CN106745302B - A kind of coralloid zinc ferrite powder of three-dimensional network and preparation method thereof - Google Patents
A kind of coralloid zinc ferrite powder of three-dimensional network and preparation method thereof Download PDFInfo
- Publication number
- CN106745302B CN106745302B CN201710109167.5A CN201710109167A CN106745302B CN 106745302 B CN106745302 B CN 106745302B CN 201710109167 A CN201710109167 A CN 201710109167A CN 106745302 B CN106745302 B CN 106745302B
- Authority
- CN
- China
- Prior art keywords
- powder
- zinc ferrite
- coralloid
- dimensional network
- znfe
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0018—Mixed oxides or hydroxides
- C01G49/0081—Mixed oxides or hydroxides containing iron in unusual valence state [IV, V, VI]
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Iron (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The present invention discloses a kind of coralloid zinc ferrite powder of three-dimensional network and preparation method thereof, including：With Zn (NO3)3·6H2O、Fe(NO3)3·9H2O is raw material, nanometer zinc ferrite presoma is prepared with hydro-thermal method, presoma molten-salt growth method is handled again, obtain the zinc ferrite of shape of octahedron, finally with N, N dimethylformamides are solvent, and hydrazine hydrate is reducing agent, methyl thioglycolate is complexing agent, and the coralloid zinc ferrite of three-dimensional network is obtained through a step etch.Preparation process of the present invention is easy to operate, and the period is short, and the coralliform zinc ferrite diameter prepared is about 75~90nm, and uniform in size, specific surface area improves.
Description
【Technical field】
The invention belongs to materials science fields, and in particular to a kind of coralloid zinc ferrite powder of three-dimensional network and its preparation
Method.
【Background technology】
Zinc ferrite (ZnFe2O4) spinel structure that belongs to cubic system, it is a kind of important low-gap semiconductor material,
Its energy gap is 1.9eV.Due to its unique magnetics, electrical and optical properties, ZnFe2O4Be widely used in making magnetic material,
Gas sensitive, catalysis material, sorbing material and lithium ion battery material etc..
Zinc ferrite is a kind of important soft magnetic ferrite, and nanometer zinc ferrite particle is in magnetic fluid, storage, drug targeting
The fields such as transmission have broad application prospects.Ferromagnetism is presented in the ferrous acid Zinc material of block, but when the size of zinc ferrite reaches
When nanoscale, crystal structure changes, this causes the magnetic of nanometer zinc ferrite to mutate, and superparamagnetism is presented.It is sharp brilliant
Stone class material has good chemical stability and thermal stability, and its high temperature coefficient of thermal expansion is small, has to the corrosion of various melts
Preferable resistivity.The resistance order of magnitude of zinc ferrite gas sensor is in 103k Ω, by the relationship for measuring conductivity and temperature
Surface Oxygen activation energy of adsorption very little can be calculated.Surface Oxygen activation energy of adsorption between surface adsorbed oxygen and adsorbed gas for reacting
Complexity, activation energy is smaller, illustrates that Surface Oxygen is more active, easier to be reacted with reducibility gas, sensitive to reducibility gas
Degree is higher.Zinc ferrite is as the semiconductor that a kind of energy gap is 1.9eV, under radiation of visible light of the wavelength more than 420nm i.e.
Photo-generate electron-hole pair can be generated, is a kind of semiconductor light-catalyst very high to visible light utilization efficiency.Zinc ferrite as lithium from
Sub- cell negative electrode material, ZnFe2O4Conversion reaction can occur, and compared with general transition metal oxide, conversion reaction life
At Zn can also with Li occur alloying reaction, thus its more general transition metal oxide have higher theoretical capacity
(1000.5mAh/g), and since its more general transition metal oxide of removal lithium embedded platform is low, in following cell negative electrode material
Application aspect has good foreground.
At present generally zinc ferrite, but zinc ferrite prepared by hydro-thermal method are prepared using hydro-thermal method, sol-gal process and solid phase method
Pattern is generally less regular；And zinc ferrite prepared by sol-gal process and solid phase method all compares reunion, specific surface area is relatively low.
【Invention content】
The purpose of the present invention is to provide coralloid zinc ferrite powders of a kind of three-dimensional network and preparation method thereof, pass through one
Corrosion reaction is walked, the zinc ferrite powder that pattern is well and evenly distributed can be prepared, specific surface area is higher.
