CN108493458A - A kind of high-performance sea urchin shape oxidation nickel cobalt acid nickel microballoon lithium oxygen battery anode catalytic material and preparation method thereof - Google Patents
A kind of high-performance sea urchin shape oxidation nickel cobalt acid nickel microballoon lithium oxygen battery anode catalytic material and preparation method thereof Download PDFInfo
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- 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
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Abstract
A kind of high-performance sea urchin shape oxidation nickel cobalt acid nickel microballoon lithium oxygen battery anode catalytic material of present invention offer and preparation method thereof.It is uniform sea urchin shape microballoon that the present invention, which prepares material, and size is 3~10 μm of diameter, and nanometer needle construction is neatly arranged in microsphere surface, makes it have higher specific surface area, can be used for the catalysis of lithium oxygen battery.Sea urchin shape oxidation nickel cobalt acid nickel micro-sphere material prepared by the present invention is applied to the anode catalytic of lithium oxygen battery, it can obtain very high specific capacity and excellent cyclical stability, preparation method is easy simultaneously, it only can be obtained by simple hydro-thermal reaction and subsequent heat treatment, great industrial production value and actual application value.
Description
Technical field
The invention belongs to electrochemistry and new energy field, and in particular to a kind of high-performance sea urchin shape oxidation nickel cobalt acid nickel is micro-
Ball lithium oxygen battery anode catalytic material and preparation method thereof.
Background technology
With the pollution exacerbation of urban environment and gradually using up for conventional fossil fuel, people are to high-energy density height and clearly
The demand of the clean energy increases severely with day.Recently, the lithium oxygen battery based on organic electrolyte due to the relatively simple structure, theoretical energy
Very high density, it is of low cost, it has also become the research hotspot of academia.The theoretical energy density of lithium oxygen battery is reachable
3505Whkg-1, it is conventional lithium ion battery energy density (360Wh kg-1) nearly ten times, therefore lithium oxygen battery will be as future
Energy storage device has a good application prospect.However, although reaction mechanism is simple, the practical application of lithium oxygen battery is still
Face many challenges, such as the high overpotential in charge and discharge process, poor high rate performance, especially relatively short cycle longevity
Life.In order to solve these problems, it is extremely urgent to research and develop a kind of novel lithium oxygen battery anode catalytic material.
Due to its preferable catalytic performance and cheap price, transition metal oxide for example cobaltosic oxide, manganese dioxide,
Cobalt acid manganese and cobalt acid nickel etc. are studied by the anode catalytic material as lithium oxygen battery extensively.In numerous transiting metal oxidations
In object material, cobalt acid nickel has abundant catalytic reaction site and preferable electric conductivity.But the pair generated in charge and discharge process
Product causes battery efficiency to reduce, and seriously hinders catalytic effect of the cobalt acid nickel in lithium oxygen battery.Research shows that nickel oxide
The by-products such as the lithium carbonate that can effectively generate during decomposition reaction, to improve the cycle performance and effect of lithium oxygen battery
Rate.
It is previous to have had research using cobalt acid nickel and nickel oxide as the anode catalytic material of lithium oxygen battery and taken
Obtained good catalytic effect.Such as Li et al. people (Li, the L.et al.Porous of Nanjing Aero-Space University
NiCo2O4nanotubes as a noble-metal-free effective bifunctional catalyst for
rechargeable Li-O2batteries[J].Journalof Materials Chemistry A 2015,3,24309-
24314.) porous cobalt acid Nickel nanotubes have been obtained by way of electrostatic spinning, has been urged as lithium oxygen battery anode
When changing material, in 200mA g-1Current density under, cycle 110 circle after discharge platform may remain in 2.4V.Xiamen University
Wang et al. (Wang, C.et al.Highly hierarchical porous structures constructed from
NiO nanosheets act as Li ion and O2pathways in long cycle life,rechargeable
Li-O2Batteries [J] .Chemical Communications2016,52,11772-11774.) it is obtained by hydro-thermal method
Porous NiO nanometer sheets, have benefited from its porous structure, this material is in 200mA g-1Current density under, with 1000mAh
g-1Fixation specific capacity can recycle 80 circles.However rarely have so far cobalt acid nickel and nickel oxide both materials progress is compound
The report studied.
