CN106277040B - Controllable stannic oxide microballoon of a kind of crystallite dimension and preparation method and application - Google Patents
Controllable stannic oxide microballoon of a kind of crystallite dimension and preparation method and application Download PDFInfo
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- CN106277040B CN106277040B CN201610695746.8A CN201610695746A CN106277040B CN 106277040 B CN106277040 B CN 106277040B CN 201610695746 A CN201610695746 A CN 201610695746A CN 106277040 B CN106277040 B CN 106277040B
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 238000001556 precipitation Methods 0.000 claims abstract description 14
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 238000001338 self-assembly Methods 0.000 claims abstract description 7
- 239000012456 homogeneous solution Substances 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000000926 separation method Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 24
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 claims description 18
- 238000013019 agitation Methods 0.000 claims description 11
- 238000011049 filling Methods 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 11
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 7
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 6
- 239000001119 stannous chloride Substances 0.000 claims description 6
- 235000011150 stannous chloride Nutrition 0.000 claims description 6
- 229910001432 tin ion Inorganic materials 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 abstract description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 5
- 239000004094 surface-active agent Substances 0.000 abstract description 5
- 230000001699 photocatalysis Effects 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 15
- -1 energy gap 3.6eV Substances 0.000 description 11
- 235000011167 hydrochloric acid Nutrition 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 239000004005 microsphere Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 238000000149 argon plasma sintering Methods 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229940031098 ethanolamine Drugs 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000000877 morphologic effect Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000013475 authorization Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- SFXJSNATBHJIDS-UHFFFAOYSA-N disodium;dioxido(oxo)tin;trihydrate Chemical compound O.O.O.[Na+].[Na+].[O-][Sn]([O-])=O SFXJSNATBHJIDS-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002169 ethanolamines Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229940079864 sodium stannate Drugs 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 1
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/02—Oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
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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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- 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
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Abstract
The present invention relates to controllable stannic oxide microballoons of a kind of crystallite dimension and preparation method and application, the stannic oxide microballoon is formed by the good stannic oxide crystallite self assembly of crystallinity, the crystallite dimension of stannic oxide crystallite is adjustable in the range of 5 30nm, a diameter of 200 400nm of stannic oxide microballoon, specific surface area ＞ 40m2/g；During preparation, concentrated hydrochloric acid, tin source are sequentially added into the mixed solution of normal propyl alcohol and water, forms clear homogeneous solution；Carry out solvent thermal reaction；It treats after reaction, to take out precipitation, washing separation, you can.Compared with prior art, present invention process route is easy, and without surfactant, even size distribution, the multilevel hierarchy SnO formed by nano microcrystalline self assembly are can be prepared by using one-step method2Microballoon, and SnO can be regulated and controled by adjusting alcohol in reaction system/water ratio2The size of crystallite, microballoon have the characteristic of high specific area and submicrometer scale, have wide practical use in solar cell, lithium ion battery and photocatalysis field.
Description
Technical field
The invention belongs to inorganic advanced technical field of nanometer material preparation, are related to a kind of controllable stannic oxide of crystallite dimension
Microballoon and preparation method and application.
Background technology
SnO2It is a kind of broad-band gap n-type semiconductor, energy gap 3.6eV, chemical stability is good, electron transfer energy
Power is fast, and with high visible light transmittance, novel solar battery, lithium ion battery, gas sensor, electrically conducting transparent with
And photocatalysis field have wide application prospect, therefore, synthesis size, pattern, structure-controllable tin dioxide nanometer material tool
It is significant.
Grain size is several nanometers or tens nanometers of SnO2Particle has high specific surface area and more active site,
Therefore, its more physics and chemical characteristic can be assigned.But there are many problems in practical application for small-size grains：Example
Such as, little crystal grain is easily reunited, and reduces its reactivity；The size of little crystal grain is much smaller than visible wavelength, uses it for the sun
It is unfavorable for the capture of sunlight during energy battery light anode material；For the material of (Asia) micron-scale, nano-scale
Little crystal grain is not easy to recycle；Little particle dense accumulation is unfavorable for the infiltration of ion, electrolyte solution or other reaction systems.Closely
It is over year research shows that, prepare the SnO of multilevel hierarchy2Microballoon can expand SnO significantly2The use scope of nano material.Multilevel hierarchy
SnO2Microballoon is by SnO2Nano-crystalline granule self assembly is assembled, it remains SnO2The advantage of nano particle high-specific surface area, together
When the advantages of being also equipped with the easy recycling of micronsize material, strong light scattering, in addition the hole of multilevel hierarchy microballoon is by nanocrystalline
Grain stacking obtains, usually mesopore size, contributes to the fully penetrated of electrolyte.Therefore, synthesis multilevel hierarchy SnO2Microballoon has
There is significant application value, especially have weight to improving the photoelectric conversion efficiency of solar cell and the cyclical stability of lithium ion battery
Want meaning.
