CN112820864B - Defect-based compound anchored single-atom composite material and preparation method and application thereof - Google Patents

Defect-based compound anchored single-atom composite material and preparation method and application thereof Download PDF

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CN112820864B
CN112820864B CN202011630829.1A CN202011630829A CN112820864B CN 112820864 B CN112820864 B CN 112820864B CN 202011630829 A CN202011630829 A CN 202011630829A CN 112820864 B CN112820864 B CN 112820864B
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defect
based compound
metal
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composite material
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CN112820864A (en
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王健
蔺洪振
程双
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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    • H01M4/02—Electrodes composed of, or comprising, active material
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    • B82—NANOTECHNOLOGY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
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    • 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
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • 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
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a defect-based compound anchored single-atom composite material and a preparation method and application thereof. The defect-based compound anchored single-atom composite material comprises a defect-based compound, a single atom loaded on the defect-based compound and sulfur-doped nanocarbon; the sulfur-doped nanocarbon has a hierarchical pore structure, and the defect-based compound is distributed in the hierarchical pore structure of the sulfur-doped nanocarbon; the content of a single atom in the defect group compound carrying the single atom is 0.1 to 20 at%; the defect-based compound includes any one or a combination of two or more of a metal oxide, a metal sulfide, and a metal nitride. The defect-based composite material loaded with the metal monoatomic is prepared by a simple method, and the method has mild conditions and is easy to realize industrialization; and the metal monoatomic and defective structure in the composite material can provide abundant catalytic activity centers, and the composite material has good application prospect in rechargeable lithium metal-based batteries.

Description

Defect-based compound anchored single-atom composite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of electrochemical energy materials, and particularly relates to a defect-based compound anchored single-atom composite material, and a preparation method and application thereof, for example, application in rechargeable lithium metal-based batteries.
Background
Currently, the energy density of conventional lithium ion batteries has not been able to meet the demand for high energy density in smart life. Based onLithium metal based lithium sulfur (Li/S) batteries have relatively high energy densities (2600 W.h.kg)-1) And has attracted a lot of attention as the most promising next-generation rechargeable battery. However, there are still a series of problems that prevent wide practical application of Li/S batteries, such as low utilization of active material sulfur and slow conversion kinetics on the positive electrode side; on the negative electrode side, lithium dendrite is easily generated in the deposition process of metal, the dendrite germination and growth on the surface of single lithium metal are often not controlled, and the disordered repeated dissolution and deposition of the lithium metal can cause volume expansion, so that the problems can cause the cycle life of the battery to be limited and the capacity to be remarkably reduced. A reasonably designed nano passivation layer or frame is used for modifying the surface of the negative electrode and adjusting the structure of the negative electrode, so that the growth and the germination of lithium dendrites on the surface of the negative electrode are prevented, and the volume expansion is inhibited. In addition, the adoption of the high-activity catalyst can reduce the conversion energy barrier of sulfur substances, improve the reaction kinetics and improve the method so as to improve the capacity and the stability of the battery.
Lithium sulfur batteries have high energy density, but their widespread use is also limited by a series of problems. The existing method for solving the problems of the lithium-sulfur battery is single, has high relative independence, and is difficult to have a comprehensive method and means for simultaneously solving the problems of the lithium cathode and the sulfur anode. On the negative electrode side, lithium metal negative electrodes face problems of dendrite growth, volume expansion, and unstable solid electrolyte interface film (SEI). The current lithium cathode protection method is often complicated, for example, the lithium cathode is pretreated by a rolling method, a smelting method, a chemical deposition method and the like, and because lithium metal is more active, the whole treatment process needs to be carried out in a protective atmosphere, so that the process is complex and the cost is high.
