CN107316987A - A kind of oxide nano thread/ZIF systems MOFs sugarcoated haws shape composites and preparation method thereof - Google Patents
A kind of oxide nano thread/ZIF systems MOFs sugarcoated haws shape composites and preparation method thereof Download PDFInfo
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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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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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
- 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
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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
- H01M4/02—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
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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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of oxide nano thread/ZIF systems MOFs sugarcoated haws shape composites and preparation method thereof, belong to nano-functional material and preparation method thereof field.The oxide nano thread/ZIF systems MOFs sugarcoated haws shapes composite is the combination product that oxide nano thread and ZIF systems MOFs are formed by the effect of surfactant, first with solvent-thermal method or hydro-thermal reaction synthesis oxide nano wire, then using oxide nano thread as substrate, add imidazoles, organic solvent, metal salt is by standing, the method such as hydro-thermal and solvent heat, growth ZIF system MOFs on nano wire are acted on using surfactant, so as to prepare the composite of sugarcoated haws shape structure.The oxide nano thread/ZIF systems MOFs sugarcoated haws shape composites have structure novel, prepare simple, the advantage such as good cycle, and raw material are cheap and easy to get, are worth with huge commercial application.
Description
Technical field
The invention belongs to lithium ion battery negative material and preparation method thereof field, and in particular to a kind of oxidate nano
Line/ZIF systems MOFs sugarcoated haws shape composites and preparation method thereof.
Background technology
Green energy resource is stored has obtained recognizing for countries in the world with distributing to the importance of people's daily life and atmospheric environment
Can, gradually received by the deterioration of urban environment by people.The imperfect combustion of fossil fuel used in orthodox car
And use of the fossil fuel in heat supply system is considered as to cause big city especially developing country's haze situation more next
More serious one of the main reasons.Therefore, with electric automobile (Electric Vehicle) and the need of inexpensive green energy resource
Continuous growth is asked, advanced energy storage and the development of energy conversion system are constantly carried out.At present, lithium ion battery
(Lithium-ion battery) is high due to energy density, and service life is long, memory-less effect and many originals such as environment-friendly
Cause, therefore electric car power supply market has been led, occupy many markets part that portable electric appts and green energy resource generate electricity
Volume.However, due to graphite (372mA h g-1) theoretical capacity it is limited, traditional LIB using graphite as negative material is
The demand of people's rapid growth can not be met therefore, material supply section scholar further investigation energy storage technology of future generation is extremely urgent, research
Focus on developing a kind of novel low-cost, the negative pole with more preferable cyclical stability under higher capacity and high magnification state
Material.
At present, except various advanced carbon materials, the silicon-based hybrid thing of nanostructured, the transition metal of nanostructured and its
Oxide or sulfide, because its lithium ion storage capacity is much higher in theory, cause the extensive concern of people.However,
During lithiumation, semiconductor or insulating property (properties) and huge Volume Changes are that they lack as LIB the intrinsic of negative material
Two in point.Wherein manganese oxide, zinc oxide and cobaltosic oxide, nickel oxide, the transition metal oxide such as iron oxide due to
Volume Changes are smaller than Si, and environment is good, therefore has been widely studied as the preferable candidate's negative material of development prospect.
In recent years, metal organic framework (the Metal organic that metal ion or cluster and multi-functional organic ligand are built
Framework) material has been subjected to the growing interest of the numerous areas such as basic scientific research and Practical multifunction application.Such as
The MOFs of ZIF-67, ZIF-8 etc. zeolite imidazole class skeleton (ZIF) type has high porosity, it is considered to be hold promise for business
One of the MOFs in industry field.Performance of the particularly ZIF carbonization derivative in LIB shows good development prospect.For example,
Carbon negative pole material derived from ZIF nanocrystals shows good cyclical stability and excellent high rate performance.However, height
Porous nanometer structure causes its relatively low tap density plus factors such as relatively low capacity, limits them as commercialization
The practicality of LIB negative material.However, the unique texture of ZIF and its derivative that is carbonized is received with composition for design is different
Rice structural transition metal and its oxide are come to improve its high rate performance and cyclical stability be very helpful.
