WO2025112780A1 - 电池、气体传感材料及其制备方法、传感器和用电设备 - Google Patents

电池、气体传感材料及其制备方法、传感器和用电设备 Download PDF

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WO2025112780A1
WO2025112780A1 PCT/CN2024/117569 CN2024117569W WO2025112780A1 WO 2025112780 A1 WO2025112780 A1 WO 2025112780A1 CN 2024117569 W CN2024117569 W CN 2024117569W WO 2025112780 A1 WO2025112780 A1 WO 2025112780A1
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mxene
metal
gas
gas sensing
composite material
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English (en)
French (fr)
Inventor
吴凯
张继君
杨志
王少飞
全文静
曾敏
杨建华
胡南滔
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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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Publication of WO2025112780A1 publication Critical patent/WO2025112780A1/zh
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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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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, which can realize gas detection in an oxygen-free or low-oxygen environment, thereby realizing the detection of gas production inside the battery.
  • a technical solution adopted in this 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 an M/MXene composite material, the composite material includes a metal (M) single atom and a MXene material, or the M/MXene composite material includes a metal M in the form of a single atom and a composite with the MXene material; and/or the M/MXene composite material includes a metal (M) cluster and a MXene material, or the M/MXene composite material includes a metal M in the form of a cluster and a composite with the MXene material.
  • This gas sensing material is a chemical resistance sensing material, which relies on the change in conductivity when the gas sensing material absorbs and desorbs gas to achieve the purpose of detection, so that the gas sensing material can perform gas detection in an oxygen-free or low-oxygen environment, thereby realizing the detection of gas production inside the battery.
  • the electronic structure of metal M can serve as a reaction center for binding to gas molecules, accelerate the charge transfer rate between gas molecules and M/MXene composites, and increase the active sites for gas-solid surface reactions, thereby improving the response sensitivity of gas sensing materials, reducing the detection limit, enhancing the selectivity, and rapidly recovering the response.
  • the M/MXene composite material includes a metal (M) nitrogen-carbon compound, and the metal nitrogen-carbon compound is loaded on the surface of the MXene material, or in the M/MXene composite material, the metal M is loaded on the surface of the MXene material in the form of a metal nitrogen-carbon compound.
  • MXene metal nitrogen-carbon compound
  • the metal M can form a strong interaction with the carrier (MXene), so that the metal M can be stably fixed on the surface of the MXene material to form a stable M/MXene composite material.
  • each metal atom M in the metal nitrogen carbon compound is bonded to four nitrogen atoms.
  • the metal nitrogen carbon compound has electronic structure characteristics similar to precious metals, can form an interface confined structure with MXene, and enhance the sensing performance through the electron spillover effect, so that the composite material has a more active sensing performance, high sensitivity, good selectivity, and a simple preparation process.
  • the metal nitrogen-carbon compound includes a graphite structure, nitrogen atoms bonded to metal atoms are embedded in the graphite layer and bonded to the carbon atoms of the graphite layer, and the graphite is bonded to the surface of the MXene material.
  • the carbon atoms in the metal nitrogen-carbon compound exist in the form of graphite, nitrogen atoms bonded to metal atoms are embedded in the graphite layer and bonded to the carbon atoms of the graphite layer, and the graphite is bonded to the surface of the MXene material.
  • connection skeleton can be provided for the metal group, so that the metal group can complete the loading, and the multi-level pore structure of the graphite layer can also provide more binding sites for gas molecules, increasing the place where the gas binding reaction occurs.
  • the metal nitrogen carbon compound is doped with an X element, and X includes one or more of sulfur, phosphorus, and boron. Due to the difference in electronegativity of the doped elements, the conductivity and gas adsorption characteristics of the gas sensing material can be adjusted by doping.
  • each metal atom M in the metal nitrogen-carbon compound is bonded to four nitrogen atoms, and the doped X element replaces one or more of the four nitrogen atoms bonded to the metal atom M.
  • the metal (M) in the M/MXene composite material is embedded in the structure of the MXene material in a single atom; or in the M/MXene composite material, the metal M is embedded in the structure of the MXene material in the form of a single atom.
  • the metal M is pinned to the defect site of the MXene in a single atom state, which is conducive to the existence of the metal in a single atom state, which is not easy to agglomerate, so that the active site exists at the atomic level, can exert quantum effects, and has the characteristics of high sensitivity and high selectivity.
  • the metal M includes one or more of Fe, Co, Ni, Mn, Cu, Zn, Cr, Pd, Pt, Au, Ag, Ir, and Ru.
  • the metal M includes one or more of Fe, Co, and Ni. By selecting different metals M, the response sensitivity and selectivity of gas sensing can be adjusted.
  • the size of a single metal atom in the M/MXene composite material is less than 1 nm; and/or the size of a metal cluster in the M/MXene composite material is 1-50 nm.
  • metal single atoms and metal clusters By setting the size of metal single atoms and metal clusters within the nanoscale range, it is beneficial to increase the adsorption sites, improve the activity of the adsorption sites, increase the efficiency of binding with gas molecules, and improve the sensitivity of the gas sensing material.
  • the size of the metal single atom in the M/MXene composite material is less than 0.5 nm; and/or the size of the metal cluster in the M/MXene composite material is 10-30 nm.
  • the atomic content (at%) of the metal M element is less than or equal to 15%.
  • the atomic content (at%) of the metal M element is less than or equal to 0.001% based on the total number of atoms of the M/MXene composite material. 10%.
  • the atomic content (at%) of the M element is less than or equal to 5%.
  • the MXene material includes M'n + 1X'nTx , wherein M' is an early transition metal element, X'n is a carbon or nitrogen element, and Tx is any one of OH- , O2- , and F - groups.
  • the gas sensing material responds to one or more of CO, NO2 , NO, H2 , CH4 , H2S , ethylene, ethane, volatile organic compounds, and volatile electrolytes.
  • the gas sensing material can adaptably meet different gas detection requirements, thereby expanding the application range of the gas sensing material.
  • the volatile organic compound includes any one of methanol, formaldehyde, toluene, styrene, phenol, and benzene.
  • the gas sensing material can adaptably meet different gas detection requirements, thereby expanding the application range of the gas sensing material.
  • the volatile electrolyte includes any one of a polyether electrolyte and a polyester electrolyte.
  • the gas sensing material can adaptively meet different gas detection requirements, thereby expanding the application range of the gas sensing material.
  • the gas sensing material has a sensing response to gas in the range of -55°C to 65°C.
  • the gas sensing material can adapt to the operating temperature of most batteries, reduce the problem of gas sensing material failure caused by ambient temperature, and help the gas sensing material adapt to different working environments.
  • a gas sensing material including an M/MXene composite material
  • the composite material includes metal (M) single atoms and MXene materials, or the M/MXene composite material includes metal M in the form of single atoms and MXene materials
  • the M/MXene composite material includes metal (M) clusters and MXene materials, or the M/MXene composite material includes metal M in the form of clusters and MXene materials.
  • This gas sensing material is a chemical resistance sensing material, which relies on the change of conductivity when the gas sensing material absorbs and desorbs gas to achieve the purpose of detection, so that the gas sensing material can detect gas in an oxygen-free or low-oxygen environment, thereby realizing the detection of gas production inside the battery.
  • another technical solution adopted in this application is: to provide a method for preparing a gas sensing material, including: providing a composite of MXene and a metal organic complex, wherein the metal organic complex is a complex of metal M and an organic ligand; calcining the composite to obtain an M/MXene composite material, wherein the metal M in the M/MXene composite material is composited with the MXene material in the form of a single atom; and/or wherein the metal M in the M/MXene composite material is composited with the MXene material in the form of a cluster.
  • the gas sensing material prepared by the above method can detect gas in an oxygen-free or low-oxygen environment.
  • calcining the composite comprises: calcining at a temperature of 700-1000° C.; and/or calcining for 1-4 hours.
  • the organic components in the metal organic complex can be pyrolyzed and carbonized to form porous carbon with a graphite phase structure, and at the same time, part of the metal ions in the metal organic complex skeleton volatilize at high temperature to form defects and active sites.
  • calcining the composite comprises: calcining the composite under a protective gas atmosphere, wherein the protective gas comprises one or more of argon, hydrogen, and nitrogen.
  • the protective gas comprises one or more of argon, hydrogen, and nitrogen.
  • the composite is calcined in a doping gas atmosphere, wherein the doping gas includes one or more of ammonia and hydrogen sulfide. While providing protection for the reaction, doping elements can also be introduced to optimize the sensing performance of the gas sensing material and enhance the adaptability of the gas sensing material to different application requirements.
  • providing a composite of MXene and a metal organic complex comprises: mixing a metal organic complex solution with a MXene solution, stirring and reacting, and obtaining a composite.
  • a composite of MXene and a metal organic complex is prepared, which is a precursor of the M/MXene composite material and a prerequisite for finally obtaining the M/MXene composite material.
  • mixing the metal organic complex solution with the MXene solution includes: dropping the MXene solution into the metal organic complex solution in a stirring state; the dropping speed of the MXene solution is 1-20 seconds/drop.
  • the stirring state is conducive to the full contact between the MXene solution and the metal organic complex solution, accelerating the reaction rate; by controlling the dropping speed, the concentration of the reaction local solution can be adjusted, which is conducive to the formation of well-dispersed crystals with uniform particle size.
  • the steps before mixing the metal organic complex solution with the MXene solution, the steps include: combining the metal organic complex with a surfactant; and/or combining the MXene material with a surfactant.
  • a surfactant By combining the surfactant in the metal organic complex or MXene, it is beneficial to improve the interfacial affinity between the metal organic complex and the MXene, and promote more efficient reactions; in addition, it is beneficial to uniformly disperse the metal organic complex and the MXene in the solution, thereby facilitating the uniformity and stability of the reaction.
  • the surfactant includes hexadecyltrimethylammonium bromide.
  • hexadecyltrimethylammonium bromide as a surfactant, the combination of the metal organic complex and MXene is facilitated, and the positive ion part of the hexadecyltrimethylammonium bromide can attract the negatively charged functional groups (such as -OH, -F) on the MXene and the negative charges on the surface of the metal organic complex, thereby facilitating the improvement of the stability of the connection.
  • combining the metal organic complex with the surfactant includes: providing a metal organic complex precursor and hexadecyl trimethyl ammonium bromide; mixing the metal organic complex precursor and hexadecyl trimethyl ammonium bromide to react, and obtaining a metal organic complex combined with hexadecyl trimethyl ammonium bromide.
  • the positive ion part of the hexadecyl trimethyl ammonium bromide can attract the surface negative charge of the metal organic complex to form an adsorption layer, and the hydrophobic alkyl chain of the hexadecyl trimethyl ammonium bromide can interact with the hydrophobic region of the metal organic complex, thereby further stabilizing the adsorption layer; this combination method can help disperse and stabilize the metal organic complex and regulate its properties.
  • the metal organic complex is modified by doping, including: providing a metal organic complex precursor and a doping precursor; mixing the metal organic complex precursor and the doping precursor to obtain a doped metal organic complex.
  • another technical solution adopted by the present application is to provide a gas sensor, which includes any of the above gas sensing materials; or includes any of the above gas sensing materials prepared by the above methods.
  • gas detection can be performed in an oxygen-free or low-oxygen environment.
  • an electric device including the above battery.
  • the device has at least the same advantages as batteries.
  • FIG. 1 is a high angle annular dark field scanning transmission electron microscope (HAADF-STEM) image of a gas sensing material according to one or more embodiments;
  • HAADF-STEM high angle annular dark field scanning transmission electron microscope
  • FIG. 2 is a transmission electron microscope (TEM) image of a gas sensing material according to one or more embodiments
  • FIG3 is a high-angle annular dark field scanning transmission electron microscope energy spectrum (HAADF-STEM EDS) image of a gas sensing material according to one or more embodiments;
  • HAADF-STEM EDS high-angle annular dark field scanning transmission electron microscope energy spectrum
  • FIG4 is a synchrotron radiation X-ray absorption spectrum (XAFS) diagram of a gas sensing material according to one or more embodiments
  • FIG5 is a synchrotron X-ray absorption spectroscopy (XAFS) of a gas sensing material according to one or more embodiments
  • FIG6 is a synchrotron radiation X-ray absorption spectrum (XAFS) diagram of a gas sensing material according to one or more embodiments
  • FIG. 7 is an X-ray diffraction pattern (XRD) of a gas sensing material according to one or more embodiments
  • FIG8 is a schematic diagram of a reaction for preparing a gas sensing material according to one or more embodiments
  • FIG9 is a schematic diagram of a gas sensing performance test according to one or more embodiments.
  • FIG. 10 is a schematic diagram of gas response of a gas sensing material Ni/MXene according to one or more embodiments
  • FIG. 11 is a schematic diagram of gas response of a gas sensing material Ni/MXene according to one or more embodiments
  • FIG. 12 is a schematic diagram of gas response of a gas sensing material Ni/MXene according to one or more embodiments
  • FIG. 13 is a schematic diagram of gas response of a gas sensing material Ni/MXene according to one or more embodiments
  • FIG. 14 is a schematic diagram of gas response of a gas sensing material Fe/MXene according to one or more embodiments
  • FIG. 15 is a schematic diagram of gas response of a gas sensing material Co/MXene according to one or more embodiments
  • FIG. 16 is a schematic diagram of gas response of a gas sensing material Ni/MXene according to one or more embodiments
  • FIG17 is a schematic diagram of an exploded structure of a battery according to one or more embodiments.
  • FIG18 is a schematic diagram of an exploded structure of a battery cell according to one or more embodiments.
  • FIG. 19 is a schematic diagram of the structure of a vehicle 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.
  • Batteries are widely used in the field of new energy, mainly including electric vehicles, energy storage systems and renewable energy.
  • lithium-ion batteries are the mainstream technology. Their high energy density, long life and fast charging characteristics enable electric vehicles to achieve longer driving range and higher performance.
  • batteries are widely used in large-scale and distributed energy storage. They can balance grid loads, store renewable energy such as solar and wind energy, and release stored energy during peak hours.
  • small rechargeable batteries are also widely used in applications such as wearable devices, drones and smart homes.
  • the development of battery technology is committed to improving energy density, extending life, reducing costs, and paying attention to environmental protection. Environmental friendliness. As the demand for clean energy and sustainable development continues to grow, the application of batteries in the field of new energy will continue to expand and promote the further development of energy transformation.
  • a gas sensor can be installed inside the battery.
  • characteristic gases are generated when the battery is working or thermally runaway.
  • ethylene carbonate an electrolyte component in lithium batteries, undergoes oxidation and decomposition on the positive electrode side to produce carbon monoxide and carbon dioxide, and reduction reactions on the negative electrode side to produce carbon monoxide and methane.
  • measures can be taken at the early stage when the internal pressure of the battery exceeds the normal level to reduce the occurrence of safety accidents.
  • existing gas sensors have defects in battery gas production detection.
  • electrochemical sensors must be used in an aerobic environment because their working principle is based on reversible oxidation-reduction reactions.
  • the inside of the battery is generally oxygen-free or low in oxygen, which limits the application of such gas sensors; for example, infrared sensors do not rely on oxygen in their working process, but their detection sensitivity for low-concentration gases needs to be improved.
  • the present application designs a gas sensing material, by compounding the metal element M in the form of a single atom or a cluster with a MXene material to prepare an M/MXene composite material.
  • This gas sensing material is a chemical resistance sensing material, which relies on the change in conductivity when the gas sensing material interacts with the adsorption and desorption of gases to achieve the detection purpose, so that the gas sensing material can respond to one or more gases including carbon monoxide (CO), nitrogen dioxide ( NO2 ), nitric oxide (NO), hydrogen ( H2 ), methane ( CH4 ), hydrogen sulfide ( H2S ), ethylene, ethane, volatile organic compounds, and volatile electrolytes in an oxygen-free or low-oxygen environment.
  • CO carbon monoxide
  • NO2 nitrogen dioxide
  • NO2 nitric oxide
  • H2 hydrogen
  • CH4 methane
  • H2S hydrogen sulfide
  • ethylene ethane
  • volatile organic compounds volatile electrolytes in an oxygen-free or low-oxygen environment.
  • the present application discloses a battery, the battery includes a gas sensor, the gas sensor includes a gas sensing material, the gas sensing material is an M/MXene composite material, the metal M in the M/MXene composite material is compounded with the MXene material in the form of a single atom; and/or the metal M is compounded with the MXene material in the form of a cluster.
  • all the metal M in the M/MXene composite material may exist in the form of a single atom, or all the metal M in the M/MXene composite material may exist in the form of a cluster, or some of the metal M in the M/MXene composite material may exist in the form of a single atom, and some of the metal M may exist in the form of a cluster.
  • the gas sensing material may be a mixture of one or more of the above-mentioned multiple M/MXene composite materials.
  • MXene materials include M'n +1X'nTx , where M' is an early transition metal element, X' is a carbon or nitrogen element, and Tx is any one of a hydroxyl ( OH- ), an oxygen anion ( O2- ), and a fluoride ion ( F- ) group.