Invention content
In view of the above-mentioned problems of the prior art, the purpose of the present invention is to provide a kind of oxidations of high-performance sea urchin shape
Nickel cobalt acid nickel microballoon lithium oxygen battery anode catalytic material and preparation method thereof, resulting materials have special three-dimensional construction, table
Face proper alignment has acicular texture, makes it have larger specific surface area, can be used as the anode catalytic material of lithium oxygen battery.Together
When preparation method it is easy, only can be obtained by simple hydro-thermal reaction and subsequent heat treatment, and without adding template, react item
Part is mild, great industrial production value and actual application value.
To achieve the above object, specifically, the present invention uses following technical scheme：
The first aspect of the invention provides a kind of preparation method of oxidation nickel cobalt acid nickel micro-sphere material, including step is such as
Under：
S1. reaction solution is prepared：By cobalt chloride, nickel chloride and urea it is soluble in water reaction solution；
S2. solid phase presoma is prepared：The reaction solution that S1. is prepared reacts 12~36h at 120~180 DEG C, instead
Solid phase presoma is purified to obtain after answering；
S3. oxidation nickel cobalt acid nickel micro-sphere material is prepared：The solid phase presoma that S2. is prepared is placed in 300~500 DEG C
It is calcined 4~6h, after reaction up to oxidation nickel cobalt acid nickel micro-sphere material；
Further, in the step S1., the molar ratio of cobalt chloride, nickel chloride and urea is 1：2：4~6；Further
, the molar ratio of the cobalt chloride, nickel chloride and urea is 1：2：5；
Further, in the step S2., the purification step includes separation, cleaning and drying, further, institute
It is to wait for centrifuging to obtain sample after reaction to state purification step, rinses sample repeatedly with alcohol and aqueous solvent, is dried in vacuo
To solid phase presoma；
Further, in the step S3., solid phase presoma is heat-treated in air atmosphere, heating rate control
It is made as 5 DEG C of min-1, 5h is calcined at 300~500 DEG C；
A kind of preparation method of oxidation nickel cobalt acid nickel micro-sphere material, including steps are as follows：
S1. reaction solution is prepared：It is 1 by molar ratio：2：5 cobalt chloride, nickel chloride and urea, which is dissolved in deionized water, to be surpassed
Sound disperses to obtain reaction solution；
S2. solid phase presoma is prepared：The reaction solution that S1. is prepared reacts 12~36h at 120~180 DEG C, instead
Solid phase presoma is purified to obtain after answering；
S3. oxidation nickel cobalt acid nickel micro-sphere material is prepared：The solid phase presoma that S2. is prepared is heat-treated, in sky
In gas atmosphere, with 5 DEG C of min-1Heating rate, at 300~500 DEG C keep the temperature 5h, after reaction up to oxidation nickel cobalt acid nickel it is micro-
Ball material；
The second aspect of the invention provides the oxidation nickel cobalt acid nickel micro-sphere material being prepared by the above method, described
Oxidation nickel cobalt acid nickel micro-sphere material particle is micron order, and particle is uniformly unified, and for grain size between 3~10 μm, average grain diameter is 5 μ
M, exterior appearance are in sea urchin shape three-dimensional structure, and particle surface, which neatly gathers, is arranged with acicular texture, and the acicular texture is in receive
Meter level, average diameter 200nm；
The third aspect of the invention provides a kind of lithium oxygen battery anode catalytic material, the lithium oxygen battery anode
Catalysis material includes above-mentioned oxidation nickel cobalt acid nickel micro-sphere material；
The fourth aspect of the invention, provides a kind of lithium oxygen battery, and the lithium oxygen battery includes above-mentioned anode catalytic
Material/or above-mentioned oxidation nickel cobalt acid nickel micro-sphere material.
Beneficial effects of the present invention：
(1) present invention builds the oxygen with sea urchin shape three-dimensional structure by adjusting hydrothermal reaction condition and heat treatment condition
Change nickel cobalt acid nickel, uniform particle sizes are unified；It should be noted that the temperature and time of hydro-thermal reaction influences the crystal knot of presoma
Structure, and the temperature (including heating rate) being heat-treated and time generate extreme influence to the secondary recrystallization of crystal, and then influence
Its catalytic performance as catalysis material；
(2) particle prepared by the present invention is micron order, 5 μm of average grain diameter, compared with nanostructure, in charge and discharge process
It is not susceptible to agglomeration；
(3) the sea urchin shape oxidation nickel cobalt acid nickel microsphere surface that prepared by the present invention is arranged with nano whiskers structure, nanometer needle set
There is porous structure and there is larger specific surface area, be advantageous to the transport of electronics and ion, assigns material excellent electrification
Learn performance；
(4) electrode anode catalysis material pattern prepared by the present invention has good repeatability with chemical property, and
Stable circulation performance is excellent, experiment proves that 100mA g-1Current density under, the specific capacity of first charge-discharge reaches 5818/
5377mAh g-1；In fixed specific capacity 100mAh g-1Lower carry out charge and discharge, after cycle 40 is enclosed, final discharging voltage remains
2.32V has good actual application value.
