CN108232142A - A kind of zinc sulphide/graphene composite material, preparation method and application - Google Patents
A kind of zinc sulphide/graphene composite material, preparation method and application Download PDFInfo
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- CN108232142A CN108232142A CN201711402881.XA CN201711402881A CN108232142A CN 108232142 A CN108232142 A CN 108232142A CN 201711402881 A CN201711402881 A CN 201711402881A CN 108232142 A CN108232142 A CN 108232142A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
This application discloses a kind of zinc sulphide/graphene composite material, the negative material includes zinc sulphide Mesoporous Spheres and graphene, and the zinc sulphide Mesoporous Spheres are by graphene coated.Zinc sulphide Mesoporous Spheres in the material include abundant meso-hole structure, as negative material, the contact area of electrode material and electrolyte can not only be increased, improve reaction rate, charge and discharge cycles can also be alleviated in the process due to electrode material volume change caused by sodium ion insertion and abjection.The characteristic that zinc sulphide is used as semiconducting electrical conductivity difference can greatly be improved by graphene coated, so as to improve the chemical property of composite material.
Description
Technical field
This application involves a kind of zinc sulphide/graphene composite material, preparation method and as negative material in the battery
Application, belong to electrochemical field.
Background technology
In recent years, power vehicle market constantly expands, lithium ion battery as the main power battery of current driving force automobile,
Its demand sharp increase so that become due to the problem of sustainable use caused by lithium resource content is less and is unevenly distributed
It becomes increasingly conspicuous.Sodium element rich content and widely distributed in the world has similar physics and chemical property to elemental lithium,
Therefore sodium-ion battery is by the extensive concern of researcher.Recent research indicate that sodium-ion battery has and lithium ion battery connects
Near chemical property, considers the reserves and price of sodium resource, and sodium-ion battery is considered as to substitute lithium ion battery to make
Match the ideal chose of stand-by power source for next-generation electric powered motor power supply and extensive energy-accumulating power station.
Since metallic sodium is during charge and discharge cycles, nonuniform deposition can occur in electrode surface, generate sodium dendrite, thorn
Diaphragm is worn to cause internal short-circuit of battery and explode, and metallic sodium fusing point is relatively low, therefore metallic sodium is not suitable for use in sodium ion
Battery cathode.The widely applied graphite cathode material on lithium ion battery since interlamellar spacing is not big enough, can not realize sodium ion
Insertion, cannot act as anode material of lithium-ion battery.Therefore, it explores and exploitation is a kind of of low cost and has height ratio capacity
Negative material with high circulation stability is one of significant challenge that lithium ion battery development faces.
Invention content
According to the one side of the application, a kind of zinc sulphide/graphene composite material is provided, which is characterized in that including sulphur
Change zinc Mesoporous Spheres and graphene, the zinc sulphide Mesoporous Spheres are by graphene coated.Zinc sulphide Mesoporous Spheres in the material include rich
Rich meso-hole structure as negative material, can not only increase the contact area of electrode material and electrolyte, improve reaction speed
Rate can also alleviate charge and discharge cycles in the process due to electrode material volume change caused by sodium ion insertion and abjection.Pass through
Graphene coated can greatly improve characteristic of the zinc sulphide as semiconducting electrical conductivity difference, so as to improve the electrochemistry of composite material
Performance.
Preferably, the zinc sulphide/graphene composite material is made of zinc sulphide Mesoporous Spheres and graphene, the zinc sulphide
Mesoporous Spheres are by graphene coated.
As a kind of embodiment, the size of the zinc sulphide Mesoporous Spheres is 80~120nm；The zinc sulphide Mesoporous Spheres contain
Have that 3~5nm's of aperture is mesoporous.
Preferably, in the zinc sulphide/graphene composite material, the mass percent of zinc sulphide is 70%~90%, stone
The mass percentage of black alkene is 10%~30%.
According to the another aspect of the application, the preparation method of the zinc sulphide/graphene composite material, the preparation are provided
Method is simple for process, low energy consumption, safety and environmental protection, is suitble to industrialized production, can stablize, satisfaction is efficiently prepared using need
Zinc sulphide/the graphene composite material asked.
