked to form an axial conductive path, which improves the conductivity of the metal organic framework material.
  • the use of metal ions to connect the basic structural units can further increase the axial conductivity of the MOFs material.
  • the conductivity in the plane direction is improved, thereby further increasing the electrical properties of the material. This can improve the response value and sensitivity of gas sensing.
  • DDA-Cu grows linearly along the coordination nodes to form a one-dimensional nanoribbon structure, which is stacked to form bulk materials through non-bonded interactions.
  • Nanomaterials based on one-dimensional building blocks can provide more adsorption sites due to their high structural regularity, chemical modular edges and adjustable structure-activity relationships.
  • 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 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.
  • the response gas of the gas sensing material includes one or more of carbon monoxide, ammonia, hydrogen sulfide, and nitrogen dioxide.
  • the gas sensing material provided in the present application can respond to a variety of gases and has a certain selectivity. Please refer to the experimental example description below for details.
  • a gas sensing material is further provided, the gas sensing material includes a metal organic framework material, the metal organic framework material includes a one-dimensional nanomaterial, the one-dimensional nanomaterial has a size of nanometer scale in at least two dimensions, and the nanometer scale is 0.1nm-100nm.
  • 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 thus can achieve gas response under non-oxygen conditions.
  • a method for preparing a gas sensing material specifically comprises: providing a metal ion solution and an organic ligand solution; 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.
  • 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 transition metal oxides such as CuO and ZnO; metal organic framework: some metal organic framework materials can also be used as metal sources to release metal ions for further construction of the metal organic framework structure; other materials: metal foil, salts, inorganic acids, etc.
  • transition metal salt such as (Cu(NO 3 ) 2 ), zinc nitrate (Zn(NO 3 ) 2 ), cobalt nitrate (Co(NO 3 ) 2 ) and other
  • 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 then the gas sensing performance can be regulated.
  • the solvent used for the metal ion solution can be deionized water, that is, the metal salt is dissolved in deionized water to obtain the metal ion solution. In other embodiments, alcohol solvents may also be used to prepare the metal ion solution.
  • the organic ligand solution is prepared by dissolving the organic ligand in a solvent.
  • the solvent of 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 solubility for metal ions and products (MOFs materials) in the reaction system. By selecting different solvents, different methods can be selected to prepare MOFs materials. At the same time, the crystallinity, pore structure, pore environment, morphology, etc. of the MOFs material can also be regulated to regulate its performance as a gas sensor, such as regulating the selectivity to gas, regulating the response value, sensitivity, etc.
  • a metal ion solution and an organic ligand solution may be combined and reacted based on a solvothermal method to obtain a metal organic framework material.
  • the metal ion solution and the organic ligand solution are uniformly mixed and then allowed to react to obtain a metal organic framework material.
  • the "standing reaction” means that the reaction solution system is not subjected to stirring, dispersion or other treatments during the reaction. That is, the solutions are first mixed, and stirring, dispersion or other operations may be performed during the mixing, but no other mixing operations such as stirring are performed during the reaction after the mixing.
  • the metal ion solution can be added dropwise to the organic ligand solution to mix the metal ion solution with the organic ligand solution.
  • the metal ion solution is added at a rate of 1-20 seconds/drop, such as 1 second/drop, 5 seconds/drop, 10 seconds/drop, 15 seconds/drop, 20 seconds/drop, etc.
  • the metal ions can be more evenly dispersed in the organic ligand solution.
  • the mixed solution can also be ultrasonically treated to make it evenly mixed.
  • the metal ion solution and the organic ligand solution are uniformly mixed, they are allowed to react for 8-15 hours; and the temperature of the reaction is 70-95°C.
  • the screw mouth of the reaction container is not completely tightened, so that oxygen can enter the reaction container 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, so 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.
  • 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., which is adjusted according to the progress of the reaction. As time goes on, the reaction will become more and more complete. Taking the time cost into consideration, in one embodiment, the reaction time can be 12 hours.
  • 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 ammonia water.
  • the pH value of the reaction system needs to be adjusted to a range suitable for crystal growth.
  • the pH value can be adjusted by acid or base, which is called pH regulator, including: concentrated ammonia water, sodium hydroxide, triethylamine, ethylenediamine, tetrabutylammonium hydroxide, hydrochloric acid, oxalic acid, phosphoric acid, etc.
  • the base includes ammonia water.
  • the role of ammonia water includes: providing an alkaline environment, which is conducive to the deprotonation of metal ions and the dissociation of organic ligands; adjusting the pH value to control the growth rate of metal organic framework materials; improving solubility, so that the metal salt and the organic ligand are completely dissolved in the synthesis solvent; accelerating the reaction and accelerating the coordination and cross-linking rate between the metal salt and the organic ligand.
  • the solution is naturally cooled to room temperature.
  • the natural cooling rate is not high, which is conducive to the growth of crystals and can form relatively regular crystals.
  • a precipitate is generated in the reaction system.
  • the obtained precipitate is washed by alternating centrifugation 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 hours.
  • the washing process can remove impurities on the surface of the metal organic framework material, including unreacted reactants and some impurity ions, which will not affect the subsequent performance test.
  • 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.
  • 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, so that the reaction system produces a two-phase interface.
  • the organic ligands and metal ions contact and react at the two-phase interface, so that metal organic framework crystals 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.
  • the metal ion solution is an aqueous solution of a metal salt
  • the organic ligand solution is a dichloromethane solution of an 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, and the organic ligand and the metal ion are assembled into a metal organic framework crystal with a specific structure by a stepwise growth method.
  • the interface 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.
  • 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:
  • the reaction cannot achieve a high yield, so the reactants need to be in excess to promote the reaction in the forward direction.
  • concentration of relatively low-priced copper ions is increased to promote the reaction in the direction of metal organic framework material generation.
  • the molar ratio of DDA to divalent copper ions is 1:(2-8).
  • it can be 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, etc.
  • 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.
  • the reaction proceeds more and more completely.
  • the morphology and crystallinity of the obtained product can also be adjusted, and then the gas response performance can be adjusted.
  • the metal ion solution includes a divalent copper salt solution
  • the divalent copper salt includes at least one of copper acetate monohydrate, copper sulfate pentahydrate, and copper chloride dihydrate.
  • the solvent of the DDA ligand includes one or more of methanol, ethanol, acetone, tetrahydrofuran, dimethyl sulfoxide, N,N-dimethylformamide, and dichloromethane.
  • the microscopic morphology, pore structure, and pore size of the metal organic framework material can be regulated, and the gas sensing performance of the material can be further regulated.
  • FIG 2 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 may be combined and reacted based on a solvothermal method to obtain a metal organic framework material.
  • the divalent copper ion solution and the DDA ligand solution were mixed, and the mixed solution was placed in a screw-mouth glass bottle, the screw mouth of the glass bottle was slightly loosened, and the mixture was kept at 95°C for 12 hours; after the reaction was completed, it was naturally cooled to room temperature, and the obtained black precipitate was alternately centrifuged and washed with deionized water and ethanol, the centrifugal speed of the centrifugal washing was 8000rpm, and the centrifugal washing time was 10 minutes. Then it was dried in a 60°C oven for 6 hours to obtain the product.
  • Figure 3 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 may be combined and reacted based on an interfacial reaction growth method to obtain a metal organic framework material.
  • 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.
  • a gas sensor which includes any of the above-mentioned gas sensing materials; or includes a gas sensing material prepared by any of the above-mentioned methods.
  • 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 achieve gas response under anaerobic conditions.
  • a gas sensor that can respond quickly to gas under anaerobic conditions and has high detection sensitivity is prepared.
  • the gas sensor provided by the present application can be used to detect gas inside a battery.
  • FIG. 4 is a schematic diagram of the exploded structure of a battery according to one or more embodiments.
  • the battery 100 includes a box body 10 and a battery cell 20, and the battery cell 20 is contained in the box body 10.
  • the box body 10 is used to provide a storage space for the battery cell 20, and the box body 10 can adopt a variety of structures.
  • the box body 10 may include a first part 11 and a second part 12, and the first part 11 and the second part 12 cover each other, and the first part 11 and the second part 12 jointly define a storage space for accommodating the battery cell 20.
  • the second part 12 may be a hollow structure with one end open, and the first part 11 may be a plate-like structure, and the first part 11 covers the open side of the second part 12, so that the first part 11 and the second part 12 jointly define a storage space; the first part 11 and the second part 12 may also be hollow structures with one side open, and the open side of the first part 11 covers the open side of the second part 12.
  • the box body 10 formed by the first part 11 and the second part 12 may be in a variety of shapes, such as a cylinder, a cuboid, etc.
  • the gas sensor may be installed inside the housing 10 .
  • 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 mixed connection.
  • a mixed connection means that the multiple battery cells 20 are both connected in series and in parallel.
  • the multiple battery cells 20 may be directly connected in series, in parallel, or in a mixed connection, and then the whole formed by the multiple battery cells 20 is accommodated in the box 10; of course, the battery 100 may also be a battery module formed by connecting multiple battery cells 20 in series, in parallel, or in a mixed connection, and then the multiple battery modules are connected in series, in parallel, or in a mixed connection to form a whole, and accommodated in the box 10.
  • the battery 100 may also include other structures, for example, the battery 100 may also include a busbar component for realizing electrical connection between the multiple battery cells 20.
  • Each battery cell 20 may be a secondary battery or a primary battery, or 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.
  • FIG5 is a schematic diagram of the exploded structure of a battery cell according to one or more embodiments.
  • a battery cell 20 refers to the smallest unit that constitutes a battery. As shown in FIG5 , a battery cell 20 includes an end cap 21 , a housing 22 , an electrode assembly 23 and other functional components.
  • 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.
  • the shape of the end cap 21 can be adapted to the shape of the shell 22 to match the shell 22.
  • the end cap 21 can be made of a material with a certain hardness and strength (such as aluminum alloy), so that the end cap 21 is not easily deformed when squeezed and collided, so that the battery cell 20 can have a 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 terminal 21a can be used to electrically connect to the electrode assembly 23 for outputting or inputting electrical energy of the battery cell 20.
  • the end cap 21 can also be provided with a pressure relief mechanism for releasing the 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 a variety of materials, including but not limited to copper, iron, aluminum, stainless steel, aluminum alloy, plastic, etc.
  • an insulating member may be provided inside the end cap 21, and the insulating member may be used to isolate the electrical connection components in the housing 22 from the end cap 21 to reduce the risk of short circuit.
  • the insulating member may be plastic, rubber, or the like.
  • the shell 22 is a component used to cooperate 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, the electrolyte and other components.
  • the shell 22 and the end cap 21 can be independent components, and an opening can be set on the shell 22, and the internal environment of the battery cell 20 is formed by covering the opening with the end cap 21 at the opening.
  • the end cap 21 and the shell 22 can also be integrated. Specifically, the end cap 21 and the shell 22 can form a common connection surface before other components are put into the shell, and when the interior of the shell 22 needs to be encapsulated, the end cap 21 covers the shell 22.
  • the shell 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 shell 22 can be determined according to the specific shape and size of the electrode assembly 23.
  • the material of the shell 22 can be various, including but not limited to copper, iron, aluminum, stainless steel, aluminum alloy, plastic, etc.
  • the electrode assembly 23 is a component in the battery cell 100 where electrochemical reactions occur.
  • One or more electrode assemblies 23 may be included 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 tab and the negative tab may be located together at one end of the main body or respectively at both ends of the main body.
  • the positive active material and the negative active material react with the electrolyte, and the tab 23a connects the electrode terminals to form a current loop.
  • the positive electrode sheet includes a current collector and a positive active layer disposed on the current collector.
