CN104577043A - Manganese oxide/zinc oxide composite hollow tubular structure and preparation method and application thereof - Google Patents
Manganese oxide/zinc oxide composite hollow tubular structure and preparation method and application thereof Download PDFInfo
- Publication number
- CN104577043A CN104577043A CN201310467592.3A CN201310467592A CN104577043A CN 104577043 A CN104577043 A CN 104577043A CN 201310467592 A CN201310467592 A CN 201310467592A CN 104577043 A CN104577043 A CN 104577043A
- Authority
- CN
- China
- Prior art keywords
- zinc oxide
- substrate
- manganese
- tubular structure
- hollow tubular
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- 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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a manganese oxide/zinc oxide composite nanotube array thin film electrode material and a preparation method thereof, wherein the method comprises the following steps: (1) impregnating a substrate with anhydrous ethanol, soaking the substrate impregnated with the anhydrous ethanol in a solution of zinc nitrate and hexamethylenetetramine, and carrying out a first hydrothermal reaction, to generate a zinc oxide nanorod array thin film on the substrate; and (2) soaking the substrate obtained in the step (1) and generated with the zinc oxide nanorod array thin film in a manganese nitrate solution, and carrying out a second hydrothermal reaction. The preparation method has no need of a template removal step and a thin film further transfer process, and has the advantages of simple process and convenient operation. In addition, the manganese oxide/zinc oxide composite hollow tubular structure is used as a negative electrode material of lithium batteries; and due to the introduction of zinc oxide, and with the use of advantages of the tubular array structure, the technical problem of relatively poor electrochemical cycle stability of a manganese oxide negative electrode material is solved.
Description
Technical field
The present invention relates to field of material preparation, more specifically, the present invention relates to the preparation method of a kind of manganese oxide/zinc oxide composite hollow tubular structure, and this manganese oxide/zinc oxide composite hollow tubular structure is as the application of electrode material.
Background technology
Along with the fast development of lithium ion battery, people are to lithium ion battery high-energy-density, and stable charge-discharge performance is had higher requirement.As the electrode material of lithium battery, require that it has higher lithium storage content on the one hand, on the other hand, cause the phenomenons such as lead rupture and the cyclical stability and the shelf life that affect its discharge and recharge further owing to having larger change in volume in the Infix and desfix process of lithium, therefore require the lead rupture phenomenon that electrode material can slow down change in volume and cause thus.
Comparing material with carbon element commercial is at present main lithium cell cathode material, and people wish to obtain the higher electrode material of energy density, and research shows, a lot of transition metal all has good chemical property and storage lithium performance.Wherein, manganese oxide, owing to having relatively low electromotive force (1.032V), therefore becomes the more promising lithium ion battery negative material of one.It is reported, when manganese oxide powder is used for lithium ion battery negative material, its specific capacity can reach 650mAh/g when 0.06C, and discharge capacity can reach 1619mAh/g first.But after 25 circulations, its capacity constantly will be reduced to 100 ~ 400mAh/g.
Except Mn, Zn also shows certain storage lithium performance, and typical Zn oxides zinc (ZnO) also has storage lithium ability, can as more promising battery material.The people such as Keon Tae Park have studied the research of ZnO nanotube/for lithium ion battery, and result of study shows that ZnO nanotube/has good cyclical stability.
In order to overcome the poor shortcoming of lithium ion battery polynary negative material cycle performance, some researchs adopt the method for oxide coated by zinc to prepare modification composite positive pole, result shows, compared with not coated material, the positive electrode after coating modification has higher efficiency first and excellent cyclical stability.Therefore, if by zinc oxide and manganese oxide compound, the mutual coordination of both utilizations and complementation also show more excellent chemical property and application thus.
The people such as Hui Xia utilize the method for anodic oxidation aluminium formwork to synthesize manganese oxide nano-tube array and show that it has good electrochemical stability and cycle performance.The people such as Gong Liangyu about the average diameter 20nm that utilizes ZnO nanorod to be templated synthesis, average length are about the α-MnO2 nanometer rods of 180nm, and show stable supercapacitor properties.But above-mentioned synthetic method needs the further transfer process removing step and film of template, and removing and destruction to material film structure and orientation in transfer process, process is loaded down with trivial details, not easy to operate.