The content of the invention
Poor for existing lithium ion battery negative material cycle performance and high rate performance, preparation method is complex,
The problems such as inefficiency and high cost, the invention provides a kind of oxide nano thread/ZIF systems MOFs sugarcoated haws shape composite woods
Material and preparation method thereof, belongs to lithium ion battery negative material and preparation method thereof field.The oxide nano thread/ZIF systems
MOFs sugarcoated haws shapes composite is the compound production that oxide nano thread and ZIF systems MOFs are formed by the effect of surfactant
Thing, first with solvent-thermal method or hydro-thermal reaction synthesis oxide nano wire, then using oxide nano thread as substrate, is added
Imidazoles, organic solvent, metal salt is by standing, and the method such as hydro-thermal and solvent heat acts on nanometer using surfactant
ZIF system MOFs are grown on line, so as to prepare the composite of sugarcoated haws shape structure.The oxide nano thread/ZIF systems MOFs
Sugarcoated haws shape composite has structure novel, prepares simple, the advantage such as good cycle, and raw material are cheap and easy to get, have
Huge commercial application value.
The purpose of the present invention is achieved through the following technical solutions.
Oxide nano thread/ZIF systems MOFs sugarcoated haws shape composites, it is characterised in that the composite has serial
Structure, ZIF systems MOFs goes here and there on oxide nano thread as sugarcoated haws string, forms the structure of sugarcoated haws shape.
The preparation method of oxide nano thread/ZIF systems MOFs sugarcoated haws shape composites, it is characterised in that preparation process
It is as follows：
S1 utilizes solvent-thermal method or hydro-thermal reaction synthesis oxide nano wire；
S2 4~6 parts surfactants of addition, 20~40 parts by weight imidazoles of addition, 30~50 parts by volume organic solvents,
20~40 shares of metal are by being stored at room temperature, hydro-thermal reaction and the different side such as solvent heat in water-bath or oil bath pan
Method prepares variety classes, oxide nano thread/ZIF systems MOFs of similar pattern composite；
The collection of S3 reaction products.
Further, the oxide nano thread described in the step S1 is manganese oxide nano wire, zinc oxide nanowire, four
Co 3 O nano wire, iron oxide nano-wire, nickel oxide nanowires.
Further, the surfactant described in the step S2 is PVP (polyvinylpyrrolidone), SDS (12
Sodium alkyl sulfate), PVA (polyvinyl alcohol), NPAM (polyacrylamide).
Further, the imidazoles in the step S2 is 2-methylimidazole, benzimidazole, 2- nitroimidazoles.
Further, the metal salt in the step S2 is cabaltous nitrate hexahydrate, zinc nitrate hexahydrate.
Further, the organic solvent in the step S2 refers to methanol, DMF.
Further, the collection of products step in the step S3 is cleans 3 times with methanol or ethanol, 60~100
Dried at DEG C.
Compared to prior art, the advantage of the invention is that：
(1) oxide nano thread/ZIF systems MOFs sugarcoated haws shape composites in the present invention, with unique pattern, structure
It is more novel；
(2) oxide nano thread/ZIF systems MOFs sugarcoated haws shape composites in the present invention, with larger specific surface area
With larger pore volume；
(3) oxide nano thread/ZIF systems MOFs sugarcoated haws shape composites in the present invention, can effectively lift lithium ion
The cycle performance of battery；
(4) the preparation method simplicity of oxide nano thread/ZIF systems MOFs sugarcoated haws shape composites, cycle in the present invention
Short, cost is low, can meet the extensive industrialization of material business and prepare.
Brief description of the drawings
Fig. 1 is ZIF-67-MnO2NWs X-ray diffracting spectrum；
Fig. 2 is ZIF-67-MnO2NWs for stereoscan photograph；
Fig. 3 is ZIF-67-MnO2NWs absorption/desorption curve；
Fig. 4 is ZIF-67-MnO2NWs graph of pore diameter distribution；
Fig. 5 is ZIF-67-MnO2NWs is in 500mAg-1Current density under charge and discharge cycles curve.
Embodiment
The implementation to the present invention is described in more detail below in conjunction with Figure of description.
Embodiment 1
Embodiment 1
1st step, MnO is prepared with the method for GO (graphene oxide) hydro-thermal reactions modified2NWs, 1. take 2mg/mL GO
Aqueous solution 7.5mL, ultrasonic disperse is uniform；2. adding 0.35g manganese sulfate solids into solution, ultrasonic disperse is uniform；3.0.5g
Potassium permanganate is dissolved in 10mL deionized waters, resulting solution in being then added into 2, and ultrasonic disperse (dark brown precipitation occurs).
