CN102030372B - Preparation method of nano spinel zinc manganate - Google Patents
Preparation method of nano spinel zinc manganate Download PDFInfo
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- CN102030372B CN102030372B CN2009101107043A CN200910110704A CN102030372B CN 102030372 B CN102030372 B CN 102030372B CN 2009101107043 A CN2009101107043 A CN 2009101107043A CN 200910110704 A CN200910110704 A CN 200910110704A CN 102030372 B CN102030372 B CN 102030372B
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- manganate
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Abstract
The invention discloses a preparation method of nano spinel zinc manganite. The method comprises the following steps of: uniformly mixing zinc nitrate and bivalent manganese salt serving as raw materials; and calcining the mixture at a low temperature so as to obtain ultrafine nano spinel zinc manganite. The method has simple preparation process, low cost and low requirement on equipment, can be implemented by calcining at a low temperature and can be used for preparing small-particle zinc manganite; and a product has high purity. The obtained zinc manganate can be taken as a magnetic material, a lithium ion battery electrode material or a zinc ion battery electrode material and the like.
Description
Technical field
The present invention relates to a kind of preparation of nm-class, particularly a kind of superfine nano spinel mangaic acid zinc (ZnMn
2O
4) the preparation method.
Background technology
Spinel mangaic acid zinc (ZnMn
2O
4) be a kind of cheapness and nontoxic material, it can be used as magneticsubstance, lithium ion battery electrode material or Zinc ion battery electrode materials.The preparation method of spinel mangaic acid zinc mainly contains methods such as polymkeric substance high-temperature decomposition, hydrothermal method and high temperature solid phase synthesis at present.These method preparation costs are higher, complex process, output is lower and can not control the pattern and the particle diameter of made sample, therefore is badly in need of the spinel mangaic acid zinc that a kind of simple method prepares various particle diameters.
Summary of the invention
First purpose of the present invention provides the preparation method of the simple nano spinel zinc manganate of a kind of preparation method.
It is simple that second purpose of the present invention provides a kind of preparation method, can prepare the preparation method of particle diameter less than the superfine nano spinel mangaic acid zinc of 10nm.
The 3rd purpose of the present invention provides a kind of preparation method that can control the nano spinel zinc manganate of product pattern and particle diameter.
We find that zinc nitrate is the therefore manganese of the higher valence state of ability oxidation bivalent manganese generation of an inorganic oxidizer under study for action; And the zinc nitrate fusing point is low; For example the zinc nitrate hexahydrate fusing point is 36.4 ℃, be heated to 37 ℃ and promptly be dissolved in crystal water, so we is raw material with zinc nitrate and manganous salt; Make spinel mangaic acid zinc with zinc nitrate oxidation manganous salt; And through the low-melting characteristic of zinc nitrate, fusing is coated on the space forming surface steric hindrance of product in reaction process, stops spinel mangaic acid zinc particle to be grown up.
In order to reach above-mentioned first purpose; The present invention provides a kind of preparation method of nano spinel zinc manganate; It is characterized in that, make by following step: be to get zinc nitrate and manganous salt in 10: 1～1: 2 1), mix by the mol ratio of zinc and manganese by zinc nitrate and manganous salt; 2) mixture that step 1) is made was calcined 40～60 hours under 50～200 ℃, promptly made the nano spinel zinc manganate.
Wherein, manganous salt can adopt manganous nitrate, manganese acetate, manganous sulfate or manganous carbonate etc.In step 1), can adopt the mechanical mixing of routines such as polishing that zinc nitrate and manganous salt are mixed; Also can adopt the dissolving hybrid system that zinc nitrate and manganous salt are mixed.When adopting the dissolving hybrid system, solvent can be selected water for use, and zinc nitrate and manganous salt are dissolved in the water fully, through behind the thermal dehydration, makes the uniform mixture of zinc nitrate and manganous salt then.
In order to reach above-mentioned second purpose; The invention provides a kind of preparation method of nano spinel zinc manganate; Can prepare the ultra-fine spinel mangaic acid zinc of particle diameter less than 10nm; It is characterized in that, make by following step: be to get zinc nitrate and manganous salt in 10: 1～2.5: 1 1), mix by the mol ratio of zinc and manganese by zinc nitrate and manganous salt; 2) mixture that step 1) is made was calcined 40～60 hours under 50～200 ℃, promptly made the nano spinel zinc manganate.
Wherein, manganous salt can adopt manganous nitrate, manganese acetate, manganous sulfate or manganous carbonate etc.In step 1), can adopt the mechanical mixing of routines such as polishing that zinc nitrate and manganous salt are mixed; Also can adopt the dissolving hybrid system that zinc nitrate and manganous salt are mixed.When adopting the dissolving hybrid system, solvent can be selected water for use, and zinc nitrate and manganous salt are dissolved in the water fully, through behind the thermal dehydration, makes the uniform mixture of zinc nitrate and manganous salt then.
In order to reach above-mentioned the 3rd purpose; The present invention is further on the technical scheme basis of above-mentioned solution first purpose or second purpose; The pattern and the particle diameter of the nano spinel zinc manganate that the mol ratio through design zinc nitrate and manganous salt makes; The zinc nitrate proportion is big more, and the particle diameter of prepared nano spinel zinc manganate is more little.
Preparation technology of the present invention is simple, and calcining can realize that cost is low at low temperatures, and is low for equipment requirements.And made product purity is high.
It utilizes the low-melting characteristic of zinc nitrate, and fusing is coated on the space forming surface steric hindrance of product in reaction process, stops spinel mangaic acid zinc particle to be grown up, and can control the pattern and the particle diameter of product.
