CN108493422A - A kind of sulfur functionalization porous graphene macroscopic view block materials and preparation method thereof - Google Patents
A kind of sulfur functionalization porous graphene macroscopic view block materials and preparation method thereof Download PDFInfo
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- CN108493422A CN108493422A CN201810313509.XA CN201810313509A CN108493422A CN 108493422 A CN108493422 A CN 108493422A CN 201810313509 A CN201810313509 A CN 201810313509A CN 108493422 A CN108493422 A CN 108493422A
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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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
The invention discloses a kind of preparation methods of sulfur functionalization porous graphene macroscopic view block materials, belong to energy-storage battery field of material technology.The preparation method is by mixing bismuthiol with graphene oxide dispersion, ultrasonic disperse obtains suspension, hydro-thermal reaction is carried out at a certain temperature, then the reaction product of hydro-thermal reaction is washed, the sulfur functionalization graphene macroscopic view block materials described in drying to obtain；It is used for sodium-ion battery using obtained sulfur functionalization graphene macroscopic view block materials as negative material, the specific capacity of battery to be high, and high rate performance is excellent.
Description
Technical field
The present invention relates to energy-storage battery field of material technology, and in particular to a kind of sulfur functionalization porous graphene macroscopic view block
The preparation method of material；
Background technology
As environmental pollution and energy shortage problem increasingly sharpen, force people continually develop it is environmentally protective it is renewable,
Sustainable new energy, especially wind power generation and solar power generation are even more focus of people's attention, however solar energy, wind energy etc.
New energy is affected by environment very big, and there are unstable and discontinuous defects to cause it can not direct grid-connected hair in energy output
Electricity, to cause energy waste and economic loss very huge.And the most effective mode to solve the above problems is exactly the big rule of installation
Mould energy storage device, lithium ion battery due to the advantage that energy density is high, has a safety feature be widely used in consumption electronic product and
Electric vehicle, however as the key element lithium for supporting its development, because resource reserve is low and distribution is serious uneven, cost it is higher at
An important factor for restrict its extensive stored energy application.Therefore, development resource is abundant, and low-cost advanced battery system is
Solve the inevitable outlet of the following extensive storing up electricity application.With the sodium of the same main group of lithium, physico-chemical property is similar to lithium, but its reserves is rich
Richness, it is widely distributed, it refines simply, considers from resource and environment etc., sodium-ion battery has cost effective advantage, therefore,
Become the extremely potential novel energy-storing equipment of extensive energy storage field by the sodium-ion battery of charge carrier of sodium ion.
Although sodium-ion battery has the advantages that cheap, environmentally protective etc. in the majority, there is also challenges simultaneously.Sodium ion
Radius is big, and alternative positive and negative pole material system is very limited, the missing for the negative material especially haveing excellent performance, serious to make
The about progress of sodium-ion battery functionization.Therefore, the storage sodium electrode material for seeking high power capacity and excellent cycling performance has become mesh
The research hotspot of preceding field of batteries.
As novel nano graphene material because of advantages such as large specific surface area, conductivity height, in entire energy storage field
It is concerned, since report is used as anode material of lithium-ion battery for the first time within 2013, has shown the potentiality of quickly storage sodium, however
, in specific capacity and high rate performance there is still a need for further being promoted, research finds to carry out sulfur doping or sulfur functionalization to graphene for it
Be conducive to electron-transport and ion diffusion with the functional group and structure three-dimensional porous network structure that introduce sulfur-bearing, be practicable
Improve the mode of capacity and high rate performance.
Invention content
In view of the deficiencies in the prior art, one of the objects of the present invention is to provide a kind of sulfur functionalization porous graphites
The preparation method of alkene macroscopic body material, this method preparation process is simple, of low cost, it is easy to accomplish large-scale production.