  • early transition metal elements include titanium (Ti), zirconium (Zr), vanadium (V), molybdenum (Mo), etc.
  • T x represents the surface functional group.
  • MXene materials are a class of two-dimensional inorganic compounds, composed of transition metal carbides, nitrides or carbonitrides with a thickness of several atomic layers. MXene is usually prepared by selectively etching the A layer elements with MAX phase as the precursor by solution or molten salt method. Among them, MAX phase is a class of ternary layered compounds.
  • M in MAX phase represents transition metal elements
  • A represents IIIA or IVA group elements such as aluminum (Al), silicon (Si), tin (Sn), and X represents carbon or nitrogen.
  • MXene has the advantages of high specific surface area, excellent conductivity, stable mechanical properties, etc. due to its graphene-like two-dimensional layered structure.
  • MXene can be Ti 3 C 2 T x , Ti 2 CT x , Nb 2 CT x , Ti 3 CNT x , TiVCT x , etc.
  • MXene materials as the base material of the composite material, the extremely high specific surface area and excellent conductivity characteristics of the MXene matrix, as well as the abundant active sites on the MXene surface, can be utilized to provide a wide range of binding sites for metal M; at the same time, the large number of surface functional groups of MXene materials can provide abundant active sites for gas adsorption and surface reactions.
  • Metal M is compounded with MXene materials in the form of single atoms, which means that the metal is loaded on the surface of the carrier (MXene) in the form of single atoms, or is pinned and embedded in the carrier (MXene) in the form of single atoms. It can be connected to the surface of the carrier (MXene) by bonding with heteroatoms, or it can be pinned in the defect sites of the carrier (MXene).
  • Figure 1 is a high-angle annular dark field scanning transmission electron microscope (HAADF-STEM) image of a gas sensing material according to one or more embodiments.
  • Figure 1 shows that the metal atoms exist in a monodisperse state, and the figure shows bright isolated metal single atomic points.
  • the metal component is reduced to the single-atom scale, and the size of the metal single atom can be less than 1nm; in one embodiment, the size of the metal single atom is less than 0.5nm.
  • Metal single atoms have the characteristics of maximizing atomic utilization and isolated active sites, which can increase the number of adsorption sites and increase the adsorption area, thereby improving the gas response sensitivity and reducing the response time.
  • the size of the active site is reduced to the single-atom size, which can exert a quantum effect and have the characteristics of high sensitivity and high selectivity.
  • Atomic clusters refer to relatively stable microscopic and submicroscopic aggregates composed of several or even thousands of atoms through physical or chemical bonding.
  • Metal M is compounded with MXene materials in the form of clusters, which means that the metal components in the composite material are not necessarily dispersed in single atoms, but can also be composed of multiple atoms.
  • FIG. 2 is a transmission electron microscope (TEM) image of a gas sensing material according to one or more embodiments
  • FIG. 2 shows that a plurality of metal atoms exist in a cluster state, which is specifically embodied as a nanocluster circled in the figure.
  • the metal atoms may exist in a plurality of clusters, and the sizes of the plurality of atomic clusters may vary, and the size may be 1-50 nm; for example, it may be 2 nm, 5 nm, 8 nm, 10 nm, 20 nm, 30 nm, 50 nm, etc.
  • the size of the metal clusters in the M/MXene composite material is 10-30 nm; for example, it can be 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, etc.
  • the metal atom clusters have a very high specific surface area and surface energy, making the surface atoms highly active, so that the chemical properties are extremely unstable and they are easy to combine with other atoms, and thus easy to combine with gas molecules, which can ultimately improve the sensitivity of the gas sensing material.
  • the loading amount of metal M in the composite material can also be increased.
  • M/MXene composite materials as gas sensing materials, in which metal M is compounded with MXene materials in the form of single atoms and/or clusters, the electrochemical properties of MXene materials can be improved.
  • the adjustability of the electronic structure of metal M and the exposure of active sites can serve as reaction centers for combining with gas molecules, accelerate the charge transfer rate between gas molecules and M/MXene composite materials, increase the active sites of gas-solid surface reactions, and improve the response sensitivity of gas sensing materials, reduce the detection limit, and enhance the selectivity.
  • it can realize the detection of gas production inside the battery, improve the safety performance of the battery, and extend the service life of the battery.
  • the metal M in the M/MXene composite material, is embedded in the structure of the MXene material in the form of a single atom. Specifically, the metal M may be pinned at the defect site of MXene in a single-atom state.
  • single atoms are prone to agglomeration due to their higher surface free energy.
  • single atoms can be anchored by forming a strong chemical reaction between the single atoms and the carrier.
  • defect engineering can be used to create defects on the carrier, and the defects can be used to fix metal single atoms. This is because compared with the complete carbon lattice, intrinsic defects, such as edge sites and in-plane topological defects, will cause charge localization by forming more electronic states near the Fermi level. Therefore, intrinsic defects are also considered to be an important type of anchoring point to obtain single-atom materials. Polyatomic vacancies capture transition metal atoms with larger radii and can maintain stability. Based on this, in one embodiment of the present application, defect sites can be created on MXene and then compounded with metal M so that metal M is pinned to the defect sites of MXene in a single-atom state.
  • doped heterogeneous non-metallic atoms can be used to anchor metal single atoms.
  • Heterogeneous non-metallic atoms can serve as additional coordination sites to anchor single metal atoms to achieve high loading.
  • Surface unsaturated sites on metal compounds can stabilize atoms by forming strong chemical bonds with atoms, where the type, number, and uniformity of surface unsaturated sites affect the loading of metal single atoms.
  • the different characteristics of the anchoring sites directly affect the electronic structure of the single metal site, thereby affecting the gas response performance of the single atom.
  • Heterogeneous atoms can achieve electronic structure regulation of active metal center sites, and can also significantly change the long-range atomic arrangement and electronic structure of the carrier.
  • Heterogeneous non-metallic atoms can be oxygen (O), carbon (C), nitrogen (N), sulfur (S), phosphorus (P), etc., which can be used as connecting atoms to form chemical bonds with metal single atoms to form stable metal single atom sites.
  • the metal atom can be connected to the surface of the carrier by bonding with the coordinating atoms on the carrier.
  • the metal M in the M/MXene composite material is loaded on the surface of the MXene material in the form of a metal nitrogen-carbon compound.
  • FIG. 3 is a high-angle annular dark field scanning transmission electron microscope energy spectrum (HAADF-STEM EDS) image of a gas sensing material according to one or more embodiments.
  • FIG. 4 is a synchrotron radiation X-ray absorption spectrum (XAFS) diagram of a gas sensing material according to one or more embodiments.
  • XAFS synchrotron radiation X-ray absorption spectrum
  • the composite material contains nickel (Ni), nitrogen (N), carbon (C) and titanium (Ti), and the nickel (Ni) is evenly distributed.
  • the XAFS spectrum of the Ni K edge was collected in fluorescence mode on the XAFCA beamline of the Singapore Synchrotron Light Source (SSLS), using Ni foil (Ni foil), nickel oxide (NiO), Ni nanoparticles (Ni NPs/NC), and Ni-NC reference (a known compound formed by metal M in the form of metal nitrogen carbon compound) as a reference.
  • the reference examples of Ni foil and Ni nanoparticles are to provide a reference for the absorption peak of Ni-Ni bond to prove whether there is a Ni-Ni bond in the composite material;
  • the reference example of nickel oxide (NiO) is to provide a reference for the absorption peak of Ni-O bond to prove whether there is a Ni-O bond in the composite material;
  • the reference example of Ni-NC reference is to provide a reference for the absorption peak of Ni-N/C bond to prove whether there is a Ni-N/C bond in the composite material.
  • the Ni/MXene composite material compared with Ni foil, nickel oxide and Ni nanoparticles, the Ni/MXene composite material has no absorption peak at the peak position of Ni-Ni bond and Ni-O bond, indicating that there is no Ni-Ni bond in the Ni/MXene composite material, and Ni exists in the form of a single atom; and compared with Ni-NC, the Ni/MXene composite material has an obvious absorption peak at the peak position of Ni-N bond, indicating that Ni and N are bonded in the Ni/MXene composite material to form a metal nitride, which is represented by MN x below.
  • metal M By combining metal M with nitrogen atoms to form bonds, metal M can form a strong interaction with the carrier, so metal M can be stably fixed on the surface of the MXene material to form a stable M/MXene composite material.
  • each metal atom M in the metal nitrogen-carbon compound is bonded to four nitrogen atoms respectively.
  • Figure 5 is a synchrotron radiation X-ray absorption near edge structure (XANES) spectrum of a gas sensing material according to one or more embodiments. It can be seen from Figure 5 that the valence state of Ni is between 0 and +2. This indicates that a nickel compound is formed, not in the form of a cluster (0 valence). In the nickel compound, the nickel atom loses two 4s electrons to form a Ni 2+ ion, and its electronic structure is [Ar] 3d ⁇ 8.
  • Figure 6 is a synchrotron radiation X-ray absorption spectrum (XAFS) of a gas sensing material according to one or more embodiments.
  • XAFS synchrotron radiation X-ray absorption spectrum
  • the metal nitrogen compound (MN 4 ) has the electronic structure characteristics of noble metals (Pd, Pt).
  • the active site of MN 4 forms an interface confinement structure with the substrate MXene (Ti 3 C 2 T x ), thereby forming a confinement effect between the substrates, and at the same time has a chemical sensitization and electronic sensitization sensing mechanism, and enhances the sensing performance through the electron spillover effect.
  • the electrons on the metal center can be transferred to the molecules adsorbed on the surface, so that the composite material has a more active sensing performance, high sensitivity, and good selectivity.
  • the occurrence of electron spillover effect is usually related to the electron density of the metal center, the adsorption mode of gas molecules and the interaction between metal and gas molecules. This makes metal nitrogen carbon compounds have a highly controllable electronic structure. Therefore, the gas sensing performance can be optimized and regulated by adjusting the electron density of the metal center and the adsorption mode of gas molecules, thereby improving the selectivity and sensitivity of gas sensing materials to the response gas.
  • carbon atoms in the metal nitrogen-carbon compound exist in the form of graphite, nitrogen atoms bonded to metal atoms are embedded in the graphite layer and bonded to the carbon atoms of the graphite layer, and the graphite is combined with the surface of the MXene material.
  • FIG. 7 is an X-ray diffraction image (XRD) of a gas sensing material according to one or more embodiments.
  • XRD X-ray diffraction image
  • a composite material of metal nickel (Ni) and MXene (Ti 3 C 2 T x ) is taken as an example to perform an X-ray diffraction test.
  • NC, Ni-NC, and Ni NPs/NC are used as references; wherein NC is a NC material without Ni doping, and the synthesis process is obtained by directly calcining ZIF-8 material; Ni-NC is a nickel-nitrogen atom nitrogen-carbon compound, and the synthesis process is obtained by calcining nickel nitrate + ZIF-8; Ni NPs/NC is a nickel nanoparticle/nitrogen-carbon compound, and the synthesis process is obtained by calcining nickel nitrate + ZIF-8, and the difference from Ni-NC is the different proportion of nickel nitrate.
  • graphite layers as carbon material carriers, it is possible to provide a connection skeleton for the MN 4 group, so that the MN 4 group can complete the loading and then combine with MXene through graphite. Furthermore, the multi-level pore structure of the graphite layer can also provide more binding sites for gas molecules, increasing the location for gas binding reactions to occur. In addition, graphite can improve the volume density, conductivity, corrosion resistance and mechanical processing properties of the carbon material carrier, thereby improving the conductivity of the gas sensing material.
  • the metal nitrogen-carbon compound is doped with an X element, where X includes one or more of sulfur (S), phosphorus (P), and boron (B).
  • the doped X element is a non-metallic element, and the non-metallic element can form bonds with metal M and carbon (C) atoms, which can capture atomically dispersed metal sites and make them less likely to be lost or released.
  • the electronegativity of elements such as sulfur, phosphorus, and boron is quite different from that of carbon and nitrogen, which means that their addition can introduce additional charge distribution or polarity properties, change the electronic structure of the material, and achieve the modification of single-atom performance.
  • the conductivity and gas adsorption characteristics of the material can be adjusted, thereby adjusting the response performance of gas sensing.
  • each metal atom M in the metal nitrogen-carbon compound is bonded to four nitrogen atoms respectively, and the doped X element replaces one or more of the four nitrogen atoms bonded to the metal atom M.
  • the bonding of metal complexes is similar to the role of positive and negative ions in ionic crystals: first, the role of metal and ligand is electrostatic, and the ligand is regarded as a point charge; second, the role of the ligand is to establish a negative charge potential field. Under the perturbation of the negative charge potential field, the d orbital of the metal undergoes energy level splitting; third, the metal's electrons fill the split d orbital from low to high, causing the total energy to decrease, resulting in an additional bonding effect.
  • the ligands have an effect on the electronic d orbital of the central metal atom M they surround, and the strength of the interaction between the metal atom and the ligand determines the rise and fall of different d orbitals in level, so the electronic structure and gas sensing performance of metal nitrogen-carbon compound materials can be regulated by adjusting the ligands around the center of the metal atom.
  • the doping element acts as a coordinating atom at the center of the metal atom, replacing part or all of the nitrogen atoms in MN x .
  • the structure of the central metal atom can be optimized, thereby improving the sensitivity, selectivity and stability of the sensor.
  • the metal M includes one or more of iron (Fe), cobalt (Co), nickel (Ni), manganese (Mn), copper (Cu), zinc (Zn), chromium (Cr), palladium (Pd), platinum (Pt), gold (Au), silver (Ag), iridium (Ir), and ruthenium (Ru).
  • the metal M includes one or more of Fe, Co, and Ni.
  • the element type of metal M belongs to transition metal elements. Transition metal elements have a special electronic structure, an unfilled valence layer d orbital and a high charge/radius ratio, and are easy to form stable coordination compounds with ligands. In addition, different metal types have different electronic structures and there are differences in the combination with gas molecules.
  • the metal M is dispersed in the composite material in the form of single atoms or clusters, and the metal single atoms and their local coordination environment constitute the metal single atom sites.
  • the active sites of each metal single atom may not be completely identical, and the inhomogeneity of the carrier surface will lead to inhomogeneous coordination environments around single atoms and differences in intrinsic activity.
  • the atomically dispersed metal and its adjacent coordination environment play a vital role in determining activity, selectivity, and stability.
  • the response sensitivity and selectivity of gas sensing can be regulated by selecting different metal elements.
  • a composite material may contain multiple different types of metal atoms at the same time, such as Fe and Ni. Different metals may be dispersed on a carrier in the form of single atoms or clusters; or they may form single-atom alloys, in which the non-metallic carrier is replaced by a metal support, and the active metal single atoms interact with the metal support in the form of metal-metal bonds.
  • the atomic content (at%) of the M element is less than or equal to 15%.
  • it can be 1%, 2%, 5%, 8%, 10%, 12%, 15%, etc., or a range consisting of any two of the above values, which can be 1%-2%, 2%-5%, 5%-8%, 8%-10%, 10%-12%, 12%-15%, etc.
  • the atomic content (at%) of the M element is less than or equal to 10%, such as 1%, 2%, 5%, 8%, 10%, etc., or a range consisting of any two of the above values, such as 1%-2%, 2%-5%, 5%-8%, 8%-10%, etc.
  • the atomic content (at%) of the M element is less than or equal to 5%, such as 0.1%, 1%, 2%, 5%, etc., or a range consisting of any two of the above values, such as 0.1%-2%, 1%-2%, 2%-5%, etc.
  • the atomic content of an element refers to the percentage of the number of atoms of the element in the total number of atoms in the material.
  • the atomic content of the M element refers to the percentage of the number of atoms of the M element in the total number of atoms in the M/MXene composite material.
  • M atoms are active centers that bind to gas molecules. Increasing the content of M atoms can increase the number of active adsorption sites, thereby increasing the detection sensitivity of the sensor to the target gas. As the content of M atoms increases, they are more likely to aggregate into clusters, which may reduce the sensing performance.
  • the sensitivity and selectivity of the gas sensing material can be adjusted. Depending on different application scenarios, either sensitivity or selectivity can be prioritized, and a trade-off can be made between the two to meet the requirements of specific applications.
  • the response gas of the gas sensing material includes any one of CO, NO 2 , NO, H 2 , CH 4 , H 2 S, ethylene, ethane, volatile organic compounds, and volatile electrolytes.
  • the volatile organic compound includes any one of methanol, formaldehyde, toluene, styrene, phenol, and benzene.
  • the volatile electrolyte includes any one of a polyether electrolyte and a polyester electrolyte.
  • a volatile electrolyte is an electrolyte commonly used in batteries or energy storage devices. It has high volatility and is usually an organic compound. In the event of a battery failure, the volatile electrolyte may evaporate and thermally decompose to produce gases including carbon monoxide, carbon dioxide and nitric oxide.
  • the gas sensor provided in this application can be used to detect different gases in the above-mentioned different batteries.
