CN105932302B - Area load has MnO2Carbon nano pipe array electrode of nanometer sheet and its preparation method and application - Google Patents
Area load has MnO2Carbon nano pipe array electrode of nanometer sheet and its preparation method and application Download PDFInfo
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- CN105932302B CN105932302B CN201610248736.XA CN201610248736A CN105932302B CN 105932302 B CN105932302 B CN 105932302B CN 201610248736 A CN201610248736 A CN 201610248736A CN 105932302 B CN105932302 B CN 105932302B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 152
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 61
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 50
- 239000006260 foam Substances 0.000 claims abstract description 47
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 46
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 10
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 10
- 239000011258 core-shell material Substances 0.000 claims abstract description 9
- 239000011159 matrix material Substances 0.000 claims abstract description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 110
- 239000011787 zinc oxide Substances 0.000 claims description 55
- 239000000243 solution Substances 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 20
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 9
- 239000008103 glucose Substances 0.000 claims description 9
- 229910006364 δ-MnO2 Inorganic materials 0.000 claims description 9
- 239000012286 potassium permanganate Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 238000005336 cracking Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000002073 nanorod Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 150000004687 hexahydrates Chemical class 0.000 claims description 2
- 239000002071 nanotube Substances 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 230000010287 polarization Effects 0.000 abstract description 7
- 239000011230 binding agent Substances 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 10
- 238000007086 side reaction Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 229910001323 Li2O2 Inorganic materials 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000002242 deionisation method Methods 0.000 description 5
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 5
- -1 polypropylene Polymers 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- QTJOIXXDCCFVFV-UHFFFAOYSA-N [Li].[O] Chemical compound [Li].[O] QTJOIXXDCCFVFV-UHFFFAOYSA-N 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- HPGPEWYJWRWDTP-UHFFFAOYSA-N lithium peroxide Chemical compound [Li+].[Li+].[O-][O-] HPGPEWYJWRWDTP-UHFFFAOYSA-N 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
-
- 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
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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
- H01M4/8803—Supports for the 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
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
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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
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
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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
- 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
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- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
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Abstract
The invention discloses one kind to be loaded with MnO2The carbon nano pipe array electrode of nanometer sheet, using three-dimensional porous foams nickel as matrix, direct growth is loaded with MnO on matrix2The carbon nano pipe array of nanometer sheet, MnO2Nanometer sheet is grown on carbon nano tube surface, forms core shell structure.The invention also discloses described to be loaded with MnO2The preparation method and application of the carbon nano pipe array electrode of nanometer sheet.Preparation technology is simple, cost is low, the cycle is short, low power consumption and other advantages, is adapted to large-scale industrial production；The core shell structure array type electrode being prepared is free of binding agent, due to nickel foam special three-dimensional porous structure and MnO2The loose structure and catalytic performance of nanometer sheet, when described array electrode is used as catalysis positive pole, lithium sky battery shows relatively low polarization and preferable cyclical stability.
Description
Technical field
The present invention relates to lithium sky cell catalyst electrode field, and in particular to a kind of area load has MnO2The carbon of nanometer sheet is received
Mitron array electrode and its preparation method and application.
Background technology
Lithium ion battery is widely used as mobile electronic device, such as smart mobile phone, notebook computer, and in electricity now
Net energy storage, electric automobile field have huge market.But the energy density of lithium ion battery is relatively low, it is limited big
Application in scale energy storage field, the large-scale use such as on electric automobile.By contrast, the energy density of lithium sky battery compared with
Height, the lithium ion battery of remote ultra-traditional, but there is tempting application prospect in extensive energy storage field, particularly electric automobile.
Different from (lithium ion) shuttle mechanism of conventional lithium ion battery, the work of lithium sky battery is based on lithium peroxide
(Li2O2) formation and decomposition, i.e.,But the electric conductivity extreme difference of lithium peroxide, it is difficult in charging process
Decompose, cause big overpotential and more serious side reaction.It is generally believed that overpotential can be reduced by introducing catalyst, it is common
Catalyst has carbon material (such as graphene, CNT), transition metal oxide (such as MnO2, Co3O4), noble metal etc..Carbon materials
Expect that cheap, electrical conductivity is high and be widely used as catalyst, but its catalytic performance is weaker, often to be answered with noble metal or oxide
Close to improve its catalytic performance.