Description of the drawings
Fig. 1 is the XRD diagram that the sea urchin shape that embodiment 1 is prepared aoxidizes nickel cobalt acid nickel microballoon；
Fig. 2 is the FESEM figures that the sea urchin shape that embodiment 1 is prepared aoxidizes nickel cobalt acid nickel microballoon, and amplification factor is
2000；
Fig. 3 is the FESEM figures that the sea urchin shape that embodiment 1 is prepared aoxidizes nickel cobalt acid nickel microballoon, and amplification factor is
10000；
Fig. 4 is the FESEM figures that the sea urchin shape that embodiment 1 is prepared aoxidizes nickel cobalt acid nickel microballoon, and amplification factor is
20000；
When Fig. 5 is that the sea urchin shape that embodiment 1 is prepared aoxidizes nickel cobalt acid nickel micro-sphere material for lithium oxygen battery test
First charge-discharge figure；
When Fig. 6 is that the sea urchin shape that embodiment 1 is prepared aoxidizes nickel cobalt acid nickel micro-sphere material for lithium oxygen battery test
Cycle performance figure.
Specific implementation mode
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another
It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific implementation mode, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singulative
It is also intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or combination thereof.
In conjunction with specific example, the present invention is further illustrated, and following instance is not right merely to the explanation present invention
Its content is defined.If the experiment actual conditions being not specified in embodiment, usually according to normal condition, or it is public according to sale
The recommended condition of department；It is not particularly limited in the present invention, raw material can be commercially available by commercial sources.
In the specific embodiment of the present invention, a kind of preparation method of oxidation nickel cobalt acid nickel micro-sphere material, packet are provided
Include that steps are as follows：
S1. reaction solution is prepared：By cobalt chloride, nickel chloride and urea it is soluble in water reaction solution；
S2. solid phase presoma is prepared：The reaction solution that S1. is prepared reacts 12~36h at 120~180 DEG C, instead
Solid phase presoma is purified to obtain after answering；
S3. oxidation nickel cobalt acid nickel micro-sphere material is prepared：The solid phase presoma that S2. is prepared is placed in 300~500 DEG C
It is calcined 4~6h, after reaction up to oxidation nickel cobalt acid nickel micro-sphere material；
The present invention still another embodiment in, in the step S1., cobalt chloride, nickel chloride and urea molar ratio
It is 1：2：4~6；Further, the molar ratio of the cobalt chloride, nickel chloride and urea is 1：2：5；Cobalt chloride, nickel chloride and urine
The molar ratio of element influences the production quantity of nickel oxide and cobalt acid nickel, and then influences later crystallization and secondary crystallization pattern；
The present invention still another embodiment in, in the step S2., the purification step include separation, cleaning and
Dry, further, the purification step is to wait for centrifuging to obtain sample after reaction, is rushed repeatedly with alcohol and aqueous solvent
Sample is washed, vacuum drying obtains solid phase presoma；
In the still another embodiment of the present invention, in the step S3., solid phase presoma is carried out in air atmosphere
Heat treatment, heating rate control are 5 DEG C of min-1, 5h is calcined at 300~500 DEG C；
In the still another embodiment of the present invention, a kind of preparation method of oxidation nickel cobalt acid nickel micro-sphere material, packet are provided
Include that steps are as follows：
S1. reaction solution is prepared：It is 1 by molar ratio：2：5 cobalt chloride, nickel chloride and urea, which is dissolved in deionized water, to be surpassed
Sound disperses to obtain reaction solution；
S2. solid phase presoma is prepared：The reaction solution that S1. is prepared reacts 12~36h at 120~180 DEG C, instead
Solid phase presoma is purified to obtain after answering；
S3. oxidation nickel cobalt acid nickel micro-sphere material is prepared：The solid phase presoma that S2. is prepared is heat-treated, in sky
In gas atmosphere, with 5 DEG C of min-1Heating rate, at 300~500 DEG C keep the temperature 5h, after reaction up to oxidation nickel cobalt acid nickel it is micro-
Ball material；
In the still another embodiment of the present invention, the oxidation nickel cobalt acid nickel microballoon being prepared by the above method is provided
Material, the oxidation nickel cobalt acid nickel micro-sphere material particle are micron order, and particle is uniformly unified, and grain size is put down between 3~10 μm
Equal grain size is 5 μm, and exterior appearance is in sea urchin shape three-dimensional structure, and particle surface, which neatly gathers, is arranged with acicular texture, the needle
Shape structure is in nanoscale, average diameter 200nm；Above-mentioned appearance structure makes it have larger specific surface area, while it is three-dimensional
Structure is conducive to the quick transmission of electronics and ion on electrode and electrolyte interface, assigns its excellent chemical property.