Disclosure of Invention
The invention mainly aims to provide a defect-based compound anchored single-atom composite material, and a preparation method and application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a defect-based compound anchoring monatomic composite material, which comprises a defect-based compound, a metal monatomic supported on the defect-based compound and sulfur-doped nanocarbon; the sulfur-doped nanocarbon has a hierarchical pore structure, and the defect-based compound is distributed in the hierarchical pore structure of the sulfur-doped nanocarbon; the content of the metal monoatomic atom in the defect group compound loading the monoatomic atom is 0.1 to 20 at%; the defect-based compound includes any one or a combination of two or more of a metal oxide, a metal sulfide, and a metal nitride.
The embodiment of the invention also provides a preparation method of the defect-based compound anchored monatomic composite material, which comprises the following steps:
uniformly mixing graphene oxide, carbon nanotubes, a surfactant, polysulfide, a metal salt precursor and a solvent, then adding a metal monoatomic precursor, and carrying out a hydrothermal reaction at 120-200 ℃ for 12 hours;
and, in NH3And/or in an inert atmosphere, carrying out heat treatment on the obtained hydrothermal reaction product at 100-500 ℃ for 10-120 min to obtain the defect-based compound anchored single-atom composite material.
Embodiments of the present invention also provide for the use of the aforementioned defect-based compound anchored monatomic composite in the preparation of rechargeable lithium metal-based batteries.
Embodiments of the present invention also provide a rechargeable lithium metal-based battery negative electrode, which includes an electrode and a protective layer on the surface of the electrode, where the protective layer includes at least the defect-based compound-anchored monatomic composite material described above.
Embodiments of the present invention also provide a rechargeable lithium metal-based battery positive electrode comprising at least the aforementioned defect-based compound-anchored monatomic composite.
The embodiment of the invention also provides a rechargeable lithium metal-based battery, which comprises a positive electrode, a negative electrode and electrolyte, wherein the negative electrode comprises the rechargeable lithium metal-based battery negative electrode, and the positive electrode at least comprises the defect-based compound anchoring monatomic composite material.
Compared with the prior art, the invention has the beneficial effects that:
(1) the defect-based compound anchoring single-atom composite material is prepared by a simple method, the adopted preparation process is simple, the condition is mild, and industrialization is easy to realize; the defect-based compound anchors metal monoatomic atoms and defect structures in the single-atom composite material to provide rich catalytic active centers, and the defect is utilized to stabilize the metal monoatomic structure, so that the prepared composite material has higher activity than a defect catalyst in the prior art;
(2) the modification method of the defect-based compound anchoring single-atom composite material on the surface of the lithium metal cathode, provided by the invention, is simple to operate, does not need inert gas protection, has strong controllability of the thickness of a protective layer, and can greatly reduce the difficulty in treatment compared with the traditional modification method of the surface of the lithium metal cathode, so that the practicability of the method is greatly improved; in addition, the protective layer on the surface of the lithium metal can adjust the lithium ion dynamics on the surface of the lithium negative electrode, resist the corrosion of the electrolyte, form a stable SEI layer, prevent the consumption of the electrolyte and inhibit the germination of lithium dendrites and the volume expansion of the negative electrode; finally, the composite material can be simultaneously applied to a positive electrode and a negative electrode, and the overall electrochemical performance of the lithium-sulfur full battery can be effectively improved by the modified sulfur positive electrode/lithium metal negative electrode.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a transmission electron micrograph of a defect-based compound-anchored nickel atom composite prepared in example 1 of the present invention;
FIG. 2 is a transmission electron micrograph of a defect-based compound-anchored cobalt atom composite prepared in example 2 of the present invention;
FIG. 3 is a transmission electron microscope image of a defect-based compound-anchored iron atom composite prepared in example 3 of the present invention;
FIG. 4 is an SEM image of a lithium metal surface after cycling prepared by example 4 of the present invention;
FIG. 5 is a graph of the cycling performance of a lithium metal-based battery prepared in example 5 of the present invention;
FIG. 6 is a tafel plot of a composite electrode prepared in example 6 of the present invention;
fig. 7 is a schematic view of a lighted bulb of pouch cell prepared in example 7 of the present invention;
fig. 8 is a graph of the cycling performance of pouch cells prepared in example 7 of the present invention;
FIG. 9 is a transmission electron micrograph of a sample prepared according to comparative example 1 of the present invention;
fig. 10 is a graph showing cycle performance of the lithium metal battery prepared in comparative example 2 of the present invention.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention has long studied and largely practiced to provide the technical solutions of the present invention, which will be clearly and completely described below. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
An aspect of an embodiment of the present invention provides a defect-based compound-anchored monatomic composite material including a defect-based compound, a metal monatomic supported on the defect-based compound, and a sulfur-doped nanocarbon; the sulfur-doped nanocarbon has a hierarchical pore structure, and the defect-based compound is distributed in the hierarchical pore structure of the sulfur-doped nanocarbon; the content of the metal monoatomic atom in the defect base compound loading the monoatomic atom is 0.1-20 at%; the defect-based compound includes any one or a combination of two or more of a metal oxide, a metal sulfide, and a metal nitride.