The reaction wherein occurred is as follows：
2KMnO4+3MnSO4+2H2O→5MnO2+K2SO4+2H2SO4
4. in the reactor for moving into 50mL specifications, 140 DEG C, 2h hydro-thermal reactions；5. the product obtained after hydro-thermal reaction is used
Respectively centrifugation three times, each 8000r/min, 5min of ethanol and deionized water；6. the solid that centrifugation is obtained is put into vacuum drying chamber
At least 12 hours of 60 DEG C of dryings, obtain manganese oxide nano wire powder.
2nd step, by the MnO of acquisition2NWs powder is ground to average grain diameter for 3~6 microns, first receives 0.04g manganese oxide
Rice noodles are dissolved in 20mL methanol solvates, and ultrasonic disperse is uniform；0.2g 2-methylimidazoles are taken to be dissolved in 10mL solvents simultaneously, point
Dissipate uniform；Backward manganese oxide nano wire methanol solution in add 0.1g PVP, ultrasonic disperse is uniform；Followed by, to addition
0.1g cabaltous nitrate hexahydrates are added in PVP solution, ultrasonic disperse is uniform；Finally by the methanol solution of 2-methylimidazole with containing
The solution mixing of cabaltous nitrate hexahydrate, sealing and standing reaction at least 20h, reaction product is cleaned 3 times by methanol, and 60 DEG C of dryings are
ZIF-67-MnO can be obtained2This materials with unique serial structure of NWs.As shown in Figure 2, it can be seen that its sugarcoated haws string-like
Pattern, its characteristic peak is clear that in Fig. 1, from Fig. 3 and Fig. 4 can be seen that the material have larger specific surface area and
Larger pore volume, Fig. 5 is shown in 500mAg-1Charge and discharge cycles curve under current density, it can be seen that it is circulated
Stability is more excellent.
Embodiment 2
1st step, the method for the hydro-thermal reaction modified with GO prepares MnO2NWs, 1. take the 2mg/mL GO aqueous solution
7.5mL, ultrasonic disperse is uniform；2. adding 0.35g manganese sulfate solids into solution, ultrasonic disperse is uniform；3.0.5g potassium permanganate
It is dissolved in 10mL deionized waters, resulting solution in being then added into 2, ultrasonic disperse (dark brown precipitation occurs).Wherein occur
Reaction it is as follows：
2KMnO4+3MnSO4+2H2O→5MnO2+K2SO4+2H2SO4
4. in the reactor for moving into 50mL specifications, 140 DEG C, 2h hydro-thermal reactions；5. the product obtained after hydro-thermal reaction is used
Respectively centrifugation three times, each 8000r, 5min of ethanol and deionized water；6. the solid that centrifugation is obtained is put into 60 DEG C of vacuum drying chamber
At least 12 hours are dried, manganese oxide nano wire powder is obtained.
2nd step, by the MnO of acquisition2NWs powder is ground to average grain diameter for 3~6 microns, first receives 0.04g manganese oxide
Rice noodles are dissolved in 20mL methanol solvates, and ultrasonic disperse is uniform；0.2g 2-methylimidazoles are taken to be dissolved in 10mL solvents simultaneously, point
Dissipate uniform；Backward manganese oxide nano wire methanol solution in add 0.15g SDS, ultrasonic disperse is uniform；Followed by, to addition
0.2g zinc nitrate hexahydrates are added in SDS solution, ultrasonic disperse is uniform；Finally by the methanol solution of 2-methylimidazole with containing
The solution mixing of zinc nitrate hexahydrate, sealing and standing reaction at least 20h, reaction product is cleaned 3 times by methanol, and 60 DEG C of dryings are
ZIF-8-MnO can be obtained2This materials with unique serial structure of NWs, it can be seen that the pattern of its sugarcoated haws string-like, the material
There are larger specific surface area and microporous properties, be suitable as lithium ion battery negative material to improve its cycle performance and forthright again
Energy.