The preparation method of the zinc sulphide/graphene composite material, which is characterized in that include the following steps：
1) zinc sulphide Mesoporous Spheres are obtained；
2) freezing processing and drying will be carried out containing the mixture of the zinc sulphide Mesoporous Spheres and graphene oxide, obtains oxygen
Graphite alkene coats zinc sulphide Mesoporous Spheres；
3) graphene oxide cladding zinc sulphide Mesoporous Spheres are placed in the atmosphere containing hydrogen material in 350~450
Reduction treatment is carried out at DEG C, obtains the compound composite material of zinc sulphide/graphene.
Zinc sulphide Mesoporous Spheres can be prepared by being commercially available, according to method of the prior art in step 1)
It arrives or the zinc salt zinc sulphide Mesoporous Spheres is prepared by method comprising the following steps：Zinc source, sulphur source, gelatin will be contained
Hydrothermal crystallizing at 100~150 DEG C is placed in the mixture of water to obtain for 36~60 hours.
Those skilled in the art can select the type of suitable zinc source and sulphur source as needed.
As a kind of embodiment, the zinc source is selected from least one of organic zinc salt.Preferably, the zinc source is selected from
The carboxylate of zinc；It is further preferred that the zinc source is zinc acetate.
As a kind of embodiment, the sulphur source is selected from least one of organic compound containing sulphur.Preferably, institute
Sulphur source is stated as thiocarbamide.
Preferably, in the mixture containing zinc source, sulphur source, gelatin and water, the molar ratio of zinc source and sulphur source is 1:3~
7；
Wherein, the molal quantity in zinc source is in terms of the molal quantity of the Zn-ef ficiency contained by it；The molal quantity of sulphur source is with contained by it
Element sulphur molal quantity meter.
Preferably, the mass ratio of zinc source and gelatin is 1:3~5；
Wherein, the quality in zinc source is in terms of the quality of zinc source in itself；The quality of gelatin is in terms of gelatin quality in itself.
Those skilled in the art can select the ratio of zinc sulphide Mesoporous Spheres and graphene oxide as needed.
As a kind of embodiment, in the step 2), the mixing containing the zinc sulphide Mesoporous Spheres and graphene oxide
The mass ratio of graphene oxide and the zinc sulphide Mesoporous Spheres is 1 in object：2~6.
Preferably, the mixture containing the zinc sulphide Mesoporous Spheres and graphene oxide first passes through before freezing processing is carried out
Cross supersound process；Sonication treatment time is no less than 10min.It is further preferred that the sonication treatment time for 20min~
40min。
Preferably, graphene oxide and the vulcanization in the mixture containing the zinc sulphide Mesoporous Spheres and graphene oxide
The mass ratio of zinc Mesoporous Spheres is 1：3~5.It is further preferred that the mixing containing the zinc sulphide Mesoporous Spheres and graphene oxide
The mass ratio of graphene oxide and the zinc sulphide Mesoporous Spheres is 1 in object：3.5~4.5.
Preferably, freezing processing described in step 2) is is placed in 10~20min of freezing in liquid nitrogen.
Preferably, it is dry for freeze-drying described in step 2).
As a kind of embodiment, freezing processing is carried out described in step 2) and drying is cold in liquid nitrogen for sample is positioned over
After jelly processing, dry 12-48h is transferred in vacuum freezing drying oven.
As a kind of embodiment, mixing of the atmosphere containing hydrogen for hydrogen and non-active gas in the step 3)
Gas.The inert atmosphere is selected from least one of nitrogen, helium, argon gas, xenon.
Preferably, the temperature of the reduction treatment in the step 3) is 350~450 DEG C.
Preferably, the heating rate of the reduction treatment in the step 3) is 0.8~1.5 DEG C/min.
Preferably, the processing time of the reduction treatment in the step 3) is 1.5~2.5h.