In the still another embodiment of the present invention, a kind of lithium oxygen battery anode catalytic material, the lithia gas are provided
Anode catalysis material includes above-mentioned oxidation nickel cobalt acid nickel micro-sphere material；
In the still another embodiment of the present invention, a kind of lithium oxygen battery is provided, the lithium oxygen battery includes above-mentioned
Anode catalytic material/or above-mentioned oxidation nickel cobalt acid nickel micro-sphere material.
Following embodiment will be further described the present invention, but not thereby limiting the invention.
Embodiment 1
Sea urchin shape aoxidizes nickel cobalt acid nickel microballoon, is made by the steps：
(1) reaction solution is prepared
2mmol nickel chlorides, 4mmol cobalt chlorides and 10mmol urea are dissolved in 75mL deionized waters, stirred and ultrasonic
Rose mixed solution is formed after 1h；
(2) solid phase presoma is prepared
Obtained solution in step (1) is transferred in 100mL polytetrafluoroethylliner liners, it is anti-to carry out high temperature and pressure hydro-thermal
It answers, at 150 DEG C, the reaction time controls for 24 hours for reaction temperature control, fully reacts postcooling to room temperature, with deionized water and second
Alcohol carries out centrifuge washing to reaction product, is dried in vacuo at 120 DEG C and obtains solid phase presoma afterwards for 24 hours；
(3) subsequent heat treatment
The presoma collected in step (2) is placed in Muffle furnace, in air atmosphere, with 5 DEG C of min-1Heating rate,
5h is kept the temperature at 400 DEG C, waits for that Muffle furnace is cooled to room temperature, and obtained black sample i.e. sea urchin shape aoxidizes nickel cobalt acid nickel micro-sphere material
Powder.
Fig. 1 is that sea urchin shape aoxidizes nickel cobalt acid nickel microsphere sample XRD diagram, diffraction data and cubic phase NiO standard cards
(JCPDS No.65-5745) and cubic spinel phase NiCo2O4Standard card (JCPDS No.20-0781) unanimously, and does not have
There is other impurities phase, shows that product is the nickel oxide and cobalt acid nickel composite of high-purity.Fig. 2-4 is that sea urchin shape aoxidizes nickel cobalt
The FESEM pictures of sour nickel microsphere sample, by picture it can be seen that the particle that the inventive method synthesizes is microspheroidal, microsphere particle grain
Diameter is at 5 μm or so；Microballoon outer layer forms for nanoneedle, and nanoneedle diameter is about 200nm.
Electrode is made as follows with 1 gained sea urchin shape of embodiment oxidation nickel cobalt acid nickel micro-sphere material：
With 4:4:2 mass ratio weighs sea urchin shape oxidation nickel cobalt acid nickel micro-sphere material, carbon black and polytetrafluoroethylene (PTFE) respectively,
The isopropanol of certain volume is added, after ultrasonic disperse is uniform, is coated uniformly on carbon paper and electrode is made, it is negative to use metal lithium sheet
Pole, electrolyte are 1mol L-1Trifluoromethanesulfonic acid lithium/tetraethylene glycol dimethyl ether, diaphragm select fibreglass diaphragm, be assembled into 2032
Type half-cell.All constant current charge-discharge tests pass through blue electrical measurement test system (LAND CT in the test box full of oxygen
2001A) carry out.Fig. 5 is institute's assembled battery in 100mA g-1Charge-discharge property under current density.Electrode material of the present invention
In 100mA g-1Under current density, charging and discharging capacity reaches 5818/5377mAh g-1.Fig. 6 is institute's assembled battery in 100mA
g-1Cycle performance under current density.Electrode material of the present invention is in fixed specific capacity 1000mAh g-1Lower charge and discharge, cycle 40
After circle, higher discharge voltage is still maintained, is 2.32V.