  • the gas sensing material has a sensing response to gas in the range of -55°C to 65°C. This is conducive to the gas sensing material adapting to different working environments and reducing the problem of gas sensing material failure caused by temperature.
  • the gas sensing material can still have a sensing response to gas at a lower temperature, indicating that the gas sensing material has a high activity and can adapt to the working environment under extremely cold conditions, which is of great significance to the safety performance of some batteries used in special environments.
  • lithium-ion batteries operate at temperatures between -20°C and 60°C, but generally, the performance of lithium batteries will decline below 0°C, and the discharge capacity will decrease accordingly, so the operating temperature at which lithium-ion batteries can fully perform is usually 0°C to 40°C; lead-acid batteries usually operate in a wider temperature range, roughly between -20°C and 50°C; lithium polymer batteries are similar to lithium-ion batteries and usually operate between -20°C and 60°C.
  • the typical operating temperature range of sodium-ion batteries is approximately between -10°C and 60°C.
  • the typical operating temperature range of lithium-sulfur batteries is usually between -20°C and 60°C. Similar to lithium-ion batteries, the performance of lithium-sulfur batteries may be limited under extreme temperature conditions.
  • gas sensing material Most of the existing other gas sensing materials can only respond to gas at temperatures of 80-90°C or even higher, and cannot be applied to battery systems.
  • the gas sensing material provided in this application has a better response effect at low temperatures and has a gas response temperature range that can match the operating temperature of most batteries.
  • gas detection can be achieved in an oxygen-free or low-oxygen environment, and the response sensitivity is high, the detection limit is low, the selectivity is strong, and the response recovery is rapid.
  • the composite of a metal single atom or cluster and a carrier can be prepared by physical methods such as atomic layer deposition and physical/chemical vapor deposition; it can also be prepared by chemical methods such as co-deposition and pyrolysis.
  • a gas sensing material including an M/MXene composite material, wherein the composite material includes metal (M) single atoms and MXene materials, or the metal M in the M/MXene composite material is composited with the MXene material in the form of single atoms; and/or the M/MXene composite material includes metal (M) clusters and MXene materials, or the metal M in the M/MXene composite material is composited with the MXene material in the form of clusters.
  • M/MXene composite material wherein the composite material includes metal (M) single atoms and MXene materials, or the metal M in the M/MXene composite material is composited with the MXene material in the form of clusters.
  • This gas sensing material is a chemical resistance sensing material, which relies on the change in conductivity when the gas sensing material absorbs and desorbs gas to achieve the purpose of detection, so that the gas sensing material can perform gas detection in an oxygen-free or low-oxygen environment, thereby realizing the detection of gas production inside the battery.
  • a method for preparing a gas sensing material comprising: providing a complex of MXene and a metal-organic complex, wherein the metal-organic complex is a complex of a metal M and an organic ligand; calcining the complex to obtain an M/MXene composite material, wherein the metal M in the M/MXene composite material is composited with the MXene material in the form of a single atom; and/or the metal M in the M/MXene composite material is composited with the MXene material in the form of a cluster.
  • Metal-organic complexes are precursors of metal single atoms and metal clusters. Precursors containing metal nodes can be used to prepare single-atom complexes by pyrolysis. During the calcination process, pyrolysis forms metal single atoms and/or metal clusters. During the high-temperature pyrolysis process, there is a strong interaction between the single atoms and the pyrolysis products to form a complex.
  • Metal-organic complexes are usually complexes formed by metal ions and organic ligands, such as metal acetates, metal nitrates, metal chlorides or organic complexes of metal-organic framework materials. During the calcination process, the metal ions will be decomposed or reduced to metal atoms or metal clusters.
  • organic ligands are molecules or ions in organic compounds, usually containing elements such as carbon, hydrogen, oxygen, and nitrogen.
  • Common organic ligands include ethylenediamine and dimethylimidazole. They can form coordination bonds with metal atoms to form metal organic complexes.
  • metal organic complexes can also provide heterogeneous non-metal atoms (carbon, nitrogen, etc.) to anchor metal single atoms and metal clusters, thereby forming stable metal atom sites.
  • the metal M in the M/MXene composite material is loaded on the surface of the MXene material in the form of a metal nitrogen-carbon compound.
  • This type of composite is hereinafter represented by an M-N-C/MXene composite material.
  • each metal atom M in the metal nitrogen-carbon compound is bonded to four nitrogen atoms respectively, and the carbon atoms in the metal nitrogen-carbon compound exist in the form of graphite.
  • the nitrogen atoms bonded to the metal atoms are embedded in the graphite layer and bonded to the carbon atoms in the graphite layer, and the graphite is bonded to the surface of the MXene material.
  • the M-N-C/MXene composite material can be prepared by calcining a composite of MXene and a metal organic complex.
  • a composite of MXene and a metal-organic complex is first prepared. Specifically, a metal-organic complex solution and a MXene solution are mixed and stirred to react to obtain a composite of MXene and a metal-organic complex.
  • the steps before mixing the metal organic complex solution with the MXene solution, the steps include: combining the metal organic complex with a surfactant; and/or combining the MXene material with a surfactant.
  • Surfactants are substances that can significantly reduce the surface tension of the target solution.
  • Surfactants have fixed hydrophilic and lipophilic groups, which can be arranged in a directional manner on the surface of the solution.
  • the molecular structure of surfactants is amphiphilic: one end is a hydrophilic group, and the other end is a hydrophobic group.
  • the hydrophilic group is often a polar group, such as carboxylic acid, sulfonic acid, sulfuric acid, amino or amine group and its salts. Hydroxyl, amide, ether bond, etc. can also be used as polar hydrophilic groups; while the hydrophobic group is often a non-polar hydrocarbon chain, such as a hydrocarbon chain with more than 8 carbon atoms.
  • Surfactants are divided into ionic surfactants (including cationic surfactants and anionic surfactants), non-ionic surfactants, amphoteric surfactants, compound surfactants, other surfactants, etc.
  • the surfactant By mixing the surfactant with at least one of the metal organic complex solutions before mixing them with the MXene solution, the surfactant is first connected to the metal organic complex or MXene.
  • the presence of the surfactant can connect the metal organic complex and MXene through the hydrophilic and lipophilic groups when the metal organic complex and MXene are mixed and reacted, acting as a bridge for the combination of the two, which is beneficial to improving the interfacial affinity between the metal organic complex and MXene and promoting more effective reactions.
  • the surfactant has the function of a dispersant, which is beneficial to the uniform dispersion of the metal organic complex and MXene in the solution, thereby facilitating the uniformity and stability of the reaction.
  • the surfactant includes hexadecyl trimethyl ammonium bromide.
  • Hexadecyl trimethyl ammonium bromide is a cationic surfactant with a hydrophilic-lipophilic balance (HLB) of 15.8.
  • HLB hydrophilic-lipophilic balance
  • This molecular structure makes CTAB both hydrophilic and lipophilic.
  • the hydrophilic group of CTAB is connected to MXene, and the lipophilic group is connected to the metal organic complex, thereby realizing the composite of the metal organic complex and MXene.
  • CTAB molecules carry a positive charge because the ammonium ions (NH 4+ ) in ammonium bromide ions carry a positive charge, which can interact with negatively charged surfaces or particles.
  • the positive ion part of CTAB can attract the negatively charged functional groups (such as -OH, -F) on MXene and the negative charges on the surface of the metal organic complex, which is beneficial to improve the stability of the connection.
  • the metal organic complex is preferably combined with a surfactant, specifically comprising: providing a metal organic complex precursor and hexadecyltrimethylammonium bromide; mixing the metal organic complex precursor and hexadecyltrimethylammonium bromide to react to obtain a metal organic complex combined with hexadecyltrimethylammonium bromide.
  • the positive ion part of CTAB can attract the negative surface charge of the metal organic framework material to form an adsorption layer, which is usually achieved through electrostatic interaction.
  • the hydrophobic alkyl chain of CTAB can interact with the hydrophobic region of the metal organic complex to further stabilize the adsorption layer. This binding mode can help disperse and stabilize the metal organic complex and regulate its properties.
  • the metal organic complex solution and the MXene solution are compounded by mixing the metal organic complex combined with hexadecyltrimethylammonium bromide with the MXene solution, stirring the mixture for reaction, and obtaining a composite.
  • surfactants play a key role. As mentioned earlier, surfactants act as a bridge between metal-organic complexes and MXene solutions, improving the interfacial affinity between metal-organic complexes and MXene and promoting more efficient reactions.
  • mixing the metal organic complex solution with the MXene solution includes: dropping the MXene solution into the metal organic complex solution in a stirring state; the dropping speed of the MXene solution is 1-20 seconds/drop.
  • the stirring state is conducive to the full contact between the MXene solution and the metal organic complex solution, accelerating the reaction rate; by controlling the dropping speed, the concentration of the reaction local solution can be adjusted, and dropwise addition can form a more uniform reaction concentration field, which is conducive to the formation of well-dispersed crystals with uniform particle size.
  • the MXene solution is dripped into the metal organic complex solution while stirring, and the dripping speed of the MXene solution is 2 seconds/drop. After the dripping is completed, stirring is continued for 24 hours. After the reaction is completed, the product is washed with methanol and vacuum dried at 60°C to obtain a complex of MXene and the metal organic complex.
  • the prepared composite of MXene and metal organic complex is calcined.
  • the composite of MXene and metal organic complex is calcined to obtain a M/MXene composite material.
  • the calcination step is the process of converting the metal organic complex precursor into a metal single atom or metal cluster complex.
  • a metal-nitrogen-carbon (M-N-C) structure can also be formed.
  • the metal organic complex precursor will undergo decomposition or reduction reactions to generate metal single atoms or metal clusters; at the same time, at high temperatures, the volatile elements in the metal organic complex precursor volatilize to form porous carbon with a graphite phase structure.
  • the metal organic complex precursor is zeolite imidazole framework-8 (ZIF-8)
  • ZIF-8 zeolite imidazole framework-8
  • the volatile zinc at high temperature is released from the structure of ZIF-8, and finally a non-metallic nitrogen-doped graphitized porous carbon material is obtained.
  • the material retains the regular rhombic dodecahedron morphology of ZIF-8, has a high nitrogen content, a high specific surface area and a multi-level pore structure.
  • FIG8 is a reaction diagram of the preparation of gas sensing materials according to one or more embodiments.
  • the metal organic complex is nickel-based zeolite imidazolate framework-8 (Ni-ZIF-8).
  • Ni-ZIF-8 nickel-based zeolite imidazolate framework-8
  • the metal organic complex Ni-ZIF-8 is first connected with the surfactant CTAB to form Ni-ZIF-8-CTAB.
  • ZIF-8 is a metal organic framework material with a network porous crystal structure.
  • CTAB wraps ZIF-8 and forms active sites on the surface of ZIF-8; then Ni-ZIF-8-CTAB is connected with Ti 3 C 2 T x through the active sites formed by CTAB, completing the self-assembly of the metal organic complex Ni-ZIF-8 and MXene Ti 3 C 2 T x . Then calcination and pyrolysis are formed to form Ni-NC/Ti 3 C 2 T x composite materials.
  • the NiN 4 structure bonds with the graphite structure formed by carbonization, as shown in the upper structure in the figure.
  • the graphite structure is composited with MXene (Ti 3 C 2 T x ).
  • the calcination temperature is 700-1000° C.; and/or the calcination time is 1-4 h.
  • the calcination temperature is 850-950°C.
  • the organic components in the metal-organic complex can undergo pyrolysis and carbonization to form porous carbon with a graphite phase structure.
  • some metal ions in the metal-organic complex skeleton volatilize at high temperatures to form defects and active sites.
  • Ni-ZIF-8 when the calcination temperature is lower than 500°C, the sample maintains the structure and morphology of ZIF-8; when the temperature reaches 600°C, ZIF-8 begins to decompose and carbonize; as the temperature rises further, Zn2 + in ZIF-8 volatilizes above 750°C, and ZIF-8 carbonizes into porous carbon with a graphite phase structure. Under oxygen-free conditions, MXene has little mass loss within this temperature range, and its structure and composition hardly change.
  • the metal M is loaded on the surface of the MXene material in the form of metal nitrogen-carbon compounds, in which the carbon atoms exist in the form of graphite, and the nitrogen atoms bonded to the metal atoms are embedded in the graphite layer and bonded to the carbon atoms of the graphite layer.
  • calcining the composite includes: calcining the composite under a protective gas atmosphere, wherein the protective gas includes one or more of argon, hydrogen, and nitrogen.
  • the protective gas is a stable gas, and its main function is to prevent oxidation reaction during calcination.
  • Argon is an inert gas with inactive chemical properties. It can be used as a protective gas to isolate the air and prevent oxidation. Nitrogen is stable and can also isolate the air and prevent oxidation. In addition to the above functions, hydrogen also has a certain reducing effect to further prevent oxidation.
  • the above protective gas can be a single gas or a mixture of two or more gases.
  • the oxidation reaction during the preparation of the gas sensing material can be reduced, which is beneficial to reducing the oxidation of MXene, protecting the activity of the active sites on the surface of the material, maintaining the normal progress of the reaction, and improving product quality.
  • the gas sensing material prepared by the above method has a confined structure of MXene and M-N-C interface, thereby forming a confinement effect between the substrates. It also has chemical sensitization and electronic sensitization sensing mechanisms, and enhances the sensing performance through the electron spillover effect.
  • the M/MXene composite material may also be doped, specifically by introducing doping elements at different process stages during the preparation of the M/MXene composite material.
  • the composite in the calcination step, may be calcined in a doping gas atmosphere to introduce doping elements through the gas atmosphere.
  • the doping gas includes one or more of ammonia and hydrogen sulfide.
  • doping gases can participate in the reaction while protecting the reaction.
  • ammonia can introduce nitrogen atoms into the metal atom ligands of the M/MXene composite material
  • hydrogen sulfide can introduce sulfur atoms. That is, the metal atom M is coordinated and bonded with the nitrogen atom or the sulfur atom, replacing one or more of the four single atoms bonded to the metal atom M, thereby optimizing the sensing performance of the gas sensing material and enhancing the adaptability of the gas sensing material to different application requirements.
  • the doping element may also be introduced at the metal organic complex stage.
  • the metal organic complex is doped and modified before the metal organic complex solution is mixed with the MXene solution.
  • the doped modified ligands can be ligands containing oxygen group elements such as O and S, such as -O, -OH, and -S. Due to the differences in the chemical properties of non-metallic elements such as N, O, and S, when they form special configurations by coordination bonding with the metal atom center, they can adjust the electrical properties of the metal center such as the spin state and d-band center, and then regulate the binding energy between the active center and the gas molecule, and finally achieve the regulation of the intrinsic activity of the gas sensing material. It can also be halogen elements such as F, Cl, Br, and I. Due to the differences in electronegativity between ligand elements, different ligands can regulate the electronic structure of the metal atom center to different degrees, and finally achieve the regulation of the responsiveness and selectivity of the gas sensing material.
  • the steps before mixing the metal organic complex solution with the MXene solution, the steps include: providing a metal organic complex precursor and a doping precursor; mixing and reacting the metal organic complex precursor and the doping precursor to obtain a doped and modified metal organic complex.
  • a doping precursor is a compound used to introduce a doping element. It can be a separate compound or a product obtained by specific treatment or modification of a metal organic complex precursor. The choice of a doping precursor depends on the desired doping element and the specific application requirements of the material.
  • Doping precursors mainly include the following: first, metal salts, such as metal nitrates, metal chlorides, metal acetates, etc., by reacting metal salts with metal organic complex precursors, the doping process can be achieved; second, organic compounds, which contain target doping elements, can be functional ligands, such as organic acids, ketones, alcohols, etc. containing specific functional groups; third, gas sources, such as the doping gas atmosphere in the calcination step described above, the doping gas is introduced into the reaction system of the metal organic complex precursor to achieve the introduction of doping elements.
  • metal salts such as metal nitrates, metal chlorides, metal acetates, etc.
  • organic compounds which contain target doping elements, can be functional ligands, such as organic acids, ketones, alcohols, etc. containing specific functional groups
  • gas sources such as the doping gas atmosphere in the calcination step described above, the doping gas is introduced into the reaction system of the metal organic complex precursor to achieve the introduction of doping elements.
  • the doping precursor is thiourea, which is an organic sulfur-containing compound with a chemical formula of CH 4 N 2 S, which can provide sulfur as a doping element.
  • thiourea is an organic sulfur-containing compound with a chemical formula of CH 4 N 2 S, which can provide sulfur as a doping element.
  • the doping precursor and the metal organic complex precursor are mixed to obtain a doped modified metal organic complex, preferably a suitable
  • the doping precursor can effectively achieve the doping purpose and realize the doping of multiple elements, which is beneficial to purposefully modify the gas sensing material and broaden the application scope of the gas sensing material.
  • the above embodiments through doping modification, can adaptively design the gas sensing material for specific application scenarios based on specific gas types and response effects, which is conducive to purposefully modifying the gas sensing material and broadening the application scope of the gas sensing material.