Xiongwen Lou et al. are tin source, sodium hydroxide for alkali source to crystallize stannous chloride, add in urea as pattern
Adjusting control agent, the multilevel hierarchy microballoon that solvent-thermal process is formed by the aggregation of tin oxide nano piece, this microballoon are used for lithium-ion electric
The specific capacity of Chi Shiyou higher and very big current density, it is most important to the formation of microballoon that they also found that urea is added in, instead
Answer can not be obtained if no urea in object size uniform microballoon (J.Phys.Chem.C 2011,115,24605-
24610).It is tin source, lithium salts as pore creating material that Peining Zhu et al., which use crystallization stannic chloride, and Jie has been synthesized by molten-salt growth method
Hole multilevel hierarchy SnO2Microballoon, for both having had high surface area absorption dyestuff sub-micro meter ruler simultaneously after dye-sensitized solar cells
The very little light scattering ability for improving battery, but the Microsphere Size that this high temperature solid-state method obtains is very uneven, it can be also in microballoon
It can residual impurity (Chem.Commun., 2012,48,10865-10867).Yu-Fen Wang et al. are using crystallization stannous chloride
For tin source, using ethylenediamine as Morphological control agent, mesoporous multilevel hierarchy SnO has been synthesized by two step of combination of ultrasound solvent heat2Microballoon,
But the Microsphere Size that this method obtains is larger (about 2.2 microns), and Microsphere Size it is uneven (J.Power Sources,
2015,280,476–482).Guanglu Shang et al. are using stannous sulfate as tin source, solvent-thermal process multilevel hierarchy SnO2
Microballoon, but Microsphere Size is distributed also uneven, diameter wider distribution, from 100 to 800nm etc., in addition as microballoon group substantially
Into unit nano-crystalline granule crystallinity nor too preferable (J.Phys.Chem.C 2012,116,20140-20145).
Above research shows that, multilevel hierarchy SnO2Microballoon has wide practical use, but there is no good methods at present
Synthesize the SnO of even size distribution (monodisperse or quasi- monodisperse)2Microballoon, additionally as the nanocrystalline of composition microballoon basic unit
Also few people refer to for the size regulation and control of particle --- actually this is to influence microsphere surface product and the key component of active site.Cause
This, is highly desirable to develop a kind of easy wet-chemical for not needing to additional additive (such as pore creating material, Morphological control agent)
Method synthesizes the SnO of even size distribution2Microballoon.
Authorization Notice No. is that the Chinese invention patent of CN102060321B discloses a kind of stannic oxide self-assembled nanometer knot
The preparation method of structure microballoon, this method step：A. it is 1 by molar ratio:2-1:3 sodium stannate trihydrates and surfactant are added to second
The in the mixed solvent of alcohol and water, in the mixed solvent ethyl alcohol are 1 with water volume ratio:3.5-3:1；Then ethanol amine, ethanol amine are added in
Addition is per 1mmol sodium stannate trihydrate 2-5ml ethanol amines；B. the solvent solute mixing in step a with glass bar is stirred, obtained
To finely dispersed mixed solution；C. by mixed solution 140-200 DEG C of temperature hydro-thermal 1-48h in reaction kettle obtained by step b, instead
Cooled to room temperature after answering；D. by precipitation water obtained by step c and absolute ethyl alcohol centrifuge washing, you can obtain stannic oxide
Self-assembled nano structures microballoon.Compared with above-mentioned patented technology, preparation method of the present invention is not needed to using surfactant, and
The size of stannic oxide microballoon obtained is more uniform.
