CN114824180B - Foam nickel with heterojunction nano-sheet layer grown on surface and preparation method and application thereof - Google Patents

Foam nickel with heterojunction nano-sheet layer grown on surface and preparation method and application thereof Download PDF

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CN114824180B
CN114824180B CN202210504090.2A CN202210504090A CN114824180B CN 114824180 B CN114824180 B CN 114824180B CN 202210504090 A CN202210504090 A CN 202210504090A CN 114824180 B CN114824180 B CN 114824180B
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heterojunction nano
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heterojunction
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CN114824180A (en
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宫勇吉
金椿乔
翟朋博
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Beihang University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes

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Abstract

The invention relates to the technical field of lithium-sulfur batteries, in particular to foam nickel with heterojunction nanosheets grown on the surface, and a preparation method and application thereof. The preparation method provided by the invention comprises the following steps: mixing urea, an oxidant and water to obtain a urea solution; placing the foam nickel into the urea solution, and sequentially performing hydrothermal reaction, annealing treatment and vulcanization reaction to obtain the foam nickel with heterojunction nano-sheets grown on the surface; the heterojunction nano-sheets in the heterojunction nano-sheet layer are NiO and Ni 3 S 2 Is composed of NiO and Ni 3 S 2 The thickness of the heterojunction nano-sheet is 1.7-3.2 nm. The thickness of the heterojunction nano-sheet on the surface of the foam nickel with the heterojunction nano-sheet layer grown on the surface is 1.7-3.2 nm, and the heterojunction nano-sheet has better active sites and strong binding property with the foam nickel.

Description

Foam nickel with heterojunction nano-sheet layer grown on surface and preparation method and application thereof
Technical Field
The invention relates to the technical field of lithium-sulfur batteries, in particular to foam nickel with heterojunction nanosheets grown on the surface, and a preparation method and application thereof.
Background
In recent years, the continuous development of portable charging devices, electric vehicles and smart grids has put new demands on the energy market, and the demand for high energy density storage has increased significantly. Lithium sulfur batteries achieve an ultra high energy density of 2567Wh/kg by coupling the sulfur of the positive electrode with the lithium metal of the negative electrode, and are considered to be the most promising next generation energy storage systems. However, in addition to the insulating properties of sulfur itself, the "shuttle effect" during cycling of lithium sulfur batteries results in degradation of the cycling performance of the battery at high loadings, severely limiting its practical application. The root cause of this is the slow kinetics of lithium polysulfide conversion, resulting in a large accumulation of lithium polysulfide during battery cycling, thereby exacerbating the "shuttle effect". The main reason is that: the discharging process of the lithium-sulfur battery is a sulfur reduction process, e.g., S 8 →Li 2 S 8 →Li 2 S 4 →Li 2 S 2 /Li 2 S and the like. Wherein Li is in liquid phase 2 S 4 Solid phase Li 2 S 2 /Li 2 The activation energy required for this step of the reaction is highest and is therefore the step of the overall discharge process. But without the help of a catalyst, will result in a large amount of liquid phase Li 2 S 4 And (5) accumulation. Excessive accumulation can lead to liquid phase Li 2 S 4 Is pulled out of the battery positive electrode, dissolves in the electrolyte, and even shuttles through the battery separator to the battery negative electrode, causing irreversible capacity loss (shuttle effect).
In order to solve the above problems, the design of the catalyst and its rational use are critical. Transition metal heterojunctions have attracted considerable attention from researchers due to their excellent electrocatalytic properties and good electrical conductivity. Lithium sulfur battery is realized by regulating and controlling structure and morphology of heterojunctionStable cycling at high loadings became a hotspot for research. However, the lack of an effective means of synthesizing ultra-thin heterojunctions generally results in thicker synthetic heterojunctions and the inability to expose more active sites for effective catalysis. Meanwhile, in the conventional preparation method at present, nano-sheets (Facile synthesis of a NiO/NiS hybrid and its use as an efficient electrode material for supercapacitor applications or Cliff-like NiO/Ni are grown on foam nickel by a method of adding a nickel source 3 S 2 Directly Grown on Ni Foam for Battery-type Electrode with High Area Capacity and Long Cycle Stability), the heterojunction nano-sheet and the foam nickel are poor in combination and easy to fall off, and stable catalysis of polysulfide lithium conversion is not realized.