Li2O2Deposition on the one hand can cause the passivation of electrode, on the other hand can cause the obstruction of electrode, influence lithium ion
With the conduction of oxygen.By electrode design into array type, Li is filled using the intrinsic space of array electrode2O2Be solution it
One, carbon material is designed to array type electrode, can further utilize the electric conductivity of carbon pipe.But due to Li2O2Growth often can not
Control, it is impossible to tackle the problem at its root.In addition, Li2O2Side reaction can occur with carbon material, cause the passivation of electrode.
More satisfactory situation is, grows a kind of effective catalyst in carbon pipe surface, such as transition metal oxide, such
Electrode design is for solving the problems, such as that lithium sky battery has important theory significance and actual application value, but there is presently no this
The document report of aspect.
The content of the invention
The invention provides a kind of MnO is loaded with for lithium sky battery2The carbon nano pipe array type electrode of nanometer sheet and its
Preparation method and application.Preparation technology is simple, and energy consumption is low, cost is low, is suitable for large-scale industrial production；The tool being prepared
There is the MnO of core shell structure2/ carbon nano pipe array possesses high conductivity, high catalytic property, suppresses side reaction and carries Li2O2Work(
Can, it is applied to the catalysis positive pole of lithium sky battery, the chemical property of lithium sky battery can be improved, polarization is particularly reduced and carry
High circulation stability.
The invention discloses a kind of area load MnO2The preparation method of the carbon nano pipe array electrode of nanometer sheet, it is special
Sign is, comprises the following steps：
1) zinc nitrate hexahydrate, hexa are dissolved in deionized water, add ammoniacal liquor, mixed after stirring
Close solution；
The mol ratio of the hexa and zinc nitrate hexahydrate is 0.5~2.0；
The volume ratio of the ammoniacal liquor and deionized water is 0.03~0.1；
Zn in the mixed solution2+Concentration is 0.01~0.05mol/L；
2) nickel foam is immersed in mixed solution, through 70~110 DEG C of 2~10h of hydro-thermal reaction, then post-treated obtains surface
The nickel foam of zinc oxide nano rod is loaded with, is designated as Ni/ZnO；
3) Ni/ZnO for obtaining step 2) is immersed in the glucose solution that concentration is 0.05~0.15mol/L, after taking-up
Carry out being thermally treated resulting in the nickel foam for being loaded with zinc oxide and CNT, be designated as Ni/ZnO/CNT；
The temperature of the heat treatment is 500~700 DEG C, and the time is 2~10h；
4) Ni/ZnO/CNT is immersed in the NaOH aqueous solution that concentration is 1~3mol/L and removes ZnO, it is post-treated to be carried
There is the nickel foam of CNT, be designated as Ni/CNT；
5) Ni/CNT is immersed to 0.005~0.2mol/L KMnO4In the aqueous solution, through 60~100 DEG C of hydro-thermal reactions 2~
5h, secondary heat treatment is carried out again after scrubbed, dry, obtaining area load has MnO2The carbon nano pipe array electrode of nanometer sheet,
It is designated as Ni/CNT/MnO2；
The temperature of the secondary heat treatment is 200~400 DEG C, and the time is 1~3h.
The present invention is directly made using three-dimensional porous foams nickel as matrix by hydro-thermal method (with reference to heat treatment) on Ni matrixes
It is standby to be loaded with MnO2The carbon nano pipe array of nanometer sheet, and the three-dimensional porous structure of nickel foam is remained, be advantageous to lithium ion and oxygen
The diffusion of gas.CNT serves double action, and only electrode does not provide electric action, and sustainable MnO2Nanometer sheet.
Described direct growth refers to：First by masterplate method on nickel foam substrate growing ZnO nanorod, then in ZnO
Heat treatment being combined with hydro-thermal method in nanometer rods and etching preparing carbon nano pipe array, heat treatment is then combined in carbon using hydro-thermal method
Nanotube surface direct growth MnO2Nanometer sheet, without any polymeric binder and；In contrast, indirect growth refers to pre-
First synthesizing carbon nanotubes and MnO2Nanometer sheet, then two kinds of raw materials and binding agent are well mixed in organic solvent, stir into slurry
Material, is then coated on nickel foam substrate.Due to without binding agent, entirely eliminated the side reaction for being related to binding agent.