  • the positive electrode active layer includes a positive electrode active material
  • the positive electrode active material may include at least one of the following materials: an olivine-structured lithium-containing phosphate, a lithium transition metal oxide, and their respective modified compounds.
  • 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.
  • lithium transition metal oxides 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 1/3 Mn 1/3 O 2 (also referred to as NCM 333 ), LiNi 0.5 Co 0.2 Mn 0.3 O 2 (also referred to as NCM 523 ), LiNi 0.5 Co 0.25 Mn 0.25 O 2 (also referred to as NCM 211 ), LiNi 0.6 Co 0.2 Mn 0.2 O 2 (also referred to as NCM 622 ), LiNi 0.8 Co 0.1 Mn 0.1 O 2 (also referred to as NCM 811 ), and LiNi 0.8 Co 0.2 Mn 0.2 O 2 (also referred to as NCM 811 ), lithium
  • lithium-containing phosphates with an olivine structure may include, but are not limited to, at least one of lithium iron phosphate (such as LiFePO 4 (also referred to as LFP)), a composite material of lithium iron phosphate and carbon, lithium manganese phosphate (such as LiMnPO 4 ), a composite material of lithium manganese phosphate and carbon, lithium iron manganese phosphate, and a composite material of lithium iron manganese phosphate and carbon.
  • lithium iron phosphate such as LiFePO 4 (also referred to as LFP)
  • LiMnPO 4 lithium manganese phosphate
  • LiMnPO 4 lithium manganese phosphate
  • LiMnPO 4 lithium manganese phosphate and carbon
  • 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.
  • the conductive agent includes one or more of conductive carbon black, conductive graphite, carbon fiber, carbon nanotubes, graphene, Ketjen black and acetylene black.
  • 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.
  • 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).
  • the binder includes one or more of polyvinylidene fluoride, polytetrafluoroethylene, acrylate, and polyurethane.
  • the positive electrode active layer further includes other optional additives, which may be thickeners and dispersants (such as sodium carboxymethyl cellulose CMC-Na) and PTC thermistor materials.
  • thickeners and dispersants such as sodium carboxymethyl cellulose CMC-Na
  • PTC thermistor materials such as sodium carboxymethyl cellulose CMC-Na
  • the negative electrode sheet includes a current collector and a negative active layer disposed on the current collector.
  • the negative electrode active layer includes negative electrode active materials, which include but are 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 include but are not limited to graphite materials, silicon-carbon materials, graphite-silicon oxide materials, nano-silicon materials, silicon oxide materials and tin-based materials; more specifically include one or more of 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 - Li4Ti5O12 , and Li-Al alloys.
  • negative electrode active materials include but are 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
  • the negative electrode active layer may further include a binder, a conductive agent and other optional additives.
  • 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.
  • 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).
  • SBR styrene-butadiene rubber
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • EVA ethylene-vinyl acetate copolymer
  • PAA polyacrylic acid
  • CMC carboxymethyl cellulose
  • PVA polyvinyl alcohol
  • PVB polyvinyl butyral
  • other optional additives may be thickeners and dispersants (e.g., sodium carboxymethyl cellulose CMC-Na), PTC thermistor materials.
  • the material of the isolation membrane can be selected from at least one of glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride.
  • the isolation membrane can be a single-layer film or a multi-layer composite film, without particular limitation.
  • the materials of each layer can be the same or different, without particular limitation.
  • the electrolyte includes one or more of carbonate solvents and ether solvents.
  • the carbonate is usually a small molecule cyclic or chain carbonate; 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, ethyl methyl carbonate, and fluorocarbonate; it can also be at least one ester solvent selected from ⁇ -butyrolactone, dimethyl sulfite, ethyl acetate, methyl acetate, methyl butyrate, ethyl butyrate, methyl propionate, ethyl propionate, propyl acetate, and fluorocarboxylic acid esters.
  • 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.
  • 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
  • the electrolyte may also include any one or a mixture of several of an amine solvent, a sulfone solvent, and a nitrile solvent.
  • Amine solvents include at least one of N-methylacetamide, N-methylformamide, dimethylformamide, and diethylformamide.
  • Sulfone solvents include at least one of dimethyl sulfoxide, cyclopentane sulfone, diphenyl sulfoxide, thionyl chloride, and dipropyl sulfone.
  • Nitrile solvents include at least one of acetonitrile, succinonitrile, adiponitrile, and glutaronitrile.
  • the electrolyte is preferably a high-voltage resistant electrolyte, which has a weakened acidity under high voltage, can facilitate the transmission of active ions, significantly reduce side reactions on the electrode surface, and improve battery stability.
  • the electrolyte further comprises an electrolyte salt, which may be selected from lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, At least one of lithium hexafluoroarsenate, lithium bis(fluorosulfonyl imide), lithium bis(trifluoromethanesulfonyl imide), lithium trifluoromethanesulfonate, lithium difluorophosphate, lithium difluorooxalatoborate, lithium dioxalatoborate, lithium difluorobis(oxalatophosphate) and lithium tetrafluorooxalatophosphate.
  • an electrolyte salt which may be selected from lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, At least one of lithium hexafluoroarsenate, lithium bis(fluorosulfonyl imide), lithium bis(trifluoromethanesulfony
  • the electrolyte further includes additives.
  • the additives may include negative electrode film-forming additives, positive electrode film-forming additives, and may also include additives that can improve certain battery properties, such as additives that improve battery overcharge performance, additives that improve battery high or low temperature performance, etc.
  • the battery disclosed in the embodiment of the present application can be used for 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.
  • 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 CDs, 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.
  • Electrical equipment can choose battery cells, battery modules or battery packs according to its usage requirements.
  • the vehicle 1000 may be a fuel vehicle, a gas vehicle or a new energy vehicle, and the new energy vehicle may 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 may be provided at the bottom, head or tail of the vehicle 1000.
  • the battery 100 may be used to power the vehicle 1000, for example, the battery 100 may be used as an operating power source for the vehicle 1000.
  • the vehicle 1000 may also include a controller 200 and a motor 300, and 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.
  • the battery 100 can not only serve as an operating power source for the vehicle 1000, but also serve 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.
  • DDA ligand Dissolve 13.61 mg of DDA ligand in 0.5 mL of N,N-dimethylformamide (DMF), and use an ultrasonic machine to sonicate for 5 minutes to dissolve the organic ligand to obtain a DDA ligand solution; dissolve 40.00 mg of cupric acetate monohydrate in 1.5 mL of deionized water, and stir thoroughly to dissolve it to obtain a divalent copper ion solution.
  • DMF N,N-dimethylformamide
  • the mixed solution was cooled to room temperature naturally, and the obtained black precipitate was washed by centrifugation with deionized water and ethanol alternately at a centrifugal speed of 8000 rpm for 10 min. It was then dried in an oven at 60°C for 6 h to obtain the nanobelt MOFs material DDA-Cu-1.
  • the preparation of the metal ion solution was changed on the basis of Example 1, except that the metal copper salt was replaced by copper sulfate pentahydrate and copper chloride dihydrate, respectively, to prepare nanobelt MOFs materials DDA-Cu-2 and DDA-Cu-3.
  • the specific reaction conditions are shown in Table 1, which lists the reactants, feed ratio, reaction system solvent, and reaction system temperature of each example.
  • Example 1 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 obtain nanobelt MOFs materials DDA-Cu-4 to DDA-Cu-9.
  • the specific reaction conditions are shown in Table 1.
  • Example 1 On the basis of Example 1, the solvent of the reaction system was changed. The difference was that the solvent was replaced with methanol, ethanol, acetone, tetrahydrofuran and dimethyl sulfoxide, respectively, to obtain nanobelt MOFs materials DDA-Cu-10 to DDA-Cu-14.
  • the specific reaction conditions are shown in Table 1.
  • the temperature of the reaction system was changed on the basis of Example 1, except 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 shown in Table 1.
  • Example 1 On the basis of Example 1, the type of metal salt is changed, the difference is that the copper acetate monohydrate is 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.
  • the surface of the sample is scanned by 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.
  • the gas sensing material was dispersed in ethanol at a concentration of 10 mg/L and ultrasonicated at 40 KHz for 10 min to make the composite material uniformly dispersed in ethanol.
  • the gold electrode was prepared by micromachining technology, and the spacing between the positive and negative electrodes was controlled to be 800 ⁇ m, and the spacing between adjacent electrodes was 300 ⁇ m. 5 ⁇ L of the above dispersion was added dropwise to the interdigital electrode and dried in vacuum at 60 ° C for 1 h to obtain a gas sensor.
  • FIG. 7 is a schematic diagram of a gas sensing performance test according to one or more embodiments.
  • the gas sensor is placed in a test chamber, and the target gas is introduced by static gas distribution at room temperature.
  • a constant working 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 an Agilent 4156C semiconductor parameter analyzer.
  • the chamber is purified with dry compressed nitrogen (MFC3) 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).
  • MFC3 dry compressed nitrogen
  • MFC2 compressed nitrogen
  • the difference in resistance of the sensor in dry nitrogen and in the target gas and the resistance ratio in dry nitrogen (
  • DDA An + is the molar ratio of DDA ligand to metal ion (A n+ ); the response value is the response value of the metal organic framework material to 50 ppm CO; the recovery time is the recovery time of the metal organic framework material to 50 ppm CO.
  • DDA-Cu-1 has a nanostructure. Ribbon-shaped, the thickness of different nanoribbons are 2.5nm, 3.0nm, 6.2nm, 8.2nm, etc., and the width is 19.0nm, 32.4nm, 66.7nm, 95.8nm, etc.
  • Figure 8 is an X-ray diffraction pattern of the gas sensing material DDA-Cu according to one or more embodiments.
  • the XRD diffraction peak position of DDA-Cu-1 is basically consistent with the XRD diffraction peak position simulated by the single crystal data obtained by Materials Studio software. It can be observed that the diffraction peaks corresponding to the (001), (100), and (010) crystal planes are relatively sharp, indicating that the crystal structure of the experimental sample is relatively orderly, the atomic arrangement inside the crystal is relatively regular, there are no excessive crystal defects or impurities, and the purity is high.
  • FIG 9 is an X-ray energy spectrum analysis (EDS) image of the gas sensing material DDA-Cu of one or more embodiments.
  • EDS X-ray energy spectrum analysis
  • Figure 10 is a scanning electron microscope (SEM) image of the gas sensing material DDA-Cu-1 obtained in Example 1
  • Figure 11 is a scanning electron microscope (SEM) image of the gas sensing material DDA-Cu-2 obtained in Example 2
  • Figure 12 is a scanning electron microscope (SEM) image of the gas sensing material DDA-Cu-3 obtained in Example 3.
  • the gas sensing materials prepared from different metal salts are also different in microscopic morphology.
  • DDA-Cu-1 and DDA-Cu-3 are in the form of nanobelts and nanosheets
  • DDA-Cu-2 is in the form of needle-shaped crystals, but all three are nanostructures.
  • the microscopic morphology of metal organic framework materials can be regulated.
  • the response data of DDA-Cu-1, DDA-Cu-2, and DDA-Cu-3 to gas are somewhat different. 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, the response and recovery performance of metal organic framework materials in gas sensing can be regulated by adjusting the type of anions in the metal salt.
  • the sensing performance of the Cu-DDA gas sensor 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 sensor material for 50ppm carbon monoxide gas is also improved, which is 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.
  • 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, and the polarity of the solvent can affect the interaction and reaction rate between the ligand and the metal ion, and can 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.
  • 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 acceptors 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.
  • the sensing performance of the Cu-DDA gas sensing material for 50ppm carbon monoxide gas is demonstrated when the temperature of the reaction system is 70°C-95°C.
  • the temperature of the reaction system is 70°C-95°C.