Goal of the invention to realize the present invention, the present invention adopt the following technical scheme that,
Include the following steps：
(1) zinc ferrite precursor powder is prepared by hydro-thermal method, reuses molten-salt growth method and ZnFe is made2O4Powder；
(2) by ZnFe obtained in step (1)2O4It is 0.2g that powder and corrosion solvent, which press mass volume ratio,：(90~180)
ML is mixed, and is carried out ultrasonic disperse, is obtained mixed liquor A；
(3) under protective atmosphere, mixed liquor A is subjected to heating water bath and is stirred, while reducing agent being added dropwise into mixed liquor A
And complexing agent, react cooling termination rapidly after 60~120min；Wherein, the volume ratio of corrosion solvent, reducing agent and complexing agent is
(30~60)：(2~4)：1；
(4) dry after being washed the sediment obtained after reaction, obtain the coralloid zinc ferrite powder of three-dimensional network.
Further, zinc ferrite precursor powder is prepared by hydro-thermal method in step (1) to specifically include：
(101) according to ZnFe2O4Stoichiometric ratio, take Zn (NO3)3·6H2O and Fe (NO3)3·9H2O is added to ultrapure
Solution is prepared in water, and orange solution is obtained after abundant magnetic agitation；Wherein Zn (NO3)3·6H2The ratio of O and ultra-pure water is
5mmol：(50~70) mL；
(102) it is slowly added to NaOH into orange solution and stirs evenly, Zn (NO3)3·6H2The molar ratio of O and NaOH
It is 5：(80~120) obtain bronzing suspension；
(103) bronzing suspension is transferred in reaction kettle, hydro-thermal reaction is carried out at 180~200 DEG C 12~24 hours；
(104) dry after the product obtained after reaction is washed after reaction kettle is cooled to room temperature, obtain ferrous acid zinc precursor
Body powder.
Further, it is stirred 30~60 minutes in step (101) and step (102)；At 40~70 DEG C in step (104)
4~6h of lower drying.
Further, ZnFe is made by molten-salt growth method in step (1)2O4Powder specifically includes：
(111) the zinc ferrite precursor powder and fused salt prepared hydro-thermal method is 1 in mass ratio：(3~6) it mixes, ball milling is simultaneously
It is dried to obtain kermesinus powder；
(112) 4~8h is calcined after grinding kermesinus powder at 800~1000 DEG C, obtains ZnFe2O4Powder and salt it is mixed
Close object；
(113) to ZnFe2O4Ultra-pure water desalination is added in the mixture of powder and salt, is dried to obtain ZnFe2O4Powder.
Further, fused salt uses mass ratio for 1 in step (111):The mixture of 1 NaCl and KCl, ball milling are to turn
4~7h of ball milling in the ball mill of fast 500r/min；After ultra-pure water is added in step (113), 4~6h is heated at 65~85 DEG C, then
1~2h of ultrasound, then filters, and obtained solid is obtained ZnFe in 40~70 DEG C of dry 4~6h2O4Powder.
Further, 20~30min of ultrasonic disperse in step (2)；Water bath heating temperature is 70~90 DEG C in step (3).
Further, corrosion solvent is n,N-Dimethylformamide in step (2)；Reducing agent is hydrazine hydrate in step (3),
Complexing agent is methyl thioglycolate.
Further, in step (3), protective atmosphere is nitrogen or inert gas；It is carried out using -2 DEG C of supercooling ethyl alcohol fast
Quickly cooling but terminates.
Further, 4~7h is dried in step (4) at 40~70 DEG C.
The pattern of zinc ferrite powder of the present invention is three-dimensional of the diameter in the mutually arranged formation of rodlike zinc ferrite of 75~90nm
Network coralliform.
Compared with prior art, the device have the advantages that：The present invention is prepared for zinc ferrite by hydro-thermal method first
Precursor powder obtains the zinc ferrite powder of the uniform shape of octahedron of complete crystal form, crystal grain, then further using molten-salt growth method
Corrosion process is carried out by a step etch, the coralloid zinc ferrite powder of three-dimensional network is made.Hydro-thermal method is used in the present invention
With the method that molten-salt growth method is combined, the octahedral shape ZnFe of favorable dispersibility is obtained2O4Presoma overcomes conventional hydrothermal legal system
Standby ZnFe2O4Group's crystal form is imperfect and traditional molten salt growth prepares ZnFe2O4Reunion serious situation.The present invention uses etching process,
ZnFe after corrosion2O4Specific surface area increases, and the condition used in preparation can be controlled preferably.What the present invention obtained
ZnFe2O4Novel in shape, particle is uniformly and equipment operation requirement is low, simple for process, low energy consumption, can operate continuously and be easier to control
System.Therefore the shortcomings that present invention overcomes crystal form bad with reunion using hydro-thermal method with the method that molten-salt growth method is combined, and in this base
Its surface is modified on plinth, finally obtains the coralloid zinc ferrite of three-dimensional network.
