CN106587179B - The preparation method of hollow ellipsoid shape nickel manganese binary sulfide - Google Patents
The preparation method of hollow ellipsoid shape nickel manganese binary sulfide Download PDFInfo
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- CN106587179B CN106587179B CN201710003156.9A CN201710003156A CN106587179B CN 106587179 B CN106587179 B CN 106587179B CN 201710003156 A CN201710003156 A CN 201710003156A CN 106587179 B CN106587179 B CN 106587179B
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- C01G53/00—Compounds of nickel
- C01G53/11—Sulfides
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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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
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
Abstract
The invention discloses a kind of preparation methods of hollow ellipsoid shape nickel manganese binary sulfide, belong to functional material preparing technical field.This method is first using polymer as surfactant, and using absolute ethyl alcohol as reaction dissolvent, solid elliposoidal nickel manganese binary precursor compound is prepared using chemical precipitation method；Then under the conditions of solvent heat, solid elliposoidal nickel manganese binary precursor compound is further processed, and then obtains hollow ellipsoid shape nickel manganese binary sulfide.This method is simple and practicable, yield is high, at low cost, favorable reproducibility, the hollow ellipsoid shape nickel manganese binary sulfide pattern rule of preparation is uniform, the length of hollow ellipsoid is about 660 nanometers, shell thickness is about 55 nanometers, and spherical shell is made of the particle that many grain sizes are about 20 50 nanometers and rough surface is uneven.
Description
Technical field
The present invention relates to a kind of preparation methods of hollow ellipsoid shape nickel manganese binary sulfide, belong to functional material technology of preparing
Field.
Background technology
Hollow structure material has many advantages, such as that density is low, large specific surface area, makes it in catalysis, sensing, drug controlled release
It has broad application prospects with fields such as electrochemical energy storages, therefore, the controlledly synthesis of hollow structure material has caused crowd
The attention of more researchers.Transient metal sulfide semiconductor is as a kind of electrochemical energy storage material, compared to oxo transition metal
Compound has preferable electric conductivity and thermal stability, thus transient metal sulfide is more promising accumulation energy type electrode material
Material.Delicate structure design is carried out to electrode material can obtain more excellent performance of energy storage device, hollow structure material because
Its peculiar property is concerned.There are multiple electrochemical active metal ions for hollow Polymetallic sulphide, it is possible to provide abundant oxygen
Change reduction reaction, it is even more important that its hollow-core construction can alleviate the volume expansion of material itself in charge and discharge process, breach
The limitation of single metal sulfide material performance is expected to realize the reasonable balance of electrode material performance and cost, therefore, in electrification
It learns energy stores application field and shows excellent application value.In view of the academic research that hollow Polymetallic sulphide material is important
Value, currently with template（Hard template and soft template）Obtain the hollow Polymetallic sulphide material of several classes.However above-mentioned side
Method is not suitable for synthesizing on a large scale but there is certain deficiencies, such as hard template method processing step are cumbersome, in removal hard template
When, the shell structurre of products therefrom also tends to become loose or even destroyed.And utilize its size of the product of soft template method preparation
Size homogeneity is poor, and the forming process of soft template is complicated, it is difficult to realize the extensive preparation of hollow structure material.Utilize masterplate method
The hollow Polymetallic sulphide prepared often is spherical shape, it is contemplated that close relation between the microstructure and properties of material is rich
The existence form of rich hollow Polymetallic sulphide, researches and develops aspherical hollow more metal sulphur that a kind of technological operation is simple, yield is high
The synthetic method of compound has very important realistic meaning.
Invention content
In view of the deficiencies of the prior art, present invention aims at provide the sky that a kind of technological operation is simple, production cost is low
The preparation method of heart elliposoidal nickel manganese binary sulfide.
Purpose to realize the present invention, in the inventive solutions, first by nickel salt, manganese salt and Polymer surfactants
Agent is dissolved in absolute ethyl alcohol, obtains reaction solution, which is carried out water-bath reflow treatment to get to before solid elliposoidal nickel manganese
Drive body compound；Then it again using solid elliposoidal nickel manganese precursor compound as raw material, using absolute ethyl alcohol as reaction dissolvent, adds in
Suitable sulphur source under the conditions of solvent heat, by way of ion exchange, finally prepares the vulcanization of hollow ellipsoid shape nickel manganese binary
Object.