To achieve the goals above, the technical solution adopted in the present invention is：
A kind of preparation method of sulfur functionalization porous graphene macroscopic body, includes the following steps：
Step 1: by graphene oxide aqueous dispersion and bismuthiol (Bismuthiol, specially dimercaptothiodiazole,
It is referred to as DMTD) mixing, stirring ultrasound, be uniformly mixed liquid A；
Hydro-thermal reaction is carried out Step 2: mixed liquor A is placed in reaction kettle, obtains reaction product B；
Step 3: reaction product B is freeze-dried, sulfur functionalization porous graphene macroscopic body material is obtained.
Preferably, graphene oxide aqueous dispersion described in step 1 is the suspension of graphene oxide and water；Wherein,
The mass-volume concentration of graphene oxide, which is subject to, can form stable suspension, and the mass-volume concentration of graphene oxide is than excellent
It is selected as 1.0~4.0mg/ml, further preferably 2.0~4.0mg/ml；
Preferably, the graphene oxide aqueous dispersion is obtained by graphite oxide through ultrasonic disperse, and graphite oxide is
It is made through Hummers methods by graphite；
Preferably, the mass ratio of the graphene oxide and bismuthiol is 1：2~2：1, further preferably 1：1~2：1；
The inventors discovered that if the mass ratio of graphene oxide and bismuthiol is less than 1:2, it will cause macroscopic body structure pines
It dissipates, it is not easily molded, and the sulfur-bearing functional group of graphene surface can reduce the electric conductivity of final product too much；If mass ratio is more than
2, it will cause the sulfur functionalization of graphene is insufficient, surface sulfur-bearing functional group is very little, and the capacity that can be contributed is limited.
Preferably, the temperature of hydro-thermal reaction described in step 2 is 150~200 DEG C, further preferably 160~180 DEG C；
The inventors discovered that hydrothermal temperature has the performance of final sulfur functionalization porous graphene macroscopic body material
It has a certain impact, when temperature is higher than 200 DEG C, some potential safety problems can be caused；When temperature be less than 150 DEG C, required reaction
Time is longer, and graphene hydrogel is not easily molded, while the reducing degree of product is relatively low, influences electric conductivity.
Preferably, the hydro-thermal reaction time is 6~12h, further preferably 8~10h；
Preferably, freeze-drying time described in step 3 be 36~55h, further preferably 44~50h, particularly preferably
48h；
Preferably, a kind of preparation method of sulfur functionalization porous graphene macroscopic body material, is as follows：
One, deionized water is added in graphite oxide, cell 1~5h of ultrasonic disperse obtains graphene oxide aqueous dispersion；
Two, it weighs bismuthiol to be added in graphene oxide aqueous dispersion, magnetic agitation, water bath sonicator, obtain uniform
Mixed liquor A；
Three, obtained mixed liquor A is added in sealing water heating kettle, is placed in explosion-proof baking oven, at 150~200 DEG C, heat preservation
6~12h obtains graphene hydrogel；
Four, graphene hydrogel is cleaned repeatedly with deionized water；
Five, by the graphene hydrogel after washing in refrigerator precooling, be subsequently placed in freeze dryer 44~50h of freeze-drying,
Obtain sulfur functionalization porous graphene macroscopic body material.
The present invention obtains a kind of sulfur functionalization graphene macroform material by the above method, has three-dimensional porous network knot
Structure, mainly based on mesoporous and macropore, and sulfur content is 7.7wt%~25.2wt%.
The present invention also aims to the sulfur functionalization graphene macroform materials that will be obtained to use as cell negative electrode material
In preparing sodium-ion battery.
Advantageous effect：
(1) compared with prior art, preparation process of the present invention is simple, it is only necessary to which the common hydro-thermal+frozen dried of a step can be obtained
The fast body material of graphene macroscopic view, and it is not necessarily to high-temperature heat treatment；
(2) in the present invention, sulfur content can be by controlling graphene oxide and bismuthiol in obtained graphene macroscopic material
Ratio be adjusted, and then as needed be made different sulfur contents three-dimensional grapheme macroscopic material；
(3) sulfur content is high in the obtained sulfur functionalization graphene macroform material of the present invention, shows to introduce and largely contains
Sulphur functional group, storage sodium capacity is obviously improved, and the presence of three-dimensional porous graphene frame structure has conducive to electron-transport and ion
Diffusion, can promote the performance of high current charge-discharge, and the sulfur functionalization graphene macroform material of preparation is applied to sodium ion electricity
Chi Zhong, under the current density of 0.1A/g, the specific capacity for obtaining battery is about 400mAh/g, under the current density of 5A/g, than
Capacity is about 120mAh/g.