In some more specific embodiments, the metal monoatomic atom includes any one of copper, molybdenum, iron, nickel, cobalt, platinum, ruthenium, and rhodium atoms, but is not limited thereto.
Further, the sulfur-doped nanocarbon is prepared from sulfur-doped graphene oxide and carbon nanotubes.
Further, the pore diameter of the sulfur-doped nano carbon is 2-200 nm, and the porosity is 500-2000 cm3/g。
Another aspect of the embodiments of the present invention also provides a method for preparing the aforementioned defect-based compound anchored monatomic composite, which includes:
uniformly mixing graphene oxide, a carbon nano tube, a surfactant, polysulfide, a metal salt precursor and a solvent, then adding a metal monoatomic precursor, and carrying out hydrothermal reaction for 12 hours at 120-200 ℃;
and, in NH3And/or in an inert atmosphere, carrying out heat treatment on the obtained hydrothermal reaction product at 100-500 ℃ for 10-120 min to obtain the defect-based compound anchored single-atom composite material.
In some more specific embodiments, the preparation method comprises: the preparation method comprises the steps of ultrasonically dispersing graphene oxide, carbon nanotubes and a surfactant in a solvent, then adding a metal salt precursor, fully mixing to form a first dispersion liquid, then adding a polysulfide solution into the obtained first dispersion liquid, mixing, and then adding a metal monoatomic precursor.
Further, the solvent includes water, and is not limited thereto.
Further, the polysulfide solution is formed by dissolving sulfur powder and sulfide in water.
Further, the sulfide includes sodium sulfide, and is not limited thereto.
In some more specific embodiments, the preparation method comprises: at NH3And/or in an inert atmosphere, raising the temperature of the mixture obtained by the hydrothermal reaction to 100-500 ℃ at a temperature raising rate of 2-10 ℃/min.
In some more specific embodiments, the surfactant includes, without limitation, polyvinylpyrrolidone.
Further, the metal salt precursor includes ferrous acetate and/or cobaltous acetate, and is not limited thereto.
Further, the polysulfide includes, but is not limited to, sodium polysulfide.
Further, the metal monoatomic precursor comprises copper acetate, molybdenum acetate, platinum acetate, ruthenium acetate, rhodium acetate, Ni (Ac)2·4H2O、Co(Ac)2、Fe(Ac)3Any one or a combination of two or more of them, and is not limited thereto.
Furthermore, the mass ratio of the graphene oxide, the carbon nano tube, the surfactant, the polysulfide, the metal salt precursor and the metal monatomic precursor is 0.01-0.1: 0.2-1: 0.001-0.01: 0.5-1: 3-8: 0.1-1.
In some more specific embodiments, the preparation method further comprises: and after the hydrothermal reaction is finished, filtering, washing and freeze-drying the obtained mixture.
Another aspect of an embodiment of the present invention also provides the use of the aforementioned defect-based compound anchored monatomic composite for the preparation of rechargeable lithium metal-based batteries.
For example, in the use of the defect-based compound to anchor a monoatomic composite material in the manufacture of a lithium sulfur battery.