Embodiment 3
1st step, 0.2g hexas, 0.6g zinc nitrate hexahydrates are separately added into beaker, then are added to the inside
60mL deionized waters, ultrasonic disperse is uniform, is synthesized using the method for solvent thermal reaction, the reaction time is 5h, and reaction temperature is 80
DEG C, products therefrom is cleaned 3 times with ethanol afterwards, 60 DEG C of dryings can obtain zinc oxide nanowire.
2nd step, is ground to average grain diameter for 3~6 microns, first by 0.05g oxygen by the powder of the zinc oxide nanowire of acquisition
Change zinc nano wire to be dissolved in 50mL DMF solvents, ultrasonic disperse is uniform；0.2g PVA are added afterwards molten
In liquid, ultrasonic disperse is uniform；Then by 0.3g cabaltous nitrate hexahydrates, it is uniform that 0.3g benzimidazoles add ultrasonic disperse in solution；
Finely dispersed solution is finally moved into three hours of 120 degree of hydro-thermal reactions in the reactor of 100mL specifications, by the product of gained
Cleaned with ethanol 3 times, 60 dryings can obtain this materials with unique serial structure of ZIF-7-ZnO NWs.
Embodiment 4
1st step, 0.2g hexas, 0.6g zinc nitrate hexahydrates are separately added into beaker, then are added to the inside
60mL deionized waters, ultrasonic disperse is uniform, is synthesized using the method for solvent thermal reaction, the reaction time is 5h, and reaction temperature is 80
DEG C, products therefrom is cleaned 3 times with ethanol afterwards, 60 DEG C of dryings can obtain zinc oxide nanowire.
2nd step, is ground to average grain diameter for 3~6 microns, first by 0.04g oxygen by the zinc oxide nanowire powder of acquisition
Change zinc nano wire to be dissolved in 50mL DMF solvents, ultrasonic disperse is uniform；0.2g NPAM are added afterwards
In solution, ultrasonic disperse is uniform；Then by 0.35g zinc nitrate hexahydrates, 0.4g 2- nitroimidazoles, 0.25g benzimidazoles are added
In solution, ultrasonic disperse is well mixed, and finely dispersed solution is finally moved into 120 degree of hydro-thermals in the reactor of 100mL specifications
4h is reacted, the product of gained is cleaned 3 times with ethanol, it is this with unique serial that 60 DEG C of dryings can obtain ZIF-68-ZnO NWs
The material of structure can see the pattern of its sugarcoated haws string-like, and the material has larger specific surface area and microporous properties, is suitable as
Improve its cycle performance and high rate performance for lithium ion battery negative material.
Embodiment 5
1st step, 0.12g ureas, 0.4g cobalt chloride hexahydrates are separately added into beaker, then into beaker add 40mL go from
Sub- water, is placed on magneton agitator and stirs 10min or so, and solution becomes clarification.Then in the reactor for moving it into 50mL specifications,
120 degree of reaction 16h, afterwards clean products therefrom 3 times, 60 degree of dryings can obtain cobaltosic oxide nano line with ethanol.
2nd step, average grain diameter is ground to for 3~6 microns by the powder of the cobaltosic oxide nano line of acquisition, first will
0.06g cobaltosic oxide nano lines are dissolved in 30mL DMF solvents, and ultrasonic disperse is uniform；Afterwards will
0.15g PVP are added in solution, and ultrasonic disperse is uniform；Then by 0.24g zinc nitrate hexahydrates, 0.2g benzimidazoles add solution
In, ultrasonic disperse is well mixed, and finely dispersed solution is finally carried out into solvent thermal reaction in oil bath pan, heating-up temperature is
130 degree, the heat time is 48h, and the product of gained is cleaned with ethanol, and drying can obtain ZIF-4-Co3O4NWs is this to be had solely
The material of special serial structure.
Embodiment 6
1st step, 0.12g ureas, 0.4g cobalt chloride hexahydrates are separately added into beaker, then into beaker add 40mL go from
Sub- water, is placed on magneton agitator and stirs 10min or so, and solution becomes clarification.Then in the reactor for moving it into 50mL specifications,
120 degree of reaction 16h, afterwards clean products therefrom 3 times, 60 degree of dryings can obtain cobaltosic oxide nano line with ethanol.