ZnFe produced by the present invention2O4Powder purity is high, crystallinity is good, pattern is uniform, obtain be a kind of nanometer rods from
The three-dimensional network coralliform structure formed is assembled, compared with before corrosion, specific surface area is from 0.381m2g-1It is increased to 76.216m2 g-1, improve over two hundred times, and the raising of specific surface area has greatly improved effect to the correlated performance of material, for example, working as material
It applies when on lithium ion battery, specific surface area increase means the promotion of lithium ion insertion and deintercalation efficiency, can be very big
Improve battery performance in ground.
【Description of the drawings】
Fig. 1 is ZnFe prepared by hydro-thermal method of the present invention2O4The XRD diagram of precursor powder.
Fig. 2 is ZnFe prepared by molten-salt growth method of the present invention2O4The XRD diagram of powder.
Fig. 3 is the three-dimensional network coralliform ZnFe that the present invention is prepared2O4XRD diagram.
Fig. 4 is ZnFe prepared by hydro-thermal method of the present invention2O4The SEM of precursor powder schemes.
Fig. 5 is ZnFe prepared by molten-salt growth method of the present invention2O4The SEM of powder schemes.
Fig. 6 is the three-dimensional network coralliform ZnFe that the present invention is prepared2O4SEM figure.
【Specific implementation mode】
By specific embodiment, the present invention is described in detail below in conjunction with the accompanying drawings.
Preparation method of the present invention, includes the following steps：
(1) by Zn (NO3)3·6H2O、Fe(NO3)3·9H2O is according to molar ratio 5mmol:10mmol is weighed, it is added to 50~
Solution, abundant magnetic agitation 30~obtain orange solution A after sixty minutes are prepared in 70mL ultra-pure waters；
(2) it is slowly added to the granular NaOH of 80~120mmol into solution A and stirs evenly, to precipitate Zn2+And Fe3+,
The time of stirring is 30~60 minutes, obtains uniform bronzing suspension B；
(3) suspension B is transferred to polytetrafluoroethyllining lining, stainless steel autoclave is put into, in homogeneous reactor
Heating carries out hydro-thermal reaction, and the temperature of hydro-thermal reaction is 180~200 DEG C, and the time of reaction is 12~24 hours；
(4) after reaction kettle is cooled to room temperature, the hydrothermal product obtained after reaction is brownish red powder, passes through deionized water
Three times, absolute ethyl alcohol dries 4~6h after washing twice at 40~70 DEG C, obtains nanometer zinc ferrite presoma powder for washing；
(5) the presoma powder and NaCl, KCl example in mass ratio prepared hydro-thermal is 1:1 weighs, presoma powder and salt
Mass ratio be 1:3~6, it is put into 4~7h of 500r/min ball millings in ball mill, kermesinus powder is obtained after dry；
(6) it is put into corundum crucible after grinding kermesinus powder, 800~1000 DEG C of 4~8h of calcining, obtain in Muffle furnace
ZnFe2O4The mixture of powder and salt；
(7) ultra-pure water is added into crucible, 4~6h and then at normal temperatures 1~2h of ultrasound are heated at 65~85 DEG C, will be mixed
Salt dissolves in object, filters, obtains ZnFe after 40~70 DEG C of dry 4~6h2O4Powder；
(8) the zinc ferrite powder and n,N-Dimethylformamide that are obtained in step 7 are mixed in silk mouth bottle, ultrasound point
Dissipate 20~30min；The mass volume ratio of zinc ferrite powder and N,N-dimethylformamide is 0.2g：(90~180) mL；
(9) gained mixed liquor in step 8 heating water bath and is stirred at 65~85 DEG C, while is passed through nitrogen and persistently protects
Shield can also use other such as helium inert gases as protective atmosphere to completely cut off air；
(10) dropwise addition hydrazine hydrate and methyl thioglycolate into mixed liquor, nitrogen sustainable protection, after reacting 60~120min,
It needs the rapid cooling of supercooling ethyl alcohol of -2 DEG C of rapid use and terminates；N,N-dimethylformamide in corrosion process：Hydrazine hydrate：Sulfydryl
The volume ratio of methyl acetate mixed liquor is (30~60)：(2~4)：1.