Summary of the invention
The object of the invention is to overcome in the method for synthesis manganese oxide nanostructure of prior art, need the further transfer process removing step and film of template, and the defect that industry is loaded down with trivial details, provide the preparation method of a kind of manganese oxide/zinc oxide composite hollow tubular structure.
The invention provides the preparation method of a kind of manganese oxide/zinc oxide composite hollow tubular structure, the method comprises the following steps: (1) floods substrate with absolute ethyl alcohol, again the impregnated substrate of this use absolute ethyl alcohol is immersed in the solution of zinc nitrate and hexamethylene tetraammonia and carries out first time hydro-thermal reaction, to generate nanometic zinc oxide rod array film in substrate; (2) there is the substrate of nanometic zinc oxide rod array film to be immersed in manganese nitrate solution the generation that step (1) obtains and carry out second time hydro-thermal reaction.
Present invention also offers a kind of manganese oxide/zinc oxide composite hollow tubular structure prepared by above-mentioned preparation method.
According to the preparation method of a kind of manganese oxide provided by the invention/zinc oxide composite hollow tubular structure, in this preparation method, the present invention utilizes nanometic zinc oxide rod array film for template, water heat transfer manganese oxide/zinc oxide composite hollow tubular nanostructures, this preparation method is without the need to the further transfer process removing step and film of template, process is simple, simple operation.In addition, using the negative material of this manganese oxide/zinc oxide composite hollow tubular structure as lithium battery, due to the free space between array, and the hollow-core construction of tubular structure, can in charge and discharge process, prevent due to volumetric expansion and shrink the lead rupture phenomenon caused, thus improving electrochemical cycle stability.Further, the tube wall of nano-scale also can shorten embedding and the deintercalation process of lithium ion.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is the SEM figure of the manganese oxide/zinc oxide composite hollow tubular structure according to embodiment of the method 1 preparation of the present invention;
Fig. 2 is the SEM figure of the manganese oxide/zinc oxide composite hollow tubular structure according to embodiment of the method 2 preparation of the present invention;
Fig. 3 is the SEM figure of the manganese oxide/zinc oxide composite hollow tubular structure according to embodiment of the method 3 preparation of the present invention;
Fig. 4 is the manganese oxide/zinc oxide composite tubular structure prepared according to comparative example 1;
Fig. 5 is the manganese oxide/zinc oxide composite tubular structure prepared according to comparative example 2.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
According to the preparation method of a kind of manganese oxide provided by the invention/zinc oxide composite hollow tubular structure, the method can comprise the following steps: (1) floods substrate with absolute ethyl alcohol, again the impregnated substrate of this use absolute ethyl alcohol is immersed in the solution of zinc nitrate and hexamethylene tetraammonia and carries out first time hydro-thermal reaction, to generate nanometic zinc oxide rod array film in substrate; (2) there is the substrate of nanometic zinc oxide rod array film to be immersed in manganese nitrate solution the generation that step (1) obtains and carry out second time hydro-thermal reaction.
According to the present invention, first, nanometic zinc oxide rod array film is prepared in target substrate on the surface.Particularly, with absolute ethyl alcohol, the substrate cleaned up can be soaked, make substrate surface with basic group.Wherein, the density of alcohol immersion time to nanometic zinc oxide rod array film plays an important role, and long-time immersion can make it with-OH by modification of surfaces, and becomes the avtive spot of zinc oxide forming core, the forming core of accelerating oxidation zinc and growth.According to the present invention, with absolute ethyl alcohol, 3-4 days is soaked in the substrate cleaned up, be preferably 2-3 days, substrate surface can be made with basic group.Then, then by the solution of zinc nitrate and hexamethylene tetraammonia and carry out first time hydro-thermal reaction, to generate nanometic zinc oxide rod array film with substrate constant temperature in water heating kettle of absolute ethyl alcohol process.
According in the present invention, in step (1), the mol ratio of described zinc nitrate and hexamethylene tetraammonia can be 1:0.8-1.2, is preferably 1:0.9-1.1, is more preferably 1:1.