Invention content
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of dispersibilities and crystallization
Property it is good, photoelectric properties are excellent, have controllable stannic oxide microballoon of crystallite dimension of bigger serface and preparation method thereof with
Using.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of controllable stannic oxide microballoon of crystallite dimension, the stannic oxide microballoon are micro- by the good stannic oxide of crystallinity
Brilliant self assembly forms, and the crystallite dimension of the stannic oxide crystallite is adjustable in the range of 5-30nm, and the stannic oxide is micro-
A diameter of 200-400nm of ball, specific surface area ＞ 40m2/g。
A kind of preparation method of the controllable stannic oxide microballoon of crystallite dimension, this method include the following steps：
(1) under agitation, concentrated hydrochloric acid, tin source are sequentially added into the mixed solution of normal propyl alcohol and water, is formed transparent
Homogeneous phase solution；
(2) clear homogeneous solution made from step (1) is added in reaction kettle and carries out solvent thermal reaction；
(3) it treats after reaction, to take out precipitation, washing separation obtains the controllable stannic oxide microballoon of crystallite dimension.
Normal propyl alcohol described in step (1) and the volume fraction of water is 0-20% in the mixed solution of water
The mixed solution of normal propyl alcohol and water described in step (1) and the volume ratio of concentrated hydrochloric acid are 100:2-5.
Tin source described in step (1) includes one or both of stannous chloride or stannous chloride dihydrate.
The molar concentration of tin ion is 0.01-0.06mol/L in the clear homogeneous solution.
The filling rate of reaction kettle described in step (2) is 50-80%.
The temperature of solvent thermal reaction described in step (2) is 160-250 DEG C, reaction time 12-18h.
A kind of application of the controllable stannic oxide microballoon of crystallite dimension, the stannic oxide microballoon are used to prepare pure dioxy
Change tinbase dye-sensitized solar cells, lithium ion battery or photochemical catalyst.
The present invention uses stannous chloride as tin source, and normal propyl alcohol and water mixed system can obtain size as reaction dissolvent
The SnO to distribute very evenly2Microballoon, and the size of nano microcrystalline can be adjusted by changing the ratio of normal propyl alcohol and water.
Common stannous chloride easily fast hydrolyzing in neutral or alkalinity pure water solution, obtains the very uneven white of Size Distribution
Amorphous SnO2Precipitation；In addition, divalent tin ion hydrolysis easily forms lamellar structure SnO, further by O2Oxidation obtains lamella knot
The SnO of structure2, therefore, lamellar structure product is easy to get by tin source of Bivalent Tin.The present invention is mainly using normal propyl alcohol as solvent, drop
Low divalent tin ion hydrolysis rate, so precursor solution integrally transparent state, while the addition of a small amount of concentrated hydrochloric acid also rises
The effect for inhibiting hydrolysis is arrived.During subsequent solvent heat, tin ion can uniformly be precipitated from solution, so as to
Homogeneous nucleation finally obtains the microballoon of size uniform.The regulation and control of alcohol/water ratio can change tin ion nucleating growth rate, water
Ratio improve, SnO can be promoted2The nucleating growth of crystallite, thus larger-sized SnO can be obtained2Crystallite.
Compared with prior art, present invention process route is easy, does not need to surfactant, i.e. available using one-step method
The multilevel hierarchy SnO that Size Distribution is highly uniform, is formed by nano microcrystalline self assembly2Microballoon, and can be by adjusting reaction system
Middle alcohol/water ratio regulates and controls SnO2The size of crystallite, microballoon is provided simultaneously with the characteristic of high specific area and submicrometer scale, too
Positive energy battery, lithium ion battery and photocatalysis field have wide application prospects, and have the characteristics that：
(1) preparation process is simple：The present invention using simple, efficient wet chemistry method synthesized Size Distribution it is highly uniform,
The multilevel hierarchy SnO formed by nano microcrystalline self assembly2Microballoon, process route is easy, and low energy consumption, and product yield is high；
(2) crystallite dimension is controllable：The present invention can regulate and control SnO by adjusting alcohol in reaction system/water ratio2Crystallite into
Nucleus growth prepares the SnO of diverse microcosmic structure so as to flexible modulation2Microballoon；
(3) it is of low cost：Compared with previous methods, the present invention can not need to surfactant or other additives
Under the conditions of the better SnO of performance is prepared2Microballoon, this not only lowers costs, also provide a kind of new preparation method；
(4) excellent product performance：The SnO that the present invention synthesizes2The specific surface area of microballoon is more than 40 square metres every gram, higher than normal
Block materials are advised, in addition, the stannic oxide microballoon dispersibility of synthesis is good with crystallinity, photoelectric properties are excellent, quick for dyestuff
4.2% photoelectric conversion efficiency is obtained after change solar cell.
