CN104528808B - A kind of preparation method of tin ash hollow microsphere - Google Patents
A kind of preparation method of tin ash hollow microsphere Download PDFInfo
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- CN104528808B CN104528808B CN201410833821.3A CN201410833821A CN104528808B CN 104528808 B CN104528808 B CN 104528808B CN 201410833821 A CN201410833821 A CN 201410833821A CN 104528808 B CN104528808 B CN 104528808B
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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
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- 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
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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Abstract
The invention discloses the preparation method of a kind of tin ash hollow microsphere, belong to technical field of nanometer material preparation.Comprise the following steps: 1) by 1:(0.1～20) mol ratio, take NaOH and SnCl2·2H2O, is dissolved in organic solvent, is uniformly mixed so as to obtain mixed solution, is stirred by this mixed solution, obtains reaction precursor liquid；Wherein, the addition of described organic solvent is that every 0.1 mmoL NaOH adds 0.1～1mL organic solvent；2) by reaction precursor liquid at 120～200 DEG C, hydro-thermal reaction 12～48h, centrifugal after cooling；3) it is dried after the centrifugal precipitation obtained being cleaned, prepares tin ash hollow microsphere.The present invention uses hydro-thermal method to prepare tin ash hollow microsphere, and preparation technology flow process is simple, and condition is moderate, it is not necessary to special process equipment, it is easy to industrialized production.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, be specifically related to the system of a kind of tin ash hollow microsphere
Preparation Method.
Background technology
Tin ash (SnO2) be a kind of important semiconductor transducer material [Yootana Pimtong-Ngama,
Sirithan Jiemsirilersb,Sitthisuntorn Supothina,Preparation of tungsten oxide–tin
oxide nanocomposites and their ethylene sensing characteristics,[J]Sensors and
Actuators A:Physical, 139 (2007) 7-11], the gas sensor prepared with it is highly sensitive, by extensively
General for various fuel gas, environmental pollution gas, industrial waste gas and the detection of harmful gas and forecast.
Meanwhile, SnO2Can also be used as the electrode material of lithium ion/sodium-ion battery, it has good electrochemistry
Performance [Zhigang Wen, Feng Zheng, Hongchun Yu, Ziran Jiang, Kanglian
Liu,Hydrothermal synthesis of flowerlike SnO2nanorod bundles and their
application for lithium ion battery,[J]Materials Characterization 76(2013)1–5]。
At present, the preparation method of the tin ash proposed both at home and abroad mainly has a solid-state chemical reaction method method, and colloidal sol-
Gel method, chemical precipitation method and hydrothermal synthesis method.Although solid phase synthesis process technique is simple, but its sintering
Temperature is higher, and temperature retention time is longer, and product morphology is wayward.Sol-gel process equipment needed thereby is simple,
Operate easily controllable, but the time of process is longer, the gel not uncomplicated laundering obtained.Sedimentation method equipment and technique letter
Single, low cost, it is easy to industrialized production, but present in preparation process, greatest problem is SnO2Micropowder
The reunion at end.And hydrothermal synthesis reaction is carried out at high temperature under high pressure, after hydrothermal treatment consists, can effectively suppress powder
Heat growth in the heat treatments such as drying and roasting, the particle size of preparation is uniform, and degree of crystallinity is high, and crystalline state is complete,
Pattern comparison rule, has higher sintering activity.But, prior art is prepared with chloride for raw material
SnO2, maximum difficulty is to be difficult to remove the chloride ion in presoma, result in the reduction of product purity, right
Its performance causes necessarily to be affected [Gao Sainan, Yuan Gaoqing, Jiang Huanfeng. stannum grain oxidation-water heat transfer nano-silica
Hua Xiliao generation army, [J] electronic component and material 12 (2006) 57-62].
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of tin ash hollow microsphere, the method operation letter
List, production cost are low, and repeatability is high, are suitable for industrialized production, through the tin ash hollow that this method prepares
Microsphere crystal property is good, and purity is high, and pattern and size are controlled.
The present invention is to be achieved through the following technical solutions:
The preparation method of a kind of tin ash hollow microsphere, comprises the following steps:
1) press 1:(0.1～20) mol ratio, take NaOH and SnCl2·2H2O, is dissolved in organic solvent,
It is uniformly mixed so as to obtain mixed solution, this mixed solution is stirred, obtain reaction precursor liquid；Wherein, institute
The addition stating organic solvent is that every 0.1mmoL NaOH adds 0.1～1mL organic solvent；
2) by reaction precursor liquid at 120～200 DEG C, hydro-thermal reaction 12～48h, centrifugal after cooling；
3) it is dried after the centrifugal precipitation obtained being cleaned, prepares tin ash hollow microsphere.
In mixed solution, the concentration of NaOH is 0.01～1mol/L；SnCl2·2H2The concentration of O is
0.05～2mol/L.
Described organic solvent is ethanol, ethylene glycol or glycerol.
Step 1) described in stir be by mixed solution magnetic agitation 10～120min.
Step 2) described in hydro-thermal reaction be that reaction precursor liquid is placed in the water using politef as liner
Carrying out in thermal response still, the packing ratio of hydrothermal reaction kettle used is 30%～70%.
Step 3) described in cleaning be that the precipitation that will centrifugal obtain is cleaned 1～5 time through deionized water successively, nothing
Water-ethanol cleans 1～3 time.
Step 3) described in dry be will clean after being deposited at 50～90 DEG C be dried 1～5h.
The tin ash hollow microsphere prepared is be made up of a diameter of 10～50nm nanometer rods a diameter of
The hollow microsphere of 5～8 μm.
Compared with prior art, the present invention has a following useful technique effect:
The present invention is with NaOH and SnCl2·2H2O is raw material, uses hydro-thermal method to be prepared for tin ash hollow
Microsphere, efficiently avoid the muriatic appearance of indissoluble in product.And the present invention can be reacted by control
SnCl in journey2: the mol ratio of NaOH, the time of hydro-thermal reaction and temperature regulate pattern and the chi of product
Very little so that the product prepared has higher purity.The inventive method preparation technology flow process is simple, condition
Moderate, it is not necessary to special process equipment, it is easy to industrialized production, in the tin ash that the present invention prepares
Empty microsphere crystal property is good, purity is high, and pattern and size are controlled, it is to avoid the particle cluster that high-temperature roasting causes
Poly-.
Accompanying drawing explanation
Fig. 1 is SnO prepared by the present invention2X-ray diffractogram.
Fig. 2 is SnO prepared by the present invention2Flied emission shape appearance figure；Wherein, the Flied emission under (a) is 11.0k
Shape appearance figure；B () is the Flied emission shape appearance figure under 22.0k.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail, described in the present invention
Explain rather than limit.
Embodiment 1
The preparation method of a kind of tin ash hollow microsphere, comprises the following steps:
1) preparation 50mL 0.05mol/L NaOH, weighs 0.06mol SnCl2·2H2O dissolves in wherein, adds
Enter 10ml ethylene glycol, be uniformly mixed so as to obtain mixed solution, by mixed solution at normal temperatures, magnetic agitation 10min,
Obtain reaction precursor liquid；
2) by reaction precursor liquid at 150 DEG C, hydro-thermal reaction 12h, centrifugal after natural cooling；
Described hydro-thermal reaction is that reaction precursor liquid is placed in the hydro-thermal reaction using politef as liner
Carrying out in still, the packing ratio of hydrothermal reaction kettle used is 30%～70%；
3) the centrifugal precipitation obtained is cleaned 1～5 time through deionized water successively, washes of absolute alcohol 1～3 times,
At 60 DEG C, it is dried 4h afterwards, obtains tin ash hollow microsphere；
Can be reflected that by Fig. 1 the product prepared by the present invention is tin ash, product crystallinity is preferable.
This tin ash microsphere is hollow structure as can be seen from Figure 2, is made up of a diameter of 50nm nano wire
The microsphere of a diameter of 7 μm.
Embodiment 2
The preparation method of a kind of tin ash hollow microsphere, comprises the following steps:
1) preparation 30mL 0.04mol/L NaOH, weighs 0.02mol SnCl2·2H2O dissolves in wherein, adds
Enter 18ml ethanol, be uniformly mixed so as to obtain mixed solution, by mixed solution at normal temperatures, magnetic agitation 20min,
Obtain reaction precursor liquid；
2) by reaction precursor liquid at 170 DEG C, hydro-thermal reaction 18h, centrifugal after natural cooling；
Described hydro-thermal reaction is that reaction precursor liquid is placed in the hydro-thermal reaction using politef as liner
Carrying out in still, the packing ratio of hydrothermal reaction kettle used is 30%～70%；
3) the centrifugal precipitation obtained is cleaned 3 times through deionized water successively, washes of absolute alcohol 2 times, it
After at 70 DEG C be dried 4h, obtain tin ash hollow microsphere；
Tin ash hollow microsphere obtained by this example is be made up of a diameter of 25nm nano wire a diameter of
The microsphere of 5 μm.
Embodiment 3
The preparation method of a kind of tin ash hollow microsphere, comprises the following steps:
1) preparation 35mL 0.07mol/L NaOH, weighs 0.03mol SnCl2·2H2O dissolves in wherein, adds
25ml glycerol, is uniformly mixed so as to obtain mixed solution, by mixed solution at normal temperatures, and magnetic agitation 30min,
To reaction precursor liquid；
2) by reaction precursor liquid at 160 DEG C, hydro-thermal reaction 28h, centrifugal after natural cooling；
Described hydro-thermal reaction is that reaction precursor liquid is placed in the hydro-thermal reaction using politef as liner
Carrying out in still, the packing ratio of hydrothermal reaction kettle used is 30%～70%；
3) the centrifugal precipitation obtained is cleaned 2 times through deionized water successively, washes of absolute alcohol 1 time, it
After at 50 DEG C be dried 5h, obtain tin ash hollow microsphere；
Tin ash hollow microsphere obtained by this example is be made up of a diameter of 40nm nano wire a diameter of
The microsphere of 6 μm.
Embodiment 4
The preparation method of a kind of tin ash hollow microsphere, comprises the following steps:
1) preparation 40mL 0.03mol/L NaOH, weighs 0.04mol SnCl2·2H2O dissolves in wherein, adds
Enter 15ml ethanol, be uniformly mixed so as to obtain mixed solution, by mixed solution at normal temperatures, magnetic agitation 80min,
Obtain reaction precursor liquid；
2) by reaction precursor liquid at 160 DEG C, hydro-thermal reaction 12h, centrifugal after natural cooling；
Described hydro-thermal reaction is that reaction precursor liquid is placed in the hydro-thermal reaction using politef as liner
Carrying out in still, the packing ratio of hydrothermal reaction kettle used is 30%～70%；
3) the centrifugal precipitation obtained is cleaned 2 times through deionized water successively, washes of absolute alcohol 1 time, it
After at 50 DEG C be dried 4h, obtain tin ash hollow microsphere；
Tin ash hollow microsphere obtained by this example is be made up of a diameter of 30nm nano wire a diameter of
The microsphere of 8 μm.
Embodiment 5
The preparation method of a kind of tin ash hollow microsphere, comprises the following steps:
1) preparation 50mL 0.09mol/L NaOH, weighs 0.1mol SnCl2·2H2O dissolves in wherein, adds
25ml ethylene glycol, is uniformly mixed so as to obtain mixed solution, by mixed solution at normal temperatures, and magnetic agitation 120min,
Obtain reaction precursor liquid；
2) by reaction precursor liquid at 190 DEG C, hydro-thermal reaction 18h, centrifugal after natural cooling；
Described hydro-thermal reaction is that reaction precursor liquid is placed in the hydro-thermal reaction using politef as liner
Carrying out in still, the packing ratio of hydrothermal reaction kettle used is 30%～70%；
3) the centrifugal precipitation obtained is cleaned 1 time through deionized water successively, washes of absolute alcohol 3 times, it
After at 90 DEG C be dried 1h, obtain tin ash hollow microsphere；
Tin ash hollow microsphere obtained by this example is be made up of a diameter of 20nm nano wire a diameter of
The microsphere of 6 μm.
Claims (6)
1. the preparation method of a tin ash hollow microsphere, it is characterised in that comprise the following steps:
1) press 1:(0.1～20) mol ratio, take NaOH and SnCl2·2H2O, is dissolved in organic solvent,
It is uniformly mixed so as to obtain mixed solution, this mixed solution is stirred, obtain reaction precursor liquid；Wherein, institute
The addition stating organic solvent is that every 0.1mmoL NaOH adds 0.1～1mL organic solvent；
In mixed solution, the concentration of NaOH is 0.01～1mol/L；SnCl2·2H2The concentration of O is
0.05～2mol/L；
2) by reaction precursor liquid at 120～200 DEG C, hydro-thermal reaction 12～48h, centrifugal after cooling；
3) it is dried after the centrifugal precipitation obtained being cleaned, prepares tin ash hollow microsphere, prepared
Tin ash hollow microsphere is that the hollow of a diameter of 5～8 μm being made up of a diameter of 10～50nm nanometer rods is micro-
Ball.
The preparation method of a kind of tin ash hollow microsphere the most according to claim 1, its feature exists
In, described organic solvent is ethanol, ethylene glycol or glycerol.
The preparation method of a kind of tin ash hollow microsphere the most according to claim 1, its feature exists
In, step 1) described in stir be by mixed solution magnetic agitation 10～120min.
The preparation method of a kind of tin ash hollow microsphere the most according to claim 1, its feature exists
In, step 2) described in hydro-thermal reaction be that reaction precursor liquid is placed in the water using politef as liner
Carrying out in thermal response still, the packing ratio of hydrothermal reaction kettle used is 30%～70%.
The preparation method of a kind of tin ash hollow microsphere the most according to claim 1, its feature exists
In, step 3) described in cleaning be that the precipitation that will centrifugal obtain is cleaned 1～5 time through deionized water successively, nothing
Water-ethanol cleans 1～3 time.
The preparation method of a kind of tin ash hollow microsphere the most according to claim 1, its feature exists
In, step 3) described in dry be that being deposited at 50～90 DEG C after cleaning is dried 1～5h.
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| CN105329937B (en) * | 2015-11-09 | 2017-03-22 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for preparing stannic oxide nanometer microspheres through supercritical method |
| CN105529455B (en) * | 2016-01-25 | 2018-07-17 | 陕西科技大学 | A kind of spherical SnO of prism assembling2Anode material of lithium-ion battery and preparation method thereof |
| CN105514405B (en) * | 2016-01-25 | 2018-08-24 | 陕西科技大学 | A kind of particle assembling cauliflower-shaped SnO2Anode material of lithium-ion battery and preparation method thereof |
| CN105514404B (en) * | 2016-01-25 | 2018-08-24 | 陕西科技大学 | A kind of spherical SnO of nano particle assembling burr2Anode material of lithium-ion battery and preparation method thereof |
| CN105552351B (en) * | 2016-01-25 | 2018-09-25 | 陕西科技大学 | A kind of spherical SnO of nano particle assembling2Anode material of lithium-ion battery and preparation method thereof |
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| CN102086044B (en) * | 2009-12-03 | 2013-01-09 | 中国科学院宁波材料技术与工程研究所 | Method for preparing hollow spherical stannic oxide nano powder |
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Effective date of registration: 20201210 Address after: No.105 Wengang South Road, Xinhe street, Yandu District, Yancheng City, Jiangsu Province (CNx) Patentee after: Yancheng hi tech Pioneer Park Co.,Ltd. Address before: No. 1, Weiyang District university garden, Xi'an, Shaanxi Province, Shaanxi Patentee before: SHAANXI University OF SCIENCE & TECHNOLOGY |