CN109904410A - One type graphene carbon coats nickelous selenide composite material and preparation method and application - Google Patents
One type graphene carbon coats nickelous selenide composite material and preparation method and application Download PDFInfo
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- CN109904410A CN109904410A CN201910058606.3A CN201910058606A CN109904410A CN 109904410 A CN109904410 A CN 109904410A CN 201910058606 A CN201910058606 A CN 201910058606A CN 109904410 A CN109904410 A CN 109904410A
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Abstract
The invention discloses a type graphene carbons to coat nickelous selenide composite material and preparation method, this method prepares carbon coating selenizing nickel composite material using one-step calcination method, dicyclopentadienyl nickel and selenium powder are put into reactor after mixing, temperature is heated to 600~700 DEG C of calcinings, reaction time be 5~15 hours to get arrive carbon coating selenizing nickel composite material.The synthesis of the method for the present invention one-step calcination, easy to operate, reaction condition is easily-controllable, is more suitable for industrialized production.Class graphene carbon obtained by nickel source and selenium source using the method for the present invention coats selenizing nickel composite material, and by-product is few, product yield high.The composite material of the method for the present invention preparation is applied to cell positive material, and battery capacity conservation rate can be made up to 92%.
Description
Technical field
The invention belongs to field of compound material, be specifically related to type graphene carbon cladding selenizing nickel composite material and its
Preparation method and application.
Background technique
Nickelous selenide (NiSe) is as a kind of important semiconductor, it is considered to be a kind of up-and-coming serial solar energy electricity
The material in pond and detection visible radiation.It is also considered to be a kind of toxicity it is smaller, to the more responsible alternative materials of environment, can be with
Substitute relevant narrow band gap lead or cadmium base semiconductor.So far, its bulk material is had focused largely on to the research of NiSe synthesis
On, such as solid-state synthesis, molecular precursor, elemental direct reaction, ultrasound synthesis, mechanical alloy (MA).
In recent years, the work of some initiatives has also been carried out in terms of NiSe nanostructure.For example, Sobhani et al. base
NiSe nanoparticle has been synthesized in the hydro-thermal method of CTAB.Yu et al. is prepared for uniform echinoid by ternary mixed solvent method
NiSe nanofiber, and the production as economical no Pt catalyst for electrochemical hydrogen.It is desirable that one kind can be found
Preparation method is simple, the method for the easily-controllable preparation selenizing nickel material of reaction condition.
Summary of the invention
In order to overcome the problems, such as that complicated, severe reaction conditions, the present invention provide the above-mentioned prior art using solvent method step
A kind of simple one-step method, reaction condition be easily-controllable, can industrialized production preparation class graphene carbon cladding selenizing nickel composite material and its
Preparation method, prepared material are applied to electrochemical field cell positive material.
Type graphene carbon of the present invention cladding selenizing nickel composite material the preparation method is as follows:
Dicyclopentadienyl nickel and selenium powder are put into reactor after mixing, temperature is heated to 600~700 DEG C of calcinings, reaction time
Selenizing nickel composite material was coated for 5~15 hours to get to class graphene carbon.
Preferably, the mass ratio of the dicyclopentadienyl nickel and selenium powder is 2~3:1.
Preferably, the reactor is stainless steel autoclave.
Preferably, the temperature is 700 DEG C, and the reaction time is 10 hours.
The present invention provides an a kind of type graphene carbons by above method preparation to coat selenizing nickel composite material.
The present invention provides a kind of type graphene carbon cladding selenizing nickel composite materials by above method preparation in electricity
Application in the positive electrode of pond, the active material as cell positive material use.
The beneficial effects of the present invention are: one-step method reaction preparation class graphene carbon coats selenizing nickel composite material, there is system
Preparation Method is simple, and the easily-controllable advantage of reaction condition is more suitable for industrialized production.Obtained by nickel source and selenium source using this method
Class graphene carbon coat selenizing nickel composite material, by-product is few, product yield high；When applied to sode cell positive electrode, hold
Amount conservation rate reaches 92%.
Detailed description of the invention
Fig. 1 is the X-ray powder diffraction spectrogram of class graphene carbon cladding selenizing nickel composite material prepared by embodiment 1.
Fig. 2 is the field emission scanning electron microscope photo of class graphene carbon cladding selenizing nickel composite material prepared by embodiment 1.
Fig. 3 is the transmission electron microscope photo of class graphene carbon cladding selenizing nickel composite material prepared by embodiment 1.
Fig. 4 is the hot weight curve of class graphene carbon cladding selenizing nickel composite material prepared by embodiment 1.
Fig. 5 is the X-ray powder diffraction spectrogram of class graphene carbon cladding selenizing nickel composite material prepared by embodiment 2.
Fig. 6 is the electron scanning micrograph of class graphene carbon cladding selenizing nickel composite material prepared by embodiment 2.
Fig. 7 is the X-ray powder diffraction spectrogram of class graphene carbon cladding selenizing nickel composite material prepared by embodiment 3.
Fig. 8 is the electron scanning micrograph of class graphene carbon cladding selenizing nickel composite material prepared by embodiment 3.
Fig. 9 is sode cell in 200mA g-1Cycle performance figure under current density.
Figure 10 is that the class graphene carbon cladding selenizing nickel composite material prepared by embodiment 1 does sode cell positive electrode activity
Cycle performance figure when substance under different current densities.
Specific embodiment
The present invention is further described below in conjunction with drawings and the specific embodiments, but does not limit the scope of the invention.
The present invention carries out object phase point to powder using Japan Rigaku D/max- γ A type X-ray powder diffraction (XRD) instrument
Analysis,Graphite monochromator, pipe pressure and electric current are respectively 40kV and 40mA, and 10.0 degree every point of scanning speed
Clock.
The present invention uses FESEM, the pattern of JEOL JSM-6300F type field emission microscopy observation carbon coating nickelous selenide.
The present invention uses the pattern of the JEM-2010 type transmission electron microscope observing carbon coating nickelous selenide of JEOL company, Japan.
The present invention use U.S. TG instrument company SDTQ600 type thermogravimetric analysis tester, under nitrogen protection with 10 DEG C/
The heating rate of min rises to 800 DEG C from room temperature.
Embodiment 1
0.374g dicyclopentadienyl nickel and 0.16g selenium powder are added in one 20 milliliters of stainless steel autoclave, seal and be placed on
It is capable of in the crucible furnace of temperature programming, then furnace temperature is tieed up with being raised to 700 DEG C from room temperature in the rate of 10 DEG C/min at 700 DEG C
Room temperature is naturally cooled to after holding 10 hours, the black deposit being sticked on kettle wall inner surface is collected with distilled water and anhydrous
Ethanol washing is multiple, and class graphene carbon cladding nickelous selenide nano material is obtained after filtering.Product type graphene carbon coats selenizing
The yield of nickel is 90%.
Place the product in drying 4 hours in 50 DEG C of vacuum ovens, finally collect for characterizing.Its pattern and characteristic
Such as Fig. 1~4.
As seen from Figure 1,2 θ at 10~80 ° have all diffraction maximums in X-ray diffraction spectrogram, and wherein diffracted intensity is high and peak shape
Sharply, all diffraction maximums in figure can be demarcated as class graphene carbon cladding nickelous selenide, other impurity peaks do not occur, it was demonstrated that
Obtained sample is pure class graphene carbon cladding nickelous selenide.
From Figure 2 it can be seen that the thickness of the class graphene carbon cladding nickelous selenide composite material granular using the method for the present invention preparation
For 50nm.
As seen from Figure 3, being averaged using the class graphene carbon cladding nickelous selenide composite material granular of the method for the present invention preparation
Having a size of 200nm.
As shown in Figure 4, class graphene carbon cladding nickelous selenide starts to be oxidized to nickel sesquioxide, dioxy at 400 degree or more
Change selenium and carbon dioxide, quality remains unchanged after 600 degree, can calculate carbon in product carbon coating nickelous selenide according to Fig. 4 and contain
Amount is 36.8%.
Embodiment 2
0.374g dicyclopentadienyl nickel and 0.16g selenium powder are added in one 20 milliliters of stainless steel autoclave, seal and be placed on
It is capable of in the crucible furnace of temperature programming, then furnace temperature is tieed up with being raised to 600 DEG C from room temperature in the rate of 10 DEG C/min at 600 DEG C
Room temperature is naturally cooled to after holding 5 hours, the black deposit being sticked on kettle wall inner surface is collected with distilled water and anhydrous
Ethanol washing is multiple, and class graphene carbon cladding nickelous selenide nano material is obtained after filtering.Product type graphene carbon coats selenizing
The yield of nickel is 80%.
Place the product in drying 4 hours in 50 DEG C of vacuum ovens, finally collect for characterizing.Its pattern and feature
As shown in Fig. 5~6.
As seen from Figure 5,2 θ at 10~80 ° have all diffraction maximums in X-ray diffraction spectrogram, and wherein diffracted intensity is high and peak shape
Sharply, all diffraction maximums in figure can be demarcated as class graphene carbon cladding nickelous selenide, other impurity peaks do not occur, it was demonstrated that
Obtained sample is pure class graphene carbon cladding nickelous selenide.
It will be appreciated from fig. 6 that the thickness of the class graphene carbon cladding nickelous selenide composite material granular using the method for the present invention preparation
For 60nm.
Embodiment 3
0.374g dicyclopentadienyl nickel and 0.16g selenium powder are added in one 20 milliliters of stainless steel autoclave, are put into after sealing
It is capable of in the crucible furnace of temperature programming, then furnace temperature is tieed up with being raised to 650 DEG C from room temperature in the rate of 10 DEG C/min at 650 DEG C
Room temperature is naturally cooled to after holding 15 hours, the black deposit being sticked on kettle wall inner surface is collected with distilled water and anhydrous
Ethanol washing is multiple, and class graphene carbon cladding nickelous selenide nano material is obtained after filtering.The receipts of product type graphene nickelous selenide
Rate is 85%.
Place the product in drying 4 hours in 50 DEG C of vacuum ovens, finally collect for characterizing.Its pattern and feature
As shown in Fig. 7~8.
As seen from Figure 7,2 θ at 10~80 ° have all diffraction maximums in X-ray diffraction spectrogram, and wherein diffracted intensity is high and peak shape
Sharply, all diffraction maximums in figure can be demarcated as class graphene carbon cladding nickelous selenide, other impurity peaks do not occur, it was demonstrated that
Obtained sample is pure class graphene carbon cladding nickelous selenide.
As shown in Figure 8, the thickness of the class graphene carbon cladding nickelous selenide composite material granular obtained using the method for the present invention
For 75nm.
Embodiment 4~9
Embodiment 4~9 is identical as the preparation method of embodiment 1, but raw material dosage and reaction condition are different, are specifically shown in Table 1.
1 embodiment of table, 4~9 raw material dosage and reaction condition
Following comparative example is prepared according to the method for the present invention through one-step calcination, the dosage of nickel source and selenium source in comparative example according to
The mole of dicyclopentadienyl nickel and selenium weighs in embodiment 1.
Comparative example 1
0.29g nickel oxalate and 0.2248g selenium dioxide are added in one 20 milliliters of stainless steel autoclave, after sealing
It is placed in the crucible furnace for capableing of temperature programming, furnace temperature is to be raised to 700 DEG C from room temperature in the rate of 10 DEG C/min, then at 700 DEG C
It is lower maintain 10 hours after naturally cool to room temperature, the black deposit being sticked on kettle wall inner surface is collected with distilled water and
Dehydrated alcohol washing repeatedly, obtains carbon coating nickelous selenide nano material after filtering.
The yield of product carbon coating nickelous selenide is 67%.
Comparative example 2
0.493g nickel acetate and 0.29g selenium disulfide are added in one 20 milliliters of stainless steel autoclave, after sealing
It is placed in the crucible furnace for capableing of temperature programming, furnace temperature is to be raised to 700 DEG C from room temperature in the rate of 10 DEG C/min, then at 700 DEG C
It is lower maintain 10 hours after naturally cool to room temperature, the black deposit being sticked on kettle wall inner surface is collected with distilled water and
Dehydrated alcohol washing repeatedly, obtains carbon coating nickelous selenide nano material after filtering.
The yield of product carbon coating nickelous selenide is 65%.
Application examples
The cladding selenizing nickel composite material of class graphene carbon made from embodiment 1 is used as sode cell positive active material, with
Lithium piece makees cathode, and glass fibre membrane makees diaphragm, and the electrolyte of use is dissolved in diethylene glycol dimethyl ether by NaPF6 to be made,
NaPF6 concentration is 0.6M in electrolyte, is then assembled into CR2016 type battery and is tested.
Performance map is as shown in Fig. 9~10.As shown in Figure 9, sode cell is in 200mA g-1First circle specific capacity exists under current density
260mAh g-1, specific capacity is 325mAh g after 100 circulations-1, the attenuation rate of specific capacity is 0.25%.As shown in Figure 10,
When the class graphene carbon cladding selenizing nickel composite material prepared by embodiment 1 does sode cell active substances in cathode materials, sode cell
In different current density 100mA g-1、200mA g-1、500mA g-1、1A g-1、2A g-1Under it is each circulation 10 times after, sode cell
Specific capacity is 300mAh g-1,325mAh g-1,275mAh g-1,250mAh g-1,225mAh g-1, when current density is returned to
200mA g-1When, the specific capacity of sode cell can return to 300mAh g again-1, capacity retention ratio 92%.
Taking the above-mentioned ideal embodiment according to the present invention as inspiration, through the above description, relevant staff is complete
Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' entirely.The technology of this invention
Property range is not limited to the contents of the specification, it is necessary to which the technical scope thereof is determined according to the scope of the claim.
Claims (7)
1. the preparation method of type graphene carbon cladding selenizing nickel composite material, which is characterized in that utilize dicyclopentadienyl nickel and selenium powder
For raw material, selenizing nickel composite material is coated through calcining preparation class graphene carbon.
2. the preparation method of type graphene carbon cladding selenizing nickel composite material according to claim 1, feature exist
In, comprising the following steps: dicyclopentadienyl nickel and selenium powder are put into reactor after mixing and are calcined, temperature is heated to 600~700
DEG C, the reaction time is 5~15 hours, and class graphene carbon cladding selenizing nickel composite material is prepared in one-step method.
3. the preparation method of type graphene carbon cladding selenizing nickel composite material according to claim 1 or 2, feature
It is, the mass ratio of the dicyclopentadienyl nickel and selenium powder is 2~3:1.
4. the preparation method of type graphene carbon cladding selenizing nickel composite material according to claim 2, feature exist
In the reactor is stainless steel autoclave.
5. the preparation method of type graphene carbon cladding selenizing nickel composite material according to claim 2, feature exist
In the temperature is 700 DEG C, and the reaction time is 10 hours.
6. the class graphene carbon cladding nickelous selenide composite wood that a kind of any one according to claim 1~5 preparation method obtains
Material.
7. the class graphene carbon cladding nickelous selenide composite wood that a kind of any one according to claim 1~5 preparation method obtains
Material is applied to cell positive material.
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| CN201910058606.3A CN109904410B (en) | 2019-01-22 | 2019-01-22 | Graphene-like carbon-coated nickel selenide composite material and preparation method and application thereof |
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| CN201910058606.3A CN109904410B (en) | 2019-01-22 | 2019-01-22 | Graphene-like carbon-coated nickel selenide composite material and preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111463418A (en) * | 2020-04-24 | 2020-07-28 | 江苏科技大学 | Carbon-coated nickel selenide ultrathin nanosheet composite material and preparation method thereof |
| CN113470983A (en) * | 2020-03-30 | 2021-10-01 | 天津大学 | Nickel selenide-nickelous diselenide nanorod composite material and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105562005A (en) * | 2016-02-29 | 2016-05-11 | 复旦大学 | Nano composite material with carbon-coated Ni nano crystal particles loaded on graphene and preparation method of nano composite material |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105562005A (en) * | 2016-02-29 | 2016-05-11 | 复旦大学 | Nano composite material with carbon-coated Ni nano crystal particles loaded on graphene and preparation method of nano composite material |
Non-Patent Citations (1)
| Title |
|---|
| BALAKRISHNAN KIRUBASANKAR等: "In situ grown nickel selenide on graphene nanohybrid electrodes for high energy density asymmetric supercapacitors", 《NANOSCALE》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113470983A (en) * | 2020-03-30 | 2021-10-01 | 天津大学 | Nickel selenide-nickelous diselenide nanorod composite material and preparation method and application thereof |
| CN111463418A (en) * | 2020-04-24 | 2020-07-28 | 江苏科技大学 | Carbon-coated nickel selenide ultrathin nanosheet composite material and preparation method thereof |
| CN111463418B (en) * | 2020-04-24 | 2022-12-27 | 江苏科技大学 | Carbon-coated nickel selenide ultrathin nanosheet composite material and preparation method thereof |
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