In step 1), the mass percent of the ammoniacal liquor is 25wt%.
Preferably, in step 2), described nickel foam need to be pre-processed, and be specially：
Nickel foam is soaked into 1h in 0.5mol/L potassium permanganate solution, it is stand-by after washing.
Preferably, in step 2), the temperature of the hydro-thermal reaction is 80~100 DEG C.
Preferably, in step 3), soak times of the Ni/ZnO in glucose solution is 2~10h.
Preferably, in step 4), soak times of the Ni/ZnO/CNT in the NaOH aqueous solution is 24~72h.
Preferably, in step 5), the temperature of the hydro-thermal reaction is 80~90 DEG C；
Preferably, in step 5), described secondary heat treatment is carried out under an ar atmosphere.
Described post processing includes washing, dried.
The invention also discloses have MnO according to the area load of above-mentioned method preparation2The carbon nano pipe array of nanometer sheet
Electrode, it is characterised in that using three-dimensional porous foams nickel as matrix, direct growth is loaded with MnO on matrix2The CNT of nanometer sheet
Array, MnO2CNT is coated in carbon nano tube surface, forms core shell structure, the core by nanometer sheet uniform load completely
A diameter of 400 nm~1 μm of shell structure.MnO2Nanometer sheet has less size, higher specific surface area and stronger catalysis
Performance, easily as catalytic active center, turn into Li2O2Forming core and organic centre, its loose structure be beneficial to carrying Li2O2, simultaneously
Beneficial to the transmission of lithium ion and oxygen.MnO2Nanometer sheet coats carbon pipe completely, suppresses carbon pipe and Li2O2Or LiO2Side reaction.
Preferably, described MnO2By the δ-MnO of laminated structure2Pile up and form, form loose structure, monolithic δ-MnO2
Size be 100~300nm, thickness is 2~5nm.
Array type CNT is advantageous to electrode and integrally soaked by electrolyte, is advantageous to the diffusion of lithium ion and oxygen；Make
To be preferred, described CNT is in amorphous state in cracking state, and length is 2~4 μm, a diameter of 200~600nm, wall thickness
For 5~10nm.Appropriate length and wall thickness is advantageous to electrode mechanical stability, and the carbon pipe of cracking is further advantageous to be beneficial to electricity
Pole is soaked by electrolyte.
Preferably, the area load has MnO2MnO in the carbon nano pipe array electrode of nanometer sheet2The carrying of nanometer sheet
Measure as 0.4~0.5mg/cm2；MnO2The bearing capacity of nanometer sheet is very few, and its catalytic effect is undesirable, and is unfavorable for carbon pipe is complete
Full cladding reduces side reaction caused by carbon；Bearing capacity is excessive, causes the waste of material, the lifting unobvious to catalytic performance, and
Reduce electrode free space and reduce electrode by the degree of wetting of electrolyte, while cause the decline (appearance of lithium sky battery of specific capacity
Amount and the weight of catalysis electrode do not have proportionate relationship).
Preferably, the area load has MnO2The bearing capacity of CNT in the carbon nano pipe array electrode of nanometer sheet
For 0.04~0.1mg/cm2, CNT primarily serves conductive and carrying MnO in the electrodes2The effect of nanometer sheet, its content mistake
It is low to weaken electrodes conduct performance and mechanical stability, and the effect of raising of the too high content to electric conductivity and mechanical performance
Unobvious, while the free space of electrode can be reduced, so as to influence the diffusion of the wetting of electrode and oxygen.It is further, since relative
In by MnO2Nanometer sheet, the catalytic performance of its own is weaker, excessive to add the specific capacity that reduce battery.Therefore institute is due to, inciting somebody to action
The content control of CNT is more reasonable within the above range.
The invention also discloses described area load MnO2The carbon nano pipe array electrode of nanometer sheet is in lithium sky battery
In application.
