CN106745284A - A kind of preparation method of manganese dioxide nano pipe and its applied in terms of lithium battery - Google Patents
A kind of preparation method of manganese dioxide nano pipe and its applied in terms of lithium battery Download PDFInfo
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- CN106745284A CN106745284A CN201710027903.2A CN201710027903A CN106745284A CN 106745284 A CN106745284 A CN 106745284A CN 201710027903 A CN201710027903 A CN 201710027903A CN 106745284 A CN106745284 A CN 106745284A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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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
- H01M10/00—Secondary cells; Manufacture thereof
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- H—ELECTRICITY
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Abstract
The present invention provides a kind of preparation method and application of manganese dioxide nano pipe in lithium battery, specially：Manganese sulfate and sodium chlorate solution are dispersed in polyvinylpyrrolidonesolution solution, mixed dispersion is obtained；Above-mentioned mixed system is carried out into hydrothermal synthesis reaction again, reacted product is filtered with vacuum apparatus, separation is washed, obtain manganese dioxide nano pipe.It is an advantage of the invention that：Product prepared by the method has larger specific surface area, can increase the contact area of active material and electrolyte；Original shape characteristic can be well kept in charge and discharge process；With good fast charging and discharging performance and cycle performance.The preparation method process is simple, it is easy to implement, be conducive to popularization and application.
Description
Technical field
The present invention relates to electrochmical power source and new energy materialses field, particularly a kind of preparation method of manganese dioxide nano pipe
And its applied in terms of lithium battery.
Background technology
Manganese dioxide is a kind of industrial materials for having extensive use in terms of electrochemistry, catalysis, with cheap and easy to get, nothing
The characteristic such as malicious, environment-friendly, safe.The basic structural unit of manganese dioxide is the manganese oxygen of 1 manganese atom and 6 oxygen atom compositions
Octahedron [MnO6], manganese atom is located at octahedra center, and oxygen atom is located on octahedral angle, composition hexagonal closs packing or cube
Close-packed structure.Rib connects into single-stranded or double-stranded, interstitial tunnel structure to these octahedrons altogether.The crystal knot of manganese dioxide
Structure have α-, β-, γ-etc. different crystal formations, due to different structure [MnO6] octahedral mode of communicating difference, it is its own
Tunnel or interlayer gap are also different.In building-up process, temperature, reaction time, precursor concentration, pH, template etc. can shadows
Crystal formation and the pattern generation for ringing final product influence, and the different-shape feature of the nano manganese oxide for synthesizing and tunnel structure
Size, the chemical property to final product has a significant impact.Therefore, high-purity, high crystalline, the manganese oxygen of morphology controllable are prepared
Compound has important industrial production meaning.
The method of synthesis manganese dioxide is many at present, and its principle is generally oxidation manganous salt or reduction MnO4
(MnO4 -), method then has hydrothermal/solvent thermal synthesis method, microwave reaction method, microemulsion method, gas phase hydrolysis method, electrodeposition process etc..Water
Thermal synthesis method in nano material synthesis because the features such as its method is simple, reaction temperature is low, controllability is good, being widely used.
Existing synthetic method, the morphology controllable synthesis to Mn oxide nanotube is still blank.And there is the tubulose electricity of one-dimentional structure
Pole material, due to comprising effective one-dimensional electrical conductance path and shorter ion diffusion path, often showing outstanding electricity
Chemical property.Meanwhile, tube wall also can bear larger STRESS VARIATION and keep original pattern in charge and discharge process.These are all
Mean that its special microstructure can bring beneficial chemical property.
The content of the invention
It is an object of the invention to regarding to the issue above, a kind of preparation method of manganese dioxide nano pipe is proposed and its in lithium
Battery aspect application, manganese dioxide nano pipe prepared by the method is used for lithium battery and carries out lithium battery test chemical, shows
Go out good cyclical stability and outstanding high rate charge-discharge performance；The preparation method raw material is cheap and easy to get, process is simple
It is controllable, convenient to carry out, be conducive to popularization and application aborning.