  • a defect vacancy anchoring method can also be used to prepare a metal single-atom composite material.
  • the lattice defects of the MXene carrier material are used to anchor the metal atom M, and the metal atom M is coordinated or bonded with the surrounding carrier atoms (generally C atoms) to become part of the lattice structure. Due to the existence of chemical bonds and the influence of the nano-confinement effect, the doped metal atom M has a high degree of stability. It may be that in the process of etching the MAX phase precursor to prepare MXene, some adjacent metal atoms in the MAX phase will fall off, thereby generating metal vacancy defects.
  • the defect has high reduction activity and can spontaneously reduce and adsorb metal ions to fix single metal atoms without adding any reducing agent, so that isolated metal atoms are stably present on the MXene carrier.
  • the metal M is embedded in the structure of the MXene material in the form of a single atom.
  • Ti 3 C 2 T x nanosheets by etching titanium aluminum carbide (Ti 3 AlC 2 ) with lithium fluoride (LiF) and hydrochloric acid (HCl) solution, the Ti-Al bond is destroyed, causing the etching of adjacent Ti atoms, resulting in the formation of Ti single vacancies or vacancy clusters.
  • This vacancy can adsorb Ni 2+ and reduce it in situ to prepare a single-atom Ni-Ti 3 C 2 T x MXene composite material.
  • the specific preparation method is detailed in the specific embodiments below.
  • 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.
  • M/MXene composite material is used as a gas sensing material.
  • the material responds to the sensing gas based on the change of surface conductivity when the gas is adsorbed and desorbed on the material surface.
  • the gas response can be achieved under anaerobic conditions.
  • a gas sensor that can respond to gas quickly and has high detection sensitivity under anaerobic conditions is prepared.
  • the gas sensor can respond to one or more gases including CO, NO 2 , NO, H 2 , CH 4 , H 2 S, ethylene, ethane, volatile organic compounds, and volatile electrolytes.
  • solution A was changed on the basis of Example 1, except that nickel nitrate hexahydrate was replaced by iron nitrate hexahydrate and cobalt nitrate hexahydrate, respectively, to prepare (Fe-N-C/MXene)-2 composite material and (Co-N-C/MXene)-3 composite material, and Fe and Co were respectively composited with MXene materials in single atom form.
  • the specific reaction conditions are detailed in Table 1, which lists the types of metal M and the existence forms of metal M in each example.
  • solution A was changed on the basis of Example 1, except that the mass of nickel nitrate hexahydrate was replaced from 50 mg to 500 mg, and a (Ni-N-C/MXene)-4 composite material was obtained, in which Ni was composited with the MXene material in the form of clusters.
  • the specific reaction conditions are detailed in Table 1.
  • Solution B was slowly added dropwise to solution A at a rate of 2 seconds per drop. The mixture was stirred for 8 hours, and then 50 mL of acetone was added. The mixture was allowed to stand overnight, washed with acetone, and dried under vacuum at 60°C to obtain a (Ni/MXene)-5 composite material in which Ni was composited with the MXene material in the form of a single atom.
  • solution A was changed on the basis of Example 1, except that 50 mg of nickel nitrate hexahydrate was replaced by 25 mg of nickel nitrate hexahydrate and 25 mg of ferric nitrate hexahydrate to obtain a (Ni-Fe-N-C/MXene)-6 composite material, in which Ni and Fe were composited with the MXene material in the form of single atoms.
  • the specific reaction conditions are detailed in Table 1.
  • 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. 9 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 (
  • Example 5 metal M is embedded in MXene in the form of single atoms, and in the examples other than Example 5, metal M is loaded on the surface of MXene material in the form of metal nitrogen-carbon compounds; in the response value column, the gas concentration tested in Examples 1-7 is 20 ppm; the response time/recovery time column is the same as above.
  • Figure 11 is a schematic diagram of the gas response of the gas sensing material Ni/MXene according to one or more embodiments
  • Figure 12 is a schematic diagram of the gas response of the gas sensing material Ni/MXene according to one or more embodiments
  • Figure 13 is a schematic diagram of the gas response of the gas sensing material Ni/MXene according to one or more embodiments.
  • Figure 11 tests the response of (Ni-N-C/MXene)-1 to CO gas of different concentrations
  • Figure 12 tests the cyclic response performance of (Ni-N-C/MXene)-1 to 1, 5, and 10 ppm CO gas
  • Figure 13 tests the response of (Ni-N-C/MXene)-1 to different gases with a concentration of 5 ppm.
  • the horizontal axis is the acquisition time and the vertical axis is the device sensitivity.
  • the response value of the (Ni-N-C/MXene)-1 composite material sensor to 50ppm carbon monoxide reached 50.2%.
  • the lowest detectable carbon monoxide concentration reached 1ppm, and the corresponding response value was 10.4%.
  • the response value of the sensor to the gas increases.
  • the response time is 40s
  • the recovery time is 120s
  • the response and recovery speed are relatively fast. Therefore, the (Ni-N-C/MXene)-1 gas sensing material provided in the present application has a high sensitivity for gas detection, a low detection limit, and a fast response recovery speed.
  • the (Ni-N-C/MXene)-1 composite material responds to 5ppm carbon monoxide, nitric oxide, nitrogen dioxide, methane, hydrogen, and ammonia, but the response values to other gases except carbon monoxide are very small. This shows that the (Ni-N-C/MXene)-1 gas sensing material provided in this application shows good selectivity for carbon monoxide.
  • Figure 14 is a schematic diagram of the gas response of the gas sensing material Fe/MXene according to one or more embodiments
  • Figure 15 is a schematic diagram of the gas response of the gas sensing material Co/MXene according to one or more embodiments
  • Figure 16 is a schematic diagram of the gas response of the gas sensing material Ni/MXene according to one or more embodiments.
  • the horizontal axis is the acquisition time
  • the vertical axis is the device sensitivity.
  • the (Ni-N-C/MXene)-1 composite material has a higher response value and a shorter response time when the concentration of the gas to be detected is the same, indicating that the gas sensing material prepared by nickel element has a higher response sensitivity among the three. Therefore, the response sensitivity of gas sensing can be adjusted by selecting different metal elements.
  • Example 1 and Example 4 (Ni-N-C/MXene)-1 composite material and (Ni-N-C/MXene)-4 composite material were prepared, and metal Ni was composited with MXene material in the form of single atoms and clusters, respectively. It can be seen that the response value of (Ni-N-C/MXene)-1 to 20ppm CO is 43.1%, while the response value of (Ni-N-C/MXene)-4 to 20ppm CO is only 5.5%. This shows that even if (Ni-N-C/MXene)-4 has more Ni atomic active sites, the Ni atoms in the form of clusters still reduce the sensing performance.
  • Example 1 and Example 5 prepared (Ni-N-C/MXene)-1 and (Ni/MXene)-5 composite materials, in which metal Ni single atoms were embedded in MXene in the form of single atoms or loaded on the surface of MXene materials in the form of metal nitrogen carbon compounds.
  • Figure 10 is a schematic diagram of the gas response of the gas sensing material Ni/MXene according to one or more embodiments. The horizontal axis is the acquisition time, and the vertical axis is the device sensitivity. It can be seen that the response value of (Ni-N-C/MXene)-1 to 20ppm CO is 43.1%, while the response value of (Ni/MXene)-5 to 20ppm CO is only 0.6%. It shows that the metal nitrogen carbon compound form optimizes the sensing performance of the gas sensing material.
  • Example 1 and Example 6 prepared (Ni-N-C/MXene)-1 and (Ni-Fe-N-C/MXene)-6 composite materials, which are metal single-atom composite materials and metal double-atom composite materials, respectively. It can be seen that the response value of (Ni-N-C/MXene)-1 to 20ppm CO is 43.1%, while the response value of (Ni-Fe-N-C/MXene)-6 to 20ppm CO is 37.5%; at the same time, the response time of (Ni-Fe-N-C/MXene)-6 is also long, but the recovery time is short.
  • Example 1 and Example 7 (Ni-NC/MXene)-1 and (Ni-NSC/MXene)-7 composite materials were prepared, and sulfur was doped in the (Ni-NSC/MXene)-7 composite material. It can be seen that the response value of (Ni-NC/MXene)-1 to 20ppm CO is 43.1%, while the response value of (Ni-NSC/MXene)-7 to 20ppm CO is 45.6%; at the same time, the recovery time of (Ni-NSC/MXene)-7 is shortened. This shows that the NiN 3 S active site has a higher reactivity than NiN 4 , so the gas sensing material can be purposefully modified by adding doping elements.
  • the gas sensing material provided by the present application has good response sensitivity and selectivity to gas. Furthermore, the gas sensing material is tested in a room temperature oxygen-free environment. Compared with the existing materials that require high temperature and oxygen to respond to gas, the conditions are milder and the application range is wider.
  • the gas sensor provided in the present application can be used to detect gas inside a battery. That is, the present application provides a battery, and the battery includes the gas sensor of the above embodiment.
  • FIG. 17 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.
  • FIG. 18 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 FIG. 18 , 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, and plastic.
  • 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 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 plate includes a negative electrode current collector and a negative electrode active layer disposed on at least one surface of the negative electrode current collector, and the negative electrode active layer includes a negative electrode active material.
  • the battery cell is an ion battery, and during the battery charging and discharging process, active ions (such as Li + , Na + ) are embedded/de-embedded in the negative electrode active material.
  • the negative electrode current collector has two surfaces opposite to each other in its thickness direction, and the negative electrode active layer may be disposed on any one or both of the two opposite surfaces of the negative electrode current collector.
  • the negative electrode current collector may be a metal foil or a composite current collector.
  • a metal foil a copper foil may be used.
  • the composite current collector may include a polymer material base layer and a metal layer formed on at least one surface of the polymer material substrate.
  • the composite current collector may be obtained by forming a metal material (copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.) on a polymer material substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
  • PP polypropylene
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PS polystyrene
  • PE polyethylene
  • 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 plate includes a negative electrode current collector and a carbonaceous coating disposed on at least one surface of the negative electrode current collector.
  • the battery cell is a metal battery, and during the battery charging and discharging process, active ions are deposited/stripped at the negative electrode plate.
  • the metal battery can be an alkali metal battery, such as a lithium metal battery, a sodium metal battery, a potassium metal battery, a zinc metal battery, and an aluminum metal battery. This type of battery can also be called a "negative electrode-free battery".
  • sodium metal is formed by depositing active ions (such as Na + ) released from the positive electrode active material onto the negative electrode current collector.
  • the provision of a carbonaceous coating facilitates more uniform metal deposition.
  • Carbonaceous materials include one or more of conductive carbon, graphite, hard carbon, and carbon nanotubes.
  • a conductive film layer may also be deposited on the negative electrode current collector.
  • alloy materials titanium-based materials, active metals (such as sodium metal), carbon-based materials deposited with metals, composite materials containing metals, alloy materials containing metals, etc.
  • the above alloy materials include but are not limited to sodium-tin alloys, sodium-germanium alloys, and sodium-antimony alloys.
  • the above titanium-based materials include but are not limited to titanium dioxide, titanates, and titanium phosphates.
  • 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 dimethyl ether, diethyl ether, tetrahydrofuran, methyltetrahydrofuran, ethylene oxide, 1,3-dioxolane, fluoroethers, DME (ethylene glycol dimethyl ether), DEE (ethylene glycol diethyl ether), DEGDME (diethylene glycol dimethyl ether), TRGDME (triethylene glycol dimethyl ether), One or more of dibutyl ether (TETRAMETHYLENE GLYCOL DIMETHYL ETHER), dipropyl ether and dibutyl 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 includes an electrolyte salt, which can be selected from at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bis(fluorosulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, lithium trifluoromethanesulfonate, lithium difluorophosphate, lithium difluorooxalatoborate, lithium dioxalatoborate, lithium difluorodioxalatophosphate and lithium tetrafluorooxalatophosphate.
  • an electrolyte salt which can be selected from at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bis(fluorosulfonyl)imide, lithium bis(trifluoromethanesulfon
  • 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 can be a fuel vehicle, a gas vehicle or a new energy vehicle.
  • the new energy vehicle can be a pure electric vehicle, a hybrid vehicle or an extended-range vehicle, etc.
  • a battery 100 is arranged inside the vehicle 1000, and the battery 100 can be arranged at the bottom, head or tail of the vehicle 1000.
  • the battery 100 can be used to power the vehicle 1000.
  • the battery 100 can be used as an operating power source for the vehicle 1000.
  • the vehicle 1000 may also include a controller 200 and a motor 300.
  • the controller 200 is used to control the battery 100 to power the motor 300, for example, for the starting, navigation and driving power requirements of the vehicle 1000.
  • the battery 100 can be used not only as an operating power source for the vehicle 1000, but also as a driving power source for the vehicle 1000, replacing or partially replacing fuel or natural gas to provide driving power for the vehicle 1000.
  • the battery can be an energy storage device.
  • the energy storage device includes an energy storage container, an energy storage cabinet, etc.

