CN109273290A

CN109273290A - A kind of Ni-Co-S@Co of bivalve layer Lacking oxygen3O4-δNanocomposite preparation new method

Info

Publication number: CN109273290A
Application number: CN201811336597.1A
Authority: CN
Inventors: 曲玉宁; 王静; 杨鑫; 谢慧娟; 胡炫; 倪梦婷
Original assignee: Tianjin Polytechnic University
Current assignee: Tianjin Polytechnic University
Priority date: 2018-11-09
Filing date: 2018-11-09
Publication date: 2019-01-25

Abstract

The invention discloses a kind of Ni-Co-S@Co of bivalve layer Lacking oxygen₃O_4‑δNanocomposite preparation new method, there is theoretical high capacity Co₃O₄One of the positive electrode of supercapacitor as most application prospect synthesizes Ni-Co-S@Co using ion-exchange-Low Temperature Heat Treatment method first using carbon paper as carrier₃O₄Nuclear-shell structured nano-composite material further obtains the Ni-Co-S@Co of bivalve layer Lacking oxygen by pervasive reduction method₃O_4‑δNanocomposite, the conducting power and ion-diffusibility of electrode is greatly improved, be novel high-performance Co₃O₄Base electrode design of material provides a kind of novel method.

Description

A kind of Ni-Co-S@Co of bivalve layer Lacking oxygen3O4-δNanocomposite preparation New method

Technical field

The present invention relates to a kind of Ni-Co-S@Co of bivalve layer Lacking oxygen₃O_4-δNanocomposite preparation new method, More particularly to ion-exchange-Low Temperature Heat Treatment method-pervasive reduction method preparation bivalve layer Lacking oxygen Ni-Co-S@Co₃O_4-δ's Nanocomposite.

Background technique

Supercapacitor is that one kind has power density height, operating temperature range wide, and energy storage device with long service life is Realize that high efficient energy sources utilize the important original part stored with renewable energy.Under the background of environmental pollution and energy crisis, capacitor The exploitation of device has important practical significance and strategic importance, has complied with the energy development strategy of country.With Co₃O₄For representative The positive electrode material of transition metal oxide fake capacitance supercapacitor have high theoretical capacity, wider potential window with And the features such as environmental-friendly, thus there is good application potential.But Co₃O₄Self-conductive is very poor and ion is in its lattice knot It is spread in structure slow.These fatal disadvantages dramatically limit Co₃O₄Anode obtains high capacity and high rate capability. Thus how to improve Co simultaneously₃O₄Electronic conduction ability (i.e. reduction self-resistance) and ion-diffusibility become and develop Have excellent performance based on Co₃O₄The key of fake capacitance electrode material.Recently, a kind of new electrode material transient metal sulfide (Co₃S₄, NiS₂And MoS₂) there is low electronegativity and excellent electronic conductivity can be used in supercapacitor and do electrode material Material.Many pertinent literature report design synthesis of metal oxide/sulfide composite materials, ternary sulphur/metal sulfide, two kinds of groups Divide and chemical property is improved by synergistic effect.Xia Hui seminar of nearest Institutes Of Technology Of Nanjing's nanometer energy and material seminar room temperature Utilize the H of sodium borohydride^-Strong reducing property capture the oxygen of oxide surface to construct amorphous shell-nuclei of crystallization heterojunction structure and introduce Lacking oxygen makes Co₃O₄Oxygen loss forms Lacking oxygen, and then reduces self-resistance, accelerates electronics conduction, and reduction process can be destroyed gradually The lattice structure on cobaltosic oxide surface layer forms amorphous shell.The isotropism of non crystalline structure can provide a large amount of transmission for ion Channel, and then greatly improve the diffusivity of ion.