(11) dry at 40~70 DEG C after by the sediment obtained after reaction by absolute ethyl alcohol and deionized water washing
4~7h obtains the coralloid zinc ferrite powder of three-dimensional network.
The present invention is with Zn (NO3)3·6H2O、Fe(NO3)3·9H2O is raw material, and nanometer zinc ferrite forerunner is prepared with hydro-thermal method
Body, then presoma molten-salt growth method is handled, the zinc ferrite of shape of octahedron is obtained, finally using n,N-Dimethylformamide as solvent,
Hydrazine hydrate is reducing agent, and methyl thioglycolate is complexing agent, and hydrazine hydrate is reacted with zinc ferrite by Fe3+It is reduced into Fe2+Generate Fe
(OH)2,Fe(OH)2With methyl thioglycolate react generate complex compound be dissolved in n,N-Dimethylformamide, corroded through above-mentioned
Journey, which falls into the ferric ion corrosion in zinc ferrite, obtains the coralloid zinc ferrite of three-dimensional network.Preparation process of the present invention operates letter
Single, the period is short, and the coralliform zinc ferrite diameter prepared is about 75~90nm, and uniform in size, specific surface area improves.
Embodiment 1
A kind of coralloid ZnFe of three-dimensional network2O4And preparation method thereof, include the following steps：
(1) by Zn (NO3)3·6H2O、Fe(NO3)3·9H2O is according to molar ratio 1:2 weigh, and are added in 60mL ultra-pure waters
Solution is prepared, orange solution A is obtained after magnetic agitation 30min；
(2) it is slowly added to 80mmol NaOH into solution A and stirs evenly 30min, obtains suspension B russet；
(3) suspension B is transferred to polytetrafluoroethyllining lining, stainless steel autoclave is put into, in homogeneous reactor
Heating carries out hydro-thermal reaction, and reaction temperature is 180 DEG C, reaction time 18h；
(4) after reaction kettle is cooled to room temperature, the product obtained after reaction is washed by deionized water and absolute ethyl alcohol
After be put into the dry 4h of 70 DEG C of baking oven, obtain hydro-thermal method preparation nanometer zinc ferrite presoma powder；
(5) the presoma powder and NaCl, KCl example 1 in mass ratio prepared hydro-thermal：1.5：1.5 weigh, and are put into ball mill
Middle ball milling 4h obtains kermesinus powder after dry；
(6) it is put into corundum crucible after grinding kermesinus powder, 800 DEG C of calcining 4h, obtain ZnFe in Muffle furnace2O4Powder
The mixture of body and salt
(7) ultra-pure water is added into crucible, 4h is heated at 65 DEG C, and then ultrasound 1h dissolves salt in mixture, suction filtration, 40
ZnFe is obtained after DEG C dry 4h2O4Powder；
(8) zinc ferrite powder metage 0.2g and the 90mL N,N-dimethylformamide obtained in step 7 is mixed in silk
In mouth bottle, ultrasonic disperse 30min；
(9) it will obtain 65 DEG C of heating water baths of solution and stir in step 8, while being passed through nitrogen；
(10) it is 6mL that volume ratio is added dropwise into mixed liquor:The hydrazine hydrate and methyl thioglycolate of 3mL, nitrogen are persistently protected
Reaction is terminated by the rapid cooling of supercooling ethyl alcohol after shield 30min, reaction 1h；
(11) after by the sediment obtained after reaction by absolute ethyl alcohol and deionized water washing, 50 DEG C of dryings of baking oven are put into
7h obtains the coralloid zinc ferrite powder of three-dimensional network.