It is as follows：
1）The preparation of solid elliposoidal nickel manganese precursor compound：Nickel salt, manganese salt, polymeric surfactant are dissolved in nothing
In water-ethanol, it is configured to reaction solution；Prepared reaction solution is transferred in flask, the back flow reaction under the conditions of 85-95 DEG C,
After reaction, cooled to room temperature centrifuges product, and washing after dry, that is, obtains solid elliposoidal nickel manganese forerunner
Body compound.A concentration of 0.02-0.028 molL of nickel salt in reaction solution-1, manganese salt and nickel salt molar concentration rate be 0.1-
0.36：1, the mass ratio of polymeric surfactant and nickel salt is 4.2-6.0：1.
2）The preparation of hollow ellipsoid shape nickel manganese binary sulfide：By the above-mentioned solid elliposoidal nickel manganese presoma prepared
Compound is distributed in absolute ethyl alcohol, adds sulphur source, and stirring is moved in reaction kettle, reacted under the conditions of 120-140 DEG C, instead
After answering, cooled to room temperature centrifuges product, washing, after dry, that is, obtains hollow ellipsoid shape nickel manganese binary sulphur
Compound.The mass ratio of wherein solid elliposoidal nickel manganese precursor compound and absolute ethyl alcohol is 0.0016-0.0025：1, it is solid ellipse
Spherical nickel-manganese precursor compound and the mass ratio of sulphur source are 0.45-0.70：1.
In the method for the present invention, the nickel salt is four hydration nickel acetates, and the manganese salt is four hydration manganese acetates, described
Polymeric surfactant is polyvinylpyrrolidone (PVP-K15), polyoxyethylene polyoxypropylene copolymer（P123）Or polyoxy
Ethylene polyoxypropylene ether block copolymers（F127）, the sulphur source is thioacetamide.
Advantage of the present invention and innovative point are as follows：
1. being surfactant as a result of polymer, make nickel manganese precursor compound nanocrystal in the process of growth
In reach well control growth result, this provides good for the anisotropic growth of elliposoidal nickel manganese precursor compound
Guiding role.2. since present invention employs self masterplate methods, operation is simple, at low cost, yield is high, up to more than 75%, and
The hollow ellipsoid shape nickel manganese binary sulfide pattern rule of preparation is uniform, and the length of hollow ellipsoid is about 660 nanometers, and spherical shell is thick
Degree is about 55 nanometers, and spherical shell is made of the particle that many grain sizes are 20-50 nanometers and rough surface is uneven.
Description of the drawings
Fig. 1 is the X-ray powder diffraction collection of the hollow ellipsoid shape nickel manganese binary sulfide of 1 gained of the embodiment of the present invention,
1- nickel manganese binary sulfides of the present invention, 2-Ni in figure3S4, 3- Ni3S2, 4- MnS2。
Fig. 2 is the Energy dispersive x-ray power spectrum of the hollow ellipsoid shape nickel manganese binary sulfide of 1 gained of the embodiment of the present invention
Figure.
Fig. 3 is the solid elliposoidal nickel manganese precursor compound of 1 gained of the embodiment of the present invention（a-c）With hollow ellipsoid shape nickel
Manganese binary sulfide（d-f）Scanning electron microscope and transmission electron microscope picture.
Specific embodiment
It is as follows for embodiment for the present invention is better described, following examples be to the present invention furtherly
It is bright, and do not limit the scope of the invention.
Embodiment 1
1. 0.55 g tetra- is hydrated nickel acetate, 0.20 g tetra- is hydrated manganese acetate and 3.0 g polyvinylpyrrolidones (PVP-
K15 it) is dissolved in 100 mL absolute ethyl alcohols, above-mentioned prepared reaction solution is transferred in round-bottomed flask, in 90 DEG C of conditions next time
Stream 6.0 h of reaction, after reaction, cooled to room temperature centrifuges product, is washed for several times with absolute ethyl alcohol, dry
Afterwards, that is, solid elliposoidal nickel manganese precursor compound is obtained.
2. 1. solid elliposoidal nickel manganese precursor compound that step is prepared is distributed in absolute ethyl alcohol, add
0.1125 g thioacetamides after stirring 30 min, reaction solution are moved in reaction kettle, reacts 12.0 under the conditions of 140 DEG C
H, after reaction, cooled to room temperature centrifuge product, are washed for several times with absolute ethyl alcohol, after dry, that is, obtain empty
Heart elliposoidal nickel manganese binary sulfide.