Disclosure of Invention
The invention aims to provide foam nickel with a heterojunction nano-sheet layer grown on the surface, a preparation method and application thereof, and the heterojunction nano-sheet with the heterojunction nano-sheet layer grown on the surface, which is prepared by the preparation method, has the thickness of 1.7-3.2 nm, has better active sites and strong bonding property with the foam nickel.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of foam nickel with heterojunction nano-sheets grown on the surface, which comprises the following steps:
mixing urea, an oxidant and water to obtain a urea solution;
placing the foam nickel into the urea solution for hydrothermal reaction to obtain foam nickel with nickel hydroxide growing on the surface;
annealing the nickel foam with nickel hydroxide supported on the surface to obtain nickel foam with nickel oxide grown on the surface;
carrying out a vulcanization reaction on the foam nickel with the nickel oxide loaded on the surface and hydrogen sulfide to obtain the foam nickel with the heterojunction nano-sheet layer grown on the surface;
the heterojunction nano-sheets in the heterojunction nano-sheet layer are NiO and Ni 3 S 2 Is composed of NiO and Ni 3 S 2 The thickness of the heterojunction nano-sheet is 1.7-3.2 nm.
Preferably, the oxidizing agent comprises a hydrogen peroxide solution or ammonium fluoride;
the mass concentration of the hydrogen peroxide solution is 1-3 wt%.
Preferably, when the oxidizing agent is a hydrogen peroxide solution, the ratio of urea to hydrogen peroxide is (100-180) mg:1mL;
when the oxidant is ammonium fluoride, the mass ratio of the urea to the ammonium fluoride is 9 (5-6).
Preferably, the temperature of the hydrothermal reaction is 120-180 ℃ and the time is 2-24 h.
Preferably, the annealing treatment is carried out at a temperature of 300-350 ℃ for 5-12 hours.
Preferably, the hydrogen sulfide is introduced at a rate of 10 to 30sccm.
Preferably, the temperature of the vulcanization reaction is 100-200 ℃ and the time is 10-30 min.
The invention also provides the foam nickel with the heterojunction nano-sheet layer grown on the surface, which is prepared by the preparation method, and comprises the foam nickel and the heterojunction nano-sheet layer grown on the surface of the foam nickel in situ;
the heterojunction nano-sheets in the heterojunction nano-sheet layer are NiO and Ni 3 S 2 Is composed of NiO and Ni 3 S 2 The thickness of the heterojunction nano-sheet is 1.7-3.2 nm.
Preferably, the NiO and Ni 3 S 2 The mass ratio of (4-11.5): 1.
the invention also provides application of the foam nickel with the heterojunction nano-sheet layer grown on the surface in the lithium-sulfur battery.
The invention provides a preparation method of foam nickel with heterojunction nano-sheets grown on the surface, which comprises the following steps: mixing urea, an oxidant and water to obtain a urea solution; placing foam nickel into the urea solution for hydrothermal reaction to obtain a tableFoam nickel with nickel hydroxide growing on the surface; annealing the nickel foam with nickel hydroxide supported on the surface to obtain nickel foam with nickel oxide grown on the surface; carrying out a vulcanization reaction on the foam nickel with the nickel oxide loaded on the surface and hydrogen sulfide to obtain the foam nickel with the heterojunction nano-sheet layer grown on the surface; the heterojunction nano-sheets in the heterojunction nano-sheet layer are NiO and Ni 3 S 2 Is composed of NiO and Ni 3 S 2 The thickness of the heterojunction nano-sheet is 1.7-3.2 nm. According to the invention, foam nickel is used as a substrate, an oxidant and urea are used as precursors, a hydrothermal method is combined to grow nickel hydroxide ultrathin nanosheets on the surface layer of the foam nickel in situ, the ultrathin heterojunction nanosheets are prepared on the surface of the foam nickel by taking the ultrathin heterojunction nanosheets as templates through annealing treatment and vulcanization treatment, and the ultrathin heterojunction nanosheets can provide abundant active sites for catalyzing lithium polysulfide after being applied to a lithium sulfur battery, so that the conversion efficiency of the lithium polysulfide is accelerated, the shuttle effect is restrained, and the cycle stability of the lithium sulfur battery is realized; meanwhile, the in-situ growth mode can enable the heterojunction nano-sheet and the foam nickel substrate to be firmly combined, and the heterojunction nano-sheet is not easy to fall off, so that the heterojunction nano-sheet can stably catalyze the transformation of lithium polysulfide.