Embodiment 2
A kind of coralloid ZnFe of three-dimensional network2O4And preparation method thereof, include the following steps：
(1) by Zn (NO3)3·6H2O、Fe(NO3)3·9H2O is according to molar ratio 1:2 weigh, and are added in 50mL ultra-pure waters
Solution is prepared, orange solution A is obtained after magnetic agitation 40min；
(2) it is slowly added to 90mmol NaOH into solution A and stirs evenly 40min, obtains suspension B russet；
(3) suspension B is transferred to polytetrafluoroethyllining lining, stainless steel autoclave is put into, in homogeneous reactor
Heating carries out hydro-thermal reaction, and reaction temperature is 180 DEG C, reaction time 12h；
(4) after reaction kettle is cooled to room temperature, the product obtained after reaction is washed by deionized water and absolute ethyl alcohol
After be put into the dry 6h of 60 DEG C of baking oven, obtain hydro-thermal method preparation nanometer zinc ferrite presoma powder；
(5) the presoma powder and NaCl, KCl example 1 in mass ratio prepared hydro-thermal：2.5：2.5 weighing, it is put into ball mill
Middle ball milling 5h obtains kermesinus powder after dry；
(6) it is put into corundum crucible after grinding kermesinus powder, 900 DEG C of calcining 5h, molten-salt growth method obtain in Muffle furnace
ZnFe2O4The mixture of powder and salt；
(7) ultra-pure water is added into crucible, 5h is heated at 80 DEG C, and then ultrasound 2h dissolves salt in mixture, suction filtration, 60
ZnFe is obtained after DEG C dry 6h2O4Powder；
(8) zinc ferrite powder metage 0.2g and the 150mL N,N-dimethylformamide obtained in step 7 is mixed in silk
In mouth bottle, ultrasonic disperse 30min；
(9) it will obtain 80 DEG C of heating water baths of solution and stir in step 8, while being passed through nitrogen；
(10) it is 9mL that volume ratio is added dropwise into mixed liquor:The hydrazine hydrate and methyl thioglycolate of 3mL, nitrogen are persistently protected
Reaction is terminated by the rapid cooling of supercooling ethyl alcohol after shield 30min, reaction 2h；
(11) after by the sediment obtained after reaction by absolute ethyl alcohol and deionized water washing, 60 DEG C of dryings of baking oven are put into
6h obtains the coralloid zinc ferrite powder of three-dimensional network.
Embodiment 3
A kind of coralloid ZnFe of three-dimensional network2O4And preparation method thereof, include the following steps：
(1) by Zn (NO3)3·6H2O、Fe(NO3)3·9H2O is according to molar ratio 1:2 weigh, and are added in 70mL ultra-pure waters
Solution is prepared, orange solution A is obtained after magnetic agitation 50min；
(2) it is slowly added to 110mmol NaOH into solution A and stirs evenly 50min, obtains suspension B russet；
(3) suspension B is transferred to polytetrafluoroethyllining lining, stainless steel autoclave is put into, in homogeneous reactor
Heating carries out hydro-thermal reaction, and reaction temperature is 190 DEG C, and the reaction time is for 24 hours；
(4) after reaction kettle is cooled to room temperature, the product obtained after reaction is washed by deionized water and absolute ethyl alcohol
After be put into the dry 6h of 50 DEG C of baking oven, obtain hydro-thermal method preparation nanometer zinc ferrite presoma powder；
(5) the presoma powder and NaCl, KCl example 1 in mass ratio prepared hydro-thermal：2：2 weigh, and are put into ball in ball mill
6h is ground, kermesinus powder is obtained after dry；
(6) it is put into corundum crucible after grinding kermesinus powder, 1000 DEG C of calcining 7h, obtain ZnFe in Muffle furnace2O4Powder
The mixture of body and salt；
(7) ultra-pure water is added into crucible, 5h is heated at 75 DEG C, and then ultrasound 1h dissolves salt in mixture, suction filtration, 50
ZnFe is obtained after DEG C dry 5h2O4Powder；
(8) zinc ferrite powder metage 0.2g and the 180mL N,N-dimethylformamide obtained in step 7 is mixed in silk
In mouth bottle, ultrasonic disperse 20min；
(9) it will obtain 85 DEG C of heating water baths of solution and stir in step 8, while being passed through nitrogen；
(10) it is 12mL that volume ratio is added dropwise into mixed liquor:The hydrazine hydrate and methyl thioglycolate of 3mL, nitrogen are persistently protected
30min is protected, is terminated by the rapid cooling of supercooling ethyl alcohol after reacting 1.5h；
(11) after by the sediment obtained after reaction by absolute ethyl alcohol and deionized water washing, 60 DEG C of dryings of baking oven are put into
4h obtains the coralloid zinc ferrite powder of three-dimensional network.