Compared with prior art, the invention has the advantages that：
1st, CNT and MnO in array type electrode prepared by the present invention2Nanometer sheet is directly grown on nickel foam substrate,
Without other conductive agents and binding agent, electrode prepares using traditional hydro-thermal and combines necessary heat treatment, has technique letter
It is single, cost is low, the cycle is short, energy consumption is low and the advantages that suitable industrialized production；
2nd, CNT while play conductive carrying in the array type electrode for preparing of the present invention and act on； MnO2Nanometer sheet is not
Only there is high catalytic performance, and CNT is coated to the side reaction for reducing and having carbon to be related to completely, so as to effectively reduce electricity
The polarization of pole and the cyclical stability for improving battery；
3rd, compared with traditional electrode slurry coating process, this preparation method can keep the original three-dimensional porous knot of nickel foam
Structure, be advantageous to the wetting of electrode；Array type electrode can further improve the diffusion of lithium ion and oxygen, so as to reduce the pole of electrode
The side reaction occurred in change and battery.
Brief description of the drawings
Fig. 1 is the MnO loaded on the carbon nanotubes prepared by embodiment 12X ray diffracting spectrum；
Fig. 2 is loaded with MnO for prepared by embodiment 12The carbon nano pipe array type electrode low power ESEM of nanometer sheet shines
Piece；
Fig. 3 is loaded with MnO for prepared by embodiment 12The high power ESEM of the carbon nano pipe array type electrode of nanometer sheet
Photo；
Fig. 4 is to be loaded with MnO with prepared by embodiment 12The carbon nano pipe array type electrode of nanometer sheet is catalysis positive pole group
The cyclical stability of the lithium sky battery of dress.
Embodiment
Embodiment 1
Zinc nitrate hexahydrate and hexa (being 1 with zinc nitrate hexahydrate mole ratio) are dissolved in deionized water,
Ammoniacal liquor (25wt%) is added, the volume of ammoniacal liquor is the 1/25 of deionization volume, stirs, prepares with Zn2+Counting concentration is
0.04mol/L solution；Taken out after nickel foam is soaked 1 hour in 0.5mol/L liquor potassic permanganate, use deionized water
Immersed after cleaning repeatedly and contain Zn2+In solution, through 90 DEG C of hydro-thermal reaction 6h, then it is scrubbed, dry after must arrive surface and be loaded with zinc oxide
The nickel foam (Ni/ZnO) of nanometer rods；Ni/ZnO is immersed in 0.07mol/L glucose solution and soaked 5 hours, is taken out
The nickel foam (Ni/ZnO/CNT) that surface is loaded with zinc oxide and CNT must be arrived for 4 hours by being heat-treated at 600 DEG C；Then by Ni/
ZnO/CNT, which is placed in 1.5mol/L NaOH solution to soak 48 hours, removes ZnO, and washs, obtains being loaded with carbon nanometer after drying
The nickel foam (Ni/CNT) of pipe, CNT are in amorphous state, and the bearing capacity of CNT is 0.04mg/cm2.Ni/CNT is immersed
0.01mol/L KMnO4In the aqueous solution, through 85 DEG C of hydro-thermal reaction 2.5h, then scrubbed, drying, then 300 DEG C of heat under an ar atmosphere
Handle 2 hours carbon pipe/MnO for obtaining being loaded in nickel foam2Nucleocapsid array (Ni/CNT/MnO2), wherein MnO2Bearing capacity be
0.41mg/cm2。
Fig. 1 is the MnO loaded on the carbon nanotubes prepared by this implementation2X-ray diffraction spectrum, the material can be attributed to δ-
MnO2。
Fig. 2 and Fig. 3 is respectively Ni/CNT/MnO manufactured in the present embodiment2Low power and high power ESEM, in terms of photo,
Monolithic δ-MnO2Size be 100~300nm, thickness is 2~5nm, the CNT/MnO of core shell structure2The μ of a diameter of 400nm~1
M, length are 2~4 μm.
With Ni/CNT/MnO manufactured in the present embodiment2As positive pole, using lithium metal as negative pole, the polypropylene film (trade mark
Celgard C480, Celgard companies of the U.S.) it is barrier film, LiClO4TRIGLYME (TEGDME) solution for electrolysis
Liquid, battery is assembled in the glove box full of argon gas.After being passed through the oxygen of 1 atmospheric pressure, charge-discharge test is carried out, it circulates bent
Line is as shown in Figure 4.
Constant volume charge-discharge test (capacity limit in 500mAh/g, current density 400mA/g, voltage range 2V~4.5V, its
Middle capacity and current density are based on carbon pipe and MnO2Gross weight) show, in secondary charge and discharge process, the equal energy of the lithium-oxygen battery
Keep stable circulation.Its charge and discharge end current potential is kept at 3.99V and 2.87V or so, show relatively low polarization and
Preferable cyclical stability.