Patent CN108283928A core-shell structure Co₃O₄#CeO₂@Fe₃O₄The preparation method of nanocrystalline fabricated in situ, this hair It is bright to be related to a kind of core-shell structure Co₃O₄#CeO₂@Fe₃O₄The synthesizing preparation method in situ of nanocomposite, it is existing in order to solve The Co of preparation₃O₄#CeO₂Partial size in composite oxide material is uneven, it is difficult to recycling and reuse that efficiency is lower asks Topic.Preparation method: one, Fe is prepared₃O₄Nanocrystalline lauryl sodium sulfate (SDS) dispersion liquid；Two, by Co (NO₃)₃·6H₂O and Ce (NO₃)₂·6H₂O, which is dissolved in secondary distilled water, is configured to cobalt cerium mixed liquor and and Fe₃O₄#SDS dispersion liquid is sufficiently mixed；Three, with SDS micella is microreactor, utilizes the interface multiple-effect of surfactant, fabricated in situ core-shell structure Co₃O₄#CeO₂@Fe₃O₄ Nanocrystalline, it is core-shell structure that this is nanocrystalline, and inside is Fe₃O₄Nanoparticle, outside are Co₃O₄#CeO₂Composite oxides, and partial size It is evenly distributed, about 50#nm.Co₃O₄#CeO₂@Fe₃O₄As photochemical catalyst, 150#min reactive navy blue W#B under ultraviolet light Degradation rate is 90% or more, and reuses four degradation rates and can reach 90%.Patent CN106975487A discloses one kind Catalyst and preparation method thereof and catalysis CO₂Application in the reaction of hydrogenation synthesizing low carbon alcohol.The catalyst is with cobalt nitrate or vinegar Sour cobalt is cobalt source, and the Co of different-shape is prepared using the method for hydrothermal crystallizing or co-precipitation₃O₄Nano particle, then isometric leaching Stain dinitroso diammonia platinum, roasting preparation Pt/Co in air₃O₄Catalyst.The catalyst can be used for CO₂Hydrogenation synthesizing low carbon alcohol Reaction, obtains higher CO under more temperate condition₂Conversion ratio and low-carbon alcohols selectivity.Pass through modulation CO₂Hydrogenation reaction temperature Selectivity of product is adjusted Deng effective.Method for preparing catalyst in the present invention is simple, and catalyst has higher in a mild condition Activity, stability, have good prospects for commercial application.

In the above patent, for Co₃O₄The preparation report of material Lacking oxygen does not have, and this patent is low using ion-exchange- Warm the Ni-Co-S@Co of facture-pervasive reduction method preparation bivalve layer Lacking oxygen₃O_4-δNanocomposite.

Summary of the invention

Provided technical solution is to realize the present invention:

(1) using carbon paper as carrier, the nickel cobalt salt and urea of precise certain mass, nickel salt and the total amount of substance of cobalt salt and The ratio between urea is that 3: 5,50mL distilled water is completely dissolved, and by above-mentioned mixed solution transfer reaction kettle, 1 × 2cm is added²Carbon paper, In 100-150 DEG C of 4~8h of heating, after the reaction was completed, respectively for several times with distilled water, ethanol rinse, 60 DEG C are dried in vacuo for 24 hours, then It is put into reaction kettle, the Na of 0.1~2mol/L of 50mL is added₂S solution, 100~150 DEG C of reaction 2-10h, after the reaction was completed, Repeatedly for several times with deionized water and ethanol rinse, nano combined in Ni-Co-S of 60 DEG C of vacuum drying for 24 hours to get carbon paper load Material；

(2) in the cobalt salt and urea for using Ni-Co-S nanocomposite as carrier, accurately weighing certain mass, cobalt salt and The ratio between amount of substance of urea is 1: 1~1: 5, in a kettle 120~180 DEG C of 4~12h of reaction, successively uses ethyl alcohol and deionization Water elutes repeatedly, and 12h is dried in vacuo at 60 DEG C, is transferred in tube furnace later, 300~450 DEG C of processing 1h, later by means of general Suitable reduction method, the NaBH of 1~5mol/L₄As reducing agent, room temperature handles 1~10h, finally prepares the Ni- of bivalve layer Lacking oxygen Co-S@Co₃O_4-δNanocomposite.

To be best understood from the present invention, the present invention will be described in further detail with reference to the following examples, but of the invention Claimed range is not limited to the range of embodiment expression.