Embodiment 4
A kind of coralloid ZnFe of three-dimensional network2O4And preparation method thereof, include the following steps：
(1) by Zn (NO3)3·6H2O、Fe(NO3)3·9H2O is according to molar ratio 1:2 weigh, and are added in 60mL ultra-pure waters
Solution is prepared, orange solution A is obtained after magnetic agitation 60min；
(2) it is slowly added to 120mmol NaOH into solution A and stirs evenly 60min, obtains suspension B russet；
(3) suspension B is transferred to polytetrafluoroethyllining lining, stainless steel autoclave is put into, in homogeneous reactor
Heating carries out hydro-thermal reaction, and reaction temperature is 200 DEG C, reaction time 12h；
(4) after reaction kettle is cooled to room temperature, the product obtained after reaction is washed by deionized water and absolute ethyl alcohol
After be put into the dry 5h of 40 DEG C of baking oven, obtain hydro-thermal method preparation nanometer zinc ferrite presoma powder；
(5) the presoma powder and NaCl, KCl example 1 in mass ratio prepared hydro-thermal：3：3 weigh, and are put into ball in ball mill
7h is ground, kermesinus powder is obtained after dry；
(6) it is put into corundum crucible after grinding kermesinus powder, 1000 DEG C of calcining 8h, obtain ZnFe in Muffle furnace2O4Powder
The mixture of body and salt；
(7) ultra-pure water is added into crucible, 6h is heated at 85 DEG C, and then ultrasound 2h dissolves salt in mixture, suction filtration, 70
ZnFe is obtained after DEG C dry 6h2O4Powder；
(8) zinc ferrite powder metage 0.2g and the 150mL N,N-dimethylformamide obtained in step 7 is mixed in silk
In mouth bottle, ultrasonic disperse 20min；
(9) silk mouth bottle is subjected to 70 DEG C of heating water baths and stirred, while being passed through nitrogen；
(10) it is 9mL that volume ratio is added dropwise into mixed liquor:The hydrazine hydrate and methyl thioglycolate of 3mL, nitrogen are persistently protected
30min is protected, is terminated by the rapid cooling of supercooling ethyl alcohol after reacting 2h；
(11) after by the sediment obtained after reaction by absolute ethyl alcohol and deionized water washing, 40 DEG C of dryings of baking oven are put into
5h obtains the coralloid zinc ferrite powder of three-dimensional network.
The product of embodiment 2 is tested, as a result as shown in Figures 1 to 6.
It will be seen from figure 1 that presoma prepared by hydro-thermal method has been the ZnFe of pure phase2O4, without other dephasigns.
Figure it is seen that being still the ZnFe of pure phase by the powder that further molten-salt growth method is handled2O4.And molten-salt growth method
Treated ZnFe2O4Diffraction peak intensity is remarkably reinforced, and crystallinity is preferable.
From figure 3, it can be seen that passing through a step corrosion process treated ZnFe2O4Still generated without dephasign, and after corroding
ZnFe2O4It is substantially reduced before diffraction peak intensity is relatively corrosive.
From fig. 4, it can be seen that the ZnFe that hydro-thermal method is prepared2O4It is the nanometer ball that grain size is 20nm or so.
From fig. 5, it can be seen that the ZnFe handled by further molten-salt growth method2O4Powder be the length of side be about 300nm~
The octahedron of 600nm, surface is smooth and smooth, and shape is uniform, favorable dispersibility.
From fig. 6, it can be seen that the ZnFe obtained after being handled by a step corrosion process2O4It is about 75~90nm's for diameter
The three-dimensional network coralliform pattern of the rodlike mutually arranged formation of zinc ferrite, compared with before corrosion, specific surface area is from 0.381m2g-1It carries
Height arrives 76.216m2 g-1, improve over two hundred times.
It is hydrazine hydrate in corrosion process to influence maximum factor in the present invention：The volume ratio of methyl thioglycolate and corrosion
Influence of the time to pattern determines best solution proportion and reaction time, experiment knot by constantly changing experimental factors
Fruit shows hydrazine hydrate：The volume ratio of methyl thioglycolate is 2~4：1, etching time can obtain between 30min~120min
Three-dimensional network coralliform zinc ferrite can be seen that wherein 3 from SEM figures:1 and 120min is optimum reaction condition.With etching time
Growth, template ferrous acid zine corrosion must be more thorough, but zinc ferrite structure can be caved in when etching time is more than 120min.