Preparing method of the present invention can prepare the ultra-fine spinel mangaic acid zinc of particle diameter less than 10nm.
Description of drawings
Fig. 1 is embodiment 1 obtained nano spinel zinc manganate TEM Electronic Speculum figure;
Fig. 2 is embodiment 2 obtained nano spinel zinc manganate SEM Electronic Speculum figure;
Fig. 3 is embodiment 3 obtained nano spinel zinc manganate SEM Electronic Speculum figure;
Fig. 4 is the obtained nano spinel zinc manganate of an embodiment 1-3 XRD structure iron.
Embodiment
Embodiment 1:
Under the room temperature, be to be dissolved in a certain amount of pure water at 3: 1 with mol ratio, then at 85 ℃ of oven dry moisture and continue this temperature (85 ℃) reaction 48 hours with a certain amount of zinc nitrate and manganese acetate.The product water soaks and filters, and with water washing 5 times, oven dry promptly obtains spinel mangaic acid zinc powder.Fig. 1 is embodiment 1 obtained nano spinel zinc manganate TEM Electronic Speculum figure, and the particle diameter that can find out obtained nano spinel zinc manganate is about 5nm, and the XRD spectra of made sample is seen (a) among Fig. 4, can know that by XRD figure prepared sample is pure spinel mangaic acid zinc.
Embodiment 2:
Under the room temperature, be to be dissolved in a certain amount of pure water at 2: 1 with mol ratio, then at 85 ℃ of oven dry moisture and continue this thermotonus 48 hours with a certain amount of zinc nitrate and manganese acetate.The product water soaks and filters, and with water washing 5 times, oven dry promptly obtains spinel mangaic acid zinc powder.Fig. 2 is embodiment 2 obtained nano spinel zinc manganate SEM Electronic Speculum figure, and the XRD spectra of made sample is seen (b) among Fig. 4, can know that by XRD figure prepared sample is pure spinel mangaic acid zinc.
Embodiment 3:
Under the room temperature, be to be dissolved in a certain amount of pure water at 1: 1 with mol ratio, then at 85 ℃ of oven dry moisture and continue this thermotonus 48 hours with a certain amount of zinc nitrate and manganese acetate.The product water soaks and filters, and with water washing 5 times, oven dry promptly obtains spinel mangaic acid zinc powder.Fig. 3 is embodiment 3 obtained nano spinel zinc manganate SEM Electronic Speculum figure, and the XRD spectra of made sample is seen (c) among Fig. 4, can know that by XRD figure prepared sample is pure spinel mangaic acid zinc.
Claims (6)
1. the preparation method of a nano spinel zinc manganate can prepare the ultra-fine spinel mangaic acid zinc of particle diameter less than 10nm, it is characterized in that, is made by following step by zinc nitrate and manganous salt:
1) is to get zinc nitrate and manganous salt in 10: 1～2.5: 1 by the mol ratio of zinc and manganese, mixes;
2) mixture that step 1) is made was calcined 40～60 hours under 50～200 ℃, promptly made the nano spinel zinc manganate.
2. the preparation method of nano spinel zinc manganate as claimed in claim 1; It is characterized in that: the pattern and the particle diameter of the nano spinel zinc manganate that makes through the mol ratio that changes zinc nitrate and manganous salt; The zinc nitrate proportion is big more, and the particle diameter of prepared nano spinel zinc manganate is more little.
3. the preparation method of nano spinel zinc manganate as claimed in claim 1 is characterized in that: said manganous salt is manganous nitrate, manganese acetate, manganous sulfate or manganous carbonate.
4. the preparation method of nano spinel zinc manganate as claimed in claim 1 is characterized in that: in the said step 1), adopt mechanical mixing that zinc nitrate and manganous salt are mixed.
5. the preparation method of nano spinel zinc manganate as claimed in claim 1 is characterized in that: in the said step 1), adopt the dissolving hybrid system that zinc nitrate and manganous salt are mixed.
6. the preparation method of nano spinel zinc manganate as claimed in claim 5; It is characterized in that: said step 1) is made solvent with pure water; Zinc nitrate and manganous salt are dissolved in the pure water fully, through behind the thermal dehydration, make the uniform mixture of zinc nitrate and manganous salt then.
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| CN102030372B true CN102030372B (en) | 2012-11-14 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102660766B (en) * | 2012-05-08 | 2015-02-25 | 陕西科技大学 | Preparation method of Y2Si2O7 whisker |
| CN106450218A (en) * | 2016-11-08 | 2017-02-22 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for in-situ synthesis of carbon-nitrogen coated zinc-manganese oxide |
| CN107720829B (en) * | 2017-09-25 | 2019-09-13 | 南京理工大学 | The preparation method of lithium ion battery negative material zinc manganate |
| CN108306059A (en) * | 2018-02-01 | 2018-07-20 | 吉首大学 | The preparation method of environmentally protective high power water system Zinc ion battery |
| CN109119608B (en) * | 2018-08-14 | 2020-10-09 | 厦门大学 | Preparation method of zinc manganate/silver composite material |
| CN110474017B (en) * | 2019-08-29 | 2022-02-11 | 瑞海泊有限公司 | Preparation method and application of zinc manganate electrode |
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| CN101274779A (en) * | 2008-05-14 | 2008-10-01 | 华中师范大学 | Nano-scaled materials ZnMn2O4 for lithium storage and preparation thereof |
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| CN101274779A (en) * | 2008-05-14 | 2008-10-01 | 华中师范大学 | Nano-scaled materials ZnMn2O4 for lithium storage and preparation thereof |
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