CN110517899A - Preparation method based on Ni-Co layered double-hydroxide derived from MOF - Google Patents

Preparation method based on Ni-Co layered double-hydroxide derived from MOF Download PDF

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Publication number
CN110517899A
CN110517899A CN201910755893.3A CN201910755893A CN110517899A CN 110517899 A CN110517899 A CN 110517899A CN 201910755893 A CN201910755893 A CN 201910755893A CN 110517899 A CN110517899 A CN 110517899A
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mof
ldh
electrode material
preparation
electrode
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CN201910755893.3A
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韩丹丹
赵远
魏金鹤
潘怡帆
申烨
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Jilin Institute of Chemical Technology
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Jilin Institute of Chemical Technology
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00Compounds of nickel
    • C01G53/006Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/24Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00Crystal-structural characteristics
    • C01P2002/70Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/01Particle morphology depicted by an image
    • C01P2004/03Particle morphology depicted by an image obtained by SEM
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13Energy storage using capacitors

Abstract

This patent is related to the preparation method based on Ni-Co LDH electrode material derived from MOF, for the product morphology in 1 attached drawing 2 of embodiment, resulting Ni-Co LDH electrode material is the three-dimensional porous structure that there are many nanometer sheets to constitute, the nanometer sheet thickness for constituting three-dimensional porous structure is 150-200 nm, Electrochemical results show that in current density be 1 Ag‑1When, specific capacitance of single electrode reaches 1872 Fg‑1, when current density increases to 16 Ag‑1When, the conservation rate of specific capacity is 88%.