Claims (8)
1. a kind of coralloid zinc ferrite raw powder's production technology of three-dimensional network, which is characterized in that comprise the steps of：
(1) zinc ferrite precursor powder is prepared by hydro-thermal method, reuses molten-salt growth method and ZnFe is made2O4Powder；
(2) by ZnFe obtained in step (1)2O4It is 0.2g that powder and corrosion solvent, which press mass volume ratio,：(90~180) mL is mixed
It closes, carries out ultrasonic disperse, obtain mixed liquor A；
(3) under protective atmosphere, mixed liquor A is subjected to heating water bath and is stirred, while reducing agent and network being added dropwise into mixed liquor A
Mixture reacts cooling termination rapidly after 60~120min；Wherein, corrode solvent, the volume ratio of reducing agent and complexing agent be (30~
60)：(2~4)：1；
(4) dry after being washed the sediment obtained after reaction, obtain the coralloid zinc ferrite powder of three-dimensional network；
Zinc ferrite precursor powder is prepared in step (1) by hydro-thermal method to specifically include：
(101) according to ZnFe2O4Stoichiometric ratio, take Zn (NO3)3·6H2O and Fe (NO3)3·9H2O is added in ultra-pure water
Solution is prepared, orange solution is obtained after abundant magnetic agitation；Wherein Zn (NO3)3·6H2The ratio of O and ultra-pure water is 5mmol：
(50~70) mL；
(102) it is slowly added to NaOH into orange solution and stirs evenly, Zn (NO3)3·6H2The molar ratio of O and NaOH is 5：
(80~120) obtain bronzing suspension；
(103) bronzing suspension is transferred in reaction kettle, hydro-thermal reaction is carried out at 180~200 DEG C 12~24 hours；
(104) dry after the product obtained after reaction is washed after reaction kettle is cooled to room temperature, obtain zinc ferrite precursor
Body；
ZnFe is made by molten-salt growth method in step (1)2O4Powder specifically includes：
(111) the zinc ferrite precursor powder and fused salt prepared hydro-thermal method is 1 in mass ratio：(3~6) it mixes, ball milling and drying
Obtain kermesinus powder；
(112) 4~8h is calcined after grinding kermesinus powder at 800~1000 DEG C, obtains ZnFe2O4The mixture of powder and salt；
(113) to ZnFe2O4Ultra-pure water desalination is added in the mixture of powder and salt, is dried to obtain ZnFe2O4Powder.
2. the coralloid zinc ferrite raw powder's production technology of a kind of three-dimensional network according to claim 1, which is characterized in that
It is stirred 30~60 minutes in step (101) and step (102)；4~6h is dried in step (104) at 40~70 DEG C.
3. the coralloid zinc ferrite raw powder's production technology of a kind of three-dimensional network according to claim 1, which is characterized in that
Fused salt uses mass ratio for 1 in step (111):The mixture of 1 NaCl and KCl, ball milling are the ball millings in rotating speed 500r/min
4~7h of ball milling in machine；After ultra-pure water is added in step (113), 4~6h, then 1~2h of ultrasound are heated at 65~85 DEG C, is then taken out
Filter, ZnFe is obtained by obtained solid in 40~70 DEG C of dry 4~6h2O4Powder.
4. the coralloid zinc ferrite raw powder's production technology of a kind of three-dimensional network according to claim 1, which is characterized in that
20~30min of ultrasonic disperse in step (2)；Water bath heating temperature is 70~90 DEG C in step (3).
5. the coralloid zinc ferrite raw powder's production technology of a kind of three-dimensional network according to claim 1, which is characterized in that
Corrosion solvent is N,N-dimethylformamide in step (2)；Reducing agent is hydrazine hydrate in step (3), and complexing agent is thioacetic acid
Methyl esters.
6. the coralloid zinc ferrite raw powder's production technology of a kind of three-dimensional network according to claim 1, which is characterized in that
In step (3), protective atmosphere is nitrogen or inert gas；Rapid cooling termination is carried out using -2 DEG C of supercooling ethyl alcohol.
7. the coralloid zinc ferrite raw powder's production technology of a kind of three-dimensional network according to claim 1, which is characterized in that
4~7h is dried in step (4) at 40~70 DEG C.