Description of the drawings
Fig. 1 is the field emission scanning electron microscope figure of stannic oxide microballoon prepared by embodiment 1；
Fig. 2 is the field emission scanning electron microscope figure of stannic oxide microballoon prepared by embodiment 2；
Fig. 3 is the field emission scanning electron microscope figure of stannic oxide microballoon prepared by embodiment 3；
Fig. 4 is the field emission scanning electron microscope figure of stannic oxide microballoon prepared by embodiment 4；
Fig. 5 is the XRD spectrum of stannic oxide microballoon prepared by Examples 1 to 4 (a~d in corresponding diagram respectively)；
Fig. 6 is the field emission scanning electron microscope figure of stannic oxide microballoon prepared by embodiment 5；
Fig. 7 is the transmission electron microscope picture of stannic oxide microballoon prepared by embodiment 5；
Fig. 8 is the field emission scanning electron microscope figure of stannic oxide microballoon prepared by embodiment 6；
Fig. 9 is the transmission electron microscope picture of stannic oxide microballoon prepared by embodiment 6；
Figure 10 is the isothermal nitrogen adsorption desorption curve of stannic oxide microballoon prepared by embodiment 7；
Figure 11 is the current -voltage curve of dye-sensitized solar cells prepared by stannic oxide microballoon in embodiment 7.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
50 milliliters of normal propyl alcohols are measured, sequentially add 1.5 milliliters of concentrated hydrochloric acids and 0.4513 gram of two water under the conditions of magnetic agitation
Stannous chloride forms transparent homogeneous phase solution；Above-mentioned clear solution is transferred in reaction kettle and carries out solvent thermal reaction, reaction kettle
Filling rate for 60%, at 200 DEG C, the reaction time is 12 hours for reaction temperature control；It treats to take out precipitation after reaction, use is pure
Water is washed, is centrifuged repeatedly.
Fig. 1 is the field emission scanning electron microscope figure of stannic oxide microballoon prepared by embodiment 1, and microballoon is can see from figure
It is dispersed preferable, even size distribution, a diameter of 200~300 nanometers of single microballoon；May be used also from the scanning electron microscope (SEM) photograph of high power
To see that microballoon is assembled by little crystal grain, about 10 nanometers of the crystallite dimension of crystallite.
Embodiment 2
2.5 milliliters of pure water and 47.5 milliliters of normal propyl alcohols are mixed, sequentially add 1.5 milliliters of dense salt under the conditions of magnetic agitation
Acid and 0.4513 gram of stannous chloride dihydrate, form transparent homogeneous phase solution；Above-mentioned clear solution is transferred in reaction kettle and is carried out
Solvent thermal reaction, the filling rate of reaction kettle is 60%, and at 200 DEG C, the reaction time is 12 hours for reaction temperature control；Treat reaction knot
Precipitation is taken out after beam, is washed, centrifuged repeatedly with pure water.
Fig. 2 is the field emission scanning electron microscope figure of stannic oxide microballoon prepared by embodiment 2, and microballoon is can see from figure
It is dispersed preferable, even size distribution, a diameter of 200~300 nanometers of single microballoon；May be used also from the scanning electron microscope (SEM) photograph of high power
To see that microballoon is assembled by little crystal grain, about 15 nanometers of the crystallite dimension of crystallite.
Embodiment 3
5 milliliters of pure water and 45 milliliters of normal propyl alcohols are mixed, sequentially add under the conditions of magnetic agitation 1.5 milliliters of concentrated hydrochloric acids and
0.4513 gram of stannous chloride dihydrate, forms transparent homogeneous phase solution；Above-mentioned clear solution is transferred in reaction kettle and carries out solvent
Thermal response, the filling rate of reaction kettle is 60%, and at 200 DEG C, the reaction time is 12 hours for reaction temperature control；It treats after reaction
Precipitation is taken out, is washed, centrifuged repeatedly with pure water.
Fig. 3 is the field emission scanning electron microscope figure of stannic oxide microballoon prepared by embodiment 3, and microballoon is can see from figure
Dispersed preferable, size is highly uniform, a diameter of 250 nanometers of single microballoon.