According to the present invention, in step (1), the condition of hydro-thermal reaction can comprise described first time: reaction temperature is 80-140 DEG C, is preferably 90-95 DEG C, is more preferably 95 DEG C; Reaction time is 1-12 hour, is preferably 4-6 hour.
According to the present invention, in step (1), the preparation method provided is wide to the practicality of substrate, and such as, described substrate can be selected from the one in quartz glass, silicon chip, metal electrode or ceramic material.Adopt preparation method of the present invention, different substrates can be changed, therefore, different catalytic carrier and different devices can be applicable to.In the present invention, described substrate is preferably quartz glass.
According to the present invention, in step (2), there is the substrate of nanometic zinc oxide rod array film to be immersed in manganese nitrate solution the above-mentioned generation prepared and carry out second time hydro-thermal reaction.
According to the present invention, the concentration of described manganese nitrate solution can not too high can not be too low, the excessive concentration or too low of described manganese nitrate solution, all cannot ensure that nanometic zinc oxide rod array film dissolves, therefore, in the present invention, need the strict concentration controlling described manganese nitrate solution, the concentration of described manganese nitrate solution can be 0.1-0.2M, and the concentration of described manganese nitrate solution is within the scope of this, and described nanometic zinc oxide rod array film can dissolve; Under preferable case, the concentration of described manganese nitrate solution can be 0.14-0.17M, is more preferably 0.15M, and within the scope of this, it is more complete that described nanometic zinc oxide rod array film dissolves.
According to the present invention, in step (2), the condition of described second time hydro-thermal reaction can comprise: reaction temperature is 80-100 DEG C, is preferably 90-95 DEG C, is more preferably 95 DEG C; Reaction time is 60-180min, is preferably 120-130min, is more preferably 120min.
According to the present invention, nanometic zinc oxide rod array film plays template action on the one hand, on the one hand as precursor, compare other template synthesis method, the preparation method that inventing provides does not need to carry out the further transfer process removing step and film to template, and the method process is simple, simple operation.
According to the present invention, along with the carrying out of hydro-thermal reaction, first manganese oxide crystal carries out forming core and crystallization on nanometic zinc oxide rod array film precursor surface, and becomes one deck grain thin film in nanometic zinc oxide rod array film surface coverage.Nanometic zinc oxide rod array film slowly dissolves and the further deposition of accelerated oxidation manganese.According to solution diffusion law and geometrical principle, because the chance of tip contact reaction solution is much larger than the contact probability of nanometic zinc oxide rod array film and reaction solution, manganese oxide is covered into the film of one deck densification on nanometic zinc oxide rod array film top, and making becomes the passage dissolved further bottom nanometic zinc oxide rod array film.With the carrying out of hydro-thermal reaction, nanometic zinc oxide rod array film dissolves further, and the final composite construction forming hollow.
According to present invention also offers a kind of manganese oxide/zinc oxide composite hollow tubular structure prepared by preparation method described above.
According to the present invention, the top closure of this manganese oxide/zinc oxide composite hollow tubular structure, the overall diameter of described manganese oxide/zinc oxide composite hollow tubular structure is 0.5-1.5 micron, be preferably 0.8-1.2 micron, be more preferably 1 micron, pipe wall thickness is 100-500nm, is preferably 200-300nm, length is 3-10 micron, is preferably 4-5 micron.
Present invention also offers the application as electrode material of manganese oxide/zinc oxide composite hollow tubular structure of being prepared by above-mentioned preparation method.
Below will be described the present invention by embodiment.
In following examples and comparative example, the pattern of the manganese oxide/zinc oxide composite nanostructure of preparation and size are recorded by field emission scanning electron microscope (purchased from HIT, model is Hitachi S-4800 to SEM); The chemicals used in embodiment and comparative example is all purchased from lark prestige company.
Embodiment 1
Prepare nanometic zinc oxide rod array film: with absolute ethyl alcohol, the quartz glass substrate cleaned up is soaked 3 days, this quartz glass substrate and 0.1M zinc nitrate and each 15ml of 0.1M hexamethylene tetraammonia solution are added in the stainless steel water heating kettle of 50ml according to volume ratio 1:1, after 95 DEG C of constant temperature carry out first time hydro-thermal reaction 4h, powder is dried, and has the quartz glass substrate of nanometic zinc oxide rod array film to rinse well length and dries.