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Abstract

本申请公开了一种电池、气体传感材料及其制备方法、传感器和用电设备。其中，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M/MXene复合材料，M/MXene复合材料包括金属(M)单原子和MXene材料；和/或M/MXene复合材料中包括金属(M)团簇和MXene材料。本申请所提供的气体传感材料能够实现在无氧或低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，加快响应和恢复速度，降低气体的检出限。

Description

电池、气体传感材料及其制备方法、传感器和用电设备
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202311644359.8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、传感器和用电设备。
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爆炸、火灾等安全问题。通过检测电池内的气体情况，能够及时预警。现有气体传感器的传感原理一般需要氧气，限制了其在无氧条件下检测气体的应用。但是电池单体内大多为无氧或低氧环境，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、传感器和用电设备，能够实现在无氧或低氧环境下进行气体检测，从而实现对电池内部产气的检测。
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M/MXene复合材料，复合材料中包括金属(M)单原子和MXene材料，或者说M/MXene复合材料中金属M以单原子的形式与MXene材料复合；和/或M/MXene复合材料中包括金属(M)团簇和MXene材料，或者说M/MXene复合材料中金属M以团簇的形式与MXene材料复合。这种气体传感材料是一种化学电阻传感材料，依靠气体传感材料吸脱附气体时电导率的变化来实现检测目的，使得气体传感材料能够在无氧或低氧环境下进行气体检测，从而实现电池内部产气的检测。
进一步地，由于金属M电子结构的可调性和活性位点的暴露，因此能够作为与气体分子结合的反应中心，加快气体分子与M/MXene复合材料之间的电荷转移速率，增加气固表面反应的活性位点，使得气体传感材料的响应灵敏度提高，检出限降低，选择性增强，响应恢复迅速。
在一实施方式中，M/MXene复合材料中包括金属(M)氮碳化合物，所述金属氮碳化合物负载于MXene材料的表面，或者说M/MXene复合材料中金属M以金属氮碳化合物的形式负载于MXene材料的表面。通过这种设置，金属M能够与载体(MXene)之间形成强相互作用，因此金属M能够稳定固定在MXene材料的表面，形成稳定的M/MXene复合材料。
在一实施方式中，金属氮碳化合物中每个金属原子M分别与四个氮原子键合。通过这种设置，金属氮碳化合物具有类贵金属的电子结构特征，能够与MXene形成界面限域结构，通过电子溢出效应增强传感性能，使得复合材料具有更高活性的传感性能，灵敏度高，选择性好，且制备过程简单。
在一实施方式中，所述金属氮碳化合物中包括石墨结构，键合有金属原子的氮原子嵌合在石墨层中，并与所述石墨层的碳原子键合，所述石墨结合在所述MXene材料表面。或者说金属氮碳化合物中碳原子以石墨的形式存在，键合有金属原子的氮原子嵌合在石墨层中，并与石墨层的碳原子键合，石墨结合在MXene材料表面。通过以石墨层作为碳材料载体，能够为金属基团提供连接骨架，使得金属基团能够完成负载，石墨层的多级孔结构也能为气体分子提供更多的结合位点，增加气体结合反应发生的场所。
在一实施方式中，金属氮碳化合物中掺杂有X元素，X包括硫、磷、硼中的一种或多种。由于掺杂元素电负性差异，通过掺杂可以调节气体传感材料的电导率和气体吸附特性。
在一实施方式中，金属氮碳化合物中每个金属原子M分别与四个氮原子键合，所掺杂的X元素替换与金属原子M键合的四个氮原子中的一个或多个。通过这种设置，能够优化中心金属原子的结构，从而提高传感器的灵敏度、选择性和稳定性。
在一实施方式中，M/MXene复合材料中所述金属(M)单原子嵌入MXene材料的结构中；或者说M/MXene复合材料中金属M以单原子的形式嵌入MXene材料的结构中。通过这种设置，金属M以单原子的状态钉扎在MXene的缺陷位点，有利于金属以单原子的状态存在，不易团聚，使活性位点存在于原子级，可以发挥量子效应，具备高灵敏，高选择性的特征。
在一实施方式中，金属M包括Fe、Co、Ni、Mn、Cu、Zn、Cr、Pd、Pt、Au、Ag、Ir、Ru中的一种或多种。通过选择不同的金属M，能够调控气体传感的响应灵敏度和选择性。
在一实施方式中，金属M包括Fe、Co、Ni中的一种或多种。通过选择不同的金属M，能够调控气体传感的响应灵敏度和选择性。
在一实施方式中，M/MXene复合材料中金属单原子的尺寸小于1nm；和/或M/MXene复合材料中金属团簇的尺寸为1-50nm。
通过设置金属单原子和金属团簇的尺寸在纳米尺度范围内，有利于增加吸附位点，提高吸附位点活性，提高与气体分子结合的效率，提高气体传感材料的灵敏度。
在一实施方式中，M/MXene复合材料中金属单原子的尺寸小于0.5nm；和/或M/MXene复合材料中金属团簇的尺寸为10-30nm。通过设置金属单原子和金属团簇的尺寸在纳米尺度范围内，有利于增加吸附位点，提高吸附位点活性，提高与气体分子结合的效率，提高气体传感材料的灵敏度。
在一实施方式中，基于M/MXene复合材料的总原子个数，金属M元素的原子含量(at％)小于或等于15％。通过对M元素的原子含量进行选择，可以对气体传感材料的灵敏度和选择性进行调整，根据不同的应用场景，以灵敏度优先或者以选择性优先，在二者之间进行权衡，以满足特定应用的要求。
在一实施方式中，基于M/MXene复合材料的总原子个数，金属M元素的原子含量(at％)小于或等于 10％。通过对M元素的原子含量进行选择，可以对气体传感材料的灵敏度和选择性进行调整，根据不同的应用场景，以灵敏度优先或者以选择性优先，在二者之间进行权衡，以满足特定应用的要求。
在一实施方式中，基于M/MXene复合材料的总原子个数，M元素的原子含量(at％)小于或等于5％。通过对M元素的原子含量进行选择，可以对气体传感材料的灵敏度和选择性进行调整，根据不同的应用场景，以灵敏度优先或者以选择性优先，在二者之间进行权衡，以满足特定应用的要求。
在一实施方式中，MXene材料包括M’n+1X’nTx，其中M’为早期过渡金属元素，X’n为碳或氮元素，Tx为OH-、O2-、F-基团中的任一种。通过选用MXene材料作为复合材料的基材，能够为金属M提供广阔的结合位点，同时MXene材料的大量表面官能团能够为气体吸附和表面反应提供丰富的活性位点。
在一实施方式中，气体传感材料的响应气体包括CO、NO2、NO、H2、CH4、H2S、乙烯、乙烷、挥发性有机化合物、挥发性电解液中的一种或多种。通过响应上述气体，使得气体传感材料能够适应性地满足不同的气体检测需求，从而扩大了气体传感材料的应用范围。
在一实施方式中，挥发性有机化合物包括甲醇、甲醛、甲苯、苯乙烯、苯酚、苯中的任一种。通过响应上述气体，使得气体传感材料能够适应性地满足不同的气体检测需求，从而扩大了气体传感材料的应用范围。
在一实施方式中，挥发性电解液包括聚醚类电解液、聚酯类电解液中的任一种。通过响应上述气体，使得气体传感材料能够适应性地满足不同的气体检测需求，从而扩大了气体传感材料的应用范围。
在一实施方式中，气体传感材料在-55℃至65℃范围内对气体有传感响应。在此情况下，气体传感材料能够适应大多数电池的工作温度，减少由于环境温度引起的气体传感材料失效的问题，有利于气体传感材料适应不同的工作环境。
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，包括M/MXene复合材料，复合材料中包括金属(M)单原子和MXene材料，或者说M/MXene复合材料中金属M以单原子的形式与MXene材料复合；和/或M/MXene复合材料中包括金属(M)团簇和MXene材料，或者说M/MXene复合材料中金属M以团簇的形式与MXene材料复合。这种气体传感材料是一种化学电阻传感材料，依靠气体传感材料吸脱附气体时电导率的变化来实现检测目的，使得气体传感材料能够在无氧或低氧环境下进行气体检测，从而实现电池内部产气的检测。
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，包括：提供MXene与金属有机配合物的复合物，金属有机配合物为金属M与有机配体的配合物；对复合物进行煅烧，得到M/MXene复合材料，M/MXene复合材料中金属M以单原子的形式与MXene材料复合；和/或M/MXene复合材料中金属M以团簇的形式与MXene材料复合。通过上述方法所制备的气体传感材料，能够在无氧或低氧环境下进行气体检测。
在一实施方式中，对复合物进行煅烧包括：煅烧的温度为700-1000℃；和/或煅烧的时间为1-4h。在该温度和时间范围内，金属有机配合物中的有机物成分可以发生热解炭化形成具有石墨相结构的多孔碳，同时金属有机配合物骨架中的部分金属离子在高温下挥发，形成缺陷和活性位点。
在一实施方式中，对复合物进行煅烧包括：在保护气体氛围下对复合物进行煅烧，保护气体包括氩气、氢气、氮气中的一种或多种。通过在煅烧步骤中引入保护气体，有利于减少反应过程中的氧化反应，有利于保护材料表面活性位点的活性，提高产品质量。
在一实施方式中，在掺杂气体氛围下对复合物进行煅烧，掺杂气体包括氨气、硫化氢中的一种或多种。在给反应提供保护的同时还可以引入掺杂元素，以此来优化气体传感材料的传感性能，增强气体传感材料对不同应用需求的适应性。
在一实施方式中，提供MXene与金属有机配合物的复合物包括：将金属有机配合物溶液与MXene溶液混合，搅拌反应，得到复合物。通过上述反应，制备得到了MXene与金属有机配合物的复合物，这是M/MXene复合材料的前驱体，是最终得到M/MXene复合材料的前提。
在一实施方式中，将金属有机配合物溶液与MXene溶液混合包括：将MXene溶液滴加入处于搅拌状态的金属有机配合物溶液中；MXene溶液的滴加速度为1-20秒/滴。搅拌状态有利于MXene溶液与金属有机配合物溶液充分接触，加快反应速率；通过控制滴加速度，能够调整反应局部溶液浓度，有利于形成分散良好，粒径均匀的晶体。
在一实施方式中，将金属有机配合物溶液与MXene溶液混合之前包括：将金属有机配合物与表面活性剂结合；和/或将MXene材料与表面活性剂结合。通过在金属有机配合物或MXene中结合表面活性剂，有利于改善金属有机配合物和MXene之间的界面亲和性，促进更有效的反应；此外，有利于金属有机配合物和MXene在溶液中的均匀分散，从而有利于反应的均匀性和稳定性。
在一实施方式中，表面活性剂包括十六烷基三甲基溴化铵。通过采用十六烷基三甲基溴化铵作为表面活性剂，有利于金属有机配合物和MXene的结合，同时十六烷基三甲基溴化铵的正离子部分能和MXene上的负电荷官能团(如-OH、-F)和金属有机配合物表面的负电荷相互吸引，从而有利于提高连接的稳定性。
在一实施方式中，将金属有机配合物与表面活性剂结合包括：提供金属有机配合物前驱体和十六烷基三甲基溴化铵；将金属有机配合物前驱体和十六烷基三甲基溴化铵混合反应，得到结合有十六烷基三甲基溴化铵的金属有机配合物。十六烷基三甲基溴化铵的正离子部分可以与金属有机配合物的表面负电荷相互吸引，形成吸附层，十六烷基三甲基溴化铵的疏水烷基链可以与金属有机配合物的疏水区域相互作用，从而进一步稳定吸附层；这种结合方式可以帮助分散和稳定金属有机配合物，并调控其性质。
在一实施方式中，对金属有机配合物进行掺杂改性包括：提供金属有机配合物前驱体和掺杂前驱体；将金属有机配合物前驱体和掺杂前驱体混合反应，得到掺杂改性的金属有机配合物。通过这种设置，能够有效实现掺杂目的，实现多种元素的掺杂，进而目的性地对气体传感材料进行改性，拓宽气体传感材料的应用范围。
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，该气体传感器包括上述任一项的气体传感材料；或包括上述任一项方法制得的气体传感材料。通过上述设置，能够在无氧或低氧环境下进行气体检测。
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为根据一个或多个实施例的气体传感材料的高角环形暗场扫描透射电子显微镜(HAADF-STEM)图像；
图2为根据一个或多个实施例的气体传感材料的透射电子显微镜(TEM)图像；
图3为根据一个或多个实施例的气体传感材料的高角环形暗场扫描透射电子显微镜的能谱图(HAADF-STEM EDS)图像；
图4为根据一个或多个实施例的气体传感材料的同步辐射X射线吸收谱(XAFS)图；
图5为根据一个或多个实施例的气体传感材料的同步辐射X射线吸收谱(XAFS)；
图6为根据一个或多个实施例的气体传感材料的同步辐射X射线吸收谱(XAFS)图；
图7为根据一个或多个实施例的气体传感材料的X射线衍射图像(XRD)；
图8为根据一个或多个实施例的气体传感材料制备的反应示意图；
图9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10为根据一个或多个实施例的气体传感材料Ni/MXene的气体响应示意图；
图11为根据一个或多个实施例的气体传感材料Ni/MXene的气体响应示意图；
图12为根据一个或多个实施例的气体传感材料Ni/MXene的气体响应示意图；
图13为根据一个或多个实施例的气体传感材料Ni/MXene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Fe/MXene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Co/MXene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Ni/MXene的气体响应示意图；
图17根据一个或多个实施例的电池的分解结构示意图；
图18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19为根据一个或多个实施例的车辆的结构示意图。
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。
电池在新能源领域的应用非常广泛，主要包括电动汽车、储能系统和可再生能源。在电动汽车领域，锂离子电池是主流技术，其高能量密度、长寿命和快速充电特性使电动汽车实现了更长的续航里程和更高的性能。在储能系统方面，电池被广泛用于大规模和分布式能源存储，它们可以平衡电网负载、储存太阳能和风能等可再生能源，并在高峰期释放储存的能量。此外，小型充电式电池还在可穿戴设备、无人机和智能家居等应用中得到广泛采用。电池技术的发展致力于提高能量密度、延长寿命、降低成本，并关注环 境友好性。随着对清洁能源和可持续发展的需求不断增长，电池在新能源领域的应用将继续扩大，并推动能源转型的进一步发展。
随着电池的充放电过程，一些副反应会产生气体，电池产生的气体若不及时排出，就会导致电池内压升高，超过正常水平。内压过高会对电池的性能及外观产生负面影响，例如，严重时对电池的性能及外观产生破坏性影响，如漏液、鼓包，电池内阻增大，放电时间及循环寿命变短等。此外，电池在使用过程中存在一些非正常操作，包括过充、过放、内部故障等，在这种情况下，电池内部的化学反应可能不受控制，并伴随着气体的剧烈释放，甚至引发电池热失控。电池热失控是指由各种诱因引发的链式反应现象，热失控散发出的大量热量和有害气体会引起电池着火和爆炸。
为了及时监测电池的产气，研究发现，可以在电池内部安装气体传感器。具体来说，电池工作或热失控时会产生特征气体，例如锂电池中的电解液成分碳酸乙烯酯，在正极侧发生氧化分解会产生一氧化碳和二氧化碳，在负极侧发生还原反应会产生一氧化碳和甲烷，通过对超过浓度阈值的特征气体进行检测并及时发出警报，能够在电池内压超过正常水平初期采取措施，减少安全事故的发生。然而，现有的气体传感器在电池产气检测方面存在缺陷，例如电化学型传感器，由于其工作原理是基于可逆的氧化-还原反应，因此必须在有氧环境下使用，而在电池气体检测的实际场景中，电池内部一般为无氧或低氧，限制这种气体传感器的应用；又比如红外型传感器，它的工作过程不依赖氧气，但是对低浓度气体的检测灵敏度有待提高。
基于以上考虑，为了解决电池中产气监测依赖氧气以及低浓度气体检测灵敏低的问题，本申请设计了一种气体传感材料，通过将金属元素M以单原子或者团簇的形式与MXene材料复合，制备得到M/MXene复合材料，这种气体传感材料是一种化学电阻传感材料，依靠气体传感材料吸脱附气体相互作用时电导率的变化来实现检测目的，使得气体传感材料能够在无氧或低氧环境下响应包括一氧化碳(CO)、二氧化氮(NO2)、一氧化氮(NO)、氢气(H2)、甲烷(CH4)、硫化氢(H2S)、乙烯、乙烷、挥发性有机化合物、挥发性电解液中的一种或多种气体。
根据本申请的一些实施例，本申请公开了一种电池，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，该气体传感材料是一种M/MXene复合材料，M/MXene复合材料中金属M以单原子的形式与MXene材料复合；和/或金属M以团簇的形式与MXene材料复合。即可以是M/MXene复合材料中所有金属M都以单原子的形式存在，也可以是M/MXene复合材料中所有金属M都以团簇的形式存在，还可以是M/MXene复合材料中部分金属M以单原子的形式存在，部分金属M以团簇的形式存在。气体传感材料可以是上述多种M/MXene复合材料中的一种或多种混合。