Yet another aspect of an embodiment of the present invention provides a rechargeable lithium metal-based battery negative electrode comprising an electrode and a protective layer on a surface of the electrode, the protective layer comprising at least the aforementioned defect-based compound-anchored monatomic composite.
Further, the protective layer is made of the membrane modified by the defect-based compound anchoring monoatomic composite.
Further, the electrode includes a lithium electrode, and is not limited thereto.
Another aspect of an embodiment of the present invention also provides a method for preparing the foregoing negative electrode for a rechargeable lithium metal-based battery, including:
and mixing the defect-based compound anchoring monoatomic composite material with a binder to form slurry, applying the slurry to the surface of a separator to form a modified separator, and forming a protective layer on the surface of an electrode by the modified separator through packaging treatment to obtain the rechargeable lithium metal-based battery cathode.
Further, the separator is a commercial separator, and is not limited thereto.
Further, the electrode includes a lithium electrode, and is not limited thereto.
Another aspect of an embodiment of the present invention also provides a rechargeable lithium metal-based battery positive electrode including at least the aforementioned defect-based compound anchored monoatomic composite material.
In some more specific embodiments, the rechargeable lithium metal-based battery positive electrode includes the defect-based compound anchored monoatomic composite, a sulfur-containing active material, a conductive agent, and a binder.
Further, the sulfur-containing active material includes lithium polysulfide, and is not limited thereto.
Further, the sulfur-containing active substance is supported on the defect-group compound-anchored monoatomic composite material.
Further, the method for preparing the positive electrode of the rechargeable lithium metal-based battery comprises the following steps:
and mixing the rechargeable lithium metal-based battery positive electrode, a sulfur-containing active substance, a conductive agent and a binder to form slurry, and then coating to obtain the rechargeable lithium metal-based battery positive electrode.
In some more specific embodiments, the rechargeable lithium metal-based battery positive electrode comprises the defect-based compound anchored single-atom composite, a sulfur-containing active species, a conductive agent, a binder, and a conductive current collector.
Further, the sulfur-containing active material includes lithium polysulfide, and is not limited thereto.
Further, the conductive current collector includes an aluminum foil, and is not limited thereto.
Further, the preparation method of the rechargeable lithium metal-based battery positive electrode comprises the following steps: and mixing the defect-based compound anchoring single-atom composite material, a conductive agent and a binder to form slurry, then applying the slurry on the conductive current collector, and then adding a sulfur-containing active material to the side, to which the slurry is applied, of the conductive current collector to prepare the rechargeable lithium metal-based battery positive electrode.
In another aspect of the embodiments of the present invention, there is provided a rechargeable lithium metal-based battery, including a positive electrode, a negative electrode, and an electrolyte, where the negative electrode includes the above rechargeable lithium metal-based battery negative electrode, and the positive electrode includes at least the above defect-based compound-anchored monatomic composite.
The defect-based compound anchoring single-atom composite material prepared by the invention can be used as a modification layer of a middle negative electrode in a rechargeable lithium metal-based battery, effectively prevents dendritic crystal growth and pulverization of metal lithium, prolongs the service life of the metal lithium negative electrode, remarkably improves the overall performance of the rechargeable lithium metal-based battery, and can be used as a carrier in a battery positive electrode material.
The invention provides a multi-in-one functional compound for the first time, and the high-activity defect-based compound anchored metal monoatomic nanoparticles are prepared by combining a hydrothermal treatment method and a heat treatment method and are loaded on a multi-element doped hierarchical pore nanocarbon network; through the design and optimization of the structure, the composite material can simultaneously optimize the electrochemical behaviors of a lithium cathode and a sulfur anode and adjust the behavior of lithium ions; in the design, the composite material is used as a carrier of the sulfur anode, so that the conversion kinetics of sulfur substances can be remarkably promoted, and the nucleation and conversion of lithium sulfide can be accelerated; meanwhile, as a modified protective layer of the metallic lithium cathode, a plurality of active sites of the protective layer can guide the initial nucleation distribution and energy barrier of deposited lithium, the dynamics of lithium ions is adjusted to promote the uniform deposition of later lithium, the growth and pulverization of dendritic crystals of the subsequently deposited metallic lithium are effectively prevented, the service life of the metallic lithium cathode is prolonged, and the overall performance of the lithium-sulfur battery is remarkably improved.