The substrate of nanometic zinc oxide rod array is had to put into the manganese nitrate solution of 0.15M by long, after 90 DEG C of constant temperature carry out second time hydro-thermal reaction 2h, can obtain homodisperse and length is about 5 microns, overall diameter is 1 micron, pipe wall thickness is the manganese oxide/zinc oxide composite hollow tubular nanostructures of 300nm, as shown in Figure 1.
Embodiment 2
The preparation of nanometic zinc oxide rod array film and identical in embodiment 1, difference is have the quartz glass substrate of nanometic zinc oxide rod array film to put into the manganese nitrate solution of 0.17M by long, after 95 DEG C of constant temperature carry out second time hydro-thermal reaction 2h, can obtain dispersed and length is about 5 microns, overall diameter is 1 micron, pipe wall thickness is the manganese oxide/zinc oxide composite hollow tubular nanostructures of 200nm, as shown in Figure 2.
Embodiment 3
The preparation of nanometic zinc oxide rod array film and identical in embodiment 1, difference is have the quartz glass substrate of nanometic zinc oxide rod array film to put into the manganese nitrate solution of 0.1M by long, after 95 DEG C of constant temperature carry out second time hydro-thermal reaction 2h, can obtain dispersed and length is about 5 microns, overall diameter is 1.2 microns, pipe wall thickness is the manganese oxide/zinc oxide composite hollow tubular nanostructures of 500nm, as shown in Figure 3.
Comparative example 1
The preparation of nanometic zinc oxide rod array film and identical in embodiment 1, difference is have the quartz glass substrate of nanometic zinc oxide rod array film to put into the manganese nitrate solution of 0.05M by long, after 100 DEG C of constant temperature carry out second time hydro-thermal reaction 2h, because nano structure of zinc oxide does not dissolve, manganese oxide/zinc oxide the composite tubular structure of preparation as shown in Figure 4, length is 3-5 micron, and diameter is 0.5-1 micron, is not hollow.
Comparative example 2
The preparation of nanometic zinc oxide rod array film and identical in embodiment 1, difference is have the quartz glass substrate of nanometic zinc oxide rod array film to put into the manganese nitrate solution of 0.15M by long, after 140 DEG C of constant temperature carry out second time hydro-thermal reaction 2h, because nano structure of zinc oxide does not dissolve, manganese oxide/zinc oxide the composite tubular structure of preparation as shown in Figure 5, length is 3-5 micron, and diameter is 0.5-1 micron, is not hollow.
EXPERIMENTAL EXAMPLE 1
The manganese oxide prepared by embodiment 1-3/zinc oxide composite hollow tubular structure and comparative example 1 manganese oxide/zinc oxide composite tubular structure, as the negative material of lithium battery, carry out battery charging and discharging test.
The copper plate electrode of MnO2-ZnO composite material is had to put into vacuum drying chamber by long, vacuumize half an hour at 80 DEG C.Dried electrode slice is transferred to immediately assembling battery in the glove box (UNLAB, German M.Braun company) being full of argon atmosphere, humidity and oxygen content are lower than 1ppm.Metal lithium sheet is as to electrode, and electrolyte is 1M LiPF6/EC:DMC (1:1, Vol).Complete in the glove box be assembled in of battery.The barrier film of Whatman company is adopted two electrode separation to be opened.Using MnO2-ZnO composite material as battery cathode, be assembled into 3020 type MnO2-ZnO/Li button cells.
Charge-discharge test: the charge-discharge performance test of material is carried out (Yongxing, Shenzhen industry Neware battery test system) having in programme controlled electro-chemical test equipment, be set to the form of constant current charge-discharge, the current density adopted is set point, and discharge and recharge cut-ff voltage scope is set to 0.005V ~ 3.0V.Charging and discharging currents adopts 50mA g-1 and 100mA g-1 respectively.