Description of the drawings
Fig. 1 be embodiment 1 prepare sulfur functionalization fire control graphene macroform scanning electron microscope (SEM) photo and
C, the energy spectrum diagram (EDS) of S, O element；
Fig. 2 is that embodiment 1 obtains sulfur functionalization graphene macroform material for sodium-ion battery in different current densities
Under specific capacity curve graph；
Fig. 3 is that embodiment 1 obtains sulfur functionalization graphene macroform material for sodium-ion battery in different current densities
Under charging and discharging curve figure；
Specific implementation mode
In the following, technical scheme of the present invention is described in detail by specific embodiment.
Embodiment 1
One, graphene oxide is prepared using Hummers methods：
The sodium nitrate of the graphite powder of 8g and 4g is placed in 1000mL beakers and is stirred, is slowly added under conditions of ice bath
The concentrated sulfuric acid of 185mL stirs 0.5h, and the potassium permanganate that 32g is added later stirs 2h, is heated to 35 DEG C until becoming paste.Then
The deionized water of 400mL is added dropwise dropwise, after be warming up to 98 DEG C, react 1h, be eventually adding the aquae hydrogenii dioxidi of 50mL 30%
Solution, the deionized water that 300mL is added dropwise continue to stir 2h.After reaction system cooling, filtered, after again plus 5%
Dilute hydrochloric acid carries out secondary suction filtration, subsequent centrifugal treating, and deionized water washs to neutrality and obtains graphene oxide；
Two, it weighs graphene oxide 160mg to be placed in 100mL plastics small beakers, adds 80mL deionized waters, it is thin in ice-water bath
Born of the same parents ultrasound 2h obtains the graphene oxide aqueous dispersions of 2mg/mL；
Three, it weighs in the graphene oxide dispersion that 160mg bismuthiols are added, magnetic agitation 20 minutes, water-bath is super
Sound 20 minutes, obtains uniform mixed liquor；
Four, obtained mixed liquor is placed in 100mL water heating kettles, seals, is placed in 180 DEG C of explosion-proof baking ovens and keeps the temperature 6h, stop
It only heats, cooled to room temperature, after being cleaned three times with deionized water to obtaining graphene hydrogel, then is placed in refrigerator
Precooling 5h, is then placed in freeze dryer and 48h is lyophilized, and obtains sulfur functionalization porous graphene macroscopic body material.
Embodiment 2
As different from Example 1, the amount for the bismuthiol being added in step 2 is 80mg, and the temperature of explosion-proof baking oven is
150 DEG C, soaking time 15h, remaining is not being repeated with embodiment 1.
Embodiment 3
As different from Example 1, the temperature of explosion-proof baking oven is 200 DEG C in step 3, keeps the temperature 12h, remaining same embodiment
1, it is not repeating.
Embodiment 4
As different from Example 1, the amount for the bismuthiol being added in step 2 be 120mg, freeze-drying time 50h,
Remaining same embodiment 1, is not repeating.
Comparative example 1
As different from Example 1, it is added without bismuthiol in step 2, remaining is not repeating, obtaining with embodiment 1
Material is porous graphene macroscopic body.