  • 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.
  • the yield of the gas sensing material finally generated is higher, so it is better in gas sensing performance.
  • 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.
  • Example 1-21 the sensing performance of the prepared gas sensing material for 50ppm carbon monoxide gas is shown when the metal salt is copper acetate monohydrate, cobalt acetate tetrahydrate and nickel acetate tetrahydrate, respectively.
  • the metal salt is copper acetate monohydrate, cobalt acetate tetrahydrate and nickel acetate tetrahydrate, respectively.
  • the metal ions are cobalt and nickel, the response value to the gas is large but cannot be restored. Therefore, copper ions can be selected as the metal ions when the gas sensing material detects carbon monoxide gas according to application requirements.
  • 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
  • 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 carbon monoxide (CO), ammonia (NH 3 ), and hydrogen sulfide (H 2 S) at a concentration of 50 ppm were tested respectively.
  • DDA-Cu, DDA-Co, and DDA-Ni all have certain response characteristics to carbon monoxide (CO), ammonia (NH 3 ), and hydrogen sulfide (H 2 S), and can be used as gas sensors to detect these gases, but the response values that can be achieved for different gases are different, and the appropriate gas sensing material can be selected according to the actual situation.
  • CO carbon monoxide
  • NH 3 ammonia
  • H 2 S hydrogen sulfide
  • FIG. 16 is a schematic diagram of the gas response of the gas sensing material DDA-Cu according to one or more embodiments. Further, the response of the sensor based on the DDA-Cu-1 gas sensing material prepared in Example 1 to 50ppm of different gases was tested at room temperature, and the results are shown in FIG. 16. 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 is more than 15%, and the response value to hydrogen sulfide is more than 20%. At the same time, the response values to the other five gases are less than 5%, so DDA-Cu-1 exhibits good gas selectivity.
  • 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.
  • the response of the sensor based on the DDA-Cu-1 gas sensing material prepared in Example 1 to carbon monoxide concentrations of 10ppm-80ppm was tested at room temperature.
  • the horizontal axis is the acquisition time
  • the vertical axis 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 aforementioned embodiment to 80ppm carbon monoxide reaches 8.8%.
  • the lowest detectable carbon monoxide concentration reaches 10ppm, and the corresponding response value is 1.1%.
  • the concentration of carbon monoxide increases, the carbon monoxide concentration increases.
  • the sensor's response value to the gas also increases, and the response values to 10, 20, 40, and 80 ppm carbon monoxide are 1.1%, 2.0%, 3.7%, and 8.8%, respectively. It can be seen that the gas sensing material provided by the present application has a more sensitive gas response and a lower detection limit.
  • the cyclic response performance of the sensor based on DDA-Cu-1 gas sensing material prepared in Example 1 to 50ppm carbon monoxide was tested at room temperature.
  • the horizontal axis is the acquisition time and the vertical axis is the response value.
  • the sensor's response time to gas is about 400s, and the recovery time is also about 400s, and the response is more sensitive.
  • the response value of the sensor remains above 3.8%, and the response time remains basically unchanged, indicating that the sensor prepared in the aforementioned embodiment has good cyclic stability.
  • the gas sensing material provided by the present application can be used for gas production detection in batteries, and has good response sensitivity and selectivity to gas. Furthermore, the gas sensing material is a gas sensing test carried out at room temperature, which is milder and has a wider range of applications than existing materials that require high temperature to respond to gas.

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Abstract

本申请公开了一种气体传感材料及其制备方法、传感器、电池和用电设备。其中，气体传感材料是具有一维纳米结构的金属有机框架材料(Metal organic frameworks，MOFs)，其气体响应机理为配位电子的转移。通过上述方式，本申请能够实现无氧环境中对目标气体的检测，可以实现对电池内部产气的检测。进一步地，能够提高气体检测的灵敏度和选择性，缩短气体响应的时间，降低气体的检出限。

Description

电池、气体传感材料及其制备方法、传感器、用电设备
相关申请的交叉引用
本申请要求享有于2023年11月30日提交的名称为“气体传感材料及其制备方法、传感器、电池和用电设备”的中国专利申请202311641758.9的优先权，该申请的全部内容通过引用并入本文中。
技术领域
本申请涉及新能源技术领域，特别是涉及电池、气体传感材料及其制备方法、传感器、用电设备。
背景技术
随着全球能源和环境问题不断加剧，新能源作为可持续发展领域之一，正快速发展。电池作为新的能源方式应用越来越广泛。其中，电池产气问题一直备受关注。电池所产生的气体易引起安全问题。通过检测电池内的气体情况，能够及时预警。现有气体传感原理需要氧气，限制了其在无氧条件下检测气体的应用。但是电池单体内为无氧环境，因此，急需开发能够在非氧条件下进行气体响应的新材料和传感器。上述的陈述仅用于提供与本申请有关的背景技术信息，而不必然地构成现有技术。
发明内容
本申请主要解决的技术问题是提供一种电池、气体传感材料及其制备方法、传感器、用电设备，气体传感材料能够在非氧条件下进行气体响应，能够实现对电池内产气的检测。
为解决上述技术问题，本申请采用的一个技术方案是：提供一种电池，电池包括气体传感器，气体传感器包括气体传感材料，气体传感材料包括金属有机框架材料，金属有机框架材料包括一维纳米材料，一维纳米材料至少在两个维度上的尺寸为纳米尺度，纳米尺度为0.1nm-100nm。金属有机框架材料作为气体敏感材料使用时，其响应机理为配位电子的转移，不依赖氧气，因此能够实现在非氧条件下的气体响应，从而能够实现对电池内产气的检测。
