CN110993971B - NiS 2 /ZnIn 2 S 4 Composite material and preparation method and application thereof - Google Patents

NiS 2 /ZnIn 2 S 4 Composite material and preparation method and application thereof Download PDF

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CN110993971B
CN110993971B CN201911272157.9A CN201911272157A CN110993971B CN 110993971 B CN110993971 B CN 110993971B CN 201911272157 A CN201911272157 A CN 201911272157A CN 110993971 B CN110993971 B CN 110993971B
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znin
nis
composite material
lithium
preparation
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CN110993971A (en
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熊杰
胡安俊
雷天宇
陈伟
胡音
晏超贻
王显福
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University of Electronic Science and Technology of China
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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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/11—Sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • 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

Abstract

The invention provides a NiS 2 /ZnIn 2 S 4 A composite material and a preparation method thereof belong to the technical field of catalyst preparation. Adding zinc acetate, indium chloride, thioacetamide and nickel nitrate into absolute ethyl alcohol according to a molar ratio of 0.5:1:4 (0.25-1.0) to perform solvothermal reaction, centrifuging, cleaning and drying in vacuum to obtain NiS 2 /ZnIn 2 S 4 A composite material. NiS 2 /ZnIn 2 S 4 The composite material is NiS 2 And ZnIn 2 S 4 Nano-sheets compounded in situ, wherein NiS 2 And ZnIn 2 S 4 The composite material is applied to the lithium-oxygen battery anode catalyst to form a heterostructure, and not only has lower overpotential (2000mA hg) ‑1 ，500mA g ‑1 The over-potential of charge and discharge is 1.19V), and the charge and discharge cycle stability is excellent, no obvious voltage attenuation is caused, and the excellent comprehensive electrochemical performance is shown.