The X-ray powder diffraction collection of gained hollow ellipsoid shape nickel manganese binary sulfide is as shown in Figure 1.As seen from Figure 1
Diffraction maximum and Ni3S4（Standard card JCPDS: 76-1813）、Ni3S2（Standard card JCPDS: 76-1870）And MnS2（Mark
Quasi- card JCPDS: 76-2051）It is consistent, shows that hollow ellipsoid shape nickel manganese binary sulfide is by Ni3S4、Ni3S2And MnS2
It is formed.Attached drawing 2 is the Energy dispersive x-ray energy spectrum diagram of hollow ellipsoid shape nickel manganese binary sulfide, is as can be seen from the figure divided
Do not come from the elemental characteristic peak of Mn, Ni and S of nickel manganese binary sulfide, the atomic ratio of wherein Mn, Ni and S are about 1: 14:
18.3.Attached drawing 3 is the scanning electron microscope and transmission electron microscope picture of nickel manganese precursor compound and hollow ellipsoid shape nickel manganese binary sulfide,
Nickel manganese precursor compound is understood as elliposoidal by Fig. 3 a and 3b, elliposoidal nickel manganese precursor compound, which can be seen, by Fig. 3 c is
Solid construction.Fig. 3 d-3f are the scanning electron microscope of nickel manganese binary sulfide and transmission electron microscope picture, and nickel manganese is should be clear from from figure
Binary sulfide is the hollow-core construction of elliposoidal, and the length of hollow ellipsoid is about 660 nanometers, and shell thickness is about 55 to receive
Rice, spherical shell is made of the particle that many grain sizes are 20-50 nanometers and rough surface is uneven.
Embodiment 2
1. 0.50 g tetra- is hydrated nickel acetate, 0.25 g tetra- is hydrated 3.0 g polyvinylpyrrolidones (PVP-K15) of manganese acetate
It is dissolved in 100 mL absolute ethyl alcohols, above-mentioned prepared reaction solution is transferred in round-bottomed flask, flow back under the conditions of 95 DEG C anti-
4.0 h are answered, after reaction, cooled to room temperature centrifuges product, is washed for several times with absolute ethyl alcohol, after dry, i.e.,
Obtain solid elliposoidal nickel manganese precursor compound.
2. 1. solid elliposoidal nickel manganese precursor compound that step is prepared is distributed in absolute ethyl alcohol, add
0.1125 g thioacetamides after stirring 60 min, reaction solution are moved in reaction kettle, 6.0 h are reacted under the conditions of 120 DEG C,
After reaction, cooled to room temperature centrifuges product, is washed for several times with absolute ethyl alcohol, after dry, you can obtain with
The identical hollow ellipsoid shape nickel manganese binary sulfide of embodiment 1.
Embodiment 3
1. 0.70 g tetra- is hydrated nickel acetate, 0.05 g tetra- is hydrated manganese acetate and the copolymerization of 3.0 g polyoxyethylene polyoxypropylenes
Object（P123）It is dissolved in 100 mL absolute ethyl alcohols, above-mentioned prepared reaction solution is transferred in round-bottomed flask, in 90 DEG C of conditions
Lower 4.0 h of back flow reaction, after reaction, cooled to room temperature centrifuges product, is washed for several times with absolute ethyl alcohol,
After drying, that is, obtain solid elliposoidal nickel manganese precursor compound.
2. 1. solid elliposoidal nickel manganese precursor compound that step is prepared is distributed in absolute ethyl alcohol, add
0.1125 g thioacetamides after stirring 30 min, reaction solution are moved in reaction kettle, 3.0 h are reacted under the conditions of 140 DEG C,
After reaction, cooled to room temperature centrifuges product, is washed for several times with absolute ethyl alcohol, after dry, you can obtain with
The identical hollow ellipsoid shape nickel manganese binary sulfide of embodiment 1.
Embodiment 4
1. 0.70 g tetra- is hydrated nickel acetate, 0.05 g tetra- is hydrated manganese acetate and 3.0 g polyoxyethylene poly-oxygen propylene aethers are embedding
Section copolymer（F127）It is dissolved in 100 mL absolute ethyl alcohols, above-mentioned prepared reaction solution is transferred in round-bottomed flask, 85
6.0 h of back flow reaction under the conditions of DEG C, after reaction, cooled to room temperature centrifuges product, is washed with absolute ethyl alcohol
For several times, after dry, that is, solid elliposoidal nickel manganese precursor compound is obtained.