Comparative example 1
The preparation technology of array type carbon nanotube electrode is similar to Example 1, and difference is to lack MnO2Nanometer sheet
Growth step.Concrete technology is as follows, by zinc nitrate hexahydrate and hexa (being 1 with zinc nitrate hexahydrate mole ratio)
Be dissolved in deionized water, add ammoniacal liquor (25wt%), the volume of ammoniacal liquor is the 1/25 of deionization volume, is stirred, prepare with
Zn2+Count the solution that concentration is 0.04 mol/L；Nickel foam is taken out after being soaked 1 hour in 0.5mol/L liquor potassic permanganate,
Immersed after being cleaned repeatedly with deionized water and contain Zn2+In solution, surface is obtained after 90 DEG C of hydro-thermal reaction 6h, then scrubbed, drying
It is loaded with the nickel foam (Ni/ZnO) of zinc oxide nano rod；It is small that Ni/ZnO is immersed to immersion 5 in 0.07mol/L glucose solution
When, the nickel foam (Ni/ZnO/CNT) that surface is loaded with zinc oxide and CNT must be arrived for 4 hours by taking out to be heat-treated at 600 DEG C；
Then Ni/ZnO/CNT is placed in 1.5mol/L NaOH solution to soak 48 hours and removes ZnO, and washed, obtained after drying
The nickel foam (Ni/CNT) of CNT is loaded with, the bearing capacity of CNT is 0.03mg/cm2.X-ray diffraction spectrum, it is deposited on
Material in nickel foam can be attributed to carbon.It was found from stereoscan photograph, CNT is in amorphous state in cracking state, length
For 2~4 μm, a diameter of 200~600nm, wall thickness is 5~20nm.
The Ni/CNT prepared using this comparative example is used as positive pole, using lithium metal as negative pole, polypropylene film (trade mark Celgard
C480, Celgard companies of the U.S.) it is barrier film, LiClO4TRIGLYME (TEGDME) solution be electrolyte, full of
Battery is assembled in the glove box of argon gas.After being passed through the oxygen of 1 atmospheric pressure, charge-discharge test is carried out.
Constant volume charge-discharge test (capacity limit in 500mAh/g, current density 100mA/g, voltage range 2V~4.5V, its
Middle capacity and current density are based on the weight of carbon pipe) show, under low current density 100mA/g, constant volume 500mAh/g electricity
Pond is only capable of maintaining a circulation, shows poor cyclical stability.
Embodiment 2
Zinc nitrate hexahydrate and hexa (being 1 with zinc nitrate hexahydrate mole ratio) are dissolved in deionized water,
Ammoniacal liquor (25wt%) is added, the volume of ammoniacal liquor is the 1/25 of deionization volume, stirs, prepares with Zn2+Counting concentration is
0.01mol/L solution；Nickel foam is taken out after being soaked 1 hour in 0.5mol/L liquor potassic permanganate, anti-with deionized water
Immersed after multiple cleaning and contain Zn2+In solution, through 80 DEG C of hydro-thermal reaction 10h, then it is scrubbed, dry after must arrive surface and be loaded with zinc oxide nano
The nickel foam (Ni/ZnO) of rice rod；Ni/ZnO is immersed in 0.07mol/L glucose solution and soaked 5 hours, is taken out 600
The nickel foam (Ni/ZnO/CNT) that surface is loaded with zinc oxide and CNT must be arrived for 4 hours by being heat-treated at DEG C；Then by Ni/ZnO/
CNT, which is placed in 1.5mol/L NaOH solution to soak 48 hours, removes ZnO, and washs, obtains being loaded with CNT after drying
Nickel foam (Ni/CNT), the wherein bearing capacity of CNT are 0.04mg/cm2.Ni/CNT is immersed into 0.01 mol/L KMnO4
In the aqueous solution, through 80 DEG C of hydro-thermal reaction 3h, then scrubbed, drying, then 300 DEG C of heat treatments are loaded in for 2 hours under Ar atmosphere
Carbon pipe/MnO of nickel foam2Nucleocapsid array (Ni/CNT/MnO2), wherein MnO2Bearing capacity be 0.40mg/cm2.X-ray diffraction
Spectrum shows that the material carried on the carbon nanotubes is δ-MnO2, CNT is in amorphous state.Stereoscan photograph shows, monolithic δ-MnO2Chi
Very little 100~300nm, thickness are 2~5nm, the CNT/MnO of core shell structure2A diameter of 400nm~1 μm, length be 2~4 μm.