The invention provides a method which has simple and controllable process, does not need inert gas protection, can synchronously modify the negative electrode in the process of assembling the battery, has obvious modification effect, good dynamic regulation effect of the modified negative electrode lithium ion and stable electrochemical performance. Compared with the prior art, the method provided by the invention is simple to operate, mild in condition and easy for large-scale production; meanwhile, the prepared protective layer has strong controllability of appearance and structure, good stability, reliable performance and practicality, and can not greatly reduce the energy density of the battery. In addition, the composite material is used as a support material of the sulfur positive electrode, and can remarkably solve the problems of slow reaction kinetics and low utilization rate of active substances; the defect-based composite material loaded with metal monoatomic atoms prepared by the invention also shows excellent stability in the modified sulfur anode/lithium metal cathode under high sulfur-loading surface density and high current density, and has important significance for accelerating the practical application of lithium-sulfur battery soft package engineering.
The invention provides a lithium metal protective layer which is simply assembled and synthesized, the thickness of the formed protective layer can be adjusted by changing the concentration of dispersion liquid or the viscosity of slurry, and the like, in addition, the preparation process of a modification layer does not need inert gas protection and a reexamination processing process, the surface modification of a negative electrode can be synchronously realized in the battery assembling process, the processing technology is simplified, and the cost is saved; the lithium metal surface protection layer obtained by processing can adjust the lithium ion dynamics on the surface of the lithium negative electrode, resist the corrosion of electrolyte, form a stable SEI layer, prevent the consumption of the electrolyte and inhibit the germination of lithium dendrites and the volume expansion of the negative electrode; the metal monoatomic-supported defect-based composite material has the advantages that the monoatomic and defect structures can provide rich active centers, the electrochemical reaction of the battery can be promoted, the catalytic efficiency can be high when the metal monoatomic-supported defect-based composite material is applied to a lithium-sulfur secondary battery, and the battery can obtain excellent electrochemical performance; the modified sulfur anode/lithium metal cathode is used for the lithium-sulfur soft package full battery and can realize high capacity and long cycle stability under high sulfur-carrying surface density and high current density.
The technical solutions of the present invention are further described in detail below with reference to several preferred embodiments and the accompanying drawings, which are implemented on the premise of the technical solutions of the present invention, and a detailed implementation manner and a specific operation process are provided, but the scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples used below were all available from conventional biochemical reagents companies, unless otherwise specified.
Example 1
720mg of sulfur powder and 580mg of sodium sulfide are weighed and stirred in 25mL of ultrapure water to form yellow sodium polysulfide solution; weighing 50mL of graphene oxide solution (4mg/mL) and 200mg of carbon nanotube powder, and effectively ultrasonically dispersing the graphene oxide solution and the carbon nanotube powder in 250mL of ultrapure water under the action of a surfactant; weighing a certain amount of ferrous acetate powder, adding into the dispersion, stirring thoroughly, slowly adding 3mL of sodium polysulfide solution into the dispersion, and adding 20mg of Ni (Ac)2·4H2Performing hydrothermal reaction at 150 ℃ for 12h, filtering, washing, and freeze-drying to obtain an initial sample; and (3) heating to 500 ℃ in the Ar atmosphere for 30min, preserving the temperature for 30min, and cooling to room temperature to obtain the defect-based compound anchoring nickel atom composite material. As can be seen from fig. 1, the nanoparticle size of the prepared composite material is relatively small.