The invention also provides the foam nickel with the heterojunction nano-sheet layer grown on the surface, which is prepared by the preparation method, and comprises the foam nickel and the heterojunction nano-sheet layer; the heterojunction nano-sheets in the heterojunction nano-sheet layer are NiO and Ni 3 S 2 Is composed of NiO and Ni 3 S 2 The thickness of the heterojunction nano-sheet is 1.7-3.2 nm. Due to NiO/Ni 3 S 2 The nano-sheet has thinner thickness and larger specific surface area, and can provide sufficient adsorption sites to lock the lithium polysulfide. Based on the calculated results of the state density, nickel oxide, nickel sulfide and NiO/Ni 3 S 2 The band gap values of the heterojunction surfaces are 0.3eV,0.04eV and 0.01eV respectively, and NiO/Ni can be seen 3 S 2 The heterojunction surface is metallic and has better conductivity. Meanwhile, since the nickel oxide has the best adsorption effect on the lithium polysulfide, but is conductivePoor performance and slow migration of lithium ions on the surface of the catalyst, so that the catalytic activity of the catalyst is poor; the lithium ion migration rate on the surface of nickel sulfide is the fastest, but the binding force of the nickel sulfide to lithium polysulfide is too weak, so that the shuttle effect is serious. Therefore, the pure nickel oxide or nickel sulfide has defects when catalyzing the lithium sulfur battery, and the NiO/Ni disclosed by the invention 3 S 2 Heterojunction surface and Li 2 S has more charge transfer between them, weakening the Li-S bond by forming Ni-S bond, and Li-S bond is at NiO/Ni 3 S 2 The heterojunction surface is elongated, niO/Ni 3 S 2 Heterojunction can accelerate Li 2 S is decomposed, thereby improving the utilization rate of sulfur.
Drawings
FIG. 1 is a schematic flow chart of the preparation method of the invention;
FIG. 2 is an SEM image and an atomic force microscope image of a heterojunction nanoplatelet of nickel foam with a heterojunction nanoplatelet layer grown on the surface as described in example 1;
FIG. 3 is a spectrum and transmission electron microscope chart of the heterojunction nanoplatelets of example 1;
FIG. 4 is an X-ray diffraction pattern, an X-ray spectrum pattern and an X-ray absorption fine structure pattern of the foam nickel with a heterojunction nano-sheet layer grown on the surface of the foam nickel in example 1;
FIG. 5 is a graph of electrochemical performance as described in test example 2.
Detailed Description
The invention provides a preparation method of foam nickel with heterojunction nano-sheets grown on the surface, which comprises the following steps:
mixing urea, an oxidant and water to obtain a urea solution;
placing the foam nickel into the urea solution for hydrothermal reaction to obtain foam nickel with nickel hydroxide growing on the surface;
annealing the nickel foam with nickel hydroxide supported on the surface to obtain nickel foam with nickel oxide grown on the surface;
carrying out a vulcanization reaction on the foam nickel with the nickel oxide loaded on the surface and hydrogen sulfide to obtain the foam nickel with the heterojunction nano-sheet layer grown on the surface (the preparation flow is shown in figure 1);
the heterojunction nano-sheets in the heterojunction nano-sheet layer are NiO and Ni 3 S 2 Is composed of NiO and Ni 3 S 2 The thickness of the heterojunction nano-sheet is 1.7-3.2 nm.
In the present invention, all the preparation materials are commercially available products well known to those skilled in the art unless specified otherwise.