As a kind of specific embodiment, the preparation method of the zinc sulphide/graphene composite material includes：
Step 1: hydro-thermal prepares zinc sulphide Mesoporous Spheres
First (such as 1 is weighed with a certain mass ratio：2) acetic acid dihydrate zinc and thiocarbamide, add it in deionized water and stir
Mix it is uniformly mixed, with a certain mass ratio (gelatin：Acetic acid dihydrate zinc=4) gelatin stirring and dissolving at 50 DEG C is weighed, by two
Liquid is mixed and stirred for uniformly, pouring into water heating kettle, is put into baking oven and hydro-thermal reaction is carried out at 120 DEG C, reaction product is centrifuged
And it is cleaned and dried to obtain zinc sulphide Mesoporous Spheres.
Step 2: prepare graphene oxide cladding zinc sulphide Mesoporous Spheres composite material
Zinc sulphide Mesoporous Spheres are mixed according to a certain mass ratio and graphene solution, then ultrasonic agitation is handled with liquid nitrogen,
Sample after freezing is put into freeze drier, graphene oxide cladding zinc sulphide Mesoporous Spheres composite material is obtained after dry.
Step 3：Prepare graphene coated zinc sulphide Mesoporous Spheres composite material
Graphene oxide is reduced to graphene by heat treatment, obtains graphene coated zinc sulphide Mesoporous Spheres composite wood
Material.
According to the another aspect of the application, a kind of cell negative electrode material is provided, the cell negative electrode material contains above-mentioned
Any zinc sulphide/graphene composite material, in zinc sulphide/graphene composite material for being prepared according to any of the above-described method
At least one.The cell negative electrode material has preferable high rate during charging-discharging and cycle performance.
According to the another aspect of the application, a kind of lithium ion battery or sodium-ion battery are provided, which is characterized in that contain
Above-mentioned cell negative electrode material.
The advantageous effect that the application can generate includes：
1) zinc sulphide/graphene composite material provided herein, low in raw material price is environmental-friendly, electrochemistry
It can be excellent；
2) zinc sulphide/graphene composite material provided herein, abundant meso-hole structure in mesoporous ZnS, no
But the contact area of electrode material and electrolyte can be increased, improve reaction rate, during can also alleviating charge and discharge cycles
Due to electrode material volume change caused by sodium ion insertion and abjection；It can greatly improve zinc sulphide by graphene coated to make
For the characteristic of semiconducting electrical conductivity difference, so as to improve the chemical property of composite material；
3) preparation method of zinc sulphide/graphene composite material of the application is easily achieved, easy to operate, favorable reproducibility,
Requirement to device and environment is relatively low；
4) electrode of the application and battery zinc sulphide/graphene composite material comprising the application have good cycle
Performance and high rate performance.
Description of the drawings
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates of zinc sulphide Mesoporous Spheres sample P 1.
Fig. 2 is the pore-size distribution collection of illustrative plates of zinc sulphide Mesoporous Spheres sample P 1.
Fig. 3 is the transmission electron microscope picture (TEM) of zinc sulphide Mesoporous Spheres sample P 1.
Fig. 4 is the scanning electron microscope (SEM) photograph (SEM) of zinc sulphide/graphene composite material S1.
Fig. 5 is the transmission electron microscope picture (TEM) of zinc sulphide/graphene composite material S1.
Fig. 6 is 100 circle cycle performance figures of the battery C1 under 100mA/g current densities.
Fig. 7 is 140 circle cycle performance figures of the battery C1 under 1A/g current densities.
Fig. 8 is the battery C1 high rate performance figures under the current density of 0.1A/g, 0.25A/g, 0.5A/g and 1A/g respectively.
Fig. 9 is 100 circle cycle performance figures of the battery C4 under 100mA/g current densities.
Figure 10 is 100 circle cycle performance figures of the battery C5 under 100mA/g current densities.
Specific embodiment
The application is described in detail, but the application is not limited to these embodiments with reference to embodiment.
Unless otherwise instructed, the raw materials and reagents in embodiments herein are bought by commercial sources, without special
Processing directly uses.
In embodiment, the transmission electron microscope of sample is characterized using high resolution transmission electron microscopy (Tecnai F20).
In embodiment, the scanning electron microscope of sample uses the field emission scanning electron microscope of Hitachi SU-8020 models
Characterization.