With Ni/CNT/MnO manufactured in the present embodiment2As positive pole, using lithium metal as negative pole, the polypropylene film (trade mark
Celgard C480, Celgard companies of the U.S.) it is barrier film, LiClO4TRIGLYME (TEGDME) solution for electrolysis
Liquid, battery is assembled in the glove box full of argon gas.After being passed through the oxygen of 1 atmospheric pressure, charge-discharge test is carried out.
Constant volume charge-discharge test (capacity limit in 500mAh/g, current density 400mA/g, voltage range 2V~4.5V, its
Middle capacity and current density are based on carbon pipe and MnO2Gross weight) show, in secondary charge and discharge process, the equal energy of the lithium-oxygen battery
Keep stable circulation.Its charge and discharge end current potential is kept at 4.01V and 2.89V or so, show relatively low polarization and
Preferable cyclical stability.
Embodiment 3
Zinc nitrate hexahydrate and hexa (being 1 with zinc nitrate hexahydrate mole ratio) are dissolved in deionized water,
Ammoniacal liquor (25wt%) is added, the volume of ammoniacal liquor is the 1/25 of deionization volume, stirs, prepares with Zn2+Counting concentration is
0.02mol/L solution；Nickel foam is taken out after being soaked 1 hour in 0.5mol/L liquor potassic permanganate, anti-with deionized water
Immersed after multiple cleaning and contain Zn2+In solution, through 100 DEG C of hydro-thermal reaction 4h, then it is scrubbed, dry after must arrive surface and be loaded with zinc oxide nano
The nickel foam (Ni/ZnO) of rice rod；Ni/ZnO is immersed in 0.07mol/L glucose solution and soaked 5 hours, is taken out 600
The nickel foam (Ni/ZnO/CNT) that surface is loaded with zinc oxide and CNT must be arrived for 4 hours by being heat-treated at DEG C；Then by Ni/ZnO/
CNT, which is placed in 1.5mol/L NaOH solution to soak 48 hours, removes ZnO, and washs, obtains being loaded with CNT after drying
Nickel foam (Ni/CNT), the wherein bearing capacity of CNT are 0.04mg/cm2.Ni/CNT is immersed into 0.01 mol/L KMnO4
In the aqueous solution, through 90 DEG C of hydro-thermal reaction 2h, then scrubbed, drying, then 300 DEG C of heat treatments are loaded in for 2 hours under Ar atmosphere
Carbon pipe/MnO of nickel foam2Nucleocapsid array (Ni/CNT/MnO2), wherein MnO2Bearing capacity be 0.41mg/cm2.X-ray diffraction
Spectrum shows that the material carried on the carbon nanotubes is δ-MnO2, CNT is in amorphous state.Stereoscan photograph shows, monolithic δ-MnO2Chi
Very little 100~300nm, thickness are 2~5nm, the CNT/MnO of core shell structure2A diameter of 400 nanometers~1 μm, length is 2~4 μ
m。
With Ni/CNT/MnO manufactured in the present embodiment2As positive pole, using lithium metal as negative pole, the polypropylene film (trade mark
Celgard C480, Celgard companies of the U.S.) it is barrier film, LiClO4TRIGLYME (TEGDME) solution for electrolysis
Liquid, battery is assembled in the glove box full of argon gas.After being passed through the oxygen of 1 atmospheric pressure, charge-discharge test is carried out.
Constant volume charge-discharge test (capacity limit in 500mAh/g, current density 400mA/g, voltage range 2V~4.5V, its
Middle capacity and current density are based on carbon pipe and MnO2Gross weight) show, in secondary charge and discharge process, the equal energy of the lithium-oxygen battery
Keep stable circulation.Its charge and discharge end current potential is kept at 3.98V and 2.88V or so, show relatively low polarization and
Preferable cyclical stability.