Embodiment 2
Sea urchin shape aoxidizes nickel cobalt acid nickel microballoon, is made by the steps：
(1) reaction solution is prepared
2mmol nickel chlorides, 4mmol cobalt chlorides and 10mmol urea are dissolved in 75mL deionized waters, stirred and ultrasonic
Rose mixed solution is formed after 1h；
(2) solid phase presoma is prepared
Obtained solution in step (1) is transferred in 100mL polytetrafluoroethylliner liners, it is anti-to carry out high temperature and pressure hydro-thermal
It answers, at 120 DEG C, the reaction time controls for 24 hours for reaction temperature control, fully reacts postcooling to room temperature, with deionized water and second
Alcohol carries out centrifuge washing to reaction product, is dried in vacuo at 120 DEG C and obtains solid phase presoma afterwards for 24 hours；
(3) subsequent heat treatment
The presoma collected in step (2) is placed in Muffle furnace, in air atmosphere, with 5 DEG C of min-1Heating rate,
5h is kept the temperature at 400 DEG C, waits for that Muffle furnace is cooled to room temperature, and obtained black sample i.e. sea urchin shape aoxidizes nickel cobalt acid nickel micro-sphere material
Powder.
Embodiment 3
Sea urchin shape aoxidizes nickel cobalt acid nickel microballoon, is made by the steps：
(1) reaction solution is prepared
2mmol nickel chlorides, 4mmol cobalt chlorides and 10mmol urea are dissolved in 75mL deionized waters, stirred and ultrasonic
Rose mixed solution is formed after 1h；
(2) solid phase presoma is prepared
Obtained solution in step (1) is transferred in 100mL polytetrafluoroethylliner liners, it is anti-to carry out high temperature and pressure hydro-thermal
It answers, at 180 DEG C, the reaction time controls for 24 hours for reaction temperature control, fully reacts postcooling to room temperature, with deionized water and second
Alcohol carries out centrifuge washing to reaction product, is dried in vacuo at 120 DEG C and obtains solid phase presoma afterwards for 24 hours；
(3) subsequent heat treatment
The presoma collected in step (2) is placed in Muffle furnace, in air atmosphere, with 5 DEG C of min-1Heating rate,
5h is kept the temperature at 400 DEG C, waits for that Muffle furnace is cooled to room temperature, and obtained black sample i.e. sea urchin shape aoxidizes nickel cobalt acid nickel micro-sphere material
Powder.
Embodiment 4
Sea urchin shape aoxidizes nickel cobalt acid nickel microballoon, is made by the steps：
(1) reaction solution is prepared
2mmol nickel chlorides, 4mmol cobalt chlorides and 10mmol urea are dissolved in 75mL deionized waters, stirred and ultrasonic
Rose mixed solution is formed after 1h；
(2) solid phase presoma is prepared
Obtained solution in step (1) is transferred in 100mL polytetrafluoroethylliner liners, it is anti-to carry out high temperature and pressure hydro-thermal
It answers, at 150 DEG C, reaction time control fully reacts postcooling to room temperature, with deionized water and second in 12h for reaction temperature control
Alcohol carries out centrifuge washing to reaction product, is dried in vacuo at 120 DEG C and obtains solid phase presoma afterwards for 24 hours；
(3) subsequent heat treatment
The presoma collected in step (2) is placed in Muffle furnace, in air atmosphere, with 5 DEG C of min-1Heating rate,
5h is kept the temperature at 400 DEG C, waits for that Muffle furnace is cooled to room temperature, and obtained black sample i.e. sea urchin shape aoxidizes nickel cobalt acid nickel micro-sphere material
Powder.