Example 2
Weighing 720mg of sulfur powder and 580mg of sodium sulfide in 25mL of ultrapure water, and stirring to form a yellow sodium polysulfide solution; weighing 50mL of graphene oxide solution (4mg/mL) and 200mg of carbon nanotube powder, and effectively ultrasonically dispersing the graphene oxide solution and the carbon nanotube powder in 250mL of ultrapure water under the action of a surfactant; weighing a certain amount of ferrous acetate powder, adding into the dispersion liquid, and fully stirring; 3mL of sodium polysulfide solution were slowly added to the dispersion, followed by 50mg of Co (Ac)2Carrying out hydrothermal reaction at 120 ℃ for 12h, then filtering, washing and freeze-drying to obtain an initial sample; at Ar/NH3Heating to 100 ℃ for 30min, keeping the temperature for 120min, and cooling to room temperature to obtain the defect-based compound anchored cobalt atom composite material, wherein the size of the nano particles of the prepared composite material is smaller and cobalt is distributed in an atomic state as can be seen from figure 2.
Example 3
Weighing 720mg of sulfur powder and 580mg of sodium sulfide in 25mL of ultrapure water, and stirring to form a yellow sodium polysulfide solution; weighing 50mL of graphene oxide solution (4mg/mL) and 200mg of carbon nanotube powder, and effectively ultrasonically dispersing the graphene oxide solution and the carbon nanotube powder in 250mL of ultrapure water under the action of a surfactant; weighing a certain amount of cobaltous acetate powder, adding the cobaltous acetate powder into the dispersion liquid, and fully stirring; then will 3Slowly adding mL of sodium polysulfide solution into the dispersion, then adding 15mg of iron acetate, carrying out hydrothermal reaction for 12h at 200 ℃, then filtering, washing, and freeze-drying to obtain an initial sample; at Ar/NH3Heating to 400 ℃ for 30min, keeping the temperature for 10min, and cooling to room temperature to obtain the defect base compound anchoring iron atom composite material. As can be seen from fig. 3, the nanoparticle size of the prepared composite material is relatively small.
Example 4
The defect-based compound anchoring nickel atom composite material in the embodiment 1 is ultrasonically dispersed in 80mL ethanol, vacuum filtration is carried out on a commercial diaphragm to obtain a modified diaphragm, the modified diaphragm is contacted with a negative electrode or a modified layer is peeled and then placed between the diaphragm and the negative electrode when a battery is assembled, the modified diaphragm is extruded on the surface of the negative electrode under the pressure action of a sealing machine during battery packaging to form a protective layer, the complex step of independently carrying out rolling modification on the surface of the negative electrode is omitted, and meanwhile, the uniformity and the thickness of the modified diaphragm obtained by vacuum filtration are higher than the controllability of a rolling method. As shown in fig. 4, the lithium metal surface after cycling exhibited a flat deposition and morphology.
Example 5
40mg of the defect-based compound anchoring cobalt atom composite material in the embodiment 2 is mixed with a certain amount of binder to form slurry, the slurry is coated on a commercial diaphragm to form a modified diaphragm, the modified diaphragm is contacted with a negative electrode when a battery is assembled, the diaphragm is extruded on the surface of the negative electrode after being modified under the pressure of a sealing machine during battery packaging to form a protective layer, the complex step of performing roll-in modification on the surface of the negative electrode independently is omitted, and meanwhile, the uniformity and the thickness of a modified layer obtained by adopting a coating mode are higher than the controllability of a roll-in method. As shown in fig. 5, the lithium metal-based battery exhibits a lower polarization overpotential.
Example 6
Iron atom composites anchored with defect based compounds prepared in example 3 were mixed with carbon black (conductive agent) and binder (PVDF) at 7: 2: 1, preparing slurry, uniformly coating the slurry on an aluminum foil, drying at 50 ℃ in vacuum for 24 hours, punching into a sheet with the diameter of 15mm as a positive electrode catalytic carrier, dropwise adding a lithium polysulfide active substance with certain concentration on the surface of the sheet, taking metal lithium as a negative electrode, taking DOL/DME (volume ratio of 1:1) solution of LiTFSI as electrolyte, and assembling the button cell by using a 2025 type cell shell. The tafel curve of the electrode was tested, and it can be seen from fig. 6 that the composite material with the single atom doped defect has stronger synergistic catalytic action than the single defect-based compound.