Embodiment 4
Zinc nitrate hexahydrate and hexa (being 1 with zinc nitrate hexahydrate mole ratio) are dissolved in deionized water,
Ammoniacal liquor (25wt%) is added, the volume of ammoniacal liquor is the 1/25 of deionization volume, stirs, prepares with Zn2+Counting concentration is
0.05mol/L solution；Nickel foam is taken out after being soaked 1 hour in 0.5mol/L liquor potassic permanganate, anti-with deionized water
Immersed after multiple cleaning and contain Zn2+In solution, through 90 DEG C of hydro-thermal reaction 8h, then it is scrubbed, dry after must arrive surface and be loaded with zinc oxide nano
The nickel foam (Ni/ZnO) of rice rod；Ni/ZnO is immersed in 0.07mol/L glucose solution and soaked 5 hours, is taken out 600
The nickel foam (Ni/ZnO/CNT) that surface is loaded with zinc oxide and CNT must be arrived for 4 hours by being heat-treated at DEG C；Then by Ni/ZnO/
CNT, which is placed in 1.5mol/L NaOH solution to soak 48 hours, removes ZnO, and washs, obtains being loaded with CNT after drying
Nickel foam (Ni/CNT), the bearing capacity of CNT is 0.04mg/cm2.Ni/CNT is immersed into 0.01mol/L KMnO4The aqueous solution
In, through 90 DEG C of hydro-thermal reaction 2.5h, then scrubbed, drying, then 300 DEG C of heat treatments obtain being loaded in foam for 2 hours under an ar atmosphere
Carbon pipe/MnO of nickel2Nucleocapsid array (Ni/CNT/MnO2), wherein MnO2Bearing capacity be 0.42mg/cm2.X-ray diffraction stave
Bright, the material carried on the carbon nanotubes is δ-MnO2, CNT is in amorphous state.Stereoscan photograph shows, monolithic δ-MnO2Size 100
~300nm, thickness are 2~5nm, the CNT/MnO of core shell structure2A diameter of 400 nanometers~1 μm, length be 2~4 μm.
With Ni/CNT/MnO manufactured in the present embodiment2As positive pole, using lithium metal as negative pole, the polypropylene film (trade mark
Celgard C480, Celgard companies of the U.S.) it is barrier film, LiClO4TRIGLYME (TEGDME) solution for electrolysis
Liquid, battery is assembled in the glove box full of argon gas.After being passed through the oxygen of 1 atmospheric pressure, charge-discharge test is carried out.
Constant volume charge-discharge test (capacity limit in 500mAh/g, current density 400mA/g, voltage range 2V~4.5V, its
Middle capacity and current density are based on carbon pipe and MnO2Gross weight) show, in secondary charge and discharge process, the equal energy of the lithium-oxygen battery
Keep stable circulation.Its charge and discharge end current potential is kept at 4.03V and 2.86V or so, show relatively low polarization and
Preferable cyclical stability.
Claims (9)
1. a kind of area load has MnO2The preparation method of the carbon nano pipe array electrode of nanometer sheet, it is characterised in that including following
Step：
1) zinc nitrate hexahydrate, hexa are dissolved in deionized water, add ammoniacal liquor, obtain mixing after stirring molten
Liquid；
The mol ratio of the hexa and zinc nitrate hexahydrate is 0.5~2.0；
The volume ratio of the ammoniacal liquor and deionized water is 0.03~0.1；
Zn in the mixed solution2+Concentration is 0.01~0.05mol/L；
2) nickel foam is immersed in mixed solution, through 70~110 DEG C of 2~10h of hydro-thermal reaction, then post-treated must be loaded with to surface
The nickel foam of zinc oxide nano rod, is designated as Ni/ZnO；
3) Ni/ZnO for obtaining step 2) is immersed in the glucose solution that concentration is 0.05~0.15mol/L, is carried out after taking-up
The nickel foam for being loaded with zinc oxide and CNT is thermally treated resulting in, is designated as Ni/ZnO/CNT；
The temperature of the heat treatment is 500~700 DEG C, and the time is 2~10h；
4) Ni/ZnO/CNT is immersed in the NaOH aqueous solution that concentration is 1~3mol/L and removes ZnO, it is post-treated to obtain being loaded with carbon
The nickel foam of nanotube, is designated as Ni/CNT；
5) Ni/CNT is immersed to 0.005~0.2mol/L KMnO4In the aqueous solution, through 60~100 DEG C of 2~5h of hydro-thermal reaction, through washing
Wash, carry out secondary heat treatment again after drying, obtaining area load has MnO2The carbon nano pipe array electrode of nanometer sheet, is designated as Ni/
CNT/MnO2；
The temperature of the secondary heat treatment is 200~400 DEG C, and the time is 1~3h.