Embodiment 4
7.5 milliliters of pure water and 42.5 milliliters of normal propyl alcohols are mixed, sequentially add 1.5 milliliters of dense salt under the conditions of magnetic agitation
Acid and 0.4513 gram of stannous chloride dihydrate, form transparent homogeneous phase solution；Above-mentioned clear solution is transferred in reaction kettle and is carried out
Solvent thermal reaction, the filling rate of reaction kettle is 60%, and at 200 DEG C, the reaction time is 12 hours for reaction temperature control；Treat reaction knot
Precipitation is taken out after beam, is washed, centrifuged repeatedly with pure water.
Fig. 4 is the field emission scanning electron microscope figure of stannic oxide microballoon prepared by embodiment 4, and microballoon is can see from figure
Dispersed preferable, size is highly uniform, a diameter of 300~400 nanometers of single microballoon.
Fig. 5 is the XRD spectrum of stannic oxide microballoon prepared by Examples 1 to 4 (a~d in corresponding diagram respectively), from collection of illustrative plates
It can be seen that all diffraction maximum with Rutile Type SnO2(JCPDS No.41-1445) standard card is consistent, miscellaneous without other
Peak, the product illustrated are pure SnO2.In addition, the diffraction maximum of all microballoons has widthization phenomenon, illustrate the crystalline substance of tin oxide
Particle size is smaller, and can further illustrate microballoon is assembled by nanocrystalline little particle.SnO is calculated using Scherrer formula2It is micro-
Brilliant crystallite dimension, respectively 10.0 nanometers, 11.8 nanometers, 14.5 nanometers, 15.4 nanometers, it can be found that forming the SnO of microballoon2
The size of crystallite is gradually increasing, consistent with scanning electron microscopic observation result.So the present invention can easily by adjust alcohol/
Water ratio regulates and controls the size of crystallite, and the ratio of water is higher, the size of crystallite is bigger.
Embodiment 5
50 milliliters of normal propyl alcohols are measured, sequentially add 1.5 milliliters of concentrated hydrochloric acids and 0.225 gram of two water chlorine under the conditions of magnetic agitation
Change stannous, form transparent homogeneous phase solution；Above-mentioned clear solution is transferred in reaction kettle and carries out solvent thermal reaction, reaction kettle
Filling rate is 60%, and at 200 DEG C, the reaction time is 12 hours for reaction temperature control；It treats to take out precipitation after reaction, uses pure water
It washs, centrifuge repeatedly.
Fig. 6 is the field emission scanning electron microscope figure of stannic oxide microballoon prepared by embodiment 5, and microballoon is can see from figure
It is dispersed preferable, even size distribution, a diameter of 200~300 nanometers of single microballoon.
Fig. 7 be embodiment 5 prepare stannic oxide microballoon transmission electron microscope picture, be apparent that from figure microballoon be by
Nano-crystalline granule is assembled, about 10 nanometers of the size of single crystal grain.
Embodiment 6
2.5 milliliters of pure water and 47.5 milliliters of normal propyl alcohols are mixed, sequentially add 1.5 milliliters of dense salt under the conditions of magnetic agitation
Acid and 0.225 gram of stannous chloride dihydrate, form transparent homogeneous phase solution；Above-mentioned clear solution is transferred in reaction kettle carry out it is molten
Agent thermal response, the filling rate of reaction kettle is 60%, and at 200 DEG C, the reaction time is 12 hours for reaction temperature control；To the end of reaction
Precipitation is taken out afterwards, is washed, centrifuged repeatedly with pure water.
Fig. 8 is the field emission scanning electron microscope figure of stannic oxide microballoon prepared by embodiment 6, and microballoon is can see from figure
It is dispersed preferable, even size distribution, a diameter of 200~300 nanometers of single microballoon.
Fig. 9 be embodiment 6 prepare stannic oxide microballoon transmission electron microscope picture, be apparent that from figure microballoon be by
Nano-crystalline granule is assembled, about 15 nanometers of the size of single crystal grain.
In conjunction with the embodiments 5 and 6, it can be found that the size of crystallite is improved with the ratio of water in reaction system and is become larger.
Embodiment 7
2.5 milliliters of pure water and 47.5 milliliters of normal propyl alcohols are mixed, sequentially add 1.5 milliliters of dense salt under the conditions of magnetic agitation
Acid and 0.4513 gram of stannous chloride dihydrate, form transparent homogeneous phase solution；Above-mentioned clear solution is transferred in reaction kettle and is carried out
Solvent thermal reaction, the filling rate of reaction kettle is 80%, and at 180 DEG C, the reaction time is 15 hours for reaction temperature control；Treat reaction knot
Precipitation is taken out after beam, is washed, centrifuged repeatedly with pure water.