The invention mixes urea, oxidant and water to obtain urea solution.
In the present invention, the oxidizing agent preferably includes a hydrogen peroxide solution or ammonium fluoride; the mass concentration of the hydrogen peroxide solution is preferably 1 to 3wt%, more preferably 1.3 to 2.0wt%, and most preferably 1.47 wt%.
In the present invention, the water is preferably deionized water.
In the present invention, when the oxidizing agent is a hydrogen peroxide solution, the ratio of the urea to hydrogen peroxide is preferably (100 to 180) mg/1 mL, more preferably 180mg:1mL; in the present invention, when the oxidizing agent is ammonium fluoride, the mass ratio of urea to ammonium fluoride is preferably 9 (5 to 6), more preferably 9:5.
In the present invention, the amount of urea and water is preferably 100 to 180 mg/15 to 20mL, more preferably 180mg:15mL.
In the present invention, the mixing is preferably performed under stirring for a period of preferably 1 to 10 minutes, more preferably 10 minutes. The stirring speed is not particularly limited in the present invention, and it is sufficient to use a speed well known to those skilled in the art and to ensure that a uniform urea solution is obtained during the above stirring time.
After the urea solution is obtained, the foam nickel is placed in the urea solution, and the hydrothermal reaction is carried out to obtain the foam nickel with nickel hydroxide growing on the surface.
The nickel foam of the present invention is not particularly limited, and commercially available products known to those skilled in the art may be used.
In the present invention, the temperature of the hydrothermal reaction is preferably 120 to 180 ℃, more preferably 150 to 180 ℃, most preferably 180 ℃, and the time is preferably 2 to 24 hours, more preferably 20 to 24 hours, most preferably 24 hours.
After the hydrothermal reaction is completed, the invention also preferably includes drying; the drying process is not particularly limited, and may be performed by a process known to those skilled in the art.
After the nickel foam with the nickel hydroxide growing on the surface is obtained, the nickel foam with the nickel hydroxide loaded on the surface is annealed to obtain the nickel foam with the nickel oxide growing on the surface.
In the present invention, the annealing treatment is preferably performed at a temperature of 300 to 350 ℃, more preferably 300 to 320 ℃, most preferably 300 ℃, for a time of 5 to 12 hours, more preferably 8 to 12 hours, most preferably 12 hours.
After the annealing treatment is completed, the invention also preferably comprises cooling; the cooling process is not particularly limited, and may be performed by a process known to those skilled in the art.
After the foam nickel with the nickel oxide growing on the surface is obtained, the foam nickel with the nickel oxide loaded on the surface and hydrogen sulfide are subjected to a vulcanization reaction to obtain the foam nickel with the heterojunction nano-sheet growing on the surface.
In the present invention, the hydrogen sulfide is introduced at a rate of preferably 10 to 30sccm, more preferably 20 to 30sccm, and most preferably 30sccm; the temperature of the vulcanization reaction is preferably 100 to 200 ℃, more preferably 100 to 150 ℃, and most preferably 100 ℃; the time is preferably 10 to 30 minutes, more preferably 10 to 20 minutes, and most preferably 10 minutes.
The invention also provides the foam nickel with the heterojunction nano-sheet layer grown on the surface, which is prepared by the preparation method, and comprises the foam nickel and the heterojunction nano-sheet layer;
the heterojunction nano-sheets in the heterojunction nano-sheet layer are NiO and Ni 3 S 2 Is composed of NiO and Ni 3 S 2 The thickness of the heterojunction nano-sheet is 1.7-3.2 nm.
In the present invention, the thickness of the heterojunction nanoplatelets is preferably 1.7 to 3.2nm, more preferably 1.7nm;
the NiO and Ni 3 S 2 The mass ratio of (2) is preferably (4-11.5): 1, more preferably (4 to 7): 1, most preferably 4:1.
The invention also provides application of the foam nickel with the heterojunction nano-sheet layer grown on the surface in the lithium-sulfur battery. In the invention, the foam nickel with the heterojunction nano sheet layer grown on the surface is directly used as the positive electrode of the lithium sulfur battery to be applied to the lithium sulfur battery; the method of the present invention is not particularly limited, and may be carried out by methods known to those skilled in the art.
The nickel foam with heterojunction nano-sheets grown on the surface and the preparation method and application thereof provided by the invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the invention.
Example 1
180mg of urea, 1mL of hydrogen peroxide solution with mass concentration of 30wt% and 15mL of deionized water are mixed and stirred for 10min to obtain urea solution;
the size is 2 x 1cm 2 Placing the foam nickel in the urea solution, performing hydrothermal reaction at 180 ℃ for 24 hours, taking out and drying to obtain the foam nickel with nickel hydroxide growing on the surface;
annealing the foamed nickel with nickel hydroxide growing on the surface at 300 ℃ for 12 hours to obtain the foamed nickel with nickel oxide growing on the surface;
introducing hydrogen sulfide gas (the introducing rate is 30 sccm) into the environment of the foam nickel with the nickel oxide grown on the surface, and performing vulcanization reaction for 10min at 100 ℃ to obtain the foam nickel with the heterojunction nano-sheets grown on the surface (the heterojunction nano-sheets in the heterojunction nano-sheets are NiO and Ni) 3 S 2 Is composed of NiO and Ni 3 S 2 The thickness of the heterojunction nano-sheet is 1.7nm, and the NiO and the Ni 3 S 2 Is 4:1 by mass ratio
Test example 1
Carrying out scanning electron microscope test and atomic force microscope test on the foam nickel with the heterojunction nano-sheet layer grown on the surface, wherein the test results are shown in figure 2, a and b are SEM images under different multiplying powers, and c is an atomic force microscope image; as can be seen from fig. 2, the thickness of the heterojunction nano-sheet in the foam nickel with the heterojunction nano-sheet layer grown on the surface according to the invention is very thin, which is 1.7nm;
carrying out energy spectrum test and transmission electron microscope test on the foam nickel with the heterojunction nano-sheet layer grown on the surface, wherein the test results are shown in figure 3, a is a low-magnification TEM image, b is a high-resolution TEM image (an embedded image at the lower right corner is a diffraction spot diagram), c is lattice stripes of nickel sulfide in the heterojunction, and d is an element mapping image of the heterojunction; as can be seen from FIG. 3, the heterojunction of the present invention has the morphology of ultrathin nanosheets, niO and Ni 3 S 2 A heterojunction structure is formed between the two elements, and Ni, O and S are uniformly distributed;
the method comprises the steps of respectively carrying out X-ray diffraction, X-ray spectrum and X-ray absorption fine structure spectrum test on the foam nickel with the heterojunction nano-sheet layer grown on the surface, wherein the test results are shown in a figure 4, a is an XRD (X-ray diffraction) diagram, b-d are XPS (X-ray absorption fine structure) diagrams, e is an X-ray absorption fine structure spectrum, and f is an R space curve obtained by secondary Fourier change in e; as can be seen from fig. 4, the heterojunction has a crystal structure (XRD pattern) with ni—o bonds and ni—s bonds (XPS pattern), and the valence state of Ni is between +1 and +2 (e pattern); f graph further accurately demonstrates the presence of Ni-O bonds and Ni-S bonds in the heterojunction;
comparative example 1
Reference example 1 differs in that the nickel foam is replaced with nickel foil.
Test example 2
Assembled in an argon atmosphere glove box with a water oxygen content of less than 1ppm.
And (3) assembling a full battery: will 13uL Li 2 S 8 (0.3M) drop NiO/Ni to 1.1cm diameter respectively 3 S 2 NiO and Ni 3 S 2 The material was then added dropwise with electrolyte ((LiTFSI in DOL/DME (v/v=1:1) with 1wt% of LiNO) 3 ) Then assembling the battery according to the sequence of the anode, the diaphragm and the lithium metal cathode;
assembling a symmetrical battery: will 13uL Li 2 S 8 (0.3M) drop NiO/Ni to 1.1cm diameter respectively 3 S 2 NiO and Ni 3 S 2 The cell is then assembled in a symmetrical fashion (e.g., niO/S-separator-NiO/S).