2nd step, average grain diameter is ground to for 3~6 microns by the cobaltosic oxide nano line powder of acquisition, first will
0.04g cobaltosic oxide nano lines are dissolved in 50mL DMF solvents, and ultrasonic disperse is uniform；Afterwards will
0.2g PVA are added in solution, and ultrasonic disperse is uniform；Then by 0.35g zinc nitrate hexahydrates, 0.4g 2- nitroimidazoles, 0.25g
Benzimidazole is added in solution, and ultrasonic disperse is well mixed, and finely dispersed solution is finally moved into the reactor of 100mL specifications
In 120 degree of hydro-thermal reaction 4h, the product of gained is cleaned 3 times with ethanol, 60 DEG C of dryings can obtain ZIF-68-Co3O4NWs is this
Material with unique serial structure, it can be seen that the pattern of its sugarcoated haws string-like, the material has larger specific surface area and micro-
Pore property, is suitable as lithium ion battery negative material to improve its cycle performance and high rate performance.
Embodiment 7
1st step, 1.2g six hydration nickel sulfates are dissolved in 200mL deionized waters, then add 9g ureas, and dissolving, mixing is equal
It is even, pH is adjusted to neutrality with sulfuric acid or ammoniacal liquor.Solution is transferred in conical flask, sealed, 98 degree of constant temperature, in magneton agitator
On at the uniform velocity stir, react 6h, product clean 3 times with ethanol afterwards, 75 degree of dryings are that can obtain nickel oxide nanowires.
2nd step, is ground to average grain diameter for 3~6 microns, first by 0.03g oxygen by the powder of the nickel oxide nanowires of acquisition
Change nickel nano wire to be dissolved in 20mL methanol solvates, ultrasonic disperse is uniform；0.2g 2-methylimidazoles are taken to be dissolved in 10mL solvents simultaneously
In, it is uniformly dispersed；Backward manganese oxide nano wire methanol solution in add 0.1g SDS, ultrasonic disperse is uniform；Followed by, to
Add and 0.1g cabaltous nitrate hexahydrates are added in SDS solution, ultrasonic disperse is uniform；Finally by the methanol solution of 2-methylimidazole with
Solution mixing containing cabaltous nitrate hexahydrate, sealing and standing reaction at least 20h, reaction product is cleaned 3 times by methanol, and 60 DEG C are done
It is dry to obtain this materials with unique serial structure of ZIF-67-NiO NWs.
Embodiment 8
1st step, 1.2g six hydration nickel sulfates are dissolved in 200mL deionized waters, then add 9g ureas, and dissolving, mixing is equal
It is even, pH is adjusted to neutrality with sulfuric acid or ammoniacal liquor.Solution is transferred in conical flask, sealed, 98 degree of constant temperature, in magneton agitator
On at the uniform velocity stir, react 6h, product clean 3 times with ethanol afterwards, 75 degree of dryings are that can obtain nickel oxide nanowires.
2nd step, is ground to average grain diameter for 3~6 microns, first by 0.05g oxygen by the powder of the nickel oxide nanowires of acquisition
Change nickel nano wire to be dissolved in 30mL DMF solvents, ultrasonic disperse is uniform；0.15g NPAM are added afterwards
In solution, ultrasonic disperse is uniform；Then by 0.24g zinc nitrate hexahydrates, 0.2g benzimidazoles are added in solution, and ultrasonic disperse is mixed
Close uniform, finely dispersed solution is finally subjected to solvent thermal reaction in oil bath pan, heating-up temperature is 130 degree, heat time
For 48h, the product of gained is cleaned with ethanol, drying can obtain this materials with unique serial structure of ZIF-4-NiO NWs
Material.
Embodiment 9
1st step, 0.5g iron chloride, 1.2g enuatrols, 10mL oleic acid, 20mL ethanol adds the mixing of 30mL deionized waters equal again
It is even, uniform mixed solution is moved into the reactor of 100mL specifications, hydro-thermal reaction, 160 degree of reaction temperature, reaction time
6h, products therefrom is cleaned 3 times with ethanol, 60 degree of dryings can obtain iron oxide nano-wire.