Result shows: the manganese oxide/zinc oxide composite hollow tubular structure prepared for embodiment of the present invention 1-3 is as the negative material of lithium battery, from the 4th circulation until the 50th circulation maintains extraordinary cyclical stability, when current density is 100mA g-1, its lithium storage content remains at 800mAh about g-1.During little multiplying power, when namely current density is 50mA g-1, its lithium storage content is about 900mAh g-1.Relative to comparative example 1 manganese oxide/zinc oxide composite tubular structure as the negative material of lithium battery, improve electrochemical cycle stability.
The manganese oxide prepared by above embodiment 1-3/zinc oxide composite hollow tubular structure is known: relative to comparative example 1-2, the manganese oxide adopting preparation method of the present invention to prepare/zinc oxide composite hollow tubular structure is as the negative material of lithium battery, owing to there is larger contact area with Li+, the injection of Li+ can be accelerated and shift out.Meanwhile, based on the distinctive hollow structure of tubulose, the volume contraction that space more freely can be had to allow electrode material in charge and discharge process and expansion.And adopting preparation method of the present invention to eliminate template removal step, technique is simple, and energy consumption is low, and preparation condition is not harsh flexibly, and is applicable to large-scale production.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned execution mode, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible compound mode.
In addition, also can carry out combination in any between various different execution mode of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. a preparation method for manganese oxide/zinc oxide composite hollow tubular structure, the method comprises the following steps:
(1) flood substrate with absolute ethyl alcohol, more impregnated for absolute ethyl alcohol substrate is immersed in the solution of zinc nitrate and hexamethylene tetraammonia carries out first time hydro-thermal reaction, to generate nanometic zinc oxide rod array film in substrate;
(2) there is the substrate of nanometic zinc oxide rod array film to be immersed in manganese nitrate solution the generation that step (1) obtains and carry out second time hydro-thermal reaction.
2. method according to claim 1, wherein, the concentration of described manganese nitrate solution is 0.1-0.2M, is preferably 0.14-0.17M.
3. method according to claim 1, wherein, in step (1), is 3-4 days with the time of absolute ethyl alcohol dipping substrate, is preferably 2-3 days.
4. method according to claim 1, wherein, in step (1), described substrate is selected from the one in quartz glass, silicon chip, metal electrode or ceramic material.
5. method according to claim 1, wherein, in step (1), the mol ratio of described zinc nitrate and hexamethylene tetraammonia is 1:0.8-1.2, is preferably 1:0.9-1.1.
6. method according to claim 1, wherein, in step (1), described first time the condition of hydro-thermal reaction comprise: reaction temperature is 80-140 DEG C, is preferably 90-95 DEG C; Reaction time is 1-12 hour, is preferably 4-6 hour.
7. method according to claim 1, wherein, in step (2), the condition of described second time hydro-thermal reaction comprises: reaction temperature is 80-100 DEG C, is preferably 90-95 DEG C; Reaction time is 60-180min, is preferably 120-130min.
8. according to manganese oxide/zinc oxide composite hollow tubular structure prepared by the method in claim 1-7 described in any one.
9. manganese oxide according to claim 8/zinc oxide composite hollow tubular structure, wherein, the overall diameter of described manganese oxide/zinc oxide composite hollow tubular structure is 0.5-1.5 micron, be preferably 0.8-1.2 micron, pipe wall thickness is 100-500nm, be preferably 200-300nm, length is 3-10 micron, is preferably 4-5 micron.