The full cell and the symmetrical cell were tested, the test results are shown in FIG. 5, wherein a is NiO/Ni 3 S 2 /S、NiO/S、Ni 3 S 2 CV test of lithium sulfur full cell with S as positive electrode: the potential interval is set to be 1.7-2.8, and the sweeping speed is set to be 0.1 mV.s -1 The test instrument was CHI 760e (Shanghai Chen Hua Co., ltd.). From a, niO/Ni 3 S 2 The current of the reduction peak of/S is 3.2mA, which is far greater than NiO/S (1.9 mA) and Ni 3 S 2 S (1.9 mA), proved NiO/Ni 3 S 2 Effectively improves the utilization rate of sulfur. At the same time NiO/Ni 3 S 2 The potential of the oxidation peak of/S was 2.37V, compared with NiO/S (2.34V), ni 3 S 2 The S (2.35V) has obvious forward movement, which proves that NiO/Ni 3 S 2 Can effectively improve the direction of lithium polysulfide to the final discharge product Li 2 S conversion;
b is NiO/Ni 3 S 2 /S、NiO/S、Ni 3 S 2 Symmetrical cell CV test of/S: the potential interval is set to be-1 to 1, and the sweeping speed is set to be 1 mV.s -1 The test instrument was CHI 760e (Shanghai Chen Hua Co., ltd.). From b, niO/Ni 3 S 2 The current of the symmetrical battery is 6.07mA, which is far greater than NiO/S (2.15 mA) and Ni 3 S 2 Demonstration of NiO/Ni by S (3.43 mA) 3 S 2 The catalyst has higher catalytic activity in the conversion of lithium polysulfide;
c is NiO/Ni 3 S 2 /S、NiO/S、Ni 3 S 2 Test of charge-discharge curve of lithium-sulfur full cell with S as positive electrode: the current density is 1C; from c, niO/Ni 3 S 2 The charge-discharge platform corresponding to/S has the minimum polarization potential of 220mV which is far smaller than NiO/S (500 mV) and Ni 3 S 2 S (510 mV), proved NiO/Ni 3 S 2 More effectively accelerating the redox kinetics of lithium polysulfide;
d is a multiplying power performance test: the current densities were 0.1C, 0.2C, 0.5C, 1C, 2C, and 0.2C, respectively; from d, niO/Ni 3 S 2 The discharge capacity of the lithium sulfur full battery taking S as the positive electrode is 1490 mA.h.g respectively under the multiplying power of 0.1C, 0.2C, 0.5C, 1C and 2C -1 ，1235mA·h·g -1 ，1082mA·h·g -1 ，833mA·h·g -1 And 632 mA.h.g -1 Far greater than NiO/S (1003 mA.h.g) -1 ，781mA·h·g -1 ，676mA·h·g -1 ，579mA·h·g -1 And 505 mA.h.g -1 ) And Ni 3 S 2 /S(798mA·h·g -1 ，669mA·h·g -1 ，524mA·h·g -1 ，281mA·h·g -1 And 112 mA.h.g -1 ) Proved by NiO/Ni 3 S 2 Discharge performance of S is superior to NiO/S, ni at each current density 3 S 2 and/S. Meanwhile, in the conversion of 2C to 0.2C current density, the corresponding discharge capacity can still be maintained, and the NiO/Ni is proved 3 S 2 Discharge stability of/S;
e is a charge-discharge cycle test: the current density is 1C; from e, niO/Ni 3 S 2 The initial ring discharge capacity of the lithium-sulfur full battery taking S as the positive electrode is 920 mA.h.g under the current density of 1C -1 The residual discharge capacity after 300 cycles was 764Ni 3 S 2 Higher than NiO/S (first turn 782 mA.h.g) -1 Finishing 340 mAh.g -1 )、Ni 3 S 2 S (first turn 527 mA.h.g) -1 End 344 mA.h.g -1 )；
f is the cycle performance test at high active loading: active material loading of 6mg cm -2 The method comprises the steps of carrying out a first treatment on the surface of the From f, niO/Ni 3 S 2 The first-ring discharge surface density of the lithium-sulfur full battery taking S as the positive electrode can reach 4.8mA.h.cm under the high load of active substances -2 The surface density of the residual discharge after 100 circles is 3.9mA.h.cm -2 Proved by NiO/Ni 3 S 2 S has a more stable cycle at high active loading;