2. 1. solid elliposoidal nickel manganese precursor compound that step is prepared is distributed in absolute ethyl alcohol, add
0.1125 g thioacetamides after stirring 30 min, reaction solution are moved in reaction kettle, reacts 12.0 under the conditions of 100 DEG C
H, after reaction, cooled to room temperature centrifuge product, are washed for several times with absolute ethyl alcohol, after dry, you can obtain
Hollow ellipsoid shape nickel manganese binary sulfide same as Example 1.
Claims (1)
1. a kind of preparation method of hollow ellipsoid shape nickel manganese binary sulfide, which is characterized in that realized by following steps：
1）The preparation of solid elliposoidal nickel manganese precursor compound：Nickel salt, manganese salt, polymeric surfactant are dissolved in anhydrous
In ethyl alcohol, it is configured to reaction solution；Prepared reaction solution is transferred in flask, the back flow reaction under the conditions of 85-95 DEG C, instead
After answering, cooled to room temperature centrifuges product, and washing after dry, that is, obtains solid elliposoidal nickel manganese presoma
Compound；A concentration of 0.02-0.028 molL of nickel salt in reaction solution-1, manganese salt and nickel salt molar concentration rate be 0.1-
0.36：1, the mass ratio of polymeric surfactant and nickel salt is 4.2-6.0：1；
2）The preparation of hollow ellipsoid shape nickel manganese binary sulfide：By the above-mentioned solid elliposoidal nickel manganese presoma chemical combination prepared
Object is distributed in absolute ethyl alcohol, adds sulphur source, and stirring is moved in reaction kettle, reacted under the conditions of 120-140 DEG C, reaction knot
Shu Hou, cooled to room temperature centrifuge product, washing, after dry, that is, obtain the vulcanization of hollow ellipsoid shape nickel manganese binary
Object；The mass ratio of wherein solid elliposoidal nickel manganese precursor compound and absolute ethyl alcohol is 0.0016-0.0025：1, solid ellipsoid
Shape nickel manganese precursor compound and the mass ratio of sulphur source are 0.45-0.70：1；
The nickel salt is four hydration nickel acetates, and the manganese salt is hydrated manganese acetates, the polymeric surfactant for four
For polyoxyethylene polyoxypropylene copolymer or polyoxyethylene poly-oxygen propylene aether block copolymer, the sulphur source is thioacetyl
Amine.
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| CN108773859B (en) * | 2018-07-25 | 2021-05-14 | 安徽师范大学 | Vulcanized nano material and preparation method and application thereof |
| CN109280938B (en) * | 2018-09-30 | 2021-02-05 | 陕西科技大学 | V-doped Ni in flower ball shape3S2NF self-supporting electrode material and preparation method thereof |
| CN109607625B (en) * | 2019-02-15 | 2021-01-15 | 安阳师范学院 | Core-shell nickel-cobalt-manganese ternary sulfide hollow spherical electrode material and preparation method thereof |
| CN115084480B (en) * | 2022-07-19 | 2023-09-01 | 成都大学 | Metal oxide-metal sulfide heterojunction material and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102824912A (en) * | 2012-09-05 | 2012-12-19 | 中国石油天然气集团公司 | High-specific surface area mesoporous nickel oxide hydrogenation catalyst and preparation method thereof |
| CN104492460A (en) * | 2014-12-11 | 2015-04-08 | 浙江大学 | Metallic oxide/metal sulfide hollow nanospheres as well as preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102824912A (en) * | 2012-09-05 | 2012-12-19 | 中国石油天然气集团公司 | High-specific surface area mesoporous nickel oxide hydrogenation catalyst and preparation method thereof |
| CN104492460A (en) * | 2014-12-11 | 2015-04-08 | 浙江大学 | Metallic oxide/metal sulfide hollow nanospheres as well as preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| Comparative investigation of hollow mesoporous NiCo2S4 ellipsoids with enhanced pseudo-capacitances towards high-performance asymmetric supercapacitors;Linrui Hou等;《Electrochimica Acta》;20160809;76–84页 * |
| Formation of NixCo3-xS4 Hollow Nanoprisms with Enhanced Pseudocapacitive Properties;Le Yu等;《Angew. Chem. Int. Ed.》;20140303;Supporting Information S1页Experimental Section * |
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