其中，MXene材料包括M’n+1X’nTx，其中M’为早期过渡金属元素，X’为碳或氮元素，Tx为羟基(OH-)、氧负离子(O2-)、氟离子(F-)基团中的任一种。
其中，n＝1-3，早期过渡金属元素包括钛(Ti)、锆(Zr)、钒(V)、钼(Mo)等，Tx代表表面官能团。MXene材料是一类二维无机化合物，由几个原子层厚度的过渡金属碳化物、氮化物或碳氮化物构成。MXene通常以MAX相为前驱体，经过溶液或熔盐法选择性刻蚀A层元素制备而成，其中MAX相是一类三元层状化合物，MAX相中的M代表过渡金属元素，A代表铝(Al)、硅(Si)、锡(Sn)等IIIA或IVA族元素，X代表碳或氮。MXene因具有类石墨烯二维层状结构，因此表现出比表面积高、导电性优良、机械性能稳定等优点。MXene可以是Ti3C2Tx、Ti2CTx、Nb2CTx、Ti3CNTx、TiVCTx等。
通过选用MXene材料作为复合材料的基材，能够利用MXene基体极高的比表面积和优异的导电性特征，以及MXene表面丰富的活性位点，为金属M提供广阔的结合位点；同时MXene材料的大量表面官能团能够为气体吸附和表面反应提供丰富的活性位点。
金属M以单原子的形式与MXene材料复合是指金属以单个原子的形式负载于载体(MXene)表面，或者以单个原子的形式钉扎嵌入载体(MXene)内部。可以是通过与异原子键合方式联接在载体(MXene)表面，也可以是钉扎在载体(MXene)的缺陷位点。
请参阅图1，图1为根据一个或多个实施例的气体传感材料的高角环形暗场扫描透射电子显微镜(HAADF-STEM)图像。图1中示出金属原子以单分散的状态存在，图中显示有明亮孤立的金属单原子点。该复合材料中，金属组分缩小到单原子尺度，金属单原子的尺寸可小于1nm；在一实施方式中，金属单原子的尺寸小于0.5nm。金属单原子具有原子利用率最大化和活性位点孤立的特点，能够增多吸附位点，增大吸附面积，进而提高气体响应敏感度、降低响应时间。进一步地，活性位点尺寸缩小到单原子尺寸，可以发挥量子效应，具备高灵敏，高选择性的特征。
原子团簇指的是由几个乃至上千个原子通过物理或化学结合方式组成的相对稳定的微观和亚微观聚集体。金属M以团簇的形式与MXene材料复合是指在复合材料中金属组分不一定都是单原子分散，也可以是多个原子组成原子簇。
请参阅图2，图2为根据一个或多个实施例的气体传感材料的透射电子显微镜(TEM)图像，图2中示出多个金属原子以团簇状态存在，具体体现为图中圈出来的纳米簇。金属原子可以以多个簇群存在，多个原子团簇的大小各异，其尺寸可为1-50nm；例如，可以是2nm、5nm、8nm、10nm、20nm、30nm、50nm等。
在一实施方式中，M/MXene复合材料中金属团簇的尺寸为10-30nm；例如，可以是10nm、15nm、20nm、25nm、30nm等。
通过这种方式，使得金属原子团簇具有非常高的比表面积和表面能，使得表面原子具有很高的活性，因此化学性质极不稳定，很容易与其他原子结合，从而容易与气体分子结合，最终能够提高气体传感材料的灵敏度。同时，因为原子团簇，还能够提高复合材料中金属M的负载量。
通过将M/MXene复合材料作为气体传感材料，在M/MXene复合材料中金属M以单原子和/或团簇的形式与MXene材料复合，能够改善MXene材料的电化学性能，同时金属M电子结构的可调性和活性位点的暴露，能够作为与气体分子结合的反应中心，加快气体分子与M/MXene复合材料之间的电荷转移速率，增加气固表面反应的活性位点，使得气体传感材料的响应灵敏度提高，检出限降低，选择性增强，应用于电池，能够实现对电池内部产气的检测，提高电池的安全性能，延长电池的使用寿命。
根据本申请的一些实施例，M/MXene复合材料中金属M以单原子的形式嵌入MXene材料的结构中。 具体地，可以是金属M以单原子的状态钉扎在MXene的缺陷位点。
其中，单原子由于较高的表面自由能，容易团聚。为了克服单原子团聚的倾向，可以通过在单原子与载体之间形成强的化学作用的方式来锚定单原子。一方面，可以利用缺陷工程在载体上制造缺陷，利用缺陷来固定金属单原子。这是因为与完整的碳晶格相比，本征缺陷，比如边缘位点和面内拓扑缺陷会通过在费米能级附近形成更多的电子态而导致电荷局域化。因此，本征缺陷也被认为是一类重要的锚定位点来获得单原子材料。多原子空位捕获具备更大半径的过渡金属原子，并能够维持稳定。基于此，本申请的一实施方式中，可以在MXene上制造缺陷位点，然后与金属M复合，以使金属M以单原子的状态钉扎在MXene的缺陷位点。
另一方面，可以利用掺杂的异质非金属原子来锚定金属单原子。异质非金属原子可以作为额外的配位位点来锚定单金属原子，以实现高负载量。金属化合物上的表面不饱和位点可以通过与原子间形成强的化合键来稳定原子，其中表面不饱和位点类型、数量、均匀性等影响金属单原子的负载量。锚定位点的不同特性直接影响单金属位点的电子结构，从而对单原子的气体响应性能产生影响。
异质原子可以实现对活性金属中心位点的电子结构调控，同时也可明显改变载体的长程原子排布和电子结构。异质非金属原子可以是氧(O)、碳(C)、氮(N)、硫(S)、磷(P)等，其可以作为连接原子，与金属单原子形成化学键，形成稳定的金属单原子位点。基于此，本申请的一实施方式中，可以是金属原子通过与载体上的配位原子键合的方式连接在载体表面。根据本申请的一些实施例，M/MXene复合材料中金属M以金属氮碳化合物的形式负载于MXene材料的表面。
请结合参阅图3和图4，图3为根据一个或多个实施例的气体传感材料的高角环形暗场扫描透射电子显微镜的能谱(HAADF-STEM EDS)图像。图4为根据一个或多个实施例的气体传感材料的同步辐射X射线吸收谱(XAFS)图。该实施方式中，以金属镍(Ni)与MXene(Ti3C2Tx)的复合材料为例，利用JEOLARM 200F仪器，在200kV条件下拍摄能谱图。从图3所示的能谱图中可以看出，复合材料中包含有镍元素(Ni)、氮元素(N)、碳元素(C)和钛元素(Ti)，且镍元素(Ni)分布均匀。进一步地，在新加坡同步加速器光源(SSLS)的XAFCA光束线上以荧光模式进行了Ni K边缘的XAFS光谱采集，使用Ni箔(Ni foil)、氧化镍(NiO)、Ni纳米粒子(Ni NPs/N-C)、Ni-N-C参比(已知的金属M以金属氮碳化合物的形式形成的化合物)作为参考。其中，Ni箔(Ni foil)、Ni纳米粒子(Ni NPs/N-C)的参考例是为了提供Ni-Ni键吸收峰的参考，以证明复合材料中是否存在Ni-Ni键；氧化镍(NiO)的参考例是为了提供Ni-O键吸收峰的参考，以证明复合材料中是否存在Ni-O键；Ni-N-C参比的参考例是为了提供Ni-N/C键吸收峰的参考，以证明复合材料中是否存在Ni-N/C键。从图4中可以看到，与Ni箔、氧化镍和Ni纳米粒子相比，在Ni-Ni键和Ni-O键的峰位置，Ni/MXene复合材料没有吸收峰，说明Ni/MXene复合材料中不存在Ni-Ni键，Ni以单原子形式存在；而与Ni-N-C相比，Ni/MXene复合材料在Ni-N键的峰位置有明显的吸收峰，说明Ni/MXene复合材料中Ni和N成键，形成有金属氮化物，下文用MNx表示。
通过金属M与氮原子结合成键，金属M能够与载体之间形成强相互作用，因此金属M能够稳定固定在MXene材料的表面，形成稳定的M/MXene复合材料。
根据本申请的一些实施例，金属氮碳化合物中每个金属原子M分别与四个氮原子键合。
请结合参阅图3至图6，图5为根据一个或多个实施例的气体传感材料的同步辐射X射线吸收近边结构(XANES)谱图。从图5中可以看出Ni的价态在0至+2之间。说明形成了镍化合物，不是以团簇(0价)的形式存在，镍化合物中，镍原子会失去两个4s电子，形成Ni2+离子，其电子结构为[Ar]3d^8。图6为根据一个或多个实施例的气体传感材料的同步辐射X射线吸收谱(XAFS)图。从图6中的Ni和N成键的吸收峰，可以看出Ni与N的配位数为4，即每个金属原子M分别与四个氮原子键合，下文用MN4表示。同时，根据图6中的化学结构对Ni-N-C/Ti3C2Tx的XAFS谱图进行了理论拟合，而实际测试结果与理论拟合结果重合，证明了复合材料中Ni的构型如图6中的化学结构所示，每个Ni分别与四个单原子键合。不同原子数和配位结构环境能够诱导金属活性位点发生电子结构的改变，从而带来气体传感响应性和选择性上的差异。
该实施方式中，金属氮化合物(MN4)具有类贵金属(Pd、Pt)的电子结构特征，通过类铂电子结构，MN4活性位点与基底MXene(Ti3C2Tx)形成界面限域结构，进而在基底之间形成限域效应，同时具备化学敏化、电子敏化的传感机制，并通过电子溢出效应(spill-over effect)来增强传感性能。具体地，在电子溢出效应中，金属中心上的电子可以转移到吸附在表面上的分子上，使得复合材料具有更高活性的传感性能，灵敏度高，选择性好。
电子溢出效应的发生通常与金属中心的电子密度、气体分子的吸附方式以及金属-气体分子之间的相互作用有关。使得金属氮碳化合物具有高度可调控的电子结构，因此可以通过调整金属中心的电子密度和气体分子的吸附方式来优化调控气体传感性能，提高气体传感材料对响应气体的选择性和灵敏性。
根据本申请的一些实施例，金属氮碳化合物中碳原子以石墨的形式存在，键合有金属原子的氮原子嵌合在石墨层中，并与石墨层的碳原子键合，石墨结合在MXene材料表面。
请参阅图7，图7为根据一个或多个实施例的气体传感材料的X射线衍射图像(XRD)。该实施方式中，以金属镍(Ni)与MXene(Ti3C2Tx)的复合材料为例，进行X射线衍射测试。使用N-C、Ni-N-C、Ni NPs/N-C为参考；其中，N-C是没有Ni掺杂的N-C材料，合成过程是ZIF-8材料直接煅烧得到的；Ni-N-C是镍氮原子氮碳化合物，合成过程是硝酸镍+ZIF-8煅烧得到的；Ni NPs/N-C是镍纳米颗粒/氮碳化合物，合成过程是硝酸镍+ZIF-8煅烧得到的，和Ni-N-C的区别是硝酸镍的比例不同。
从图7可以看出Ni/MXene复合材料的谱图中包括2θ＝6.2°左右的Ti3C2Tx的特征衍射峰，2θ＝26.4°左右出现了石墨的特征衍射峰。
通过以石墨层作为碳材料载体，能够为MN4基团提供连接骨架，使得MN4基团能够完成负载，再通过石墨与MXene结合。进一步地，石墨层的多级孔结构也能为气体分子提供更多的结合位点，增加气体结合反应发生的场所。此外，石墨能够提升碳材料载体的体积密度、导电率、抗腐蚀性能及机械加工性能，从而使得气体传感材料的导电性能得到改善。
根据本申请的一些实施例，金属氮碳化合物中掺杂有X元素，X包括硫(S)、磷(P)、硼(B)中的一种或多种。
掺杂的X元素是非金属元素，并且该非金属元素能够与金属M和碳(C)原子配位成键，可以捕获原子级分散的金属位点，使其不容易失去或释放。硫、磷、硼等元素的电负性与碳和氮之间的电负性差异较大，这意味着它们的加入可以引入额外的电荷分布或极性性质，改变材料的电子结构，实现对单原子性能的修饰，此外由于电负性的差异，可以调节材料的电导率和气体吸附特性，进而调整气体传感的响应性能。
进一步地，金属氮碳化合物中每个金属原子M分别与四个氮原子键合，所掺杂的X元素替换与金属原子M键合的四个氮原子中的一个或多个。
根据配体场理论，金属配合物的成键类似于离子晶体中正负离子的作用：一是金属与配体的作用为静电作用，配体视为点电荷；二是配体的作用是建立一个负电荷势场，在负电荷势场的微扰下，金属的d轨道发生能级分裂；三是金属的电子从低到高填充分裂后的d轨道，使总能量下降，产生附加成键效应。因此配体对它们所包围的中心金属原子M的电子d轨道有影响，金属原子与配体相互作用的强度决定了不同d轨道在水平上的升降，所以可以通过调节金属原子中心周围的配体来调控金属氮碳化合物材料的电子结构和气体传感性能。
掺杂元素作为金属原子中心的配位原子取代了MNx中部分或全部氮原子的位置，通过构建不同的配体类型，能够优化中心金属原子的结构，从而提高传感器的灵敏度、选择性和稳定性。
根据本申请的一些实施例，金属M包括铁(Fe)、钴(Co)、镍(Ni)、锰(Mn)、铜(Cu)、锌(Zn)、铬(Cr)、钯(Pd)、铂(Pt)、金(Au)、银(Ag)、铱(Ir)、钌(Ru)中的一种或多种。
在一实施方式中，金属M包括Fe、Co、Ni中的一种或多种。
金属M的元素种类属于过渡金属元素，过渡金属元素具有特殊的电子结构，具有未充满的价层d轨道和较高的电荷/半径比，容易与配位体形成稳定的配位化合物。此外，不同的金属种类具有不同的电子结构，在与气体分子的结合上存在差异。
其中，金属M以单原子或团簇的方式分散在复合材料中，金属单原子及其局部配位环境构成金属单原子位。每个金属单原子的活性位未必完全等同，载体表面的不均匀性等会导致单原子周围的配位环境不均一和本征活性的差异。原子分散的金属及其邻近的配位环境在确定活性、选择性和稳定性方面起着至关重要的作用。可以通过选择不同的金属元素来调控气体传感的响应灵敏度和选择性。
在一实施方式中，一种复合材料中可以同时含有多个不同种类的金属原子，例如同时含有Fe和Ni等。不同的金属可以分别以单原子或团簇的方式分散在载体上；也可以形成单原子合金，单原子合金中的非金属载体被金属支撑所取代，活性金属单原子以金属-金属键的形式与金属支撑相互作用。
根据本申请的一些实施例，基于M/MXene复合材料的总原子个数，M元素的原子含量(at％)小于或等于15％。例如可以是1％、2％、5％、8％、10％、12％、15％等，或者是上述任意两个数值组成的范围，可以是1％-2％、2％-5％、5％-8％、8％-10％、10％-12％、12％-15％等。
在一实施方式中，M元素的原子含量(at％)小于或等于10％。例如可以是1％、2％、5％、8％、10％等，或者是上述任意两个数值组成的范围，例如可以是1％-2％、2％-5％、5％-8％、8％-10％等。
在一实施方式中，M元素的原子含量(at％)小于或等于5％。例如可以是0.1％、1％、2％、5％等，或者是上述任意两个数值组成的范围，例如可以是0.1％-2％、1％-2％、2％-5％等。
元素的原子含量是指该元素的原子数目占材料总原子数目的百分比，M元素的原子含量是指M元素的原子数目占M/MXene复合材料总原子数目的百分比。M原子作为与气体分子结合的活性中心，增加M原子的含量可以增多活性吸附位点，从而增加传感器对目标气体的检测灵敏度。随着M原子含量的增加，更容易团聚成簇，反而可能会降低传感性能。
通过对M元素的原子含量进行选择，可以对气体传感材料的灵敏度和选择性进行调整，根据不同的应用场景，以灵敏度优先或者以选择性优先，在二者之间进行权衡，以满足特定应用的要求。
在本申请的一些实施例中，气体传感材料的响应气体包括CO、NO2、NO、H2、CH4、H2S、乙烯、乙烷、挥发性有机化合物、挥发性电解液中的任一种。
在一实施方式中，挥发性有机化合物包括甲醇、甲醛、甲苯、苯乙烯、苯酚、苯中的任一种。
在一实施方式中，挥发性电解液包括聚醚类电解液、聚酯类电解液中的任一种。
在电池的充放电的正常工作过程中以及电池热失控发生时，不同种类的电池会产生不同的气体，例如铅酸蓄电池会产生氢气，锂离子电池会产生一氧化碳、二氧化碳以及烃类气体包括甲烷、乙烷和乙烯等，钠离子电池也会产生氢气，锂硫电池则可能产生氢气和硫化氢气体。此外，挥发性电解液是一种电池或储能设备中常用的电解质，它具有较高的挥发性，通常是有机化合物，在电池故障的情况下，挥发性电解液有可能会发生挥发和热分解，产生包括一氧化碳、二氧化碳和一氧化氮在内的气体。本申请所提供的气体传感器可以适用于上述不同电池中实现不同气体的检测。
在本申请的一些实施例中，气体传感材料在-55℃至65℃范围内对气体有传感响应。这有利于气体传感材料适应不同的工作环境，减少由于温度引起的气体传感材料失效的问题，特别是该气体传感材料能够在较低的温度下依然对气体有传感响应，说明气体传感材料的活性较高，能够适应极寒条件下的工作环境，这对一些应用于特殊环境中的电池的安全性能有重要意义。
常规的锂离子电池工作温度在-20℃至60℃之间，不过一般低于0℃后锂电池性能就会下降，放电能力就会相应降低，所以锂离子电池性能完全的工作温度常见是0℃～40℃；铅酸电池通常在较宽的温度范围内工作，大致在-20℃至50℃之间；锂聚合物电池与锂离子电池相似，通常在-20℃至60℃之间工作。钠离子电池的典型工作温度范围大约在-10℃至60℃之间。锂硫电池典型工作温度范围通常在-20℃至60℃之间，与锂离子电池相似，锂硫电池的性能在极端温度条件下可能会受到限制。
而现有的其他气体传感材料，大多在80-90℃甚至更高的温度下才会有气体响应效果，并不能适用到电池体系中。而本申请所提供的气体传感材料，在低温下就有较好的响应效果，同时具有能够与大多数电池的工作温度相匹配的气体响应温度范围。
以上实施方式中，通过选用金属单原子或团簇与载体的复合物作为气体传感材料，能够实现在无氧或低氧环境下进行气体检测，且响应灵敏度高，检出限低，选择性强，响应恢复迅速。金属单原子或团簇与载体的复合物可以通过原子层沉积、物理/化学气相沉积等物理方法制备；也可以通过共沉积、裂解法等化学方法制备。
本申请的一些实施例中，还提供一种气体传感材料，包括M/MXene复合材料，复合材料中包括金属(M)单原子和MXene材料，或者说M/MXene复合材料中金属M以单原子的形式与MXene材料复合；和/或M/MXene复合材料中包括金属(M)团簇和MXene材料，或者说M/MXene复合材料中金属M以团簇的形式与MXene材料复合。这种气体传感材料是一种化学电阻传感材料，依靠气体传感材料吸脱附气体时电导率的变化来实现检测目的，使得气体传感材料能够在无氧或低氧环境下进行气体检测，从而实现电池内部产气的检测。