Embodiment 5
Sea urchin shape aoxidizes nickel cobalt acid nickel microballoon, is made by the steps：
(1) reaction solution is prepared
2mmol nickel chlorides, 4mmol cobalt chlorides and 10mmol urea are dissolved in 75mL deionized waters, stirred and ultrasonic
Rose mixed solution is formed after 1h；
(2) solid phase presoma is prepared
Obtained solution in step (1) is transferred in 100mL polytetrafluoroethylliner liners, it is anti-to carry out high temperature and pressure hydro-thermal
It answers, at 150 DEG C, reaction time control fully reacts postcooling to room temperature, with deionized water and second in 36h for reaction temperature control
Alcohol carries out centrifuge washing to reaction product, is dried in vacuo at 120 DEG C and obtains solid phase presoma afterwards for 24 hours；
(3) subsequent heat treatment
The presoma collected in step (2) is placed in Muffle furnace, in air atmosphere, with 5 DEG C of min-1Heating rate,
5h is kept the temperature at 400 DEG C, waits for that Muffle furnace is cooled to room temperature, and obtained black sample i.e. sea urchin shape aoxidizes nickel cobalt acid nickel micro-sphere material
Powder.
Embodiment 6
Sea urchin shape aoxidizes nickel cobalt acid nickel microballoon, is made by the steps：
(1) reaction solution is prepared
2mmol nickel chlorides, 4mmol cobalt chlorides and 10mmol urea are dissolved in 75mL deionized waters, stirred and ultrasonic
Rose mixed solution is formed after 1h；
(2) solid phase presoma is prepared
Obtained solution in step (1) is transferred in 100mL polytetrafluoroethylliner liners, it is anti-to carry out high temperature and pressure hydro-thermal
It answers, at 150 DEG C, the reaction time controls for 24 hours for reaction temperature control, fully reacts postcooling to room temperature, with deionized water and second
Alcohol carries out centrifuge washing to reaction product, is dried in vacuo at 120 DEG C and obtains solid phase presoma afterwards for 24 hours；
(3) subsequent heat treatment
The presoma collected in step (2) is placed in Muffle furnace, in air atmosphere, with 5 DEG C of min-1Heating rate,
5h is kept the temperature at 300 DEG C, waits for that Muffle furnace is cooled to room temperature, and obtained black sample i.e. sea urchin shape aoxidizes nickel cobalt acid nickel micro-sphere material
Powder.
Embodiment 7
Sea urchin shape aoxidizes nickel cobalt acid nickel microballoon, is made by the steps：
(1) reaction solution is prepared
2mmol nickel chlorides, 4mmol cobalt chlorides and 10mmol urea are dissolved in 75mL deionized waters, stirred and ultrasonic
Rose mixed solution is formed after 1h；
(2) solid phase presoma is prepared
Obtained solution in step (1) is transferred in 100mL polytetrafluoroethylliner liners, it is anti-to carry out high temperature and pressure hydro-thermal
It answers, at 150 DEG C, the reaction time controls for 24 hours for reaction temperature control, fully reacts postcooling to room temperature, with deionized water and second
Alcohol carries out centrifuge washing to reaction product, is dried in vacuo at 120 DEG C and obtains solid phase presoma afterwards for 24 hours；
(3) subsequent heat treatment
The presoma collected in step (2) is placed in Muffle furnace, in air atmosphere, with 5 DEG C of min-1Heating rate,
5h is kept the temperature at 500 DEG C, waits for that Muffle furnace is cooled to room temperature, and obtained black sample i.e. sea urchin shape aoxidizes nickel cobalt acid nickel micro-sphere material
Powder.
The foregoing is merely the preferred embodiments of the application, are not intended to limit this application, for the skill of this field
For art personnel, the application can have various modifications and variations.Within the spirit and principles of this application, any made by repair
Change, equivalent replacement, improvement etc., should be included within the protection domain of the application.
Claims (10)
1. a kind of preparation method of oxidation nickel cobalt acid nickel micro-sphere material, which is characterized in that including steps are as follows：
S1. reaction solution is prepared：By cobalt chloride, nickel chloride and urea it is soluble in water reaction solution；
S2. solid phase presoma is prepared：The reaction solution that S1. is prepared reacts 12~36h, reaction knot at 120~180 DEG C
Solid phase presoma is purified to obtain after beam；
S3. oxidation nickel cobalt acid nickel micro-sphere material is prepared：The solid phase presoma that S2. is prepared is placed in 300~500 DEG C of calcination 4
~6h, after reaction up to oxidation nickel cobalt acid nickel micro-sphere material.
2. a kind of preparation method as described in claim 1, which is characterized in that in the step S1., cobalt chloride, nickel chloride and
The molar ratio of urea is 1：2：4~6.
3. a kind of preparation method as claimed in claim 2, which is characterized in that the cobalt chloride, nickel chloride and urea mole
Than being 1：2：5.