Description

Preparation method based on Ni-Co layered double-hydroxide derived from MOF
Technical field
The invention belongs to ultracapacitor device technical fields, and in particular to based on the double hydrogen-oxygens of Ni-Co stratiform derived from MOF The preparation method of compound.
Background technique
Supercapacitor can most determine supercapacitor capacitive character mainly by diaphragm, electrode material and electrolyte composition Energy is exactly electrode material, and therefore, the research and development of active electrode material become the emphasis studied and applied for SCs, in general, Electrode material for SCs includes Carbon Materials, metal oxide, metal hydroxides and conducting polymer etc..Carbon Materials electricity The electric double layer storage energy (electric double layer capacitance) that pole is formed by the interface of electrolyte and electrode;Metal oxide, metallic hydrogen The redox reaction that oxide and conducting polymer materials electrode then pass through Rapid reversible obtains faraday's capacitor (fake capacitance), This faraday's capacitor is typically much deeper than the electric double layer capacitance of Carbon Materials acquisition.Wherein, in metal hydroxides, the double hydrogen-oxygens of stratiform Compound can provide bigger serface, either high redox active reaction sites due to its layer structure to improve the counterfeit electricity of faraday Hold.
Application No. is 201811337880.6 Chinese invention patents to disclose a kind of cotton calcining self-control carbon cloth load The preparation method of MOF-LDH mixing array electrode material for super capacitor, specifically discloses and utilizes cobalt nitrate and aqueous solution of urea It carries out hydro-thermal reaction to prepare nano-wire array and prepare MOF array with nano-wire array to sacrifice template, be synthesized then at room temperature The method of MOF-LDH;Application No. is 201810841975.5 Chinese invention patents to disclose a kind of vulcanization Ni-Co-Al LDH The preparation method of electrode composite material specifically discloses and is modified Ni-Co-Al LDH substrate in nickel foam with the method for electro-deposition On electrode, then nickel foam is added in the aqueous solution containing thioacetamide and carries out heating reaction preparation vulcanization Ni-Co-Al LDH Electrode composite material.The purpose of above-mentioned patent is all to improve the specific capacity of LDH material, but preparation method is complicated, and product compares table The defects of area is limited is still the key for limiting high performance electrode material and further applying.
Due to porosity characteristic and stable structure, specific surface area with higher is metal-organic framework materials (MOF) It is derivatized to various metal oxides or the ideal of hydroxide porous active material sacrifices template, while MOF is used for super electricity Container can provide reaction site abundant and short ion diffusion path, to improve electrode performance.The chemical combination derived from MOF In object, have porosity high based on layered double-hydroxide derived from MOF, the big feature of surface area can be electronics and ion It provides and good transports environment;In addition, NiCo-LDH three-dimensional porous structure is made of many small nanometer sheets, be conducive to from Son enters electrode surface, is effectively shortened ion diffusion path, reduces the resistance of ion transport.Utilize the nanometer sheet of MOF Array structure introduces the high electrochemical performance that LDH realizes electrode material.
Summary of the invention
The present invention first by the derivative Co-MOF of MOF, then with Ni (NO3)2·6H2O is led in ethanol by hydrothermal synthesis method It crosses ion exchange and double-metal hydroxide array that etching reaction obtains, and is applied to electrode material for super capacitor, provide It is a kind of with high specific capacity and the preparation method of the electrode material for super capacitor of excellent multiplying power property.
In order to solve the above technical problems, the present invention adopts the following technical scheme that:
Preparation method based on the Ni-Co LDH material electrode of super capacitor as derived from MOF of the invention, first in flexible base A room temperature step in situ generates (in order to distinguish existing patent) Co-MOF nano-chip arrays on the carbon cloth of bottom, then passes through hydrothermal synthesis method Ni-Co LDH material is obtained by ion exchange and etching reaction in ethanol solution.Specifically comprise the following steps:
(1) by the Co (NO of 50 mmol3)2·6H2O, the C of 0.4 mol4H6N2, it is dissolved in 40 mL distilled water, sufficiently dissolves respectively After mixing, carbon cloth is placed in solution in 60o, 4 h is reacted at room temperature, obtains CC/Co-MOF after washing and drying.
(2) CC/Co-MOF electrode is immersed into the Ni (NO containing 30-40 mL ethyl alcohol and 0.07-0.09 mmol3)2·6H2O Mixed solution in, be then transferred to the autoclave of 50 mL.After reacting 2-3 h at 120-150 DEG C, with water and ethyl alcohol Sufficiently cleaning, 60 DEG C of dryings.Obtain classifying porous nano-chip arrays CC/Ni-Co LDH.
Resulting Co-MOF material is the well-regulated two-dimensional sheet form of tool, smooth surface, thus it can be used as it is excellent Different function precursor, and be uniformly securely grown on carbon fiber.Ni-Co LDH material is by the Co in Co-MOF2+ / Co3+With Ni2+Co-precipitation obtains, the three-dimensional porous structure that there are Ni-Co LDH many nanometer sheets to constitute, nanometer sheet with a thickness of 150- 200 nm, Electrochemical results show that in current density be 1 Ag-1When, specific capacitance of single electrode reaches 1872 Fg-1, When current density increases to 16 Ag-1When, the conservation rate of specific capacity is 88%.
Detailed description of the invention
Fig. 1 is Ni-Co LDH material XRD curve prepared in embodiment 1.
Fig. 2 is Ni-Co LDH scanning of materials electromicroscopic photograph prepared in embodiment 1.
Fig. 3 is Co-MOF array scanning electromicroscopic photograph prepared in embodiment 1.
Fig. 4 is the cyclic voltammetry curve of Ni-Co LDH material prepared in embodiment 1.
Fig. 5 is the charging and discharging curve of Ni-Co LDH material prepared in embodiment 1.
Specific embodiment
Technical solution of the present invention and effect are further described below with reference to embodiment.But it is used specific Method, formula and explanation are not limitation of the present invention.
Embodiment 1: CC/Co-MOF electrode is immersed into the Ni (NO containing 30 mL ethanol solutions and 0.07 mmol3)2· 6H2In O, it is then transferred in the autoclave of 50 mL.After reacting 2 h at 120 DEG C, sufficiently cleaned with water and ethyl alcohol, 60 DEG C of dryings.Obtain CC/Ni-Co LDH.
Embodiment 2: CC/Co-MOF electrode is immersed into the Ni (NO containing 40 mL ethanol solutions and 0.09 mmol3)2· 6H2In O, it is then transferred in the autoclave of 50 mL.After reacting 2 h at 120 DEG C, sufficiently cleaned with water and ethyl alcohol, 60 DEG C of dryings.Obtain CC/Ni-Co LDH.
Embodiment 3: CC/Co-MOF electrode is immersed into the Ni (NO containing 30 mL ethanol solutions and 0.07 mmol3)2· 6H2In O, it is then transferred in the autoclave of 50 mL.After reacting 2 h at 130 DEG C, sufficiently cleaned with water and ethyl alcohol, 60 DEG C of dryings.Obtain CC/Ni-Co LDH.
Embodiment 4: CC/Co-MOF electrode is immersed into the Ni (NO containing 30 mL ethanol solutions and 0.07 mmol3)2· 6H2In O, it is then transferred in the autoclave of 50 mL.After reacting 2 h at 140 DEG C, sufficiently cleaned with water and ethyl alcohol, 60 DEG C of dryings.Obtain CC/Ni-Co LDH.
Embodiment 5: CC/Co-MOF electrode is immersed into the Ni (NO containing 30 mL ethanol solutions and 0.07 mmol3)2· 6H2In O, it is then transferred in the autoclave of 50 mL.After reacting 3 h at 120 DEG C, sufficiently cleaned with water and ethyl alcohol, 60 DEG C of dryings.Obtain CC/Ni-Co LDH.