In embodiment, the X-ray diffraction analysis (XRD) of sample is characterized using Miniflex 600.
In embodiment, the mesoporous data of sample are levied using Hiden IGA100B type nitrogen physisorptions instrument.
The preparation of 1 zinc sulphide Mesoporous Spheres sample of embodiment
By 0.22g acetic acid dihydrates zinc (Zn (OAc)2·2H2) and 0.38g thiocarbamides CH O4N2S is added to 30ml deionized waters
In, dissolving is uniformly mixed；0.8780g gelatin is added in 30ml deionized waters, magnetic agitation dissolves at 50 DEG C；The two is molten
10min is stirred at room temperature after liquid mixing, is transferred in water heating kettle, baking oven is put into after sealing, the hydro-thermal reaction under the conditions of 120 DEG C
48h, it is dry in vacuum drying chamber after reaction product is centrifuged and is cleaned with deionized water and ethyl alcohol, it is mesoporous to obtain zinc sulphide
Ball is denoted as P1.
Specific steps are with the preparation of P1, data feed change proportioning and preparation condition on the basis of P1 in table 1,
Obtain P2~P6.
Table 1
The preparation of 2 zinc sulphide of embodiment/graphene composite material sample
It weighs the dried zinc sulphide Mesoporous Spheres P1 of 80mg to be scattered in 20ml deionized waters, adds in a concentration of 2mg/ of 10ml
The graphene oxide solution of ml, ultrasonic (power 200W), which handles 30min and stir, to be made to be uniformly mixed；Mixed solution is poured into 50ml
In plastic cup, it is positioned in liquid nitrogen container after freezing processing 10min, is put into freeze drier, 24 are freeze-dried at -45 DEG C
Hour, obtain graphene oxide cladding zinc sulphide Mesoporous Spheres composite material SO1；Graphene oxide cladding zinc sulphide Mesoporous Spheres are answered
Condensation material SO1, in hydrogen argon gas reducing atmosphere (H2/Ar：5%/95%) 400 DEG C of processing 2h in, heating rate are 1 DEG C/min.
To graphene coated zinc sulphide Mesoporous Spheres composite material S1.
It weighs the dried zinc sulphide Mesoporous Spheres P1 of 80mg to be scattered in 20ml deionized waters, adds in a concentration of 2mg/ of 10ml
The graphene oxide solution of ml, ultrasonic (power 200W), which handles 30min and stir, to be made to be uniformly mixed, and mixed solution is poured into 50ml
In plastic cup, it is positioned in liquid nitrogen container after freezing processing 10min, is put into freeze drier, 24 are freeze-dried at -45 DEG C
Hour, obtain graphene oxide cladding zinc sulphide Mesoporous Spheres composite material SO2；Graphene oxide cladding zinc sulphide Mesoporous Spheres are answered
Condensation material SO2, in hydrogen argon gas reducing atmosphere (H2/Ar：5%/95%) in 450 DEG C processing 1.5h, heating rate for 1.5 DEG C/
min.Obtain graphene coated zinc sulphide Mesoporous Spheres composite material S2.
It weighs the dried zinc sulphide Mesoporous Spheres P1 of 80mg to be scattered in 20ml deionized waters, adds in a concentration of 2mg/ of 10ml
The graphene oxide solution of ml, ultrasonic (power 200W), which handles 30min and stir, to be made to be uniformly mixed, and mixed solution is poured into 50ml
In plastic cup, it is positioned in liquid nitrogen container after freezing processing 10min, is put into freeze drier, 24 are freeze-dried at -45 DEG C
Hour, obtain graphene oxide cladding zinc sulphide Mesoporous Spheres composite material SO3；Graphene oxide cladding zinc sulphide Mesoporous Spheres are answered
Condensation material SO3, in hydrogen argon gas reducing atmosphere (H2/Ar：5%/95%) in 350 DEG C processing 2.5h, heating rate for 0.8 DEG C/
min.Obtain graphene coated zinc sulphide Mesoporous Spheres composite material S3.