Above-described embodiment 1 is obtained into sulfur functionalization porous graphene macroscopic body material as negative material for sodium ion electricity
Pond, specific preparation process are as follows：
1, negative material and conductive agent Super-P, binder PVDF are pressed 7:2:1 ratio (70mg:20mg:10mg) exist
It is uniformly mixed, is coated on aluminium foil in NMP, and the dry 12h in 110 DEG C of vacuum drying ovens；
2, electrode slice obtained above is washed into the round pole piece of diameter 12mm as sodium-ion battery electrode, single circle
The load capacity of sulfur functionalization porous graphene macroscopic body is between 0.5-1mg on pole piece, and half-cell is assembled in glove box, with
Metallic sodium is cathode.
3, assembled half-cell stands 12h, then tests chemical property in blue electric equipment.
Performance detection is tested：Fig. 1 is the scanning electron microscopy of sulfur functionalization porous graphene macroscopic body prepared by embodiment 1
The energy spectrum diagram (EDS) of C, S, O are incorporated to Fig. 1 by mirror figure (SEM) for the ease of comparison；
It can be seen that there are three-dimensional porous crosslinked graphene frames in obtained final product, and S elements are equal
It is even to be distributed on entire frame, this is because graphene oxide layer restores in water-heat process and mutually overlaps structure between lamella
At three-dimensional porous crosslinked frame structure, while bismuthiol reacts with the oxygen-containing functional group on graphene oxide, is formed
Sulfur-bearing functional group be uniformly distributed in entire graphene macroform.
Electrochemical property test：Fig. 2 and Fig. 3 is respectively that embodiment 1 obtains sulfur functionalization graphene macroform material and is used for
Specific capacity curve graph and charging and discharging curve figure of the sodium-ion battery under different current densities, and related data is included in table 1, by
Data result in watch is it is found that the sulfur functionalization graphene macroform material that the present invention obtains shows higher storage sodium capacity and fast
Fast charge-discharge characteristic.
Table 1
| Current density (A/g) | Specific capacity (mAh/g) |
| 0.1 | 397 |
| 0.2 | 345 |
| 0.5 | 275 |
| 1.0 | 224 |
| 2.0 | 182 |
| 5.0 | 123 |
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Any one skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of sulfur functionalization porous graphene macroscopic body material, which is characterized in that include the following steps：
One, graphene oxide aqueous dispersion is mixed with bismuthiol, stirring ultrasound, be uniformly mixed liquid A；
Two, mixed liquor A is placed in reaction kettle and carries out hydro-thermal reaction, obtain reaction product B；
Three, reaction product B is freeze-dried, obtains sulfur functionalization porous graphene macroscopic body material.
2. according to the preparation method of functionalization porous graphene macroscopic body described in claim 1, which is characterized in that
Graphene oxide aqueous dispersion described in step 1 is the suspension of graphene oxide and water；The graphene oxide
Mass-volume concentration is than being preferably 1.0~4mg/ml, further preferably 2.0~4mg/ml.
3. according to the preparation method of functionalization porous graphene macroscopic body described in claims 1 or 2, which is characterized in that the oxygen
Graphite alkene is made by graphene through Hummers methods；Preferably, the mass ratio of the graphene oxide and bismuthiol be 1: 2~
2：1, further preferably 1: 1~2：1.
4. according to the preparation method of any one of the claim 1-3 functionalization porous graphene macroscopic bodies, which is characterized in that step
The temperature of rapid two hydro-thermal reaction is 150~200 DEG C, further preferably 160~180 DEG C.
5. according to the preparation method of any one of the claim 1-4 functionalization porous graphene macroscopic bodies, which is characterized in that institute
It is 6~12h, further preferably 8~10h to state the hydro-thermal reaction time.
6. according to the preparation method of any one of the claim 1-5 functionalization porous graphene macroscopic bodies, which is characterized in that step
Freeze-drying time described in rapid three is 36~55h, further preferably 44~50h, particularly preferably 48h.