进一步地，一维纳米结构使得金属有机框架材料具备了更高的表面积与体积比，为气体分子提供了大量吸附位点，从而提高了传感灵敏度；同时气体在一维纳米结构上的扩散速率明显更快，使得响应时间更短。
在一实施方式中，金属有机框架材料包括纳米带材料，纳米带材料的厚度为1-10nm；纳米带的宽度为10-100nm。通过这种设置，金属有机框架材料的导电性得到显著提高，同时电阻明显随气体吸附的变化而变化，因此可以有效提高气体响应的灵敏度和速度。
在一实施方式中，金属有机框架材料包括纳米带材料，纳米带材料的厚度为3-8nm；纳米带的宽度为15-70nm。通过这种设置，金属有机框架材料的导电性得到显著提高，同时电阻明显随气体吸附的变化而变化，因此可以有效提高气体响应的灵敏度和速度。
在一实施方式中，金属有机框架材料包括金属离子与有机配体的配合物，金属元素包括铜、镍、钴、锌、铁中的一种或多种。通过这种设置，有利于提高金属有机框架材料的稳定性，同时金属离子可以作为气体的吸附位点，改善对吸附气体的敏感性和选择性。
在一实施方式中，有机配体包括式(1)所示结构：
其中，R1、R2为羟基、氨基或巯基。有利于和金属离子形成配位键，使金属有机框架材料带状生长。
在一实施方式中，有机配体包括1,5-二氨基-4,8-二羟基蒽醌。1,5-二氨基-4,8-二羟基蒽醌是一种含氨基和羟基取代基的蒽醌类化合物，能够通过取代基与金属离子形成稳定的配位键，从而构建金属有机框架材料。通过这种设置，金属离子与有机配体形成的配位键能够建立有效的电荷传输通路，有利于产生小带隙和高电荷迁移率；另外，能够形成π-d共轭平面以及π-π堆叠，从而提供平面上的导电路径，改善金属有机框架材料的导电性。
在一实施方式中，气体传感材料的响应气体包括一氧化碳、氨气、硫化氢、二氧化氮中的一种或多种。在对多种气体有响应的同时，气体传感材料还具备一定的选择性。
为解决上述技术问题，本申请采用的另一个技术方案是：提供一种气体传感材料，气体传感材料包括金属有机框架材料，金属有机框架材料包括一维纳米材料，一维纳米材料至少在两个维度上的尺寸为纳米尺度，纳米尺度为0.1nm-100nm。金属有机框架材料作为气体敏感材料使用时，其响应机理为配位电子的转移，不依赖氧气，因此能够实现在非氧条件下的气体响应。
为解决上述技术问题，本申请采用的另一个技术方案是：提供一种气体传感材料的制备方法，气体传感材料的制备方法包括：提供金属离子溶液和有机配体溶液；使金属离子溶液与有机配体溶液结合反应，得到金属有机框架材料，金属有机框架材料包括一维纳米材料，所述一维纳米材料至少在两个维度上的尺寸为纳米尺度，所述纳米尺度为0.1nm-100nm。一维纳米结构使得金属有机框架材料具备了更高的表面积与体积比，为气体分子提供了大量吸附位点，从而提高了传感灵敏度；同时气体在一维纳米结构上的扩散速率明显更快，使得响应时间更短。
在一实施方式中，使金属离子溶液与有机配体溶液结合反应包括：将金属离子溶液与有机配体溶液均匀混合后，静置反应，得到金属有机框架材料。通过这种设置，能够调控所得金属有机框架材料的微观结构，以得到一维纳米结构。
在一实施方式中，静置反应的时间为8-15h；和/或静置反应的温度为70-95℃。通过调控反应体系的反应时间和温度，能够调控最终生成的金属有机框架材料的产率和微观结构，进而利于调控气体传感性能。
在一实施方式中，将金属离子溶液与有机配体溶液均匀混合包括：将金属离子溶液滴加入有机配体溶液中混合；金属离子溶液的滴加速度为1-20秒/滴。通过这种设置，能够使金属离子更均匀的分散在有机配体溶液中。
在一实施方式中，向金属离子溶液与有机配体溶液的混合液中加入碱，碱包括了氨水。通过这种设置，有利于金属离子的脱质子和有机配体的解离，可以控制金属有机框架材料的生长速率。
在一实施方式中，使金属离子溶液与有机配体溶液结合反应包括：将金属离子溶液与有机配体溶液置于同一容器中，金属离子溶液与有机配体溶液不互溶，利用界面反应，制得金属有机框架材料。通过调节界面上反应物的相互作用，可以实现对金属有机框架材料形貌和结构的控制，进而实现对传感材料灵敏度的调控。
在一实施方式中，有机配体溶液包括1,5-二氨基-4,8-二羟基蒽醌溶液，金属离子溶液包括二价铜离子溶液，1,5-二氨基-4,8-二羟基蒽醌与二价铜离子的物质的量比为1:(2-8)。通过这种设置，使得铜离子在反应中过量，可以促进反应向生成反应物的正反应方向进行，有利于提高金属有机框架材料的产率。
在一实施方式中，有机配体溶液包括1,5-二氨基-4,8-二羟基蒽醌溶液，金属离子溶液包括二价铜离子溶液，1,5-二氨基-4,8-二羟基蒽醌与二价铜离子的物质的量比为1:(4-6)。通过这种设置，使得铜离子在反应中过量，可以促进反应向生成反应物的正反应方向进行，有利于提高金属有机框架材料的产率。
在一实施方式中，有机配体溶液的溶剂包括甲醇、乙醇、丙酮、四氢呋喃、N,N-二甲基甲酰胺、二甲基亚砜、二氯甲烷中的一种或多种。通过选用不同的溶剂，能够选择不同的方法制备金属有机框架材料，同时还可以调控金属有机框架材料的结晶度、孔隙结构、孔内环境、形貌等，进一步可以调控对气体的选择性、响应值、灵敏度等。
在一实施方式中，金属离子溶液包括二价铜盐溶液，二价铜盐包括一水合乙酸铜、五水合硫酸铜、二水合氯化铜中的至少一种。通过选择不同的阴离子，可以调控金属有机框架材料的微观形貌、孔隙结构、孔径大小，进一步调控材料的气体传感性能。
为解决上述技术问题，本申请采用的另一个技术方案是：提供一种气体传感器，传感器包括上述气体传感材料；或包括上述任一项的方法制得的气体传感材料。通过上述设置，能够实现对目标气体的高灵敏度响应。
为解决上述技术问题，本申请采用的另一个技术方案是：提供一种用电设备，包括上述电池。用电设备至少具有与电池相同的优势。
上述说明仅是本申请技术方案的概述，为了能够更清楚了解本申请的技术手段，而可依照说明书的内容予以实施，并且为了让本申请的上述和其它目的、特征和优点能够更明显易懂，以下特举本申请的具体实施方式。
附图说明
为了更清楚地说明本申请实施例中的技术方案，下面将对实施例描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其它的附图。
图1为一个或多个实施例的金属有机框架材料的透射电子显微镜(TEM)图像；
图2为根据一个或多个实施例的气体传感材料制备方法的示意图；
图3为根据一个或多个实施例的气体传感材料制备方法的示意图；
图4为根据一个或多个实施例的电池的分解结构示意图；
图5为根据一个或多个实施例的电池单体的分解结构示意图；
图6为根据一个或多个实施例的用电设备的结构示意图。
图7为根据一个或多个实施例的气体传感性能测试的示意图；
图8为根据一个或多个实施例的气体传感材料DDA-Cu的X射线衍射图谱(XRD)；
图9为根据一个或多个实施例的气体传感材料DDA-Cu的X射线能谱分析图像(EDS)；
图10为实施例1所得气体传感材料DDA-Cu-1的扫描电镜(SEM)图像；
图11为实施例2所得气体传感材料DDA-Cu-2的扫描电镜(SEM)图像；
图12为实施例3所得气体传感材料DDA-Cu-3的扫描电镜(SEM)图像；
图13为根据一个或多个实施例的气体传感材料DDA-Cu的气体响应示意图；
图14为根据一个或多个实施例的气体传感材料DDA-Co的气体响应示意图；
图15为根据一个或多个实施例的气体传感材料DDA-Ni的气体响应示意图；
图16为根据一个或多个实施例的气体传感材料DDA-Cu的气体响应示意图；
图17为根据一个或多个实施例的气体传感材料DDA-Cu的气体响应示意图；
图18为根据一个或多个实施例的气体传感材料DDA-Cu的气体响应示意图；
附图中：
1000、车辆；300、马达；200、控制器；100、电池；10、箱体；11、第一部分；12、第二部分；20、电池单体；21、端盖；21a、电极端子；22、壳体；23、电极组件。
具体实施方式
为使本申请的目的、技术方案及效果更加清楚、明确，以下将结合附图对本申请技术方案的实施例进行详细的描述。以下实施例仅用于更加清楚地说明本申请的技术方案，因此只作为示例，而不能以此来限制本申请的保护范围。
除非另有定义，本文所使用的所有的技术和科学术语与属于本申请的技术领域的技术人员通常理解的含义相同；本文中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本申请；本申请的说明书和权利要求书及上述附图说明中的术语“包括”和“具有”以及它们的任何变形，意图在于覆盖不排他的包含。
在本申请实施例的描述中，技术术语“第一”“第二”等仅用于区别不同对象，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量、特定顺序或主次关系。在本申请实施例的描述中，术语“多个”指的是两个以上(包括两个)，同理，“多组”指的是两组以上(包括两组)，“多片”指的是两片以上(包括两片)，除非另有明确具体的限定。
在本文中提及“实施例”意味着，结合实施例描述的特定特征、结构或特性可以包含在本申请的至少一个实施例中。在说明书中的各个位置出现该短语并不一定均是指相同的实施例，也不是与其它实施例互斥的独立的或备选的实施例。本领域技术人员显式地和隐式地理解的是，本文所描述的实施例可以与其它实施例相结合。
在本申请实施例的描述中，术语“和/或”仅仅是一种描述关联对象的关联关系，表示可以存在三种关系，例如A和/或B，可以表示：单独存在A，同时存在A和B，单独存在B这三种情况。另外，本文中字符“/”，一般表示前后关联对象是一种“或”的关系。
本文中以范围格式呈现量、比率和其它数值。应理解，此类范围格式是用于便利及简洁起见，且应灵活地理解，不仅包含明确地指定为范围限制的数值，而且包含涵盖于所述范围内的所有个别数值或子范围，如同明确地指定每一数值及子范围一般。
如果没有特别的说明，本申请的所有步骤可以顺序进行，也可以随机进行，还可以并列进行，优选是顺序进行的。例如，所述方法包括步骤(a)和(b)，表示所述方法可包括顺序进行的步骤(a)和(b)，也可以包括顺序进行的步骤(b)和(a)，还可以是步骤(a)和(b)同时并行。例如，所提到所述方法还可包括步骤(c)，表示步骤(c)可以任意顺序加入到所述方法，例如，所述方法可以包括步骤(a)、(b)和(c)，也可包括步骤(a)、(c)和(b)，也可以包括步骤(c)、(a)和(b)等。
由于动力电池具备各种优越性能，已经在人们的生活、新能源汽车及储能等行业中得到了广泛应用，新能源汽车和电化学储能是动力电池应用最多的领域，未来电池的发展目标是高能量密度、高安全性、长寿命、低成本。在电池的充电或放电过程中，由于电化学反应导致的物质转化和气体释放，电池会产生气体。
在充电过程中，电池将外部电能转化为化学能以储存，同时还有一些副反应会产生气体。例如，铅酸 电池在充电时会发生电解水分解的副反应，导致产生氧气和氢气气体。在放电过程中，电池中的化学能被转化为电能，同时也会发生一些气体产生的反应。例如，锂离子电池在放电过程中可能发生锂金属的氧化反应，产生一些有害气体如氟化碳化合物。
另外，电池在使用过程中可能会由于过充、过放、内部故障或不正确的操作而产生气体。这种情况下，电池内的化学反应可能不受控制，剧烈释放气体，甚至引发电池热失控现象。