g is the charge-discharge cycle test of substituting the material of example 1 for the material of comparative example 1, and the test conditions are the same as above, and it is known from g that NiO/Ni 3 S 2 The initial ring discharge capacity of the lithium-sulfur full cell 1C with S as the positive electrode is 693mA.h.g -1 The residual discharge capacity after 300 cycles was 654 mA.h.g -1 It was demonstrated that the material replaced with comparative example 1 also allows stable cycling:
h is a cycle performance test at high active loading (comparative example 1), active loading of 3mg cm -2 From h, niO/Ni 3 S 2 First-turn discharge capacity of the lithium-sulfur full cell 1C with S as the positive electrode is 542 mAh.g -1 The residual discharge capacity after 50 cycles was 500mAh g -1 It was demonstrated that, instead of the material of comparative example 1, a stable cycle can be achieved also at high loadings of active substance.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (10)

1. The preparation method of the foam nickel with the heterojunction nano-sheet layer grown on the surface is characterized by comprising the following steps:
mixing urea, an oxidant and water to obtain a urea solution;
placing the foam nickel into the urea solution for hydrothermal reaction to obtain foam nickel with nickel hydroxide growing on the surface;
annealing the nickel foam with nickel hydroxide supported on the surface to obtain nickel foam with nickel oxide grown on the surface;
carrying out a vulcanization reaction on the foam nickel with the nickel oxide loaded on the surface and hydrogen sulfide to obtain the foam nickel with the heterojunction nano-sheet layer grown on the surface;
the heterojunction nano-sheets in the heterojunction nano-sheet layer are NiO and Ni 3 S 2 Is composed of NiO and Ni 3 S 2 The thickness of the heterojunction nano-sheet is 1.7-3.2 nm;
the foam nickel with the heterojunction nano-sheet layer grown on the surface is applied to a lithium-sulfur battery.
2. The method of claim 1, wherein the oxidizing agent comprises a hydrogen peroxide solution or ammonium fluoride;
the mass concentration of the hydrogen peroxide solution is 1-3 wt%.
3. The method of claim 2, wherein when the oxidizing agent is a hydrogen peroxide solution, the ratio of urea to hydrogen peroxide is (100-180) mg:1mL;
when the oxidant is ammonium fluoride, the mass ratio of the urea to the ammonium fluoride is 9 (5-6).
4. The method according to claim 1, wherein the hydrothermal reaction is carried out at a temperature of 120 to 180 ℃ for a time of 2 to 24 hours.
5. The method according to claim 1, wherein the annealing treatment is performed at a temperature of 300 to 350 ℃ for a time of 5 to 12 hours.
6. The method according to claim 1, wherein the hydrogen sulfide is introduced at a rate of 10 to 30sccm.
7. The method according to claim 1, wherein the temperature of the vulcanization reaction is 100 to 200 ℃ for 10 to 30 minutes.
8. The foam nickel with the heterojunction nano-sheet layer grown on the surface and prepared by the preparation method as claimed in any one of claims 1 to 7, which is characterized by comprising the foam nickel and the heterojunction nano-sheet layer grown on the surface of the foam nickel in situ;
the heterojunction nano-sheets in the heterojunction nano-sheet layer are NiO and Ni 3 S 2 Is composed of NiO and Ni 3 S 2 Is a heterojunction nano-meter of (2)The thickness of the sheet is 1.7-3.2 nm.
9. The nickel foam with heterojunction nanoplatelets grown on the surface of claim 8, wherein NiO and Ni 3 S 2 The mass ratio of (4-11.5): 1.
10. use of the nickel foam with heterojunction nanoplatelets grown on the surface as claimed in claim 8 or 9 in lithium sulfur batteries.
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