Technical scheme：
A kind of preparation method of manganese dioxide nano pipe, the crystal formation of the manganese dioxide nano pipe is Beta- manganese dioxide,
Comprise the following steps：
1) manganese sulfate and sodium chlorate are dispersed in and mixed liquor is obtained in polyvinylpyrrolidonesolution solution, sulphur in mixed liquor
Sour manganese is 1 with the mol ratio of sodium chlorate:2, the concentration of manganese sulfate is 0.2mol/L, and the molecular weight of the polyvinylpyrrolidone is
K30-k90, the concentration of polyvinylpyrrolidonesolution solution is 0.20-0.40mol/L；
2) above-mentioned mixed liquor is carried out into hydro-thermal reaction in the case where temperature is for 130-170 DEG C, the reaction time is 14-40h, through vacuum
Filter under -1MPa suction filtration, washed respectively with distilled water and alcohol three times, Mn oxide nanotube is obtained after separation, make
The mean inside diameter of the Mn oxide nanotube for obtaining is 100-300nm, and external diameter is 150-650nm, and length is 1-3 μm, and draw ratio is
2-8, specific surface area is more than 3m2/g。
A kind of application of obtained manganese dioxide nano pipe, for electrode material of lithium battery, the lithium battery include positive pole,
Lithium anode, barrier film and electrolyte；Positive pole is made up of manganese oxide electrode material, conductive agent and binding agent, wherein manganese oxidation
Thing is Beta- manganese dioxide, and conductive agent is in carbon nano-fiber, electrically conductive graphite, acetylene black, Denka Black, Super P
The mixture of one or more arbitrary proportions；Binding agent is to gather inclined tetrafluoroethene；The quality percentage of conductive agent and binding agent
Than being respectively 5-20%, 5-10%, Mn oxide is surplus, and barrier film is polyethylene or fibreglass diaphragm, and electrolyte is carbonic acid
Propylene (PC), ethyl carbonate (EC), dimethyl carbonate (DMC), one or more any ratios of diethyl carbonate (DEC)
The mixture of example, electrolyte is lithium hexafluoro phosphate (LiPF6), concentration is 1mol/L.
It is an advantage of the invention that：By controlling reaction time, temperature and manganese sulfate solution concentration, it is possible to achieve manganese dioxide
The controllable preparation of nanotube；Simultaneously one-dimensional tubular structure, is conducive to improving electronics conduction and ion spreads, and tube wall is in discharge and recharge
During also can bear larger STRESS VARIATION and keep original pattern, so as to show excellent chemical property；The system
Preparation Method raw material is cheap and easy to get, and process is simple is controllable, convenient to carry out, is conducive to popularization and application aborning.
Brief description of the drawings
Fig. 1 schemes for the gained Beta- manganese dioxide nano pipes SEM of embodiment 1.
Fig. 2 schemes for the gained Beta- manganese dioxide nano pipes SEM of embodiment 2.
Fig. 3 schemes for the gained Beta- manganese dioxide nano pipes SEM of embodiment 3.
Fig. 4 is the gained Beta- manganese dioxide nano pipe XRDs of embodiment 1~3.
Fig. 5 is the charge and discharge of the first time circulation of the lithium battery with the gained Beta- manganese dioxide nano pipes of embodiment 1 as positive pole
Electric curve map.
Fig. 6 is the stable circulation figure of the lithium battery with the gained Beta- manganese dioxide nano pipes of embodiment 1 as positive pole.
Fig. 7 is the charge and discharge of the first time circulation of the lithium battery with the gained Beta- manganese dioxide nano pipes of embodiment 2 as positive pole
Electric curve map.
Fig. 8 is the stable circulation figure of the lithium battery with the gained Beta- manganese dioxide nano pipes of embodiment 2 as positive pole.
Fig. 9 is the charge and discharge of the first time circulation of the lithium battery with the gained Beta- manganese dioxide nano pipes of embodiment 3 as positive pole
Electric curve map.
Figure 10 is the stable circulation figure of the lithium battery with the gained Beta- manganese dioxide nano pipes of embodiment 3 as positive pole.
Specific embodiment
Embodiment：
Preferred scheme of the invention is described with reference to specific embodiment, these descriptions are simply to further illustrating
The features and advantages of the present invention, are not limiting to the claimed invention.
Embodiment 1：
A kind of preparation method of manganese dioxide nano pipe, the crystal formation of the manganese dioxide nano pipe is Beta- manganese dioxide,
Comprise the following steps：
1) it is 1 by mol ratio:2 manganese sulfate and sodium chlorate is dissolved in deionized water simultaneously, is stirred, sulfuric acid in solution
The concentration of manganese is 0.2mol/L, is subsequently adding polyvinylpyrrolidone and stirs completely, the polyvinylpyrrolidone
Molecular weight is k30-k90, and the concentration of polyvinylpyrrolidonesolution solution is 0.25mol/L；
2) gained mixed solution is fitted into 100mL polytetrafluoroethylliner liners and is transferred into water heating kettle carries out Hydrothermal Synthesiss
Reaction, reaction temperature is 140 DEG C, and the reaction time is 14h, through vacuum apparatus under -1MPa suction filtration, with distilled water and alcohol
Wash three times respectively, Mn oxide nanotube is obtained after separation.
The XRD of example 1 shows in Fig. 4, and the manganese dioxide nano pipe of synthesis is Beta phase manganese dioxide.The SEM figures of Fig. 1
Show, the manganese dioxide nano pipe pipe range of synthesis is about 1.9 μm, and caliber is about 300nm, and draw ratio is about 6.3.