电池热失控是电池安全研究的重要部分，电池热失控是由各种诱因引发的链式反应现象。新能源汽车的电池包通常是密封的，并且在正常操作中为无氧环境，如果电池包发生热失控，会释放出一些特征气体，电池热失控的特征气体包括二氧化碳、一氧化碳、氢气、乙烯、甲烷、乙烷和丙烯等，对电池热失控特征气体进行检测能够在热失控发生早期时做出预警并及时采取相应措施，减少生命和财产安全的损害。目前，在电池热失控检测领域，化学电阻传感器具有可靠的应用前景，它依靠传感材料与特征气体相互作用时电导率的变化来实现检测目的，具有简单、通用、低功耗和成本效益高的优点。然而，现有的金属氧化物传感器需要氧气，限制了其在无氧条件下检测电池热失控产生气体的应用。但是电池单体内为无氧环境，因此，急需开发新材料和传感器，在非氧条件下稳定工作并准确检测电池热失控产生的气体。
为了实现无氧环境中对电池热失控特征气体的高灵敏度检测，研究发现金属有机框架材料(MOFs)具有可调控的表面性质和化学反应活性，可以作为气体传感材料。具体地，金属有机框架材料(Metal organic frameworks，MOFs)是通过在金属节点之间有序拼接有机连接体而构建形成的典型的多孔结晶材料。MOFs材料独特的骨架与孔道结构特征决定了它们具有独特的大比表面积、高孔隙率和化学可调性等特性。MOFs材料的大比表面积和可调的多孔结构，可为气体吸附提供大量位点，吸附气体分子后会导致配位键的形成或断裂，引起电子转移，从而改变MOFs材料的电学性质，实现对吸附气体的响应。也即，MOFs材料作为气体敏感材料使用时，其响应机理为配位电子的转移。基于该原理，使得MOFs材料即使在无氧条件下也能实现气体响应，拓展了其作为气体传感材料的应用场景。
在本申请中，提供一种电池，电池包括气体传感器，气体传感器包括气体传感材料，气体传感材料包括金属有机框架材料，金属有机框架材料包括一维纳米材料，一维纳米材料至少在两个维度上的尺寸为纳米尺度，纳米尺度为0.1nm-100nm。
金属有机框架材料作为气体敏感材料使用时，其响应机理为配位电子的转移，不依赖氧气，因此能够实现在非氧条件下的气体响应，从而能够实现对电池内产气的检测。
在一实施方式中，金属有机框架材料(MOFs)可以是具有纳米结构的材料。纳米结构(Nanostructure)是尺寸介于分子和微米尺度间的物体的结构；这些物质的线度一般在0.1-100nm范围内。纳米结构包括一维的、二维的、三维的体系，这些物质单元包括纳米微粒、纳米管、纳米棒、纳米丝、纳米带以及纳米尺寸的孔洞等。
通过将金属有机框架材料(MOFs)做成具有纳米结构的材料，能够使其具有大的比表面积，可为气体吸附提供大量位点，提高气体传感材料的灵敏度。进一步研究发现，大部分的金属有机框架材料(MOFs)具有二维纳米结构，即为二维纳米MOFs材料。且一些二维纳米MOFs材料吸附气体后无法快速释放，即具有响应不可逆性，导致气体传感器无法实现重复使用；还有一些二维纳米MOFs材料导电性较差，导致灵敏度不足。
基于此，本申请提供一种具有一维纳米结构的金属有机框架材料(MOFs)，即为一维纳米MOFs材料。一维纳米材料是指在两个维度上的尺寸为纳米尺度，并且在第三个维度上的尺寸超过纳米尺度的材料，纳米尺度定义为0.1nm-100nm。例如，从长度、宽度、高度(厚度)三个维度上来看，一维纳米MOFs材料可以是宽度和高度(厚度)具有纳米尺度，但长度大于纳米尺度的材料；还可以是宽度和长度具有纳米尺度，但高度(厚度)大于纳米尺度的材料。一维纳米MOFs材料具有更高的比表面积与体积比，这有利于气体分子的吸附，从而提高了传感灵敏度；同时气体分子在一维纳米结构上的扩散速率明显更快，具有更快的气体扩散速率，使得响应时间更短。
本申请的一些实施例中，金属有机框架材料包括纳米带材料，即为纳米带MOFs材料。其中，纳米带材料的厚度为1-10nm，宽度为10-100nm。请参阅图1和图10，图1为根据一个或多个实施例的金属有机框架材料的透射电子显微镜(TEM)图像，图7为根据一个或多个实施例的金属有机框架材料的扫面电子显微镜(SEM)图像。从图像中可以观察到，纳米带MOFs材料的厚度为1-10nm，宽度为10-100nm，长度则较大，超过了几十纳米，可达到微米级别。例如厚度可以是1nm，2nm，3nm，5nm，6nm，8nm，10nm；宽度可以为10nm，15nm，20nm，30nm，40nm，60nm，80nm，100nm等。
在一实施方式中，金属有机框架材料包括纳米带材料，纳米带材料的厚度为3-8nm；纳米带的宽度为15-70nm。例如厚度可以是3nm，5nm，6nm，8nm等；宽度可以是15nm，20nm，30nm，40nm，60nm，70nm等。
得益于一维纳米结构，本申请中的纳米带MOFs材料比二维和三维金属有机框架材料具有更高的结构 自由度，为创造导电路径提供了更多机会，使得材料的导电性得到显著提高；结构稳定有序，具有更高的表面积与体积比，为气体分子的吸附提供了更广阔的场地，同时能够加快气体在传感材料上的扩散速率，使得电阻明显随气体吸附的变化而变化，因此可以有效提高气体响应的灵敏度和速度。
本申请的一些实施例中，金属有机框架材料在化学成分上包括金属与有机配体的配合物，金属元素包括铜、镍、钴、锌、铁中的一种或多种。其中，可以是金属离子与有机配体的配合物，金属离子包括铜离子、镍离子、钴离子、锌离子、铁离子中的一种或多种。
金属离子与有机配体之间通过配位键形成配合物，金属离子可以作为配位中心与有机配体上的多个原子配位，以形成较稳定的形态，提高金属有机框架材料的稳定性。同时，金属离子可以作为气体的吸附位点，吸附的气体分子会导致配位键的形成或断裂，引起电子转移，从而改变MOFs的电学和光学性质，实现对吸附气体的敏感性和选择性。具体地，可以是气体分子通过配位键与金属离子相连接，并发生电子转移，从而实现对气体的响应。
本申请的一些实施例中，金属有机框架材料(MOFs)中可以只有一种金属离子；也可以同时有多种不同类型的金属离子，形成不同的配位中心。金属离子可以有多个，形成多个配位中心。不同种类的金属离子能够赋予金属有机框架材料对不同气体的响应选择性，可以通过调控金属离子的类型和数量，提供金属有机框架材料的气体选择性。
本申请的一些实施例中，有机配体包括1,5-二氨基-4,8-二羟基蒽醌(1,5-diamino-4,8-dihydroxy anthraquinone，DDA)，其结构式为这是一种具有芳香核的配体，分子呈中心对称。具体地，DDA是一种含氨基和羟基取代基的蒽醌类化合物，其分子式为C14H10N2O4，分子量为270.24，含有一个蒽醌母核，1号位和5号位被氨基基团取代，4号位和8号位被羟基基团取代。蒽醌环与氨基及羟基之间存在共轭效应。分子中的氨基、羟基和羰基可以作为配位原子与多种金属离子形成稳定的配位键，得到结构性能不同的金属有机框架材料，具有很强的设计灵活性。再者，芳香的蒽醌环可以形成π-π堆叠相互作用，增强MOFs的稳定性。最后，由于1,5-二氨基-4,8-二羟基蒽醌为平面构型，因此易于通过自组装扩展成一维纳米带形式。
与该配体配位形成的金属有机框架材料(MOFs)中金属离子与有机配体形成的配位键能够建立有效的电荷传输通路，特别是活泼的过渡金属离子，它们具有合适的原子半径以获得与配体更好的轨道重叠，有利于产生小带隙和高电荷迁移率；另外，具有芳香环的有机配体还能够形成π-d共轭平面，以及π-π堆叠，从而能够提供平面上的导电路径，有利于金属有机框架材料导电性的改善。从而能够提高气体传感的响应值和灵敏度。
本申请的一些实施例中，有机配体还可以带有羧基(COOH)、巯基(SH)等易形成配位键的取代基；有机配体还可以是其他缩合多环芳香化合物作为母核，如蒽、菲等大环面化合物等。
本申请的一些实施例中，有机配体包括如下结构：
其中R1、R2为羟基(OH)、氨基(NH2)或巯基(SH)。
即蒽醌环上的取代基还可以是巯基。母核还可以拓展至更大的共轭结构。
本申请的一些实施例中，一种金属有机框架材料为二价铜离子与1,5-二氨基-4,8-二羟基蒽醌配位形成的配合物(以下简称DDA-Cu)，DDA-Cu的结构式为
根据DDA-Cu的结构式，DDA-Cu中铜离子配位在DDA配体中的三个氧原子及一个氮原子的中心，使铜离子处于一个稳定的形态，同时，层与层之间的铜离子d轨道相堆叠，形成了轴向导电通路，改善了金属有机框架材料的导电性。此外，使用金属离子将基础结构单元相连接，可以进一步增加MOFs材料的轴向导电性，同时由于形成了平面内的大π键体系，提高了平面方向的导电性，从而进一步增加该材料的电性能。进而能够提高气体传感的响应值和灵敏度。
进一步地，由于双金属位点对结构平面度的高度限制，DDA-Cu沿配位节点线性生长，形成一维纳米带结构，一维纳米带通过非键相互作用堆积形成块状材料。基于一维构建块的纳米材料由于具有高度的结构规整性、化学上的模块化边缘和可调的构效关系。能够提供更多的吸附位点。
该实施方式中的一维纳米带金属有机框架材料具备多个导电性优异的高度共轭结构单元，同时比二维和三维金属有机框架材料具有更高的结构自由度，为创造导电路径提供了更多机会，使得材料的导电性得到显著提高；结构稳定有序，具有更高的表面积与体积比，为气体分子的吸附提供了更广阔的场地，同时能够加快气体在传感材料上的扩散速率，使得电阻明显随气体吸附的变化而变化，因此可以有效提高气体响应的灵敏度和速度。
在一些实施例中，气体传感材料的响应气体包括一氧化碳、氨气、硫化氢、二氧化氮中的一种或多种。本申请提供的气体传感材料可以对多种气体有响应，且具备一定的选择性。具体请参阅下文实验例描述。
本申请的一些实施例中，还提供一种气体传感材料，气体传感材料包括金属有机框架材料，金属有机框架材料包括一维纳米材料，一维纳米材料至少在两个维度上的尺寸为纳米尺度，纳米尺度为0.1nm-100nm。金属有机框架材料作为气体敏感材料使用时，其响应机理为配位电子的转移，不依赖氧气，因此能够实现在非氧条件下的气体响应。
本申请的一些实施例中，还提供一种气体传感材料的制备方法，气体传感材料的制备方法具体包括：提供金属离子溶液和有机配体溶液；使金属离子溶液与有机配体溶液结合反应，得到金属有机框架材料。所得金属有机框架材料具有一维纳米结构，即为一维纳米MOFs材料。
其中，金属离子溶液由金属盐溶于溶剂制得。金属盐是金属有机框架材料的金属源，可以是过渡金属盐：如(Cu(NO3)2)、硝酸锌(Zn(NO3)2)、硝酸钴(Co(NO3)2)等过渡金属的无机盐；过渡金属有机配合物：如醋酸铜(Cu2(CH3COO)4)、琥珀酸亚铁等；氧化物前驱体：如CuO、ZnO等过渡金属氧化物；金属有机框架:部分金属有机框架材料也可以作为金属源，释放出金属离子用于继续构建金属有机框架结构；其他材料：金属箔片、盐类、无机酸等。通过选用不同的金属盐来制作金属离子溶液，能够调控所得金属有机框架材料的形貌、结晶等，进而调控所得金属有机框架材料的形貌和结晶性，进而调控气体传感性能。金属离子溶液所用溶剂可以为去离子水，即将金属盐溶于去离子水制得金属离子溶液。在其他实施方式中，还可以使用醇类溶剂制备金属离子溶液。
有机配体溶液由有机配体溶于溶剂制得。有机配体溶液的溶剂包括甲醇、乙醇、丙酮、四氢呋喃、N,N-二甲基甲酰胺、二甲基亚砜、二氯甲烷中的一种或多种。这些溶剂的极性不同，在反应体系中对金属离子和产物(MOFs材料)的溶解度不同。通过选用不同的溶剂，能够选择不同的方法制备MOFs材料，同时还可以调控MOFs材料的结晶度、孔隙结构、孔内环境、形貌等，进行调控其作为气体传感的性能，如调控对气体的选择性、调控响应值、灵敏度等。
本申请的一些实施例中，可以基于溶剂热法使金属离子溶液与有机配体溶液结合反应，得到金属有机框架材料。
具体地，将金属离子溶液与有机配体溶液均匀混合后，静置反应，制得金属有机框架材料。其中，静置反应是指反应过程中不对反应溶液体系进行搅拌、分散等处理。即先将溶液进行混合，混合时可以进行搅拌、分散等操作，但混合后反应时不再进行搅拌等其他混合操作。