Description

NiS 2 /ZnIn 2 S 4 Composite material and preparation method and application thereof
Technical Field
The invention relates to the technical field of catalyst preparation, and particularly relates to NiS 2 /ZnIn 2 S 4 A composite material, a preparation method thereof and application thereof as a lithium-oxygen battery anode catalyst.
Background
Rechargeable lithium-oxygen batteries have a higher theoretical energy density (3608Wh kg) than current commercial lithium-ion batteries -1 ) Considered to be one of the most promising next generation energy storage devices. The lithium-oxygen battery is a novel fuel battery which uses active metal Li as a negative electrode and oxygen as a positive electrode, and has the advantages of no pollution, abundant materials, renewable utilization, stable discharge voltage, high specific energy, long storage life, low price and the like, thereby being a new energy storage system with great development and application prospects.
Although lithium-oxygen batteries have the various advantages described above, their higher charge overpotentials result in poor overall electrochemical performance and poor cycling performance during current use.
Disclosure of Invention
Aiming at the problem of higher overpotential of a lithium-oxygen battery in the prior art, the invention provides NiS 2 /ZnIn 2 S 4 The composite material, the preparation method thereof and the application thereof as the anode catalyst of the lithium-oxygen battery solve the technical problems of higher overpotential and poor cycle stability of the lithium-oxygen battery in the charging process.
The technical scheme of the invention is as follows:
NiS 2 /ZnIn 2 S 4 Composite material, characterized in that said NiS 2 /ZnIn 2 S 4 The composite material is NiS 2 And ZnIn 2 S 4 Nano-sheets compounded in situ, wherein NiS 2 And ZnIn 2 S 4 Forming a heterostructure, the NiS 2 And ZnIn 2 S 4 The molar ratio of (0.5-2.0) to (1), and the thickness of the nano sheet is 10-50 nm.
Preparing the NiS 2 /ZnIn 2 S 4 A method of compounding a material, comprising the steps of:
step 1: zinc acetate (Zn (CH) with a molar ratio of 0.5:1:4 (0.25-1.0) 3 COO) 2 ·2H 2 O), indium chloride (InCl) 3 ·4H 2 O), Thioacetamide (TAA), nickel nitrate (Ni (NO) 3 ) 2 ·6H 2 O) adding the mixture into absolute ethyl alcohol for mixing to obtain a mixed solution A; wherein the concentration of the zinc acetate in the mixed solution A is 8.33 mmol/L;
step 2: pouring the mixed solution A into a reaction kettle, carrying out solvothermal reaction for 20-26 h at 160-200 ℃, naturally cooling to room temperature after the reaction is finished, centrifuging, washing, and drying in vacuum to finally obtain NiS 2 /ZnIn 2 S 4 A composite material.
Further, zinc acetate is replaced by zinc nitrate or zinc chloride, and nickel nitrate is replaced by nickel acetate or nickel chloride in the step 1.
The invention further provides the application of the NiS 2 /ZnIn 2 S 4 The composite material is applied to a lithium-oxygen battery as an application of a positive electrode catalyst.
The invention has the beneficial effects that:
the invention provides a nano-flaky NiS 2 /ZnIn 2 S 4 The composite material is applied to the lithium-oxygen battery anode catalyst and has lower over potential (2000mA hg) -1 ，500mA g -1 The over-potential of charge and discharge is 1.19V), and the charge and discharge cycle stability is excellent, no obvious voltage attenuation is caused, and the excellent comprehensive electrochemical performance is shown.
Drawings
FIG. 1 shows NiS obtained in example 3 2 /ZnIn 2 S 4 XRD pattern of the composite;
FIG. 2 shows NiS obtained in example 3 2 /ZnIn 2 S 4 SEM images of the composite;
FIG. 3 shows NiS obtained in example 3 2 /ZnIn 2 S 4 TEM images of the composite;
FIG. 4 shows NiS obtained in example 3 2 /ZnIn 2 S 4 The first charge-discharge diagram obtained by electrochemical performance test of the lithium-oxygen battery made of the composite material is compared with that of pure NiS 2 And pure ZnIn 2 S 4 As a battery anode catalyst for comparison;
FIG. 5 shows NiS obtained in example 3 2 /ZnIn 2 S 4 The lithium-oxygen battery of the composite material is subjected to a cycle performance diagram obtained by electrochemical performance test and is compared with pure NiS 2 And pure ZnIn 2 S 4 The catalyst is used as a battery anode catalyst for comparison.
Detailed Description
The technical scheme of the invention is detailed below by combining the accompanying drawings and the embodiment.
Example 1
Step 1: adding 0.5mmol of zinc acetate, 1mmol of indium chloride, 4mmol of thioacetamide and 0.25mmol of nickel nitrate into 60ml of absolute ethyl alcohol for mixing to obtain a mixed solution A; wherein the concentration of the zinc acetate in the mixed solution A is 8.33 mmol/L;
and 2, step: pouring the mixed solution A into a 100mL reaction kettle for solvothermal reaction at 160 ℃, carrying out solvothermal reaction for 24h, naturally cooling to room temperature, transferring the reacted mixed solution into a 50mL centrifuge tube, centrifuging at 8000r/min for 10min, cleaning with absolute ethyl alcohol and deionized water, repeating for three times, and drying in a vacuum drying oven at 60 ℃ for 12h to finally obtain NiS 2 /ZnIn 2 S 4 A composite material.
Example 2
Preparation of NiS according to the procedure of example 1 2 /ZnIn 2 S 4 The composite material is prepared by only adjusting the content of nickel nitrate in the step 1 from 0.25mmol to 0.5mmol, and the other steps are not changed.
Example 3
Preparation of NiS according to the procedure of example 1 2 /ZnIn 2 S 4 The composite material is prepared by only adjusting the content of nickel nitrate in the step 1 from 0.25mmol to 0.75mmol, and the other steps are not changed.
Example 4
Preparation of NiS according to the procedure of example 1 2 /ZnIn 2 S 4 The composite material is prepared by only adjusting the content of nickel nitrate in the step 1 from 0.25mmol to 1.0mmol, and the other steps are not changed.
Example 5
Preparation of NiS according to the procedure of example 1 2 /ZnIn 2 S 4 The composite material is prepared by only adjusting the solvothermal reaction temperature in the step 2 from 160 ℃ to 200 ℃, and keeping other steps unchanged.
The NiS obtained in the invention example 3 is used 2 /ZnIn 2 S 4 The composite material and the PVDF binder are mixed, then the mixture is coated on a carbon paper current collector to be used as a positive electrode, and the carbon paper current collector is assembled into a lithium-oxygen battery to be subjected to electrochemical test, and the obtained relevant characteristics and performance test results are as follows:
as can be seen from FIG. 1, NiS 2 /ZnIn 2 S 4 All typical peaks of the composite material can be associated with ZnIn of hexagonal phase 2 S 4 (JCPDS cards: 65-2023) and cubic phase NiS 2 (JCPDS card: 88-1709) exact match, evidence ZnIn 2 S 4 And NiS 2 Coexisting in the composite material.
As can be seen from FIG. 2, NiS 2 /ZnIn 2 S 4 The morphology of the composite material is in a nanometer sheet shape.
As can be seen in FIG. 3, NiS 2 /ZnIn 2 S 4 Two crystal faces and the crystal face spacing of the composite material respectively correspond to NiS 2 And ZnIn 2 S 4 The (200) and (102) planes of (a), the presence of coupling interfaces and clear intersecting lattice fringes, without distinct amorphous regions, confirming NiS 2 And ZnIn 2 S 4 A heterostructure is formed.
As can be seen from FIG. 4, when the capacity is limited to 2000mA hg -1 At 500mA g -1 At a current density of (2) based on NiS 2 /ZnIn 2 S 4 The charging and discharging overpotential (half capacity) of the lithium-oxygen battery made of the composite material is 1.19V and is lower than that of pure NiS 2 And pure ZnIn 2 S 4 The overpotential of (c).
As can be seen from FIG. 5, when the capacity is limited to 500mA hg -1 At 500mA g -1 At a current density of (2) based on NiS 2 /ZnIn 2 S 4 The lithium-oxygen battery of the composite material can be cycled 497 times without obvious voltage attenuation, and pure NiS 2 And pure ZnIn 2 S 4 Compared with the stable cycle performance.

