CN108400342A - A kind of nano flower array flexible air electrode material and preparation method thereof, application - Google Patents
A kind of nano flower array flexible air electrode material and preparation method thereof, application Download PDFInfo
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- CN108400342A CN108400342A CN201810130156.XA CN201810130156A CN108400342A CN 108400342 A CN108400342 A CN 108400342A CN 201810130156 A CN201810130156 A CN 201810130156A CN 108400342 A CN108400342 A CN 108400342A
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- preparation
- nano flower
- electrode material
- air electrode
- flexible air
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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
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
-
- 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
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8846—Impregnation
- H01M4/885—Impregnation followed by reduction of the catalyst salt precursor
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
-
- 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
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
-
- 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
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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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
- 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 discloses a kind of preparation methods of nano flower array flexible air electrode material, nickel acetate, cobalt acetate and vulcanized sodium are add to deionized water stirring and form homogeneous mixture solotion, mixed solution and carbon cloth are subjected to hydro-thermal reaction again, product is taken out after being cooled to room temperature after reaction, obtaining growth has CoNi2S4The CP of nano flower array.The present invention has excellent mechanical strength stability and excellent chemical property, including high round-trip efficiency, good high rate performance and cyclical stability.
Description
Technical field
The present invention relates to electrode fields, and in particular to a kind of nano flower array flexible air electrode material and its preparation side
Method, application.
Background technology
In recent years, flexible electronic devices are becoming increasingly popular, because they can be bent to a certain extent, are distorted, rolling
Dynamic or stretching, but still keep its function.Flexible energy storage device fairly perfect at this stage has become the main bottle of research field
Neck.Lithium ion battery (LIB) is considered as the first choice in flexible power supply recently, but the low theory of commercial lithium-ion batteries at present
Energy density substantially limits their applications in next-generation flexible device.Fortunately, chargeable lithium-oxygen (Li-O2)
Battery is due to high (the about 3600Whkg of its theoretical energy density-1), it has also become one of most promising electrochemical energy storage technology.
Although a kind of flexible Li-O of exploitation2Battery can theoretically meet active demand of the flexible device to high energy density cells,
But the technology still be in the starting stage, before put into practical application there is also problems (such as round-trip efficiency is low, unstability with
Cycle life is poor etc.).
To solve the above-mentioned problems, it is to realize Li-O to develop suitable catalyst2The key link of battery practical application.One
Aspect, high performance catalyst can accelerate to improve the dynamics of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), reduce simultaneously
Li-O2The overpotential of battery, on the other hand, active catalyst can effectively catalytic solid discharging product formation/decomposition, this
Li-O will be improved2The cycle performance and high rate performance of battery.In recent years, metal sulfide is due to its excellent thermal stability and height
Electro catalytic activity and including evolving hydrogen reaction (HER), be explored in the various applications including carbon dioxide conversion and ORR.So
And their low electric conductivity limits its chemical property.In order to overcome this problem, improve electronic conductivity one is effective
Approach is the carrier for using electronic conductive material as catalyst.Carbon cloth is due to its unique porous structure and excellent electric conductivity
And it is widely used as Li-O2The collector of battery.Meanwhile this carrier should contain a large amount of mesoporous material, to store Li2O2
More memory spaces are provided, the form of metal sulfide is also vital to catalytic activity.
Invention content
In view of the above technical problems, the purpose of the present invention is to provide a kind of nano flower array flexible air electrode material and
Preparation method, application.Nano flower array flexible air electrode material produced by the present invention is made a living with CoNi2S4Nano flower battle array
The CP of row.
The present invention is achieved through the following technical solutions：
Nickel acetate, cobalt acetate and vulcanized sodium are added a kind of preparation method of nano flower array flexible air electrode material
Homogeneous mixture solotion is formed to stirring in deionized water, then mixed solution and carbon cloth are subjected to hydro-thermal reaction, it is cold after reaction
But to product is taken out after room temperature, obtaining growth has CoNi2S4The CP of nano flower array.
Hydrothermal temperature is 180~200 DEG C.
The hydro-thermal reaction time is 12~12.5h.
Molar ratio between nickel acetate, cobalt acetate and vulcanized sodium is 2：1:8.
It is 45~60min to mixing time in deionized water.
The cleaning of carbon cloth is that ethyl alcohol and deionized water is used to be cleaned by ultrasonic 30~45min successively.
The nano flower array flexible air electrode material that foregoing preparation method obtains.
Application of the nano flower array flexible air electrode material in flexible and wearable power supply.