It weighs the dried zinc sulphide Mesoporous Spheres P1 of 90mg to be scattered in 20ml deionized waters, adds in a concentration of 2mg/ of 10ml
The graphene oxide solution of ml, ultrasonic (power 200W), which handles 30min and stir, to be made to be uniformly mixed, and mixed solution is poured into 50ml
In plastic cup, it is positioned in liquid nitrogen container after freezing processing 10min, is put into freeze drier, 24 are freeze-dried at -45 DEG C
Hour, obtain graphene oxide cladding zinc sulphide Mesoporous Spheres composite material SO4.Graphene oxide cladding zinc sulphide Mesoporous Spheres are answered
Condensation material SO4, in hydrogen argon gas reducing atmosphere (H2/Ar：5%/95%) in 350 DEG C processing 2.5h, heating rate for 0.8 DEG C/
min.Obtain graphene coated zinc sulphide Mesoporous Spheres composite material S4.
It weighs the dried zinc sulphide Mesoporous Spheres P1 of 70mg to be scattered in 20ml deionized waters, adds in a concentration of 2mg/ of 10ml
The graphene oxide solution of ml, ultrasonic (power 200W), which handles 30min and stir, to be made to be uniformly mixed, and mixed solution is poured into 50ml
In plastic cup, it is positioned in liquid nitrogen container after freezing processing 20min, is put into freeze drier, 24 are freeze-dried at -45 DEG C
Hour, obtain graphene oxide cladding zinc sulphide Mesoporous Spheres composite material SO5.Graphene oxide cladding zinc sulphide Mesoporous Spheres are answered
Condensation material SO5, in hydrogen argon gas reducing atmosphere (H2/Ar：5%/95%) in 350 DEG C processing 2.5h, heating rate for 0.8 DEG C/
min.Obtain graphene coated zinc sulphide Mesoporous Spheres composite material S5.
With sample S1, the difference lies in replace with zinc sulphide Mesoporous Spheres P1 respectively for specific preparation method and condition
P2, P3, P4, P5, P6, gained sample are denoted as S6, S7, S8, S9, S10 respectively.
The material phase analysis of 3 zinc sulphide Mesoporous Spheres sample of embodiment
Powder x-ray diffraction analysis is carried out to 1~P6 of zinc sulphide Mesoporous Spheres sample P respectively, the results show that zinc sulphide
On the XRD spectra of 1~P6 of Mesoporous Spheres sample P, (powder diffraction standard association is entrusted by the position of each diffraction maximum and the JCPDS of zinc sulphide
Member's meeting) data in card (72-0162) are consistent.It is Typical Representative, XRD spectra and the comparison with standard spectrogram with sample P 1
As shown in Figure 1.The XRD spectra of P2~P6 is similar with P1, that is, peak position is identical, according to preparation condition difference, peak intensity ±
10% range changing.
The nitrogen physisorption analysis of 4 zinc sulphide Mesoporous Spheres sample of embodiment
The mesoporous pore size in 1~P6 of zinc sulphide Mesoporous Spheres sample P is analyzed using nitrogen physisorption.Zinc sulphide
1~P6 of Mesoporous Spheres sample P comprising abundant mesoporous.
Graph of pore diameter distribution Fig. 2 of the Mesoporous Spheres sample P 1 obtained according to BJH formula can be seen that Mesoporous Spheres sample P 1 and contain
Abundant aperture is the mesoporous of 3~5nm.
The scanning electron microscope and transmission electron microscope analysis of 5 sample of embodiment
1~P6 of zinc sulphide Mesoporous Spheres sample P, zinc sulphide/graphene composite material sample S1~S10 are swept respectively
Retouch electron microscope analysis and transmission electron microscope analysis.
Scanning electron microscope the results show that the Size Distribution of 1~P6 of zinc sulphide Mesoporous Spheres sample P between 80~120nm, pattern
It is regular.Transmission electron microscope results show that including for 1~P6 of zinc sulphide Mesoporous Spheres sample P is mesoporous；Zinc sulphide/graphene composite wood
Expect in sample S1~S10, graphene coated is outside zinc sulphide Mesoporous Spheres.