Claims (3)

1.NiS 2 /ZnIn 2 S 4 The application of the composite material as the anode catalyst of the lithium-oxygen battery is characterized in that the NiS 2 /ZnIn 2 S 4 The composite material is NiS 2 And ZnIn 2 S 4 Nano-sheets compounded in situ, wherein NiS 2 And ZnIn 2 S 4 Forming a heterostructure, the NiS 2 And ZnIn 2 S 4 The molar ratio of (0.5-2.0) to (1), and the thickness of the nano sheet is 10-50 nm;
The NiS 2 /ZnIn 2 S 4 The preparation method of the composite material comprises the following steps:
step 1: adding zinc acetate, indium chloride, thioacetamide and nickel nitrate into absolute ethyl alcohol according to the molar ratio of 0.5:1:4 (0.25-1.0) to obtain a mixed solution A; wherein the concentration of the zinc acetate in the mixed solution A is 8.33 mmol/L;
step 2: pouring the mixed solution A into a reaction kettle, carrying out solvothermal reaction for 20-26 h at 160-200 ℃, naturally cooling to room temperature after the reaction is finished, centrifuging, washing, and drying in vacuum to finally obtain NiS 2 /ZnIn 2 S 4 A composite material.
2. The NiS of claim 1 2 /ZnIn 2 S 4 The application of the composite material as a lithium-oxygen battery anode catalyst is characterized in that zinc acetate is replaced by zinc nitrate or zinc chloride in the step 1.
3. The NiS of claim 1 2 /ZnIn 2 S 4 Composite materials as lithium-oxygen gasThe application of the battery anode catalyst is characterized in that nickel nitrate in the step 1 is replaced by nickel acetate or nickel chloride.
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CN111097450B (en) * 2019-12-12 2022-05-03 电子科技大学 Preparation method of sulfur-indium-zinc-based composite electrode
CN111525128B (en) * 2020-04-20 2022-11-04 电子科技大学 Ruthenium-doped sulfur vacancy-containing transition metal sulfide electrode and preparation method thereof
CN114917959B (en) * 2022-06-14 2023-06-23 攀枝花学院 Ni-ZIS/MIL-101 catalyst and preparation method thereof

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