Conventional cathode is that active catalytic material is coated to the cathode constituted on the current collector, this hair using polymer adhesive
It is bright to be prepared for that there is flexible, self-supporting and recoverable CoNi using a step hydrothermal growth process2S4Nano flower array growth exists
(f-CoNi on carbon cloth2S4/ CP), avoid traditional electrode because use polymer adhesive occur lead to the problem of by-product.f-
CoNi2S4/ CP has excellent mechanical strength stability and good chemical property, including height as a kind of novel cathode
Discharge capacity, good high rate performance and cyclical stability.The novel designs of this Flexible cathodes show it in other flexibilities
With the potential application in wearable power supply.
Compared with prior art, the present invention having the following advantages and advantages：
1, the present invention obtains the nano flower array flexible air with excellent properties by well-designed technical solution
Electrode material product, the product have excellent mechanical strength stability and excellent chemical property, including high round-trip efficiency,
Good high rate performance and cyclical stability；
2, the chemical property of product produced by the present invention：1) charge-discharge property：With f-CoNi2S4/ CP cathodes
Li-O2Battery provides the~high discharge capacity of 7850mAh/g under the current density of 200mA/g.2) high rate performance：With f-
CoNi2S4The Li-O of/CP cathodes2Battery tests its high rate performance under different current densities respectively, when current density is restored to just
When beginning current density, blanking voltage shows there is good times of forthright and restorability almost without decaying.3) cycle performance：
With f-CoNi2S4The Li-O of/CP cathodes2Battery stablizes under the current density of 500mA/g and Reversible Cycle 100 times, and nothing
Apparent voltage change, cycle performance are good.
Description of the drawings
Attached drawing described herein is used for providing further understanding the embodiment of the present invention, constitutes one of the application
Point, do not constitute the restriction to the embodiment of the present invention.In the accompanying drawings：
Fig. 1 amplifies 15000 times of SEM figures by the nano flower array flexible air electrode material that embodiment 1 provides；
Fig. 2 amplifies 200000 times of SEM figures by the nano flower array flexible air electrode material that embodiment 1 provides；
The nano flower array flexible air electrode material BET figures that Fig. 3 is provided by embodiment 1；
The XRD diagram for the nano flower array flexible air electrode material that Fig. 4 is provided by embodiment 1；
Head of the nano flower array flexible air electrode material that Fig. 5 is provided by embodiment 1 as lithium air electrode material
Secondary charge and discharge electrograph；
Times of the nano flower array flexible air electrode material that Fig. 6 is provided by embodiment 1 as lithium air electrode material
Rate performance map；
Nano flower array flexible air electrode material the following as lithium air electrode material that Fig. 7 is provided by embodiment 1
Ring performance map.
Specific implementation mode
To make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiment and attached drawing, to this
Invention is described in further detail, and exemplary embodiment of the invention and its explanation are only used for explaining the present invention, do not make
For limitation of the invention.
Embodiment 1
1) carbon cloth pre-processes：
The hydro-thermal reaction time is 12~12.5h.
Acetone, ethyl alcohol and deionized water is used to be cleaned by ultrasonic 30min, dried for standby respectively commodity carbon cloth.
2)f-CoNi2S4The synthesis of/CP：By 2mmol nickel acetates, 1mmol cobalt acetates and 8mmol vulcanized sodium are added to 60ml
1h is stirred in deionized water and forms homogeneous mixture solotion, and the high pressure that mixed solution and carbon cloth (CP) are then transferred to 100ml is anti-
It answers in kettle, reacts 12h in 180 DEG C.After hydro-thermal reaction, CP is taken out at room temperature, and ethyl alcohol and deionized water is used in combination to wash for several times
After dry, finally obtain growth has CoNi2S4CP (the i.e. f-CoNi of nano flower array2S4/CP)。
F-CoNi is obtained by embodiment 12S4The pattern of/CP is as shown in Figure 1, 2, and Fig. 3 schemes for its BET, and Fig. 4 is its XRD diagram.
Charge-discharge property：With f-CoNi2S4The Li-O of/CP cathodes2Battery under the current density of 200mA/g, provide~
The high discharge capacity of 7850mAh/g.(such as Fig. 5).2) high rate performance：With f-CoNi2S4The Li-O of/CP cathodes2Battery exists respectively
Its high rate performance is tested under different current densities, when current density is restored to initial current density, blanking voltage almost without
Decaying shows there is good times of forthright and restorability (such as Fig. 6).3) cycle performance：With f-CoNi2S4/ CP cathodes
Li-O2Battery stablizes under the current density of 500mA/g and Reversible Cycle 100 times, and without apparent voltage change (as schemed
7), cycle performance is good.
Embodiment 2
1) carbon cloth pre-processes：
Acetone, ethyl alcohol and deionized water is used to be cleaned by ultrasonic 30min, dried for standby respectively commodity carbon cloth.