Typical Representative such as sample P 1 and S1, the transmission electron microscope photo of sample P 1 is as shown in figure 3, as seen from Figure 3, in P1
Containing abundant mesoporous, the average grain diameter of P1 is about 100nm.The scanning electron microscope and transmission electron microscope photo of sample S1 is respectively such as Fig. 4
Shown in Fig. 5, it can be seen that graphene coated contains abundant hole outside zinc sulphide Mesoporous Spheres in sample S1 in sample S1
Diameter is the mesoporous of 3~5nm.
6 composite sample of embodiment is prepared as the sodium-ion battery of negative material
The performance using sample S1~S10 as negative material is measured respectively, specially：
By gained zinc sulphide/graphene composite material sample and conductive black, sodium carboxymethylcellulose (CMC) according to 8:1:
1 mass ratio uniformly mixes, and adds a small amount of deionized water is ground to be thoroughly mixed to form uniform paste, coated in copper foil substrate
Upper to be used as test electrode, vacuum drying 10h obtains negative plate at 100 DEG C.
Battery assembles and test：Negative plate is struck out directly as the electrode slice of 10mm, using metallic sodium piece as cathode, electrolysis
Liquid is 1M NaClO4/EC:DEC(1:1)+5wt%FEC is assembled into CR2032 button cells in the glove box full of argon gas.
The battery being prepared respectively using sample S1~S10 as negative material, is denoted as C1~C10 respectively.
7 Cell Performance Evaluation of embodiment
At room temperature, constant current charge-discharge test is carried out with the current density of 100mA/g, charge and discharge by voltage for 0.01~
3.0V。
The results show that the sodium-ion battery prepared using the application zinc sulphide/graphene composite material as negative material has
Good cycle performance and high rate performance.
Fig. 6 is 100 circle cycle performance figures of the C1 under 100mA/g current densities.From attached drawing 5 as can be seen that in 100mA/g
Current density under, for the first time discharge capacity be 1049mAh/g, cycle 100 circle after reversible capacity be 441mAh/g.
Fig. 7 is 140 circle cycle performance figures of the C1 under 1A/g current densities.The electric current in 1A/g is can be seen that from attached drawing 6
Under density, reversible capacity is 319mAh/g after 140 circle of cycle, and the later coulombic efficiency of 5 circle of cycle illustrates this all close to 100%
Material has preferable high rate during charging-discharging.
Fig. 8 is cycle performance figures of the battery C1 respectively under the current density of 0.1A/g, 0.25A/g, 0.5A/g and 1A/g.
From attached drawing 8 as can be seen that under the current density of 0.1A/g, 0.25A/g, 0.5A/g, 1A/g, reversible specific capacity is respectively
804mAh/g, 698mAh/g, 602mAh/g, 524mAh/g illustrate the high rate performance of the application zinc sulphide/graphene composite material
Well.
100 circle cycle performance tests under 100mA/g current densities, the same embodiment of test method are carried out to battery C4 and C5
7, as a result as shown in Figure 9 and Figure 10.
From attached drawing 9 as can be seen that battery C4 is under the current density of 100mA/g, discharge capacity is 710mAh/g for the first time, is followed
Reversible capacity is 267mAh/g after ring 100 encloses.
From attached drawing 10 as can be seen that battery C5 is under the current density of 100mA/g, discharge capacity is 776mAh/g for the first time,
Reversible capacity is 248mAh/g after 100 circle of cycle.
The above is only several embodiments of the application, any type of limitation is not done to the application, although this Shen
Please disclosed as above with preferred embodiment, however not to limit the application, any person skilled in the art is not taking off
In the range of technical scheme, make a little variation using the technology contents of the disclosure above or modification is equal to
Case study on implementation is imitated, is belonged in the range of technical solution.
Claims (10)
1. a kind of zinc sulphide/graphene composite material, which is characterized in that including zinc sulphide Mesoporous Spheres and graphene, the vulcanization
Zinc Mesoporous Spheres are by graphene coated.
2. zinc sulphide/graphene composite material according to claim 1, which is characterized in that the zinc sulphide Mesoporous Spheres
Size is 80~120nm；
The zinc sulphide Mesoporous Spheres contain the mesoporous of 3~5nm of aperture.