Obtained manganese dioxide nano pipe be used for electrode material of lithium battery, the lithium battery include positive pole, lithium anode,
Barrier film and electrolyte；Positive pole is made up of manganese oxide electrode material, conductive agent and binding agent, and wherein Mn oxide is Beta- bis-
Manganese oxide, conductive agent is Super P；Binding agent is to gather inclined tetrafluoroethene；The mass percent of conductive agent and binding agent is respectively
20%th, 10%, Mn oxide is surplus, and barrier film is polyethylene diagrams, and electrolyte is ethyl carbonate (EC)/dimethyl carbonate
(DMC)/diethyl carbonate (DEC) (volume ratio is 1:1:1) mixed solution, electrolyte is lithium hexafluoro phosphate (LiPF6), concentration
It is 1mol/L.
The preparation of nanotube manganese dioxide positive pole：
By nanotube manganese dioxide, Super P, gather inclined tetrafluoroethene by 70:20:10 mass ratio and 20mLN- methyl pyrroles
Pyrrolidone is adjusted to uniform pulpous state in refiner, is coated on the aluminium foil disk of 500 μm of thickness, diameter 10mm as electrode slice.
By pole piece in 120 DEG C of dried in vacuum overnight, pushed 10 seconds in 20MPa pressure after taking-up, obtain nanotube manganese dioxide positive pole
Piece.
The assembling of button cell and lithium battery test chemical：
It it is 500 μm using thickness, the lithium piece of diameter 14mm is used as negative plate；Polyethylene/polypropylene/polyethylene trilamellar membrane composition
Celgard 2320 as barrier film；Lithium hexafluoro phosphate (LiPF6) concentration for 1mol/L ethyl carbonate (EC)/dimethyl carbonate
(DMC) (volume ratio is 1 to/diethyl carbonate (DEC):1:1) solution is used as electrolyte, above-mentioned positive pole, negative pole, barrier film and electrolyte
In the glove box full of argon gas, CR2032 button cells are constituted.
Fig. 5 is that gained Beta- manganese dioxide nanos pipe is the charging and discharging curve figure of the first time circulation of the lithium battery of positive pole,
Result shows that its discharge capacity reaches 157mAh/g.Fig. 6 is with the gained Beta- manganese dioxide nano pipes of embodiment 1 as positive pole
The stable circulation figure of lithium battery, shows after 300 circle circulations, capacity remains at 127mAh/g, and capability retention reaches in figure
81%.
Embodiment 2：
A kind of preparation method of manganese dioxide nano pipe, the crystal formation of the manganese dioxide nano pipe is Beta- manganese dioxide,
Comprise the following steps：
1) it is 1 by mol ratio:2 manganese sulfate and sodium chlorate is dissolved in deionized water simultaneously, is stirred, sulfuric acid in solution
The concentration of manganese is 0.2mol/L, is subsequently adding polyvinylpyrrolidone and stirs completely, the polyvinylpyrrolidone
Molecular weight is k30-k90, and the concentration of polyvinylpyrrolidonesolution solution is 0.25mol/L；
2) gained mixed solution is fitted into 100mL polytetrafluoroethylliner liners and is transferred into water heating kettle carries out Hydrothermal Synthesiss
Reaction, reaction temperature is 140 DEG C, and the reaction time is 18h, through vacuum apparatus under -1MPa suction filtration, with distilled water and alcohol
Wash three times respectively, Mn oxide nanotube is obtained after separation.
The XRD of example 2 shows in Fig. 4, and the manganese dioxide nano pipe of synthesis is Beta phase manganese dioxide.The SEM figures of Fig. 2
Show, nanotube manganese dioxide pipe range is about 2.3 μm, and caliber is about 450nm, and draw ratio is about 5.
Gained target product is carried out into lithium battery assembling and electro-chemical test：Method is with embodiment 1
Fig. 7 shows that its discharge capacity reaches 192mAh/g；Fig. 8 shows that after 300 circle circulations capacity is remained at
174mAh/g, capability retention reaches 90%.
Embodiment 3：
A kind of preparation method of manganese dioxide nano pipe, the crystal formation of the manganese dioxide nano pipe is Beta- manganese dioxide,
Comprise the following steps：
1) it is 1 by mol ratio:2 manganese sulfate and sodium chlorate is dissolved in deionized water simultaneously, is stirred, sulfuric acid in solution
The concentration of manganese is 0.2mol/L, is subsequently adding polyvinylpyrrolidone and stirs completely, the polyvinylpyrrolidone
Molecular weight is k30-k90, and the concentration of polyvinylpyrrolidonesolution solution is 0.25mol/L；
2) gained mixed solution is fitted into 100mL polytetrafluoroethylliner liners and is transferred into water heating kettle carries out Hydrothermal Synthesiss
Reaction, reaction temperature is 140 DEG C, and the reaction time is 24h, through vacuum apparatus under -1MPa suction filtration, with distilled water and alcohol
Wash three times respectively, Mn oxide nanotube is obtained after separation.