7. a kind of preparation method of sulfur functionalization porous graphene macroscopic body material, which is characterized in that the specific steps are：
One, deionized water is added graphene oxide into, 1~5h of ultrasonic disperse obtains graphene oxide aqueous dispersions；
Two, it weighs bismuthiol to be added in graphene oxide aqueous dispersion, magnetic agitation, water bath sonicator is uniformly mixed
Liquid；
Three, obtained mixed liquor is placed in water heating kettle, seals, is placed in explosion-proof baking oven at 150 ~ 200 DEG C, kept the temperature 6 ~ 12h, obtain
To graphene hydrogel；
Four, graphene hydrogel is cleaned repeatedly with deionized water；
Five, by the graphene hydrogel after washing in refrigerator precooling, it is subsequently placed in 44 ~ 50h of freeze-drying in freeze dryer, obtains sulphur work(
Porous graphene macroscopic body material can be changed.
8. a kind of sulfur functionalization porous graphene macroscopic body material obtained using any one of the claim 1-7 preparation methods
Material, which is characterized in that the sulfur content of the sulfur functionalization porous graphene macroscopic body material is 7.7wt% ~ 25.2wt%.
9. a kind of sulfur functionalization porous graphene macroscopic body material obtained using any one of the claim 1-7 preparation methods
Material, which is characterized in that the sulfur functionalization porous graphene macroscopic body material is with mesoporous and macropore three-dimensional porous network
The compound of structure.
10. a kind of sodium-ion battery, which is characterized in that the sulphur work(obtained using any one of the claim 1-7 preparation methods
Porous graphene macroscopic body material can be changed and be applied to sodium-ion battery as negative material.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103811731A (en) * | 2012-11-09 | 2014-05-21 | 中国科学院金属研究所 | Graphene-sulfur composite electrode material, preparation method and application thereof |
| CN104069815A (en) * | 2014-07-22 | 2014-10-01 | 西南民族大学 | Sulfur doped grapheme foam, preparation method thereof and sewage treatment method employing same |
| CN104201350A (en) * | 2014-08-22 | 2014-12-10 | 南京中储新能源有限公司 | Secondary battery based on graphene aerogel/sulphur composite material |
| CN106517162A (en) * | 2016-12-15 | 2017-03-22 | 中国航空工业集团公司北京航空材料研究院 | Preparation method of nitrogen/ sulphur co-doping three-dimensional graphene sponge |
| CN107742701A (en) * | 2017-09-20 | 2018-02-27 | 东华大学 | Graphene titania aerogel composite and its preparation and application |
| US20180083289A1 (en) * | 2016-09-20 | 2018-03-22 | Nanotek Instruments, Inc. | Metal-Sulfur Battery Cathode Containing Humic Acid-Derived Conductive Foam Impregnated with Sulfur or Sulfide |
-
2018
- 2018-04-10 CN CN201810313509.XA patent/CN108493422A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103811731A (en) * | 2012-11-09 | 2014-05-21 | 中国科学院金属研究所 | Graphene-sulfur composite electrode material, preparation method and application thereof |
| CN104069815A (en) * | 2014-07-22 | 2014-10-01 | 西南民族大学 | Sulfur doped grapheme foam, preparation method thereof and sewage treatment method employing same |
| CN104201350A (en) * | 2014-08-22 | 2014-12-10 | 南京中储新能源有限公司 | Secondary battery based on graphene aerogel/sulphur composite material |
| US20180083289A1 (en) * | 2016-09-20 | 2018-03-22 | Nanotek Instruments, Inc. | Metal-Sulfur Battery Cathode Containing Humic Acid-Derived Conductive Foam Impregnated with Sulfur or Sulfide |
| CN106517162A (en) * | 2016-12-15 | 2017-03-22 | 中国航空工业集团公司北京航空材料研究院 | Preparation method of nitrogen/ sulphur co-doping three-dimensional graphene sponge |
| CN107742701A (en) * | 2017-09-20 | 2018-02-27 | 东华大学 | Graphene titania aerogel composite and its preparation and application |
Non-Patent Citations (1)
| Title |
|---|
| XIAOLEI WANG: "Sulfur covalently bonded graphene with large capacity and high rate for high-performance sodium-ion batteries anodes", 《NANO ENERGY》 * |
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Application publication date: 20180904 |