3. zinc sulphide/graphene composite material according to claim 1, which is characterized in that the zinc sulphide/graphene is multiple
In condensation material, the mass percent of zinc sulphide is 70%~90%, and the mass percentage of graphene is 10%~30%.
4. the preparation method of zinc sulphide/graphene composite material in claims 1 to 3 described in any one, which is characterized in that
It the described method comprises the following steps：
1) zinc sulphide Mesoporous Spheres are obtained；
2) freezing processing and drying will be carried out containing the mixture of the zinc sulphide Mesoporous Spheres and graphene oxide, obtains oxidation stone
Black alkene coats zinc sulphide Mesoporous Spheres；
3) graphene oxide cladding zinc sulphide Mesoporous Spheres are placed in the atmosphere containing hydrogen and are carried out at 350~450 DEG C
Reduction treatment obtains the compound composite material of zinc sulphide/graphene.
5. preparation method according to claim 4, which is characterized in that the zinc salt zinc sulphide Mesoporous Spheres are by including following step
Rapid method is prepared：
Mixture containing zinc source, sulphur source, gelatin and water is placed in hydrothermal crystallizing at 120~180 DEG C to obtain within 12~48 hours.
6. preparation method according to claim 5, which is characterized in that the zinc source in organic zinc salt at least one
Kind；Preferably, the zinc source is selected from the carboxylate of zinc；It is further preferred that the zinc source is zinc acetate；
The sulphur source is selected from least one of organic compound containing sulphur；Preferably, the sulphur source is thiocarbamide；
Preferably, in the mixture containing zinc source, sulphur source, gelatin and water, the molar ratio of zinc source and sulphur source is 1:3~7；
Wherein, the molal quantity in zinc source is in terms of the molal quantity of the Zn-ef ficiency contained by it；The molal quantity of sulphur source is with the sulphur contained by it
The molal quantity meter of element；
The mass ratio of zinc source and gelatin is 1:3~5；
Wherein, the quality in zinc source is in terms of the quality of zinc source in itself；The quality of gelatin is in terms of gelatin quality in itself.
7. preparation method according to claim 4, which is characterized in that mesoporous containing the zinc sulphide in the step 2)
The mass ratio of graphene oxide and the zinc sulphide Mesoporous Spheres is 1 in the mixture of ball and graphene oxide：2~6；
Preferably, graphene oxide is situated between with the zinc sulphide in the mixture containing the zinc sulphide Mesoporous Spheres and graphene oxide
The mass ratio of hole ball is 1：3~5.
8. preparation method according to claim 4, which is characterized in that freezing processing described in the step 2) is is placed in liquid
10~20min is freezed in nitrogen.
9. a kind of negative material, which is characterized in that compound containing zinc sulphide/graphene described in any one of claims 1 to 3
At least one in material, the zinc sulphide/graphene composite material being prepared according to any one of claim 4 to 8 the method
Kind.
10. a kind of lithium ion battery or sodium-ion battery, which is characterized in that contain the negative material described in claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711402881.XA CN108232142B (en) | 2017-12-22 | 2017-12-22 | Zinc sulfide/graphene composite material, and preparation method and application thereof |
Applications Claiming Priority (1)
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| CN109728283A (en) * | 2018-12-29 | 2019-05-07 | 桑德集团有限公司 | The preparation method and negative electrode material of composite material with graphene coated layer |
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| CN111293295B (en) * | 2020-01-13 | 2021-08-03 | 博尔特新材料(银川)有限公司 | Electrode material for waste rubber material-based secondary battery and preparation method thereof |
| CN112142096A (en) * | 2020-08-11 | 2020-12-29 | 中国科学院福建物质结构研究所 | Zinc sulfide composite electrode material prepared by zinc-containing ionic liquid |
| CN112768656A (en) * | 2021-01-11 | 2021-05-07 | 昆明理工大学 | Carbon-coated mesoporous transition metal sulfide negative electrode material and preparation method and application thereof |
| CN116443956A (en) * | 2023-04-28 | 2023-07-18 | 天能电池集团股份有限公司 | Preparation method of nano nickel oxide/graphene composite electrode material |
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