本申请的一些实施例中，可以是将金属离子溶液滴加入有机配体溶液中，以使金属离子溶液与有机配体溶液混合。在一实施方式中，金属离子溶液的滴加速度为1-20秒/滴，例如可以是1秒/滴、5秒/滴、10秒/滴、15秒/滴、20秒/滴等。通过这种设置，能够使金属离子更均匀地分散在有机配体溶液中。进一步地，滴加完成后还可以对混合液进行超声处理，以使其混合均匀。
本申请的一些实施例中，金属离子溶液与有机配体溶液均匀混合后，静置反应，静置反应的时间为8-15h；静置反应的温度为70-95℃。
其中，静置反应时，反应容器螺口不完全拧紧，使得氧气能够进入反应容器并参与反应。反应在加热条件下进行，加热温度为70℃、75℃、80℃、85℃、90℃、95℃等。可以将容器放入恒温烘箱中进行加热。随着温度的升高，反应体系的反应速率会加快，因此晶体的生长速度会加快，在相同的反应时间里，能达到更高的产率。但加热温度不宜太高，以防反应速度过快，导致晶体生长过快，难以维持一维纳米结构。进一步地，通过控制加热温度还能够调控产物的结晶度，进而调控气体响应性能。反应时间为8h、9h、10h、11h、12h、13h、14h、15h等，具体根据反应进程调整。随着时间的延长，反应会进行得越来越完 全，考虑到时间成本，在一实施方式中，反应时间可以为12h。
本申请的一些实施例中，还可以向金属离子与有机配体的反应混合液中加入了碱，以促进反应。所加入碱为弱碱，例如可以是氨水。
其中，在金属有机框架材料合成过程中，需要将反应体系的pH值调整至适合晶体生长的范围，可利用酸或碱对pH值进行调节，称之为pH值调节剂，包括：浓氨水、氢氧化钠、三乙胺、乙二胺、四丁基氢氧化铵、盐酸、草酸、磷酸等。在一实施方式中，碱包括氨水。氨水的作用包括：提供碱性环境，有利于金属离子的脱质子和有机配体的解离；调节pH值，从而控制金属有机框架材料的生长速率；改善溶解性，使金属盐和有机配体完全溶解于合成溶剂中；加快反应，加快金属盐和有机配体之间的配位交联速率。
金属离子溶液与有机配体溶液反应结束后自然冷却至室温，自然冷却的降温速度不高，有利于晶体的长大，能够形成较为规则的晶体。反应体系中有沉淀生成，将所得的沉淀使用去离子水和乙醇交替离心清洗，之后在烘箱中干燥制得产物金属有机框架材料，干燥的温度为60℃，干燥的时间为6h。洗涤过程可以除去金属有机框架材料表面的杂质，包括未反应的反应物和一些杂质离子等，在后续性能测试中不会因此产生影响。
本申请的一些实施例中，可以基于界面生长反应法使金属离子溶液与有机配体溶液结合反应，得到金属有机框架材料。
具体地，将金属离子和有机配体分别溶于两种不互溶的溶剂，得到金属离子溶液和有机配体溶液，将互不相溶的金属离子溶液与有机配体溶液置于同一容器中，因金属离子溶液与有机配体溶液不互溶，会呈现分层状态，使反应体系产生两相界面，有机配体和金属离子在两相界面上接触并发生反应，使得金属有机框架晶体在两相界面上生长，两种制备MOFs的原料会在界面处相互扩散，在界面处生产出MOFs膜。
本申请的一些实施例中，金属离子溶液为金属盐的水溶液，有机配体溶液为有机配体的二氯甲烷溶液。有机配体溶液在下层，金属离子溶液在上层，金属离子溶液和有机配体溶液在界面上相互作用，通过逐步生长方式，将有机配体和金属离子组装成具有特定结构的金属有机框架晶体。
通过调节界面上反应物的相互作用，可以实现对金属有机框架材料形貌和结构的控制，实现对传感材料灵敏度的调控；界面生长法为传感材料的重构提供了便利，可以实现传感材料的反复装配和重构，从而可实现多功能传感器的设计和应用。
本申请的一些实施例中，一种金属有机框架材料为二价铜离子与1,5-二氨基-4,8-二羟基蒽醌配位形成的配合物(以下简称DDA-Cu)。DDA-Cu的制备方法包括：使1,5-二氨基-4,8-二羟基蒽醌溶液与二价铜离子溶液结合反应。其反应式为：
从反应式中可以看出，每个DDA配体需要与四倍当量的铜离子相配位，而每个铜离子又与两个DDA配体进行连接，因此理论投料比为DDA:铜离子＝1:2(物质的量)。然而，实际工况下，金属有机框架材料的合成和分解是可逆反应，按照理论投料比反应无法达到较高产率，因此需要将反应物过量以促进反应向正反应方向进行。进一步地，为了控制成本，将价格相对较低的铜离子的浓度提高来促进反应向金属有机框架材料生成的方向进行。
本申请的一些实施例中，DDA与二价铜离子的物质的量比为1:(2-8)。例如，可以为1:2、1:3、1:4、1:5、1:6、1:7、1:8等。
在一实施方式中，DDA与二价铜离子的物质的量比为1:(4-6)。例如，可以为1:4、1:4.5、1:5、1:5.5、1:6等。
随着铜离子物质的量的增加，反应进行得越来越完全。同时，通过调控投料比，还能够调控所得产物的形貌和结晶性，进而调控气体响应性能。
本申请的一些实施例中，金属离子溶液包括二价铜盐溶液，二价铜盐包括一水合乙酸铜、五水合硫酸铜、二水合氯化铜中的至少一种。通过选择不同的阴离子，可以调控金属有机框架材料的微观形貌、孔隙结构、孔径大小，进一步调控材料的气体传感性能。
本申请的一些实施例中，DDA配体的溶剂包括甲醇、乙醇、丙酮、四氢呋喃、二甲基亚砜、N,N-二甲基甲酰胺、二氯甲烷中的一种或多种。通过选择不同的溶剂，可以调控金属有机框架材料的微观形貌、孔隙结构、孔径大小，进一步调控材料的气体传感性能。
请参考图2，图2为根据一个或多个实施例的气体传感材料制备方法的示意图。可以基于溶剂热法使二价铜离子溶液与DDA配体溶液结合反应，得到金属有机框架材料。
具体地，将二价铜离子溶液与DDA配体溶液混合，混合液置于螺口玻璃瓶中，将玻璃瓶螺口微松放置，95℃下保温12h；反应结束后使其自然冷却至室温，将所得的黑色沉淀使用去离子水和乙醇交替离心清洗，离心清洗的离心速度为8000rpm，离心清洗的时间为10min。之后在60℃烘箱中干燥6h，制得产物。
请参考图3，图3为根据一个或多个实施例的气体传感材料制备方法的示意图。可以基于界面反应生长法使二价铜离子溶液与DDA配体溶液结合反应，得到金属有机框架材料。
具体地，将DDA配体溶于二氯甲烷中，将二价铜离子的水溶液加入到盛有DDA配体溶液的容器中，两种溶液分层，静置反应一周，界面处生长有MOFs薄膜。
本申请的一些实施例中，还提供一种气体传感器，该气体传感器包括上述任一项的气体传感材料；或包括利用上述任一项方法制得的气体传感材料。
具体地，利用一维纳米MOFs材料作为气体传感材料，该材料基于配位电子转移原理实现对感应气体的响应，能够在无氧条件下实现气体响应，制备了一种在无氧条件下可对气体做出迅速响应且检测灵敏高的气体传感器。
本申请的一些实施例中，本申请所提供的气体传感器可用于电池内部气体的检测。
请参照图4，图4为根据一个或多个实施例的电池的分解结构示意图。电池100包括箱体10和电池单体20，电池单体20容纳于箱体10内。其中，箱体10用于为电池单体20提供容纳空间，箱体10可以采用多种结构。在一些实施例中，箱体10可以包括第一部分11和第二部分12，第一部分11与第二部分12相互盖合，第一部分11和第二部分12共同限定出用于容纳电池单体20的容纳空间。第二部分12可以为一端开口的空心结构，第一部分11可以为板状结构，第一部分11盖合于第二部分12的开口侧，以使第一部分11与第二部分12共同限定出容纳空间；第一部分11和第二部分12也可以是均为一侧开口的空心结构，第一部分11的开口侧盖合于第二部分12的开口侧。当然，第一部分11和第二部分12形成的箱体10可以是多种形状，比如，圆柱体、长方体等。气体传感器可以安装在箱体10的内侧。
在电池100中，电池单体20可以是多个，多个电池单体20之间可串联或并联或混联，混联是指多个电池单体20中既有串联又有并联。多个电池单体20之间可直接串联或并联或混联在一起，再将多个电池单体20构成的整体容纳于箱体10内；当然，电池100也可以是多个电池单体20先串联或并联或混联组成电池模块形式，多个电池模块再串联或并联或混联形成一个整体，并容纳于箱体10内。电池100还可以包括其他结构，例如，该电池100还可以包括汇流部件，用于实现多个电池单体20之间的电连接。
其中，每个电池单体20可以为二次电池或一次电池；还可以是锂硫电池、钠离子电池或镁离子电池，但不局限于此。电池单体20可呈圆柱体、扁平体、长方体或其它形状等。
请参照图5，图5为根据一个或多个实施例的电池单体的分解结构示意图。电池单体20是指组成电池的最小单元。如图5，电池单体20包括有端盖21、壳体22、电极组件23以及其他的功能性部件。
端盖21是指盖合于壳体22的开口处以将电池单体20的内部环境隔绝于外部环境的部件。不限地，端盖21的形状可以与壳体22的形状相适应以配合壳体22。在一实施方式中，端盖21可以由具有一定硬度和强度的材质(如铝合金)制成，这样，端盖21在受挤压碰撞时就不易发生形变，使电池单体20能够具备更高的结构强度，安全性能也可以有所提高。端盖21上可以设置有如电极端子21a等的功能性部件。电极端子21a可以用于与电极组件23电连接，以用于输出或输入电池单体20的电能。在一些实施例中，端盖21上还可以设置有用于在电池单体20的内部压力或温度达到阈值时泄放内部压力的泄压机构。端盖21的材质也可以是多种的，包括但不限于铜、铁、铝、不锈钢、铝合金、塑胶等。在一些实施例中，在端盖21的内侧还可以设置有绝缘件，绝缘件可以用于隔离壳体22内的电连接部件与端盖21，以降低短路的风险。示例性的，绝缘件可以是塑料、橡胶等。
壳体22是用于配合端盖21以形成电池单体20的内部环境的组件，其中，形成的内部环境可以用于容纳电极组件23、电解液以及其他部件。壳体22和端盖21可以是独立的部件，可以于壳体22上设置开口，通过在开口处使端盖21盖合开口以形成电池单体20的内部环境。不限地，也可以使端盖21和壳体22一体化，具体地，端盖21和壳体22可以在其他部件入壳前先形成一个共同的连接面，当需要封装壳体22的内部时，再使端盖21盖合壳体22。壳体22可以是多种形状和多种尺寸的，例如长方体形、圆柱体形、六棱柱形等。具体地，壳体22的形状可以根据电极组件23的具体形状和尺寸大小来确定。壳体22的材质可以是多种，包括但不限于铜、铁、铝、不锈钢、铝合金、塑胶等。
电极组件23是电池单体100中发生电化学反应的部件。壳体22内可以包含一个或更多个电极组件23。电极组件23主要由正极片和负极片卷绕或层叠放置形成，并且通常在正极片与负极片之间设有隔膜。正极片和负极片具有活性物质的部分构成电极组件的主体部，正极片和负极片不具有活性物质的部分各自构成极耳23a。正极极耳和负极极耳可以共同位于主体部的一端或是分别位于主体部的两端。在电池的充放电过程中，正极活性物质和负极活性物质与电解液发生反应，极耳23a连接电极端子以形成电流回路。
在一实施方式中，正极极片包括集流体和设置在集流体上的正极活性层。
正极活性层包括正极活性材料，正极活性材料可包括以下材料中的至少一种：橄榄石结构的含锂磷酸盐、锂过渡金属氧化物及其各自的改性化合物。但本申请并不限定于这些材料，还可以使用其他可被用作电池正极活性材料的传统材料。这些正极活性材料可以仅单独使用一种，也可以将两种以上组合使用。其中，锂过渡金属氧化物的示例可包括但不限于锂钴氧化物(如LiCoO2)、锂镍氧化物(如LiNiO2)、锂锰氧化物(如LiMnO2、LiMn2O4)、锂镍钴氧化物、锂锰钴氧化物、锂镍锰氧化物、锂镍钴锰氧化物(如LiNi1/3Co1/3Mn1/3O2(也可以简称为NCM333)、LiNi0.5Co0.2Mn0.3O2(也可以简称为NCM523)、LiNi0.5Co0.25Mn0.25O2(也可以简称为NCM211)、LiNi0.6Co0.2Mn0.2O2(也可以简称为NCM622)、LiNi0.8Co0.1Mn0.1O2(也可以简称为NCM811)、锂镍钴铝氧化物(如LiNi0.85Co0.15Al0.05O2)及其改性化合物等中的至少一种。橄榄石结构的含锂磷酸盐的示例可包括但不限于磷酸铁锂(如LiFePO4(也可以简称为LFP))、磷酸铁锂与碳的复合材料、磷酸锰锂(如LiMnPO4)、磷酸锰锂与碳的复合材料、磷酸锰铁锂、磷酸锰铁锂与碳的复合材料中的至少一种。