8. a kind of existed using the coralloid zinc ferrite powder of three-dimensional network, feature made from preparation method described in claim 1
In the pattern of the zinc ferrite powder is three-dimensional network coral of the diameter in the mutually arranged formation of rodlike zinc ferrite of 75~90nm
Shape.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710109167.5A CN106745302B (en) | 2017-02-27 | 2017-02-27 | A kind of coralloid zinc ferrite powder of three-dimensional network and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710109167.5A CN106745302B (en) | 2017-02-27 | 2017-02-27 | A kind of coralloid zinc ferrite powder of three-dimensional network and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106745302A CN106745302A (en) | 2017-05-31 |
| CN106745302B true CN106745302B (en) | 2018-07-27 |
Family
ID=58959031
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710109167.5A Active CN106745302B (en) | 2017-02-27 | 2017-02-27 | A kind of coralloid zinc ferrite powder of three-dimensional network and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106745302B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107960050A (en) * | 2017-12-12 | 2018-04-24 | 陕西科技大学 | A kind of preparation method of graphene/three-dimensional flower-shaped bismuth ferrite composite wave-suction material |
| CN108358604B (en) * | 2018-03-29 | 2021-04-20 | 广西钦州市品艺堂坭兴陶有限公司 | Manufacturing method of colored nixing pottery |
| CN108766780B (en) * | 2018-05-16 | 2020-07-14 | 陕西科技大学 | Lithium ferrite @ PPy supercapacitor electrode material with core-shell structure and preparation method thereof |
| CN108793261B (en) * | 2018-08-22 | 2020-06-05 | 浙江理工大学 | Preparation method of nano zinc ferrite by taking calamine as raw material |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101289228A (en) * | 2008-06-03 | 2008-10-22 | 浙江理工大学 | Method for preparing porous zinc ferrite nano-rods |
| CN102531067B (en) * | 2012-03-20 | 2014-04-09 | 新疆大学 | Solid state method for preparing zinc ferrite nanorods |
| CN103803658B (en) * | 2014-01-20 | 2015-08-26 | 复旦大学 | A kind of etching prepares the method for porous magnetic nanometer crystal druse |
-
2017
- 2017-02-27 CN CN201710109167.5A patent/CN106745302B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN106745302A (en) | 2017-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106745302B (en) | A kind of coralloid zinc ferrite powder of three-dimensional network and preparation method thereof | |
| CN105304893A (en) | Preparation method of lithium ion battery anode active material lithium nickel manganese oxide | |
| CN105244501B (en) | A kind of active material of lithium ion battery electrode presoma manganese carbonate nickel | |
| CN109778301A (en) | The preparation of one type monocrystalline lithium-rich oxide material and application | |
| CN102694167B (en) | Modified lithium manganate positive pole material and preparation method thereof | |
| CN106711434B (en) | One type sea urchin shape positive electrode of lithium-rich containing sodium and preparation method thereof | |
| CN105322154B (en) | Electrode active substance precursor nickel manganese oxide with special morphology | |
| CN101335348A (en) | Preparing method of lithium ionic cell 5V anode material spherical LiNi*Mn*O* | |
| CN106698521B (en) | A kind of three-dimensional flower-shaped bismuth ferrite powder and preparation method thereof | |
| CN109179518B (en) | Preparation method of high-density doped nickel cobalt hydroxide precursor | |
| CN108054371A (en) | A kind of high-tap density, high magnification and long-life lithium-rich manganese-based anode material and preparation method thereof | |
| CN109626447A (en) | Nickelic anode material for lithium-ion batteries of a kind of concentration gradient magnesium doping and preparation method thereof | |
| WO2022188480A1 (en) | Precursor of composite positive electrode material for lithium battery and preparation method for composite positive electrode material | |
| CN111908519A (en) | High-capacity nickel-rich precursor, positive electrode material and preparation method thereof | |
| CN102054976A (en) | Preparation method of lithium ion battery cathode material | |
| CN105118983A (en) | Method for preparing lithium nickel manganese oxide anode material | |
| CN109904402A (en) | A kind of lithium-rich manganese base material and its preparation and application | |
| CN107910527A (en) | A kind of concrete dynamic modulus nickel cobalt aluminium ternary material precursor and preparation method thereof | |
| CN107863526A (en) | A kind of preparation method for adulterating cobalt acid lithium | |
| CN109411724A (en) | A kind of preparation method of core-shell structure tertiary cathode material | |
| CN102751484A (en) | Preparation method for cobaltosic oxide electrode material having one-dimensional nanometer chain structure or spherical structure | |
| CN111646520A (en) | Preparation and doping modification method of monocrystal nickel-cobalt lithium aluminate anode material | |
| CN106745303B (en) | A kind of three-dimensional flower ball-shaped cadmium ferrite bismuth meal body and preparation method thereof | |
| CN105720242A (en) | Method for modifying lithium ion battery cathode material | |
| CN110282665A (en) | A kind of anode material of lithium battery presoma and preparation method thereof with mesoscopic structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |