CN108502934A - Nanometer sheet sulfide hollow ball and its preparation method and application - Google Patents
Nanometer sheet sulfide hollow ball and its preparation method and application Download PDFInfo
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention discloses a kind of nanometer sheet sulfide hollow balls and its preparation method and application, the nanometer sheet sulfide hollow ball includes hollow ball and multi-disc nanometer sheet, multi-disc nanometer sheet is distributed in the surface of hollow ball, and the average diameter of hollow ball is 300 400nm, and nanometer sheet meets:Average length is 25 40nm, and average thickness is 0.5 1nm;The ingredient of nanometer sheet sulfide hollow ball is at least one of cobalt sulfide, nickel sulfide and cobalt sulfide nickel.The nanometer sheet sulfide hollow ball has excellent chemical property, and then can be used as the electrode material of lithium battery, while the preparation method has the advantages that process is simple and raw material is easy to get.
Description
Technical field
The present invention relates to nano materials, and in particular, to a kind of nanometer sheet sulfide hollow ball and preparation method thereof and answers
With.
Background technology
Increasingly increase with social energy shortage and the mankind to energy demand, traditional energy is in reserves, energy efficiency, ring
Border is polluted and the constraint of cost etc. is increasingly prominent.Therefore some high-energy of active demand, the energy storage material of high power density
Energy crisis is solved, lithium ion battery comes into being as energy storage device.Lithium ion battery has voltage height, small, electricity
The advantages that capacity is big and pollution-free;But in lithium ion battery, graphite negative electrodes material reaches the theoretical capacity of 372mAh/g
Limiting value seriously constrains the development of power battery.
Sulfide has many advantages, such as higher theoretical capacity, low cost, superior security performance, is easy to be made;In cathode
There is good application prospect as high power capacity high rate capability material in material.But sulfide material has in charge and discharge
Journey poorly conductive, coulombic efficiency is low for the first time, and material structure is unstable, easily smashes and reunites, so as to cause the rapid of battery capacity
The shortcomings of decaying.
Invention content
The object of the present invention is to provide a kind of nanometer sheet sulfide hollow ball and its preparation method and application, the nanometer sheet sulphur
Compound hollow ball has excellent chemical property, and then can be used as the electrode material of lithium battery, while the preparation side
Method has the advantages that process is simple and raw material is easy to get.
To achieve the goals above, the present invention provides a kind of nanometer sheet sulfide hollow ball, the nanometer sheet sulfide is empty
Bulbus cordis includes hollow ball and multi-disc nanometer sheet, and multi-disc nanometer sheet is distributed in the surface of hollow ball, and being averaged for hollow ball is straight
Diameter is 300-400nm, and nanometer sheet meets:Average length is 25-40nm, average thickness 0.5-1nm;Nanometer sheet sulfide hollow
The ingredient of ball is at least one of cobalt sulfide, nickel sulfide and cobalt sulfide nickel.
The present invention also provides a kind of preparation methods of above-mentioned nanometer sheet sulfide hollow ball, which is characterized in for preparing
Method is:
1) source metal, sulphur source, silica spheres, urea and water are subjected to haptoreaction, then post-processed so that black is made
Precipitation;
2) black precipitate is heat-treated so that black powder is made;
Wherein, source metal is cobalt source and/or nickel source.
Invention further provides a kind of above-mentioned nanometer sheet sulfide hollow ball answering in chargeable lithium ion battery
With.
In the above-mentioned technical solutions, the present invention is using silica spheres as template, using sulphur source as complexant, in aqueous systems
Middle progress pyroreaction is to be made the nanometer sheet sulfide hollow containing at least one of cobalt sulfide, nickel sulfide and cobalt sulfide nickel
The grain size of ball, the hollow ball is 300-400nm.Learn that the nano material has excellent electrochemistry by Electrochemical Detection
Can, and then can be used as the electrode material of lithium battery.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Attached drawing is to be used to provide further understanding of the present invention, an and part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the scanning electron microscope (SEM) photograph for detecting A1 in example 1;
Fig. 2 is the transmission electron microscope picture for detecting A6 in example 1;
Fig. 3 is the scanning electron microscope (SEM) photograph for detecting A7 in example 1;
Fig. 4 is the transmission electron microscope picture for detecting A1 in example 1;
Fig. 5 is the scanning electron microscope (SEM) photograph for detecting A6 in example 1;
Fig. 6 is the transmission electron microscope picture for detecting A7 in example 1;
Fig. 7 is the XRD diagram for detecting A1 in example 1;
Fig. 8 is the XRD diagram for detecting A6 in example 1;
Fig. 9 is the XRD diagram for detecting A7 in example 1;
Figure 10 is the charge and discharge cycles curve graph for detecting A1 in example 1.
Figure 11 is the charge and discharge cycles curve graph for detecting A6 in example 1.
Figure 12 is the charge and discharge cycles curve graph for detecting A7 in example 1.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of nanometer sheet sulfide hollow ball, the nanometer sheet sulfide hollow ball include hollow ball and
Multi-disc nanometer sheet, multi-disc nanometer sheet are distributed in the surface of hollow ball, and the average diameter of hollow ball is 300-400nm, nanometer
Piece meets:Average length is 25-40nm, average thickness 0.5-1nm;The ingredient of nanometer sheet sulfide hollow ball be cobalt sulfide,
At least one of nickel sulfide and cobalt sulfide nickel.
In the present invention, the concrete structure of nanometer sheet can select in a wide range, but in order to enable the nanometer sheet
Sulfide hollow ball has superior chemical property, it is preferable that the distance between adjacent nano piece is 1-2nm.
The present invention also provides a kind of preparation methods of above-mentioned nanometer sheet sulfide hollow ball, which is characterized in for preparing
Method is:
1) source metal, sulphur source, silica spheres, urea and water are subjected to haptoreaction, then post-processed so that black is made
Precipitation;
2) black precipitate is heat-treated so that black powder is made;
Wherein, source metal is cobalt source and/or nickel source.
In the present invention, the dosage of each material can select in a wide range, but better in order to make product have
Yield and chemical property, it is preferable that in step 1), source metal, sulphur source, urea, silica spheres and water amount ratio
For 1-3mmol:3-10mmol:2.5-8mmol:0.04-0.12g:40-45mL.
In the case of source metal is cobalt source and nickel source, the molar ratio of cobalt source and nickel source can also be selected in a wide range
It selects, but in order to make nanometer sheet sulfide hollow ball have superior chemical property, it is preferable that mole of cobalt source and nickel source
Than for 1-3:0.3-1.
In the step 1) of the present invention, catalytic condition can select in a wide range, but in order to make product
With superior yield and chemical property, it is preferable that in step 1), haptoreaction meets the following conditions:Reaction temperature
It is 150-200 DEG C, reaction time 12-24h.
In the step 1) of the present invention, the specific type of sulphur source can select in a wide range, but in order to make product have
There is superior yield, it is preferable that in step 1), sulphur source is thiocarbamide and/or thioacetamide.
In the step 1) of the present invention, the specific type of cobalt source can select in a wide range, but in order to make product have
It is Cobalt monosulfate heptahydrate and/or acetylacetone cobalt to have superior yield, cobalt source.
In the step 1) of the present invention, the specific type of nickel source can select in a wide range, but in order to make product have
It is at least one of six hydration nickel sulfate, nickel nitrate and nickel acetate to have superior yield, nickel source.
In the step 1) of the present invention, in order to be extracted in black precipitate autoreaction system, it may be used in this field
Various ways, such as centrifugation, decompression filter mode, but in order to farthest reduce the loss of black precipitate, it is preferable that
In step 1), post-processes and be:System after reaction is stood, suction filtration is then carried out and takes filter cake;Wherein, standing
Time is 6-24h.
In the step 2) of the present invention, the various ways in this field may be used in heat treatment, but in order to enable obtained
Nanometer sheet sulfide hollow ball has superior chemical property, it is preferable that in step 2), it is heat-treated to be dried,
Dry temperature is 50-80 DEG C, and the dry time is 12-24h.
In the step 1) of the present invention, the average grain diameter of silica spheres can select in a wide range, but in order to make
Obtaining nanometer sheet sulfide hollow ball obtained has superior chemical property, it is preferable that in step 1), silica spheres
Average grain diameter be 300-400nm.
Invention further provides a kind of above-mentioned nanometer sheet sulfide hollow ball answering in chargeable lithium ion battery
With.
The present invention will be described in detail by way of examples below.In embodiment, thiocarbamide and cobaltous sulfate are traditional Chinese medicines collection
The commercially available product of chemical reagent Co., Ltd of group.
Preparation example 1
SiO2The preparation of ball:
In entitled " Tailoring the Void Size of Iron Oxide@Carbon Yolk-Shell
It is improved preparation on the basis of Structure for Optimized Lithium Storage " methods recorded in the literature
And obtain, specially:6ml tetraethyl orthosilicates (TEOS) are instilled into 160mL isopropanols and 40mL distilled water (H first2O stirring 15 in)
Minute, then by 6mL NH3·H2O is added in above-mentioned clear solution stir about 10 minutes until clear solution gradually becomes breast
White, and continue stirring 24 hours at 25 DEG C;White precipitate is finally collected by centrifugation, number is washed with deionized water and absolute ethyl alcohol
It is secondary, then it is dried overnight in vacuum drying oven at 60 DEG C.
Embodiment 1
1) by the CoSO of 3mmol4·7H2The thiocarbamide of O and 10mmol is dissolved in the aqueous solution of 20mL, separately by 0.120g's
SiO2Ball (average grain diameter 350nm) is uniformly scattered in the aqueous solution of urea (content of urea is 8mmol) of 20mL, then
After the two again continual stirring, reacted 24 hours at 150 DEG C;Then system is subjected to standing 12h, suction filtration takes filter
Cake obtains black precipitate;
2) black precipitate is dried to (dry temperature is 70 DEG C, and the dry time is 20h) in vacuum drying chamber to perseverance
Weight, obtains black powder, i.e. nanometer sheet sulfide hollow ball A1.
Embodiment 2
It carries out that nanometer sheet sulfide hollow ball A2 is made according to the method for embodiment 1, the difference is that CoSO4·7H2O's
Dosage is 1mmol, and the dosage of thiocarbamide is 3mmol, and the dosage of urea is 2.5mmol, SiO2The dosage of ball is 0.04g.
Embodiment 3
It carries out that nanometer sheet sulfide hollow ball A3 is made according to the method for embodiment 1, the difference is that CoSO4·7H2O's
Dosage is 2mmol, and the dosage of thiocarbamide is 6mmol, and the dosage of urea is 5mmol, SiO2The dosage of ball is 0.08g.
Embodiment 4
It carries out that nanometer sheet sulfide hollow ball A4 is made according to the method for embodiment 1, the difference is that reaction temperature is
200 DEG C, reaction time 12h.
Embodiment 5
It carries out that nanometer sheet sulfide hollow ball A5 is made according to the method for embodiment 1, the difference is that reaction temperature is
180 DEG C, reaction time 18h.
Embodiment 6
It carries out that nanometer sheet sulfide hollow ball A6 is made according to the method for embodiment 1, the difference is that by 3mmol's
CoSO4·7H2O is changed to the nickel sulfate of 3mmol, and thiocarbamide is changed to thioacetamide.
Embodiment 7
It carries out that nanometer sheet sulfide hollow ball A7 is made according to the method for embodiment 1, the difference is that by 3mmol's
CoSO4·7H2O is changed to the nickel acetate of 1.5mmol and the CoSO of 1.5mmol4·7H2O。
Detect example 1
1) Electronic Speculum detection is scanned to A1, A6 and A7 by Hitachi S-4800, the result is shown in Figure 1, Fig. 3 and Fig. 5 can
Know, the pattern of A1, A6 and A7 are uniform and surface forms for nano flake.
2) transmission electron microscope detection is carried out to A1, A6 and A7 by FEI TECNAI-G2, as a result sees Fig. 2, Fig. 4 and Fig. 6, it can
Know, the main body of A1, A6 and A7 have apparent hollow ball structure.
To sum up by retouching Electronic Speculum and transmission electron microscope detection it is found that nanometer sheet sulfide hollow ball includes hollow ball and multi-disc
Nanometer sheet, multi-disc nanometer sheet are distributed in the surface of hollow ball, and the average diameter of hollow ball is 300-400nm, and nanometer sheet is full
Foot:Average length is 25-40nm, average thickness 0.5-1nm, and the distance between adjacent nano piece is 1-2nm.
3) X-ray diffraction spectra is carried out to A1, A6 and A7 by D8Advance X-ray power diffactometer
Detection, is as a result shown in Fig. 7, Fig. 8 and Fig. 9, is compareed with standard card respectively it is found that A1 is CoS, A6 NiS, A7 NiCo2S4。
4) pass through Mikrouna, Super (1220/750/900) glove box (H2O<0.1ppm, O2<1ppm) to A1, A6 and
A7 is 100A.g in current density-1When pass through multiple cycle charge discharge electro-detection, the result is shown in Figure 10, Figure 11 and Figure 12, as seen from the figure,
The capacity of charge and discharge 50-60 rear A1, A6 and A7 still are able to keep stablizing, and illustrate that the material has good cyclical stability.
Same detection is also carried out to A2-A5 by the above method, testing result is substantially consistent with A1.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (10)
1. a kind of nanometer sheet sulfide hollow ball, which is characterized in that the nanometer sheet sulfide hollow ball include hollow ball and
Multi-disc nanometer sheet, the multi-disc nanometer sheet are distributed in the surface of the hollow ball, and the average diameter of the hollow ball is
300-400nm, the nanometer sheet meet:Average length is 25-40nm, average thickness 0.5-1nm;The nanometer sheet sulfide
The ingredient of hollow ball is at least one of cobalt sulfide, nickel sulfide and cobalt sulfide nickel.
2. nanometer sheet sulfide hollow ball according to claim 1, wherein the distance between described nanometer sheet is 1-
2nm。
3. a kind of preparation method of nanometer sheet sulfide hollow ball as claimed in claim 1 or 2, which is characterized in that the system
Preparation Method is:
1) source metal, sulphur source, silica spheres, urea and water are subjected to haptoreaction, then post-processed so that black precipitate is made;
2) black precipitate is heat-treated so that black powder is made;
Wherein, the source metal is cobalt source and/or nickel source.