2nd step, is ground to average grain diameter for 3~6 microns, first by 0.07g oxygen by the powder of the iron oxide nano-wire of acquisition
Change Fe nanowire to be dissolved in 20mL methanol solvates, ultrasonic disperse is uniform；0.2g 2-methylimidazoles are taken to be dissolved in 10mL solvents simultaneously
In, it is uniformly dispersed；Backward manganese oxide nano wire methanol solution in add 0.15g PVA, ultrasonic disperse is uniform；Followed by,
0.2g zinc nitrate hexahydrates are added into the solution for adding PVA, ultrasonic disperse is uniform；Finally by the methanol solution of 2-methylimidazole
Mixed with the solution containing zinc nitrate hexahydrate, sealing and standing reaction at least 20h, reaction product is cleaned 3 times, 60 DEG C by methanol
Drying can obtain ZIF-8-Fe2O3This materials with unique serial structure of NWs.
Embodiment 10
1st step, 0.5g iron chloride, 1.2g enuatrols, 10mL oleic acid, 20mL ethanol adds the mixing of 30mL deionized waters equal again
It is even, uniform mixed solution is moved into the reactor of 100mL specifications, hydro-thermal reaction, 160 DEG C of reaction temperature, reaction time
6h, products therefrom is cleaned 3 times with ethanol, 60 DEG C of dryings can obtain iron oxide nano-wire.
2nd step, is ground to average grain diameter for 3~6 microns, first by 0.08g oxygen by the powder of the iron oxide nano-wire of acquisition
Change Fe nanowire to be dissolved in 50mL DMF solvents, ultrasonic disperse is uniform；0.2g SDS are added afterwards molten
In liquid, ultrasonic disperse is uniform；Then by 0.3g cabaltous nitrate hexahydrates, it is uniform that 0.3g benzimidazoles add ultrasonic disperse in solution；
Finely dispersed solution is finally moved into three hours of 120 DEG C of hydro-thermal reactions in the reactor of 100mL specifications, by the product of gained
Cleaned with ethanol 3 times, 60 DEG C of dryings can obtain ZIF-7-Fe2O3This materials with unique serial structure of NWs, it can be seen that
The pattern of its sugarcoated haws string-like, the material has larger specific surface area and microporous properties, is suitable as negative electrode of lithium ion battery material
Expect to improve its cycle performance and high rate performance.
Schematically the invention and embodiments thereof are described above, the description does not have restricted, accompanying drawing
Shown in be also the invention one of embodiment, actual structure is not limited thereto.So, if this area
Those of ordinary skill enlightened by it, in the case where not departing from this creation objective, designed and the technology without creative
The similar frame mode of scheme and embodiment, all should belong to the protection domain of this patent.
Claims (8)
1. a kind of oxide nano thread/ZIF systems MOFs sugarcoated haws shape composites, it is characterised in that the composite has string
Row structure, ZIF systems MOFs goes here and there on oxide nano thread, forms sugarcoated haws shape and structure.
2. the preparation method of a kind of oxide nano thread/ZIF systems MOFs sugarcoated haws shape composites, it is characterised in that prepare step
It is rapid as follows：
S1 utilizes solvent-thermal method or hydro-thermal reaction synthesis oxide nano wire；
S2 4~6 parts surfactants of addition, 20~40 parts by weight imidazoles of addition, 30~50 parts by volume organic solvents, 20~
40 shares of metal are by being stored at room temperature, hydro-thermal reaction and the different method system such as solvent heat in water-bath or oil bath pan
It is standby to obtain variety classes, oxide nano thread/ZIF systems MOFs of similar pattern composite；
The collection of S3 reaction products.
3. a kind of preparation side of oxide nano thread according to claim 2/ZIF systems MOFs sugarcoated haws shape composites
Method, it is characterised in that the oxide nano thread described in the step S1 is manganese oxide nano wire, zinc oxide nanowire, four oxidations
Three cobalt nanowires, iron oxide nano-wire, nickel oxide nanowires.
4. a kind of preparation side of oxide nano thread according to claim 2/ZIF systems MOFs sugarcoated haws shape composites
Method, it is characterised in that the surfactant described in the step S2 is PVP (polyvinylpyrrolidone), SDS (dodecyls
Sodium sulphate), PVA (polyvinyl alcohol), NPAM (polyacrylamide).
5. a kind of preparation side of oxide nano thread according to claim 2/ZIF systems MOFs sugarcoated haws shape composites
Method, it is characterised in that the imidazoles in the step S2 is 2-methylimidazole, benzimidazole, 2- nitroimidazoles.