The XRD of example 3 shows in Fig. 4, and the manganese dioxide nano pipe of synthesis is Beta phase manganese dioxide.The SEM figures of Fig. 3
Show, pipe range is about 1.7 μm, and caliber is about 480nm, and draw ratio is about 3.5.
Gained target product is carried out into lithium battery assembling and electro-chemical test：Method is with embodiment 1
Fig. 9 shows that its discharge capacity reaches 171mAh/g；Figure 10 shows that after 300 circle circulations capacity is remained at
142mAh/g, capability retention reaches 83%.
Claims (2)
1. a kind of preparation method of manganese dioxide nano pipe, it is characterised in that the crystal formation of the manganese dioxide nano pipe is Beta-
Manganese dioxide, comprises the following steps：
1) manganese sulfate and sodium chlorate are dispersed in and mixed liquor is obtained in polyvinylpyrrolidonesolution solution, manganese sulfate in mixed liquor
It is 1 with the mol ratio of sodium chlorate:2, the concentration of manganese sulfate is 0.2mol/L, and the molecular weight of the polyvinylpyrrolidone is k30-
K90, the concentration of polyvinylpyrrolidonesolution solution is 0.20-0.40mol/L；
2) above-mentioned mixed liquor is carried out into hydro-thermal reaction in the case where temperature is for 130-170 DEG C, the reaction time is 14-40h, through vacuum filter
Device under -1MPa suction filtration, washed respectively with distilled water and alcohol three times, Mn oxide nanotube is obtained after separation, it is obtained
The mean inside diameter of Mn oxide nanotube is 100-300nm, and external diameter is 150-650nm, and length is 1-3 μm, and draw ratio is 2-8,
Specific surface area is more than 3m2/g。
2. the application of manganese dioxide nano pipe obtained in a kind of claim 1, it is characterised in that：For electrode material of lithium battery,
The lithium battery includes positive pole, lithium anode, barrier film and electrolyte；Positive pole is by manganese oxide electrode material, conductive agent and glues
Knot agent composition, wherein Mn oxide are Beta- manganese dioxide, and conductive agent is carbon nano-fiber, electrically conductive graphite, acetylene black, Denka
The mixture of one or more arbitrary proportions in Black, Super P；Binding agent is to gather inclined tetrafluoroethene；Conductive agent and
The mass percent of binding agent is respectively 5-20%, 5-10%, and Mn oxide is surplus, barrier film be polyethylene or glass fibre every
Film, electrolyte is propene carbonate (PC), ethyl carbonate (EC), dimethyl carbonate (DMC), one kind of diethyl carbonate (DEC)
Or the mixture of two or more arbitrary proportions, electrolyte is lithium hexafluoro phosphate (LiPF6), concentration is 1mol/L.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107628650A (en) * | 2017-07-24 | 2018-01-26 | 上海纳米技术及应用国家工程研究中心有限公司 | With MnO2Nanotube is that template prepares ternary nano pipe positive electrode method |
| CN109585842A (en) * | 2018-10-08 | 2019-04-05 | 北京大学 | A kind of hybrid electrochemical energy storage system based on absorption counterfeit potential and embedded reactive |
| CN111617759A (en) * | 2020-05-06 | 2020-09-04 | 青岛理工大学 | Manganese dioxide nano catalytic film for catalyzing ozone to degrade organic wastewater and preparation method thereof |
| CN112662292A (en) * | 2020-12-14 | 2021-04-16 | 陕西科技大学 | Water-based paint with air purification function and preparation method thereof |
-
2017
- 2017-01-16 CN CN201710027903.2A patent/CN106745284A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107628650A (en) * | 2017-07-24 | 2018-01-26 | 上海纳米技术及应用国家工程研究中心有限公司 | With MnO2Nanotube is that template prepares ternary nano pipe positive electrode method |
| CN109585842A (en) * | 2018-10-08 | 2019-04-05 | 北京大学 | A kind of hybrid electrochemical energy storage system based on absorption counterfeit potential and embedded reactive |
| CN111617759A (en) * | 2020-05-06 | 2020-09-04 | 青岛理工大学 | Manganese dioxide nano catalytic film for catalyzing ozone to degrade organic wastewater and preparation method thereof |
| CN111617759B (en) * | 2020-05-06 | 2022-05-31 | 青岛理工大学 | Manganese dioxide nano catalytic film for catalyzing ozone to degrade organic wastewater and preparation method thereof |
| CN112662292A (en) * | 2020-12-14 | 2021-04-16 | 陕西科技大学 | Water-based paint with air purification function and preparation method thereof |
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Application publication date: 20170531 |