4. preparation method according to claim 1, wherein in step 1), the source metal, sulphur source, urea, titanium dioxide
The amount ratio of silicon ball and water is 1-3mmol:3-10mmol:2.5-8mmol:0.04-0.120g:40-45mL.
5. preparation method according to claim 1, wherein in step 1), the haptoreaction meets the following conditions:Instead
It is 150-200 DEG C to answer temperature, reaction time 12-24h.
6. according to the preparation method described in any one of claim 3-5, wherein in step 1), the sulphur source is thiocarbamide
And/or thioacetamide;Cobalt source is Cobalt monosulfate heptahydrate and/or acetylacetone cobalt;Nickel source be six hydration nickel sulfate, nickel nitrate and
At least one of nickel acetate.
7. according to the preparation method described in any one of claim 3-5, wherein in step 1), the post-processing is:It will
System after reaction is stood, and is then carried out suction filtration and is taken filter cake;Wherein, the time of standing is 6-24h.
8. according to the preparation method described in any one of claim 3-5, wherein in step 2), the heat treatment is dry
Dry processing, dry temperature are 50-80 DEG C, and the dry time is 12-24h.
9. preparation method according to claim 1, wherein in step 1), the average grain diameter of the silica spheres is
300-400nm。
10. a kind of application of nanometer sheet sulfide hollow ball as claimed in claim 1 or 2 in chargeable lithium ion battery.
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109133191A (en) * | 2018-09-17 | 2019-01-04 | 陕西科技大学 | A kind of three-dimensional pure phase cobalt sulfide nanosphere anode material of lithium-ion battery and preparation method thereof |
CN110330058A (en) * | 2019-06-20 | 2019-10-15 | 东华大学 | A kind of supercapacitor NixCoySzElectrode material and its preparation and application |
CN110467225A (en) * | 2019-09-03 | 2019-11-19 | 大连理工大学 | A kind of preparation method of the hollow sandwich microballoon of monodisperse cobalt sulfide |
CN111599996A (en) * | 2020-05-07 | 2020-08-28 | 武汉理工大学 | NiS2@CoS2@ C graded hollow nanosphere material and preparation method and application thereof |
CN111740088A (en) * | 2020-07-02 | 2020-10-02 | 莱西市星脉先进材料技术中心 | Preparation method of lithium ion battery cathode and application of lithium ion battery cathode in lithium ion battery |
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-
2018
- 2018-03-06 CN CN201810181486.1A patent/CN108502934A/en active Pending
Non-Patent Citations (1)
Title |
---|
TING ZHU等: "Hierarchical nickel sulfide hollow spheres for high performance supercapacitors", 《RSC ADVANCES》 * |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
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CN109133191A (en) * | 2018-09-17 | 2019-01-04 | 陕西科技大学 | A kind of three-dimensional pure phase cobalt sulfide nanosphere anode material of lithium-ion battery and preparation method thereof |
CN109133191B (en) * | 2018-09-17 | 2020-09-29 | 陕西科技大学 | Three-dimensional pure-phase cobalt sulfide nano microsphere sodium ion battery cathode material and preparation method thereof |
US11123717B2 (en) * | 2019-05-30 | 2021-09-21 | Korea University Research And Business Foundation | Catalyst for oxygen reduction reaction and oxygen evolution reaction and method for manufacturing of the same |
CN110330058A (en) * | 2019-06-20 | 2019-10-15 | 东华大学 | A kind of supercapacitor NixCoySzElectrode material and its preparation and application |
CN110467225A (en) * | 2019-09-03 | 2019-11-19 | 大连理工大学 | A kind of preparation method of the hollow sandwich microballoon of monodisperse cobalt sulfide |
CN111599996A (en) * | 2020-05-07 | 2020-08-28 | 武汉理工大学 | NiS2@CoS2@ C graded hollow nanosphere material and preparation method and application thereof |
CN111599996B (en) * | 2020-05-07 | 2021-08-24 | 武汉理工大学 | NiS2@CoS2@ C graded hollow nanosphere material and preparation method and application thereof |
CN111740088A (en) * | 2020-07-02 | 2020-10-02 | 莱西市星脉先进材料技术中心 | Preparation method of lithium ion battery cathode and application of lithium ion battery cathode in lithium ion battery |
CN112563471A (en) * | 2020-12-10 | 2021-03-26 | 潍坊科技学院 | Preparation method of cobalt disulfide/carbon hollow nanoflower composite material and prepared composite material |
CN114497541A (en) * | 2022-01-27 | 2022-05-13 | 广东工业大学 | Preparation and application of hollow nickel disulfide ball |
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