Example 7
The defect-based compound-anchored cobalt atom composite material prepared in example 2 was loaded with 80 wt% of sulfur as a carrier under an inert atmosphere in a glove box, and was mixed with carbon black (conductive agent) and a binder (PVDF) in a mass ratio of 7: 2: 1, coating the mixture to form a positive electrode, taking the lithium electrode containing the modified diaphragm as a negative electrode, and adding 1M LiFSI and 1% LiNO3The DOL/DME solution is used as electrolyte to manufacture large-area high-sulfur-carrying surface density soft package batteries. The soft package battery can light one set of LED lamps (as shown in figure 7) for a long time, and potential of future device application is embodied. In addition, the cycle performance test shows that the soft package battery has more excellent performance than the lithium sulfur soft package battery prepared at present. As shown in fig. 8, the lithium metal-based battery exhibited a lower polarization overpotential.
Comparative example 1
720mg of sulfur powder and 580mg of sodium sulfide were weighed out and stirred in 25mL of ultrapure water to form a yellow sodium polysulfide solution. 50mL of graphene oxide solution (4mg/mL) and 200mg of carbon nanotube powder are weighed, the graphene oxide solution and the carbon nanotube powder are effectively ultrasonically dispersed in 250mL of ultrapure water under the action of a surfactant, a certain amount of ferrous acetate powder is weighed and added into the dispersion liquid, and the mixture is fully stirred. Then 3mL of sodium polysulfide solution was slowly added to the dispersion, and the mixture was subjected to hydrothermal reaction for 12 hours, followed by filtration, washing, and freeze-drying to obtain an initial sample. And (3) raising the temperature to 500 ℃ in the Ar atmosphere for 30min, preserving the temperature for 30min, and cooling to room temperature to obtain the final sample. FIG. 9 is a transmission electron micrograph of a sample prepared according to this comparative example; by comparison with examples 1 and 2, it can be seen that examples 1 and 2 succeeded in producing defect-based compound-anchored nickel atom composites and defect-based compound-anchored cobalt atom composites.
Comparative example 2
The final sample prepared in the comparative example 1 of 30mg is mixed with a certain amount of binder to form slurry, the slurry is coated on a commercial diaphragm to form a modified diaphragm, the modified diaphragm is contacted with a negative electrode when a battery is assembled, and the modified layer is extruded on the surface of the negative electrode under the pressure of a sealing machine when the battery is packaged to form a protective layer, so that the complex step of independently performing roll-pressing modification on the surface of the negative electrode is omitted, and meanwhile, the uniformity and thickness of the modified layer obtained by adopting a coating mode are higher than the controllability of a roll-pressing method. As shown in fig. 10, the cycle performance of the lithium metal battery was tested and had poor performance.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.

Claims (19)

1. A defect-based compound-anchored monatomic composite material characterized by comprising a defect-based compound, a metal monatomic supported on the defect-based compound, and a sulfur-doped nanocarbon; the sulfur-doped nanocarbon has a hierarchical pore structure, and the defect-based compound is distributed in the hierarchical pore structure of the sulfur-doped nanocarbon; the content of the metal monoatomic atom in the defect base compound loading the monoatomic atom is 0.1-20 at%; the defect base compound is selected from any one or combination of more than two of metal oxide, metal sulfide and metal nitride;
the preparation method of the defect-based compound anchoring monoatomic composite material comprises the following steps:
uniformly mixing graphene oxide, a carbon nano tube, a surfactant, polysulfide, a metal salt precursor and a solvent, then adding a metal monoatomic precursor, and carrying out hydrothermal reaction for 12 hours at 120-200 ℃;
and, in NH3And/or in an inert atmosphere, carrying out heat treatment on the obtained hydrothermal reaction product at 100-500 ℃ for 10-120 min to obtain the defect-based compound anchored single-atom composite material.
2. The defect-based compound anchored monatomic composite of claim 1, wherein: the metal single atom is selected from any one of copper, molybdenum, iron, nickel, cobalt, platinum, ruthenium and rhodium atoms.