在一实施方式中，正极活性层还包括导电剂，从而赋予电极导电性。正极导电材料可以包括任何导电材料，只要它不引起化学变化。正极导电材料的非限制性示例包括基于碳的材料(例如，天然石墨、人造石墨、碳黑、乙炔黑、科琴黑、碳纤维等)、基于金属的材料(例如，金属粉、金属纤维等，包括例如铜、镍、铝、银等)、导电聚合物(例如，聚亚苯基衍生物)和它们的混合物。在一实施方式中，导电剂包括导电炭黑、导电石墨、碳纤维、碳纳米管、石墨烯、科琴黑以及乙炔黑中的一种或多种。
在一实施方式中，正极活性层还包括粘结剂，以提高活性层的粘附稳定性，降低掉粉情况发生的概率。粘结剂可以为丁苯橡胶(SBR)、水性丙烯酸树脂(water-based acrylic resin)、聚偏二氟乙烯(PVDF)、聚四氟乙烯(PTFE)、乙烯-醋酸乙烯酯共聚物(EVA)、聚丙烯酸(PAA)、羧甲基纤维素(CMC)、聚乙烯醇(PVA)及聚乙烯醇缩丁醛(PVB)中的一种或几种。在一实施方式中，粘结剂包括聚偏氟乙烯、聚四氟乙烯、丙烯酸酯、聚氨酯中的一种或几种。
在一实施方式中，正极活性层还包括其他可选助剂，其他可选助剂可以是增稠及分散剂(例如羧甲基纤维素钠CMC-Na)、PTC热敏电阻材料。
在一些实施方式中，负极极片包括集流体和设置在集流体上的负极活性层。
负极活性层包括负极活性材料，负极活性材料包括但不限于碳基负极材料、硅基负极材料、锡基负极材料、钛酸锂负极材料、金属锂负极材料等；具体包括但不限于石墨材料、硅碳材料、石墨-氧化亚硅材料、纳米硅材料、氧化亚硅材料和锡基材料；更具体的包括天然石墨、人造石墨、中间相微碳球(简称为MCMB)、硬碳、软碳、硅、硅-碳复合物、Li-Sn合金、Li-Sn-O合金、Sn、SnO、SnO2、尖晶石结构的锂化TiO2-Li4Ti5O12、Li-Al合金中的一种或几种。
在一些实施方式中，负极活性层还可以包括粘结剂、导电剂和其他可选助剂。作为示例，导电剂可以为超导碳、乙炔黑、炭黑、科琴黑、碳点、碳纳米管、Super P(SP)、石墨烯及碳纳米纤维中一种或几种。作为示例，粘结剂可以为丁苯橡胶(SBR)、水性丙烯酸树脂(water-based acrylic resin)、聚偏二氟乙烯(PVDF)、聚四氟乙烯(PTFE)、乙烯-醋酸乙烯酯共聚物(EVA)、聚丙烯酸(PAA)、羧甲基纤维素(CMC)、聚乙烯醇(PVA)及聚乙烯醇缩丁醛(PVB)中的一种或几种。作为示例，其他可选助剂可以是增稠及分散剂(例如羧甲基纤维素钠CMC-Na)、PTC热敏电阻材料。
在一些实施方式中，隔离膜的材质可选自玻璃纤维、无纺布、聚乙烯、聚丙烯及聚偏二氟乙烯中的至少一种。隔离膜可以是单层薄膜，也可以是多层复合薄膜，没有特别限制。在隔离膜为多层复合薄膜时，各层的材料可以相同或不同，没有特别限制。
在一实施方式中，电解液包括碳酸酯类溶剂、醚类溶剂中的一种或多种。
碳酸酯通常为小分子的环状或链状碳酸酯；包括但不限于碳酸乙烯酯、碳酸丙烯酯、碳酸丁烯酯、碳酸亚乙烯酯、碳酸甲丙酯、碳酸二丙酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、氟代碳酸酯中的一种或多种；还可以是γ-丁内酯、亚硫酸二甲酯、乙酸乙酯、乙酸甲酯、丁酸甲酯、丁酸乙酯、丙酸甲酯、丙酸乙酯、乙酸丙酯、氟代羧酸酯中的至少一种酯类溶剂。
醚类溶剂包括但不限于二甲醚、二乙醚、四氢呋喃、甲基四氢呋喃、环氧乙烷、1,3-二氧戊环、氟代醚、DME(乙二醇二甲醚)、DEE(乙二醇二乙醚)、DEGDME(二乙二醇二甲醚)、TRGDME(三乙二醇二甲醚)、TEGDME(四乙二醇二甲醚)、二丙基醚以及二丁醚中的一种或多种。
在其他实施方式中，电解液还可以包括胺类溶剂，砜类溶剂以及腈类溶剂中任意一种或几种组成的混合物。胺类溶剂包括N-甲基乙酰胺、N-甲基甲酰胺、二甲基甲酰胺、二乙基甲酰胺中的至少一种。砜类溶剂包括二甲基亚砜，环丁砜，二苯基亚砜、氯化亚砜，二丙砜中的至少一种。腈类溶剂包括乙腈、丁二腈、己二腈、戊二腈中的至少一种。电解液优先耐高压电解液，其在高电压下的酸性减弱，能够利于活性离子的传输，明显降低电极表面副反应，提高电池稳定性。
在一些实施方式中，电解液还包括电解质盐，电解质盐可选自六氟磷酸锂、四氟硼酸锂、高氯酸锂、 六氟砷酸锂、双氟磺酰亚胺锂、双三氟甲磺酰亚胺锂、三氟甲磺酸锂、二氟磷酸锂、二氟草酸硼酸锂、二草酸硼酸锂、二氟二草酸磷酸锂及四氟草酸磷酸锂中的至少一种。
在一些实施方式中，电解液还包括添加剂。例如添加剂可以包括负极成膜添加剂、正极成膜添加剂，还可以包括能够改善电池某些性能的添加剂，例如改善电池过充性能的添加剂、改善电池高温或低温性能的添加剂等。
本申请实施例公开的电池可以用于使用电池作为电源的用电设备或者使用电池作为储能元件的各种储能系统。即本申请提供一种用电设备，用电设备包括上述实施例的电池。在一些实施例中，本申请的用电设备可用于，但不限于，笔记本电脑、笔输入型计算机、移动电脑、电子书播放器、便携式电话、便携式传真机、便携式复印机、便携式打印机、头戴式立体声耳机、录像机、液晶电视、手提式清洁器、便携CD机、迷你光盘、收发机、电子记事本、计算器、存储卡、便携式录音机、收音机、备用电源、电机、汽车、摩托车、助力自行车、自行车、轮船、航天器、照明器具、玩具、游戏机、钟表、电动工具、闪光灯、照相机、家庭用大型蓄电池和锂离子电容器等。
用电设备可以根据其使用需求来选择电池单体、电池模块或电池包。
请参照图6，图6为根据一个或多个实施例的车辆的结构示意图。车辆1000可以为燃油汽车、燃气汽车或新能源汽车，新能源汽车可以是纯电动汽车、混合动力汽车或增程式汽车等。车辆1000的内部设置有电池100，电池100可以设置在车辆1000的底部或头部或尾部。电池100可以用于车辆1000的供电，例如，电池100可以作为车辆1000的操作电源。车辆1000还可以包括控制器200和马达300，控制器200用来控制电池100为马达300供电，例如，用于车辆1000的启动、导航和行驶时的工作用电需求。
在本申请一些实施例中，电池100不仅可以作为车辆1000的操作电源，还可以作为车辆1000的驱动电源，代替或部分地代替燃油或天然气为车辆1000提供驱动动力。
为了使本申请实施例所解决的技术问题、技术方案及有益效果更加清楚，以下将结合实施例和附图进行进一步详细说明。显然，所描述的实施例仅仅是本申请一部分实施例，而不是全部的实施例。以下对至少一个示例性实施例的描述实际上仅仅是说明性的，决不作为对本申请及其应用的任何限制。基于本申请中的实施例，本领域普通技术人员在没有付出创造性劳动前提下所获得的所有其他实施例都属于本申请保护的范围。
一、气体传感材料的制备
实施例1
1、称取13.61mg(0.05mmol)的DDA配体和40.00mg(0.20mmol)的一水合乙酸铜。
2、将13.61mg DDA配体溶于0.5mL N,N-二甲基甲酰胺(DMF)中，使用超声波机超声5min，使得有机配体溶解，得到DDA配体溶液；将40.00mg一水合乙酸铜溶于1.5mL去离子水中，充分搅拌使其溶解，得到二价铜离子溶液。
3、将二价铜离子溶液加入DDA配体溶液中并混合均匀。可以将乙酸铜溶液以1-20秒/滴的速度缓缓滴入DDA配体溶液中；再在上述混合溶液中加入0.2mL 14.0mol/L的浓氨水；使用超声波机超声10min，使得混合溶液混合均匀。
4、将混合液置于20mL螺口玻璃瓶中，将玻璃瓶螺口微松放置，在85℃下保温12h。
5、反应结束后使混合溶液自然冷却至室温，将所得的黑色沉淀使用去离子水和乙醇交替离心清洗，离心清洗的离心速度为8000rpm，离心清洗的时间为10min。之后在60℃烘箱中干燥6h，制得纳米带MOFs材料DDA-Cu-1。
实施例2-3
在实施例1的基础上改变金属离子溶液的制备，区别在于金属铜盐分别替换为五水合硫酸铜和二水合氯化铜，制得纳米带MOFs材料DDA-Cu-2和DDA-Cu-3。具体反应条件详见表1，表1列出了各实施例的反应物、投料比、反应体系溶剂、反应体系温度。
实施例4-9
在实施例1的基础上改变DDA配体与二价铜离子的投料比，区别在于投料比从1:4分别调整为1:2、1:3、1:5、1:6、1:7、1:8，制得纳米带MOFs材料DDA-Cu-4至DDA-Cu-9，具体反应条件详见表1。
实施例10-14
在实施例1的基础上改变反应体系的溶剂，区别在于溶剂分别替换为甲醇、乙醇、丙酮、四氢呋喃和二甲基亚砜，制得纳米带MOFs材料DDA-Cu-10至DDA-Cu-14，具体反应条件详见表1。
实施例15-19
在实施例1的基础上改变反应体系的温度，区别在于温度从85℃分别调整为70℃、75℃、80℃、90℃、95℃，制得纳米带MOFs材料DDA-Cu-15至DDA-Cu-19，具体反应条件详见表1。
实施例20-21
在实施例1的基础上改变金属盐的种类，区别在于将一水合乙酸铜分别替换为四水合乙酸钴和四水合乙酸镍，制得纳米带MOFs材料DDA-Co和DDA-Ni，具体反应条件详见表1。
二、气体传感材料的测试
(1)透射电子显微镜(TEM)
参照JY/T 0581-2020透射电子显微镜分析方法通则，利用电子束穿透样品，测定金属有机框架材料的TEM图像。
(2)X射线衍射(XRD)
参照JIS K 0131-1996X射线衍射分析法通则，使用CuKα1射线测定金属有机框架材料的X射线衍射图谱。
(3)扫描电子显微镜(SEM)和X射线能谱分析(EDS)
参照JY/T010-1996分析型扫描电子显微镜方法通则，利用电子束扫描样品表面，测定金属有机框架材料的SEM图像，同时获得金属有机框架材料的能谱图。
三、气体传感器的制备
将气体传感材料以10mg/L的浓度分散在乙醇中，以40KHz超声处理10min，使得复合材料均匀分散在乙醇中。采用微机械加工工艺制备金电极，控制正负电极的间距为800μm，相邻电极的间距为300μm。取5μL上述分散液，将其滴加在叉指电极上，60℃真空干燥1h，从而得到气体传感器。
四、气体传感性能测试
请参阅图7，图7为根据一个或多个实施例的气体传感性能测试的示意图。将气体传感器放入测试腔中，在室温条件下，采用静态配气的方式引入目标气体，在传感器电极之间施加500mV的恒定工作电压，通过安捷伦4156C半导体参数分析仪对在惰性气体及目标气体环境下传感器的电阻变化实施检测。其中，在引入目标气体之前，使用干燥的压缩氮气(MFC3)净化腔室以稳定基线信号，用压缩氮气(MFC2)作为载气稀释目标气体，目标气体由质量流量控制器(MFC1)控制。传感器在干燥氮气中和目标气体中的电阻差值与干燥氮气中电阻比(|Ra-Rg|/Ra×100％)即为器件对目标气体的响应值，响应和恢复时间通过达到响应和恢复曲线的90％饱和度来定义。
表1各实施例的反应参数和性能参数表
注：DDA:An+是DDA配体与金属离子(An+)的物质的量比；响应值为金属有机框架材料对浓度为50ppm的CO的响应值；恢复时间为金属有机框架材料对浓度为50ppm的CO的恢复时间。