Embodiment 1:

(1) using carbon paper as carrier, nickel, cobalt salt, the urea of precise certain mass, nickel salt and the total amount of substance of cobalt salt and The ratio between urea and ammonium fluoride are that 3: 5,50mL distilled water is completely dissolved, and above-mentioned mixed solution is shifted in autoclave, is added Carbon paper, in 120 DEG C of heating 6h, after the reaction was completed, respectively for several times with distilled water, ethanol rinse, 60 DEG C of vacuum drying for 24 hours, then are put Enter in reaction kettle, the Na of the 0.1mol/L of 50mL is added₂S solution, 140 DEG C of reaction 8h use deionized water after the reaction was completed repeatedly For several times with ethanol rinse, it is dried in a vacuum drying oven at 60 DEG C for 24 hours to get the Ni-Co-S nanocomposite of carbon paper load；

(2) in the cobalt salt that using step (1) product Ni-Co-S nanocomposite as carrier, accurately weighs certain mass and The ratio between amount of substance of urea, cobalt salt and urea is 1: 5, in a kettle 150 DEG C of reaction 12h, successively uses ethyl alcohol and deionized water It elutes repeatedly, 12h is dried in vacuo at 60 DEG C, is transferred in tube furnace later, 350 DEG C of processing 1h, later by means of pervasive reduction Method, the NaBH of 2mol/L₄As reducing agent, room temperature handles 8h, the last Ni-Co-S@Co up to bivalve layer Lacking oxygen₃O_4-δNanometer Composite material.

Embodiment 2: change Na₂The concentration of S solution is 0.5mol/L, other steps are empty to get bivalve layer oxygen with embodiment 1 The Ni-Co-S@Co of position₃O_4-δNanocomposite.

Embodiment 3: change NaBH₄Concentration be 4mol/L, other steps are with embodiment 1 to get bivalve layer Lacking oxygen Ni-Co-S@Co₃O_4-δNanocomposite.

Embodiment 4: change vulcanization time is 10h, other steps are with embodiment 1 to get the Ni-Co- of bivalve layer Lacking oxygen S@Co₃O_4-δNanocomposite.

Claims

1. a kind of Ni-Co-S@Co of bivalve layer Lacking oxygen₃O_4-δNanocomposite preparation new method, the specific steps are as follows:

(1) using carbon paper as carrier, the nickel cobalt salt and urea of precise certain mass, nickel salt and the total amount of substance and urea of cobalt salt The ratio between be completely dissolved for 3: 5,50mL distilled water, by above-mentioned mixed solution transfer reaction kettle, 1 × 2cm is added²Carbon paper, 100-150 DEG C of 4~8h of heating, after the reaction was completed, respectively for several times with distilled water, ethanol rinse, 60 DEG C of vacuum drying for 24 hours, then are put Enter in reaction kettle, the Na of 0.1~2mol/L of 50mL is added₂S solution, 100~150 DEG C of 2~10h of reaction, after the reaction was completed, instead Deionized water and ethanol rinse are multiplexed for several times, in 60 DEG C of vacuum drying for 24 hours to get the nano combined material of Ni-Co-S of carbon paper load Material；

(2) in the cobalt salt and urea for using Ni-Co-S nanocomposite as carrier, accurately weighing certain mass, cobalt salt and urea The ratio between amount of substance be 1: 1~1: 5,120~180 DEG C of 4~12h of reaction, successively use ethyl alcohol and deionized water anti-in a kettle It is multiple to elute, it is dried in vacuo 12h at 60 DEG C, is transferred in tube furnace later, 300~450 DEG C of processing 1h, is gone back later by means of pervasive Former method, the NaBH of 1~5mol/L₄As reducing agent, room temperature handles 1~10h, finally prepares the Ni-Co-S@of bivalve layer Lacking oxygen Co₃O_4-δNanocomposite.

2. a kind of Ni-Co-S@Co of bivalve layer Lacking oxygen as described in claim 1₃O_4-δNanocomposite preparation it is new Method, it is characterised in that: nickel salt and cobalt salt can be nickel nitrate and cobalt nitrate, nickel chloride and cobalt chloride, nickel acetate and cobalt acetate.