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，包括：提供MXene与金属有机配合物的复合物，金属有机配合物为金属M与有机配体的配合物；对复合物进行煅烧，得到M/MXene复合材料，M/MXene复合材料中金属M以单原子的形式与MXene材料复合；和/或M/MXene复合材料中金属M以团簇的形式与MXene材料复合。
金属有机配合物是金属单原子和金属团簇的前驱体，含金属节点的前驱体通过热解可以用于制备单原子复合物。在煅烧过程中热解形成金属单原子和/或金属团簇，在高温热解过程中，单原子与热解产物之间存在强烈的相互作用，形成复合物。
金属有机配合物通常是金属离子与有机配体形成的复合物，例如金属醋酸盐、金属硝酸盐、金属氯化物或金属有机框架材料的有机配合物。在煅烧过程中，金属离子会被分解或还原，成为金属原子或金属团簇。
其中，有机配体是有机化合物中的分子或离子，通常包含碳、氢、氧、氮等元素，常见的有机配体比如乙二胺、二甲基咪唑等。它们可以与金属原子形成配位键，从而构成金属有机配合物。进一步地，在制备金属单原子复合物时，金属有机配合物还能够提供异质非金属原子(碳、氮等)来锚定金属单原子和金属团簇，从而能够形成稳定的金属原子位点。
在本申请的一些实施例中，M/MXene复合材料中金属M以金属氮碳化合物的形式负载于MXene材料的表面，下文以M-N-C/MXene复合材料来表示这一类复合物。具体地，可以是金属氮碳化合物中每个金属原子M分别与四个氮原子键合，金属氮碳化合物中碳原子以石墨的形式存在，键合有金属原子的氮原子嵌合在石墨层中，并与石墨层的碳原子键合，石墨结合在MXene材料表面。可以通过对MXene与金属有机配合物的复合物进行煅烧来制备M-N-C/MXene复合材料。
在本申请的一些实施例中，先制备MXene与金属有机配合物的复合物，具体地，可以是将金属有机配合物溶液与MXene溶液混合，搅拌反应，得到MXene与金属有机配合物的复合物。
在本申请的一些实施例中，将金属有机配合物溶液与MXene溶液混合之前包括：将金属有机配合物与表面活性剂结合；和/或将MXene材料与表面活性剂结合。
表面活性剂是指是能使目标溶液表面张力显著下降的物质。表面活性剂具有固定的亲水亲油基团，在溶液的表面能定向排列，表面活性剂的分子结构具有两性：一端为亲水基团，另一端为疏水基团，亲水基团常为极性基团，如羧酸、磺酸、硫酸、氨基或胺基及其盐，羟基、酰胺基、醚键等也可作为极性亲水基团；而疏水基团常为非极性烃链，如8个碳原子以上的烃链。表面活性剂分为离子型表面活性剂(包括阳离子表面活性剂与阴离子表面活性剂)、非离子型表面活性剂、两性表面活性剂、复配表面活性剂、其他表面活性剂等。
通过在将金属有机配合物溶液与MXene溶液混合之前将表面活性剂与其中至少一种进行混合，先在金属有机配合物或MXene上连接表面活性剂，表面活性剂的存在，能够使金属有机配合物与MXene混合反应时通过亲水亲油基团将金属有机配合物和MXene连接起来，充当二者结合的桥梁，有利于改善金属有机配合物和MXene之间的界面亲和性，促进更有效的反应。此外，表面活性剂具有分散剂的功能，有利于金属有机配合物和MXene在溶液中的均匀分散，从而有利于反应的均匀性和稳定性。
在一实施方式中，表面活性剂包括十六烷基三甲基溴化铵。十六烷基三甲基溴化铵(CTAB)属于阳离子表面活性剂，亲水亲油平衡值(HLB)为15.8。CTAB分子结构中有一个疏水烷基链(十六烷基)，具有亲油性质，同时CTAB分子中的溴化铵离子部分则具有亲水性质，这种分子结构使CTAB同时具有亲水和亲油两性。CTAB的亲水基团与MXene连接，亲油基团与金属有机配合物连接，实现了金属有机配合物和MXene的复合。
此外，CTAB分子带有正电荷，这是因为溴化铵离子中的铵离子(NH4+)带有正电荷，这种正电荷可以与带有负电荷的表面或颗粒相互作用。通过采用CTAB作为表面活性剂，CTAB的正离子部分能和MXene上的负电荷官能团(如-OH、-F)和金属有机配合物表面的负电荷相互吸引，从而有利于提高连接的稳定性。
进一步地，在本申请的一些实施例中，优选将金属有机配合物与表面活性剂结合，具体包括：提供金属有机配合物前驱体和十六烷基三甲基溴化铵；将金属有机配合物前驱体和十六烷基三甲基溴化铵混合反应，得到结合有十六烷基三甲基溴化铵的金属有机配合物。
如前所述，CTAB的正离子部分可以与金属有机框架材料的表面负电荷相互吸引，形成吸附层，这种吸附通常是通过静电相互作用来实现的。CTAB的疏水烷基链可以与金属有机配合物的疏水区域相互作用，从而进一步稳定吸附层。这种结合方式可以帮助分散和稳定金属有机配合物，并调控其性质。
接下来，进行金属有机配合物溶液与MXene溶液的复合，可以是将结合有十六烷基三甲基溴化铵的金属有机配合物与MXene溶液混合，搅拌反应，得到复合物。
在金属有机配合物和MXene溶液的复合中，表面活性剂发挥了关键作用，如前所述，表面活性剂作为金属有机配合物和MXene溶液之间结合的桥梁，改善了金属有机配合物和MXene之间的界面亲和性，促进了更有效的反应。
根据本申请的一些实施例，将金属有机配合物溶液与MXene溶液混合包括：将MXene溶液滴加入处于搅拌状态的金属有机配合物溶液中；MXene溶液的滴加速度为1-20秒/滴。搅拌状态有利于MXene溶液与金属有机配合物溶液充分接触，加快反应速率；通过控制滴加速度，能够调整反应局部溶液浓度，逐滴添加可形成较均匀的反应浓度场，有利于形成分散良好，粒径均匀的晶体。
具体地，边搅拌边将MXene溶液滴入金属有机配合物溶液中，MXene溶液的滴加速度为2秒/滴，待滴加完成后继续搅拌24小时，反应结束后将生成物用甲醇洗涤并在60℃下真空干燥，得到MXene与金属有机配合物的复合物。
通过上述反应，制备得到了MXene与金属有机配合物的复合物，这是M/MXene复合材料的前驱体，是最终得到M/MXene复合材料的前提。
进一步地，对制备得到的MXene与金属有机配合物的复合物进行煅烧。根据本申请的一些实施例，对MXene与金属有机配合物的复合物进行煅烧，得到M/MXene复合材料。
煅烧步骤是将金属有机配合物前驱体转化为金属单原子或金属团簇复合物的过程，煅烧时还可以形成金属-氮-碳(M-N-C)结构。在高温下，金属有机配合物前驱体会发生分解或还原反应，生成金属单原子或金属团簇；同时在高温下，金属有机配合物前驱体中的可挥发性元素挥发，形成了具有石墨相结构的多孔碳。例如金属有机配合物前驱体为沸石型咪唑酸框架-8(ZIF-8)时，在热解炭化温度为900℃时，高温下具有可挥发性的锌从ZIF-8的结构中脱出，最终得到非金属氮掺杂的石墨化多孔碳材料，该材料保留了ZIF-8规整的菱形十二面体形貌，而且氮含量高，拥有高的比表面积和多级孔结构。
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制备的反应示意图。以金属镍(Ni)与MXene(Ti3C2Tx)的复合材料为例，此时金属有机配合物为镍基沸石咪唑酸盐框架-8(Ni-ZIF-8)。金属有机配合物Ni-ZIF-8首先和表面活性剂CTAB连接形成Ni-ZIF-8-CTAB。ZIF-8是金属有机框架材料，具有网络多孔晶体结构。CTAB将ZIF-8包裹起来，在ZIF-8表面形成活性位点；接下来Ni-ZIF-8-CTAB通过CTAB形成的活性位点与Ti3C2Tx连接，完成金属有机配合物Ni-ZIF-8和MXene Ti3C2Tx的自组装。然后煅烧，热解形成Ni-N-C/Ti3C2Tx复合材料。Ni-N-C/Ti3C2Tx复合材料中Ni分别与四个N成键，形成NiN4结构，图中上层结构中黑色中心区域所示结构，然后NiN4结构与炭化形成的石墨结构键合，图中上层结构，最后石墨结构与MXene(Ti3C2Tx)复合。
根据本申请的一些实施例，煅烧的温度为700-1000℃；和/或煅烧的时间为1-4h。
在一实施方式中，煅烧的温度为850-950℃。
在该温度和时间范围内，金属有机配合物中的有机物成分可以发生热解炭化形成具有石墨相结构的多孔碳，同时金属有机配合物骨架中的部分金属离子在高温下挥发，形成缺陷和活性位点。
请继续参阅图8，以金属有机配合物为Ni-ZIF-8为例，当煅烧温度低于500℃时，样品保持ZIF-8的结构及形貌；温度达到600℃时，ZIF-8开始分解碳化；随着温度的进一步升高，750℃以上ZIF-8中的Zn2+挥发，ZIF-8碳化成为具有石墨相结构的多孔碳。而无氧条件下，MXene在此温度范围内质量损失很小，且结构和成分几乎不发生变化。
通过煅烧过程中发生的热解炭化和金属离子挥发，金属M以金属氮碳化合物的形式负载于MXene材料的表面，其中碳原子以石墨的形式存在，键合有金属原子的氮原子嵌合在石墨层中，并与石墨层的碳原子键合。
根据本申请的一些实施例，对复合物进行煅烧包括：在保护气体氛围下对复合物进行煅烧，保护气体包括氩气、氢气、氮气中的一种或多种。
保护气体是性质稳定的气体，主要作用是在煅烧过程中防止发生氧化反应。其中氩气是惰性气体，化学性质不活泼，用它做保护气，可以隔绝空气，防止氧化，氮气性质稳定，也能起到隔绝空气，防止氧化的作用，而氢气除了上述作用外，还具有一定的还原作用，进一步防止氧化。上述保护气体可以是单一气体，也可以是两种或两种以上气体的混合气体。
通过在煅烧步骤中引入保护气体，首先能够减少气体传感材料制备过程中的氧化反应，有利于减少MXene的氧化，有利于保护材料表面活性位点的活性，维持反应的正常进行，提高产品质量。
通过上述方法所制备的气体传感材料，具有MXene与M-N-C界面限域结构，进而在基底之间形成限域效应，同时具备化学敏化、电子敏化的传感机制，并通过电子溢出效应增强传感性能。
根据本申请的一些实施例，还可以对M/MXene复合材料进行掺杂，具体可以是在M/MXene复合材料的制备过程中，在不同的工序阶段引入掺杂元素。
根据本申请的一些实施例，可以在煅烧步骤中，在掺杂气体氛围下对复合物进行煅烧，通过气体氛围引入掺杂元素。在一实施方式中，掺杂气体包括氨气、硫化氢中的一种或多种。
与保护气体不同，掺杂气体在保护反应的同时，还可以参与反应，例如氨气可以在M/MXene复合材料的金属原子配体中引入氮原子，硫化氢可以引入硫原子，即金属原子M与氮原子或硫原子之间配位成键，替换与金属原子M键合的四个单原子中的一个或多个，以此来优化气体传感材料的传感性能，增强气体传感材料对不同应用需求的适应性。
根据本申请的一些实施例，掺杂元素还可以在金属有机配合物阶段引入，具体地，将金属有机配合物溶液与MXene溶液混合之前对金属有机配合物进行掺杂改性。
掺杂改性的配体可以是含有O、S等氧族元素的配体，如-O，-OH，-S，由于N，O，S等非金属元素本身化学性质的差异，它们在与金属原子中心配位键合形成特殊构型时，可以调节金属中心的自旋态、d带中心等电学性质，进而调控活性中心与气体分子的结合能，最终达到对气体传感材料本征活性的调控。还可以是F、Cl、Br、I等卤族元素，由于配体元素之间电负性的差异，不同的配体能够对金属原子中心的电子结构进行不同程度的调控，最终能够实现对气体传感材料的响应性、选择性等的调控。
本申请的一些实施例中，将金属有机配合物溶液与MXene溶液混合之前包括：提供金属有机配合物前驱体和掺杂前驱体；将金属有机配合物前驱体和掺杂前驱体混合反应，得到掺杂改性的金属有机配合物。
掺杂前驱体是指用于引入掺杂元素的化合物，它可以是一个单独的化合物，也可以是由金属有机配合物前驱体通过特定处理或修饰得到的产物。掺杂前驱体的选择取决于所需的掺杂元素以及材料的特定应用需求。
掺杂前驱体主要包括以下几种，一是金属盐类，如金属硝酸盐、金属氯化物、金属醋酸盐等，通过将金属盐与金属有机配合物前驱体反应，可以实现掺杂过程；二是有机化合物，该有机化合物含有目标掺杂元素，可以是功能性配体，例如含有特定官能团的有机酸、酮、醇等；三是气体源，如前所述煅烧步骤中的掺杂气体氛围，将掺杂气体引入金属有机配合物前驱体的反应体系中，可以实现掺杂元素的引入。在本申请的一实施例中，掺杂前驱体为硫脲，是一种有机含硫化合物，化学式为CH4N2S，可提供硫元素作为掺杂元素，具体的掺杂步骤详见后文具体实施例。
通过将掺杂前驱体和金属有机配合物前驱体进行混合反应得到掺杂改性的金属有机配合物，优选合适 的掺杂前驱体，能够有效实现掺杂目的，实现多种元素的掺杂，进而有利于目的性地对气体传感材料进行改性，有利于拓宽气体传感材料的应用范围。
以上实施例，通过掺杂改性，能够针对特定的应用场景，从特定的气体种类和响应效果出发，对气体传感材料进行适应性设计，有利于目的性地对气体传感材料进行改性，有利于拓宽气体传感材料的应用范围。
在本申请的一些实施例中，还可以利用缺陷空位锚定法制备金属单原子复合材料。利用MXene载体材料的晶格缺陷，对金属原子M进行锚定，金属原子M与周边载体原子(一般为C原子)配位或成键而成为晶格结构的一部分，因化学键的存在和纳米限域效应的影响，所掺杂的金属原子M具有高度稳定性。可以是在蚀刻MAX相前驱体制备MXene的过程中，会导致MAX相中一些相邻的金属原子掉落，从而产生金属空位缺陷，该缺陷具有高还原活性，可以在不添加任何还原剂的情况下自发还原吸附金属离子来固定单个金属原子，从而使孤立的金属原子稳定存在于MXene载体上。该方法所制得的金属单原子复合材料中金属M以单原子的形式嵌入MXene材料的结构中。
具体地，在本申请的一实施例中，用氟化锂(LiF)和盐酸(HCl)溶液刻蚀钛碳化铝(Ti3AlC2)制备Ti3C2Tx纳米片的过程中，Ti-Al键被破坏，引起相邻Ti原子的刻蚀，导致Ti单空位或空位簇的形成。此空位可以吸附Ni2+并将其原位还原，制备得到单原子Ni修饰的Ni-Ti3C2Tx MXene复合材料。具体的制备方法详见后文的具体实施例。
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M/MXene复合材料作为气体传感材料，该材料基于气体在材料表面吸脱附时表面电导率的变化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。该气体传感器可以响应包括CO、NO2、NO、H2、CH4、H2S、乙烯、乙烷、挥发性有机化合物、挥发性电解液中的一种或多种气体。
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、将0.96g六水硝酸锌溶于67mL甲醇中，再加入50mg六水硝酸镍搅拌均匀，得溶液A；
2、将0.4g十六烷基三甲基溴化铵(CTAB)和2.19g二甲基咪唑溶于67mL甲醇溶液中，搅拌至完全溶解作为溶液B；
3、边搅拌边将溶液B滴入溶液A中，溶液B的滴加速度为2秒/滴，待滴加完成后继续搅拌2h，取35mL的混合溶液，作为溶液C；
4、将0.2g MXene溶于5mL甲醇溶液中，超声至完全溶解作为溶液D；
5、边搅拌边将溶液D滴入溶液C中，溶液D的滴加速度为2秒/滴，待滴加完成后继续搅拌24h，甲醇洗涤并于60℃真空干燥，将产物置于管式炉内在氮气气氛下900℃煅烧2h，制得(Ni-N-C/MXene)-1复合材料，Ni以单原子形式与MXene材料复合。
实施例2-3
在实施例1的基础上改变溶液A的制备，区别在于六水硝酸镍分别替换为六水硝酸铁和六水硝酸钴，制得(Fe-N-C/MXene)-2复合材料和(Co-N-C/MXene)-3复合材料，Fe和Co分别以单原子形式与MXene材料复合。具体反应条件详见表1，表1列出了各实施例的金属M种类和金属M存在形式。
实施例4
在实施例1的基础上改变溶液A的制备，区别在于六水硝酸镍的质量从50mg替换为500mg，制得(Ni-N-C/MXene)-4复合材料，Ni以团簇形式与MXene材料复合，具体反应条件详见表1。
实施例5
1、将1g氟化锂(LiF)加入10mL盐酸(HCl)溶液中，搅拌1h，随后加入1g钛碳化铝(Ti3AlC2)粉末，在35℃下水浴加热，反应24h；将水浴后得到的溶液用去离子水反复离心洗涤至PH≥5.5，离心速率为9000rpm，每次离心时间为5min；在离心产物中加入40mL去离子水，超声30min得悬浮液，得到Ti3C2Tx MXene溶液，取8mL悬浮液作为溶液A；
2、称取0.002g六水合氯化铁加入50mL去离子水中，超声30min，得到溶液B；
3、将溶液B缓慢滴加至溶液A中，溶液B的滴加速度为2秒/滴，搅拌8h，后加入50mL丙酮，静置一晚，丙酮洗涤并于60℃真空干燥，制得(Ni/MXene)-5复合材料，Ni以单原子形式与MXene材料复合。
实施例6
在实施例1的基础上改变溶液A的制备，区别在于将50mg六水硝酸镍替换为25mg六水硝酸镍和25mg六水硝酸铁，制得(Ni-Fe-N-C/MXene)-6复合材料，Ni和Fe以单原子形式与MXene材料复合，具体反应条件详见表1。
实施例7
在实施例1的基础上改变溶液A的制备，区别在于在加入六水硝酸镍的同时加入了0.5g硫脲，制得(Ni-N-S-C/MXene)-7复合材料，Ni以单原子形式与MXene材料复合，具体反应条件详见表1。
二、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。
三、气体传感性能测试
请参阅图9，图9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：实施例5中金属M以单原子的形式嵌入MXene中，实施例5以外的实施例中金属M以金属氮碳化合物的形式负载于MXene材料的表面；响应值一栏，实施例1-7测试的气体浓度为20ppm；响应时间/恢复时间一栏同上。