请参阅图1和图10，从TEM图像和SEM图像中可以观察到，DDA-Cu-1具有纳米结构，具体呈纳米 带状，不同纳米带的厚度有2.5nm、3.0nm、6.2nm、8.2nm等，宽度有19.0nm、32.4nm、66.7nm、95.8nm等。
请参阅图8，图8为根据一个或多个实施例的气体传感材料DDA-Cu的X射线衍射图谱。如图所示，DDA-Cu-1的XRD衍射峰位与Materials Studio软件得到的单晶数据模拟的XRD衍射峰值位基本一致，可以观察到对应于(001)、(100)、(010)晶面衍射峰，峰形较为尖锐，说明实验样品的晶体结构较为有序，晶体内部的原子排列较为规则，没有过多的晶体缺陷或杂质，纯度较高。
请继续参阅图9，图9为一个或多个实施例的气体传感材料DDA-Cu的X射线能谱分析(EDS)图像。如图所示，在气体传感材料中，氧元素(O)、氮元素(N)和铜元素(Cu)在气体传感材料中均匀分布。
请参阅图10至图12，图10为实施例1所得气体传感材料DDA-Cu-1的扫描电镜(SEM)图像，图11为实施例2所得气体传感材料DDA-Cu-2的扫描电镜(SEM)图像，图12为实施例3所得气体传感材料DDA-Cu-3的扫描电镜(SEM)图像。如图所示，不同的金属盐制备得到的气体传感材料在微观形貌上也不同，DDA-Cu-1、DDA-Cu-3呈纳米带、纳米片状，DDA-Cu-2呈针状结晶形态，但是三者都是纳米结构。通过选择不同的铜盐来制备金属离子，可以调控金属有机框架材料的微观形貌。
请结合参阅表1，DDA-Cu-1、DDA-Cu-2、DDA-Cu-3对气体的响应数据有一定的差异，相对于DDA-Cu-1和DDA-Cu-2，DDA-Cu-3对CO的响应值更高，但恢复时间也延长了。因此，可通过调整金属盐中阴离子的种类，调控金属有机框架材料在气体传感中的响应和恢复性能。
在实施例1、4-9中，展示了当投料比为1:2-1:8时，Cu-DDA气体传感材料对50ppm一氧化碳气体的传感性能。随着铜离子物质的量的增加，反应进行得越来越完全，Cu-DDA气体传感材料对50ppm一氧化碳气体的传感性能也随之得到改善，具体表现为响应值变大，恢复时间减小。但是当投料比超过1:4时，传感性能的改善不再明显，因此，考虑到原料成本，在一实施方式中，投料比为1,5-二氨基-4,8-二羟基蒽醌：铜离子＝1:4(物质的量)，此时既能提高产物的气体传感性能，又能节约原料。
在实施例1、10-14中，展示了当反应体系溶剂不同时，Cu-DDA气体传感材料对50ppm一氧化碳气体的传感性能。不同溶剂的极性不同，溶剂的极性可以影响配体和金属离子的相互作用和反应速率，还会影响金属有机框架材料的孔隙结构和孔内环境，进一步影响金属有机框架材料的气体传感性能。当溶剂不同时，金属有机框架材料的气体响应值不同，其中二甲基亚砜的极性较高，能够有效地与DDA的氢键受体和给体基团进行相互作用。因此，可以更彻底地溶解DDA。此时Cu-DDA金属有机框架材料对一氧化碳的响应值高，恢复时间也短。
在实施例1、15-19中，展示了当反应体系温度为70℃-95℃时，Cu-DDA气体传感材料对50ppm一氧化碳气体的传感性能。随着温度的升高，反应体系的反应速率会加快，因此晶体的生长速度会加快，在相同的反应时间里，能达到更高的产率。通过调控反应体系的温度，最终生成的气体传感材料产率更高，因此在气体传感性能上更优秀。随着静置反应温度的提高，反应进行得越来越完全，对一氧化碳气体的响应值增加，同时恢复时间减小，但是温度超过85℃后，气体传感性能的改善不再明显。在一实施方式中，温度可设置为85℃，此时Cu-DDA金属有机框架材料的传感性能较好，同时不浪费能源。
在实施例1、20-21中，展示了当金属盐分别为一水合乙酸铜、四水合乙酸钴和四水合乙酸镍时，所制备的气体传感材料50ppm一氧化碳气体的传感性能。当金属离子为钴和镍时，对气体的响应值虽然较大，但不能恢复。因此，可以根据应用需求选择铜离子作为气体传感材料检测一氧化碳气体时的金属离子。
请参阅图13至图15，图13为根据一个或多个实施例的气体传感材料DDA-Cu的气体响应示意图，图14为根据一个或多个实施例的气体传感材料DDA-Co的气体响应示意图，图15为根据一个或多个实施例的气体传感材料DDA-Ni的气体响应示意图。分别测试了不同气体传感材料对浓度为50ppm的一氧化碳(CO)、氨气(NH3)、硫化氢(H2S)的响应情况。检测发现DDA-Cu、DDA-Co、DDA-Ni对一氧化碳(CO)、氨气(NH3)、硫化氢(H2S)均有一定的响应特性，能够作为气体传感器对这些气体进行检测，但针对不同气体能达到的响应值不同，可根据实际情况选择合适的气体传感材料。
请参阅图16，图16为根据一个或多个实施例的气体传感材料DDA-Cu的气体响应示意图。进一步地，在室温下测试了实施例一所制备的基于DDA-Cu-1气体传感材料的传感器对50ppm不同气体的响应情况，结果如图16所示。可以看到，DDA-Cu-1气体传感材料对一氧化碳的响应值为9％左右，对氨气的响应值超过15％，对硫化氢的响应值超过20％，同时对其他五种气体的响应值均未超过5％，因此DDA-Cu-1表现出良好的气体选择性。
请参阅图17和18，图17为根据一个或多个实施例的气体传感材料DDA-Cu的气体响应示意图，图18为根据一个或多个实施例的气体传感材料DDA-Cu的气体响应示意图。在室温下测试了实施例一所制备的基于DDA-Cu-1气体传感材料的传感器对浓度为10ppm-80ppm一氧化碳的响应情况。在图中，横坐标为采集时间，纵坐标为响应值。由图可知，前述实施例制得的DDA-Cu-1基传感器对80ppm一氧化碳的响应值达到了8.8％。可检测的最低一氧化碳浓度达到了10ppm，对应的响应值为1.1％。随着一氧化碳浓度的 增加，传感器对气体的响应值也随之增加，对10、20、40、80ppm一氧化碳的响应值分别为1.1％、2.0％、3.7％和8.8％。由此可知，本申请所提供的气体传感材料气体响应更灵敏，检出限低。
进一步地，在室温下测试了实施例一所制备的基于DDA-Cu-1气体传感材料的传感器对50ppm一氧化碳的循环响应性能。在图中，横坐标为采集时间，纵坐标为响应值。传感器对气体的响应时间在400s左右，恢复时间也在400s左右，响应更灵敏。且在经过六次响应-恢复循环之后，传感器的响应值维持在3.8％以上，响应时间基本维持不变，说明前述实施例制得的传感器具有良好的循环稳定性。
以上实施例，本申请所提供的气体传感材料可用于电池内产气检测，且对气体有较好的响应灵敏度和选择性。进一步地，上述气体传感材料是在室温下进行的气体传感测试，相对于现有的需要高温才能够气体响应的材料，条件更温和，应用范围更广。
以上所述仅为本申请的实施方式，并非因此限制本申请的专利范围，凡是利用本申请说明书及附图内容所作的等效结构或等效流程变换，或直接或间接运用在其他相关的技术领域，均同理包括在本申请的专利保护范围内。

Claims (20)

  1. 一种电池，其中，包括气体传感器；
    所述气体传感器包括气体传感材料，所述气体传感材料包括金属有机框架材料，所述金属有机框架材料包括一维纳米材料，所述一维纳米材料至少在两个维度上的尺寸为纳米尺度，所述纳米尺度为0.1-100nm。
  2. 根据权利要求1所述的电池，其中，
    所述金属有机框架材料包括纳米带材料，所述纳米带材料的厚度为1-10nm；所述纳米带的宽度为10-100nm。
  3. 根据权利要求1或2所述的电池，其中，
    所述金属有机框架材料包括纳米带材料，所述纳米带材料的厚度为3-8nm；所述纳米带的宽度为15-70nm。
  4. 根据权利要求1至3任一项所述的电池，其中，
    所述金属有机框架材料包括金属与有机配体的配合物，所述金属包括铜、镍、钴、锌、铁中的一种或多种。
  5. 根据权利要求1至4任一项所述的电池，其中，
    所述有机配体包括式(1)所示结构：
    其中，R1、R2包括羟基、氨基或巯基中的任一种。
  6. 根据权利要求1至5任一项所述的电池，其中，
    所述有机配体包括1,5-二氨基-4,8-二羟基蒽醌。
  7. 根据权利要求1至6任一项所述的电池，其中，
    所述气体传感材料的响应气体包括一氧化碳、氨气、硫化氢、二氧化氮中的一种或多种。
  8. 一种气体传感材料，其中，包括：
    金属有机框架材料，所述金属有机框架材料包括一维纳米材料，所述一维纳米材料至少在两个维度上的尺寸为纳米尺度，所述纳米尺度为0.1-100nm。
  9. 一种气体传感材料的制备方法，其中，包括：
    提供金属离子溶液和有机配体溶液；
    使所述金属离子溶液与所述有机配体溶液结合反应，得到金属有机框架材料，所述金属有机框架材料包括一维纳米材料，所述一维纳米材料至少在两个维度上的尺寸为纳米尺度，所述纳米尺度为0.1nm-100nm。
  10. 根据权利要求9所述的气体传感材料的制备方法，其中，
    所述使金属离子溶液与有机配体溶液结合反应包括：
    将所述金属离子溶液与所述有机配体溶液均匀混合后，静置反应，得到所述金属有机框架材料。
  11. 根据权利要求10所述的气体传感材料的制备方法，其中，
    所述静置反应的时间为8-15h；和/或
    所述静置反应的温度为70-95℃。
  12. 根据权利要求10或11所述的气体传感材料的制备方法，其中，
    所述将所述金属离子溶液与所述有机配体溶液均匀混合包括：
    将所述金属离子溶液滴加入所述有机配体溶液中混合；
    所述金属离子溶液的滴加速度为1-20秒/滴。
  13. 根据权利要求10至12任一项所述的气体传感材料的制备方法，其中，还包括：
    向所述金属离子溶液与有机配体溶液的混合液中加入碱；
    所述碱包括氨水。
  14. 根据权利要求9所述的气体传感材料的制备方法，其中，
    所述使金属离子溶液与有机配体溶液结合反应包括：
    将所述金属离子溶液与所述有机配体溶液置于同一容器中，所述金属离子溶液与所述有机配体溶液不互溶，利用界面反应，制得所述金属有机框架材料。
  15. 根据权利要求9至14任一项所述的气体传感材料的制备方法，其中，
    所述有机配体溶液包括1,5-二氨基-4,8-二羟基蒽醌溶液，所述金属离子溶液包括二价铜离子溶液，所述1,5-二氨基-4,8-二羟基蒽醌与所述二价铜离子的物质的量比为1:(2-8)。
  16. 根据权利要求9至15任一项所述的气体传感材料的制备方法，其中，
    所述有机配体溶液包括1,5-二氨基-4,8-二羟基蒽醌溶液，所述金属离子溶液包括二价铜离子溶液，所述1,5-二氨基-4,8-二羟基蒽醌与所述二价铜离子的物质的量比为1:(4-6)。
  17. 根据权利要求9至16任一项所述的气体传感材料的制备方法，其中，
    所述有机配体溶液的溶剂包括甲醇、乙醇、丙酮、四氢呋喃、N,N-二甲基甲酰胺、二甲基亚砜、二氯甲烷中的一种或多种。
  18. 根据权利要求9至17任一项所述的气体传感材料的制备方法，其中，
    所述金属离子溶液包括二价铜盐溶液，所述二价铜盐包括一水合乙酸铜、五水合硫酸铜、二水合氯化铜中的至少一种。
  19. 一种气体传感器，其中，包括如权利要求8所述的气体传感材料；或包括利用如权利要求9至18任一项所述的方法制得的气体传感材料。
  20. 一种用电设备，其中，包括权利要求1-7任一项所述的电池。
PCT/CN2024/117564 2023-11-30 2024-09-06 电池、气体传感材料及其制备方法、传感器、用电设备 Pending WO2025112779A1 (zh)

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