Claims (2)

1. one kind is based on Ni-Co LDH material derived from MOF, which is characterized in that the electrode material is that Co-MOF is closed in hydro-thermal At what is obtained derived from process, and the preparation process of Co-MOF at room temperature complete by a step, resulting Ni-Co LDH electrode material It is the three-dimensional porous structure that there are many nanometer sheets to constitute, the nanometer sheet thickness for constituting three-dimensional porous structure is 150-200 nm.
2. a kind of preparation method based on Ni-Co LDH material derived from MOF, which comprises the steps of: by 50 Co (the NO of mmol3)2·6H2O, the C of 0.4 mol4H6N2, it is dissolved in 40 mL distilled water respectively, sufficiently after dissolution mixing, by carbon Cloth is placed in solution in 60o, is reacted at room temperature 4 h, is obtained CC/Co-MOF after washing and drying;The immersion of CC/Co-MOF electrode is contained There are 30-40 mL ethyl alcohol and the Ni (NO of 0.07-0.09 mmol3)2·6H2In the mixed solution of O, it is then transferred to 50 mL Autoclave, at 120-150 DEG C react 2-3 h after, sufficiently cleaned with water and ethyl alcohol, 60 DEG C of dryings obtain classifying porous Nanometer sheet Ni-Co LDH electrode material introduces the high electrochemical that LDH realizes electrode material using the nano-chip arrays structure of MOF Performance.
CN201910755893.3A 2019-08-16 2019-08-16 Preparation method based on Ni-Co layered double-hydroxide derived from MOF Pending CN110517899A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111115694A (en) * 2020-01-21 2020-05-08 河南科技大学 Preparation method of hollow Co-Fe LDH material
CN111554525A (en) * 2020-04-30 2020-08-18 浙江农林大学 Preparation method of carbon cloth supported double-metal hydroxide material
CN111921529A (en) * 2020-08-18 2020-11-13 三峡大学 Preparation method and application of nickel-cobalt metal organic framework/nickel-cobalt metal hydroxide heterogeneous material
CN113299485A (en) * 2021-04-26 2021-08-24 江苏大学 Bimetallic (Ni, Co) Se2Preparation method of heterostructure and application of heterostructure in super capacitor
CN113314356A (en) * 2021-05-26 2021-08-27 陕西科技大学 Electrode material of HKUST-1-LDH super capacitor derived from electrodeposited MOF and preparation method thereof
CN113926430A (en) * 2021-11-19 2022-01-14 太原理工大学 Preparation method and application of MOF derivative/LDH double-site adsorption membrane
CN116282202A (en) * 2023-05-18 2023-06-23 山东泰和科技股份有限公司 Petal-shaped lithium battery anode material rich in oxygen vacancies and preparation method and application thereof

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CN104659358A (en) * 2015-01-30 2015-05-27 南京工业大学 Preparation method of hollow nickel cobaltate nano polyhedron
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CN109585182A (en) * 2018-10-23 2019-04-05 江苏大学 The preparation method of the nickel-cobalt alloy nano chip arrays of sulphur cobalt nickel coated

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111115694A (en) * 2020-01-21 2020-05-08 河南科技大学 Preparation method of hollow Co-Fe LDH material
CN111554525A (en) * 2020-04-30 2020-08-18 浙江农林大学 Preparation method of carbon cloth supported double-metal hydroxide material
CN111554525B (en) * 2020-04-30 2021-07-13 浙江农林大学 Preparation method of carbon cloth supported double-metal hydroxide material
CN111921529A (en) * 2020-08-18 2020-11-13 三峡大学 Preparation method and application of nickel-cobalt metal organic framework/nickel-cobalt metal hydroxide heterogeneous material
CN111921529B (en) * 2020-08-18 2022-03-04 三峡大学 Preparation method and application of nickel-cobalt metal organic framework/nickel-cobalt metal hydroxide heterogeneous material
CN113299485A (en) * 2021-04-26 2021-08-24 江苏大学 Bimetallic (Ni, Co) Se2Preparation method of heterostructure and application of heterostructure in super capacitor
CN113314356A (en) * 2021-05-26 2021-08-27 陕西科技大学 Electrode material of HKUST-1-LDH super capacitor derived from electrodeposited MOF and preparation method thereof
CN113314356B (en) * 2021-05-26 2022-11-08 陕西科技大学 Electrode material of HKUST-1-LDH super capacitor derived from electrodeposited MOF and preparation method thereof
CN113926430A (en) * 2021-11-19 2022-01-14 太原理工大学 Preparation method and application of MOF derivative/LDH double-site adsorption membrane
CN113926430B (en) * 2021-11-19 2023-10-20 太原理工大学 Preparation method and application of MOF derivative/LDH double-site adsorption membrane
CN116282202A (en) * 2023-05-18 2023-06-23 山东泰和科技股份有限公司 Petal-shaped lithium battery anode material rich in oxygen vacancies and preparation method and application thereof
CN116282202B (en) * 2023-05-18 2023-08-22 山东泰和科技股份有限公司 Petal-shaped lithium battery anode material rich in oxygen vacancies and preparation method and application thereof

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