10. manganese oxide/zinc oxide composite hollow tubular structure is according to claim 8 or claim 9 as the application of electrode material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310467592.3A CN104577043B (en) | 2013-10-09 | 2013-10-09 | Manganese oxide/zinc oxide composite hollow tubular structure and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310467592.3A CN104577043B (en) | 2013-10-09 | 2013-10-09 | Manganese oxide/zinc oxide composite hollow tubular structure and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104577043A true CN104577043A (en) | 2015-04-29 |
| CN104577043B CN104577043B (en) | 2017-04-26 |
Family
ID=53092623
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310467592.3A Active CN104577043B (en) | 2013-10-09 | 2013-10-09 | Manganese oxide/zinc oxide composite hollow tubular structure and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104577043B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105514374A (en) * | 2015-12-11 | 2016-04-20 | 武汉理工大学 | Graphitized carbon coated manganese-fluorine oxide material and preparation method thereof |
| CN109585822A (en) * | 2018-11-23 | 2019-04-05 | 重庆文理学院 | A kind of preparation method of manganese monoxide/zinc oxide negative electrode material |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102181927A (en) * | 2011-03-30 | 2011-09-14 | 北京科技大学 | Method for preparing zinc oxide nano-array on flexible substrate at low temperature |
| CN102417201B (en) * | 2011-08-31 | 2014-06-11 | 北京大学 | Method for preparing one-dimensional self-assembly material with ZnO nanorod array as template |
-
2013
- 2013-10-09 CN CN201310467592.3A patent/CN104577043B/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105514374A (en) * | 2015-12-11 | 2016-04-20 | 武汉理工大学 | Graphitized carbon coated manganese-fluorine oxide material and preparation method thereof |
| CN105514374B (en) * | 2015-12-11 | 2019-01-01 | 武汉理工大学 | A kind of graphitized carbon cladding manganese OXYFLUORIDE MATERIALS and preparation method thereof |
| CN109585822A (en) * | 2018-11-23 | 2019-04-05 | 重庆文理学院 | A kind of preparation method of manganese monoxide/zinc oxide negative electrode material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104577043B (en) | 2017-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108520985B (en) | Method for prolonging cycle life of zinc battery and application thereof | |
| CN105720236B (en) | A kind of sodium-ion battery cathode nickel foam self-supporting sheet Ni3P/C composite materials and preparation method thereof | |
| CN105140477B (en) | Si-C composite material and preparation method thereof | |
| CN102576878B (en) | Nano-structured lithium-sulfur battery and manufacture method thereof | |
| CN103311529B (en) | A kind of pod-like carbon coated manganese oxide composite material of core-shell structure and its preparation method and application | |
| US9985273B2 (en) | Three-dimensional nanosized porous metal oxide electrode material of lithium ion battery and preparation method thereof | |
| KR101758967B1 (en) | Battery | |
| CN102013330B (en) | Film for graphene/porous nickel oxide composite super capacitor and preparation method thereof | |
| WO2016107564A1 (en) | Composite positive material for lithium-sulphur battery with high rate performance and preparation method | |
| CN103236525B (en) | A kind of Si-C composite material and preparation method thereof, lithium ion battery | |
| CN103682272B (en) | A kind of lithium ion battery cathode material and its preparation method | |
| CN102969488B (en) | A kind of amorphous porous silicon and preparation method thereof, lithium ion battery containing this material | |
| CN110176601A (en) | Carbon-coated silicon monoxide negative electrode material and preparation method and application thereof | |
| CN104319402A (en) | Preparation method for multi-layer carbon hollow sphere anode material | |
| CN104393245B (en) | A kind of lithium ion battery preparation method of the nano silicon-based negative pole of loose structure | |
| CN103872330A (en) | Lithium ion battery negative electrode material and preparation method thereof | |
| CN103413920B (en) | A kind of lithium ion battery silicon/aligned carbon nanotube composite negative pole material and preparation method thereof | |
| CN106505200A (en) | Carbon nano tube/graphene/silicon composite lithium ion battery negative material and preparation method thereof | |
| CN110078053A (en) | A kind of porous carbon materials and its preparation method and application applied to battery diaphragm coating | |
| CN105006553A (en) | Preparation method of sulfur/carbon/oxide combined electrode material | |
| CN106207090B (en) | Three-D nano-porous copper/one-dimensional nano cuprous oxide wire network-type negative electrode of lithium ion battery and one one-step preparation method | |
| CN105047877A (en) | Negative active material and preparation method and application thereof | |
| CN110739446B (en) | Silicon/carbon composite anode material and preparation method thereof | |
| CN109809498A (en) | A kind of three-dimensional multistage hole cobaltosic oxide material and its preparation method and application | |
| CN108963267A (en) | The preparation method of three-dimensional porous carbon coating zinc oxide collector for lithium an- ode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |