CN103880089A - Self-support ZnMn2O4 multistage hollow microsphere and preparation method thereof - Google Patents
Self-support ZnMn2O4 multistage hollow microsphere and preparation method thereof Download PDFInfo
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- CN103880089A CN103880089A CN201410076936.2A CN201410076936A CN103880089A CN 103880089 A CN103880089 A CN 103880089A CN 201410076936 A CN201410076936 A CN 201410076936A CN 103880089 A CN103880089 A CN 103880089A
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Abstract
The invention discloses a self-support ZnMn2O4 multistage hollow microsphere and a preparation method thereof. The self-support ZnMn2O4 multistage hollow microsphere comprises multistage hollow microspheres and nanometer branch knots for supporting, wherein the microspheres are supported and connected by the naturally growing nanometer branch knots, and thus a complete three-dimensional building structure is formed; the multistage hollow microspheres comprise mesopore sphere shells and mesopore inner cores. The self-support ZnMn2O4 multistage hollow microsphere is completed by a hydrothermal combined annealing method. According to the self-support ZnMn2O4 multistage hollow microsphere, the defect of the hollow microsphere on the aspect of the preparation of an electrode is overcome, a structure can be prevented from being damaged by accumulation and pressing in an electrode preparation process, and electron conduction and liquid diffusion between the microspheres can be realized, so that the prepared electrode is simple and convenient, is good in stability, and capable of fully taking the structure advantage of the microspheres in the application to electronics, catalysis, and energy storage and conversion. The preparation method disclosed by the invention is simple, free from pollution, rich in raw materials, low in price, and suitable for preparation of a low-cost electrode material.
Description
Technical field
The invention belongs to micro-nano material preparing technical field, particularly a kind of self-supporting ZnMn
2o
4multistage hollow microsphere and preparation method thereof.
Background technology
ZnMn
2o
4belong to spinel structure magnetic compound, there is the features such as abundant, cheap, the environmental friendliness of storage, multivalence state, outstanding Jahn – Teller effect, cause broad interest in fields such as electronics, catalysis, magnetic, stored energy conversions.ZnMn
2o
4multistage hollow microsphere, with its unique constructional feature, has very strong magnetism in the application of above-mentioned numerous areas.The ZnMn of preparation at present
2o
4multistage hollow microsphere mostly is the isolated microballoon of dispersion, there is no each other structure connection, aspect the preparation of electrode materials, there are a lot of difficulties in it, the at present preparation of electrode materials needs mixing, accumulation, compressing tablet or conventionally with the crosslinked independently microballoon of organism etc., between the structure destructible of microballoon itself and microballoon, can not form good electron propagation ducts, cause low dynamic characteristic and poor stability, thereby limit its application.Self-supporting ZnMn by hydro-thermal in conjunction with annealing preparation
2o
4multistage hollow microsphere; nanometer minor matters support and connection by self-sow between microballoon form complete three-dimensional building structure; not only protect microballoon self structure but also form electron propagation ducts and solution swapace, become good electrode materials thereby overcome above deficiency.
Summary of the invention
The object of the invention is to overcome the deficiency of existing technologies, a kind of self-supporting ZnMn is provided
2o
4multistage hollow microsphere and preparation method thereof.
A kind of self-supporting ZnMn
2o
4multistage hollow microsphere, comprises multistage hollow microsphere and the nanometer minor matters for supporting;
Described multistage hollow microsphere, comprises mesoporous outer spherical shell and mesoporous kernel, and outer spherical shell diameter is 500-2000 nm, and interior nuclear diameter is 100-800 nm, and outer shell thickness is 100-300 nm; The described nanometer minor matters for supporting, its diameter is 10-100 nm, length is 100-1000 nm.
Between multistage hollow microsphere, support and be connected by the nanometer minor matters of self-sow, thereby forming a complete three-dimensional building structure.
A kind of self-supporting ZnMn
2o
4the preparation method of multistage hollow microsphere, comprises the steps:
Step (1). polymkeric substance polymer is added in organic solvent, forms clear solution;
Described polymkeric substance polymer is polyvinylpyrrolidone, in every 100ml organic solvent, adds 0.1-0.3 g; Described organic solvent is ethylene glycol;
Step (2). divalent zinc salt, manganous salt are joined in clear solution, dissolve completely, obtain mixed solution; In mixed solution, divalent zinc salt concentration is 0.5-1.5 mM; Manganous salt concentration is 1.5-3 mM;
Described divalent zinc salt and manganous salt are divalent zinc salt and the manganous salts that can be dissolved into ethylene glycol; In clear solution in described step (2), zine ion and mn ion mol ratio are 1:2;
Step (3). the clear solution of step (2) is transferred to container, then put into the dry 70-90 min of loft drier 160-180 ° C, obtain suspension liquid after naturally cooling to 70-90 ° of C.
Step (4). the suspension liquid that step (3) is obtained, in the centrifugal 2-5min of 6000-8000 rpm, is got precipitation, adds dehydrated alcohol, and concussion is evenly again centrifugal; After repeating to clean 2-4 time with dehydrated alcohol, obtain product.
Step (5). by the product of step (4) in air, with 1-3 ° of C/ min heat-up rate to 400-600 ° of C, the 3-5 h that anneals under 400-600 ° of C constant temperature, annealed rear naturally drop to normal temperature take out.
Beneficial effect of the present invention is as follows:
In the present invention, prepare self-supporting ZnMn by hydro-thermal in conjunction with the most fiery method
2o
4multistage hollow microsphere.This self-supporting material, the microballoon of each separation is realized support and connection by nanometer minor matters, thereby forms a complete self-supporting building structure.Overcome microballoon at electrode the deficiency aspect preparing, can avoid suppressing owing to piling up the structure deteriorate causing in electrode production process, can realize again effectively electronic conduction and liquid diffusion between microballoon, make the easy and good stability of electrode of preparation, can give full play to the structural advantage in application such as electronics, catalysis, stored energy conversions of multistage microballoon.
In a word, preparation technology of the present invention is simple, pollution-free, abundant raw materials, cheapness, and device is stable, is particularly suitable for preparing low cost electrode materials.
brief description of the drawings:
Fig. 1 is self-supporting ZnMn of the present invention
2o
4the low power scanning electron microscope diagram of multistage hollow microsphere;
Fig. 2 is self-supporting ZnMn
2o
4the high power scanning electron microscope diagram of multistage hollow microsphere;
Fig. 3 is ZnMn
2o
4the internal structure scanning electron microscope diagram of multistage hollow microsphere;
Fig. 4 is self-supporting ZnMn
2o
4the X ray diffracting spectrum of multistage hollow microsphere;
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described.
A kind of self-supporting ZnMn
2o
4multistage hollow microsphere, comprises multistage hollow microsphere and the nanometer minor matters for supporting;
Described multistage hollow microsphere, comprises mesoporous outer spherical shell and mesoporous kernel, and outer spherical shell diameter is 500-2000 nm, and interior nuclear diameter is 100-800 nm, and outer shell thickness is 100-300 nm; The described nanometer minor matters for supporting, its diameter is 10-100 nm, length is 100-1000 nm.
Between multistage hollow microsphere, support and be connected by the nanometer minor matters of self-sow, thereby forming a complete three-dimensional building structure.
A kind of self-supporting ZnMn
2o
4the preparation method of multistage hollow microsphere, comprises the steps:
Step (1). polymkeric substance polymer is added in organic solvent, forms clear solution;
Described polymkeric substance polymer is polyvinylpyrrolidone, in every 100ml organic solvent, adds 0.1-0.3 g; Described organic solvent is ethylene glycol;
Step (2). divalent zinc salt, manganous salt are joined in clear solution, dissolve completely, obtain mixed solution; In mixed solution, divalent zinc salt concentration is 0.5-1.5 mM; Manganous salt concentration is 1.5-3 mM;
Described divalent zinc salt and manganous salt are divalent zinc salt and the manganous salts that can be dissolved into ethylene glycol; In clear solution in described step (2), zine ion and mn ion mol ratio are 1:2;
Step (3). the clear solution of step (2) is transferred to container, then put into the dry 70-90 min of loft drier 160-180 ° C, obtain suspension liquid after naturally cooling to 70-90 ° of C.
Step (4). the suspension liquid that step (3) is obtained, in the centrifugal 2-5min of 6000-8000 rpm, is got precipitation, adds dehydrated alcohol, and concussion is evenly again centrifugal; After repeating to rinse 2-4 time with dehydrated alcohol, obtain product.
Step (5). by the product of step (4) in air, with 1-3 ° of C/ min heat-up rate to 400-600 ° of C, the 3-5 h that anneals under 400-600 ° of C constant temperature, annealed rear naturally drop to normal temperature take out.
embodiment 1
Step (1). polyvinylpyrrolidone is dissolved in ethylene glycol according to the ratio of 0.22 g/100ml, forms clear solution;
Step (2). by Zn (CH
3cOO)
22H
2o and Mn (CH
3cOO)
24H
2o is dissolved into clear solution according to the ratio of 1 mM/100ml and 2 mM/100ml respectively.
Zn (CH in solution in described step (2)
3cOO)
22H
2o and Mn (CH
3cOO)
24H
2o mol ratio is 1/2;
Step (3). the clear solution of completing steps (2) is transferred to container, then put into dry 80 min of 170 ° of C of loft drier.Naturally cool to 80 ° of C and take out container.
Step (4). the suspension liquid in container is transferred to the centrifugal 3min of centrifuge tube 7000 rpm, make lower leaf on suspension liquid in centrifuge tube, supernatant liquid is outwelled, add dehydrated alcohol, and concussion is evenly again centrifugal; After repeating to clean 3 times with dehydrated alcohol, obtain product.
Step (5). by the product of step (4) 500 ° of C degree in air 4 h that anneal, heat-up rate is 1 ° of C/ min, naturally drops to normal temperature and takes out.
The self-supporting ZnMn obtaining
2o
4multistage hollow microsphere is as Fig. 1, and shown in 2, as shown in Figure 3, X-ray diffractogram shown in Fig. 4 shows that product is pure ZnMn to the internal structure of microballoon
2o
4.
Step (1). polyvinylpyrrolidone is dissolved in ethylene glycol according to the ratio of 0.1 g/100ml, forms clear solution;
Step (2). by Zn (NO
3)
2and Mn (NO
3)
24H
2o is dissolved into above-mentioned solution according to the ratio of 0.5 mM/100ml and 1.5 mM/100ml respectively.
Zn (NO in solution in described step (2)
3)
2and Mn (NO
3)
24H
2o mol ratio is 1/2;
Step (3). the clear solution of completing steps (2) is transferred to container, then put into dry 70 min of 160 ° of C of loft drier.Naturally cool to 70 ° of C and take out container.
Step (4). the suspension liquid in container is transferred to the centrifugal 5min of centrifuge tube 6000 rpm, make lower leaf on suspension liquid in centrifuge tube, supernatant liquid is outwelled, add dehydrated alcohol, and concussion is evenly again centrifugal; After repeating to rinse 2 times with dehydrated alcohol, obtain product.
Step (5). by the product of step (4) 400 ° of C degree in air 5 h that anneal, heat-up rate is 2 ° of C/ min, naturally drops to normal temperature and takes out.
embodiment 3
Step (1). polyvinylpyrrolidone is dissolved in ethylene glycol according to the ratio of 0.3 g/100ml, forms clear solution;
Step (2). by Zn (NO
3)
2and Mn (CH
3cOO)
24H
2o is dissolved into above-mentioned solution according to the ratio of 1.5 mM/100ml and 3 mM/100ml respectively.
Zn (NO in solution in described step (2)
3)
2and Mn (CH
3cOO)
24H
2o mole is 1/2;
Step (3). the clear solution of completing steps (2) is transferred to container, then put into dry 90 min of 180 ° of C of loft drier.Naturally cool to 90 ° of C and take out container.