2)f-CoNi2S4The synthesis of/CP：By 2mmol nickel acetates, 1mmol cobalt acetates and 8mmol vulcanized sodium are added to 60ml
1h is stirred in deionized water and forms homogeneous mixture solotion, and the high pressure that mixed solution and carbon cloth (CP) are then transferred to 100ml is anti-
It answers in kettle, reacts 12.5h in 200 DEG C.After hydro-thermal reaction, CP is taken out at room temperature, and ethyl alcohol and deionized water is used in combination to wash number
Dry after secondary, finally obtaining growth has CoNi2S4CP (the i.e. f-CoNi of nano flower array2S4/CP)。
For the product that the embodiment of the present invention 1 and embodiment 2 produce due to containing carbon cloth, other are flexible and wearable
It can effectively be applied in power supply.
Above-described specific implementation mode has carried out further the purpose of the present invention, technical solution and advantageous effect
It is described in detail, it should be understood that the foregoing is merely the specific implementation mode of the present invention, is not intended to limit the present invention
Protection domain, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done should all include
Within protection scope of the present invention.
Claims (8)
1. a kind of preparation method of nano flower array flexible air electrode material, which is characterized in that by nickel acetate, cobalt acetate and sulphur
Change sodium is add to deionized water stirring and forms homogeneous mixture solotion, then mixed solution and carbon cloth are carried out hydro-thermal reaction, reaction
After be cooled to room temperature after take out product, obtaining growth has CoNi2S4The CP of nano flower array.
2. preparation method according to claim 1, which is characterized in that hydrothermal temperature is 180~200 DEG C.
3. preparation method according to claim 1, which is characterized in that the hydro-thermal reaction time is 12~12.5h.
4. preparation method according to claim 1, which is characterized in that mole between nickel acetate, cobalt acetate and vulcanized sodium
Than being 2：1:8.
5. preparation method according to claim 1, which is characterized in that mixing time in deionized water be 45~60min.
6. preparation method according to claim 1, which is characterized in that the cleaning of carbon cloth is to use ethyl alcohol and deionized water successively
It is cleaned by ultrasonic 30~45min.
7. the nano flower array flexible air electrode material that the preparation method according to claim 1-6 obtains.
8. the nano flower array flexible air electrode material that preparation method as claimed in claim 7 obtains is flexible and wearable
Application in power supply.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810130156.XA CN108400342A (en) | 2018-02-08 | 2018-02-08 | A kind of nano flower array flexible air electrode material and preparation method thereof, application |
| CN201810979115.8A CN109273727A (en) | 2018-02-08 | 2018-08-24 | A kind of nano flower array flexible air electrode material and preparation method thereof, application |
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| CN201810979115.8A Pending CN109273727A (en) | 2018-02-08 | 2018-08-24 | A kind of nano flower array flexible air electrode material and preparation method thereof, application |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109621981A (en) * | 2018-10-31 | 2019-04-16 | 中山大学 | A kind of compound analysis oxygen elctro-catalyst of metal oxide-sulfide and its preparation method and application |
| CN112551585A (en) * | 2020-12-24 | 2021-03-26 | 齐鲁工业大学 | Surfactant-induced MoS2Preparation method and application of nanoflower electrode material |
| CN114371202A (en) * | 2020-10-14 | 2022-04-19 | 东华大学 | Carbon fiber composite material and preparation method and application thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110137511A (en) * | 2019-05-10 | 2019-08-16 | 深圳大学 | Y-oxides doping lithium air battery positive electrode and preparation method thereof and lithium-air battery |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106732649A (en) * | 2017-02-20 | 2017-05-31 | 天津理工大学 | A kind of preparation method of alkaline oxygen evolution reaction elctro-catalyst |
| CN107492657B (en) * | 2017-07-12 | 2019-12-10 | 三峡大学 | preparation method of cobalt-nickel sulfide positive and negative electrode batteries and application of cobalt-nickel sulfide positive and negative electrode batteries in alkaline recyclable batteries |
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2018
- 2018-02-08 CN CN201810130156.XA patent/CN108400342A/en active Pending
- 2018-08-24 CN CN201810979115.8A patent/CN109273727A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109621981A (en) * | 2018-10-31 | 2019-04-16 | 中山大学 | A kind of compound analysis oxygen elctro-catalyst of metal oxide-sulfide and its preparation method and application |
| CN109621981B (en) * | 2018-10-31 | 2022-04-15 | 中山大学 | Metal oxide-sulfide composite oxygen evolution electrocatalyst and preparation method and application thereof |
| CN114371202A (en) * | 2020-10-14 | 2022-04-19 | 东华大学 | Carbon fiber composite material and preparation method and application thereof |
| CN114371202B (en) * | 2020-10-14 | 2023-05-02 | 东华大学 | Carbon fiber composite material and preparation method and application thereof |
| CN112551585A (en) * | 2020-12-24 | 2021-03-26 | 齐鲁工业大学 | Surfactant-induced MoS2Preparation method and application of nanoflower electrode material |
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| CN109273727A (en) | 2019-01-25 |
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Application publication date: 20180814 |