6. a kind of preparation side of oxide nano thread according to claim 2/ZIF systems MOFs sugarcoated haws shape composites
Method, it is characterised in that the metal salt in the step S2 is cabaltous nitrate hexahydrate, zinc nitrate hexahydrate.
7. a kind of preparation side of oxide nano thread according to claim 2/ZIF systems MOFs sugarcoated haws shape composites
Method, it is characterised in that the organic solvent in the step S2 refers to methanol, DMF.
8. a kind of preparation side of oxide nano thread according to claim 2/ZIF systems MOFs sugarcoated haws shape composites
Method, it is characterised in that the collection of products step in the step S3 is dried to be cleaned with methanol or ethanol 3 times at 60~100 DEG C
It is dry.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107827145A (en) * | 2017-11-22 | 2018-03-23 | 中南大学 | A kind of nano zinc oxide material and preparation method thereof |
| CN109675636A (en) * | 2019-01-31 | 2019-04-26 | 上海师范大学 | It is carried on ZnO nano needle and ZIF-67 compound catalysis material and its preparation and application of cobalt piece |
| CN109853030A (en) * | 2017-11-30 | 2019-06-07 | 中国科学院福建物质结构研究所 | A kind of metallic oxide nanocrystal and its preparation method and application of metal organic frame film coated |
| CN110212194A (en) * | 2019-06-12 | 2019-09-06 | 合肥工业大学 | A kind of preparation method and applications of one-dimensional MOF@ZIF core-shell structure |
| CN110270379A (en) * | 2019-07-15 | 2019-09-24 | 四川大学 | A kind of MnOx- MOF-Gr composite material and preparation method and application |
| CN111482617A (en) * | 2020-01-30 | 2020-08-04 | 浙江大学 | Preparation method of silver nanowire surface in-situ growth metal oxide core point composite material |
| CN113161533A (en) * | 2021-04-08 | 2021-07-23 | 中北大学 | MOF-derived ZnO @ C composite material and application thereof |
| CN114570369A (en) * | 2022-01-07 | 2022-06-03 | 华南理工大学 | MOFs derived nanosheet self-assembly grading double-layer hollow nanomaterial and preparation method thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107827145A (en) * | 2017-11-22 | 2018-03-23 | 中南大学 | A kind of nano zinc oxide material and preparation method thereof |
| CN107827145B (en) * | 2017-11-22 | 2020-05-12 | 中南大学 | Nano zinc oxide material and preparation method thereof |
| CN109853030A (en) * | 2017-11-30 | 2019-06-07 | 中国科学院福建物质结构研究所 | A kind of metallic oxide nanocrystal and its preparation method and application of metal organic frame film coated |
| CN109853030B (en) * | 2017-11-30 | 2020-11-20 | 中国科学院福建物质结构研究所 | Metal oxide nanocrystalline coated by metal organic framework film and preparation method and application thereof |
| CN109675636A (en) * | 2019-01-31 | 2019-04-26 | 上海师范大学 | It is carried on ZnO nano needle and ZIF-67 compound catalysis material and its preparation and application of cobalt piece |
| CN109675636B (en) * | 2019-01-31 | 2021-08-20 | 上海师范大学 | Cobalt sheet-loaded ZnO nanoneedle and ZIF-67 composite photocatalytic material and preparation and application thereof |
| CN110212194A (en) * | 2019-06-12 | 2019-09-06 | 合肥工业大学 | A kind of preparation method and applications of one-dimensional MOF@ZIF core-shell structure |
| CN110270379A (en) * | 2019-07-15 | 2019-09-24 | 四川大学 | A kind of MnOx- MOF-Gr composite material and preparation method and application |
| CN111482617A (en) * | 2020-01-30 | 2020-08-04 | 浙江大学 | Preparation method of silver nanowire surface in-situ growth metal oxide core point composite material |
| CN113161533A (en) * | 2021-04-08 | 2021-07-23 | 中北大学 | MOF-derived ZnO @ C composite material and application thereof |
| CN114570369A (en) * | 2022-01-07 | 2022-06-03 | 华南理工大学 | MOFs derived nanosheet self-assembly grading double-layer hollow nanomaterial and preparation method thereof |
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