3. The defect-based compound anchored monatomic composite of claim 1, wherein: the sulfur-doped nano carbon is prepared from sulfur-doped graphene oxide and a carbon nano tube; the pore diameter of the sulfur-doped nano carbon is 2-200 nm, and the porosity is 500-2000 cm3/g。
4. The defect-based compound anchored monatomic composite of claim 1, wherein: ultrasonically dispersing graphene oxide, carbon nanotubes and a surfactant in a solvent, then adding a metal salt precursor, fully mixing to form a first dispersion liquid, then adding a polysulfide solution into the obtained first dispersion liquid, mixing, and then adding a metal monatomic precursor.
5. The defect-based compound anchored monatomic composite of claim 4, wherein: the solvent is selected from water; the polysulfide solution is formed by dissolving sulfur powder and sulfide in water; the sulfide is selected from sodium sulfide.
6. The defect-based compound anchored monatomic composite of claim 1, wherein: at NH3And/or in an inert atmosphere, raising the temperature of the mixture obtained by the hydrothermal reaction to 100-500 ℃ at a temperature raising rate of 2-10 ℃/min.
7. The defect-based compound anchored monatomic composite of claim 1, wherein: the surfactant is selected from polyvinylpyrrolidone.
8. The defect-based compound anchored monatomic composite of claim 1, wherein: the metal salt precursor is selected from ferrous acetate and/or cobaltous acetate.
9. The defect-based compound anchored monatomic composite of claim 1, wherein: the polysulphide is selected from sodium polysulphides.
10. The defect-based compound anchored monatomic composite of claim 1, wherein: the metal monoatomic precursor is selected from copper acetate, molybdenum acetate, platinum acetate, ruthenium acetate, rhodium acetate, Ni (Ac)2∙4H2O、Co(Ac)2、Fe(Ac)3Any one or a combination of two or more of them.
11. The defect-based compound anchored monatomic composite of claim 1, wherein: the mass ratio of the graphene oxide to the carbon nano tube to the surfactant to the polysulfide to the metal salt precursor to the metal monatomic precursor is 0.01-0.1: 0.2-1: 0.001-0.01: 0.5-1: 3-8: 0.1-1.
12. The defect-based compound anchored monatomic composite of claim 1, wherein: the preparation method of the defect-based compound anchored monatomic composite material further includes: and after the hydrothermal reaction is finished, filtering, washing and freeze-drying the obtained mixture.
13. Use of the defect-based compound anchored monatomic composite of any of claims 1-12 in the preparation of a rechargeable lithium metal-based battery.
14. Use according to claim 13, characterized in that: the use is of a defect-based compound to anchor a single-atom composite material in the preparation of a lithium-sulfur battery or a lithium-air battery.
15. A rechargeable lithium metal-based battery negative electrode comprising an electrode and a protective layer on the surface of the electrode, the protective layer comprising at least the defect-based compound anchored monatomic composite material of any one of claims 1 to 12.
16. The rechargeable lithium metal-based battery negative electrode of claim 15, wherein: the protective layer is prepared by the defect group compound anchoring monoatomic composite material modified diaphragm; the electrode is selected from lithium electrodes.
17. A method of making a negative electrode for a rechargeable lithium metal-based battery according to claim 15 or 16, comprising: mixing the defect-based compound anchoring monatomic composite material of any one of claims 1 to 12 with a binder to form a slurry, then applying the slurry to the surface of a separator to form a modified separator, and forming a protective layer on the surface of an electrode through an encapsulation treatment, thereby producing a rechargeable lithium metal-based battery negative electrode.
18. The method of manufacturing according to claim 17, wherein: the membrane is a commercial membrane; the electrode is selected from lithium electrodes.
19. A rechargeable lithium metal-based battery comprises a positive electrode, a negative electrode and electrolyte, and is characterized in that: the anode comprises the rechargeable lithium metal-based battery anode of claim 15 or 16, and the cathode comprises at least the defect-based compound-anchored monatomic composite of any of claims 1-12.
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