请参阅图11至图13，图11为根据一个或多个实施例的气体传感材料Ni/MXene的气体响应示意图，图12为根据一个或多个实施例的气体传感材料Ni/MXene的气体响应示意图，图13为根据一个或多个实施例的气体传感材料Ni/MXene的气体响应示意图。图11测试了(Ni-N-C/MXene)-1对不同浓度CO气体的响应情况，图12测试了(Ni-N-C/MXene)-1对1、5、10ppm CO气体的循环响应性能，图13测试了(Ni-N-C/MXene)-1对浓度为5ppm的不同气体的响应情况。在图11和图12中，横坐标为采集时间，纵坐标为器件灵敏度。
由图11可知，(Ni-N-C/MXene)-1复合材料传感器对50ppm一氧化碳的响应值达到了50.2％。可检测的最低一氧化碳浓度达到了1ppm，对应的响应值为10.4％。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。一氧化碳气体浓度为5ppm时，响应时间为40s，恢复时间为120s，响应和恢复的速度较快。因此，本申请提供的(Ni-N-C/MXene)-1气体传感材料气体检测的灵敏度较高，检出限较低，响应恢复速度较快。
由图12可知，在三种不同的气体浓度下，经过五次响应-恢复循环之后，(Ni-N-C/MXene)-1复合材料传感器的响应值和响应时间基本维持不变，说明本申请提供的(Ni-N-C/MXene)-1气体传感材料在气体响应方面具有良好的循环稳定性。
由图13可知，(Ni-N-C/MXene)-1复合材料对5ppm一氧化碳、一氧化氮、二氧化氮、甲烷、氢气、氨气均有响应，但除一氧化碳之外，对其他气体的响应值均很小。说明本申请提供的(Ni-N-C/MXene)-1气体传感材料对一氧化碳表现出良好的选择性。
请参阅图14至图16，图14为根据一个或多个实施例的气体传感材料Fe/MXene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Co/MXene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Ni/MXene的气体响应示意图。横坐标为采集时间，纵坐标为器件灵敏度。
在图14中，测试了(Fe-N-C/MXene)-2复合材料对不同浓度NH3气体的响应情况。(Fe-N-C/MXene)-2复合材料传感器对20ppm氨气的响应值达到了30.9％。可检测的最低氨气浓度达到了1ppm，对应的响应值为25.6％。随着氨气浓度的增加，传感器对气体的响应值也随之增加。氨气气体浓度为20ppm时，响应时间为80s，恢复时间为100s。因此，本申请提供的(Fe-N-C/MXene)-2气体传感材料气体检测的灵敏度较高，检出限较低，响应恢复速度较快。
在图15中，测试了(Co-N-C/MXene)-3复合材料对20ppm NO2气体的响应情况。(Co-N-C/MXene)-3复合材料传感器对20ppm二氧化氮的响应值为6.4％，响应时间为60s，恢复时间为80s，同时在两次循环内响应值和响应时间基本维持不变。因此，本申请提供的(Co-N-C/MXene)-3气体传感材料可应用于二氧化氮气体检测。
在图16中，测试了(Ni-N-C/MXene)-4复合材料对20ppm CO气体的响应情况。(Ni-N-C/MXene)-4复合材料传感器对20ppm一氧化碳的响应值为5.5％，响应时间为40s，恢复时间为90s，同时在五次循环内响应值和响应时间基本维持不变。因此，本申请提供的(Ni-N-C/MXene)-4复合材料可应用于一氧化碳气体检测且气体响应循环稳定性较好。
请参阅表1，实施例1-3中制得了(Ni-N-C/MXene)-1复合材料、(Fe-N-C/MXene)-2复合材料和(Co-N-C/MXene)-3复合材料，这三种复合材料中金属M的种类不同，因此三种复合材料响应气体的种类也不同，分别是CO、NH3和NO2。说明不同的金属种类在与气体分子的结合上存在差异。因此可以通过 选择不同的金属元素来调控气体传感的选择性。
另外，相比于(Fe-N-C/MXene)-2复合材料和(Co-N-C/MXene)-3复合材料，(Ni-N-C/MXene)-1复合材料在待检测气体浓度相同的情况下，具有更高的响应值和更短的响应时间，说明在三者中镍元素制备的气体传感材料具有更高的响应灵敏度。因此可以通过选择不同的金属元素来调控气体传感的响应灵敏度。
实施例1和实施例4制得了(Ni-N-C/MXene)-1复合材料和(Ni-N-C/MXene)-4复合材料，金属Ni分别以单原子的形式和团簇的形式与MXene材料复合。可以看到，(Ni-N-C/MXene)-1对20ppm CO的响应值为43.1％，而(Ni-N-C/MXene)-4对20ppm CO的响应值仅为5.5％。说明即使(Ni-N-C/MXene)-4具有更多的Ni原子活性位点，但团簇形式的Ni原子仍然使得传感性能降低了。
实施例1和实施例5制得了(Ni-N-C/MXene)-1和(Ni/MXene)-5复合材料，金属Ni单原子分别以单原子的形式嵌入MXene中或者以金属氮碳化合物的形式负载于MXene材料的表面。请结合参阅图10，图10为根据一个或多个实施例的气体传感材料Ni/MXene的气体响应示意图。横坐标为采集时间，纵坐标为器件灵敏度。可以看到，(Ni-N-C/MXene)-1对20ppm CO的响应值为43.1％，而(Ni/MXene)-5对20ppm CO的响应值仅为0.6％。说明金属氮碳化合物形式优化了气体传感材料的传感性能。
实施例1和实施例6制得了(Ni-N-C/MXene)-1和(Ni-Fe-N-C/MXene)-6复合材料，这两种复合材料分别为金属单原子复合材料和金属双原子复合材料。可以看到，(Ni-N-C/MXene)-1对20ppm CO的响应值为43.1％，而(Ni-Fe-N-C/MXene)-6对20ppm CO的响应值为37.5％；同时(Ni-Fe-N-C/MXene)-6的响应时间也较长，但恢复时间较短。说明复合材料中的Ni原子一部分被Fe原子取代后，对于CO的传感性能并未被改善，原因是Ni原子对CO的选择性响应效果好，而Fe原子对CO的响应不如Ni原子。
实施例1和实施例7制得了(Ni-N-C/MXene)-1和(Ni-N-S-C/MXene)-7复合材料，(Ni-N-S-C/MXene)-7复合材料中掺杂了硫元素。可以看到，(Ni-N-C/MXene)-1对20ppm CO的响应值为43.1％，而(Ni-N-S-C/MXene)-7对20ppm CO的响应值为45.6％；同时(Ni-N-S-C/MXene)-7的恢复时间缩短。说明NiN3S活性位点比NiN4具有更高的反应活性，因此可以通过加入掺杂元素的方式有目的地对气体传感材料进行改性。
以上实施例说明，本申请所提供的气体传感材料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无氧环境下进行的气体传感测试，相对于现有的需要高温以及有氧气参与才能够气体响应的材料，条件更温和，应用范围更广。
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。即本申请提供一种电池，电池包括上述实施例的气体传感器。
请参照图17，图17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18，图18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18，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。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。
在一实施方式中，负极极片包括负极集流体和设置在负极集流体至少一个表面上的负极活性层，负极活性层包括负极活性材料。该实施方式中，电池单体为离子电池，在电池充放电过程中，活性离子(如Li+、Na+)在负极活性材料中嵌入/脱嵌。
作为示例，负极集流体具有在其自身厚度方向相对的两个表面，负极活性层可以设置在负极集流体相对的两个表面的其中任意一者或两者上。
在一个实施例中，负极集流体可采用金属箔片或复合集流体。例如，作为金属箔片，可以采用铜箔。复合集流体可包括高分子材料基层和形成于高分子材料基材至少一个表面上的金属层。复合集流体可通过将金属材料(铜、铜合金、镍、镍合金、钛、钛合金、银及银合金等)形成在高分子材料基材(如聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚苯乙烯(PS)、聚乙烯(PE)等的基材)上而得到。
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。
在一实施方式中，负极极片包括负极集流体和设置在负极集流体至少一个表面上的含碳涂层。该实施方式中，电池单体为金属电池，在电池充放电过程中，活性离子在负极极片处沉积/剥离。金属电池可以是碱金属电池，例如锂金属电池、钠金属电池、钾金属电池、锌金属电池、铝金属电池的一种。该类型的电池也可以称为“无负极电池”。在充电过程中，依靠从正极活性材料中脱出的活性离子(例如Na+)沉积至负极集流体上形成钠金属。含碳涂层的设置利于使金属沉积更均匀。含碳材料包括导电碳、石墨、硬碳、碳纳米管类中的一种或多种。
在另一些实施方式中，也可以在负极集流体上沉积一层导电的膜层。例如合金材料、钛基材料、活性金属(例如钠金属)、沉积有金属的碳基材料、含有金属的复合材料、含有金属的合金材料等。上述合金材料包括但不限于钠锡合金、钠锗合金、钠锑合金。上述钛基材料包括但不限于二氧化钛、钛酸盐、钛磷酸盐。
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19，图19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。在一些实施例中，电池可以为储能装置。储能装置包括储能集装箱、储能电柜等。
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 (32)

  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M/MXene复合材料，所述M/MXene复合材料中包括金属(M)单原子和MXene材料；和/或
    所述M/MXene复合材料中包括金属(M)团簇和MXene材料。
  2. 根据权利要求1所述的电池，其中，
    所述M/MXene复合材料中包括金属(M)氮碳化合物，所述金属氮碳化合物负载于所述MXene材料的表面。
  3. 根据权利要求2所述的电池，其中，
    所述金属氮碳化合物中每个金属原子M分别与四个氮原子键合。
  4. 根据权利要求3所述的电池，其中，
    所述金属氮碳化合物包括石墨结构，键合有所述金属原子M的氮原子嵌合在所述石墨结构中，并与所述石墨结构的碳原子键合，所述石墨结构结合在所述MXene材料的表面。
  5. 根据权利要求2至4任一项所述的电池，其中，
    所述金属氮碳化合物中掺杂有X元素，X包括硫、磷、硼中的一种或多种。
  6. 根据权利要求5所述的电池，其中，
    所述金属氮碳化合物中每个金属原子M分别与四个氮原子键合，所掺杂的X元素替换与金属原子M键合的四个氮原子中的一个或多个。
  7. 根据权利要求1所述的电池，其中，
    所述M/MXene复合材料中所述金属(M)单原子嵌入所述MXene材料的结构中。
  8. 根据权利要求1至7任一项所述的电池，其中，
    所述金属M包括Fe、Co、Ni、Mn、Cu、Zn、Cr、Pd、Pt、Au、Ag、Ir、Ru中的一种或多种。
  9. 根据权利要求1至8任一项所述的电池，其中，
    所述金属M包括Fe、Co、Ni中的一种或多种。
  10. 根据权利要求1至9任一项所述的电池，其中，
    所述M/MXene复合材料中所述金属(M)单原子的尺寸小于1nm；和/或
    所述M/MXene复合材料中所述金属(M)团簇的尺寸为1-50nm。
  11. 根据权利要求1至10任一项所述的电池，其中，
    所述M/MXene复合材料中所述金属(M)单原子的尺寸小于0.5nm；和/或
    所述M/MXene复合材料中所述金属(M)团簇的尺寸为10-30nm。
  12. 根据权利要求1至11任一项所述的电池，其中，
    基于所述M/MXene复合材料的总原子个数，金属M元素的原子含量(at％)小于或等于15％。
  13. 根据权利要求1至12任一项所述的电池，其中，
    基于所述M/MXene复合材料的总原子个数，金属M元素的原子含量(at％)小于或等于10％。
  14. 根据权利要求1至13任一项所述的电池，其中，
    基于所述M/MXene复合材料的总原子个数，金属M元素的原子含量(at％)小于或等于5％。
  15. 根据权利要求1至14任一项所述的电池，其中，
    所述MXene材料包括M’n+1X’nTx，其中M’为早期过渡金属元素，X’为碳或氮元素，Tx为OH-、O2-、F-基团中的任一种。
  16. 根据权利要求1至15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CO、NO2、NO、H2、CH4、H2S、乙烯、乙烷、挥发性有机化合物、挥发性电解液中的一种或多种。
  17. 根据权利要求16所述的电池，其中，
    所述挥发性有机化合物包括甲醇、甲醛、甲苯、苯乙烯、苯酚、苯中的至少一种。
  18. 根据权利要求16或17所述的电池，其中，
    所述挥发性电解液包括聚醚类电解液、聚酯类电解液中的至少一种。
  19. 根据权利要求1至18任一项所述的电池，其中，
    所述气体传感材料在-55℃至65℃范围内对气体有传感响应。
  20. 一种气体传感材料，其中，所述气体传感材料包括M/MXene复合材料，所述M/MXene复合材料中包括金属(M)单原子和MXene材料；和/或
    所述M/MXene复合材料中包括金属(M)团簇和MXene材料。
  21. 一种气体传感材料的制备方法，其中，包括：
    提供MXene与金属有机配合物的复合物，所述金属有机配合物为金属M与有机配体的配合物；
    对所述复合物进行煅烧，得到M/MXene复合材料，所述M/MXene复合材料中包括金属(M)单原子和MXene材料；和/或所述M/MXene复合材料中包括金属(M)团簇和MXene材料。
  22. 根据权利要求21所述的气体传感材料的制备方法，其中，所述对所述复合物进行煅烧包括：
    所述煅烧的温度为700-1000℃；和/或
    所述煅烧的时间为1-4h。
  23. 根据权利要求21或22所述的气体传感材料的制备方法，其中，所述对所述复合物进行煅烧包括：
    在保护气体氛围下对所述复合物进行煅烧，所述保护气体包括氩气、氢气、氮气中的一种或多种；和/或
    在掺杂气体氛围下对所述复合物进行煅烧，所述掺杂气体包括氨气、硫化氢中的一种或多种。
  24. 根据权利要求21至23任一项所述的气体传感材料的制备方法，其中，所述提供MXene与金属有机配合物的复合物包括：
    将金属有机配合物溶液与MXene溶液混合，搅拌反应，得到所述复合物。
  25. 根据权利要求24所述的气体传感材料的制备方法，其中，所述将金属有机配合物溶液与MXene溶液混合包括：
    将所述MXene溶液滴加入处于搅拌状态的所述金属有机配合物溶液中；
    所述MXene溶液的滴加速度为1-20秒/滴。
  26. 根据权利要求24或25所述的气体传感材料的制备方法，其中，所述将金属有机配合物溶液与MXene溶液混合之前包括：
    将所述金属有机配合物与表面活性剂结合；和/或
    将所述MXene溶液与表面活性剂结合。
  27. 根据权利要求26所述的气体传感材料的制备方法，其中，
    所述表面活性剂包括十六烷基三甲基溴化铵。
  28. 根据权利要求27所述的气体传感材料的制备方法，其中，所述将金属有机配合物与表面活性剂结合包括：
    提供金属有机配合物前驱体和十六烷基三甲基溴化铵；
    将所述金属有机配合物前驱体和十六烷基三甲基溴化铵混合反应，得到结合有十六烷基三甲基溴化铵的金属有机配合物。
  29. 根据权利要求24至28任一项所述的气体传感材料的制备方法，其中，所述将金属有机配合物溶液与MXene溶液混合之前包括：
    提供金属有机配合物前驱体和掺杂前驱体；
    将所述金属有机配合物前驱体和掺杂前驱体混合反应，得到带有掺杂元素的金属有机配合物。
  30. 一种气体传感材料的制备方法，其中，包括：
    对MXene材料前驱体进行刻蚀，得到带有缺陷空位的MXene材料；
    将金属有机配合物与所述带有缺陷空位的MXene材料复合反应，得到M/MXene复合材料，所述M/MXene复合材料中包括金属(M)单原子和MXene材料；和/或所述M/MXene复合材料中包括金属(M)团簇和MXene材料。
  31. 一种气体传感器，其中，包括如权利要求20所述的气体传感材料；或包括利用如权利要求21至30任一项所述的方法制得的气体传感材料。
  32. 一种用电设备，其中，包括权利要求1至19任一项所述的电池。
PCT/CN2024/117569 2023-11-30 2024-09-06 电池、气体传感材料及其制备方法、传感器和用电设备 Pending WO2025112780A1 (zh)

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