4. a kind of preparation method as described in claim 1, which is characterized in that in the step S2., the purification step includes
Separation, cleaning and drying.
5. a kind of preparation method as claimed in claim 4, which is characterized in that the purification step is to wait for centrifuging after reaction
Sample is detached to obtain, rinses sample repeatedly with alcohol and aqueous solvent, vacuum drying obtains solid phase presoma.
6. a kind of preparation method as described in claim 1, which is characterized in that in the step S3., to solid in air atmosphere
Phase precursor is heat-treated, and heating rate control is 5 DEG C of min-1, 5h is calcined at 300~500 DEG C.
7. a kind of preparation method of oxidation nickel cobalt acid nickel micro-sphere material, which is characterized in that including steps are as follows：
S1. reaction solution is prepared：It is 1 by molar ratio：2：5 cobalt chloride, nickel chloride and urea is dissolved in ultrasound point in deionized water
Dissipate to obtain reaction solution；
S2. solid phase presoma is prepared：The reaction solution that S1. is prepared reacts 12~36h, reaction knot at 120~180 DEG C
Solid phase presoma is purified to obtain after beam；
S3. oxidation nickel cobalt acid nickel micro-sphere material is prepared：The solid phase presoma that S2. is prepared is heat-treated, in air gas
In atmosphere, with 5 DEG C of min-1Heating rate, at 300~500 DEG C keep the temperature 5h, after reaction up to oxidation nickel cobalt acid nickel microballoon material
Material.
8. the oxidation nickel cobalt acid nickel micro-sphere material that the preparation method as described in claim any one of 1-7 is prepared, feature exist
In, the oxidation nickel cobalt acid nickel micro-sphere material particle is micron order, and for grain diameter between 3~10 μm, average grain diameter is 5 μm,
Particle appearance pattern is in sea urchin shape three-dimensional structure, and particle surface, which neatly gathers, is arranged with acicular texture, and the acicular texture is in receive
Meter level, average diameter 200nm.
9. a kind of lithium oxygen battery anode catalytic material, which is characterized in that the lithium oxygen battery anode catalytic material includes power
Profit requires the 8 oxidation nickel cobalt acid nickel micro-sphere materials.
10. a kind of lithium oxygen battery, which is characterized in that the lithium oxygen battery include claim 9 described in anode catalytic material/
Or nickel cobalt acid nickel micro-sphere material is aoxidized described in claim 8.
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| CN111298822A (en) * | 2020-02-14 | 2020-06-19 | 江苏师范大学 | Nitrogen/sulfur doped carbon coated NiCo2O4Synthetic method of/NiO hollow micron rod |
| CN112259745A (en) * | 2020-09-09 | 2021-01-22 | 温州大学新材料与产业技术研究院 | Oxygen reduction electrocatalyst based on nitrogen and sulfur co-doped carbon microsphere/carbon sheet material and application thereof |
| CN113745530A (en) * | 2021-09-08 | 2021-12-03 | 山东大学 | High-performance spherical phosphorus-doped nickel oxide lithium carbon dioxide battery positive electrode catalytic material and preparation method thereof |
| CN114497588A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Flow battery anode catalyst and preparation method and application thereof |
| CN114678492A (en) * | 2022-03-08 | 2022-06-28 | 山东大学 | Micron flower material with flower-shaped cobalt disulfide surface loaded with nickel disulfide and preparation method thereof |
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| 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 |
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| CN114497588B (en) * | 2020-10-26 | 2024-07-23 | 中国石油化工股份有限公司 | Flow battery anode catalyst and preparation method and application thereof |
| CN113745530A (en) * | 2021-09-08 | 2021-12-03 | 山东大学 | High-performance spherical phosphorus-doped nickel oxide lithium carbon dioxide battery positive electrode catalytic material and preparation method thereof |
| CN113745530B (en) * | 2021-09-08 | 2023-02-28 | 山东大学 | High-performance spherical phosphorus-doped nickel oxide lithium carbon dioxide battery positive electrode catalytic material and preparation method thereof |
| CN114678492A (en) * | 2022-03-08 | 2022-06-28 | 山东大学 | Micron flower material with flower-shaped cobalt disulfide surface loaded with nickel disulfide and preparation method thereof |
| CN115974180A (en) * | 2023-02-10 | 2023-04-18 | 烟台大学 | Sea urchin-shaped NiCo 2 O 4 @ C wave-absorbing material and preparation method thereof |
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