2. area load according to claim 1 has MnO2The preparation method of the carbon nano pipe array electrode of nanometer sheet, it is special
Sign is, in step 2), described nickel foam need to be pre-processed, and is specially：
Nickel foam is soaked into 1h in 0.5mol/L potassium permanganate solution, it is stand-by after washing；
The temperature of the hydro-thermal reaction is 80~100 DEG C.
3. area load according to claim 1 has MnO2The preparation method of the carbon nano pipe array electrode of nanometer sheet, it is special
Sign is, in step 3), soak times of the Ni/ZnO in glucose solution is 2~10h.
4. area load according to claim 1 has MnO2The preparation method of the carbon nano pipe array electrode of nanometer sheet, it is special
Sign is, in step 4), soak times of the Ni/ZnO/CNT in the NaOH aqueous solution is 24~72h.
5. area load according to claim 1 has MnO2The preparation method of the carbon nano pipe array electrode of nanometer sheet, it is special
Sign is, in step 5), the temperature of the hydro-thermal reaction is 80~90 DEG C；
Described secondary heat treatment is carried out under an ar atmosphere.
6. area load prepared by a kind of method according to Claims 1 to 5 any claim has MnO2The carbon of nanometer sheet
Nanometer pipe array electrode, it is characterised in that using three-dimensional porous foams nickel as matrix, direct growth is loaded with MnO on matrix2Nanometer sheet
Carbon nano pipe array, MnO2CNT is coated in carbon nano tube surface, forms nucleocapsid knot by nanometer sheet uniform load completely
Structure CNT/MnO2, the core shell structure CNT/MnO2A diameter of 400nm~1 μm.
7. area load according to claim 6 has MnO2The carbon nano pipe array electrode of nanometer sheet, it is characterised in that institute
The MnO stated2By the δ-MnO of laminated structure2Pile up and form, form loose structure, monolithic δ-MnO2Size be 100~300nm,
Thickness is 2~5nm；
Described CNT be in amorphous state in cracking state, and length is 2~4 μm, a diameter of 200~600nm, wall thickness for 5~
10nm。
8. area load according to claim 7 has MnO2The carbon nano pipe array electrode of nanometer sheet, it is characterised in that institute
Stating area load has MnO2MnO in the carbon nano pipe array electrode of nanometer sheet2The bearing capacity of nanometer sheet is 0.4~0.5mg/cm2；
The bearing capacity of CNT is 0.04~0.1mg/cm2。
9. a kind of area load according to claim 6 has MnO2The carbon nano pipe array electrode of nanometer sheet is in lithium sky battery
In application.
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| CN106841344B (en) * | 2017-04-07 | 2018-12-11 | 西北师范大学 | The preparation and application of a kind of poroid single-walled carbon nanotube and its modified electrode |
| CN108417793B (en) * | 2018-02-01 | 2021-02-26 | 复旦大学 | Composite film of carbon-based frame loaded with manganese dioxide nanosheets and preparation method and application thereof |
| CN108461726B (en) * | 2018-03-12 | 2020-09-29 | 陕西科技大学 | Polycrystalline manganese dioxide/carbon nanotube composite material and preparation method and application thereof |
| CN109346734A (en) * | 2018-05-04 | 2019-02-15 | 盐城师范学院 | A kind of preparation method of manganese bioxide/carbon nano tube complex fuel battery negative pole oxygen reduction catalyst |
| CN110371924B (en) * | 2019-07-25 | 2022-06-14 | 许昌学院 | Fe2O3 porous nanowire electrode material, preparation method and application |
| CN110993371B (en) * | 2019-11-22 | 2021-09-03 | 南京理工大学 | LiMnxOy@ C three-dimensional nanosheet array, preparation method and application thereof |
| CN111740125B (en) * | 2020-07-08 | 2022-04-15 | 宁波大学 | Zinc-air battery cathode material, all-solid-state zinc-air battery and preparation method thereof |
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