Step (4). the suspension liquid in container is transferred to the centrifugal 2min of centrifuge tube 8000 rpm, make lower leaf on suspension liquid in centrifuge tube, supernatant liquid is outwelled, add dehydrated alcohol, and concussion is evenly again centrifugal; After repeating to clean 4 times with dehydrated alcohol, obtain product.
Step (5). by the product of step (4) 600 ° of C degree in air 3 h that anneal, heat-up rate is 3 ° of C/ min, naturally drops to normal temperature and takes out.
Claims (5)
1. a self-supporting ZnMn
2o
4multistage hollow microsphere, is characterized in that comprising multistage hollow microsphere and the nanometer minor matters for supporting;
Described multistage hollow microsphere, comprises mesoporous outer spherical shell and mesoporous kernel, and outer spherical shell diameter is 500-2000 nm, and interior nuclear diameter is 100-800 nm, and outer shell thickness is 100-300 nm; The described nanometer minor matters for supporting, its diameter is 10-100 nm, length is 100-1000 nm; Between multistage hollow microsphere, support and be connected by the nanometer minor matters of self-sow, thereby forming a complete three-dimensional building structure.
2. a self-supporting ZnMn
2o
4the preparation method of multistage hollow microsphere, is characterized in that comprising the steps:
Step (1). polymkeric substance polymer is added in organic solvent, forms clear solution; In every 100ml organic solvent, add 0.1-0.3 g;
Step (2). divalent zinc salt, manganous salt are joined in clear solution, dissolve completely, obtain mixed solution; In mixed solution, divalent zinc salt concentration is 0.5-1.5 mM; Manganous salt concentration is 1.5-3 mM; In clear solution in described step (2), zine ion and mn ion mol ratio are 1:2;
Step (3). the clear solution of step (2) is transferred to container, then put into the dry 70-90 min of loft drier 160-180 ° C, obtain suspension liquid after naturally cooling to 70-90 ° of C;
Step (4). the suspension liquid that step (3) is obtained, in the centrifugal 2-5min of 6000-8000 rpm, is got precipitation, adds dehydrated alcohol, and concussion is evenly again centrifugal; After repeating to clean 2-4 time with dehydrated alcohol, obtain product;
Step (5). by the product of step (4) in air, with 1-3 ° of C/ min heat-up rate to 400-600 ° of C, the 3-5 h that anneals under 400-600 ° of C constant temperature, annealed rear naturally drop to normal temperature take out.
3. a kind of self-supporting ZnMn as claimed in claim 2
2o
4the preparation method of multistage hollow microsphere, is characterized in that described polymkeric substance polymer is polyvinylpyrrolidone; Described organic solvent is ethylene glycol.
4. a kind of self-supporting ZnMn as claimed in claim 2
2o
4the preparation method of multistage hollow microsphere, is characterized in that described divalent zinc salt and manganous salt are divalent zinc salt and the manganous salts that can be dissolved into ethylene glycol.