Figure 10 is the SnO that embodiment 7 is prepared2The isothermal nitrogen adsorption desorption curve of microballoon, test result show microballoon
Specific surface area for 43 square metres every gram, aperture size is about 9 nanometers, so the SnO that the present invention obtains2Microballoon is situated between to be typical
Hole multilevel structure material.
By the SnO in the present embodiment2Pure tin dioxide dye-sensitized solar cells is made in microballoon, tests the light of battery
Electrical property, the current -voltage curve of battery are as shown in figure 11：Battery short circuit current density is every square centimeter up to 12.2 milliamperes, electricity
Pond efficiency is up to 4.2%；This efficiency is higher than battery efficiency prepared by conventional tin oxide nano particles, fully demonstrates in the present invention
SnO2Advantage in terms of Dye Adsorption that good crystallinity, high-specific surface area and the light scattering effect of microballoon are brought and light capture,
Show its broad prospect of application.
Embodiment 8
10 milliliters of pure water and 40 milliliters of normal propyl alcohols are mixed, sequentially add 2.5 milliliters of concentrated hydrochloric acids under the conditions of magnetic agitation
With 0.113 gram of stannous chloride dihydrate, transparent homogeneous phase solution is formed；Above-mentioned clear solution is transferred in reaction kettle and carries out solvent
Thermal response, the filling rate of reaction kettle is 50%, and at 250 DEG C, the reaction time is 18 hours for reaction temperature control；It treats after reaction
Precipitation is taken out, is washed, centrifuged repeatedly with pure water.
Embodiment 9
10 milliliters of pure water and 20 milliliters of normal propyl alcohols and 20 milliliters of n-butanols are mixed, are sequentially added under the conditions of magnetic agitation
2.5 milliliters of concentrated hydrochloric acids and 0.113 gram of stannous chloride dihydrate, form transparent homogeneous phase solution；Above-mentioned clear solution is transferred to instead
It answers and solvent thermal reaction is carried out in kettle, the filling rate of reaction kettle is 50%, and at 240 DEG C, the reaction time is small for 12 for reaction temperature control
When；It treats to take out precipitation after reaction, is washed, centrifuged repeatedly with pure water.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously can easily make these embodiments various modifications, and described herein general
Principle is applied in other embodiment without having to go through creative labor.Therefore, the present invention is not limited to above-described embodiment, abilities
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be the present invention's
Within protection domain.
Claims (1)
1. the preparation method of the controllable stannic oxide microballoon of a kind of crystallite dimension, which is characterized in that the stannic oxide microballoon is by tying
The good stannic oxide crystallite self assembly of crystalline substance forms, and the crystallite dimension of the stannic oxide crystallite can in the range of 5-30nm
It adjusts, a diameter of 200-400nm of the stannic oxide microballoon, specific surface area ＞ 40m2/g；
The preparation method of the controllable stannic oxide microballoon of the crystallite dimension, includes the following steps：
(1) under agitation, concentrated hydrochloric acid, tin source are sequentially added into the mixed solution of normal propyl alcohol and water, forms clear homogeneous
Solution；
(2) clear homogeneous solution made from step (1) is added in reaction kettle and carries out solvent thermal reaction；
(3) it treats after reaction, to take out precipitation, washing separation obtains the controllable stannic oxide microballoon of crystallite dimension；
Normal propyl alcohol described in step (1) and the volume fraction of water is 0-20% in the mixed solution of water；
The mixed solution of normal propyl alcohol and water described in step (1) and the volume ratio of concentrated hydrochloric acid are 100:2-5；
Tin source described in step (1) includes one or both of stannous chloride or stannous chloride dihydrate；The clear homogeneous
The molar concentration of tin ion is 0.01-0.06mol/L in solution；
The filling rate of reaction kettle described in step (2) is 50-80%；
The temperature of solvent thermal reaction described in step (2) is 160-250 DEG C, reaction time 12-18h；
Alcohol/water ratio is adjusted to regulate and control the crystallite dimension of stannic oxide crystallite, is obtained by the ratio for increasing water larger-sized
Stannic oxide crystallite.
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| "表面活性剂对SnO2微球水热制备的影响";宋玉哲等;《功能材料信息》;20120429;第9卷(第2期);第27页左栏第1段，第28-29页第3.1.1部分以及图1和表1，第3.1.2部分以及图2 * |
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