5. a kind of self-supporting ZnMn as claimed in claim 2
2o
4the preparation method of multistage hollow microsphere, is characterized in that the described divalent zinc salt of step (2) comprises Zn (CH
3cOO)
22H
2o, Zn (NO
3)
2, described manganous salt comprises Mn (CH
3cOO)
24H
2o, Mn (NO
3)
24H
2o.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106783200A (en) * | 2016-11-30 | 2017-05-31 | 天津大学 | A kind of preparation method of the copper cobalt sulphur microballoon electrode material with hollow structure |
| CN107293748A (en) * | 2017-06-21 | 2017-10-24 | 盐城工学院 | A kind of ZnMn2S4Nanoparticle, its preparation method and application |
| CN107658453A (en) * | 2017-09-20 | 2018-02-02 | 中南大学 | Negative electrode of lithium ion battery manganese monoxide/graphene composite material and preparation method thereof |
| CN108899532A (en) * | 2018-05-09 | 2018-11-27 | 桂林电子科技大学 | A kind of mesoporous micro-pipe shape ZnMn2O4Lithium/anode material of lithium-ion battery and preparation method thereof |
| CN111547774A (en) * | 2020-04-14 | 2020-08-18 | 西北大学 | Double-shell hollow ZnMn for water-based zinc ion battery2O4Preparation method of positive electrode material |
| CN114132968A (en) * | 2021-12-15 | 2022-03-04 | 济南大学 | ZnMn2O4Hollow folded microsphere and preparation method and application thereof |
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| CN101092232A (en) * | 2007-04-28 | 2007-12-26 | 西安交通大学 | Method for preparing inorganic Nano / micro tube |
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| CN101092232A (en) * | 2007-04-28 | 2007-12-26 | 西安交通大学 | Method for preparing inorganic Nano / micro tube |
Non-Patent Citations (2)
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|---|
| CHANGZHOU YUAN ET AL.: "Template-Free Fabrication of Mesoporous Hollow ZnMn2O4 Sub-microspheres with Enhanced Lithium Storage Capability towards High-Performance Li-Ion Batteries", 《PART. PART. SYST. CHARACT.》, vol. 31, 4 February 2014 (2014-02-04), pages 657 - 663 * |
| GENQIANG ZHANG ET AL.: "Formation of ZnMn2O4 Ball-in-Ball Hollow Microspheres as a High-Performance Anode for Lithium-Ion Batteries", 《ADV. MATER.》, vol. 24, 22 June 2012 (2012-06-22), pages 4609 - 4613 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106783200A (en) * | 2016-11-30 | 2017-05-31 | 天津大学 | A kind of preparation method of the copper cobalt sulphur microballoon electrode material with hollow structure |
| CN106783200B (en) * | 2016-11-30 | 2018-12-18 | 天津大学 | A kind of preparation method of the copper cobalt sulphur microballoon electrode material with hollow structure |
| CN107293748A (en) * | 2017-06-21 | 2017-10-24 | 盐城工学院 | A kind of ZnMn2S4Nanoparticle, its preparation method and application |
| CN107293748B (en) * | 2017-06-21 | 2019-09-06 | 盐城工学院 | A kind of ZnMn2S4Nanosphere, preparation method and application |
| CN107658453A (en) * | 2017-09-20 | 2018-02-02 | 中南大学 | Negative electrode of lithium ion battery manganese monoxide/graphene composite material and preparation method thereof |
| CN107658453B (en) * | 2017-09-20 | 2020-06-05 | 中南大学 | Manganese monoxide/graphene composite material for negative electrode of lithium ion battery and preparation method of manganese monoxide/graphene composite material |
| CN108899532A (en) * | 2018-05-09 | 2018-11-27 | 桂林电子科技大学 | A kind of mesoporous micro-pipe shape ZnMn2O4Lithium/anode material of lithium-ion battery and preparation method thereof |
| CN111547774A (en) * | 2020-04-14 | 2020-08-18 | 西北大学 | Double-shell hollow ZnMn for water-based zinc ion battery2O4Preparation method of positive electrode material |
| CN111547774B (en) * | 2020-04-14 | 2021-09-07 | 西北大学 | Double-shell hollow ZnMn for water-based zinc ion battery2O4Preparation method of positive electrode material |
| CN114132968A (en) * | 2021-12-15 | 2022-03-04 | 济南大学 | ZnMn2O4Hollow folded microsphere and preparation method and application thereof |
| CN114132968B (en) * | 2021-12-15 | 2023-10-24 | 济南大学 | ZnMn (zinc sulfide) 2 O 4 Hollow fold microsphere and preparation method and application thereof |
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Effective date of registration: 20230630 Address after: Room 302, 3rd Floor, Building 15, National University Science and Technology Park, No. 26 Fengnan Road, Ouhai Economic Development Zone, Wenzhou City, Zhejiang Province, 325000 Patentee after: Wenzhou zinc Times Energy Co.,Ltd. Address before: 310027 No. 38, Zhejiang Road, Hangzhou, Zhejiang, Xihu District Patentee before: ZHEJIANG University |
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